Knowledge paper inside.cdr 2

Knowledge & Strategy Partners

IIT - Delhi EIL

Knowledge & Strategy Paper on Technology Upgradation in

April 2013New Delhi

CHEMICAL PETROCHEMICAL INDUSTRY

&

For further details please contact...

Mr P. S. SinghHead-Chemicals Division, FICCI

Federation House, 1 Tansen Marg, New Delhi-110001

Tel: +91-11-2331 6540 (Dir)

EPBX: +91-11-23738760-70 (Extn 395)

Fax: +91-11-2332 0714/2372 1504

Email: [email protected]

Ms Charu SmitaAssistant Director-Chemicals Division, FICCI


Tel: +91-112335 7350 (Dir)

EPBX: +91-1123738760-70 (Extn 474)

Fax: +91-112332 0714/2372 1504


R.P. LuthraDirector Administration

Indian Institute of Chemical Engineers (Northern Regional Center)C-27, Qutab Institutional Area, New Delhi-110016

Tel. .: 011-26532060, 26533539, E-Mail : [email protected] : www.iichenrc.org

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01

Coal Gasification

Dr. Siddhartha Mukherjee, Director - TechnologyAir Liquide Global E&C Solutions India Private Limited

Introduction

History

Chemical Reactions

The term gasification covers the conversion of any carbonaceous fuel to a gaseous product

with a usable heating value. The process includes pyrolysis, partial oxidation and

hydrogenation but excludes combustion because the product flue gas has no residual

heating value. The dominant technology is partial oxidation which produces a synthesis

gas consisting of hydrogen and carbon monoxide in varying ratios.

The process of producing energy using the gasification method has been in use for more

than 180 years. The most important gaseous fuel used in the early nineteenth century was

town gas. This was produced by two processes namely pyrolysis of coal which produces a

gas with a relatively high heating value, and the water gas process, in which coke is

converted into a mixture of hydrogen and carbon monoxide to produce a medium Btu gas.

The coke oven and the water gas reactors were operated at pressures less than 2 bar. This

resulted in voluminous equipment.

The fully continuous gasification process was developed only after Carl von Linde

commercialised the cryogenic separation of air. Gasification processes using oxygen were

now developed for the production of synthesis gas. Following this, some important

gasification processes were developed viz. the Winkler fluid-bed process (1926), the Lurgi

moving bed process (1931) and the Koppers-Totzek entrained flow process (1940s).

The chemistry of gasification is extremely complex. The most important reactions relevant

to the gasification process are similar to those of gas reforming. The processes of

gasification and reforming therefore have a lot in common. Both take place at relatively

high temperatures (approximately 1000 oC or more), which is a result of the heat of

exothermic combustion (oxidation) reactions driving the endothermic reduction

reactions. The basic gasification reactions are the following:

Oxidation:

C + ½ O CO ∆H = -111 kJ/mol (1)2

CO + ½ O →CO H = -283 kJ/mol2

H + ½ O →H O ∆H = -242 kJ/mol (3)2 2 2

→

∆ (2)2


IIT - Delhi EIL


April 2013New Delhi


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The Indian chemical industry, an integral component of the Indian

economy has key linkages with several other industries such as

automotive, consumer durables, engineering, food processing etc and

produces & supplies more than 80000 products. With Asia's

increasing contribution to the global chemical industry, India

emerges as one of the focus destinations for chemical companies

worldwide.

Challenges to the Indian industry include growing competition from

other countries, sustainability of the business & perception issues of

the sector. In order to be competitive in the international market, the

chemical industry has to promote sustainable development by

investing in technologies that are water/energy/feedstock efficient,

protect the environment & stimulate growth while balancing

economic needs & financial constraints.

I am delighted that FICCI, jointly with the Department of Chemicals &

Petrochemicals, Government of India & Indian Institute of Chemical

Engineers (IIChE) is organising a Seminar on "Technology

Upgradation in the Chemicals and Petrochemicals industry" at New

Delhi on April 15-16, 2013.

I am confident the Seminar will achieve its objectives and wish it every

success.

Sd/-

Naina Lal KidwaiPresidentFICCI

Message Message

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The Indian chemical industry, an integral component of the Indian

economy has key linkages with several other industries such as

automotive, consumer durables, engineering, food processing etc and

produces & supplies more than 80000 products. With Asia's

increasing contribution to the global chemical industry, India

emerges as one of the focus destinations for chemical companies

worldwide.

Challenges to the Indian industry include growing competition from

other countries, sustainability of the business & perception issues of

the sector. In order to be competitive in the international market, the

chemical industry has to promote sustainable development by

investing in technologies that are water/energy/feedstock efficient,

protect the environment & stimulate growth while balancing

economic needs & financial constraints.

I am delighted that FICCI, jointly with the Department of Chemicals &

Petrochemicals, Government of India & Indian Institute of Chemical

Engineers (IIChE) is organising a Seminar on "Technology

Upgradation in the Chemicals and Petrochemicals industry" at New

Delhi on April 15-16, 2013.

I am confident the Seminar will achieve its objectives and wish it every

success.

Sd/-

Naina Lal KidwaiPresidentFICCI

Message Message

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stnetnoC foT ea lb

1. Coal Gasification- Dr Siddhartha Mukherjee . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 01Director Technology, Air Liquide Global E&C Solutions India Pvt. Ltd.

1

2 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 01

3 Chemical Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 01

4 Criteria for Assessment of Different Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 02

5 Gasification Processes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 02

6 Applications of Coal Gasification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 04

7 Coal Gasification - the Indian Perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 07

8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 08

2. Latest Developments in the Fertilizer (Ammonia) Industry- . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 09Dr S. Nand; Mr V. K. Goyal and Mr Manish Goswami, Fertilizers Association of India

Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 09

1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 09

2 Growth of ammonia industry in India . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

3 Energy conservation efforts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

4 Benchmarking of Energy Efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

5 Developments in ammonia technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

5.1 Reforming of hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

5.2 Conversion of CO to CO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

5.3 Synthesis gas Purification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

5.4 Ammonia synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

6 Future Developments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

7 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

3. Petrochemicals- Engineers India Limited . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

1 Introduction To Petrochemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

2 Petrochemicals from Steam Cracking of Hydrocarbons. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

2.1 Feedstock options. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

2.2 Directly saleable products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

2.3 Basic building blocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

2.4 Byproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

2.5 Block flow diagram and brief process description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

2.6 Technology suppliers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 01

Executive Summary

The Indian chemical industry is an integral component of the Indian economy. The

industry has key linkages with several other downstream industries such as automotive,

construction, consumer durables, engineering, food processing etc. The industry

produces and supplies more than 80000 products. The chemicals industry which includes,

(as per national Industrial Classification) basic chemicals & its products, petrochemicals,

fertilizers, paints and varnishes, gases, soaps, perfumes and toiletries is one of the most

diversified of all industrial sectors covering thousands of commercial products. The robust

growth of this sector is important for the national economy.

The Indian chemicals industry generated total revenue of about USD 108 billion in 2010

(Source: CMIE). The relevance of the chemical industry to the overall manufacturing sector

can be gauged by the fact that 'Basic chemicals and chemical products' account for about

14% in overall Index of Industrial Production (IIP).

In the Chemical Sector, 100 percent Foreign Direct Investment (FDI) is permissible thru

automatic route. Manufacture of most chemical products including organic / inorganic,

dyestuffs and pesticides is de-licensed. With Asia's increasing contribution to the global

chemical industry, India emerges as one of the focus destinations for chemical companies

worldwide. There is huge unrealised potential of further growth as indicated by the

present very low per capita consumptions in the country. The domestic demand is rapidly

increasing, and is being fuelled by approx. 200 million Indian middle class consumers. The

new National Manufacturing Policy has set the target of increasing the share of

manufacturing in GDP to at least 25% by 2025 (from current 16%). These all are

indications of the days of growth for this important sector.

However, for that to be possible, significant investments in capacity creation, R&D, feed

stock availability and infrastructure need to be created to enable the industry to be

globally competitive. If that is not done, the market forces will play and it will get served

through manufacturing done in other countries. The chemical industry in the coming

decades has to promote sustainable development by investing in technologies that

protects environment and stimulates growth while balancing economic needs and

financial constraints. This Seminar gives focus to this aspect.

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1. Coal Gasification- Dr Siddhartha Mukherjee . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 01Director Technology, Air Liquide Global E&C Solutions India Pvt. Ltd.

1

2 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 01

3 Chemical Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 01

4 Criteria for Assessment of Different Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 02

5 Gasification Processes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 02

6 Applications of Coal Gasification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 04

7 Coal Gasification - the Indian Perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 07

8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 08

2. Latest Developments in the Fertilizer (Ammonia) Industry- . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 09Dr S. Nand; Mr V. K. Goyal and Mr Manish Goswami, Fertilizers Association of India

Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 09

1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 09

2 Growth of ammonia industry in India . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

3 Energy conservation efforts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

4 Benchmarking of Energy Efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

5 Developments in ammonia technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

5.1 Reforming of hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

5.2 Conversion of CO to CO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

5.3 Synthesis gas Purification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

5.4 Ammonia synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

6 Future Developments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

7 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

3. Petrochemicals- Engineers India Limited . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

1 Introduction To Petrochemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

2 Petrochemicals from Steam Cracking of Hydrocarbons. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

2.1 Feedstock options. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

2.2 Directly saleable products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

2.3 Basic building blocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

2.4 Byproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

2.5 Block flow diagram and brief process description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

2.6 Technology suppliers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 01

Executive Summary

The Indian chemical industry is an integral component of the Indian economy. The

industry has key linkages with several other downstream industries such as automotive,

construction, consumer durables, engineering, food processing etc. The industry

produces and supplies more than 80000 products. The chemicals industry which includes,

(as per national Industrial Classification) basic chemicals & its products, petrochemicals,

fertilizers, paints and varnishes, gases, soaps, perfumes and toiletries is one of the most

diversified of all industrial sectors covering thousands of commercial products. The robust

growth of this sector is important for the national economy.

The Indian chemicals industry generated total revenue of about USD 108 billion in 2010

(Source: CMIE). The relevance of the chemical industry to the overall manufacturing sector

can be gauged by the fact that 'Basic chemicals and chemical products' account for about

14% in overall Index of Industrial Production (IIP).

In the Chemical Sector, 100 percent Foreign Direct Investment (FDI) is permissible thru

automatic route. Manufacture of most chemical products including organic / inorganic,

dyestuffs and pesticides is de-licensed. With Asia's increasing contribution to the global

chemical industry, India emerges as one of the focus destinations for chemical companies

worldwide. There is huge unrealised potential of further growth as indicated by the

present very low per capita consumptions in the country. The domestic demand is rapidly

increasing, and is being fuelled by approx. 200 million Indian middle class consumers. The

new National Manufacturing Policy has set the target of increasing the share of

manufacturing in GDP to at least 25% by 2025 (from current 16%). These all are

indications of the days of growth for this important sector.

However, for that to be possible, significant investments in capacity creation, R&D, feed

stock availability and infrastructure need to be created to enable the industry to be

globally competitive. If that is not done, the market forces will play and it will get served

through manufacturing done in other countries. The chemical industry in the coming

decades has to promote sustainable development by investing in technologies that

protects environment and stimulates growth while balancing economic needs and

financial constraints. This Seminar gives focus to this aspect.

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3 Pathways for Production of Various Petrochemicals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

3.1 Petrochemicals from Ethylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

3.2 Petrochemicals from Propylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

3.3 Petrochemicals from C4 fractions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35


3.5 Petrochemicals from Aromatics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38

3.6 Petrochemicals from Methanol. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51

4 Major Applications of Petrochemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55

5 Technology Suppliers for Production Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58

6. Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60

4. Breakthrough Applications of Ionic Liquids: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61A Platform Technology- Alak Bhattarcharya; Joe Kocal; Manuela Serban; UOP LLC, a Honeywell Company; Soumendra Banerjee; UOP IPL, a Honeywell Company

1 Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61

2 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61

3 Synthesis of Ionic Liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63

4 General Applications of Ionic Liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64

5 Industrially Significant Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65

6 Current Honeywell-PMT/UOP Technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66

7 Denitrogenation of Low sulfur Diesel: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67

8 Other applications of Ionic Liquids: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69

9 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71

10 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72

5. Scope of Fuel Cell Technology in India- . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75Dr. Suddhasatwa Basu, Dept. of Chemical Engineering, IIT Delhi

1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75

1.1 India - a growing economy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75

2. Energy Landscape. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76

2.1 Electricity Demand supply situation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77

3. Policy Landscape . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78

4. R&d Situation In India. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80

5. Markets For Fuel Cells In India . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83

5.1 Stationary Power . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84

5.2 Fuel cell markets in automotive sector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89

6. Electrocoagulation for the Treatment of Industry Effluent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92Dr. Anil K Saroha, Dept. of Chemical Engineering, IIT Delhi

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7. Strengthening of Mithi River Bridge Under N1 Taxiway at . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100Mumbai International AirportDr. Gopal L. Rai, CEO, R&M International Group

Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100

2. Strengthening of the Bridge Under Runway [2] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101

3. Strengthening of bridge under the Taxiway . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102

4. Summary and Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113

4. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113

8. Technical Paper-Introduction to Poly . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114Tetra Fluoroethylene ( PTFE )& Its ApplicationsKapil Malhotra, Vice President Marketing andRajeev Chauhan, Sr. General Manager- R & D, Gujarat Fluoro Chemicals Limited

1. PTFE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114

1.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114

1.2. Raw Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114

1.3. The Manufacturing Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115

1.4. Making the TFE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115

1.5. Quality Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117

2. PTFE - PRODUCT INFORMATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117

2.1. Form. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118

2.2. Function . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118

2.3. Characteristics of PTFE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119

2.4. Classification of PTFE. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119

2.5. Fillers for Coumpounded PTFE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123

2.6. Application of PTFE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127

9. About IIT Delhi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128

10. About Engineers India Limited . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128

11. About IIChE. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128

12. About FICCI. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128

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3 Pathways for Production of Various Petrochemicals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

3.1 Petrochemicals from Ethylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

3.2 Petrochemicals from Propylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30



3.5 Petrochemicals from Aromatics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38

3.6 Petrochemicals from Methanol. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51

4 Major Applications of Petrochemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55

5 Technology Suppliers for Production Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58

6. Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60

4. Breakthrough Applications of Ionic Liquids: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61A Platform Technology- Alak Bhattarcharya; Joe Kocal; Manuela Serban; UOP LLC, a Honeywell Company; Soumendra Banerjee; UOP IPL, a Honeywell Company

1 Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61

2 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61

3 Synthesis of Ionic Liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63

4 General Applications of Ionic Liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64

5 Industrially Significant Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65

6 Current Honeywell-PMT/UOP Technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66

7 Denitrogenation of Low sulfur Diesel: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67

8 Other applications of Ionic Liquids: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69

9 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71

10 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72

5. Scope of Fuel Cell Technology in India- . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75Dr. Suddhasatwa Basu, Dept. of Chemical Engineering, IIT Delhi

1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75

1.1 India - a growing economy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75

2. Energy Landscape. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76

2.1 Electricity Demand supply situation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77

3. Policy Landscape . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78

4. R&d Situation In India. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80

5. Markets For Fuel Cells In India . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83

5.1 Stationary Power . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84

5.2 Fuel cell markets in automotive sector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89

6. Electrocoagulation for the Treatment of Industry Effluent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92Dr. Anil K Saroha, Dept. of Chemical Engineering, IIT Delhi

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7. Strengthening of Mithi River Bridge Under N1 Taxiway at . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100Mumbai International AirportDr. Gopal L. Rai, CEO, R&M International Group

Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100

2. Strengthening of the Bridge Under Runway [2] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101

3. Strengthening of bridge under the Taxiway . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102

4. Summary and Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113

4. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113

8. Technical Paper-Introduction to Poly . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114Tetra Fluoroethylene ( PTFE )& Its ApplicationsKapil Malhotra, Vice President Marketing andRajeev Chauhan, Sr. General Manager- R & D, Gujarat Fluoro Chemicals Limited

1. PTFE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114

1.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114

1.2. Raw Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114

1.3. The Manufacturing Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115

1.4. Making the TFE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115

1.5. Quality Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117

2. PTFE - PRODUCT INFORMATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117

2.1. Form. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118

2.2. Function . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118

2.3. Characteristics of PTFE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119

2.4. Classification of PTFE. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119

2.5. Fillers for Coumpounded PTFE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123

2.6. Application of PTFE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127

9. About IIT Delhi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128

10. About Engineers India Limited . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128

11. About IIChE. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128

12. About FICCI. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128

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01

Coal Gasification


Introduction

History

Chemical Reactions
























Oxidation:

C + ½ O CO ∆H = -111 kJ/mol (1)2

CO + ½ O →CO H = -283 kJ/mol2

H + ½ O →H O ∆H = -242 kJ/mol (3)2 2 2

→

∆ (2)2

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01

Coal Gasification


Introduction

History

Chemical Reactions
























Oxidation:

C + ½ O CO ∆H = -111 kJ/mol (1)2

CO + ½ O →CO H = -283 kJ/mol2

H + ½ O →H O ∆H = -242 kJ/mol (3)2 2 2

→

∆ (2)2

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Reduction:

C + CO 2 CO H = 172 kJ/mol (4)2

C + H O→CO + H2 ∆H = 131 kJ/mol (5)2

Methane formation:

C + 2 H → CH ∆H = -75 kJ/mol (6)2 4

Water-gas shift:

CO + H O→CO + H2 ∆H = -41 kJ/mol (7)2 2

→ ∆

The reactions 1, 2 and 3 are essentially complete and do not need to be considered in

determining an equilibrium synthesis gas composition. However, the gas and solid phase

reactions 4, 5 and 6 have a role in determining the rate.

Practically speaking, the overall reaction can be written as:

n/2 m/2C H + O nCO + Hn m 2 2

where,

for gas as pure methane, m = 4, n =1

for oil, m/n = approx. 2

for coal, m/n = approx. 1

Besides economics and availability, efficiency and other process performance criteria

characterize individual gasification processes and aid in their comparison and

assessment. Some commonly used criteria for practical purposes are defined as follows:

Cold Gas Efficiency = (higher heating value of product gas) / (higher heating value of solid

feedstock)

Carbon Efficiency = 1 - (carbon in gasification residue) / (carbon in solid feedstock)

In practice, gasification processes use a broad range of reactor types. These reactor types

can be grouped into the following categories:

1. Moving Bed Gasifiers

2. Fluid Bed Gasifiers

3. Entrained Flow Gasifiers

Moving Bed Gasifiers : In moving bed gasifiers (sometimes called fixed-bed gasifiers) the

gasifying medium passes through a bed of granular or lump coal. The bed of coal moves

slowly downward under gravity as it is gasified, generally in a countercurrent blast. Such a

→

Criteria for Assessment of Different Processes

Gasification Processes

countercurrent arrangement gives high thermal efficiencies because the outgoing ash

heats the incoming gases, while the outgoing product gas heats the incoming solid

feedstock. Moving bed processes operate on lump coal. The long residence time (typically

1 hour), together with the temperature profile of the countercurrent system, gives high

carbon efficiencies (typically 96 - 99%). Among the moving bed processes, the oxygen

consumption for the Lurgi Fixed Bed Dry Bottom Gasifiers is very low since the operation is

below the ash fusion temperature, and therefore no additional oxygen is required to melt

the ash. However, pyrolysis products are present in the raw gas which report in the gas

liquor after gas cooling. The Lurgi Fixed Bed Dry Bottom Gasifiers are therefore ideal for

low rank coals since they operate below the ash softening point. The high ash content

would need a very high amount of oxygen if they were to operate above the ash softening

point.

Fluid-Bed Gasifier : Fluid-bed gasifiers are characterized by linear velocities of gasifying

medium sufficient to lift the solid particles. This requires smaller particle sizes, typically in

the 0.5 - 5 mm range. Such gasifiers offer very good mixing between feed and oxidant,

which promotes both heat and mass transfer. This ensures an even distribution of material

in the bed and hence a certain amount of partially reacted fuel is inevitably removed with

the ash. This places a limitation on the carbon conversion which is of the order of 90 - 95 %

for fluid-bed gasifiers. The operation of fluid-bed gasifiers are generally restricted to

temperatures below the ash softening point, since ash slagging will disturb the fluidization

in the bed. Sizes of particles in the feed is critical. Material that are too fine will get

entrained (cyclones installed downstream will only partially recapture them). The lower

temperature operation means that this process is also suited to low-rank coals.

Entrained Flow Gasifier : In entrained-flow gasifiers, solid particles are carried or

entrained by the reacting gases. Thus, solids and gases move in the same direction with

approximately the same velocity. To achieve this, the particles must be smaller than in

other systems (typically less than 500 microns). The retention time in these processes is

only a few seconds. This, together with high gasification temperatures (typically 1200 -

1900 oC) allows gasification rates high enough to ensure acceptable carbon conversion

during the short solids residence time in the gasifier. At such high temperatures, operation

is therefore in the slagging range. The high temperatures however create a high demand

for oxygen. Coals with high ash content would therefore call for oxygen demand to levels

that would make alternative processes have an economic advantage.

Refer table 1 for a comparative data on the three different types of gasifiers.

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Reduction:

C + CO 2 CO H = 172 kJ/mol (4)2

C + H O→CO + H2 ∆H = 131 kJ/mol (5)2

Methane formation:

C + 2 H → CH ∆H = -75 kJ/mol (6)2 4

Water-gas shift:

CO + H O→CO + H2 ∆H = -41 kJ/mol (7)2 2

→ ∆

The reactions 1, 2 and 3 are essentially complete and do not need to be considered in

determining an equilibrium synthesis gas composition. However, the gas and solid phase

reactions 4, 5 and 6 have a role in determining the rate.

Practically speaking, the overall reaction can be written as:

n/2 m/2C H + O nCO + Hn m 2 2

where,

for gas as pure methane, m = 4, n =1

for oil, m/n = approx. 2

for coal, m/n = approx. 1

Besides economics and availability, efficiency and other process performance criteria

characterize individual gasification processes and aid in their comparison and

assessment. Some commonly used criteria for practical purposes are defined as follows:

Cold Gas Efficiency = (higher heating value of product gas) / (higher heating value of solid

feedstock)

Carbon Efficiency = 1 - (carbon in gasification residue) / (carbon in solid feedstock)

In practice, gasification processes use a broad range of reactor types. These reactor types

can be grouped into the following categories:

1. Moving Bed Gasifiers

2. Fluid Bed Gasifiers

3. Entrained Flow Gasifiers

Moving Bed Gasifiers : In moving bed gasifiers (sometimes called fixed-bed gasifiers) the

gasifying medium passes through a bed of granular or lump coal. The bed of coal moves

slowly downward under gravity as it is gasified, generally in a countercurrent blast. Such a

→

Criteria for Assessment of Different Processes

Gasification Processes

countercurrent arrangement gives high thermal efficiencies because the outgoing ash

heats the incoming gases, while the outgoing product gas heats the incoming solid

feedstock. Moving bed processes operate on lump coal. The long residence time (typically

1 hour), together with the temperature profile of the countercurrent system, gives high

carbon efficiencies (typically 96 - 99%). Among the moving bed processes, the oxygen

consumption for the Lurgi Fixed Bed Dry Bottom Gasifiers is very low since the operation is

below the ash fusion temperature, and therefore no additional oxygen is required to melt

the ash. However, pyrolysis products are present in the raw gas which report in the gas

liquor after gas cooling. The Lurgi Fixed Bed Dry Bottom Gasifiers are therefore ideal for

low rank coals since they operate below the ash softening point. The high ash content

would need a very high amount of oxygen if they were to operate above the ash softening

point.

Fluid-Bed Gasifier : Fluid-bed gasifiers are characterized by linear velocities of gasifying

medium sufficient to lift the solid particles. This requires smaller particle sizes, typically in

the 0.5 - 5 mm range. Such gasifiers offer very good mixing between feed and oxidant,

which promotes both heat and mass transfer. This ensures an even distribution of material

in the bed and hence a certain amount of partially reacted fuel is inevitably removed with

the ash. This places a limitation on the carbon conversion which is of the order of 90 - 95 %

for fluid-bed gasifiers. The operation of fluid-bed gasifiers are generally restricted to

temperatures below the ash softening point, since ash slagging will disturb the fluidization

in the bed. Sizes of particles in the feed is critical. Material that are too fine will get

entrained (cyclones installed downstream will only partially recapture them). The lower

temperature operation means that this process is also suited to low-rank coals.

Entrained Flow Gasifier : In entrained-flow gasifiers, solid particles are carried or

entrained by the reacting gases. Thus, solids and gases move in the same direction with

approximately the same velocity. To achieve this, the particles must be smaller than in

other systems (typically less than 500 microns). The retention time in these processes is

only a few seconds. This, together with high gasification temperatures (typically 1200 -

1900 oC) allows gasification rates high enough to ensure acceptable carbon conversion

during the short solids residence time in the gasifier. At such high temperatures, operation

is therefore in the slagging range. The high temperatures however create a high demand

for oxygen. Coals with high ash content would therefore call for oxygen demand to levels

that would make alternative processes have an economic advantage.

Refer table 1 for a comparative data on the three different types of gasifiers.

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Applications of Coal Gasification

Coal gasification can be used to generate a wide variety of products. The raw synthesis gas

from the gasifier is treated in an acid gas removal unit (AGR) to remove the acid

components from gasification viz. hydrogen sulphide (H2S) and carbon oxysulphide (COS)

and also carbon dioxide (CO2).

The treated synthesis gas from acid gas removal unit as mixture of carbon monoxide and

hydrogen can be directly used in a gas turbine to generate power. The synthesis gas can

also be used in a direct reduction (DRI) furnace to produce steel. Depending on the type of

gasification process used, a CO Shift unit may or may not be needed to adjust the synthesis

gas composition to meet the required stoichoimetric proportion (figure 1).

The synthesis gas can be methanated to produce a methane rich gas by the reactions :

CO + 3 H CH + H O 2 2

CO + 4 H ? CH + 2 H O2 2 4 2

The product gas called substitute natural gas and can be used as a fuel (figure 1).

→ 4

Table 1 : Data of Different Types of Gasifiers Figure 1 : Production of Syngas for DRI and SNG for Fuel

Description Fixed Bed Fluidized Bed Entrained Flow

Type Fixed Bed Fluidized Bed Entrained flow

Combustion type Grate fired combustors Fluidized bed Pulverized coal

combustors combustors

Feed State Solids only Solids only Solids or liquids

Feed Size 5-50 mm 0.5-5 mm < 500 microns

Fuel Retention Time 15-60 minutes 5-50 seconds 1-10 seconds

Oxidant Air-or oxygen-blown Air-or oxygen-blown Almost always

oxygen-blown

Gasifier Outlet 400- 600°C 900 -1100°C 1200 -1900°C

Temperature

Ash Conditions Slagging/non-slagging Non-slagging Always slagging

H2/CO Ratio 1.7-2.3 0.9 0.4-0.5

kg O2 / kg daf 0.3-0.5 0.5-0.7 0.9-1.1

CH4, raw gas 9-16 mol% 2-3 mol% < 0.1 mol%

Carbon Conversion 96-99 % 90-95 % > 99.5 %

Cold Gas Efficiency 85-90 % 60-80 % 77-82 %TMLicensors Lurgi FBDB , BGL SES / U-Gas, HTW, KBR GE Energy, Shell,

Prenflo

If ammonia synthesis gas is the desired product, then the synthesis gas after CO Shift and

AGR is washed by liquid nitrogen. The product hydrogen after AGR still contains

contaminants such as oxygen, argon, carbon monoxide and methane. These are washed by

liquid nitrogen. The product of the liquid nitrogen wash is purified hydrogen along with

nitrogen. Additional nitrogen is added to adjust the hydrogen - nitrogen ratio to that

required for ammonia synthesis (figure 2).

Figure 2 : Production of Ammonia Syngas

CoalPreparation

Elemental Sulfur

CO2

N2

Ammonia Syngas

Ash

Acid GasRemoval

Nitrogen WashUnit

CO ShiftGasificationHP Steam

Air SeparationUnit

Sulfur RecoveryUnit

If hydrogen is the desired product, then the raw from the gasifier is first shifted whereby

the carbon monoxide is first converted to carbon dioxide and hydrogen. The carbon

dioxide is removed in the AGR. The product hydrogen from the AGR is treated in the

pressure swing adsorption (PSA) to produce hydrogen of the desired purity (figure 3).

CO2

SNG

Syngas for DRI

N2

Elemental Sulfur

Acid GasRemoval

Methanation

CO Shift(depending on raw gas

composition)

Ash

HP Steam

CoalPreparation

Gasification

Air SeparationUnit

Sulfur RecoveryUnit

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Applications of Coal Gasification

Coal gasification can be used to generate a wide variety of products. The raw synthesis gas

from the gasifier is treated in an acid gas removal unit (AGR) to remove the acid

components from gasification viz. hydrogen sulphide (H2S) and carbon oxysulphide (COS)

and also carbon dioxide (CO2).

The treated synthesis gas from acid gas removal unit as mixture of carbon monoxide and

hydrogen can be directly used in a gas turbine to generate power. The synthesis gas can

also be used in a direct reduction (DRI) furnace to produce steel. Depending on the type of

gasification process used, a CO Shift unit may or may not be needed to adjust the synthesis

gas composition to meet the required stoichoimetric proportion (figure 1).

The synthesis gas can be methanated to produce a methane rich gas by the reactions :

CO + 3 H CH + H O 2 2

CO + 4 H ? CH + 2 H O2 2 4 2

The product gas called substitute natural gas and can be used as a fuel (figure 1).

→ 4

Table 1 : Data of Different Types of Gasifiers Figure 1 : Production of Syngas for DRI and SNG for Fuel

Description Fixed Bed Fluidized Bed Entrained Flow

Type Fixed Bed Fluidized Bed Entrained flow

Combustion type Grate fired combustors Fluidized bed Pulverized coal

combustors combustors

Feed State Solids only Solids only Solids or liquids

Feed Size 5-50 mm 0.5-5 mm < 500 microns

Fuel Retention Time 15-60 minutes 5-50 seconds 1-10 seconds

Oxidant Air-or oxygen-blown Air-or oxygen-blown Almost always

oxygen-blown

Gasifier Outlet 400- 600°C 900 -1100°C 1200 -1900°C

Temperature

Ash Conditions Slagging/non-slagging Non-slagging Always slagging

H2/CO Ratio 1.7-2.3 0.9 0.4-0.5

kg O2 / kg daf 0.3-0.5 0.5-0.7 0.9-1.1

CH4, raw gas 9-16 mol% 2-3 mol% < 0.1 mol%

Carbon Conversion 96-99 % 90-95 % > 99.5 %

Cold Gas Efficiency 85-90 % 60-80 % 77-82 %TMLicensors Lurgi FBDB , BGL SES / U-Gas, HTW, KBR GE Energy, Shell,

Prenflo

If ammonia synthesis gas is the desired product, then the synthesis gas after CO Shift and

AGR is washed by liquid nitrogen. The product hydrogen after AGR still contains

contaminants such as oxygen, argon, carbon monoxide and methane. These are washed by

liquid nitrogen. The product of the liquid nitrogen wash is purified hydrogen along with

nitrogen. Additional nitrogen is added to adjust the hydrogen - nitrogen ratio to that

required for ammonia synthesis (figure 2).

Figure 2 : Production of Ammonia Syngas

CoalPreparation

Elemental Sulfur

CO2

N2

Ammonia Syngas

Ash

Acid GasRemoval

Nitrogen WashUnit

CO ShiftGasificationHP Steam

Air SeparationUnit

Sulfur RecoveryUnit

If hydrogen is the desired product, then the raw from the gasifier is first shifted whereby

the carbon monoxide is first converted to carbon dioxide and hydrogen. The carbon

dioxide is removed in the AGR. The product hydrogen from the AGR is treated in the

pressure swing adsorption (PSA) to produce hydrogen of the desired purity (figure 3).

CO2

SNG

Syngas for DRI

N2

Elemental Sulfur

Acid GasRemoval

Methanation


composition)

Ash

HP Steam

CoalPreparation

Gasification

Air SeparationUnit

Sulfur RecoveryUnit

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If both hydrogen and carbon monoxide are required as products, the synthesis gas is

routed to a CO Cold box where the carbon monoxide and hydrogen are separated. The

carbon monoxide is taken as a product. The impure hydrogen is purified in a PSA to the

desired level (figure 4). Coal Gasification - the Indian Perspective

Indian coals have the advantage of relatively low sulphur content. The problem however

lies in the extremely high ash content, which could be as high as 40% or more. This high

ash content with a high melting point (typically above 1200 oC) presents great difficulties

to all slagging processes. Any gasifier operating in the slagging mode will consume more

oxygen because of the heat required to keep the slag molten. In most coals, this drawback is

outweighed by the advantage of high temperature operation such as elimination of all

volatiles in the gas. Thus, modern process developments have taken the high temperature

route. The high ash content of Indian coals however, makes the modern high temperature

processes extremely expensive in terms of oxygen demand.

India has the world's third largest reserves of coal and the fuel is primarily used for the

production of steel and power. Gasification of coal rather than combustion, provides an

alternative solution to meet the energy demands of countries having surplus resources of

domestic coal. Coal gasification is a commercially proven technology and with substantial

technical advancements, it is now enjoying a considerable attention. This is because of the

development of new applications such as gas-to-liquids projects based on Fischer-Tropsch

technology, Methanol Synthesis, Substitute Natural gas etc. Further, the prospects of

increased efficiency and environmental friendly emissions including CO2 capture through

the use of Integrated Gasification Combined-Cycle (IGCC) in the power industry, favour the

deployment of such a process. The portfolio of Lurgi technologies provides solutions for

developing complete Coal to Liquid processes worldwide. As a member of the Air Liquide

Group since 2007, Lurgi technologies are a worldwide reference in the fields of process

engineering and technology licensing.

Figure 3 : Production of Hydrogen

Air Separation Unit

Sulfur RecoveryUnit

CoalPreparation

CO2

N2

Hydrogen

Elemental Sulfur

Gasification CO ShiftAcid GasRemoval

PressureSwing

Adsorption

Ash

HP Steam

Figure 4 : Production of Hydrogen and Carbon Monoxide

Air Separation Unit

Sulfur RecoveryUnit

CoalPreparation

Hydrogen

CO

Elemental Sulfur

CO2

N2

CO Cold Box

PressureSwing

Adsorption

CO Shift(depending on the splitrequired)

Acid GasRemoval

Gasification

Ash

HP Steam

If methanol is the desired product, then hydrogen, carbon monoxide and carbon dioxide

are desired in the methanol synthesis gas in a particular stoichiometric ratio. In such a

case, a part of the raw gas is passed through a CO Shift reactor, whereby some hydrogen and

carbon dioxide is produced. The shifted gas is then routed through the AGR to remove a

part of the carbon dioxide to achieve the desired stiochiometric quantities (figure 5). The

resultant synthesis gas is then sent for methanol synthesis.

Air Separation Unit

Acid GasRemoval

Sulfur RecoveryUnit

Elemental Sulfur

CO2

N2

GasificationHP Steam

Ash

MethanolSynthesis

CoalPreparation

Methanol


composition)

Figure 5 : Production of Methanol

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If both hydrogen and carbon monoxide are required as products, the synthesis gas is

routed to a CO Cold box where the carbon monoxide and hydrogen are separated. The

carbon monoxide is taken as a product. The impure hydrogen is purified in a PSA to the

desired level (figure 4). Coal Gasification - the Indian Perspective

Indian coals have the advantage of relatively low sulphur content. The problem however

lies in the extremely high ash content, which could be as high as 40% or more. This high

ash content with a high melting point (typically above 1200 oC) presents great difficulties

to all slagging processes. Any gasifier operating in the slagging mode will consume more

oxygen because of the heat required to keep the slag molten. In most coals, this drawback is

outweighed by the advantage of high temperature operation such as elimination of all

volatiles in the gas. Thus, modern process developments have taken the high temperature

route. The high ash content of Indian coals however, makes the modern high temperature

processes extremely expensive in terms of oxygen demand.

India has the world's third largest reserves of coal and the fuel is primarily used for the

production of steel and power. Gasification of coal rather than combustion, provides an

alternative solution to meet the energy demands of countries having surplus resources of

domestic coal. Coal gasification is a commercially proven technology and with substantial

technical advancements, it is now enjoying a considerable attention. This is because of the

development of new applications such as gas-to-liquids projects based on Fischer-Tropsch

technology, Methanol Synthesis, Substitute Natural gas etc. Further, the prospects of

increased efficiency and environmental friendly emissions including CO2 capture through

the use of Integrated Gasification Combined-Cycle (IGCC) in the power industry, favour the

deployment of such a process. The portfolio of Lurgi technologies provides solutions for

developing complete Coal to Liquid processes worldwide. As a member of the Air Liquide

Group since 2007, Lurgi technologies are a worldwide reference in the fields of process

engineering and technology licensing.

Figure 3 : Production of Hydrogen

Air Separation Unit

Sulfur RecoveryUnit

CoalPreparation

CO2

N2

Hydrogen

Elemental Sulfur

Gasification CO ShiftAcid GasRemoval

PressureSwing

Adsorption

Ash

HP Steam

Figure 4 : Production of Hydrogen and Carbon Monoxide

Air Separation Unit

Sulfur RecoveryUnit

CoalPreparation

Hydrogen

CO

Elemental Sulfur

CO2

N2

CO Cold Box

PressureSwing

Adsorption

CO Shift(depending on the splitrequired)

Acid GasRemoval

Gasification

Ash

HP Steam

If methanol is the desired product, then hydrogen, carbon monoxide and carbon dioxide

are desired in the methanol synthesis gas in a particular stoichiometric ratio. In such a

case, a part of the raw gas is passed through a CO Shift reactor, whereby some hydrogen and

carbon dioxide is produced. The shifted gas is then routed through the AGR to remove a

part of the carbon dioxide to achieve the desired stiochiometric quantities (figure 5). The

resultant synthesis gas is then sent for methanol synthesis.

Air Separation Unit

Acid GasRemoval

Sulfur RecoveryUnit

Elemental Sulfur

CO2

N2

GasificationHP Steam

Ash

MethanolSynthesis

CoalPreparation

Methanol


composition)

Figure 5 : Production of Methanol

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Abbreviations

AGR Acid Gas Removal

DRI Direct Reduction Iron

IGCC Integrated Gasification Combined Cycle

PSA Pressure Swing Adsorption

SNG Substitute Natural Gas

Higman, C., Maarten van der, B., Gasification, Gulf Publishing Company, 2003.

Elvers, B., Hawkins, S., Ravenscroft, M., Rounsaville, J. F., Schulz, G., Ullmann's Encyclopedia

of Industrial Chemistry, Volume A12, 5th Edition, VCH Verlagsgesellschaft mBH, 1989.

References

Latest Developments in the Fertilizer (Ammonia) Industry

Dr S Nand, V. K. Goyal and Manish GoswamiFertiliser Association of India

For Seminar on “Technology Upgradation in Chemical Industry”

on April 15-16, 2013, at IIChE, New Delhi

Abstract

1.0 Introduction

Fertilizer industry in India has evolved progressively during the last five decades keeping

pace with the developments in respect to technology and energy efficiency. The

developments in building of ammonia capacity and technological upgradation in existing

plants have been discussed in the paper. The paper also gives the performance of Indian

ammonia industry with respect to energy efficiency. The performance of Indian plants has

been compared with world ammonia plants. The paper has brought out various

developments in ammonia technology in the world during last few decades. The concept

of adiabatic pre-reformer, heat exchange reactor, auto-thermal reformer, synthesis gas

purification, multi synthesis converters and gas turbine for power generation along with

heat recovery for steam generation have been introduced by different technology

suppliers. Other major developments are in material of reformer tubes, burner design,

improved catalysts, efficient and reliable machinery/equipment, automation in process

control, etc. It became more and more viable to construct single stream ammonia plants of

larger capacities of 2000 tpd with lower and lower specific energy consumption. Apart

from adopting these developments in new plants, almost all old vintage plants have been

revamped by incorporating many of these improvements.

Fertiliser industry in India has grown to its present size during five decades starting

large scale production in 1950s. With the total production of about 38.6 Mt of

fertilizer products containing 16.5 Mt of plant nutrients (N + P2 O5) in 2011-12,

India is the third largest producer of fertilizers in the world and with consumption of

28.12 Mt nutrients or 60 Mt of products, it is the second largest consumer of

fertilizers in the world. Fertiliser industry in India is world class in terms of size of

plant, technology used and efficiency levels achieved.

Ammonia is the major building block for production of all nitrogenous fertilizers. It is

also technology and energy intensive. India produced 13.6 Mt of ammonia in 2011-

12. There have been challenges in improving operating factors and energy efficiency

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Abbreviations

AGR Acid Gas Removal

DRI Direct Reduction Iron

IGCC Integrated Gasification Combined Cycle

PSA Pressure Swing Adsorption

SNG Substitute Natural Gas

Higman, C., Maarten van der, B., Gasification, Gulf Publishing Company, 2003.

Elvers, B., Hawkins, S., Ravenscroft, M., Rounsaville, J. F., Schulz, G., Ullmann's Encyclopedia

of Industrial Chemistry, Volume A12, 5th Edition, VCH Verlagsgesellschaft mBH, 1989.

References

Latest Developments in the Fertilizer (Ammonia) Industry

Dr S Nand, V. K. Goyal and Manish GoswamiFertiliser Association of India

For Seminar on “Technology Upgradation in Chemical Industry”

on April 15-16, 2013, at IIChE, New Delhi

Abstract

1.0 Introduction

Fertilizer industry in India has evolved progressively during the last five decades keeping

pace with the developments in respect to technology and energy efficiency. The

developments in building of ammonia capacity and technological upgradation in existing

plants have been discussed in the paper. The paper also gives the performance of Indian

ammonia industry with respect to energy efficiency. The performance of Indian plants has

been compared with world ammonia plants. The paper has brought out various

developments in ammonia technology in the world during last few decades. The concept

of adiabatic pre-reformer, heat exchange reactor, auto-thermal reformer, synthesis gas

purification, multi synthesis converters and gas turbine for power generation along with

heat recovery for steam generation have been introduced by different technology

suppliers. Other major developments are in material of reformer tubes, burner design,

improved catalysts, efficient and reliable machinery/equipment, automation in process

control, etc. It became more and more viable to construct single stream ammonia plants of

larger capacities of 2000 tpd with lower and lower specific energy consumption. Apart

from adopting these developments in new plants, almost all old vintage plants have been

revamped by incorporating many of these improvements.

Fertiliser industry in India has grown to its present size during five decades starting

large scale production in 1950s. With the total production of about 38.6 Mt of

fertilizer products containing 16.5 Mt of plant nutrients (N + P2 O5) in 2011-12,

India is the third largest producer of fertilizers in the world and with consumption of

28.12 Mt nutrients or 60 Mt of products, it is the second largest consumer of

fertilizers in the world. Fertiliser industry in India is world class in terms of size of

plant, technology used and efficiency levels achieved.

Ammonia is the major building block for production of all nitrogenous fertilizers. It is

also technology and energy intensive. India produced 13.6 Mt of ammonia in 2011-

12. There have been challenges in improving operating factors and energy efficiency

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of ammonia plants. The present paper is limited to capture developments of Indian

ammonia industry and concomitant developments in various process steps of

ammonia manufacturing process.

During nineteen sixties and early seventies, ammonia plants were based mainly on

naphtha, fuel oil, which were then available as surplus from oil refineries. Initially,

the capacities of fertiliser plants were small, around 500 tpd. Reciprocating

compressors were used to meet the high pressure requirement of chemical

reactions.

During mid seventies, with the advent of centrifugal compressors, single stream

ammonia capacity of 900 tpd became norm for new projects.

During eighties, with the discovery of large quantities of natural gas in "Bombay High

/ South Basin" and laying of gas pipeline from Hazira (Gujarat) to Jagdishpur (UP) as

well as improvement in technology by way of gas turbines/ Heat Recovery Unit

(HRU), radial synthesis converter, electronic instrumentation, led to installation of

new gas based fertiliser plants of 1350 - 1500 tpd capacity.

During nineties, the technology got further supplemented by simultaneous

improvements in materials of construction, catalysts, advance process control, etc;

resulted in lower specific energy consumption. However, there has been no new

plant in India after 1999.

The first phase (1980s), of energy conservation measures included installation of

gas turbine power generation with heat recovered from exhaust gas for steam

generation at higher pressure, reducing specific energy consumption by 0.20 Gcal/te

ammonia. Change of internals of synthesis converter in old plants from axial flow to

radial or radial - axial flow, also resulted in 0.15-0.25 Gcal/te ammonia. Seven large

scale energy efficient ammonia plants of 1520 tpd using gas as feedstock also came

up in India during this period. The design energy of these plants was around 8.04

Gcal per tonne of ammonia.

The second phase (1990s), saw new concept of providing gas turbine (GT) drive

for process air compressor with heat recovery from exhaust gas. Other major energy

efficiency measures included revamp of CO2 removal system by way of change to

better solvent, better packing in absorption and desorption towers for higher mass

transfer efficiency, change over from LP condensate stripper to MP condensate

stripper etc.

2.0 Growth of ammonia industry in India

3.0 Energy conservation efforts

The other most significant development was availability of reformed tubes of better

metallurgy than that of HK-40 or equivalent used earlier in most reformers. The new

metallurgy like IN519 had higher strength and it was possible to use thinner wall

tubes. This allowed larger inner space for packing of catalyst and hence higher

throughput. This not only increased the reformer capacity but also helped to

improve energy efficiency of operation. Additional heat recovery from reformer

furnace flue gas also helped to reduce energy consumption of ammonia plants.

Replacement of analog instrumentation with Distributed Control Systems (DCS) and

Programmable Logic Controllers (PLC) became the norm.

Large ammonia capacity of about 5 million tonnes was added during this period

through 9 new plants. The design energy consumption of these plants was 7.5 to 8.0

Gcal/te ammonia on annual basis.

The third phase (2000 onwards), saw no new ammonia plant. Energy became

scarce and expensive. There was a renewed attempt to revamp older plants;

including those set up during eighties and even nineties.

During second half of last decade, demand for fertilizers accelerated, prompting a

number of plants to undertake debottlenecking projects for capacity enhancement.

These plants implemented energy saving measures simultaneously. A few of these

measures included (i) installation of combustion air pre-heater in reformer stack to

bring down exhaust temperature to as low as 120oC in case of low sulphur in natural

gas (ii) low temperature shift (LTS) guard (iii) change from single to two stage

regeneration in CO2 removal section for reduced energy consumption (iv) changing

of single stage flash vessel system in regenerator section with multistage flash vessel

with ejectors including a mechanical steam compressor (v) installation hydraulic

turbine to recover energy from high pressure process fluid, etc.

Advance process control (APC), were installed to optimize operating parameters

which gave marginal saving in energy in addition to maintaining smooth operation of

plants.

There have also been some process modifications in the synthesis loop. Installation

of S-50 converter with medium pressure waste heat boiler has increased ammonia

conversion from 14 to 19 per cent or even higher resulting in saving in recycle

energy. Similarly, one of the units has installed S-300 converter.

During this decade, additional gas became available from KG-D6 basin, and plants

based on naphtha / mixed feed were change to gas.

As a result of the energy conservation efforts of the industry and addition of capacity

through more efficient plants, the weighted average energy consumption of

ammonia plants in the country was reduced from 12.48 Gcal/te in 1987-88 to 8.82

Gcal/te in 2011-12, showing an improvement of almost 30 per cent in energy

efficiency of ammonia production.

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of ammonia plants. The present paper is limited to capture developments of Indian

ammonia industry and concomitant developments in various process steps of

ammonia manufacturing process.

During nineteen sixties and early seventies, ammonia plants were based mainly on

naphtha, fuel oil, which were then available as surplus from oil refineries. Initially,

the capacities of fertiliser plants were small, around 500 tpd. Reciprocating

compressors were used to meet the high pressure requirement of chemical

reactions.

During mid seventies, with the advent of centrifugal compressors, single stream

ammonia capacity of 900 tpd became norm for new projects.

During eighties, with the discovery of large quantities of natural gas in "Bombay High

/ South Basin" and laying of gas pipeline from Hazira (Gujarat) to Jagdishpur (UP) as

well as improvement in technology by way of gas turbines/ Heat Recovery Unit

(HRU), radial synthesis converter, electronic instrumentation, led to installation of

new gas based fertiliser plants of 1350 - 1500 tpd capacity.

During nineties, the technology got further supplemented by simultaneous

improvements in materials of construction, catalysts, advance process control, etc;

resulted in lower specific energy consumption. However, there has been no new

plant in India after 1999.

The first phase (1980s), of energy conservation measures included installation of

gas turbine power generation with heat recovered from exhaust gas for steam

generation at higher pressure, reducing specific energy consumption by 0.20 Gcal/te

ammonia. Change of internals of synthesis converter in old plants from axial flow to

radial or radial - axial flow, also resulted in 0.15-0.25 Gcal/te ammonia. Seven large

scale energy efficient ammonia plants of 1520 tpd using gas as feedstock also came

up in India during this period. The design energy of these plants was around 8.04

Gcal per tonne of ammonia.

The second phase (1990s), saw new concept of providing gas turbine (GT) drive

for process air compressor with heat recovery from exhaust gas. Other major energy

efficiency measures included revamp of CO2 removal system by way of change to

better solvent, better packing in absorption and desorption towers for higher mass

transfer efficiency, change over from LP condensate stripper to MP condensate

stripper etc.

2.0 Growth of ammonia industry in India

3.0 Energy conservation efforts

The other most significant development was availability of reformed tubes of better

metallurgy than that of HK-40 or equivalent used earlier in most reformers. The new

metallurgy like IN519 had higher strength and it was possible to use thinner wall

tubes. This allowed larger inner space for packing of catalyst and hence higher

throughput. This not only increased the reformer capacity but also helped to

improve energy efficiency of operation. Additional heat recovery from reformer

furnace flue gas also helped to reduce energy consumption of ammonia plants.

Replacement of analog instrumentation with Distributed Control Systems (DCS) and

Programmable Logic Controllers (PLC) became the norm.

Large ammonia capacity of about 5 million tonnes was added during this period

through 9 new plants. The design energy consumption of these plants was 7.5 to 8.0

Gcal/te ammonia on annual basis.

The third phase (2000 onwards), saw no new ammonia plant. Energy became

scarce and expensive. There was a renewed attempt to revamp older plants;

including those set up during eighties and even nineties.

During second half of last decade, demand for fertilizers accelerated, prompting a

number of plants to undertake debottlenecking projects for capacity enhancement.

These plants implemented energy saving measures simultaneously. A few of these

measures included (i) installation of combustion air pre-heater in reformer stack to

bring down exhaust temperature to as low as 120oC in case of low sulphur in natural

gas (ii) low temperature shift (LTS) guard (iii) change from single to two stage

regeneration in CO2 removal section for reduced energy consumption (iv) changing

of single stage flash vessel system in regenerator section with multistage flash vessel

with ejectors including a mechanical steam compressor (v) installation hydraulic

turbine to recover energy from high pressure process fluid, etc.

Advance process control (APC), were installed to optimize operating parameters

which gave marginal saving in energy in addition to maintaining smooth operation of

plants.

There have also been some process modifications in the synthesis loop. Installation

of S-50 converter with medium pressure waste heat boiler has increased ammonia

conversion from 14 to 19 per cent or even higher resulting in saving in recycle

energy. Similarly, one of the units has installed S-300 converter.

During this decade, additional gas became available from KG-D6 basin, and plants

based on naphtha / mixed feed were change to gas.

As a result of the energy conservation efforts of the industry and addition of capacity

through more efficient plants, the weighted average energy consumption of

ammonia plants in the country was reduced from 12.48 Gcal/te in 1987-88 to 8.82

Gcal/te in 2011-12, showing an improvement of almost 30 per cent in energy

efficiency of ammonia production.

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4.0 Benchmarking of Energy Efficiency

5.0 Developments in ammonia technology

International agencies like International Fertilizer Industry Association (IFA) carry

out benchmarking of energy efficiency of ammonia plants in the world and these are

reported in various publications(1). The average net energy efficiency of 93

ammonia plant surveyed by IFA in 2008 was 8.75 Gcal/te of ammonia. The best

plant operated in around 6.69 Gcal/te of ammonia. The overall weighted energy

consumption of gas based ammonia plants in India for the year 2008-09 was 8.47

Gcal/te ammonia. A majority of Indian gas based ammonia plants have energy

consumption in the range of 7.53 to 8.50 Gcal/te ammonia.

During the last five decades, ammonia technology has evolved significantly almost in

all fields. All the technology suppliers have strived hard to keep pace with the latest

developments in process flow sheet, sub-processes, catalysts, equipment,

machinery, material of construction, process controls etc. Some of the

improvements have been adopted as retrofits while carrying out major revamp of

the plant. Various options for incorporating such improvements are enumerated

here:-

Reforming process comprise of steam reforming of NG / naphtha in primary

reformer and then in secondary reformer. Some developments aim at shifting

the reforming duty from primary reformer to secondary reformer, achieving

5.1 Reforming of hydrocarbons

12.48

8.82

Year

13.0

12.5

12.0

11.5

11.0

10.5

10.0

9.5

9.0

8.5

1987-88

1988-89

1990-91

1992-93

1993-94

1994-95

1995-96

1996-97

1997-98

1998-99

1999-00

2000-01

2007-02

2002-03

2003-04

2004-05

2005-06

2006-07

2007-08

2008-09

2009-10

2010-11

2011-12

1989-90

1991-92

En

erg

y (G

Cal

/te

of

amm

on

ia)

Figure 1: Energy consumption trend for Ammonia Industry in India reduction in investment and more flexibility w.r.t hydrocarbons as well as

process parameters.

5.1.1 Adiabatic Pre-reformer

Adiabatic pre-reformer, generally used for steam reforming of naphtha, is now

widely used for improving capacity (10-20%) as well as energy efficiency of

natural gas steam reformer. Feed gas before entering pre-reformer is pre-

heated in the primary reformer stack. Gas coming out of the pre-reformer then

enters the primary reformer tubes. The advantages are manifold viz.

protecting downstream catalysts from sulphur poisoning, reducing steam to

carbon ratio, avoiding carbon formation in top portion of reformer tubes and

thus avoiding hot bending of catalyst tubes. In fact, it imparts a lot of flexibility

in plant operation with varying feedstocks, sulphur in feedstock, plant

capacity, etc. Energy saving is about 0.2 Gcal/te ammonia by way of reduction

in primary reformer furnace heat duty and lower steam to carbon ratio.

Almost all technology suppliers are offering pre-reformer as retrofit measure

to meet requirement of using naphtha as feedstock due to shortage in gas

supply.

5.1.2 Primary Reformer

a. Improved material for reformer tubes

Centrifugally cast reformer tubes made of alloy A 698 HK 40 have

been widely used, In the last decade, newer alloys such as A 297 HP,

Manaurite 36X were developed. Manaurite 36 X has a higher nickel

content, little more chromium and is stabilized with niobium. Its

creep rupture behavior is superior to HK40 and A 297 HP.

A comparison between the conventional IN 519 and modified

material HP - Mod Nb (25Cr :35 Ni : 1.5 Nb) reveals that the modified

material offers expected tubes life of 200000 hrs against 100000 hrs;

due to reduction in thickness, 6-7 % more catalyst can be charged.

This results in either increasing reformer capacity or reducing

pressure drop leading to reduction in energy consumption

b. Catalyst

Steam reforming of hydrocarbons is carried out with catalyst

containing nickel on a calcium aluminate base promoted by alkali.

In some top-fired furnaces, where the critical temperature for

thermal cracking is reached close to the inlet and for hydrocarbon

feeds containing higher hydrocarbons, low alkali promoted catalysts

are installed. The pre-reduced catalyst reduced in manufacturing

facilities in dry hydrogen at optimal conditions, results in higher

activity than what is obtained by in-situ reduction.

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4.0 Benchmarking of Energy Efficiency

5.0 Developments in ammonia technology

International agencies like International Fertilizer Industry Association (IFA) carry

out benchmarking of energy efficiency of ammonia plants in the world and these are

reported in various publications(1). The average net energy efficiency of 93

ammonia plant surveyed by IFA in 2008 was 8.75 Gcal/te of ammonia. The best

plant operated in around 6.69 Gcal/te of ammonia. The overall weighted energy

consumption of gas based ammonia plants in India for the year 2008-09 was 8.47

Gcal/te ammonia. A majority of Indian gas based ammonia plants have energy

consumption in the range of 7.53 to 8.50 Gcal/te ammonia.

During the last five decades, ammonia technology has evolved significantly almost in

all fields. All the technology suppliers have strived hard to keep pace with the latest

developments in process flow sheet, sub-processes, catalysts, equipment,

machinery, material of construction, process controls etc. Some of the

improvements have been adopted as retrofits while carrying out major revamp of

the plant. Various options for incorporating such improvements are enumerated

here:-

Reforming process comprise of steam reforming of NG / naphtha in primary

reformer and then in secondary reformer. Some developments aim at shifting

the reforming duty from primary reformer to secondary reformer, achieving

5.1 Reforming of hydrocarbons

12.48

8.82

Year

13.0

12.5

12.0

11.5

11.0

10.5

10.0

9.5

9.0

8.5

1987-88

1988-89

1990-91

1992-93

1993-94

1994-95

1995-96

1996-97

1997-98

1998-99

1999-00

2000-01

2007-02

2002-03

2003-04

2004-05

2005-06

2006-07

2007-08

2008-09

2009-10

2010-11

2011-12

1989-90

1991-92

En

erg

y (G

Cal

/te

of

amm

on

ia)

Figure 1: Energy consumption trend for Ammonia Industry in India reduction in investment and more flexibility w.r.t hydrocarbons as well as

process parameters.

5.1.1 Adiabatic Pre-reformer

Adiabatic pre-reformer, generally used for steam reforming of naphtha, is now

widely used for improving capacity (10-20%) as well as energy efficiency of

natural gas steam reformer. Feed gas before entering pre-reformer is pre-

heated in the primary reformer stack. Gas coming out of the pre-reformer then

enters the primary reformer tubes. The advantages are manifold viz.

protecting downstream catalysts from sulphur poisoning, reducing steam to

carbon ratio, avoiding carbon formation in top portion of reformer tubes and

thus avoiding hot bending of catalyst tubes. In fact, it imparts a lot of flexibility

in plant operation with varying feedstocks, sulphur in feedstock, plant

capacity, etc. Energy saving is about 0.2 Gcal/te ammonia by way of reduction

in primary reformer furnace heat duty and lower steam to carbon ratio.

Almost all technology suppliers are offering pre-reformer as retrofit measure

to meet requirement of using naphtha as feedstock due to shortage in gas

supply.

5.1.2 Primary Reformer

a. Improved material for reformer tubes

Centrifugally cast reformer tubes made of alloy A 698 HK 40 have

been widely used, In the last decade, newer alloys such as A 297 HP,

Manaurite 36X were developed. Manaurite 36 X has a higher nickel

content, little more chromium and is stabilized with niobium. Its

creep rupture behavior is superior to HK40 and A 297 HP.

A comparison between the conventional IN 519 and modified

material HP - Mod Nb (25Cr :35 Ni : 1.5 Nb) reveals that the modified

material offers expected tubes life of 200000 hrs against 100000 hrs;

due to reduction in thickness, 6-7 % more catalyst can be charged.

This results in either increasing reformer capacity or reducing

pressure drop leading to reduction in energy consumption

b. Catalyst

Steam reforming of hydrocarbons is carried out with catalyst

containing nickel on a calcium aluminate base promoted by alkali.

In some top-fired furnaces, where the critical temperature for

thermal cracking is reached close to the inlet and for hydrocarbon

feeds containing higher hydrocarbons, low alkali promoted catalysts

are installed. The pre-reduced catalyst reduced in manufacturing

facilities in dry hydrogen at optimal conditions, results in higher

activity than what is obtained by in-situ reduction.

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5.1.3 Secondary reformer

About 10-12% of the hydrocarbon feed remains unconverted in the

primary reformer. The process gas from primary reformer is mixed with

the air in a burner and then passed over a nickel-containing secondary

reformer catalyst. The reformer outlet temperature is around 1,000 °C,

and up to 99% of the hydrocarbon feed (to the primary reformer) is

converted, giving a residual methane content of 0.2-0.3% (dry gas base).

The process gas is cooled to 350-400°C in a waste heat steam boiler or

steam boiler/super-heater. Major improvement has been done in

burner and catalyst.

5.1.4 Autothermal reformer (ATR)

Auto-thermal reforming (ATR) is a process in which pre-reformed gas is

directly sent to ATR in which hydrocarbons are combusted with oxygen.

By omitting the tubular reformer, the steam addition to the feed streams

can be reduced significantly. The technology is in operation for many

years.

Burners : Because of high temperature there are problems of erosion of

burner nozzles, sintering of catalyst, hot spots on reformer wall, etc. The

burners used in these reformers are being improved in design

continuously by almost all the process licensors. Tools such as

computational fluid dynamics (CFD) and stress analysis with finite

element analysis are used to optimize burner design.

Different designers claim to achieve above mentioned objectives to

varying degree. The CTS concept was developed by HTAS in 1991, have

been in operation in both oxygen blown and ATR reformers. Johnson

Matthey through its ICI heritage, has extensive experience of secondary

reformer with burner. They have developed the KATALCO high intensity

ring burner (HIRB). Casale Chemicals has developed and commissioned

proprietary burner designs.

Another critical consideration is thermal stability of catalyst, for which

various improvements have been made

5.1.4 Heat exchanger reformer

The reformer exchanger offers an alternative to the conventional

primary reformer. The reforming is done in a tubular exchanger with

tubes filled with catalyst. The high-level heat of the secondary reformer

outlet gas at temperatures around 1,000 °C, serves as heat source for

reforming. Surplus air over the stoichiometric demand or oxygen-

enriched air is required in the secondary reformer to meet the heat

balance in this concept.

Chiyoda proposed this concept in 1984. However, ICI was the first one to

commercialize the Gas Heat Reformer (GHR) as part of their Leading

Concept Ammonia (LAC) process in 1988. M.W.Kellogg developed and

commercialized Kellogg Reforming Reformer System (KRES), in 1994.

Haldor Topsoe exchange reformer (HTER) has been developed and

commercialized.

5.2.1 HT Shift Converter

The process gas from the secondary reformer contains 12-15% CO (dry

gas base) and most of the CO is converted to CO2. In the High

Temperature Shift (HTS) conversion, the gas is passed through a bed of

iron oxide/chromium oxide catalyst at around 400 °C, where the CO

content is reduced to about 3% (dry gas base), limited by the shift

equilibrium at the actual operating temperature. There is a tendency to

use copper containing catalyst for increased conversion.

5.2.2 LT Shift Converter

The gas from the HTS is cooled and passed through the Low

Temperature Shift (LTS) converter. This LTS converter is filled with a

copper oxide/zinc oxide-based catalyst and operates at about 200-

220°C. The residual CO content in the converted gas is about 0.2-0.4%

(dry gas base). A low residual CO content is important for the efficiency

of the process.

5.2.3 LT Shift Guard

Haldor Topsoe (HTAS) is incorporating an additional Shift Guard reactor

along with BFW pre-heater upstream of existing LT Shift Converter. CO

slip is reduced from 0.2-0.4 to 0.1 to 0.2 mole%. This saves consumption

of hydrogen in methanator with corresponding increase in ammonia

production. Also there will be corresponding reduction in inerts in

synthesis loop. Heat recovery also improves.

5.3.1 CO2 removal

The process gas from the low temperature shift converter contains

mainly H2, N2, CO2, CO, CH4, inerts and the excess process steam.

Separation of CO2 is carried out by selective absorption of CO2 in a

liquid medium i.e. hot K2CO3, MEA or MDEA etc and subsequently

releasing it by depressurization and heating of the solution.

5.2 Conversion of CO to CO2

5.3 Synthesis gas Purification

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5.1.3 Secondary reformer

About 10-12% of the hydrocarbon feed remains unconverted in the

primary reformer. The process gas from primary reformer is mixed with

the air in a burner and then passed over a nickel-containing secondary

reformer catalyst. The reformer outlet temperature is around 1,000 °C,

and up to 99% of the hydrocarbon feed (to the primary reformer) is

converted, giving a residual methane content of 0.2-0.3% (dry gas base).

The process gas is cooled to 350-400°C in a waste heat steam boiler or

steam boiler/super-heater. Major improvement has been done in

burner and catalyst.

5.1.4 Autothermal reformer (ATR)

Auto-thermal reforming (ATR) is a process in which pre-reformed gas is

directly sent to ATR in which hydrocarbons are combusted with oxygen.

By omitting the tubular reformer, the steam addition to the feed streams

can be reduced significantly. The technology is in operation for many

years.

Burners : Because of high temperature there are problems of erosion of

burner nozzles, sintering of catalyst, hot spots on reformer wall, etc. The

burners used in these reformers are being improved in design

continuously by almost all the process licensors. Tools such as

computational fluid dynamics (CFD) and stress analysis with finite

element analysis are used to optimize burner design.

Different designers claim to achieve above mentioned objectives to

varying degree. The CTS concept was developed by HTAS in 1991, have

been in operation in both oxygen blown and ATR reformers. Johnson

Matthey through its ICI heritage, has extensive experience of secondary

reformer with burner. They have developed the KATALCO high intensity

ring burner (HIRB). Casale Chemicals has developed and commissioned

proprietary burner designs.

Another critical consideration is thermal stability of catalyst, for which

various improvements have been made

5.1.4 Heat exchanger reformer

The reformer exchanger offers an alternative to the conventional

primary reformer. The reforming is done in a tubular exchanger with

tubes filled with catalyst. The high-level heat of the secondary reformer

outlet gas at temperatures around 1,000 °C, serves as heat source for

reforming. Surplus air over the stoichiometric demand or oxygen-

enriched air is required in the secondary reformer to meet the heat

balance in this concept.

Chiyoda proposed this concept in 1984. However, ICI was the first one to

commercialize the Gas Heat Reformer (GHR) as part of their Leading

Concept Ammonia (LAC) process in 1988. M.W.Kellogg developed and

commercialized Kellogg Reforming Reformer System (KRES), in 1994.

Haldor Topsoe exchange reformer (HTER) has been developed and

commercialized.

5.2.1 HT Shift Converter

The process gas from the secondary reformer contains 12-15% CO (dry

gas base) and most of the CO is converted to CO2. In the High

Temperature Shift (HTS) conversion, the gas is passed through a bed of

iron oxide/chromium oxide catalyst at around 400 °C, where the CO

content is reduced to about 3% (dry gas base), limited by the shift

equilibrium at the actual operating temperature. There is a tendency to

use copper containing catalyst for increased conversion.

5.2.2 LT Shift Converter

The gas from the HTS is cooled and passed through the Low

Temperature Shift (LTS) converter. This LTS converter is filled with a

copper oxide/zinc oxide-based catalyst and operates at about 200-

220°C. The residual CO content in the converted gas is about 0.2-0.4%

(dry gas base). A low residual CO content is important for the efficiency

of the process.

5.2.3 LT Shift Guard

Haldor Topsoe (HTAS) is incorporating an additional Shift Guard reactor

along with BFW pre-heater upstream of existing LT Shift Converter. CO

slip is reduced from 0.2-0.4 to 0.1 to 0.2 mole%. This saves consumption

of hydrogen in methanator with corresponding increase in ammonia

production. Also there will be corresponding reduction in inerts in

synthesis loop. Heat recovery also improves.

5.3.1 CO2 removal

The process gas from the low temperature shift converter contains

mainly H2, N2, CO2, CO, CH4, inerts and the excess process steam.

Separation of CO2 is carried out by selective absorption of CO2 in a

liquid medium i.e. hot K2CO3, MEA or MDEA etc and subsequently

releasing it by depressurization and heating of the solution.

5.2 Conversion of CO to CO2

5.3 Synthesis gas Purification

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The important considerations are :-

(i) Selection of absorbent so as to yield high efficiency of absorption,

lower CO2 slip in the process gas, higher purity of CO2 product,

reduced corrosion , non-volatile, less corrosive, chemically stable,

etc.

(ii) Selection of activator, corrosion inhibitor, stabilizer etc.

(iii)Design of regenerator stages / temperature to minimize energy

consumption.

(iv)Design of internals and packing to cause low pressure drop.

(v) Auxiliaries like side stream filters for removal of suspended matter,

recovery and reutilization of process condensate, hydraulic turbine

to recover expansion energy.

The solvents used in chemical absorption processes are hot potassium

carbonate solution, Mono Ethanolamine (MEA), Methyl Di-

ethanolamine (MDEA) and Diglycoamine. Improvement involves low

regeneration energy requirement, not very susceptible to degradation

and is substantially non-corrosive.

Physical solvents viz. glycol dimethylethers (Selexol), propylene

carbonate and others.

Various developments in the technology have resulted in reduction in

energy requirement as well as corrosion. For CO2 removal from

ammonia synthesis gas, following major processes have been adopted

in various ammonia plants:-

(a) Benfield's Lo-heat process

The commercially proven UOP Benfield ACT- 1 activator claim lower

steam consumption, lower tower packed heights and easier solvent

maintenance. Mostly carbon steel construction is used and the process

is oxygen tolerant without solution degradation.

(b)Giammarco-Vetrocoke ( GV) low energy process

Since 1980, GV has introduced their low-energy process with Dual-

pressure regeneration which allows a reduction on the specific energy

consumption by 35-45% as compared to conventional single stage

regeneration process. Further, the GV Dual-activated solution started

since 1990, allows a considerable reduction on the CO2 slip coupled

with a lower sizing requirement of the columns.

GV has developed a proprietary Filtration / aeration system for re-

oxidising the corrosion inhibitor and maintaining the required ratio

between the total and pentavalent form of vanadium. Their Dual

activated absorbing solution which is a mix of selected activators e.g.

glycine & DEA is much more effective than a single activator.

(c) BASF's - a MDEA process using piperazine as activator

BASF's, "activated Methyldiethanolamine (a MDEA)" is employed for

removal of carbon dioxide (CO2) from process gas. The process is

claimed to be having flexibility in operation. Its low energy demand and

non-corrosive nature of the solvent keeps operating and maintenance

costs low. It also claims to provide a high level of gas purity and a large

yield of product gas as well as low levels of solvent losses.

(d)Physical absorption processes

Concepts such as Pressure Swing Adsorption (PSA) is also incorporated

in some new plants.

(e) Retrofits

Six Indian plants using the conventional Hot potassium carbonate

technology of yesteryear have been converted to GV low-energy process

with Dual-pressure two stage regeneration in the course of a normal

plant turnaround. The overall benefit depends on the existing plant

configuration and its operating efficiency. The saving is claimed to be

as high as 40 to 50% on the specific regeneration heat with a CO2 slip of

200- 300 ppmv. Alternatively, the plant capacity can increase to the

extent of 30 -50%.

5.3.2 Methanation

The small amounts of CO and CO2, remaining in the synthesis gas, are

poisonous for the ammonia synthesis catalyst and are removed by

conversion to CH4 in the methanator. The reactions take place at around

300°C in a reactor filled with a nickel containing catalyst.

5.3.3 Nitrogen wash

In the cryogenic purifier all the methane and the excess nitrogen are

removed from the synthesis gas as well as a part of the argon. The

purified synthesis gas is then practically free of all impurities, except for

a small amount of argon. The cryogenic unit also receives the purge from

the synthesis section and delivers an off-gas for fuel.

The removal of all impurities from the make-up synthesis gas is a

significant improvement, compared to the conventional purification by

methanation only. This results in higher conversion per pass and

reduced purge flow.

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The important considerations are :-

(i) Selection of absorbent so as to yield high efficiency of absorption,

lower CO2 slip in the process gas, higher purity of CO2 product,

reduced corrosion , non-volatile, less corrosive, chemically stable,

etc.

(ii) Selection of activator, corrosion inhibitor, stabilizer etc.

(iii)Design of regenerator stages / temperature to minimize energy

consumption.

(iv)Design of internals and packing to cause low pressure drop.

(v) Auxiliaries like side stream filters for removal of suspended matter,

recovery and reutilization of process condensate, hydraulic turbine

to recover expansion energy.

The solvents used in chemical absorption processes are hot potassium

carbonate solution, Mono Ethanolamine (MEA), Methyl Di-

ethanolamine (MDEA) and Diglycoamine. Improvement involves low

regeneration energy requirement, not very susceptible to degradation

and is substantially non-corrosive.

Physical solvents viz. glycol dimethylethers (Selexol), propylene

carbonate and others.

Various developments in the technology have resulted in reduction in

energy requirement as well as corrosion. For CO2 removal from

ammonia synthesis gas, following major processes have been adopted

in various ammonia plants:-

(a) Benfield's Lo-heat process

The commercially proven UOP Benfield ACT- 1 activator claim lower

steam consumption, lower tower packed heights and easier solvent

maintenance. Mostly carbon steel construction is used and the process

is oxygen tolerant without solution degradation.

(b)Giammarco-Vetrocoke ( GV) low energy process

Since 1980, GV has introduced their low-energy process with Dual-

pressure regeneration which allows a reduction on the specific energy

consumption by 35-45% as compared to conventional single stage

regeneration process. Further, the GV Dual-activated solution started

since 1990, allows a considerable reduction on the CO2 slip coupled

with a lower sizing requirement of the columns.

GV has developed a proprietary Filtration / aeration system for re-

oxidising the corrosion inhibitor and maintaining the required ratio

between the total and pentavalent form of vanadium. Their Dual

activated absorbing solution which is a mix of selected activators e.g.

glycine & DEA is much more effective than a single activator.

(c) BASF's - a MDEA process using piperazine as activator

BASF's, "activated Methyldiethanolamine (a MDEA)" is employed for

removal of carbon dioxide (CO2) from process gas. The process is

claimed to be having flexibility in operation. Its low energy demand and

non-corrosive nature of the solvent keeps operating and maintenance

costs low. It also claims to provide a high level of gas purity and a large

yield of product gas as well as low levels of solvent losses.

(d)Physical absorption processes

Concepts such as Pressure Swing Adsorption (PSA) is also incorporated

in some new plants.

(e) Retrofits

Six Indian plants using the conventional Hot potassium carbonate

technology of yesteryear have been converted to GV low-energy process

with Dual-pressure two stage regeneration in the course of a normal

plant turnaround. The overall benefit depends on the existing plant

configuration and its operating efficiency. The saving is claimed to be

as high as 40 to 50% on the specific regeneration heat with a CO2 slip of

200- 300 ppmv. Alternatively, the plant capacity can increase to the

extent of 30 -50%.

5.3.2 Methanation

The small amounts of CO and CO2, remaining in the synthesis gas, are

poisonous for the ammonia synthesis catalyst and are removed by

conversion to CH4 in the methanator. The reactions take place at around

300°C in a reactor filled with a nickel containing catalyst.

5.3.3 Nitrogen wash

In the cryogenic purifier all the methane and the excess nitrogen are

removed from the synthesis gas as well as a part of the argon. The

purified synthesis gas is then practically free of all impurities, except for

a small amount of argon. The cryogenic unit also receives the purge from

the synthesis section and delivers an off-gas for fuel.

The removal of all impurities from the make-up synthesis gas is a

significant improvement, compared to the conventional purification by

methanation only. This results in higher conversion per pass and

reduced purge flow.

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5.4 Ammonia synthesis

The synthesis of ammonia takes place on an iron catalyst at pressures usually in

the range 100-250 bar and temperatures in the range 350-550°C. Conversion

per pass is 16-23%. The conventional commercial ammonia synthesis catalyst

is activated magnetite ore (Fe3O4) fused with Al2O3 and K2O.

Since the introduction of two-bed S-200 radial flow ammonia converter in

1976, this type of converter is widely used world over. Subsequently, three bed

radial flow converter (S-300) has been developed and commercialized since

1999. This design allows for higher conversion and energy savings. The S-300

ammonia converter features three radial flow catalysts beds with two inter-bed

heat exchangers. Catalyst volume can be reduced by about 20% compared to S-

200 converter for the same ammonia conversion. Alternatively, for the same

catalyst volume, ammonia conversion can be increased thus reducing specific

energy consumption.

Haldor Topsoe A/S (HTAS) have introduced one additional single bed converter

basket (S-50) along with WHB at the downstream of existing ammonia

converter. Ammonia conversion efficiency improves by 4% and net energy

saving is around 0.13 Gcal/te of ammonia.

Some of the proprietary ammonia synthesis converter technologies are KAAP

catalyst consisting of ruthenium on a stable graphite carbon base and KAAP

plus, synergistically combining the advantages of three KBR ammonia

technologies viz KRES, Purifier and KAAP. This technology is being offered for

new ammonia plants.

Some of the improvements in ammonia synthesis catalyst comprise of cobalt

promoted catalyst which was first developed in 1980s for use at low pressure

(around 90 bar) in ICI AMV and LCA process. It also brings benefit to operation

at higher pressure applications and allows reduction at lower temperature.

During 1980s, ammonia synthesis catalyst from "Wustite (FeO)", used in

commercial production, claims to have faster reduction, improved pore

structure, higher activity and increased thermal resistance compared to

conventional magnetite based catalyst. This catalyst is triply promoted by

potassium, calcium and aluminum oxides in different form and proportion.

Recently developed ruthenium catalyst is proprietary and integral part of

Kellogg Advanced Ammonia Process (KAAP). The catalyst is up to twenty times

more active than conventional magnetite based catalyst. Although its

investment cost is higher, the benefits of using this catalyst are found in lower

synthesis loop pressure, greater flexibility in synthesis compressor selection,

vessels, piping, and fittings being of lower thickness and lighter weight.

6.0 Future Developments

Production of ammonia comprises of two major steps which are independent of

each other. The first step involves preparation of ammonia synthesis gas and

second step is independent of first one and involves synthesis of ammonia.

Synthesis gas is the mixture of hydrogen and nitrogen in required stoichiometry

and requisite purity. Various technological advancements have been introduced by

technology suppliers in either or both steps. It may be possible to improve

efficiency by installing a custom make plant from the best available technological

steps.

Large scale single train ammonia plants are being designed by all major

technology suppliers for capacity as high as 3300 tpd and even higher. The

suppliers have improved upon basic technology to improve energy efficiency by

incorporating systems for efficient heat utilization, improvement in

vessels/converters internals, increasing conversion efficiency of synthesis by

better design, operational changes and improved catalysts, use of better material

of construction, efficient equipments, and better maneuverability of operational

parameters due to advance control systems, etc.

Future developments in ammonia technology are expected to go in the following

directions:-

Further shifting of duty from primary to secondary reformer

Lowering the steam to carbon ratio

Improved final purification step with lower energy consumption.

Improved synthesis loop efficiency

Improvement in major drives and compressors

Low NOx burners

Non iron based ammonia synthesis catalyst

The new autothermal concepts are expected to be developed further.

Higher capacity Ammonia Plants of more than 4000 tonnes per day.

New generation ammonia / urea plants of large capacities more than 3000 tpd

ammonia are now available. Energy efficiency levels of 6.6 to 6.8 Gcal/te ammonia

are claimed by the suppliers. Under Indian conditions, the energy consumption

may be little higher due to high ambient temperature, higher cooling water

temperature and ensuring high purity of carbon-di-oxide for urea production.

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5.4 Ammonia synthesis

The synthesis of ammonia takes place on an iron catalyst at pressures usually in

the range 100-250 bar and temperatures in the range 350-550°C. Conversion

per pass is 16-23%. The conventional commercial ammonia synthesis catalyst

is activated magnetite ore (Fe3O4) fused with Al2O3 and K2O.

Since the introduction of two-bed S-200 radial flow ammonia converter in

1976, this type of converter is widely used world over. Subsequently, three bed

radial flow converter (S-300) has been developed and commercialized since

1999. This design allows for higher conversion and energy savings. The S-300

ammonia converter features three radial flow catalysts beds with two inter-bed

heat exchangers. Catalyst volume can be reduced by about 20% compared to S-

200 converter for the same ammonia conversion. Alternatively, for the same

catalyst volume, ammonia conversion can be increased thus reducing specific

energy consumption.

Haldor Topsoe A/S (HTAS) have introduced one additional single bed converter

basket (S-50) along with WHB at the downstream of existing ammonia

converter. Ammonia conversion efficiency improves by 4% and net energy

saving is around 0.13 Gcal/te of ammonia.

Some of the proprietary ammonia synthesis converter technologies are KAAP

catalyst consisting of ruthenium on a stable graphite carbon base and KAAP

plus, synergistically combining the advantages of three KBR ammonia

technologies viz KRES, Purifier and KAAP. This technology is being offered for

new ammonia plants.

Some of the improvements in ammonia synthesis catalyst comprise of cobalt

promoted catalyst which was first developed in 1980s for use at low pressure

(around 90 bar) in ICI AMV and LCA process. It also brings benefit to operation

at higher pressure applications and allows reduction at lower temperature.

During 1980s, ammonia synthesis catalyst from "Wustite (FeO)", used in

commercial production, claims to have faster reduction, improved pore

structure, higher activity and increased thermal resistance compared to

conventional magnetite based catalyst. This catalyst is triply promoted by

potassium, calcium and aluminum oxides in different form and proportion.

Recently developed ruthenium catalyst is proprietary and integral part of

Kellogg Advanced Ammonia Process (KAAP). The catalyst is up to twenty times

more active than conventional magnetite based catalyst. Although its

investment cost is higher, the benefits of using this catalyst are found in lower

synthesis loop pressure, greater flexibility in synthesis compressor selection,

vessels, piping, and fittings being of lower thickness and lighter weight.

6.0 Future Developments

Production of ammonia comprises of two major steps which are independent of

each other. The first step involves preparation of ammonia synthesis gas and

second step is independent of first one and involves synthesis of ammonia.

Synthesis gas is the mixture of hydrogen and nitrogen in required stoichiometry

and requisite purity. Various technological advancements have been introduced by

technology suppliers in either or both steps. It may be possible to improve

efficiency by installing a custom make plant from the best available technological

steps.

Large scale single train ammonia plants are being designed by all major

technology suppliers for capacity as high as 3300 tpd and even higher. The

suppliers have improved upon basic technology to improve energy efficiency by

incorporating systems for efficient heat utilization, improvement in

vessels/converters internals, increasing conversion efficiency of synthesis by

better design, operational changes and improved catalysts, use of better material

of construction, efficient equipments, and better maneuverability of operational

parameters due to advance control systems, etc.

Future developments in ammonia technology are expected to go in the following

directions:-

Further shifting of duty from primary to secondary reformer

Lowering the steam to carbon ratio

Improved final purification step with lower energy consumption.

Improved synthesis loop efficiency

Improvement in major drives and compressors

Low NOx burners

Non iron based ammonia synthesis catalyst

The new autothermal concepts are expected to be developed further.

Higher capacity Ammonia Plants of more than 4000 tonnes per day.

New generation ammonia / urea plants of large capacities more than 3000 tpd

ammonia are now available. Energy efficiency levels of 6.6 to 6.8 Gcal/te ammonia

are claimed by the suppliers. Under Indian conditions, the energy consumption

may be little higher due to high ambient temperature, higher cooling water

temperature and ensuring high purity of carbon-di-oxide for urea production.

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7.0 Conclusion

8.0 References

Ammonia production is technology and energy intensive. Indian ammonia

industry has evolved over the years incorporating state of the art technology in

new plants. Old and later generation plants have also upgraded technology to keep

pace with developments in process configuration, material of construction,

catalyst, design of major rotating and static equipment like reactors, heat

exchangers etc. The average energy efficiency of Indian ammonia plants compares

well similar plants in the world.

The paper has also enumerated various developments in ammonia technology.

Future plants in India and abroad will have capacity more than 2000 tpd with

energy efficiency of less than 7.0 Gcal per tonne of ammonia.

(1) "Energy Efficiency on CO2 Emission in Ammonia Production", December

2009, International Fertilizer Industry Association (IFA).

(2) S Nand and Manish Goswami, "Energy Efficiency and CO2 Generation in

Indian Ammonia Plants", Proceedings of Ammonia Safety Symposium of

American Institute of Chemical Engineers, Montreal, Canada, Vol. 52, pp 191-

198,September 12-14, 2011.

Nomenclature

1. Million Tonne = Mt

2. Tonnes per day = tpd

3. Giga Calorie= GCal

4. Tonne= te

Disclaimer

The information is based on literature survey. Review of technology development is

illustrative and not exhaustive. The authors do not promote or favour any technology

reviewed in the paper.

Petrochemicals Engineers India LimitedBhikaji Cama Place, New Delhi

Seminar on Technology Upgradation in Chemical Industry Department of Chemical Engineering, Indian Institute of Technology

1.0 Introduction to Petrochemicals

Petrochemicals are chemical products generally derived from petroleum or natural

gas. These are those high value organic compounds that go into the production of

useful materials and are not burned as fuel. These useful materials enhance the

quality of life of society as a whole.

Various petrochemical products are synthesized from a few basic petrochemicals

forming the building blocks for the industry. Three such main petrochemical

classes are:

lOlefins, including Ethylene, Propylene, Butene-1 and 1,3 Butadiene, among

others

lAromatics, including Benzene, Toluene and Xylene isomers (ortho,meta, para),

collectively known as BTX

lMethanol

Oil refineries produce olefins and aromatics by fluid catalytic cracking of petroleum

fractions. Aromatics are also produced by the catalytic reforming of naphtha.

Petrochemical plants produce olefins and aromatics by the steam cracking of

naphtha and natural gas liquids. Methanol is produced from synthesis gas

produced by the reaction of coal or natural gas with steam.

Olefins and aromatics are the building-blocks for a wide range of materials such as

solvents, detergents, and adhesives. Olefins are the basis for polymers and

oligomers used in plastics, resins, fibers, elastomers and gels. Methanol is used as a

solvent and is also a chemical intermediate for the production of various

petrochemicals.

This paper starts with the description of a typical steam cracker followed by

explanations of pathways for the manufacture of various petrochemicals starting

from the above mentioned basic petrochemicals. This is followed by a listing of

major applications of petrochemical products. Finally, a partial listing of

technology suppliers for some important petrochemical production processes are

provided.

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7.0 Conclusion

8.0 References

Ammonia production is technology and energy intensive. Indian ammonia

industry has evolved over the years incorporating state of the art technology in

new plants. Old and later generation plants have also upgraded technology to keep

pace with developments in process configuration, material of construction,

catalyst, design of major rotating and static equipment like reactors, heat

exchangers etc. The average energy efficiency of Indian ammonia plants compares

well similar plants in the world.

The paper has also enumerated various developments in ammonia technology.

Future plants in India and abroad will have capacity more than 2000 tpd with

energy efficiency of less than 7.0 Gcal per tonne of ammonia.

(1) "Energy Efficiency on CO2 Emission in Ammonia Production", December

2009, International Fertilizer Industry Association (IFA).

(2) S Nand and Manish Goswami, "Energy Efficiency and CO2 Generation in

Indian Ammonia Plants", Proceedings of Ammonia Safety Symposium of

American Institute of Chemical Engineers, Montreal, Canada, Vol. 52, pp 191-

198,September 12-14, 2011.

Nomenclature

1. Million Tonne = Mt

2. Tonnes per day = tpd

3. Giga Calorie= GCal

4. Tonne= te

Disclaimer

The information is based on literature survey. Review of technology development is

illustrative and not exhaustive. The authors do not promote or favour any technology

reviewed in the paper.

Petrochemicals Engineers India LimitedBhikaji Cama Place, New Delhi

Seminar on Technology Upgradation in Chemical Industry Department of Chemical Engineering, Indian Institute of Technology

1.0 Introduction to Petrochemicals

Petrochemicals are chemical products generally derived from petroleum or natural

gas. These are those high value organic compounds that go into the production of

useful materials and are not burned as fuel. These useful materials enhance the

quality of life of society as a whole.

Various petrochemical products are synthesized from a few basic petrochemicals

forming the building blocks for the industry. Three such main petrochemical

classes are:

lOlefins, including Ethylene, Propylene, Butene-1 and 1,3 Butadiene, among

others

lAromatics, including Benzene, Toluene and Xylene isomers (ortho,meta, para),

collectively known as BTX

lMethanol

Oil refineries produce olefins and aromatics by fluid catalytic cracking of petroleum

fractions. Aromatics are also produced by the catalytic reforming of naphtha.

Petrochemical plants produce olefins and aromatics by the steam cracking of

naphtha and natural gas liquids. Methanol is produced from synthesis gas

produced by the reaction of coal or natural gas with steam.

Olefins and aromatics are the building-blocks for a wide range of materials such as

solvents, detergents, and adhesives. Olefins are the basis for polymers and

oligomers used in plastics, resins, fibers, elastomers and gels. Methanol is used as a

solvent and is also a chemical intermediate for the production of various

petrochemicals.

This paper starts with the description of a typical steam cracker followed by

explanations of pathways for the manufacture of various petrochemicals starting

from the above mentioned basic petrochemicals. This is followed by a listing of

major applications of petrochemical products. Finally, a partial listing of

technology suppliers for some important petrochemical production processes are

provided.

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Through this paper, an attempt has been made to compile the available knowledge

on the various classes of petrochemicals in a concise manner. The information

contained herein is taken from open domains and is believed to be accurate and up

to date, however, no representation to this effect is being made.

A steam cracker can be designed to operate with one or more of the following

feedstock options:

lEthane from natural gas processing (C2)

lPropane from natural gas processing (C3)

lEthane-Propane mixtures

lButanes from natural gas processing (C4's)

lLiquefied Petroleum Gas (LPG)

lNatural gas liquids (NGL) or condensate

lNaphtha from petroleum refining (naphtha)

Depending upon the intent of cracker design, it is usually designed to operate

either with C2/C3/C4's/NGL or with LPG/naphtha. However, a cracker

designed to operate with all above feeds can also be contemplated.

These are:

lHydrogenated Pyrolysis Gasoline (HPG)

lHeavy Fuel Oil

These are sold as fuel.

These are:

lEthylene

lPropylene

l1,3 Butadien

lBenzene

2.0 Petrochemicals from Steam Cracking of Hydrocarbons

2.1 Feedstock options

2.2 Directly saleable products

2.3 Basic Building Blocks

These are routed to other processing units in the petrochemical complex to

convert them to high value products for sale. In case no processing unit is

installed for any of the above products (for example Benzene or 1,3

Butadiene), the same is sold.

These are:

lMethane

lOther C4 hydrocarbons

lCoke (during decoking of furnaces)

Out of the above, methane is sent to the fuel gas system and is burnt in the

cracking furnaces as fuel. Any excess quantity is exported for burning in

other fuel gas consumers of the complex (like power plant, for example).

Other C4 hydrocarbons are sent to storage, from where they are recycled

back to the steam cracker for re-conversion to lower molecular weight

fractions.

Coke, formed during the decoking of furnaces is disposed off.

A typical block flow diagram for a steam cracker is as follows:

2.4 Byproducts

2.5 Block flow diagram and brief process description

ETHANEFEED

PYROLYSIS

CRACKING

HP Steam

QUENCH GAS DRYINGCOMP

HEAVY FUEL OIL

DILUTIONSTEAM

RESIDUE GAS

BENZENE

ETHYLENE

HYDROGENATEDPYROLYSIS GASOLINE

SC3'

SC4'

RECOVERYSECTION

RECYCLE ETHANE

EFFLUENTHEATEXCHANGE

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Through this paper, an attempt has been made to compile the available knowledge

on the various classes of petrochemicals in a concise manner. The information

contained herein is taken from open domains and is believed to be accurate and up

to date, however, no representation to this effect is being made.

A steam cracker can be designed to operate with one or more of the following

feedstock options:

lEthane from natural gas processing (C2)

lPropane from natural gas processing (C3)

lEthane-Propane mixtures

lButanes from natural gas processing (C4's)

lLiquefied Petroleum Gas (LPG)

lNatural gas liquids (NGL) or condensate

lNaphtha from petroleum refining (naphtha)

Depending upon the intent of cracker design, it is usually designed to operate

either with C2/C3/C4's/NGL or with LPG/naphtha. However, a cracker

designed to operate with all above feeds can also be contemplated.

These are:

lHydrogenated Pyrolysis Gasoline (HPG)

lHeavy Fuel Oil

These are sold as fuel.

These are:

lEthylene

lPropylene

l1,3 Butadien

lBenzene

2.0 Petrochemicals from Steam Cracking of Hydrocarbons

2.1 Feedstock options

2.2 Directly saleable products

2.3 Basic Building Blocks

These are routed to other processing units in the petrochemical complex to

convert them to high value products for sale. In case no processing unit is

installed for any of the above products (for example Benzene or 1,3

Butadiene), the same is sold.

These are:

lMethane

lOther C4 hydrocarbons

lCoke (during decoking of furnaces)

Out of the above, methane is sent to the fuel gas system and is burnt in the

cracking furnaces as fuel. Any excess quantity is exported for burning in

other fuel gas consumers of the complex (like power plant, for example).

Other C4 hydrocarbons are sent to storage, from where they are recycled

back to the steam cracker for re-conversion to lower molecular weight

fractions.

Coke, formed during the decoking of furnaces is disposed off.

A typical block flow diagram for a steam cracker is as follows:

2.4 Byproducts

2.5 Block flow diagram and brief process description

ETHANEFEED

PYROLYSIS

CRACKING

HP Steam

QUENCH GAS DRYINGCOMP

HEAVY FUEL OIL

DILUTIONSTEAM

RESIDUE GAS

BENZENE

ETHYLENE

HYDROGENATEDPYROLYSIS GASOLINE

SC3'

SC4'

RECOVERYSECTION

RECYCLE ETHANE

EFFLUENTHEATEXCHANGE

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Hydrocarbon feeds to the steam cracker are mixed with steam and subjected to

cracking in pyrolysis furnaces. Furnace effluents are quenched to stop further

reactions. In this operation, the heavy hydrocarbons separate out as heavy fuel oil.

Gaseous effluents from the quench section are passed through a heat exchange

section, where their heat is used to generate steam. The cooled gases are

compressed and dried. The dried gases are passed to the recovery section where

the various hydrocarbon fractions are separated through successive distillations.

Unconverted ethane is recycled back to the cracking furnaces, whereas other

products are sent to storage.

Some companies, having steam cracking technology, and offering it for

licensing are:

lLummus Technology

lShaw Stone and Webster

lLinde Engineering

lTechnip

lKBR

2.6 Technology suppliers

BUTENE-1

ETHANOL

ACETIC ACID

Hydration

Acetaldehyde Oxidation

+ Acetic Acid

+ OxygenVINYL ACETATE

PolymerisationPOLY VINYLACETATE

Hydrolysis

POLY VINYL ALCOHOL

TETRA CHLORO ETHYLENE

TRICHLORO ETHYLENE

VINYLCHLORIDE

POLY VINYLCHLORIDE (PVC)

PolymerisationPyrolysis

(-HCL)

+CHLORINE

1,2 -DICHLOROETHANE(EDC)

ETHYLENE

SBR RUBBER

ABS RESINS

SAN RESINS

POLYSTYRENE

+ Butadiene

+ Acryonitrile,+ Butadiene

Polymerisation

Polymerisation

+ Acryonitrile

Polymerisation

Polymerisation

STYRENEMONOMER

ETHYLBENZENE (-H2)

Dehydrogenation+ Benzene

POLYESTERS

ETHOXYLATES

GLYCOL ETHERS

+ DMT or PTA+ Alcohols

ENGINE COOLANT+Water+ Oxygen ETHYLENE

OXIDEETHYLENEGLYCOL

POLY ETHYLENEPOLYMERISATION, (+ CO-MONOMERS AS REQUIRED)

A description of the various chemical reactions involved and the typical

conditions under which main chemicals are produced is presented below:

l

Polyethylenes are produced by the polymerization of ethylene, either with

itself, or through copolymerization with certain other molecules (called co-

monomers, e.g. Propylene, Butene-1, Hexene-1, Octene-1, etc.), to achieve

the desired product properties. Additionally, a small quantity of hydrogen is

added as a chain terminator (or telogen) to stop further polymer chain

propagation and hence control the molecular weight (and properties) of the

polymer produced.

Polyethylene grades produced industrially are broadly classified based on

their density as low density (LDPE), medium density (MDPE), high density

(HDPE) and linear low density (LLDPE) polyethylenes. Out of these, the

most widely manufactured grades fall in the LLDPE and HDPE categories.

Polyethylenes

3.0 Pathways for Production of Various Petrochemicals

3.1 Petrochemicals from ethylene

These are schematically depicted by the following flowchart.

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Hydrocarbon feeds to the steam cracker are mixed with steam and subjected to

cracking in pyrolysis furnaces. Furnace effluents are quenched to stop further

reactions. In this operation, the heavy hydrocarbons separate out as heavy fuel oil.

Gaseous effluents from the quench section are passed through a heat exchange

section, where their heat is used to generate steam. The cooled gases are

compressed and dried. The dried gases are passed to the recovery section where

the various hydrocarbon fractions are separated through successive distillations.

Unconverted ethane is recycled back to the cracking furnaces, whereas other

products are sent to storage.

Some companies, having steam cracking technology, and offering it for

licensing are:

lLummus Technology

lShaw Stone and Webster

lLinde Engineering

lTechnip

lKBR

2.6 Technology suppliers

BUTENE-1

ETHANOL

ACETIC ACID

Hydration

Acetaldehyde Oxidation

+ Acetic Acid

+ OxygenVINYL ACETATE

PolymerisationPOLY VINYLACETATE

Hydrolysis

POLY VINYL ALCOHOL

TETRA CHLORO ETHYLENE

TRICHLORO ETHYLENE

VINYLCHLORIDE

POLY VINYLCHLORIDE (PVC)

PolymerisationPyrolysis

(-HCL)

+CHLORINE

1,2 -DICHLOROETHANE(EDC)

ETHYLENE

SBR RUBBER

ABS RESINS

SAN RESINS

POLYSTYRENE

+ Butadiene

+ Acryonitrile,+ Butadiene

Polymerisation

Polymerisation

+ Acryonitrile

Polymerisation

Polymerisation

STYRENEMONOMER

ETHYLBENZENE (-H2)

Dehydrogenation+ Benzene

POLYESTERS

ETHOXYLATES

GLYCOL ETHERS

+ DMT or PTA+ Alcohols

ENGINE COOLANT+Water+ Oxygen ETHYLENE

OXIDEETHYLENEGLYCOL

POLY ETHYLENEPOLYMERISATION, (+ CO-MONOMERS AS REQUIRED)



l

Polyethylenes are produced by the polymerization of ethylene, either with

itself, or through copolymerization with certain other molecules (called co-

monomers, e.g. Propylene, Butene-1, Hexene-1, Octene-1, etc.), to achieve

the desired product properties. Additionally, a small quantity of hydrogen is

added as a chain terminator (or telogen) to stop further polymer chain

propagation and hence control the molecular weight (and properties) of the

polymer produced.

Polyethylene grades produced industrially are broadly classified based on

their density as low density (LDPE), medium density (MDPE), high density

(HDPE) and linear low density (LLDPE) polyethylenes. Out of these, the

most widely manufactured grades fall in the LLDPE and HDPE categories.

Polyethylenes

3.0 Pathways for Production of Various Petrochemicals

3.1 Petrochemicals from ethylene


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There are many processes available for manufacturing polyethylene.

Therefore, the operating conditions for manufacturing the particular class of

polyethylene are process specific (for example the common slurry process

for manufacturing HDPE in a hexane solvent operates its reactor at around 6

kg/cm2g pressure and around 60 deg C, whereas another process for

manufacturing LLDPE in a cyclohexane solvent operates its reactor at

around 116-173 kg/cm2g and 200-305 deg C). Most polyethylene processes

use the Ziegler-Natta (Z-N) catalyst system however, chromium based

catalyst systems producing metallocene grades are also practised.

l

Ethylene glycol is produced from ethylene via the intermediate ethylene

oxide. Ethylene oxide is produced by the partial oxidation of ethylene with

pure oxygen according to the chemical equation:

2 C H + O →2 C H O 2 4 2 2 4

Ethylene oxide reacts with water to produce ethylene glycol according to the

chemical equation:

C H O + H O→HO-CH CH -OH2 4 2 2 2

This reaction can be catalyzed by either acids or bases, or can occur at

neutral pH under elevated temperatures. The highest yields of ethylene

glycol occur at acidic or neutral pH with a large excess of water. Under these

conditions, ethylene glycol yields of 90% can be achieved. The major

byproducts are the ethylene glycol oligomers di-ethylene glycol, tri-ethylene

glycol and tetra-ethylene glycol.

A higher selectivity is achieved by use of the Shell's OMEGA process. In the

OMEGA process, the ethylene oxide is first converted with carbon dioxide

(CO2) to ethylene carbonate to then react with water in a second step to

selectively produce mono-ethylene glycol. The carbon dioxide is released in

this step again and can be fed back into the process circuit. The carbon

dioxide comes in part from the ethylene oxide production, where a part of

the ethylene is completely oxidized.

Ethylene glycol is used in engine coolants as antifreeze. It is also an

intermediate in the manufacture of polyesters.

lStyrene based (PS / SAN / ABS / SBR) resins / Styrene

Ethylbenzene:

These are an important class of plastics used in industry. These are

produced by the polymerization of styrene, either with itself or with other

copolymers. Main copolymers used and the resultant resins produced in

industry are:

Ethylene Glycol / Ethylene Oxide

- Self polymerization to produce Polystyrene

- Acrylonitrile to produce Styrene Acrylonitrile (SAN) resins

- Acrylonitrile and Butadiene to produce Acrylonitrile Butadiene Styrene

(ABS) resins

- Butadiene to produce Styrene Butadiene Rubber (SBR)

Styrene is most commonly produced by the catalytic dehydrogenation of

ethylbenzene. Ethylbenzene is mixed in the gas phase with 10-15 times its

volume in high-temperature steam, and passed over a solid catalyst bed.

Most ethylbenzene dehydrogenation catalysts are based on iron(III) oxide,

promoted by several percent potassium oxide or potassium carbonate.

Steam serves several roles in this reaction. It is the source of heat for

powering the endothermic reaction, and it removes coke that tends to form

on the iron oxide catalyst through the water gas shift reaction. The potassium

promoter enhances this decoking reaction. The steam also dilutes the

reactant and products, shifting the position of chemical equilibrium towards

products. The main byproducts are benzene and toluene. To inhibit

polymerization of styrene, additives are injected into the reactor effluents

prior to styrene separation from ethylbenze by distillation.

Another less common route for combined styrene and propylene oxide

manufacture is the POSM (Lyondell Chemical Company) or SM/PO (Shell)

process.. In this process ethylbenzene is treated with oxygen to form the

ethylbenzene hydroperoxide. This hydroperoxide is then used to oxidize

propylene to propylene oxide. The resulting 2-phenylethanol is dehydrated

to give styrene:

C H CH CH + O2→C H CH CH O H6 5 2 3 6 5 2

C H CH CH2O H + CH CH=CH →C H CH CH OH + CH CHCH O6 5 2 2 3 2 6 5 2 2 3 2

C H CH CH OH→C H CH=CH + H O6 5 2 2 6 5 2 2

Ethylbenzene is produced in on a large scale by combining benzene (C6H6)

and ethylene (C2H4) in an acid-catalyzed chemical reaction:

C6H6 + C2H4→ C6H5CH2CH3

2 2

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There are many processes available for manufacturing polyethylene.

Therefore, the operating conditions for manufacturing the particular class of

polyethylene are process specific (for example the common slurry process

for manufacturing HDPE in a hexane solvent operates its reactor at around 6

kg/cm2g pressure and around 60 deg C, whereas another process for

manufacturing LLDPE in a cyclohexane solvent operates its reactor at

around 116-173 kg/cm2g and 200-305 deg C). Most polyethylene processes

use the Ziegler-Natta (Z-N) catalyst system however, chromium based

catalyst systems producing metallocene grades are also practised.

l

Ethylene glycol is produced from ethylene via the intermediate ethylene

oxide. Ethylene oxide is produced by the partial oxidation of ethylene with

pure oxygen according to the chemical equation:

2 C H + O →2 C H O 2 4 2 2 4

Ethylene oxide reacts with water to produce ethylene glycol according to the

chemical equation:

C H O + H O→HO-CH CH -OH2 4 2 2 2

This reaction can be catalyzed by either acids or bases, or can occur at

neutral pH under elevated temperatures. The highest yields of ethylene

glycol occur at acidic or neutral pH with a large excess of water. Under these

conditions, ethylene glycol yields of 90% can be achieved. The major

byproducts are the ethylene glycol oligomers di-ethylene glycol, tri-ethylene

glycol and tetra-ethylene glycol.

A higher selectivity is achieved by use of the Shell's OMEGA process. In the

OMEGA process, the ethylene oxide is first converted with carbon dioxide

(CO2) to ethylene carbonate to then react with water in a second step to

selectively produce mono-ethylene glycol. The carbon dioxide is released in

this step again and can be fed back into the process circuit. The carbon

dioxide comes in part from the ethylene oxide production, where a part of

the ethylene is completely oxidized.

Ethylene glycol is used in engine coolants as antifreeze. It is also an

intermediate in the manufacture of polyesters.

lStyrene based (PS / SAN / ABS / SBR) resins / Styrene

Ethylbenzene:

These are an important class of plastics used in industry. These are

produced by the polymerization of styrene, either with itself or with other

copolymers. Main copolymers used and the resultant resins produced in

industry are:

Ethylene Glycol / Ethylene Oxide

- Self polymerization to produce Polystyrene

- Acrylonitrile to produce Styrene Acrylonitrile (SAN) resins

- Acrylonitrile and Butadiene to produce Acrylonitrile Butadiene Styrene

(ABS) resins

- Butadiene to produce Styrene Butadiene Rubber (SBR)

Styrene is most commonly produced by the catalytic dehydrogenation of

ethylbenzene. Ethylbenzene is mixed in the gas phase with 10-15 times its

volume in high-temperature steam, and passed over a solid catalyst bed.

Most ethylbenzene dehydrogenation catalysts are based on iron(III) oxide,

promoted by several percent potassium oxide or potassium carbonate.

Steam serves several roles in this reaction. It is the source of heat for

powering the endothermic reaction, and it removes coke that tends to form

on the iron oxide catalyst through the water gas shift reaction. The potassium

promoter enhances this decoking reaction. The steam also dilutes the

reactant and products, shifting the position of chemical equilibrium towards

products. The main byproducts are benzene and toluene. To inhibit

polymerization of styrene, additives are injected into the reactor effluents

prior to styrene separation from ethylbenze by distillation.

Another less common route for combined styrene and propylene oxide

manufacture is the POSM (Lyondell Chemical Company) or SM/PO (Shell)

process.. In this process ethylbenzene is treated with oxygen to form the

ethylbenzene hydroperoxide. This hydroperoxide is then used to oxidize

propylene to propylene oxide. The resulting 2-phenylethanol is dehydrated

to give styrene:

C H CH CH + O2→C H CH CH O H6 5 2 3 6 5 2

C H CH CH2O H + CH CH=CH →C H CH CH OH + CH CHCH O6 5 2 2 3 2 6 5 2 2 3 2

C H CH CH OH→C H CH=CH + H O6 5 2 2 6 5 2 2

Ethylbenzene is produced in on a large scale by combining benzene (C6H6)

and ethylene (C2H4) in an acid-catalyzed chemical reaction:

C6H6 + C2H4→ C6H5CH2CH3

2 2

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VCM and water are introduced into the reactor and a polymerization

initiator, along with other additives. The reaction vessel is pressure tight to

contain the VCM. The contents of the reaction vessel are continually mixed to

maintain the suspension and ensure a uniform particle size of the PVC resin.

The polymerization of VCM is started by compounds called initiators that are

mixed into the droplets. These compounds break down to start the radical

chain reaction. Typical initators include dioctanoyl peroxide and dicetyl

peroxydicarbonate, both of which have fragile O-O bonds. After the polymer

has grown by about 10x, the short polymer precipitates inside the droplet of

VCM, and polymerization continues with the precipitated, solvent-swollen

particles.

Vinyl chloride monomer (VCM) is produced by the dehydrochlorination of

ethylene dichloride (1,2-dichloroethane) . When heated to 500 °C at 15-30

atm (1.5 to 3 MPa) pressure, EDC vapor decomposes to produce vinyl

chloride and anhydrous HCl

ClCH2CH2Cl → CH2=CHCl + HCl

The thermal cracking reaction is highly endothermic, and is generally

carried out in a fired heater. Even though residence time and temperature are

carefully controlled, it produces significant quantities of chlorinated

hydrocarbon side products. In practice, EDC conversion is relatively low (50

to 60 percent).

The furnace effluent is immediately quenched with cold EDC to stop

undesirable side reactions.

1,2-dichloro-ethane (EDC) is prepared by reacting ethylene and chlorine. In

the presence of iron(III) chloride as a catalyst, these compounds react

exothermically:

CH2=CH2 + Cl2→ClCH2CH2C

This process is very selective, resulting in high purity EDC and high yields.

However any dissolved catalyst and moisture must be removed before EDC

enters the vinyl chloride production process.

Additionally, vinyl chloride plants use recycled HCl to produce more EDC via

oxychlorination, which entails the reaction of ethylene, oxygen, and

hydrogen chloride over a copper(II) chloride catalyst to produce more EDC:

CH2=CH2 + 2 HCl + ½ O2→ClCH2CH2Cl + H2O.

The reaction is highly exothermic.

lPolyvinyl Alcohol (PVA) / Polyinyl Acetate (PVAc) /

Vinyl Acetate (VAM)

Polyvinyl Alchol (PVA), a water soluble synthetic polymer, is prepared by the

partial or complete hydrolysis of polyvinyl acetate to remove acetate groups.

Polyvinyl Acetate (PVAc) is formed by the polymerization of Vinyl Acetate

(VAM).

VAM is produced from acetic acid through a reaction of ethylene and acetic

acid with oxygen over a palladium catalyst.

2 H3C-COOH + 2 C2H4 + O2→ 2 H3C-CO-O-CH=CH2 + 2 H2O

lAcetic Acid / Acetaldehyde

One of the pathways for acetic acid manufacture is through acetaldehyde

oxidation. This is carried out through reaction of liquid acetaldehyde with

air at high temperature (around 150 oC) in the presence of various metal

ions, including those of manganese, cobalt, and chromium, according to the

equation:

2 CH3CHO + O2 →2 CH3COOH

Acetaldehyde for the above reaction may be produced from ethylene through

the Wacker process, wherein ethylene is oxidized with oxygen in the

presence of tetrachloropalladate catalyst to yield acetaldehyde. This

reaction takes place in an aqueous environment.

lEthanol

Ethanol for use as an industrial feedstock or solvent (sometimes referred to

as synthetic ethanol) is manufactured by the acid-catalyzed hydration of

ethylene, represented by the chemical equation

C2H4 + H2O → CH3CH2OH

The catalyst is phosphoric acid adsorbed onto a porous support such as silica

gel or diatomaceous earth. The reaction is carried out with an excess of high

pressure steam at 300 °C.

Polyvinyl chloride (PVC) / Vinyl Chloride (VCM) / 1,2-

Dichloroethane (EDC)

These resins are produced by the polymerization of vinyl chloride

monomer (VCM), as shown

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VCM and water are introduced into the reactor and a polymerization

initiator, along with other additives. The reaction vessel is pressure tight to

contain the VCM. The contents of the reaction vessel are continually mixed to

maintain the suspension and ensure a uniform particle size of the PVC resin.

The polymerization of VCM is started by compounds called initiators that are

mixed into the droplets. These compounds break down to start the radical

chain reaction. Typical initators include dioctanoyl peroxide and dicetyl

peroxydicarbonate, both of which have fragile O-O bonds. After the polymer

has grown by about 10x, the short polymer precipitates inside the droplet of

VCM, and polymerization continues with the precipitated, solvent-swollen

particles.

Vinyl chloride monomer (VCM) is produced by the dehydrochlorination of

ethylene dichloride (1,2-dichloroethane) . When heated to 500 °C at 15-30

atm (1.5 to 3 MPa) pressure, EDC vapor decomposes to produce vinyl

chloride and anhydrous HCl

ClCH2CH2Cl → CH2=CHCl + HCl

The thermal cracking reaction is highly endothermic, and is generally

carried out in a fired heater. Even though residence time and temperature are

carefully controlled, it produces significant quantities of chlorinated

hydrocarbon side products. In practice, EDC conversion is relatively low (50

to 60 percent).

The furnace effluent is immediately quenched with cold EDC to stop

undesirable side reactions.

1,2-dichloro-ethane (EDC) is prepared by reacting ethylene and chlorine. In

the presence of iron(III) chloride as a catalyst, these compounds react

exothermically:

CH2=CH2 + Cl2→ClCH2CH2C

This process is very selective, resulting in high purity EDC and high yields.

However any dissolved catalyst and moisture must be removed before EDC

enters the vinyl chloride production process.

Additionally, vinyl chloride plants use recycled HCl to produce more EDC via

oxychlorination, which entails the reaction of ethylene, oxygen, and

hydrogen chloride over a copper(II) chloride catalyst to produce more EDC:

CH2=CH2 + 2 HCl + ½ O2→ClCH2CH2Cl + H2O.

The reaction is highly exothermic.

lPolyvinyl Alcohol (PVA) / Polyinyl Acetate (PVAc) /

Vinyl Acetate (VAM)

Polyvinyl Alchol (PVA), a water soluble synthetic polymer, is prepared by the

partial or complete hydrolysis of polyvinyl acetate to remove acetate groups.

Polyvinyl Acetate (PVAc) is formed by the polymerization of Vinyl Acetate

(VAM).

VAM is produced from acetic acid through a reaction of ethylene and acetic

acid with oxygen over a palladium catalyst.

2 H3C-COOH + 2 C2H4 + O2→ 2 H3C-CO-O-CH=CH2 + 2 H2O

lAcetic Acid / Acetaldehyde

One of the pathways for acetic acid manufacture is through acetaldehyde

oxidation. This is carried out through reaction of liquid acetaldehyde with

air at high temperature (around 150 oC) in the presence of various metal

ions, including those of manganese, cobalt, and chromium, according to the

equation:

2 CH3CHO + O2 →2 CH3COOH

Acetaldehyde for the above reaction may be produced from ethylene through

the Wacker process, wherein ethylene is oxidized with oxygen in the

presence of tetrachloropalladate catalyst to yield acetaldehyde. This

reaction takes place in an aqueous environment.

lEthanol

Ethanol for use as an industrial feedstock or solvent (sometimes referred to

as synthetic ethanol) is manufactured by the acid-catalyzed hydration of

ethylene, represented by the chemical equation

C2H4 + H2O → CH3CH2OH

The catalyst is phosphoric acid adsorbed onto a porous support such as silica

gel or diatomaceous earth. The reaction is carried out with an excess of high

pressure steam at 300 °C.

Polyvinyl chloride (PVC) / Vinyl Chloride (VCM) / 1,2-

Dichloroethane (EDC)

These resins are produced by the polymerization of vinyl chloride

monomer (VCM), as shown

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lButene-1

Butene-1, a comonomer in many polyolefins manufacturing process, is

produced by the dimerization of ethylene as per the chemical equation:

2 C2H4 → C4H8

The reaction is carried out at around 55 deg C in a Butene-1 medium.

Triethyl Aluminium (TEAL) is used to catalyze the reaction. An inhibitor is

added to prevent production of the undesirable isomer Butene-2.


3.2 Petrochemicals from propylene



lPolypropylenes

Polypropylenes are produced by the polymerization of propylene, either

with itself, or through copolymerization with certain other molecules

(called co-monomers, e.g. Ethylene, Butene-1, etc.), to achieve the desired

product properties. Additionally, a small quantity of hydrogen is added as a

chain terminator (or telogen) to stop further polymer chain propagation and

hence control the molecular weight (and properties) of the polymer

produced. A particular class of polypropylenes, called the heterophasic

impact (HI) propylene is produced by polymerizing ethylene on

homopolymer polypropylene powder.

There are many processes available for manufacturing polypropylene.

Broadly, these fall into two main categories:

- Liquid phase polymerization, and

- Gas phase polymerization

The liquid phase polymerization process performs the polymerization

reaction in liquid propylene, whereas the gas phase polymerization process

performs the same in a vapour propylene environment. Most polyethylene

process use the Ziegler-Natta (Z-N) catalyst systems, however, proprietary

catalyst systems of the technology suppliers are also used.

lIsopropyl Alcohol

Isopropyl alcohol is mainly produced by combining water and propylene in a

hydration reaction. There are two routes for the hydration process:

- Indirect hydration via the sulfuric acid process, and

- Direct hydration

The indirect hydration process reacts propylene with sulfuric acid to form a

mixture of sulfate esters. Subsequent hydrolysis of these esters by steam

produces isopropyl alcohol, which is distilled. Diisopropyl ether is a

significant by-product of this process. It is recycled back to the process and

hydrolyzed to give isopropyl alcohol.

Direct hydration reacts propylene and water, either in gas or liquid phases, at

high pressures in the presence of solid or supported acidic catalysts. Higher

purity propylene (> 90%) tends to be required for this type of process.

Both processes require that the isopropyl alcohol be separated from water

and other by-products by distillation. Isopropyl alcohol and water form an

azeotrope and simple distillation gives a material which is 87.9% by weight

isopropyl alcohol and 12.1% by weight water. Pure (anhydrous) isopropyl

alcohol is made by azeotropic distillation of the wet isopropyl alcohol using

either diisopropyl ether or cyclohexane as azeotroping agents.

lAcrylonitrile

Acrylonitrile is an important monomer for the production of various

important polymeric petrochemicals like SAN, ABS, etc. (see above under

POLYPROPYLENEPolymerisation

Hydration

ISOPROPLY ALCHOL

Catalytic Ammoxidation

ACRYLONITRILE

(+NH +O )3 2

OxidationACRYLICACID

PolymerizationACRYLICPOLYMERS

ChlorinationHydrochlorination

(+HOCL)/

Polymerisation

Alkali Treatment

(+NaOH)

(+Cl )2

ALLYLCHLORIDE

EPICHLOROHYDRIN EPOXY RESINS

Polymerization With Ethylene Oxide

POLYOL

Hydration

PROPYLENEGLYCOL

+ Alcohols

GLYCOL ETHER

PROPYLENEOXIDE

Co-Oxidation

(+O )/2

Hydrochlorination

PROPYLENE

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lButene-1

Butene-1, a comonomer in many polyolefins manufacturing process, is

produced by the dimerization of ethylene as per the chemical equation:

2 C2H4 → C4H8

The reaction is carried out at around 55 deg C in a Butene-1 medium.

Triethyl Aluminium (TEAL) is used to catalyze the reaction. An inhibitor is

added to prevent production of the undesirable isomer Butene-2.


3.2 Petrochemicals from propylene



lPolypropylenes

Polypropylenes are produced by the polymerization of propylene, either

with itself, or through copolymerization with certain other molecules

(called co-monomers, e.g. Ethylene, Butene-1, etc.), to achieve the desired

product properties. Additionally, a small quantity of hydrogen is added as a

chain terminator (or telogen) to stop further polymer chain propagation and

hence control the molecular weight (and properties) of the polymer

produced. A particular class of polypropylenes, called the heterophasic

impact (HI) propylene is produced by polymerizing ethylene on

homopolymer polypropylene powder.

There are many processes available for manufacturing polypropylene.

Broadly, these fall into two main categories:

- Liquid phase polymerization, and

- Gas phase polymerization

The liquid phase polymerization process performs the polymerization

reaction in liquid propylene, whereas the gas phase polymerization process

performs the same in a vapour propylene environment. Most polyethylene

process use the Ziegler-Natta (Z-N) catalyst systems, however, proprietary

catalyst systems of the technology suppliers are also used.

lIsopropyl Alcohol

Isopropyl alcohol is mainly produced by combining water and propylene in a

hydration reaction. There are two routes for the hydration process:

- Indirect hydration via the sulfuric acid process, and

- Direct hydration

The indirect hydration process reacts propylene with sulfuric acid to form a

mixture of sulfate esters. Subsequent hydrolysis of these esters by steam

produces isopropyl alcohol, which is distilled. Diisopropyl ether is a

significant by-product of this process. It is recycled back to the process and

hydrolyzed to give isopropyl alcohol.

Direct hydration reacts propylene and water, either in gas or liquid phases, at

high pressures in the presence of solid or supported acidic catalysts. Higher

purity propylene (> 90%) tends to be required for this type of process.

Both processes require that the isopropyl alcohol be separated from water

and other by-products by distillation. Isopropyl alcohol and water form an

azeotrope and simple distillation gives a material which is 87.9% by weight

isopropyl alcohol and 12.1% by weight water. Pure (anhydrous) isopropyl

alcohol is made by azeotropic distillation of the wet isopropyl alcohol using

either diisopropyl ether or cyclohexane as azeotroping agents.

lAcrylonitrile

Acrylonitrile is an important monomer for the production of various

important polymeric petrochemicals like SAN, ABS, etc. (see above under

POLYPROPYLENEPolymerisation

Hydration

ISOPROPLY ALCHOL

Catalytic Ammoxidation

ACRYLONITRILE

(+NH +O )3 2

OxidationACRYLICACID

PolymerizationACRYLICPOLYMERS

ChlorinationHydrochlorination

(+HOCL)/

Polymerisation

Alkali Treatment

(+NaOH)

(+Cl )2

ALLYLCHLORIDE

EPICHLOROHYDRIN EPOXY RESINS

Polymerization With Ethylene Oxide

POLYOL

Hydration

PROPYLENEGLYCOL

+ Alcohols

GLYCOL ETHER

PROPYLENEOXIDE

Co-Oxidation

(+O )/2

Hydrochlorination

PROPYLENE

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ethylene derivatives). Industrially, it is produced by the catalytic

ammoxidation of propylene as per the following equation:

2CH3-CH=CH2 + 2NH3 + 3O2 → 2CH2=CH-C →N + 6H2O

lAcrylate Polymers / Acrylic Acid

Acrylate polymers, also commonly known as Acrylics or Polyacrylates are

formed by the polymerization of Acrylic acid, either with itself or with other

monomers like Methyl Methacrylate, Acrylonitrile, etc.

Acrylic acid is produced from propylene by oxidation as per the following

equation:

CH2=CHCH3 + 1.5 O2 →CH2=CHCO2H + H2O

lEpoxy Resins / Epichlorohydrin / Allyl Chloride

Epoxy resins are low molecular weight pre-polymers or higher molecular

weight polymers which normally contain at least two epoxide groups. The

epoxide group is also sometimes referred to as a glycidyl or oxirane group.

Epoxy resins are an important category of industrial chemicals and can be

thermosetting or thermoplastic.

A wide range of epoxy resins are produced industrially. A few major classes

are:

- Bisphenol A epoxy resins formed by the reaction of epichlorohydrin with

Bisphenol A

- Bisphenol F epoxy resins formed by the reaction of epichlorohydrin with

Bisphenol F

- Novolac epoxy resins formed by the reaction of phenol with

formaldehyde and then with epichlorohydrin

- Glycidyl epoxy resins formed by the reaction of aliphatic alcohols or

polyols with epichlorohydrin

- Glycidylamine epoxy resins formed by the reaction of aromatic amines

with epichlorohydrin

Epichlorohydrin is manufactured from allyl chloride in two steps, beginning

with the hydrochlorination using hypochlorous acid, which affords a

mixture of two alcohols:

CH2=CHCH2Cl + HOCl → HOCH2CHClCH2Cl and, or ClCH2CH(OH)CH2Cl

In the second step, this mixture is treated with base to give the epoxide:

HOCH2CHClCH2Cl and, or ClCH2CH(OH)CH2Cl + NaOH CH2CHOCH2Cl +

NaCl + H2O

→

Allyl chloride is prepared by the reaction of propylene with chlorine. At

lower temperatures, the main product is 1,2-dichloropropane, but at 500 °C,

allyl chloride predominates, being formed via a free radical reaction:

CH3CH=CH2 + Cl2 →ClCH2CH=CH2 + HCl

l

Industrially, propylene glycol is produced from propylene oxide by

hydration.

Different manufacturers use either non-catalytic high-temperature process

at 200 to 220 °C, or a catalytic method, which proceeds at 150 to180 °C in the

presence of ion exchange resin or a small amount of sulfuric acid or alkali.

Final products contain 20% 1,2-propanediol, 1.5% of dipropylene glycol and

small amounts of other polypropylene glycols. Further purification produces

finished grade propylene glycol that is typically 99.5% or greater.

Industrial production of propylene oxide starts from propylene. Two general

approaches are employed, one involving hydrochlorination and the other

involving oxidation.

Propylene Glycol / Propylene Oxide

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ethylene derivatives). Industrially, it is produced by the catalytic

ammoxidation of propylene as per the following equation:

2CH3-CH=CH2 + 2NH3 + 3O2 → 2CH2=CH-C →N + 6H2O

lAcrylate Polymers / Acrylic Acid

Acrylate polymers, also commonly known as Acrylics or Polyacrylates are

formed by the polymerization of Acrylic acid, either with itself or with other

monomers like Methyl Methacrylate, Acrylonitrile, etc.

Acrylic acid is produced from propylene by oxidation as per the following

equation:

CH2=CHCH3 + 1.5 O2 →CH2=CHCO2H + H2O

lEpoxy Resins / Epichlorohydrin / Allyl Chloride

Epoxy resins are low molecular weight pre-polymers or higher molecular

weight polymers which normally contain at least two epoxide groups. The

epoxide group is also sometimes referred to as a glycidyl or oxirane group.

Epoxy resins are an important category of industrial chemicals and can be

thermosetting or thermoplastic.

A wide range of epoxy resins are produced industrially. A few major classes

are:

- Bisphenol A epoxy resins formed by the reaction of epichlorohydrin with

Bisphenol A

- Bisphenol F epoxy resins formed by the reaction of epichlorohydrin with

Bisphenol F

- Novolac epoxy resins formed by the reaction of phenol with

formaldehyde and then with epichlorohydrin

- Glycidyl epoxy resins formed by the reaction of aliphatic alcohols or

polyols with epichlorohydrin

- Glycidylamine epoxy resins formed by the reaction of aromatic amines

with epichlorohydrin

Epichlorohydrin is manufactured from allyl chloride in two steps, beginning

with the hydrochlorination using hypochlorous acid, which affords a

mixture of two alcohols:

CH2=CHCH2Cl + HOCl → HOCH2CHClCH2Cl and, or ClCH2CH(OH)CH2Cl

In the second step, this mixture is treated with base to give the epoxide:

HOCH2CHClCH2Cl and, or ClCH2CH(OH)CH2Cl + NaOH CH2CHOCH2Cl +

NaCl + H2O

→

Allyl chloride is prepared by the reaction of propylene with chlorine. At

lower temperatures, the main product is 1,2-dichloropropane, but at 500 °C,

allyl chloride predominates, being formed via a free radical reaction:

CH3CH=CH2 + Cl2 →ClCH2CH=CH2 + HCl

l

Industrially, propylene glycol is produced from propylene oxide by

hydration.

Different manufacturers use either non-catalytic high-temperature process

at 200 to 220 °C, or a catalytic method, which proceeds at 150 to180 °C in the

presence of ion exchange resin or a small amount of sulfuric acid or alkali.

Final products contain 20% 1,2-propanediol, 1.5% of dipropylene glycol and

small amounts of other polypropylene glycols. Further purification produces

finished grade propylene glycol that is typically 99.5% or greater.

Industrial production of propylene oxide starts from propylene. Two general

approaches are employed, one involving hydrochlorination and the other

involving oxidation.

Propylene Glycol / Propylene Oxide

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Lime is often used as a chlorine absorber.

Co-oxidation of propylene

The other general route to propylene oxide involves co-oxidation of the

organic chemicals isobutane or ethylbenzene. In the presence of catalyst, air

oxidation occurs as follows:

CH3CH=CH2 + Ph-CH2CH3 + O2 →CH3CHCH2O + Ph-CH=CH2 + H2O

The co-product of these reactions, t-butyl alcohol or styrene, is useful

feedstock for other products. For example, t-butyl alcohol reacts with

methanol to give MTBE, an additive for gasoline.

The reaction produces a mixture of 1-chloro-2-propanol and 2-chloro-1-

propanol, which is then dehydrochlorinated. For example:



Petrochemicals from C4 fractions are mainly produced from three types of

base chemicals:

l1,3-Butadiene

lIsobutylene

lButene-1

These are covered separately below.

PETROCHEMICALS FROM BUTADIENE

lStyrene-Butadiene-Rubber (SBR)

This is already covered under Styrene in section 3.1-Petrochemicals from

Ethylene above.

Hydrochlorination route

The traditional route proceeds via the conversion of propylene to

chloropropanols:

1,3 BUTADIENE STYRENE BUTADIENERUBBER (SBR)

Copolymerization

(+Styrene)

Copolymerization

Polymerization

(+ Acrylonitrile, +Styrene)

ACRYLONITRILE, STYRENE,BUTADIENE (ABS) RESINS

POLYBUTADIENERUBBER (PBR)

ISOBUTYLENEMETHYL TERTIARY BUTYLETHER (MTBE)

3.3 Petrochemicals from C4 fractions


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Lime is often used as a chlorine absorber.

Co-oxidation of propylene

The other general route to propylene oxide involves co-oxidation of the

organic chemicals isobutane or ethylbenzene. In the presence of catalyst, air

oxidation occurs as follows:

CH3CH=CH2 + Ph-CH2CH3 + O2 →CH3CHCH2O + Ph-CH=CH2 + H2O

The co-product of these reactions, t-butyl alcohol or styrene, is useful

feedstock for other products. For example, t-butyl alcohol reacts with

methanol to give MTBE, an additive for gasoline.

The reaction produces a mixture of 1-chloro-2-propanol and 2-chloro-1-

propanol, which is then dehydrochlorinated. For example:



Petrochemicals from C4 fractions are mainly produced from three types of

base chemicals:

l1,3-Butadiene

lIsobutylene

lButene-1


PETROCHEMICALS FROM BUTADIENE

lStyrene-Butadiene-Rubber (SBR)


Ethylene above.

Hydrochlorination route

The traditional route proceeds via the conversion of propylene to

chloropropanols:

1,3 BUTADIENE STYRENE BUTADIENERUBBER (SBR)

Copolymerization

(+Styrene)

Copolymerization

Polymerization

(+ Acrylonitrile, +Styrene)

ACRYLONITRILE, STYRENE,BUTADIENE (ABS) RESINS

POLYBUTADIENERUBBER (PBR)

ISOBUTYLENEMETHYL TERTIARY BUTYLETHER (MTBE)



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lAcrylonitrile-Butadiene-Styrene Resins (ABS Resins)


Ethylene above.

lPoly-Butadiene Rubber (PBR)

Polybutadiene is a synthetic rubber that is a polymer formed from the

polymerization process of the monomer 1,3-butadiene. Due to its high

resistance to wear, it is used in the manufacture of tires. It is also used to

manufacture golf balls, various elastic objects and to coat or encapsulate

electronic assemblies, offering high electrical resistivity.

Polybutadiene forms by linking many 1,3-butadiene monomers to make a

much longer polymer chain molecule. In terms of the connectivity of the

polymer chain, butadiene can polymerize in three different ways, called cis,

trans and vinyl. The cis and trans forms arise by connecting the butadiene

molecules end-to-end, so-called 1,4-polymerisation. The properties of the

resulting isomeric forms of polybutadiene differ. For example, "high cis"-

polybutadiene has a high elasticity and is very popular, whereas the so-called

"high trans" is a plastic crystal with few useful application. The vinyl content

of polybutadiene is typically no more than a few percent.

A description of the chemical reactions involved and the typical conditions

under which synthetic rubber is produced is presented below:

lSynthetic Natural Rubber

Synthetic rubber is any type of artificial elastomer mainly synthesised from

petroleum byproducts. An elastomer is a material with the mechanical (or

material) property that it can undergo much more elastic deformation under

stress than most materials and still return to its previous size without

permanent deformation.

Synthetic natural rubber is made by the polymerization of isoprene (2-

methyl-1,3-butadiene), chloroprene (2-chloro-1,3-butadiene), and

isobutylene (methyl propene) with a small percentage of isoprene for cross-

linking. These and other monomers can be mixed in various proportions to

be copolymerized to produce products with a range of physical, mechanical,

and chemical properties. The monomers can be produced pure and the

addition of impurities or additives can be controlled by design to give

optimal properties. Polymerization of pure monomers can be better

controlled to give a desired proportion of cis and trans double bonds.

many

1,3-butadiene

HC

C CC

H H

H

HH

1 2

3 4

polymerization

H

C

H H

H HH

H

CC

CC

CC

C

H

HH

H

H

H H H H

CC

CC C

C C

CC

H H H H H HH H

H

H

trans 1,4-addition

1,2-addition

trans 1,4-addition

cis 1,4-addition

double bond in branchallows cross-linking cis bond makes

bend in chain

It has been found that a substantial percentage of cis double bond

configurations in the polymer will result in a material with flexible elastomer

(rubber-like) qualities. In free radical polymerization, both cis and trans

double bonds will form in percentages that depend on temperature. The

catalysts influence the cis vs trans ratio.

High cis-Polybutadiene is characterized by a high proportion of cis (typically

over 92%) and a small proportion of vinyl (less than 4%). It is manufactured

using Ziegler-Natta catalysts based on transition metals. Depending on the

metal used, the properties vary slightly. Using cobalt gives branched

molecules, resulting in a low viscosity material that is ease of use, but its

mechanical strength is relatively low. Neodymium gives the most linear

structure (and therefore higher mechanical strength) and a higher

percentage of 98% cis. Other less used catalysts include nickel and titanium.

Low cis-Polybutadiene is produced by using an alkyllithium (e.g.

butyllithium) as the catalyst. It typically contains 36% cis, 54% trans and

10% vinyl. Because of its high liquid-glass transition, low cis polybutadiene

is not used in tire manufacturing, but it can be used as an additive in plastics.

High vinyl Polybutadiene (over 70%), despite having a high liquid-glass

transition, is used in combination with high cis in tires. This material is

produced with an alkyllithium catalyst.

PETROCHEMICALS FROM ISOBUTYLENE

lMethyl-Tertiary Butyl Ether (MTBE)

This is covered in section 3.6-Petrochemicals from Methanol.

Useful C5 fraction extracted from the steam cracking of hydrocarbons is

mainly Isoprene. This is the precursor for the manufacture of synthetic

natural rubber.


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lAcrylonitrile-Butadiene-Styrene Resins (ABS Resins)


Ethylene above.

lPoly-Butadiene Rubber (PBR)

Polybutadiene is a synthetic rubber that is a polymer formed from the

polymerization process of the monomer 1,3-butadiene. Due to its high

resistance to wear, it is used in the manufacture of tires. It is also used to

manufacture golf balls, various elastic objects and to coat or encapsulate

electronic assemblies, offering high electrical resistivity.

Polybutadiene forms by linking many 1,3-butadiene monomers to make a

much longer polymer chain molecule. In terms of the connectivity of the

polymer chain, butadiene can polymerize in three different ways, called cis,

trans and vinyl. The cis and trans forms arise by connecting the butadiene

molecules end-to-end, so-called 1,4-polymerisation. The properties of the

resulting isomeric forms of polybutadiene differ. For example, "high cis"-

polybutadiene has a high elasticity and is very popular, whereas the so-called

"high trans" is a plastic crystal with few useful application. The vinyl content

of polybutadiene is typically no more than a few percent.

A description of the chemical reactions involved and the typical conditions

under which synthetic rubber is produced is presented below:

lSynthetic Natural Rubber

Synthetic rubber is any type of artificial elastomer mainly synthesised from

petroleum byproducts. An elastomer is a material with the mechanical (or

material) property that it can undergo much more elastic deformation under

stress than most materials and still return to its previous size without

permanent deformation.

Synthetic natural rubber is made by the polymerization of isoprene (2-

methyl-1,3-butadiene), chloroprene (2-chloro-1,3-butadiene), and

isobutylene (methyl propene) with a small percentage of isoprene for cross-

linking. These and other monomers can be mixed in various proportions to

be copolymerized to produce products with a range of physical, mechanical,

and chemical properties. The monomers can be produced pure and the

addition of impurities or additives can be controlled by design to give

optimal properties. Polymerization of pure monomers can be better

controlled to give a desired proportion of cis and trans double bonds.

many

1,3-butadiene

HC

C CC

H H

H

HH

1 2

3 4

polymerization

H

C

H H

H HH

H

CC

CC

CC

C

H

HH

H

H

H H H H

CC

CC C

C C

CC

H H H H H HH H

H

H

trans 1,4-addition

1,2-addition

trans 1,4-addition

cis 1,4-addition

double bond in branchallows cross-linking cis bond makes

bend in chain

It has been found that a substantial percentage of cis double bond

configurations in the polymer will result in a material with flexible elastomer

(rubber-like) qualities. In free radical polymerization, both cis and trans

double bonds will form in percentages that depend on temperature. The

catalysts influence the cis vs trans ratio.

High cis-Polybutadiene is characterized by a high proportion of cis (typically

over 92%) and a small proportion of vinyl (less than 4%). It is manufactured

using Ziegler-Natta catalysts based on transition metals. Depending on the

metal used, the properties vary slightly. Using cobalt gives branched

molecules, resulting in a low viscosity material that is ease of use, but its

mechanical strength is relatively low. Neodymium gives the most linear

structure (and therefore higher mechanical strength) and a higher

percentage of 98% cis. Other less used catalysts include nickel and titanium.

Low cis-Polybutadiene is produced by using an alkyllithium (e.g.

butyllithium) as the catalyst. It typically contains 36% cis, 54% trans and

10% vinyl. Because of its high liquid-glass transition, low cis polybutadiene

is not used in tire manufacturing, but it can be used as an additive in plastics.

High vinyl Polybutadiene (over 70%), despite having a high liquid-glass

transition, is used in combination with high cis in tires. This material is

produced with an alkyllithium catalyst.

PETROCHEMICALS FROM ISOBUTYLENE

lMethyl-Tertiary Butyl Ether (MTBE)

This is covered in section 3.6-Petrochemicals from Methanol.

Useful C5 fraction extracted from the steam cracking of hydrocarbons is

mainly Isoprene. This is the precursor for the manufacture of synthetic

natural rubber.


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3.5 Petrochemicals from Aromatics


Isoprene

Poly-Isoprene (Synthetic Natural Rubber)



Petrochemicals from aromatics are mainly produced from three types of

base chemicals:

lBenzene

lToluene

lXylenes

+ETHYLENE

BENZENEETHYL BENZENE

DEHYDROGENATION

STYRENE MONOMER

POLYMERISATION

STYRENE RESINS

CONDENSATIONPARTIALOXIDATION

HYDROGENATION

+PROPYLENE

CUMENE

CATALTICOXIDATION

TREATMENTWITH HNO.

BISPHENOLPHENOL

ACETONE

ADIPIC ACID

CATALYTIC OXIDATION

TREATMENT WITHNH OH,H SO NH2 2 4 3

HYDROGENATION

ANILLINENITROBENZENENITRATION

+HNO H SO H O3, 2 4, 2

+LINEAR

MONOOLEFINS

CHLORUNATION

LAB

SULFONATION

CHLOROBENZENE

DETERGENTS

+PHOSGENEMDI

+FORMAIDFHYDF

CAPROLACTAMPOLYMERISATION

RING OPENING

+HFXAMFTHYI FNFDIAMINF

6-6 NYLON

NYLON 6

POLYOLSPURIFICATION

PURE(4,4)MDI

POLYUREETHANES

CYCIOHFXANF

POLYCONDFNSATION

EPOXYRESINS DIPHENYL

CARBONATE

+PHOSGENE

+EPICHLOROHYDRIN

+COMONOMER

POLYCARBONATE

(+H )2

+Cl (FeCl CATALYST)2 3

HYDRODEALKYLATION

TOLUENE DISPROPOTINATION

DOUBLE NITRATION

BENZENETOLUENE

TOLUENEDIISOCYANATES(TDI)

+POLYOLS

(-HCL)

POLYURETHANE

BENZOIC ACID

PARTIAL OXIDATION

HYDROGENATION/PHOSGENATION

CATALYTIC OXIDATION

+O2

CATALYTIC OXIDATION

m-XYLENE

+O2

ISOPHTHALIC ACID

PHTHALICANHYDRIDE

+POLYOLS

ALKYD RESINS

+UNSATURATED DICARBOXYLICACID+GLYCOLS+STYRENE

AMIDE

POLYAMIDE RESINS

UNSATURATEDPOLYESTERS

+MEG

POLYESTERDIMETHYLTEREPHTHALATE

OXIDATION+METHYLESTERIFICATION

OXIDATION(+O )2

p-XYLENE

+MEG

POLYESTERTEREPHTHALIC ACID

O-XYLENE

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3.5 Petrochemicals from Aromatics


Isoprene

Poly-Isoprene (Synthetic Natural Rubber)



Petrochemicals from aromatics are mainly produced from three types of

base chemicals:

lBenzene

lToluene

lXylenes

+ETHYLENE

BENZENEETHYL BENZENE

DEHYDROGENATION

STYRENE MONOMER

POLYMERISATION

STYRENE RESINS

CONDENSATIONPARTIALOXIDATION

HYDROGENATION

+PROPYLENE

CUMENE

CATALTICOXIDATION

TREATMENTWITH HNO.

BISPHENOLPHENOL

ACETONE

ADIPIC ACID

CATALYTIC OXIDATION

TREATMENT WITHNH OH,H SO NH2 2 4 3

HYDROGENATION

ANILLINENITROBENZENENITRATION

+HNO H SO H O3, 2 4, 2

+LINEAR

MONOOLEFINS

CHLORUNATION

LAB

SULFONATION

CHLOROBENZENE

DETERGENTS

+PHOSGENEMDI

+FORMAIDFHYDF

CAPROLACTAMPOLYMERISATION

RING OPENING

+HFXAMFTHYI FNFDIAMINF

6-6 NYLON

NYLON 6

POLYOLSPURIFICATION

PURE(4,4)MDI

POLYUREETHANES

CYCIOHFXANF

POLYCONDFNSATION

EPOXYRESINS DIPHENYL

CARBONATE

+PHOSGENE

+EPICHLOROHYDRIN

+COMONOMER

POLYCARBONATE

(+H )2

+Cl (FeCl CATALYST)2 3

HYDRODEALKYLATION

TOLUENE DISPROPOTINATION

DOUBLE NITRATION

BENZENETOLUENE

TOLUENEDIISOCYANATES(TDI)

+POLYOLS

(-HCL)

POLYURETHANE

BENZOIC ACID

PARTIAL OXIDATION

HYDROGENATION/PHOSGENATION

CATALYTIC OXIDATION

+O2

CATALYTIC OXIDATION

m-XYLENE

+O2

ISOPHTHALIC ACID

PHTHALICANHYDRIDE

+POLYOLS

ALKYD RESINS

+UNSATURATED DICARBOXYLICACID+GLYCOLS+STYRENE

AMIDE

POLYAMIDE RESINS

UNSATURATEDPOLYESTERS

+MEG

POLYESTERDIMETHYLTEREPHTHALATE

OXIDATION+METHYLESTERIFICATION

OXIDATION(+O )2

p-XYLENE

+MEG

POLYESTERTEREPHTHALIC ACID

O-XYLENE

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PETROCHEMICALS FROM BENZENE

lEthylbenzene / Styrene / Styrene Resins (i.e., Polystyrene, SAN Resins,

ABS Resins, SBR Rubber)

This is covered under the section on petrochemicals from ethylene above.

lCumene (Isopropyl Benzene)

Cumene, the name by which isopropyl benzene is normally referred, is

produced by the Friedel-Crafts alkylation of benzene with propylene in the

presence of a zeolite based catalyst.

C6H6 + CH3CHCH2 → C6H5CH(CH3)2

Nearly all the cumene that is produced is used for the syhnthesis of other

industrially important chemicals, primarily phenol and acetone.

lPhenol and Acetone

Because of phenol's commercial importance, many methods have been

developed for its production. The dominant current route involves the

partial oxidation of cumene (isopropylbenzene) as per the equation:

C6H5CH(CH3)2 + O2 → C6H5OH + (CH3)2CO

Acetone, another industrially important chemical is the by product of the

above synthesis.

However, there do exist other less common processes for the manufacture of

Acetone. These are either based on the direct oxidation of propylene or the

hydration of propylene to give 2-propanol, which is then oxidized to acetone.

lBisphenol-A / Epoxy Resins / Polycarbonate

Bisphenol-A is synthesized from the condensation of one molecule of

Acetone with two molecules of Phenol as per the equation:

(CH3)2CO + 2 C6H5OH → (CH3)2C(C6H4OH)2 + H2O

Bisphenol-A is a component of many polymers such as polycarbonates,

polyurethanes, and epoxy resins.

The production of epoxy resins, including epoxy resins based on Bisphenol-

A, is covered under the section on petrochemicals from propylene above.

Polycarbonates are polymers containing carbonate groups (-O-(C=O)-O-). A

balance of useful features including temperature resistance, impact

resistance and optical properties position polycarbonates as an important

type of plastic materials.

The main polycarbonate material is produced by the reaction of Bisphenol-A

(BPA) and phosgene COCl2. The overall reaction can be written as follows:

The first step of the synthesis involves treatment of Bisphenol-A with sodium

hydroxide, which deprotonates the hydroxyl groups of the Bisphenol-A

(HOC6H4)2C(CH3)2 + 2 NaOH→ (NaOC6H4)2C(CH3)2 + 2 H2O

The diphenoxide ((NaOC6H4)2C(CH3)2) reacts with phosgene to give a

chloroformate, which subsequently is attacked by another phenoxide. The

net reaction from the diphenoxide is:

(NaOC6H4)2C(CH3)2 + COCl2→ 1/n [OC(OC6H4)2C(CH3)2]n + 2 NaCl

An alternative route to polycarbonates entails transesterification from BPA

and diphenyl carbonate:

(HOC6H4)2C(CH3)2 + (C6H5O)2CO→ 1/n [OC(OC6H4)2C(CH3)2]n + 2

C6H5OH

The diphenyl carbonate was derived in part from carbon monoxide, this

route being greener than the phosgene method.

lCyclohexane

Cyclohexane is produced by reacting benzene with hydrogen.

C6H6 + 3 H2→ C6H12

Most of cyclohexane produced is converted into cyclohexanone-

cyclohexanol mixture (or "KA oil") by catalytic oxidation. KA oil is then used

as a raw material for Adipic Acid and Caprolactam manufacture.

lAdipic Acid / Nylon 6-6

Adipic acid is the most important dicarboxylic acid with the formula

(CH2)4(COOH)2. It is a precursor for the production of Nylon 6.

Adipic acid is produced from a mixture of cyclohexanol and cyclohexanone

called "KA oil", the abbreviation of "ketone-alcohol oil." The KA oil is oxidized

with nitric acid to give adipic acid.

HOC6H11 + HNO3 → OC6H10 + HNO2 + H2O

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PETROCHEMICALS FROM BENZENE

lEthylbenzene / Styrene / Styrene Resins (i.e., Polystyrene, SAN Resins,

ABS Resins, SBR Rubber)

This is covered under the section on petrochemicals from ethylene above.

lCumene (Isopropyl Benzene)

Cumene, the name by which isopropyl benzene is normally referred, is

produced by the Friedel-Crafts alkylation of benzene with propylene in the

presence of a zeolite based catalyst.

C6H6 + CH3CHCH2 → C6H5CH(CH3)2

Nearly all the cumene that is produced is used for the syhnthesis of other

industrially important chemicals, primarily phenol and acetone.

lPhenol and Acetone

Because of phenol's commercial importance, many methods have been

developed for its production. The dominant current route involves the

partial oxidation of cumene (isopropylbenzene) as per the equation:

C6H5CH(CH3)2 + O2 → C6H5OH + (CH3)2CO

Acetone, another industrially important chemical is the by product of the

above synthesis.

However, there do exist other less common processes for the manufacture of

Acetone. These are either based on the direct oxidation of propylene or the

hydration of propylene to give 2-propanol, which is then oxidized to acetone.

lBisphenol-A / Epoxy Resins / Polycarbonate

Bisphenol-A is synthesized from the condensation of one molecule of

Acetone with two molecules of Phenol as per the equation:

(CH3)2CO + 2 C6H5OH → (CH3)2C(C6H4OH)2 + H2O

Bisphenol-A is a component of many polymers such as polycarbonates,

polyurethanes, and epoxy resins.

The production of epoxy resins, including epoxy resins based on Bisphenol-

A, is covered under the section on petrochemicals from propylene above.

Polycarbonates are polymers containing carbonate groups (-O-(C=O)-O-). A

balance of useful features including temperature resistance, impact

resistance and optical properties position polycarbonates as an important

type of plastic materials.

The main polycarbonate material is produced by the reaction of Bisphenol-A

(BPA) and phosgene COCl2. The overall reaction can be written as follows:

The first step of the synthesis involves treatment of Bisphenol-A with sodium

hydroxide, which deprotonates the hydroxyl groups of the Bisphenol-A

(HOC6H4)2C(CH3)2 + 2 NaOH→ (NaOC6H4)2C(CH3)2 + 2 H2O

The diphenoxide ((NaOC6H4)2C(CH3)2) reacts with phosgene to give a

chloroformate, which subsequently is attacked by another phenoxide. The

net reaction from the diphenoxide is:

(NaOC6H4)2C(CH3)2 + COCl2→ 1/n [OC(OC6H4)2C(CH3)2]n + 2 NaCl

An alternative route to polycarbonates entails transesterification from BPA

and diphenyl carbonate:

(HOC6H4)2C(CH3)2 + (C6H5O)2CO→ 1/n [OC(OC6H4)2C(CH3)2]n + 2

C6H5OH

The diphenyl carbonate was derived in part from carbon monoxide, this

route being greener than the phosgene method.

lCyclohexane

Cyclohexane is produced by reacting benzene with hydrogen.

C6H6 + 3 H2→ C6H12

Most of cyclohexane produced is converted into cyclohexanone-

cyclohexanol mixture (or "KA oil") by catalytic oxidation. KA oil is then used

as a raw material for Adipic Acid and Caprolactam manufacture.

lAdipic Acid / Nylon 6-6

Adipic acid is the most important dicarboxylic acid with the formula

(CH2)4(COOH)2. It is a precursor for the production of Nylon 6.

Adipic acid is produced from a mixture of cyclohexanol and cyclohexanone

called "KA oil", the abbreviation of "ketone-alcohol oil." The KA oil is oxidized

with nitric acid to give adipic acid.

HOC6H11 + HNO3 → OC6H10 + HNO2 + H2O

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Side products of the method include glutaric and succinic acids.

Nylon 6-6, also referred to as nylon 6,6, is a polyamide from nylon class. The

polymer is made of hexamethylenediamine and adipic acid, which give nylon

6,6 a total of 12 carbon atoms in each repeating unit, and its name.

Hexamethylenediamine and Adipic acid, monomers used for

polycondensation of Nylon 6,6.

The process is called polycondensation of hexamethylenediamine and adipic

acid. This reaction is first carried out in a water medium wherein a nylon salt

is produced. Excess water is removed from this nylon salt by evaporation

followed by continuous polymerization to molten Nylon 6-6 in a reaction

vessel. Molten nylon 6-6 is extruded in a spinneret and air dried to form

nylon fibres. The reaction occurs at a high pressure and at around 260 deg C.

lCaprolactam / Nylon 6

Caprolactam is an organic compound with the formula (CH2)5C(O)NH. This

colourless solid is a lactam or a cyclic amide of caproic acid. Caprolactam is

the precursor to Nylon 6, a widely used synthetic polymer.

Caprolactam is synthesized from cyclohexanone (produced by the catalytic

oxidation of cyclohexane) (1 below), which is first converted to its oxime (2

below). Treatment of this oxime with acid gives Caprolactam (3 below):

The immediate product of the acid-induced rearrangement is the bisulfate

salt of caprolactam. This salt is neutralized with ammonia to release the free

lactam and cogenerate ammonium sulfate. In optimizing the industrial

practices, much attention is directed toward minimizing the production of

ammonium salts.

The other major industrial route involves formation of the oxime from

cyclohexane using nitrosyl chloride. The advantage of this method is that

cyclohexane is less expensive than cyclohexanone.

Almost all caprolactam produced goes into the production of Nylon-6. The

conversion entails a ring-opening polymerization. Caprolactam has 6

carbons, hence 'Nylon 6'. When caprolactam is heated at about 260 deg C in

an inert atmosphere of nitrogen for about 4-5 hours, the ring breaks and

undergoes polymerization. Then the molten mass is passed through

spinnerets to form fibres of Nylon 6.

During polymerization, the peptide bond within each caprolactam molecule

is broken, with the active groups on each side re-forming two new bonds as

the monomer becomes part of the polymer backbone.

lNitrobenzene / Aniline / Methylene Diphenyl Diisocyanate /

Polyurethanes

Nitrobenzene is an organic compound with the chemical formula C6H5NO2.

It is produced on a large scale from benzene as a precursor to aniline by the

nitration of benzene at 50-60 deg C with a mixture of concentrated sulfuric

acid, water, and nitric acid. This mixture is sometimes called "mixed acid."

The reaction is highly exothermic, making this one of the most dangerous

processes conducted in the chemical industry.

HO

O

O

HO

ADIPIC ACID

H N2

NH2

HEXAMETHYLENEDIAMINE

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Side products of the method include glutaric and succinic acids.

Nylon 6-6, also referred to as nylon 6,6, is a polyamide from nylon class. The

polymer is made of hexamethylenediamine and adipic acid, which give nylon

6,6 a total of 12 carbon atoms in each repeating unit, and its name.

Hexamethylenediamine and Adipic acid, monomers used for

polycondensation of Nylon 6,6.

The process is called polycondensation of hexamethylenediamine and adipic

acid. This reaction is first carried out in a water medium wherein a nylon salt

is produced. Excess water is removed from this nylon salt by evaporation

followed by continuous polymerization to molten Nylon 6-6 in a reaction

vessel. Molten nylon 6-6 is extruded in a spinneret and air dried to form

nylon fibres. The reaction occurs at a high pressure and at around 260 deg C.

lCaprolactam / Nylon 6

Caprolactam is an organic compound with the formula (CH2)5C(O)NH. This

colourless solid is a lactam or a cyclic amide of caproic acid. Caprolactam is

the precursor to Nylon 6, a widely used synthetic polymer.

Caprolactam is synthesized from cyclohexanone (produced by the catalytic

oxidation of cyclohexane) (1 below), which is first converted to its oxime (2

below). Treatment of this oxime with acid gives Caprolactam (3 below):

The immediate product of the acid-induced rearrangement is the bisulfate

salt of caprolactam. This salt is neutralized with ammonia to release the free

lactam and cogenerate ammonium sulfate. In optimizing the industrial

practices, much attention is directed toward minimizing the production of

ammonium salts.

The other major industrial route involves formation of the oxime from

cyclohexane using nitrosyl chloride. The advantage of this method is that

cyclohexane is less expensive than cyclohexanone.

Almost all caprolactam produced goes into the production of Nylon-6. The

conversion entails a ring-opening polymerization. Caprolactam has 6

carbons, hence 'Nylon 6'. When caprolactam is heated at about 260 deg C in

an inert atmosphere of nitrogen for about 4-5 hours, the ring breaks and

undergoes polymerization. Then the molten mass is passed through

spinnerets to form fibres of Nylon 6.

During polymerization, the peptide bond within each caprolactam molecule

is broken, with the active groups on each side re-forming two new bonds as

the monomer becomes part of the polymer backbone.

lNitrobenzene / Aniline / Methylene Diphenyl Diisocyanate /

Polyurethanes

Nitrobenzene is an organic compound with the chemical formula C6H5NO2.

It is produced on a large scale from benzene as a precursor to aniline by the

nitration of benzene at 50-60 deg C with a mixture of concentrated sulfuric

acid, water, and nitric acid. This mixture is sometimes called "mixed acid."

The reaction is highly exothermic, making this one of the most dangerous

processes conducted in the chemical industry.

HO

O

O

HO

ADIPIC ACID

H N2

NH2

HEXAMETHYLENEDIAMINE

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Aniline is produced from nitrobenzene by hydrogenation, typically at 200-

300 °C in presence of various metal catalysts:

C6H5NO2 + 3 H2 ? C6H5NH2 + 2 H2O

An alternate method of producing aniline from the reaction of phenol with

ammonia also exists.

The largest application of aniline is for the preparation of methylene

diphenyl diisocyanate, a precursor to polyurethane resins. This is prepared

in two steps. First aniline is alkylated with formaldehyde to produce

methylene dianiline as per the equation:

2 C6H5NH2 + CH2O→ CH2(C6H4NH2)2 + H2O

Next, the methylene dianiline is condensed with phosgene to give mixed

Methylene diphenyl diisocyanate (MDI).

Mixed MDI contains three different kinds of MDI isomers (depending on the

position of connection of the cyanate groups):

l2,2-MDI

l2,4-MDI

l4,4-MDI

These are depicted below:

Out of the above, 4,4-MDI is called pure MDI and is used for polyurethanes

manufacture. Purification of mixed MDI's to obtain pure MDI is performed

by fractionation.

Polyurethanes are produced from the condensation of polyols with

diisocyanates as per the following equation:

l

Linear alkylbenzene is a family of organic compounds with the formula

C6H5CnH2n+1. Typically, n lies between 10 and 16, although generally

supplied as a tighter cut, such as C12-C15, C12-C13 and C10-C13, for

detergent use. The CnH2n+1 chain is unbranched.

Hydrotreated kerosene is a typical feedstock for high purity linear paraffins,

which are subsequently dehydrogenated to linear olefins:

CnH2n+2 → CnH2n + H2

The linear mono-olefins react with benzene in the presence of a catalyst to

produce the LABs. Hydrogen fluoride (HF) and aluminium chloride (AlCl3)

are the two major catalysts for the alkylation of benzene with linear mono-

olefins. The HF-based process is commercially dominant.

Linear alkylbenzene is sulfonated to produce linear alkylbenzene sulfonate

(LAS), a biodegradable surfactant and a constituent of detergents.

lChlorobenzene

Chlorobenzene is used as an intermediate in the production of commodities

such as herbicides, dyestuffs, and rubber. It is also used as a high-boiling

solvent in many industrial applications as well as in the laboratory

It is manufactured by chlorination of benzene in the presence of a catalytic

amount of Lewis acid such as ferric chloride and anhydrous aluminium

chloride:

Linear Alkyl Benzene (LAB) / Detergents

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Aniline is produced from nitrobenzene by hydrogenation, typically at 200-

300 °C in presence of various metal catalysts:

C6H5NO2 + 3 H2 ? C6H5NH2 + 2 H2O

An alternate method of producing aniline from the reaction of phenol with

ammonia also exists.

The largest application of aniline is for the preparation of methylene

diphenyl diisocyanate, a precursor to polyurethane resins. This is prepared

in two steps. First aniline is alkylated with formaldehyde to produce

methylene dianiline as per the equation:

2 C6H5NH2 + CH2O→ CH2(C6H4NH2)2 + H2O

Next, the methylene dianiline is condensed with phosgene to give mixed

Methylene diphenyl diisocyanate (MDI).

Mixed MDI contains three different kinds of MDI isomers (depending on the

position of connection of the cyanate groups):

l2,2-MDI

l2,4-MDI

l4,4-MDI

These are depicted below:

Out of the above, 4,4-MDI is called pure MDI and is used for polyurethanes

manufacture. Purification of mixed MDI's to obtain pure MDI is performed

by fractionation.

Polyurethanes are produced from the condensation of polyols with

diisocyanates as per the following equation:

l

Linear alkylbenzene is a family of organic compounds with the formula

C6H5CnH2n+1. Typically, n lies between 10 and 16, although generally

supplied as a tighter cut, such as C12-C15, C12-C13 and C10-C13, for

detergent use. The CnH2n+1 chain is unbranched.

Hydrotreated kerosene is a typical feedstock for high purity linear paraffins,

which are subsequently dehydrogenated to linear olefins:

CnH2n+2 → CnH2n + H2

The linear mono-olefins react with benzene in the presence of a catalyst to

produce the LABs. Hydrogen fluoride (HF) and aluminium chloride (AlCl3)

are the two major catalysts for the alkylation of benzene with linear mono-

olefins. The HF-based process is commercially dominant.

Linear alkylbenzene is sulfonated to produce linear alkylbenzene sulfonate

(LAS), a biodegradable surfactant and a constituent of detergents.

lChlorobenzene

Chlorobenzene is used as an intermediate in the production of commodities

such as herbicides, dyestuffs, and rubber. It is also used as a high-boiling

solvent in many industrial applications as well as in the laboratory

It is manufactured by chlorination of benzene in the presence of a catalytic

amount of Lewis acid such as ferric chloride and anhydrous aluminium

chloride:

Linear Alkyl Benzene (LAB) / Detergents

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The catalyst enhances the electrophilicity of the chlorine. Because chlorine is

electronegative, C6H5Cl exhibits decreased susceptibility to attack by other

electrophiles. For this reason, the chlorination process produces only small

amounts of dichloro- and trichlorobenzenes.

PETROCHEMICALS FROM TOLUENE

lBenzene

Benzene can be produced from toluene by two routes:

lToluene hydrodealkylatio

lToluene disproportionation

The Toluene hydrodealkylation process converts toluene to benzene. In this

hydrogen-intensive process, toluene is mixed with hydrogen, then passed

over a chromium, molybdenum, or platinum oxide catalyst at 500-600 °C and

40-60 atm pressure. Sometimes, higher temperatures are used instead of a

catalyst (at the similar reaction condition). Under these conditions, toluene

undergoes dealkylation to benzene and methane as per the chemical

equation:

C6H5CH3 + H2→C6H6 + CH4

This irreversible reaction is accompanied by an equilibrium side reaction

that produces biphenyl (aka diphenyl) at higher temperature:

2 C6H6 H2 + C6H5-C6H5

If the raw material stream contains much non-aromatic components

(paraffins or naphthenes), those are likely decomposed to lower

hydrocarbons such as methane, which increases the consumption of

hydrogen.

A typical reaction yield exceeds 95%. Sometimes, xylenes and heavier

aromatics are used in place of toluene, with similar efficiency.

This is often called "on-purpose" methodology to produce benzene,

compared to conventional BTX (benzene-toluene-xylene) extraction

processes.

The Toluene Disproportionation process for the production of Benzene from

Toluene produces an equal molar quantity of Xyelene. This route finds

favour in those complexes where there exist similar demands for both

benzene and xylene.

In the broad sense, this process reacts 2 toluene molecules and rearranges

the methyl groups from one toluene molecule to the other, yielding one

benzene molecule and one xylene molecule.

Given that demand for para-xylene (p-xylene) substantially exceeds demand

for other xylene isomers, a refinement of the TDP process called Selective

TDP (STDP) may be used. In this process, the xylene stream exiting the TDP

unit is approximately 90% paraxylene.

l

Toluene diisocyanate (TDI) is an organic compound with the formula

CH3C6H3(NCO)2. Two of the six possible isomers are commercially

important:2,4-TDI and 2,6-TDI. 2,4-TDI is produced in the pure state, but TDI

is often marketed as 80/20 and 65/35 mixtures of the 2,4 and 2,6 isomers

respectively.

2,4-TDI is prepared in three steps from toluene, which is doubly nitrated

with nitric acid to give dinitrotoluene. This step determines the isomer ratio

of the ultimate TDI. Hydrogenation of the dinitrotoluene produces the

corresponding isomers of diaminotoluene (TDA). Finally, the TDA is

subjected to phosgenation, i.e. treatment with phosgene to form TDI. This

final step produces HCl as a byproduct and is a major source of industrial

hydrochloric acid.

Distillation of the crude TDI mixture produces an 80:20 mixture of 2,4-TDI

and 2,6-TDI, known as TDI (80/20). Differentiation or separation of the TDI

(80/20) can be used to produce pure 2,4-TDI and a 65:35 mixture of 2,4-TDI

and 2,6-TDI, known as TDI (65/35).

Production of polyurethanes from TDI is similar to the process described

above under MDI.

lBenzoic Acid

Benzoic acid is produced commercially by partial oxidation of toluene with

oxygen. The process is catalyzed by cobalt or manganese naphthenates. The

process uses cheap raw materials, proceeds in high yield.

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The catalyst enhances the electrophilicity of the chlorine. Because chlorine is

electronegative, C6H5Cl exhibits decreased susceptibility to attack by other

electrophiles. For this reason, the chlorination process produces only small

amounts of dichloro- and trichlorobenzenes.

PETROCHEMICALS FROM TOLUENE

lBenzene

Benzene can be produced from toluene by two routes:

lToluene hydrodealkylatio

lToluene disproportionation

The Toluene hydrodealkylation process converts toluene to benzene. In this

hydrogen-intensive process, toluene is mixed with hydrogen, then passed

over a chromium, molybdenum, or platinum oxide catalyst at 500-600 °C and

40-60 atm pressure. Sometimes, higher temperatures are used instead of a

catalyst (at the similar reaction condition). Under these conditions, toluene

undergoes dealkylation to benzene and methane as per the chemical

equation:

C6H5CH3 + H2→C6H6 + CH4

This irreversible reaction is accompanied by an equilibrium side reaction

that produces biphenyl (aka diphenyl) at higher temperature:

2 C6H6 H2 + C6H5-C6H5

If the raw material stream contains much non-aromatic components

(paraffins or naphthenes), those are likely decomposed to lower

hydrocarbons such as methane, which increases the consumption of

hydrogen.

A typical reaction yield exceeds 95%. Sometimes, xylenes and heavier

aromatics are used in place of toluene, with similar efficiency.

This is often called "on-purpose" methodology to produce benzene,

compared to conventional BTX (benzene-toluene-xylene) extraction

processes.

The Toluene Disproportionation process for the production of Benzene from

Toluene produces an equal molar quantity of Xyelene. This route finds

favour in those complexes where there exist similar demands for both

benzene and xylene.

In the broad sense, this process reacts 2 toluene molecules and rearranges

the methyl groups from one toluene molecule to the other, yielding one

benzene molecule and one xylene molecule.

Given that demand for para-xylene (p-xylene) substantially exceeds demand

for other xylene isomers, a refinement of the TDP process called Selective

TDP (STDP) may be used. In this process, the xylene stream exiting the TDP

unit is approximately 90% paraxylene.

l

Toluene diisocyanate (TDI) is an organic compound with the formula

CH3C6H3(NCO)2. Two of the six possible isomers are commercially

important:2,4-TDI and 2,6-TDI. 2,4-TDI is produced in the pure state, but TDI

is often marketed as 80/20 and 65/35 mixtures of the 2,4 and 2,6 isomers

respectively.

2,4-TDI is prepared in three steps from toluene, which is doubly nitrated

with nitric acid to give dinitrotoluene. This step determines the isomer ratio

of the ultimate TDI. Hydrogenation of the dinitrotoluene produces the

corresponding isomers of diaminotoluene (TDA). Finally, the TDA is

subjected to phosgenation, i.e. treatment with phosgene to form TDI. This

final step produces HCl as a byproduct and is a major source of industrial

hydrochloric acid.

Distillation of the crude TDI mixture produces an 80:20 mixture of 2,4-TDI

and 2,6-TDI, known as TDI (80/20). Differentiation or separation of the TDI

(80/20) can be used to produce pure 2,4-TDI and a 65:35 mixture of 2,4-TDI

and 2,6-TDI, known as TDI (65/35).

Production of polyurethanes from TDI is similar to the process described

above under MDI.

lBenzoic Acid

Benzoic acid is produced commercially by partial oxidation of toluene with

oxygen. The process is catalyzed by cobalt or manganese naphthenates. The

process uses cheap raw materials, proceeds in high yield.

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PETROCHEMICALS FROM XYLENES (ortho, meta, para)

lPhthallic Anhydride (from ortho Xylene)

Phthalic anhydride is the organic compound with the formula C6H4(CO)2O.

It is the anhydride of phthalic acid. This colourless solid is an important

industrial chemical, especially for the large-scale production of plasticizers

for plastics.

Phthalic anhydride is manufactured by catalytic oxidation of ortho-xylene

and naphthalene by the Gibbs phthalic anhydride process:

C6H4(CH3)2 + 3 O2→ C6H4(CO)2O + 3 H2O

C10H8 + 4.5 O2→ C6H4(CO)2O + 2 H2O + 2 CO2

The catalyst that is used for the oxidation of xylene is a modified vanadium

pentoxide (V2O5). Phthalic anhydride is purified by separating it from

byproducts such as o-xylene in water, or maleic anhydride through

fractionation.

lIsophthalic Acid (from meta Xylene)

Isophthalic acid is an organic compound with the formula C6H4(CO2H)2.

This colourless solid is an isomer of phthalic acid and terephthalic acid.

These aromatic dicarboxylic acids are used as precursors (in form of acyl

chlorides) to commercially important polymers, e.g. the fire-resistant

material Nomex. Mixed with terephthalic acid, isophthalic acid is used in the

production of resins for drink bottles. The high-performance polymer

polybenzimidazole is produced from isophthalic acid.

Isophthalic acid is produced by oxidizing meta-xylene using oxygen. The

process employs a cobalt-manganese catalyst.

lAlkyd Resins (from dicarboxylic acids like isophthalic acid)

An alkyd is a polyester modified by the addition of fatty acids and other

components. They are derived from polyols and a dicarboxylic acid or

carboxylic acid anhydride. The inclusion of the fatty acid confers a tendency

to form flexible coating. Alkyds are used in paints and in moulds for casting.

They are the dominant resin or "binder" in most commercial "oil-based"

coatings.

Alkyd resins are produced from dicarboxylic acids or anhydrides, such as

phthalic anhydride or maleic anhydride, and polyols, such as trimethylo lpro

pane, glycerine, or pentaerythritol.

Unsaturated Polyesters (from dicarboxylic acids like isophthalic

acid)

Unsaturated polyesters are thermosetting plastics.

These are copolyesters-that is, polyesters prepared from a saturated

dicarboxylic acid (for example isophthalic acid) or its anhydride (for

example phthalic anhydride) as well as an unsaturated dicarboxylic acid or

anhydride (for example maleic anhydride). These two acid constituents are

reacted with one or more dialcohols, such as ethylene glycol or propylene

glycol, to produce the characteristic ester groups that link the precursor

molecules together into long, chainlike, multiple-unit polyester molecules.

The maleic anhydride units of this copolyester are unsaturated because they

contain carbon-carbon double bonds that are capable of undergoing further

polymerization under the proper conditions.

These conditions are created when the copolyester is dissolved in a

monomer such as styrene and the two are subjected to the action of free-

radical initiators.

The mixture, at this point usually poured into a mold, then copolymerizes

(sets) rapidly to form a three-dimensional network structure that bonds well

with fibres or other reinforcing materials.

lDimethyl Terephthalate (from para Xylene)

Dimethyl terephthalate (DMT) is an organic compound with the formula

C6H4(CO2CH3)2. It is a white solid that melts to give a distillable colourless

liquid.

DMT can be produced by alternating oxidation and methyl-esterification

steps from p-xylene via methy p-toluate.

lTerephthalic Acid (from para Xylene)

Terephthalic acid is the organic compound with formula C6H4(COOH)2. This

colourless solid is a commodity chemical, used principally as a precursor to

the polyester and PET, used to make clothing and plastic bottles respectively.

It is one of three isomeric phthalic acids.

Terephthalic acid is produced by oxidation of p-xylene by oxygen in air:

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PETROCHEMICALS FROM XYLENES (ortho, meta, para)

lPhthallic Anhydride (from ortho Xylene)

Phthalic anhydride is the organic compound with the formula C6H4(CO)2O.

It is the anhydride of phthalic acid. This colourless solid is an important

industrial chemical, especially for the large-scale production of plasticizers

for plastics.

Phthalic anhydride is manufactured by catalytic oxidation of ortho-xylene

and naphthalene by the Gibbs phthalic anhydride process:

C6H4(CH3)2 + 3 O2→ C6H4(CO)2O + 3 H2O

C10H8 + 4.5 O2→ C6H4(CO)2O + 2 H2O + 2 CO2

The catalyst that is used for the oxidation of xylene is a modified vanadium

pentoxide (V2O5). Phthalic anhydride is purified by separating it from

byproducts such as o-xylene in water, or maleic anhydride through

fractionation.

lIsophthalic Acid (from meta Xylene)

Isophthalic acid is an organic compound with the formula C6H4(CO2H)2.

This colourless solid is an isomer of phthalic acid and terephthalic acid.

These aromatic dicarboxylic acids are used as precursors (in form of acyl

chlorides) to commercially important polymers, e.g. the fire-resistant

material Nomex. Mixed with terephthalic acid, isophthalic acid is used in the

production of resins for drink bottles. The high-performance polymer

polybenzimidazole is produced from isophthalic acid.

Isophthalic acid is produced by oxidizing meta-xylene using oxygen. The

process employs a cobalt-manganese catalyst.

lAlkyd Resins (from dicarboxylic acids like isophthalic acid)

An alkyd is a polyester modified by the addition of fatty acids and other

components. They are derived from polyols and a dicarboxylic acid or

carboxylic acid anhydride. The inclusion of the fatty acid confers a tendency

to form flexible coating. Alkyds are used in paints and in moulds for casting.

They are the dominant resin or "binder" in most commercial "oil-based"

coatings.

Alkyd resins are produced from dicarboxylic acids or anhydrides, such as

phthalic anhydride or maleic anhydride, and polyols, such as trimethylo lpro

pane, glycerine, or pentaerythritol.

Unsaturated Polyesters (from dicarboxylic acids like isophthalic

acid)

Unsaturated polyesters are thermosetting plastics.

These are copolyesters-that is, polyesters prepared from a saturated

dicarboxylic acid (for example isophthalic acid) or its anhydride (for

example phthalic anhydride) as well as an unsaturated dicarboxylic acid or

anhydride (for example maleic anhydride). These two acid constituents are

reacted with one or more dialcohols, such as ethylene glycol or propylene

glycol, to produce the characteristic ester groups that link the precursor

molecules together into long, chainlike, multiple-unit polyester molecules.

The maleic anhydride units of this copolyester are unsaturated because they

contain carbon-carbon double bonds that are capable of undergoing further

polymerization under the proper conditions.

These conditions are created when the copolyester is dissolved in a

monomer such as styrene and the two are subjected to the action of free-

radical initiators.

The mixture, at this point usually poured into a mold, then copolymerizes

(sets) rapidly to form a three-dimensional network structure that bonds well

with fibres or other reinforcing materials.

lDimethyl Terephthalate (from para Xylene)

Dimethyl terephthalate (DMT) is an organic compound with the formula

C6H4(CO2CH3)2. It is a white solid that melts to give a distillable colourless

liquid.

DMT can be produced by alternating oxidation and methyl-esterification

steps from p-xylene via methy p-toluate.

lTerephthalic Acid (from para Xylene)

Terephthalic acid is the organic compound with formula C6H4(COOH)2. This

colourless solid is a commodity chemical, used principally as a precursor to

the polyester and PET, used to make clothing and plastic bottles respectively.

It is one of three isomeric phthalic acids.

Terephthalic acid is produced by oxidation of p-xylene by oxygen in air:

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This reaction proceeds through a p-toluic acid intermediate which is then

oxidized to terephthalic acid.

The commercial process utilizes acetic acid as solvent and a catalyst

composed of cobalt and manganese salts, with a bromide promoter.

The most problematic impurity is 4-formylbenzoic acid (commonly known

in the field as 4-carboxybenzaldehyde or 4-CBA), which is removed by

hydrogenation of a hot aqueous solution.

This solution is then cooled in a stepwise manner to crystallize highly pure

terephthalic acid.

lPolyester (from either Dimethyl Terephthalate or Terephthalic Acid)

Polyester is a synthetic polymer made of purified terephthalic acid (PTA) or

its dimethyl ester dimethyl terephthalate (DMT) and mono ethylene glycol

(MEG). To facilitate the above reaction, a catalyst is employed. The most

common catalyst is antimony trioxide (or antimony tri acetate).

Polyesters are an important class of polymers due to various reasons. These

are mainly:

- The relatively easy accessible raw materials PTA or DMT and MEG

- The very well understood and described simple chemical process of

polyester synthesis

- The low toxicity level of all raw materials and side products during

polyester production and processing

- The possibility to produce PET in a closed loop at low emissions to the

environment

- The outstanding mechanical and chemical properties of polyester

- The recyclability

The wide variety of intermediate and final products made of polyester


3.6 Petrochemicals from Methanol



lFormaldehyde

Formaldehyde is produced by dehydrogenating and partially oxidating

methanol as per the following equations:

CH3OH→ H2CO + H2

CH3OH + ½ O2 → H2CO + H2O

Commercial production of formaldehyde uses one of three industrial

processes:

Dehydrogenation/Partial Oxidation

(Ag)

METHANOL

+Isobutylene

(Acidic lon Exchange)

+CO

(Carbonylation)

(Zeolites)

(AI203)

Homologation

(Co)

FORMALDEHYDE

ACETIC ACID

OLEFINS AND SYNTHETIC FUELS

DIMETHYL ETHER

ETHANOL

MTBE

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This reaction proceeds through a p-toluic acid intermediate which is then

oxidized to terephthalic acid.

The commercial process utilizes acetic acid as solvent and a catalyst

composed of cobalt and manganese salts, with a bromide promoter.

The most problematic impurity is 4-formylbenzoic acid (commonly known

in the field as 4-carboxybenzaldehyde or 4-CBA), which is removed by

hydrogenation of a hot aqueous solution.

This solution is then cooled in a stepwise manner to crystallize highly pure

terephthalic acid.

lPolyester (from either Dimethyl Terephthalate or Terephthalic Acid)

Polyester is a synthetic polymer made of purified terephthalic acid (PTA) or

its dimethyl ester dimethyl terephthalate (DMT) and mono ethylene glycol

(MEG). To facilitate the above reaction, a catalyst is employed. The most

common catalyst is antimony trioxide (or antimony tri acetate).

Polyesters are an important class of polymers due to various reasons. These

are mainly:

- The relatively easy accessible raw materials PTA or DMT and MEG

- The very well understood and described simple chemical process of

polyester synthesis

- The low toxicity level of all raw materials and side products during

polyester production and processing

- The possibility to produce PET in a closed loop at low emissions to the

environment

- The outstanding mechanical and chemical properties of polyester

- The recyclability

The wide variety of intermediate and final products made of polyester


3.6 Petrochemicals from Methanol



lFormaldehyde

Formaldehyde is produced by dehydrogenating and partially oxidating

methanol as per the following equations:

CH3OH→ H2CO + H2

CH3OH + ½ O2 → H2CO + H2O

Commercial production of formaldehyde uses one of three industrial

processes:

Dehydrogenation/Partial Oxidation

(Ag)

METHANOL

+Isobutylene

(Acidic lon Exchange)

+CO

(Carbonylation)

(Zeolites)

(AI203)

Homologation

(Co)

FORMALDEHYDE

ACETIC ACID

OLEFINS AND SYNTHETIC FUELS

DIMETHYL ETHER

ETHANOL

MTBE

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- The BASF process involves partial oxidation and dehydrogenation with

air in the presence of a silver crystals, steam, and excess methanol at a

temperature of 680-720°C. The conversion rate of methanol to

formaldehyde is 97-98%.

- A variation of the BASF process uses crystalline silver or silver gauze at a

temperature of 600-650 °C. The product is distilled and the unreacted

methanol recycled. The conversion rate for this process is 77-87%.

- The third process (the Formox process) involves oxidation with a lean

m e t h a n o l - a i r m i x t u r e i n t h e p r e s e n c e o f a m o d i f i e d

iron/molybdenum/vanadium oxide catalyst [Fe2(MoO4)3] at a

temperature of 250-400°C. The methanol conversion for this process is

98-99%. This reaction is more exothermic than the silver (Ag) process

and heat removal is required (Satterfield, 1991). Excessive reactor

temperatures cause volatilization of molybdenum oxide, which reduces

the selectivity of the process. A high oxygen partial pressure is required

to maintain catalyst activity. Catalyst activity is also lost in the presence

of excess methanol.

Formaldehyde is combined with phenol, urea, or melamine to make resins

used in the manufacture of various construction board products, and its

demand is driven by the construction industry. Other products

manufactured with formaldehyde include paints, explosives and permanent

press textiles.

lMethyl Tertiary Butyl Ether (MTBE)

MTBE is produced by reacting isobutene with methanol in the presence of an

acidic catalyst as per the equation:

iso-C4H8 + CH3OH → C(CH3)3COCH3

The reaction occurs in a liquid phase at temperatures of 30-100°C and

pressure at 7-14 kg/cm2g. Different catalysts can be used including solid

acids, zeolites (H-ZSM-5) and macroporous sulfonic acid ion-exchange

resins. A molar excess of methanol is used to increase isobutene conversion

and inhibit its dimerization and oligomerization. Conversion yields of up to

90% can be achieved at optimum reaction conditions.

MTBE is produced by refinery/petrochemical plants using by-product

isobutylene, by merchant plants which isomerize n- and iso-butane and

dehydrogenate isobutane to isobutylene, and by tertiary butyl alcohol (TBA)

plants which react by-product TBA from propylene oxide production with

methanol.

MTBE is used primarily (95%) as an oxygenate in gasoline. MTBE is also

used in the petrochemical industry to produce isobutene, methacrolein,

methycrylic acid, isoprene, and industrial solvents.

lAcetic Acid

The third most abundant chemical synthesized from methanol is acetic acid.

It is produced by the carbonylation of methanol as per the equation:

CH3OH + CO →CH3COOH

The Monsanto process for acetic acid manufacture uses a Rh/iodine catalyst

[RhI2(CO)2] and process conditions of 180°C and 30-40 kg/cm2g with over

99% selectivity. It is a liquid phase process initiated by the reaction of

methanol with HI to yield methyl iodide. Insertion of the methyl iodide is the

rate limiting step. Acetic acid is formed by the hydrolysis of the eliminated

acetyl iodide (CH3COI) that also regenerates HI.

Acetic acid is used for the manufacture of industrially important chemicals

like Vinyl Acetate, Acetic Anhydride and Terephthalic Acid.

lOlefins and Synthetic Fuels

Methanol can be used to produce Synthetic Gasoline (the MTG process),

Olefins (the MTO process), and Synthetic Gasoline and Diesel fuels (the

MODG process).

These processes involve conversion of methanol to hydrocarbons over

zeolite catalysts. The reaction is carried out with catalyst being either in

fixed bed or fluidized bed reactors. Superheated vapours consisting of

methanol and steam is partially dehydrated over an alumina catalyst to yield

an equilibrium mixture of methanol, dimethyl ether and water. This mixture

is then reacted with heated recycled syngas and introduced into a reactor

containing ZSM-5 zeolite catalyst to produce hydrocarbons and water as per

the following general equations:

2 CH3OH→ CCH3OCH3 + H2O

CH3OCH3→ CC2-C5 Olefins

C2-C5 olefins→ CParaffins, Cycloparaffins, Aromatics

Reaction conditions and catalyst activity can be manipulated to obtain

desired yields of Olefins, Aromatics or Paraffins in the product stream.

lDimethyl Ether

Dimethyl Ether (DME). is used as the starting material to produce dimethyl

sulfate which is used as an aerosol propellant. DME could also potentially be

used as a diesel fuel or as a cooking fuel, a refrigerant, or a chemical

feedstock.

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- The BASF process involves partial oxidation and dehydrogenation with

air in the presence of a silver crystals, steam, and excess methanol at a

temperature of 680-720°C. The conversion rate of methanol to

formaldehyde is 97-98%.

- A variation of the BASF process uses crystalline silver or silver gauze at a

temperature of 600-650 °C. The product is distilled and the unreacted

methanol recycled. The conversion rate for this process is 77-87%.

- The third process (the Formox process) involves oxidation with a lean

m e t h a n o l - a i r m i x t u r e i n t h e p r e s e n c e o f a m o d i f i e d

iron/molybdenum/vanadium oxide catalyst [Fe2(MoO4)3] at a

temperature of 250-400°C. The methanol conversion for this process is

98-99%. This reaction is more exothermic than the silver (Ag) process

and heat removal is required (Satterfield, 1991). Excessive reactor

temperatures cause volatilization of molybdenum oxide, which reduces

the selectivity of the process. A high oxygen partial pressure is required

to maintain catalyst activity. Catalyst activity is also lost in the presence

of excess methanol.

Formaldehyde is combined with phenol, urea, or melamine to make resins

used in the manufacture of various construction board products, and its

demand is driven by the construction industry. Other products

manufactured with formaldehyde include paints, explosives and permanent

press textiles.

lMethyl Tertiary Butyl Ether (MTBE)

MTBE is produced by reacting isobutene with methanol in the presence of an

acidic catalyst as per the equation:

iso-C4H8 + CH3OH → C(CH3)3COCH3

The reaction occurs in a liquid phase at temperatures of 30-100°C and

pressure at 7-14 kg/cm2g. Different catalysts can be used including solid

acids, zeolites (H-ZSM-5) and macroporous sulfonic acid ion-exchange

resins. A molar excess of methanol is used to increase isobutene conversion

and inhibit its dimerization and oligomerization. Conversion yields of up to

90% can be achieved at optimum reaction conditions.

MTBE is produced by refinery/petrochemical plants using by-product

isobutylene, by merchant plants which isomerize n- and iso-butane and

dehydrogenate isobutane to isobutylene, and by tertiary butyl alcohol (TBA)

plants which react by-product TBA from propylene oxide production with

methanol.

MTBE is used primarily (95%) as an oxygenate in gasoline. MTBE is also

used in the petrochemical industry to produce isobutene, methacrolein,

methycrylic acid, isoprene, and industrial solvents.

lAcetic Acid

The third most abundant chemical synthesized from methanol is acetic acid.

It is produced by the carbonylation of methanol as per the equation:

CH3OH + CO →CH3COOH

The Monsanto process for acetic acid manufacture uses a Rh/iodine catalyst

[RhI2(CO)2] and process conditions of 180°C and 30-40 kg/cm2g with over

99% selectivity. It is a liquid phase process initiated by the reaction of

methanol with HI to yield methyl iodide. Insertion of the methyl iodide is the

rate limiting step. Acetic acid is formed by the hydrolysis of the eliminated

acetyl iodide (CH3COI) that also regenerates HI.

Acetic acid is used for the manufacture of industrially important chemicals

like Vinyl Acetate, Acetic Anhydride and Terephthalic Acid.

lOlefins and Synthetic Fuels

Methanol can be used to produce Synthetic Gasoline (the MTG process),

Olefins (the MTO process), and Synthetic Gasoline and Diesel fuels (the

MODG process).

These processes involve conversion of methanol to hydrocarbons over

zeolite catalysts. The reaction is carried out with catalyst being either in

fixed bed or fluidized bed reactors. Superheated vapours consisting of

methanol and steam is partially dehydrated over an alumina catalyst to yield

an equilibrium mixture of methanol, dimethyl ether and water. This mixture

is then reacted with heated recycled syngas and introduced into a reactor

containing ZSM-5 zeolite catalyst to produce hydrocarbons and water as per

the following general equations:

2 CH3OH→ CCH3OCH3 + H2O

CH3OCH3→ CC2-C5 Olefins

C2-C5 olefins→ CParaffins, Cycloparaffins, Aromatics

Reaction conditions and catalyst activity can be manipulated to obtain

desired yields of Olefins, Aromatics or Paraffins in the product stream.

lDimethyl Ether

Dimethyl Ether (DME). is used as the starting material to produce dimethyl

sulfate which is used as an aerosol propellant. DME could also potentially be

used as a diesel fuel or as a cooking fuel, a refrigerant, or a chemical

feedstock.

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DME is produced by first synthesizing methanol from syngas and then

dehydrating it using an acid catalyst (e.g., y-alumina) at methanol synthesis

conditions as per the following reaction steps:

CO + 2 H2→ CH3OH

2 CH3OH → CH3OCH3 + H2O

H2O + CO → H2 + CO2

The net reaction of the above steps is:

3H2 + 3CO → CH3OCH3 +CO2

There exists a synergy in the above different reaction steps, since one

product in each reaction step is consumed by another reaction. Due to this,

syngas conversion to DME gives higher conversions than syngas conversion

to methanol.

The optimum H2:CO ratio for DME synthesis is lower than that for methanol

synthesis and ideally should be around one. Recent improvements to the

DME synthesis process involve the development of bifunctional catalysts to

produce DME in a single gas phase step (i.e., one reactor) and the use of a

slurry reactor for liquid phase dimethyl ether (LPDME) synthesis.

These are presented in the table below:

Starting Final product Application

petrochemical

Olefin - Ethylene Ethanol Industrial solvent used in paints industry

Ethylene glycols (Mono-, Engine coolant, polyesters

di- & tri-)

Poly vinyl acetate Paints and adhesives, fiber for clothing

Poly vinyl chloride Pipes, electrical insulation

Per (tetra) chloro ethylene Dry cleaning solvent, degreaser

Polyethylene (Linear low Plastics for containers, pipes, films, bags

density (LLD) and High and moulded products like hard luggage,

density (HD)) furniture, etc.

Olefin - Propylene Isopropyl alcohol Industrial solvent, rubbing alcohol

Styrene Acrylonitrile Food containers, kitchenware, computer

(SAN) resins products, packaging materials, battery

cases and plastic optical fibres

Acrylonitrile Butadiene Drain-waste-vent (DWV) pipe systems,

Styrene (ABS) resins musical instruments (recorders, plastic

clarinets, and piano movements), golf

club heads, automotive trim components,

automotive bumper bars, medical devices

for blood access, enclosures for electrical

and electronic assemblies, protective

headgear, whitewater canoes, buffer edging

for furniture and joinery panels, luggage

and protective carrying cases, small kitchen

appliances, toys

Propylene glycol Engine coolant, aircraft deicing fluid

Acrylic polymers Acrylic elastomers for automotive oil seals,

Break resistant glass ("Plexiglass"), Paints,

Fiber, Superabsorbent polymer (SAP) used

in diapers etc., Superglue ("Cyanoacrylate"),

Flocculation agent in water treatment

("Polyacrylamide")

Epoxy resins Coatings, Adhesives and Composite

materials such as those using carbon fiber

and fibreglass reinforcements

Polypropylene Including packaging and labeling, textiles

(e.g., ropes, thermal underwear and

carpets), stationery, plastic parts and

reusable containers of various types,

4. Major Applications of Petrochemicals

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DME is produced by first synthesizing methanol from syngas and then

dehydrating it using an acid catalyst (e.g., y-alumina) at methanol synthesis

conditions as per the following reaction steps:

CO + 2 H2→ CH3OH

2 CH3OH → CH3OCH3 + H2O

H2O + CO → H2 + CO2

The net reaction of the above steps is:

3H2 + 3CO → CH3OCH3 +CO2

There exists a synergy in the above different reaction steps, since one

product in each reaction step is consumed by another reaction. Due to this,

syngas conversion to DME gives higher conversions than syngas conversion

to methanol.

The optimum H2:CO ratio for DME synthesis is lower than that for methanol

synthesis and ideally should be around one. Recent improvements to the

DME synthesis process involve the development of bifunctional catalysts to

produce DME in a single gas phase step (i.e., one reactor) and the use of a

slurry reactor for liquid phase dimethyl ether (LPDME) synthesis.

These are presented in the table below:


petrochemical

Olefin - Ethylene Ethanol Industrial solvent used in paints industry

Ethylene glycols (Mono-, Engine coolant, polyesters

di- & tri-)

Poly vinyl acetate Paints and adhesives, fiber for clothing

Poly vinyl chloride Pipes, electrical insulation

Per (tetra) chloro ethylene Dry cleaning solvent, degreaser

Polyethylene (Linear low Plastics for containers, pipes, films, bags

density (LLD) and High and moulded products like hard luggage,

density (HD)) furniture, etc.

Olefin - Propylene Isopropyl alcohol Industrial solvent, rubbing alcohol

Styrene Acrylonitrile Food containers, kitchenware, computer

(SAN) resins products, packaging materials, battery

cases and plastic optical fibres

Acrylonitrile Butadiene Drain-waste-vent (DWV) pipe systems,

Styrene (ABS) resins musical instruments (recorders, plastic

clarinets, and piano movements), golf

club heads, automotive trim components,

automotive bumper bars, medical devices

for blood access, enclosures for electrical

and electronic assemblies, protective

headgear, whitewater canoes, buffer edging

for furniture and joinery panels, luggage

and protective carrying cases, small kitchen

appliances, toys

Propylene glycol Engine coolant, aircraft deicing fluid

Acrylic polymers Acrylic elastomers for automotive oil seals,

Break resistant glass ("Plexiglass"), Paints,

Fiber, Superabsorbent polymer (SAP) used

in diapers etc., Superglue ("Cyanoacrylate"),

Flocculation agent in water treatment

("Polyacrylamide")

Epoxy resins Coatings, Adhesives and Composite

materials such as those using carbon fiber

and fibreglass reinforcements

Polypropylene Including packaging and labeling, textiles

(e.g., ropes, thermal underwear and

carpets), stationery, plastic parts and

reusable containers of various types,

4. Major Applications of Petrochemicals

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petrochemical

laboratory equipment, loudspeakers,

automotive components, and polymer

banknotes

Olefins - C4s Butene-1 Comonomer for many polyethylene and

polypropylene resins used as plastics

Isobutylene Methyl tertiary butyl ether (MTBE) used as

gasoline additive, Butyl rubber (through

copolymerization with a small percentage

of isoprene) used for elastomer

applications

1,3 Butadiene Monomer of comonomer for the production

of synthetic rubbers like polybutadiene

rubber (PBR) and styrene butadiene rubber

(SBR). Also used as comonomer for

acrylonitrile-butadiene-styrene (ABS), a

class of plastics.

Olefins - Higher Hexene-1 Copolymerized with ethylene to enhance

alpha olefins properties of polyethylene formed

Octene-1 Copolymerized with ethylene for the

production of linear low density

polyethylene (LLDPE) having desired

properties

Poly-alpha-olefins Industrial lubricants

Higher alcohols Detergent alcohols

Aromatics - Polystyrene Protective packaging (such as CD and DVD

Benzene cases), Containers (such as "Clamshells"),

Lids, Bottles, Trays, Tumblers and

Disposable cutlery

Epoxy resins See above under propylene

Polycarbonate plastic Various transparent plastic applications like

infant feeding bottles, laboratory

equipment, etc.

Solvents Industrial applications

Nylon 6 Automotive gears, fittings and bearings,

material for power tools housings, thread in

bristles for toothbrushes, surgical sutures

and strings for acoustic and classical

musical instruments, including guitars,

sitars, violins, violas, and cellos, used in the

manufacture of a large variety of threads,

ropes, filaments, nets, tire cords, hosiery

and knitted garments.


petrochemical

Nylon 66 Ball bearing cages, Electro-insulating

elements, Pipes, Profiles and various

machine parts. Carpet fibers, Apparel,

Airbags, Tires, Zip ties, Ropes, Conveyor

belts and Hoses

Polyurethanes Low temperature insulating material

Alkyl Benzenes Detergents

Aromatics - Benzene derivates See above under benzene

Toluene

Aromatics - Polyesters Apparel, Industrial films

para Xylene Polyethylene Terephthalate Transparent bottles for the packaging of

(PET) soft drinks, bottled water, etc.

Aromatics - Alkyd resins Paints, moulds for castings

meta Xylene Amide resins Fibers

Unsaturated polyesters Casting materials, fibreglass laminating

resins, body parts for cars

Aromatics - Phthallic Anhydride Production of plasticizers for resins,

ortho Xylene intermediate for production of alkyd resins

Methanol MTBE Gasoline additive

Dimethyl Ether Propellant in aerosol sprays, substitute for

propane in LPG, precursor to other

chemicals

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petrochemical

laboratory equipment, loudspeakers,

automotive components, and polymer

banknotes

Olefins - C4s Butene-1 Comonomer for many polyethylene and

polypropylene resins used as plastics

Isobutylene Methyl tertiary butyl ether (MTBE) used as

gasoline additive, Butyl rubber (through

copolymerization with a small percentage

of isoprene) used for elastomer

applications

1,3 Butadiene Monomer of comonomer for the production

of synthetic rubbers like polybutadiene

rubber (PBR) and styrene butadiene rubber

(SBR). Also used as comonomer for

acrylonitrile-butadiene-styrene (ABS), a

class of plastics.

Olefins - Higher Hexene-1 Copolymerized with ethylene to enhance

alpha olefins properties of polyethylene formed

Octene-1 Copolymerized with ethylene for the

production of linear low density

polyethylene (LLDPE) having desired

properties

Poly-alpha-olefins Industrial lubricants

Higher alcohols Detergent alcohols

Aromatics - Polystyrene Protective packaging (such as CD and DVD

Benzene cases), Containers (such as "Clamshells"),

Lids, Bottles, Trays, Tumblers and

Disposable cutlery

Epoxy resins See above under propylene

Polycarbonate plastic Various transparent plastic applications like

infant feeding bottles, laboratory

equipment, etc.

Solvents Industrial applications

Nylon 6 Automotive gears, fittings and bearings,

material for power tools housings, thread in

bristles for toothbrushes, surgical sutures

and strings for acoustic and classical

musical instruments, including guitars,

sitars, violins, violas, and cellos, used in the

manufacture of a large variety of threads,

ropes, filaments, nets, tire cords, hosiery

and knitted garments.


petrochemical

Nylon 66 Ball bearing cages, Electro-insulating

elements, Pipes, Profiles and various

machine parts. Carpet fibers, Apparel,

Airbags, Tires, Zip ties, Ropes, Conveyor

belts and Hoses

Polyurethanes Low temperature insulating material

Alkyl Benzenes Detergents

Aromatics - Benzene derivates See above under benzene

Toluene

Aromatics - Polyesters Apparel, Industrial films

para Xylene Polyethylene Terephthalate Transparent bottles for the packaging of

(PET) soft drinks, bottled water, etc.

Aromatics - Alkyd resins Paints, moulds for castings

meta Xylene Amide resins Fibers

Unsaturated polyesters Casting materials, fibreglass laminating

resins, body parts for cars

Aromatics - Phthallic Anhydride Production of plasticizers for resins,

ortho Xylene intermediate for production of alkyd resins

Methanol MTBE Gasoline additive

Dimethyl Ether Propellant in aerosol sprays, substitute for

propane in LPG, precursor to other

chemicals

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A brief list of technology suppliers for the production processes for some key petrochemicals is as follows:

lPolyethylene (HDPE, HDPE/LLDPE Swing)

o Lyondell Basell

o Nova Chemicals

o Univation

o Mitsui

o Ineos Technologies

o Borealis

o Novacore

o Du Pont / Nova

o Montell

o CB (Enichem group)

lPolypropylene

o Lyondell Basell

o Borealis

o Exxon Mobil


o Japan Polypropylene Corporation

o Mitsui

o Novolen Technologies

o Lummus Novolen

o UCC

o Montell

o Unipol (Dow chemicals)

lPolyvinyl Chloride

o B. F. Goodrich

o Chisso Corporation

o European Vinyls Corporation

o Hoechst / Uhde

o Oxyvinyls

o Vinnolit

lEthyl Benzene / Styrene

o Mobil / Badger / FIN

o CD Tech

o Industrial Export Import (Romania)

o Monsanto / ABB / Lummus Crest / UOP

o Petroflex

o Stone & Webster (Styrene only)

o Unocal

o Norsolor (CDF Chimie)

lPolystyrene

o Atochem

o Badger

o FINA

o Chevron

o Huntsman Chemical Corporation

o TOYO

o Montedipe

o Sulzer-Dai Nippon Ink and Chemicals

lPoly Butyl Rubber (PBR)

o Thyssen Krupp / Uhde

lAcrylonitrile

o KBR

o Ineos

o Du Pont

5. Technology Suppliers for Production Processes

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A brief list of technology suppliers for the production processes for some key petrochemicals is as follows:

lPolyethylene (HDPE, HDPE/LLDPE Swing)

o Lyondell Basell

o Nova Chemicals

o Univation

o Mitsui


o Borealis

o Novacore

o Du Pont / Nova

o Montell

o CB (Enichem group)

lPolypropylene

o Lyondell Basell

o Borealis

o Exxon Mobil


o Japan Polypropylene Corporation

o Mitsui

o Novolen Technologies

o Lummus Novolen

o UCC

o Montell

o Unipol (Dow chemicals)

lPolyvinyl Chloride

o B. F. Goodrich

o Chisso Corporation

o European Vinyls Corporation

o Hoechst / Uhde

o Oxyvinyls

o Vinnolit

lEthyl Benzene / Styrene

o Mobil / Badger / FIN

o CD Tech

o Industrial Export Import (Romania)

o Monsanto / ABB / Lummus Crest / UOP

o Petroflex

o Stone & Webster (Styrene only)

o Unocal

o Norsolor (CDF Chimie)

lPolystyrene

o Atochem

o Badger

o FINA

o Chevron

o Huntsman Chemical Corporation

o TOYO

o Montedipe

o Sulzer-Dai Nippon Ink and Chemicals

lPoly Butyl Rubber (PBR)

o Thyssen Krupp / Uhde

lAcrylonitrile

o KBR

o Ineos

o Du Pont

5. Technology Suppliers for Production Processes

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An overview of the petrochemical industry is provided in the figure below.

6. Concluding Remarks Breakthrough Applications of Ionic Liquids: A Platform Technology

Alak Bhattacharyya, Joe Kocal, Manuela Serban, Soumendra Banerjee

UOP IPL, a Honeywell Company

Abstract

Introduction

Ionic liquids are fluids composed entirely of ions which by definition melt below 100 C.

Many ionic liquids are highly polar and non-coordinating, therefore ideal for catalytic

reactions. Ionic liquids differ from organic solvents in that they have no measurable vapor

pressure and no flammability. Ionic liquids also have a wide range of thermal stability,

stability to oxidation, and solvating properties for diverse kinds of materials. Besides use

as a media in which to conduct catalysis, ionic liquids could potentially be used as

electrolytes for batteries, heat transfer fluids, solvents for difficult separations, and

solvents to digest raw biomass to enable more facile upgrading to fuels and chemicals. SM-

UOP is developing technology for nitrogen removal from hydrocarbon fuels like diesel.

This enables more facile sulfur removal during subsequent hydrotreating to ultra low

sulfur diesel (ULSD). Because of the infinite possible combinations of molecular structure

and therefore properties, ionic liquids may be tuned for particular properties and

applications. Ionic liquids may be the basis for a platform of technologies which may

impact many of Honeywell's businesses in both the near and more distant future. One

purpose of this article is to inspire other potential uses of ionic liquids across Honeywell.

Ionic liquids are attracting significant industrial and academic interest. There are

currently over 10,000 publications and 2,000 patents in this area. The seed of the ionic

liquid concept was planted in 1914 with the determination of the physical properties of

ethylammonium nitrate (melting point 13-14 C)1. Figure 1 shows the exponential

increase in patents spurred by the 1998 seminal article on ionic liquids published in

Chemical and Engineering News2. Over the past decade the potential uses of ionic liquids

have been investigated and the time for commercialization of some of these technologies

appears to be imminent.

Figure 1: Ionic Liquid Publications by Year

"Ionic Liquid" Publications by Year

0

500

1000

1500

2000

2500

1992

1993

1994

1995

1996

1997

1998

1999

2000

2001

2002

2003

2004

2005

2006

2007

2008

2009

2010

Year

C&EN IL article - Mar 30,1998

Nu

mb

er o

f P

ub

lica

tio

ns

RAW MATERIAL OILFRACTIONS

NATURAL GAS

CRACKING & OTHER PROCESSES

SALES TO THE CHEMICAL INDUSTRYBASE CHEMICALS OLEFINS

& AROMATICS

PURCHASED CHEMICALS

CHEMICAL CONVERSION

MAIN PRODUCT GROUPS INDUSTRIAL CHEMICALS, PLASTICS, RESINS, ELASTOMERS

CONSUMER NEEDFOOD, CLOTHING, HOUSING, HEALTH, TRANSPORTATION ETC

CHEMICAL PROCESS INDUSTRIES

RUBBER & PLASTIC GOODS FIBRES, PAINTS, DETERGENTS, DYESTUFFS,

PHARMACEUTICALS, AGROCHEMICALS, ADHESIVES.ETC

OTHER INDUSTRIES

METALS, GLASS, CEMENT, ETC MOTORVEHICAL, TEXTILES, PAPER, FOOD

PRODUCTS, AGRICULTURE, ETC

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An overview of the petrochemical industry is provided in the figure below.

6. Concluding Remarks Breakthrough Applications of Ionic Liquids: A Platform Technology

Alak Bhattacharyya, Joe Kocal, Manuela Serban, Soumendra Banerjee

UOP IPL, a Honeywell Company

Abstract

Introduction

Ionic liquids are fluids composed entirely of ions which by definition melt below 100 C.

Many ionic liquids are highly polar and non-coordinating, therefore ideal for catalytic

reactions. Ionic liquids differ from organic solvents in that they have no measurable vapor

pressure and no flammability. Ionic liquids also have a wide range of thermal stability,

stability to oxidation, and solvating properties for diverse kinds of materials. Besides use

as a media in which to conduct catalysis, ionic liquids could potentially be used as

electrolytes for batteries, heat transfer fluids, solvents for difficult separations, and

solvents to digest raw biomass to enable more facile upgrading to fuels and chemicals. SM-

UOP is developing technology for nitrogen removal from hydrocarbon fuels like diesel.

This enables more facile sulfur removal during subsequent hydrotreating to ultra low

sulfur diesel (ULSD). Because of the infinite possible combinations of molecular structure

and therefore properties, ionic liquids may be tuned for particular properties and

applications. Ionic liquids may be the basis for a platform of technologies which may

impact many of Honeywell's businesses in both the near and more distant future. One

purpose of this article is to inspire other potential uses of ionic liquids across Honeywell.

Ionic liquids are attracting significant industrial and academic interest. There are

currently over 10,000 publications and 2,000 patents in this area. The seed of the ionic

liquid concept was planted in 1914 with the determination of the physical properties of

ethylammonium nitrate (melting point 13-14 C)1. Figure 1 shows the exponential

increase in patents spurred by the 1998 seminal article on ionic liquids published in

Chemical and Engineering News2. Over the past decade the potential uses of ionic liquids

have been investigated and the time for commercialization of some of these technologies

appears to be imminent.

Figure 1: Ionic Liquid Publications by Year

"Ionic Liquid" Publications by Year

0

500

1000

1500

2000

2500

1992

1993

1994

1995

1996

1997

1998

1999

2000

2001

2002

2003

2004

2005

2006

2007

2008

2009

2010

Year

C&EN IL article - Mar 30,1998

Nu

mb

er o

f P

ub

lica

tio

ns

RAW MATERIAL OILFRACTIONS

NATURAL GAS

CRACKING & OTHER PROCESSES

SALES TO THE CHEMICAL INDUSTRYBASE CHEMICALS OLEFINS

& AROMATICS

PURCHASED CHEMICALS

CHEMICAL CONVERSION

MAIN PRODUCT GROUPS INDUSTRIAL CHEMICALS, PLASTICS, RESINS, ELASTOMERS

CONSUMER NEEDFOOD, CLOTHING, HOUSING, HEALTH, TRANSPORTATION ETC

CHEMICAL PROCESS INDUSTRIES

RUBBER & PLASTIC GOODS FIBRES, PAINTS, DETERGENTS, DYESTUFFS,

PHARMACEUTICALS, AGROCHEMICALS, ADHESIVES.ETC

OTHER INDUSTRIES

METALS, GLASS, CEMENT, ETC MOTORVEHICAL, TEXTILES, PAPER, FOOD

PRODUCTS, AGRICULTURE, ETC

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Ionic liquids are fluids composed entirely of ions, typically large organic cations and small

inorganic anions. By definition an ionic liquid melts below 100°C3. There are a large

number of fluids that are liquids at room temperature. These are designated 'Room

Temperature Ionic Liquids" or RTILs. These solvents strongly resemble ionic melts that

may be produced by heating inorganic salts to high temperatures (800°C +). Many ionic

liquids are highly polar and non-coordinating , therefore ideal for catalytic reactions. Many

are immiscible with water, saturated hydrocarbons, dialkyl ethers, and a number of

common organic solvents. This provides flexibility for reaction and separation schemes.

Typical cations in ionic liquids are depicted in Figure 2. Typical anions include fluoride,

chloride, bromide, hexafluorophosphate, tetrafluoroborate, formate, alkylsulphate,

alkylphosphate, glycolate, bistriflimide, triflate or tosylate. The difference in size between

the cations and anions leads to the very low melting points relative to better known salts

such as NaCl. The asymmetry in the cations makes stacking of the cations and anions

difficult. This reduces the lattice energy of the crystalline structure and results in a low

melting point salt. These simple liquid salts (single anion and cation) can be mixed with

other salts (including inorganic salts) to form multi-component ionic liquids.

Figure 2: Typical Cations in Ionic Liquids

The notable characteristics4 of ionic liquids include no measurable vapor pressure, no

flammability, thermal stability, wide liquid range, and solvating properties for diverse

kinds of materials. The ionic liquids are designable so that they can be miscible with water

or organic solvents. This miscibility can be tuned through choice of cation and anion as

well as carbon chain length and structure. Ionic liquids possess the following properties5:

lLiquid range of -96 to +200 C

l

lAcidic compositions are superacids (pKa of -20)

lSome are water sensitive; others are hydrophobic and air stable

lSome thermally stable to 500 C (although most practical compositions stable to ca.

200 C)

lNo measurable vapor pressure

lNonflammable

lExhibit Bronsted, Lewis, Franklin, and super acidity

Ionic liquids in general are denser than water with values typically ranging from 1 to 1.6 3g/cm . Their densities decrease with increase in the length of the alkyl chain in the cation6.

The order of increasing density for ionic liquids composed of a single cation is: [CH SO ]- ͌ 3 3

[BF ] < [CF CO ] < [CF SO ] < [C F7CO ] < [(CF SO ) N] . In many cases the densities of 4 3 2 3 3 3 2 3 2 2

7ionic liquids decrease almost linearly with increasing temperatures . Phosphonium ion

salts do not follow this pattern and change logarithmically. The densities of ionic liquids

are also affected by the identity of anions. For example, the densities of 1-butyl-3-

methylimidazolium type ionic liquids with different anions, such as [BF ] - , [PF ] - , and 4 6

3 3 3[Tf N] - are 1.2 g/cm , 1.37 g/cm and 1.43 g/cm , respectively.2

Generally, ionic liquids are more viscous than common molecular solvents and their

viscosities range from 10 mPa to about 500 mPa at room temperature. The viscosity of

ionic liquids is determined by van der Waals forces and hydrogen bonding. Alkyl chain 8

lengthening in the cation leads to an increase in viscosity , due to stronger van der Waals

forces between cations leading to increase in the energy required for molecular motion.

Also, the ability of anions to form hydrogen bonding has a pronounced effect on viscosity.

The fluorinated anions such as [BF ]- and [PF ]- form viscous ionic liquids due to the 4 6

9formation of complexes with hydrogen bonding donors . Electrostatic forces may also

play an important role. In general, all ionic liquids show a significant decrease in viscosity 7, 10, 11, 12, 13

as the temperature increases . Ionic liquids should be free of impurities or

moisture, because contamination of the ILs with chloride led to an increase of the 10, 11

viscosity .

1The first ionic liquid, ethylammonium nitrate, was produced in 1914 . This compound was

formed by the addition of concentrated nitric acid to ethylamine, after which water was

removed by distillation to give the pure salt, which was liquid at room temperature (mp 12

⍰C). The protonation of suitable starting materials, such as amines and phosphines, still

represents the simplest method for the formation of ionic liquids, but, unfortunately, it can

only be applied for a few useful salts. Most ILs are formed from cations that do not contain

Excellent solvents for organic, inorganic, and polymeric materials

- - - - -

Synthesis of Ionic Liquids

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Ionic liquids are fluids composed entirely of ions, typically large organic cations and small

inorganic anions. By definition an ionic liquid melts below 100°C3. There are a large

number of fluids that are liquids at room temperature. These are designated 'Room

Temperature Ionic Liquids" or RTILs. These solvents strongly resemble ionic melts that

may be produced by heating inorganic salts to high temperatures (800°C +). Many ionic

liquids are highly polar and non-coordinating , therefore ideal for catalytic reactions. Many

are immiscible with water, saturated hydrocarbons, dialkyl ethers, and a number of

common organic solvents. This provides flexibility for reaction and separation schemes.

Typical cations in ionic liquids are depicted in Figure 2. Typical anions include fluoride,

chloride, bromide, hexafluorophosphate, tetrafluoroborate, formate, alkylsulphate,

alkylphosphate, glycolate, bistriflimide, triflate or tosylate. The difference in size between

the cations and anions leads to the very low melting points relative to better known salts

such as NaCl. The asymmetry in the cations makes stacking of the cations and anions

difficult. This reduces the lattice energy of the crystalline structure and results in a low

melting point salt. These simple liquid salts (single anion and cation) can be mixed with

other salts (including inorganic salts) to form multi-component ionic liquids.

Figure 2: Typical Cations in Ionic Liquids

The notable characteristics4 of ionic liquids include no measurable vapor pressure, no

flammability, thermal stability, wide liquid range, and solvating properties for diverse

kinds of materials. The ionic liquids are designable so that they can be miscible with water

or organic solvents. This miscibility can be tuned through choice of cation and anion as

well as carbon chain length and structure. Ionic liquids possess the following properties5:

lLiquid range of -96 to +200 C

l

lAcidic compositions are superacids (pKa of -20)

lSome are water sensitive; others are hydrophobic and air stable

lSome thermally stable to 500 C (although most practical compositions stable to ca.

200 C)

lNo measurable vapor pressure

lNonflammable

lExhibit Bronsted, Lewis, Franklin, and super acidity

Ionic liquids in general are denser than water with values typically ranging from 1 to 1.6 3g/cm . Their densities decrease with increase in the length of the alkyl chain in the cation6.

The order of increasing density for ionic liquids composed of a single cation is: [CH SO ]- ͌ 3 3

[BF ] < [CF CO ] < [CF SO ] < [C F7CO ] < [(CF SO ) N] . In many cases the densities of 4 3 2 3 3 3 2 3 2 2

7ionic liquids decrease almost linearly with increasing temperatures . Phosphonium ion

salts do not follow this pattern and change logarithmically. The densities of ionic liquids

are also affected by the identity of anions. For example, the densities of 1-butyl-3-

methylimidazolium type ionic liquids with different anions, such as [BF ] - , [PF ] - , and 4 6

3 3 3[Tf N] - are 1.2 g/cm , 1.37 g/cm and 1.43 g/cm , respectively.2

Generally, ionic liquids are more viscous than common molecular solvents and their

viscosities range from 10 mPa to about 500 mPa at room temperature. The viscosity of

ionic liquids is determined by van der Waals forces and hydrogen bonding. Alkyl chain 8

lengthening in the cation leads to an increase in viscosity , due to stronger van der Waals

forces between cations leading to increase in the energy required for molecular motion.

Also, the ability of anions to form hydrogen bonding has a pronounced effect on viscosity.

The fluorinated anions such as [BF ]- and [PF ]- form viscous ionic liquids due to the 4 6

9formation of complexes with hydrogen bonding donors . Electrostatic forces may also

play an important role. In general, all ionic liquids show a significant decrease in viscosity 7, 10, 11, 12, 13

as the temperature increases . Ionic liquids should be free of impurities or

moisture, because contamination of the ILs with chloride led to an increase of the 10, 11

viscosity .

1The first ionic liquid, ethylammonium nitrate, was produced in 1914 . This compound was

formed by the addition of concentrated nitric acid to ethylamine, after which water was

removed by distillation to give the pure salt, which was liquid at room temperature (mp 12

⍰C). The protonation of suitable starting materials, such as amines and phosphines, still

represents the simplest method for the formation of ionic liquids, but, unfortunately, it can

only be applied for a few useful salts. Most ILs are formed from cations that do not contain

Excellent solvents for organic, inorganic, and polymeric materials

- - - - -

Synthesis of Ionic Liquids

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acidic protons. The synthesis of ILs can generally be split into two parts: formation of the 14

desired cation, and anion exchange to form the desired product (see Fig. 3) . The organic

ammonium cation is formed in the initial step by reaction of imidazole with an organic 15, 16

halide . The anion (in this case tetrafluoroborate) is then added in a salt metathesis step

to form the ionic liquid and sodium halide.

Figure 3: General Synthesis of Ionic Liquids

There are estimated to be hundreds of thousands of simple ion combinations to make ionic

liquids, and a near endless (1018) number of potential ionic liquid mixtures. This implies

that it should be possible to design an ionic liquid with the desired properties to suit a

particular application by selecting anions, cations, and mixture concentrations. Ionic

liquids can be adjusted or tuned to provide a specific melting point, viscosity, density,

hydrophobicity, miscibility, etc. for specific applications. The thermodynamics and

reaction kinetics of processes carried out in ionic liquids are different from those in

conventional media. This creates new opportunities for catalytic reactions, separations,

combined reaction/separation processes, heat transfer agents, hydraulic fluids, paint

additives, electrochemistry applications, as well as many others. Ionic liquids have no

detectable vapor pressure and do not emit volatile organic compounds (VOCs), providing a

basis for clean manufacturing or "green chemistry." The environmental impact of

synthesis of ionic liquids, toxicity, and long-term fate of these materials is currently under 17, 18, 19

investigation .

To date most of the studies involving ionic liquids have been focused on catalysis and

separations. The scientific literature reports numerous chemical reactions in which ionic

liquids are the media in which the reaction occurs. These include cracking20, 21, 22, 23, 24 25, hydrogenation olefin dimerization olefin oligomerization aromatic and isoparaffin

26 27, 28, 29, 30, 31 alkylation with olefins, Heck and Suzuki Coupling Oxidation with air or oxygen, 32, 33, 34,

hydrogenation halogenation35, and Diels Alder36 reaction amongst others. They

are used as solvents and are capable of dissolving or digesting recalcitrant materials such 37

as whole biomass . The ionic liquids used as a reaction media or as catalytic systems are

reported in many cases to show better activity, selectivity, and stability than traditional

systems., although they have not been widely commercialized due to some failure to

General Applications of Ionic Liquids

achieve better overall performance than existing commercial technology and/or because

the cost of producing the ionic liquid is still prohibitive. Reactions in ionic liquids may

occur at significantly lower temperatures and pressures than conventional reactions due

to improved kinetics, resulting in lower energy costs and capital equipment costs. Ionic

liquids can act as both catalyst and solvent. In many systems, the reaction products can be

separated by simple liquid-liquid extraction, avoiding energy-intensive and costly

distillation.

Use of ionic liquids for separations applications have been increasing. Some progress has

been made in the area of paraffin/olefin separation and oxygen/nitrogen separation. A

technical breakthrough in either of these areas would eliminate costly cryogenic

separation. These areas are still quite far from commercialization.

Table 1 lists a number of processes that either are commercial or are (or have been)

demonstrated on a pilot scale.

Industrially Significant Processes

Company Process/Product IL Function Scale

BASF BASIL Acid Scavenging Commercial

Eastman Chemical 2,5-dihydrofuran Catalyst Commercial until 2004

BASF Chloronation Solvent Commercial

Eli Lilly Ether Cleavage Catalyst/Reagent Pilot

Degussa Hydrosilylation Solvent Pilot

Arkema Fluorination Sovent Pilot

IFP Olefin Dimerization Solvent Pilot

Chevron Phillips Oligomerization Catalyst Pilot

BASF Extractive Distillation Extractant Pilot

University of Twente AromaticExtraction Extractant Pilot

Scionix Electroplating (Cr) Electrolyte Pilot

Degussa Compataibilizer Performance Additive Commercial

Iolitec/Wandres Cleaning Fluid Performance Additive Commercial

Air Products Gas Storage Liquid Support Pilot

Linde Gas Compression Liquid Piston Pilot

Chevron Isobutane Alkylation Catalyst Pilot

Petrochina Isobutane Alkylation Catalyst Pilot

Table 1 lists a number of processes that either are commercial or are (or have been) demonstrated on a pilot scale.

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acidic protons. The synthesis of ILs can generally be split into two parts: formation of the 14

desired cation, and anion exchange to form the desired product (see Fig. 3) . The organic

ammonium cation is formed in the initial step by reaction of imidazole with an organic 15, 16

halide . The anion (in this case tetrafluoroborate) is then added in a salt metathesis step

to form the ionic liquid and sodium halide.

Figure 3: General Synthesis of Ionic Liquids

There are estimated to be hundreds of thousands of simple ion combinations to make ionic

liquids, and a near endless (1018) number of potential ionic liquid mixtures. This implies

that it should be possible to design an ionic liquid with the desired properties to suit a

particular application by selecting anions, cations, and mixture concentrations. Ionic

liquids can be adjusted or tuned to provide a specific melting point, viscosity, density,

hydrophobicity, miscibility, etc. for specific applications. The thermodynamics and

reaction kinetics of processes carried out in ionic liquids are different from those in

conventional media. This creates new opportunities for catalytic reactions, separations,

combined reaction/separation processes, heat transfer agents, hydraulic fluids, paint

additives, electrochemistry applications, as well as many others. Ionic liquids have no

detectable vapor pressure and do not emit volatile organic compounds (VOCs), providing a

basis for clean manufacturing or "green chemistry." The environmental impact of

synthesis of ionic liquids, toxicity, and long-term fate of these materials is currently under 17, 18, 19

investigation .

To date most of the studies involving ionic liquids have been focused on catalysis and

separations. The scientific literature reports numerous chemical reactions in which ionic

liquids are the media in which the reaction occurs. These include cracking20, 21, 22, 23, 24 25, hydrogenation olefin dimerization olefin oligomerization aromatic and isoparaffin

26 27, 28, 29, 30, 31 alkylation with olefins, Heck and Suzuki Coupling Oxidation with air or oxygen, 32, 33, 34,

hydrogenation halogenation35, and Diels Alder36 reaction amongst others. They

are used as solvents and are capable of dissolving or digesting recalcitrant materials such 37

as whole biomass . The ionic liquids used as a reaction media or as catalytic systems are

reported in many cases to show better activity, selectivity, and stability than traditional

systems., although they have not been widely commercialized due to some failure to

General Applications of Ionic Liquids

achieve better overall performance than existing commercial technology and/or because

the cost of producing the ionic liquid is still prohibitive. Reactions in ionic liquids may

occur at significantly lower temperatures and pressures than conventional reactions due

to improved kinetics, resulting in lower energy costs and capital equipment costs. Ionic

liquids can act as both catalyst and solvent. In many systems, the reaction products can be

separated by simple liquid-liquid extraction, avoiding energy-intensive and costly

distillation.

Use of ionic liquids for separations applications have been increasing. Some progress has

been made in the area of paraffin/olefin separation and oxygen/nitrogen separation. A

technical breakthrough in either of these areas would eliminate costly cryogenic

separation. These areas are still quite far from commercialization.

Table 1 lists a number of processes that either are commercial or are (or have been)

demonstrated on a pilot scale.

Industrially Significant Processes

Company Process/Product IL Function Scale

BASF BASIL Acid Scavenging Commercial

Eastman Chemical 2,5-dihydrofuran Catalyst Commercial until 2004

BASF Chloronation Solvent Commercial

Eli Lilly Ether Cleavage Catalyst/Reagent Pilot

Degussa Hydrosilylation Solvent Pilot

Arkema Fluorination Sovent Pilot

IFP Olefin Dimerization Solvent Pilot

Chevron Phillips Oligomerization Catalyst Pilot

BASF Extractive Distillation Extractant Pilot

University of Twente AromaticExtraction Extractant Pilot

Scionix Electroplating (Cr) Electrolyte Pilot

Degussa Compataibilizer Performance Additive Commercial

Iolitec/Wandres Cleaning Fluid Performance Additive Commercial

Air Products Gas Storage Liquid Support Pilot

Linde Gas Compression Liquid Piston Pilot

Chevron Isobutane Alkylation Catalyst Pilot

Petrochina Isobutane Alkylation Catalyst Pilot

Table 1 lists a number of processes that either are commercial or are (or have been) demonstrated on a pilot scale.

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A few processes involving ionic liquids have been commercialized or at least

demonstrated on a semi-commercial scale. The most successful industrial application is 38the BASIL (Biphasic Acid Scavenging utilizing Ionic Liquids) process developed by BASF.

A by-product of the synthesis of alkoxyphenylphosphines (used as photoinitiators) is HCl

acid (Equation Below). Originally the HCl was reacted with trimethylamine base to form

insoluble trimethylammonium chloride. This solid caused numerous problems including

reduction of reaction and heat transfer rates, reduction of product yield, and difficult and

costly solids separation. BASF demonstrated it could react the HCl acid with 1-

methylimidazole (MIA) to form the 1-methylimidazolium chloride ionic liquid. The ionic

liquid is easily removed by liquid-liquid phase separation from the product phase. The

imidazole is regenerated with basic NaOH and then recycled.

+ 2 R3N àC

6H

5-P-(OC

2H

5)2

+ 2 R3N*HCl

C6H

5-P-Cl

2+ 2 C

2H

5OH

+2 MIA àC6H

5-P-(OC

2H

5)2

+ 2 MIA*HCl

+ 2 R3N àC

6H

5-P-(OC

2H

5)2

+ 2 R3N*HCl

C6H

5-P-Cl

2+ 2 C

2H

5OH

+2 MIA àC6H

5-P-(OC

2H

5)2

+ 2 MIA*HCl

+ NaOH

NaCl

The ionic liquid technology provides the added advantage of having the alkyimidazole act

as a nucleophilic catalyst, thereby improving reaction rates, and increasing product yields

and selectivities. An increase in space/time yield of the reaction by a factor of 80,000 is

observed in the modified process. The BASIL process has been in commercial operation

since 2004.

In 1996, Eastman launched commercial operation for production of 2,5-dihydrofuran.

This compound is a valuable intermediate in the synthesis of many commodity, fine, and

specialty chemicals. The continuous liquid-phase process uses trialkyltin iodide Lewis

acid and tetraalkylphosphonium iodide ionic liquid to catalyze the rearrangement of 3,4-39

epoxy-1-butene to 2,5-dihydrofuran .

The continuous rearrangement process requires that the catalysts are essentially

nonvolatile so that they do not co-distill with their product. The co-catalyst system gives a

high selectivity for 2,5-dihydrofuran and provides an efficient means for catalyst recovery.

The process was a technical success and was run by Eastman until 2004. At that time

Eastman exited the fine chemicals business and the plant was shut down.

For the past several years, UOP has been working with various nitrogen as well as

phosphorus-based ionic liquids to invent new or to improve current processes or products

for the refining and petrochemical industries. Three such potential applications of ionic

liquids are described here.

Current Honeywell-PMT/UOP Technologies

Figure 4. Extraction Experiments: Ionic Liquids Remove Nitrogen Efficiently from Diesel Blends.

Denitrogenation of Low sulfur Diesel:

Diesel is a hydrocarbon fuel used throughout the world. However, diesel fuel contains

sulfur as well as nitrogen containing molecules, which upon combustion yield the well

know pollutants SOx, and NOx. Therefore, there is an ever increasing need to provide

diesel fuels that have ultra low sulfur content. A typical way of removing sulfur from diesel

is by catalytic hydrodesulfurization (HDS). It is, however, becoming more expensive to

hydrodesulfurize diesel fuels to even lower levels of sulfur now required. Ionic liquids

provide a new means to efficiently hydrodesulfurize diesel fuel.

Low sulfur requirements can be achieved with conventional HDS catalysts and processes

with low nitrogen containing feeds. We have developed a low temperature and low

pressure process for selectively removing the nitrogen compounds from a diesel fuel that 43does not have a low nitrogen content using proper ionic liquids . Ionic liquids act as

solvents in which reactions can be performed and, because the liquids are made of ions

rather than neutral molecules, such reactions/interactions provide distinct selectivities

when compared to conventional organic solvents. More than 70% total nitrogen and more

than 90% basic nitrogen may be removed at or around room temperature and

atmospheric pressure from diesel blends by proper selection of ionic liquid and process

conditions (Figure 4). We found that nitrogen extraction equilibrium may be reached

quickly such as in less than 5 minutes. Due to considerable differences in densities and

liquid phase polarity, two layers tend to separate rapidly such that the denitrogenated

diesel phase can be easily separated from contaminated ionic liquid phase without much

cross contamination. Thus, it is possible to denitrogenate a diesel fuel with acidic ionic

liquids in an extraction zone to selectively remove the nitrogen compounds and produce a

denitrogenated diesel.

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A few processes involving ionic liquids have been commercialized or at least

demonstrated on a semi-commercial scale. The most successful industrial application is 38the BASIL (Biphasic Acid Scavenging utilizing Ionic Liquids) process developed by BASF.

A by-product of the synthesis of alkoxyphenylphosphines (used as photoinitiators) is HCl

acid (Equation Below). Originally the HCl was reacted with trimethylamine base to form

insoluble trimethylammonium chloride. This solid caused numerous problems including

reduction of reaction and heat transfer rates, reduction of product yield, and difficult and

costly solids separation. BASF demonstrated it could react the HCl acid with 1-

methylimidazole (MIA) to form the 1-methylimidazolium chloride ionic liquid. The ionic

liquid is easily removed by liquid-liquid phase separation from the product phase. The

imidazole is regenerated with basic NaOH and then recycled.

+ 2 R3N àC

6H

5-P-(OC

2H

5)2

+ 2 R3N*HCl

C6H

5-P-Cl

2+ 2 C

2H

5OH

+2 MIA àC6H

5-P-(OC

2H

5)2

+ 2 MIA*HCl

+ 2 R3N àC

6H

5-P-(OC

2H

5)2

+ 2 R3N*HCl

C6H

5-P-Cl

2+ 2 C

2H

5OH

+2 MIA àC6H

5-P-(OC

2H

5)2

+ 2 MIA*HCl

+ NaOH

NaCl

The ionic liquid technology provides the added advantage of having the alkyimidazole act

as a nucleophilic catalyst, thereby improving reaction rates, and increasing product yields

and selectivities. An increase in space/time yield of the reaction by a factor of 80,000 is

observed in the modified process. The BASIL process has been in commercial operation

since 2004.

In 1996, Eastman launched commercial operation for production of 2,5-dihydrofuran.

This compound is a valuable intermediate in the synthesis of many commodity, fine, and

specialty chemicals. The continuous liquid-phase process uses trialkyltin iodide Lewis

acid and tetraalkylphosphonium iodide ionic liquid to catalyze the rearrangement of 3,4-39

epoxy-1-butene to 2,5-dihydrofuran .

The continuous rearrangement process requires that the catalysts are essentially

nonvolatile so that they do not co-distill with their product. The co-catalyst system gives a

high selectivity for 2,5-dihydrofuran and provides an efficient means for catalyst recovery.

The process was a technical success and was run by Eastman until 2004. At that time

Eastman exited the fine chemicals business and the plant was shut down.

For the past several years, UOP has been working with various nitrogen as well as

phosphorus-based ionic liquids to invent new or to improve current processes or products

for the refining and petrochemical industries. Three such potential applications of ionic

liquids are described here.

Current Honeywell-PMT/UOP Technologies

Figure 4. Extraction Experiments: Ionic Liquids Remove Nitrogen Efficiently from Diesel Blends.

Denitrogenation of Low sulfur Diesel:

Diesel is a hydrocarbon fuel used throughout the world. However, diesel fuel contains

sulfur as well as nitrogen containing molecules, which upon combustion yield the well

know pollutants SOx, and NOx. Therefore, there is an ever increasing need to provide

diesel fuels that have ultra low sulfur content. A typical way of removing sulfur from diesel

is by catalytic hydrodesulfurization (HDS). It is, however, becoming more expensive to

hydrodesulfurize diesel fuels to even lower levels of sulfur now required. Ionic liquids

provide a new means to efficiently hydrodesulfurize diesel fuel.

Low sulfur requirements can be achieved with conventional HDS catalysts and processes

with low nitrogen containing feeds. We have developed a low temperature and low

pressure process for selectively removing the nitrogen compounds from a diesel fuel that 43does not have a low nitrogen content using proper ionic liquids . Ionic liquids act as

solvents in which reactions can be performed and, because the liquids are made of ions

rather than neutral molecules, such reactions/interactions provide distinct selectivities

when compared to conventional organic solvents. More than 70% total nitrogen and more

than 90% basic nitrogen may be removed at or around room temperature and

atmospheric pressure from diesel blends by proper selection of ionic liquid and process

conditions (Figure 4). We found that nitrogen extraction equilibrium may be reached

quickly such as in less than 5 minutes. Due to considerable differences in densities and

liquid phase polarity, two layers tend to separate rapidly such that the denitrogenated

diesel phase can be easily separated from contaminated ionic liquid phase without much

cross contamination. Thus, it is possible to denitrogenate a diesel fuel with acidic ionic

liquids in an extraction zone to selectively remove the nitrogen compounds and produce a

denitrogenated diesel.

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Once the diesel feed is substantially denitrogenated, it is much easier to hydrodesulfurize

the feed. It is clear from the Figure 5 the HDS process becomes much less severe. By

utilizing a fraction of the catalyst bed, or by running the HDS at a temperature about 20 C

cooler, one can achieve similar sulfur level in the product. Running HDS at a lower

temperature or by utilizing less volume of catalyst, the HDS process becomes more

efficient and cost effective. When ionic liquid pre-treated diesel is hydrotreated, it is

possible to have up to 50% HDS catalyst cost savings.

Figure 5, Hydrodesulfurization Runs of Various Feeds: Product Sulfur vs. Catalyst Bed Utilization

The nitrogen compound-contaminated ionic liquid needs to be regenerated and 44, 45

recycled . We found that nitrogen compounds can be stripped from the ionic liquid

either by nitrogen or preferably by steam. Laboratory experiments show that only <50

ppm N-compounds remain in the regenerated ionic liquid. Figure 6 describes the

recyclability of the regenerated ionic liquids. Steam-stripped, spent ionic liquid retains

about 95% of its nitrogen extraction capacity even after fourth recycle. It is clear that a

simple but selective extraction of nitrogen from diesel fuel provides an economic and

efficient process for hydrodesulfurization to produce ultra low sulfur diesel.

0

10

20

30

40

50

60

70

80

90

100

0 10 20 30 40 50 60 70 80 90 100

Basic Nitrogen Removed (%)

Nit

rog

en

Re

mo

ve

d(%

)

Feed = LCO:LCGO:SR = 3:3:4652 ppm N; 220 ppm basic N; 1.35% S; 104 ppm H 2O

No Regeneration

Steam Stripping I at 150 oC

N2 Stripping at 150 oC

Steam Stripping II at 150 oC

1st Cycle

2nd Cycle3rd Cycle

4th Cycle

3rd Cycle

2nd, 3rd Cycles2nd, 3 rd, 4 th Cycles

Condensate + Stripped

Species

IL Level

Steam

Steam Stripping at 150 oC

Stripping conditions: 1L/min steam at 150 oC for 1 h + 1L/min N 2 at 150 oC for 1 h

Figure 6: Efficient Ionic Liquid Regeneration by Steam Stripping

Other applications of Ionic Liquids:

There are several other applications of ionic liquids that UOP is not working on currently.

However it would be beneficial to make a brief mention of these potential applications. A

few of them has been discussed in the following paragraphs.

Over the past decade, ionic liquids have attracted much interest for their use as non-53,54,55aaqueous electrolytes in electrochemical applications . In this context, their

conductivity and electrochemical stability are the most important physical properties.

Together with other desirable properties such as their negligible vapor pressure and their

non-flammability, they appear to be ideal electrolytes for many interesting applications.

For example, ionic liquid as an electrolyte provides high current efficiency, improved

surface finish, and improved corrosion resistance for electro-polishing technology and can 55b

replace toxic hexavalent chromium as raw material for chromium plating . For electro-

deposition of rare earth metals water fails as a solvent because hydrogen evolves before

the metal deposits. For such purposes, ionic liquids are ideal solvents because of their

suitable properties including wide electrochemical window. The next advancement in Li

ion batteries may come from using ionic liquid as electrolyte because it eliminates the

toxicity and instability of organic electrolytes and provides higher thermal stability and 55bgood electrochemical stability (>5V vs. Li) . Energy densities from 900-1600 watt-hours

55bper kilogram appear possible . A key issue to be addressed is the stabilities of the ionic

liquid and Li metal electrode over long term operation.

450

400

350

300

250

200

150

100

50

00 10 20 30 40 50 60 70 80 90 100

% of Bed

Untreated-655°F

Denitrogenated-655°F

Untreated-680°F

Pro

du

ct S

ulf

ur,

wp

pm

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Once the diesel feed is substantially denitrogenated, it is much easier to hydrodesulfurize

the feed. It is clear from the Figure 5 the HDS process becomes much less severe. By

utilizing a fraction of the catalyst bed, or by running the HDS at a temperature about 20 C

cooler, one can achieve similar sulfur level in the product. Running HDS at a lower

temperature or by utilizing less volume of catalyst, the HDS process becomes more

efficient and cost effective. When ionic liquid pre-treated diesel is hydrotreated, it is

possible to have up to 50% HDS catalyst cost savings.

Figure 5, Hydrodesulfurization Runs of Various Feeds: Product Sulfur vs. Catalyst Bed Utilization

The nitrogen compound-contaminated ionic liquid needs to be regenerated and 44, 45

recycled . We found that nitrogen compounds can be stripped from the ionic liquid

either by nitrogen or preferably by steam. Laboratory experiments show that only <50

ppm N-compounds remain in the regenerated ionic liquid. Figure 6 describes the

recyclability of the regenerated ionic liquids. Steam-stripped, spent ionic liquid retains

about 95% of its nitrogen extraction capacity even after fourth recycle. It is clear that a

simple but selective extraction of nitrogen from diesel fuel provides an economic and

efficient process for hydrodesulfurization to produce ultra low sulfur diesel.

0

10

20

30

40

50

60

70

80

90

100

0 10 20 30 40 50 60 70 80 90 100

Basic Nitrogen Removed (%)

Nit

rog

en

Re

mo

ve

d(%

)

Feed = LCO:LCGO:SR = 3:3:4652 ppm N; 220 ppm basic N; 1.35% S; 104 ppm H 2O

No Regeneration

Steam Stripping I at 150 oC

N2 Stripping at 150 oC

Steam Stripping II at 150 oC

1st Cycle

2nd Cycle3rd Cycle

4th Cycle

3rd Cycle

2nd, 3rd Cycles2nd, 3 rd, 4 th Cycles

Condensate + Stripped

Species

IL Level

Steam

Steam Stripping at 150 oC

Stripping conditions: 1L/min steam at 150 oC for 1 h + 1L/min N 2 at 150 oC for 1 h

Figure 6: Efficient Ionic Liquid Regeneration by Steam Stripping

Other applications of Ionic Liquids:

There are several other applications of ionic liquids that UOP is not working on currently.

However it would be beneficial to make a brief mention of these potential applications. A

few of them has been discussed in the following paragraphs.

Over the past decade, ionic liquids have attracted much interest for their use as non-53,54,55aaqueous electrolytes in electrochemical applications . In this context, their

conductivity and electrochemical stability are the most important physical properties.

Together with other desirable properties such as their negligible vapor pressure and their

non-flammability, they appear to be ideal electrolytes for many interesting applications.

For example, ionic liquid as an electrolyte provides high current efficiency, improved

surface finish, and improved corrosion resistance for electro-polishing technology and can 55b

replace toxic hexavalent chromium as raw material for chromium plating . For electro-

deposition of rare earth metals water fails as a solvent because hydrogen evolves before

the metal deposits. For such purposes, ionic liquids are ideal solvents because of their

suitable properties including wide electrochemical window. The next advancement in Li

ion batteries may come from using ionic liquid as electrolyte because it eliminates the

toxicity and instability of organic electrolytes and provides higher thermal stability and 55bgood electrochemical stability (>5V vs. Li) . Energy densities from 900-1600 watt-hours

55bper kilogram appear possible . A key issue to be addressed is the stabilities of the ionic

liquid and Li metal electrode over long term operation.

450

400

350

300

250

200

150

100

50

00 10 20 30 40 50 60 70 80 90 100

% of Bed

Untreated-655°F

Denitrogenated-655°F

Untreated-680°F

Pro

du

ct S

ulf

ur,

wp

pm

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71

Ionic Liquids as Heat Transfer Fluids

Ionic liquids have thermophysical and chemical properties that may be suitable for heat

transfer and short-term heat storage in power plants using parabolic trough solar

collectors. Thermal properties important for heat transfer applications are melting point, 56

boiling point, liquid range, heat capacity , heat of fusion, vapor pressure, and thermal

conductivity. Other properties needed to evaluate the usefulness of ionic liquids are

density, viscosity, and chemical compatibility with certain metals. The thermal properties

of ionic liquids indicate that they are suited for use as heat transfer fluids. In many ways,

they are superior to present commercial heat transfer fluids. They are stable over a wider

temperature range, can store substantial heat, and have the advantage of low vapor

pressure. Ionic liquids can be a functional part of devices, equipment, and machinery that

are used in automotive, aircraft, energy, and electronic industries. The so-called "ionic

compressor" uses ionic liquids as a liquid piston allowing an almost isothermal high-57

pressure compression of gases .

Biosensors

Over recent years a significant effort has been directed towards the fabrication and 58,59,60

application of ionic liquid based electrochemical sensing layers . Applications for

electrochemical sensors include (bio) molecules such as NADH, dopamine, uric acid, 61

ascorbic acid, glucose, and ethanol amongst others . The multifunctional properties of

the ionic liquid based composite materials coupled with simple preparation procedures

favor the development of highly sensitive, selective, and reproducible electrochemical

biosensors. There are fundamental challenges and obstacles related to designing highly

stable and reliable continuous sensors. The fundamental understanding of the underlying

biochemistry, surface chemistry, electrochemistry, and material chemistry is needed.

Media for Conversion of Lignocellulosic Biomass

Selected ionic liquids have been shown to dissolve low-cost raw biomass or other

biopolymers such as cellulose, hemicellulose, and lignin under mild conditions. This

ability to dissolve biomass components opens a variety of possibilities for the conversion 62

of the depolymerized components to fuels and chemicals . Butyl-methylimidizolium 63

acetate seems to be one of the best ionic liquids for whole biomass dissolution . To date

there is very little published literature on the successful upgrading of the

dissolved/depolymerized biomass to fuels or chemicals. This is an area of tremendous

opportunity to develop economical breakthrough technology.

Olefin/Paraffin Separation

Today propylene is separated from propane utilizing expensive cryogenic distillation. A

more cost efficient process to produce high purity propylene for polymer synthesis would

be rapidly accepted in the market. There have been a few publications on the use of ionic

liquids for the separation of propylene from propane. Since both hydrocarbons have

extremely low solubility in most ionic liquids, scientists have used copper or silver ions in

the ionic liquid to complex with the olefin and draw it into the ionic liquid phase while the 65

propane is allowed to pass through64, . Several problems need to be solved to

commercialize such a revolutionary technology. This includes developing sufficiently

stable metal complexes and a regeneration procedure to free propylene from the ionic

liquid without propylene oligomerization. In order to meet the high purity requirements

a hybrid technology may be required. This hybrid technology could use ionic liquids to

make a significant increase in the propylene purity followed by adsorption or membrane

separation to achieve required purity. The reverse order of this proposed hybrid system

should also be evaluated as a possible technically and economically acceptable alternative.

Air Separation

There is preliminary evidence that ionic liquids may be used for separation of air into 66

oxygen and nitrogen . To date the separation selectivity must be improved and the

stability of the metal complexes used to coordinate the oxygen from the air stream needs to

be significantly improved. Significant technological developments will be required to

make this technology competitive with current cryogenic oxygen separation from air. A

robust, efficient and economical technology however, would be highly competitive.

In this paper, we have described the variety of properties exhibited by ionic liquids and

several potential promising applications for their use. UOP is developing technology for

the removal of nitrogen from diesel. This technology has potential applications for Indian

refiners.

India currently has two separate Diesel Fuel quality specifications. Bharat Stage IV

(Euro IV) is applicable to 14 major cities, where as Bharat Stage III (Euro III) is applicable

nationwide. Targeted Bharat Stage IV specification is to be implemented in 50 additional

cities by 2015. The total loaded Hydrotreating catalyst volume in India was projected to be

12000 m3 in 2012. The ULSD catalyst demand in India was projected to be 3000 m3/year

by 2012. This is expected to increase in future.

Incorporating an IL extraction as a feed pretreatment process can have significant impact

in cutting back on the catalyst requirement and enable easier add on revamps for existing

units to produce ULSD in future.

Numerous other process technologies have also been mentioned in this paper which

Honeywell has the capabilities to develop in the future. Because ionic liquid properties

such as thermal stability, liquid temperature range, polarity, no measurable vapor

pressure, and inflammability can be varied based on the specific cations and anions used to

produce the ionic liquid, we believe ionic liquids will provide a platform from which

numerous valuable technologies will be derived.

Conclusions

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71

Ionic Liquids as Heat Transfer Fluids

Ionic liquids have thermophysical and chemical properties that may be suitable for heat

transfer and short-term heat storage in power plants using parabolic trough solar

collectors. Thermal properties important for heat transfer applications are melting point, 56

boiling point, liquid range, heat capacity , heat of fusion, vapor pressure, and thermal

conductivity. Other properties needed to evaluate the usefulness of ionic liquids are

density, viscosity, and chemical compatibility with certain metals. The thermal properties

of ionic liquids indicate that they are suited for use as heat transfer fluids. In many ways,

they are superior to present commercial heat transfer fluids. They are stable over a wider

temperature range, can store substantial heat, and have the advantage of low vapor

pressure. Ionic liquids can be a functional part of devices, equipment, and machinery that

are used in automotive, aircraft, energy, and electronic industries. The so-called "ionic

compressor" uses ionic liquids as a liquid piston allowing an almost isothermal high-57

pressure compression of gases .

Biosensors

Over recent years a significant effort has been directed towards the fabrication and 58,59,60

application of ionic liquid based electrochemical sensing layers . Applications for

electrochemical sensors include (bio) molecules such as NADH, dopamine, uric acid, 61

ascorbic acid, glucose, and ethanol amongst others . The multifunctional properties of

the ionic liquid based composite materials coupled with simple preparation procedures

favor the development of highly sensitive, selective, and reproducible electrochemical

biosensors. There are fundamental challenges and obstacles related to designing highly

stable and reliable continuous sensors. The fundamental understanding of the underlying

biochemistry, surface chemistry, electrochemistry, and material chemistry is needed.

Media for Conversion of Lignocellulosic Biomass

Selected ionic liquids have been shown to dissolve low-cost raw biomass or other

biopolymers such as cellulose, hemicellulose, and lignin under mild conditions. This

ability to dissolve biomass components opens a variety of possibilities for the conversion 62

of the depolymerized components to fuels and chemicals . Butyl-methylimidizolium 63

acetate seems to be one of the best ionic liquids for whole biomass dissolution . To date

there is very little published literature on the successful upgrading of the

dissolved/depolymerized biomass to fuels or chemicals. This is an area of tremendous

opportunity to develop economical breakthrough technology.

Olefin/Paraffin Separation

Today propylene is separated from propane utilizing expensive cryogenic distillation. A

more cost efficient process to produce high purity propylene for polymer synthesis would

be rapidly accepted in the market. There have been a few publications on the use of ionic

liquids for the separation of propylene from propane. Since both hydrocarbons have

extremely low solubility in most ionic liquids, scientists have used copper or silver ions in

the ionic liquid to complex with the olefin and draw it into the ionic liquid phase while the 65

propane is allowed to pass through64, . Several problems need to be solved to

commercialize such a revolutionary technology. This includes developing sufficiently

stable metal complexes and a regeneration procedure to free propylene from the ionic

liquid without propylene oligomerization. In order to meet the high purity requirements

a hybrid technology may be required. This hybrid technology could use ionic liquids to

make a significant increase in the propylene purity followed by adsorption or membrane

separation to achieve required purity. The reverse order of this proposed hybrid system

should also be evaluated as a possible technically and economically acceptable alternative.

Air Separation

There is preliminary evidence that ionic liquids may be used for separation of air into 66

oxygen and nitrogen . To date the separation selectivity must be improved and the

stability of the metal complexes used to coordinate the oxygen from the air stream needs to

be significantly improved. Significant technological developments will be required to

make this technology competitive with current cryogenic oxygen separation from air. A

robust, efficient and economical technology however, would be highly competitive.

In this paper, we have described the variety of properties exhibited by ionic liquids and

several potential promising applications for their use. UOP is developing technology for

the removal of nitrogen from diesel. This technology has potential applications for Indian

refiners.

India currently has two separate Diesel Fuel quality specifications. Bharat Stage IV

(Euro IV) is applicable to 14 major cities, where as Bharat Stage III (Euro III) is applicable

nationwide. Targeted Bharat Stage IV specification is to be implemented in 50 additional

cities by 2015. The total loaded Hydrotreating catalyst volume in India was projected to be

12000 m3 in 2012. The ULSD catalyst demand in India was projected to be 3000 m3/year

by 2012. This is expected to increase in future.

Incorporating an IL extraction as a feed pretreatment process can have significant impact

in cutting back on the catalyst requirement and enable easier add on revamps for existing

units to produce ULSD in future.

Numerous other process technologies have also been mentioned in this paper which

Honeywell has the capabilities to develop in the future. Because ionic liquid properties

such as thermal stability, liquid temperature range, polarity, no measurable vapor

pressure, and inflammability can be varied based on the specific cations and anions used to

produce the ionic liquid, we believe ionic liquids will provide a platform from which

numerous valuable technologies will be derived.

Conclusions

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2. C&E News, March 30, 1998.

3. A. Stark and K. R. Seddon, in Kirk-Othmer Encyclopedia of Chemical Technology, A. Seidel

Ed., John Wiley & Sons, Inc., New Jersey, 2007, 26, pp. 836-920.

4. G. W. Meindersma, M. Maase, and A. B. De Haan, Ullmann's Encyclopedia, Weinheim Wiley

VCH, 2007, 1-33.

5. G. Fitzwater, et. al., "Ionic Liquids: Sources of Innovation", Report Q002, QUILL, Belfast, 2005.

6. K. N. Marsh, J. A. Boxall, R. Lichtenthaler, "Room Temperature Ionic Liquids and Their

Mixtures-a Review", Fluid Phase Equilib., 2004, 219, 93-98.

7. S. V. Dzyuba, R. A. Bartsch, "Influence of Structural Variations in 1-Alkyl(aralkyl)-3-

Methylimidazolium Hexafluorophosphates and Bis(trifluoromethylsulfonyl)imides on

Physical Properties of the Ionic Liquids", Chem. Phys. Chem, 2002, 161-166.

8. P. Bonhote, A. P. Dias, N. Papageorgiou, K. Kalvanasundaram, M. Gratzel, "Hydrophobic,

Highly Conductive Ambient-Temperature Molten Salts", Inorg. Chem, 1996, 35, 168-1178.

9. P. A. Z. Suarez, S. Einloft, J. E. L. Dullius, R. F. De Souza, J. Dupont, "Synthesis and Physical-

Chemical Properties of Ionic Liquids Based on 1-n-butyl-3-methylimidazolium Cation", J.

Chem Phys. Phys.-Chem. Biol. 1998, 95, 626-1639.

10. K. R. Seddon, A. Stark, M. J. Torres, "Influence of Chloride, Waterk and Organic Solvents on

the Physical Properties of Ionic Liquids", Pure Appl. Chem. 2000, 72, 2275-2287.

11. K. R. Seddon, A. Stark, M. J. Torres, "Viscosity and Density of 1-alkyl-3-methylimidazoliium

Ionic Liquids", in M. Abraham, L. Moens(eds.), Clean Solvents: Alternative Media for

Chemical Reactions and Processing, ACS Symp. Ser Vol 819, American Chemical Society,

Washington, D. C., 2002, 34-49.

12. O. O. Okoturo, T. J. VanderNoot, "Temperature Dependence of Viscosity for Room

Temperature Ionic Liquids", J. Electroanal. Chem., 2004, 568,167-181.

13. P. Wasserscheid, R. Van Hal, A. Bosmann, "1-n-Butyl-3-methylimidazolium (bmim)

octylsulfate-an Even Greener Ionic Liquid", Green Chem. 2002, 4, 400-404.

14. P. Wasserscheid, W. Keim, "Ionic Liquids-New Solutions for Transition Metal Catalysis",

Angew. Chem. Int. Ed., 2000, 39, 3772-3789.

15. J. S. Wilkes, J. A. Levisky, R. A. Wilson, C. L. Hussey, "Dialkyimidazolium chloroaluminate

Melts: a New Class of Room-temperature Ionic Liquids for Electrochemistry, Spectroscopy,

and Synthesis", Inorg. Chem., 1982, 21,1263-1264.

16. C. L. Hussey, "Room Temperature Haloaluminate Ionic Liquids. Novel Solvents for Transition

Metal Solution Chemistry", Pure Appl. Chem., 1988, 60, 1763-1772.

17. M. Petkovic, K. R. Seddon, L Paulo, N. Rebelo, and C. S. Pereira, Chem. Soc. Rev., 2011, 40,

1383-1403.

18. J. Palomar, J. S. Torrecilla, V. R. Ferrro, and F. Rodriguez, Phys. Chem. Chem. Phys., 2010, 12,

1991-2000.

19. J. S. Torrecilla, J. Palomar, J. Lemus, and F. Rodriguez, Green Chem., 2010, 12, 123-134.

20. C. J. Adams, M. J. Earle, K. R. Seddon, "Catalytic Cracking Reactions of Polyethylene to Light

Alkanes in Ionic Liquids", Green Chem., 2000, 2, 21-24.

21. K. Anderson, P. Goodrich, C. Hardacre, S. E. J. McCath, WO 02 094740.

22. Y. Chauvin, Angew, Chem. Int. Ed., 2006, 45, 3740-3747.

23. L. Pei, X. Liu, H. Gao, Q. Wu, Applied Organometallic Chemistry, 2009, 23, 455-459.

24. H. Zhu, C. Z. Cao, Y. Wu, X, Mu, Catalysis Society of India, 2007, 6, 83-89

25. C. P. Huang, Z. C. Liu, C. M. Xu, B. H. Chen, and Y. F. Liu, Appl. Catal., A, General, 2004, 41-43.

26. S. Elomari, et al. U.S. Patent 7,432,409, 2008.

27. S. Kobayashi, K. A. Jorgensen (eds.), Wiley-VCH, Weinheim, 2002, 154.

28. D. E. Kauffmann, M. Nouroozian, H. Henze, Synlett, 1996, 1091-1092.

29. B. McCormac, K. R. Seddon, Org. Lett., 1999, 1, 997-1000.

30. I. P. Beletskaya, A. V. Cheprakov, Chem. Rev., 2000, 100, 3009-3066.

31. K. R. Seddon, A. Stark, Green Chem., 2002, 4, 119-123.

32. K. Anderson, P. Goodrich, C. Hardacre, S. E. J. McCath, WO 094740

33. P. J. Dyson, D. J. Ellis, D. G. Parker, T. Welton, Chem. Commun., 1999, 25-26.

34. C. J. Adams, M. J. Earle, K. R. Seddon, Chem. Commun., 1999, 1043-1044.

35. N. Winterton, K. R Seddon, Y. Patell, WO 0037400

36. M. J. Earle, P. B. McCormac, K. R. Seddon, Green Chem., 1999, 1,23-25.

37. N. Sun, H. Rodriguez, M. Rahman, and R. D. Rogers, Chem. Commun., 2011, 47, 1405-1421.

38. M. Maase and K. Massonne, American Chemical Society, Washington D. C., 2005, 902, 126-

132.

39. S. N. Falling, S. A. Godlieski, J. R. Monnier, G. W. Phillips, and J. S. Kanel, Book of Abstracts, 1st

International Congress on Ionic Liquids, Salzurg Austria, 2005, 58-59.

40. S. N. Falling, S. A. Godleski, L. W. McGarry, T. R. Nolen, and J. S. Kanel. U.S. Patent 5,238,889,

1993.

41. G. W. Phillips, S. N. Falling, S. A. Godleski, J. R. Monnier, U.S. Patent 5,315,019, 1994.

42. J. S. Kanel, S. N. Falling, G. W. Phillips, J. R. Monnier, S. A. Godlieski, AIChE Annual Meeting, San

Francisco, 2006.

43. M. Serban, J. A. Kocal, U. S. Patent 7,749,377, July 06, 2010.

44. P. Wasserscheid, et al. U.S. Patent 7,553,406 B2, 2010.

45. D.N. Myers et al., US Patent 8,127,938 B2, March 06, 2012, M. Serban et al., US

Patent 8,383,538 B2, February 26, 2013.

46. A. Feller, J. a. Lercher, Adv. Catal, 2004, 48, 229-295.

47. A. Corma and A. Martinez, Catal. Rev. Sci. Eng. 1993, 35,483.

48. P. Kumar, W. Vermeiren, J-P. Dath, and W. F. Hoelderich, Appl. Catal. A: General, 2006, 131,

304.

49. P. Kumar, W. Vermeiren, J-P Dath, W. Hoeldrich, Appl. Catal. A, 2006, 304,131.

50. K. Yoo, V. N. Namboodiri, R. S. Varma, P. G. Smirniotis, J. Catal., 2004, 222, 511-519.

51. T. V. Harris, et al. U. S. Patent 7,531,707, 2009.

52. Honeywell-UOP, U. S. Patent Applications under Preparation, 2011.

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References1. P. Walden, Bull. Acad. Imper. Sci. St. Petersburg, 1914, 8, 405-422.

2. C&E News, March 30, 1998.

3. A. Stark and K. R. Seddon, in Kirk-Othmer Encyclopedia of Chemical Technology, A. Seidel

Ed., John Wiley & Sons, Inc., New Jersey, 2007, 26, pp. 836-920.

4. G. W. Meindersma, M. Maase, and A. B. De Haan, Ullmann's Encyclopedia, Weinheim Wiley

VCH, 2007, 1-33.

5. G. Fitzwater, et. al., "Ionic Liquids: Sources of Innovation", Report Q002, QUILL, Belfast, 2005.

6. K. N. Marsh, J. A. Boxall, R. Lichtenthaler, "Room Temperature Ionic Liquids and Their

Mixtures-a Review", Fluid Phase Equilib., 2004, 219, 93-98.

7. S. V. Dzyuba, R. A. Bartsch, "Influence of Structural Variations in 1-Alkyl(aralkyl)-3-

Methylimidazolium Hexafluorophosphates and Bis(trifluoromethylsulfonyl)imides on

Physical Properties of the Ionic Liquids", Chem. Phys. Chem, 2002, 161-166.

8. P. Bonhote, A. P. Dias, N. Papageorgiou, K. Kalvanasundaram, M. Gratzel, "Hydrophobic,

Highly Conductive Ambient-Temperature Molten Salts", Inorg. Chem, 1996, 35, 168-1178.

9. P. A. Z. Suarez, S. Einloft, J. E. L. Dullius, R. F. De Souza, J. Dupont, "Synthesis and Physical-

Chemical Properties of Ionic Liquids Based on 1-n-butyl-3-methylimidazolium Cation", J.

Chem Phys. Phys.-Chem. Biol. 1998, 95, 626-1639.

10. K. R. Seddon, A. Stark, M. J. Torres, "Influence of Chloride, Waterk and Organic Solvents on

the Physical Properties of Ionic Liquids", Pure Appl. Chem. 2000, 72, 2275-2287.

11. K. R. Seddon, A. Stark, M. J. Torres, "Viscosity and Density of 1-alkyl-3-methylimidazoliium

Ionic Liquids", in M. Abraham, L. Moens(eds.), Clean Solvents: Alternative Media for

Chemical Reactions and Processing, ACS Symp. Ser Vol 819, American Chemical Society,

Washington, D. C., 2002, 34-49.

12. O. O. Okoturo, T. J. VanderNoot, "Temperature Dependence of Viscosity for Room

Temperature Ionic Liquids", J. Electroanal. Chem., 2004, 568,167-181.

13. P. Wasserscheid, R. Van Hal, A. Bosmann, "1-n-Butyl-3-methylimidazolium (bmim)

octylsulfate-an Even Greener Ionic Liquid", Green Chem. 2002, 4, 400-404.

14. P. Wasserscheid, W. Keim, "Ionic Liquids-New Solutions for Transition Metal Catalysis",

Angew. Chem. Int. Ed., 2000, 39, 3772-3789.

15. J. S. Wilkes, J. A. Levisky, R. A. Wilson, C. L. Hussey, "Dialkyimidazolium chloroaluminate

Melts: a New Class of Room-temperature Ionic Liquids for Electrochemistry, Spectroscopy,

and Synthesis", Inorg. Chem., 1982, 21,1263-1264.

16. C. L. Hussey, "Room Temperature Haloaluminate Ionic Liquids. Novel Solvents for Transition

Metal Solution Chemistry", Pure Appl. Chem., 1988, 60, 1763-1772.

17. M. Petkovic, K. R. Seddon, L Paulo, N. Rebelo, and C. S. Pereira, Chem. Soc. Rev., 2011, 40,

1383-1403.

18. J. Palomar, J. S. Torrecilla, V. R. Ferrro, and F. Rodriguez, Phys. Chem. Chem. Phys., 2010, 12,

1991-2000.

19. J. S. Torrecilla, J. Palomar, J. Lemus, and F. Rodriguez, Green Chem., 2010, 12, 123-134.

20. C. J. Adams, M. J. Earle, K. R. Seddon, "Catalytic Cracking Reactions of Polyethylene to Light

Alkanes in Ionic Liquids", Green Chem., 2000, 2, 21-24.

21. K. Anderson, P. Goodrich, C. Hardacre, S. E. J. McCath, WO 02 094740.

22. Y. Chauvin, Angew, Chem. Int. Ed., 2006, 45, 3740-3747.

23. L. Pei, X. Liu, H. Gao, Q. Wu, Applied Organometallic Chemistry, 2009, 23, 455-459.

24. H. Zhu, C. Z. Cao, Y. Wu, X, Mu, Catalysis Society of India, 2007, 6, 83-89

25. C. P. Huang, Z. C. Liu, C. M. Xu, B. H. Chen, and Y. F. Liu, Appl. Catal., A, General, 2004, 41-43.

26. S. Elomari, et al. U.S. Patent 7,432,409, 2008.

27. S. Kobayashi, K. A. Jorgensen (eds.), Wiley-VCH, Weinheim, 2002, 154.

28. D. E. Kauffmann, M. Nouroozian, H. Henze, Synlett, 1996, 1091-1092.

29. B. McCormac, K. R. Seddon, Org. Lett., 1999, 1, 997-1000.

30. I. P. Beletskaya, A. V. Cheprakov, Chem. Rev., 2000, 100, 3009-3066.

31. K. R. Seddon, A. Stark, Green Chem., 2002, 4, 119-123.

32. K. Anderson, P. Goodrich, C. Hardacre, S. E. J. McCath, WO 094740

33. P. J. Dyson, D. J. Ellis, D. G. Parker, T. Welton, Chem. Commun., 1999, 25-26.

34. C. J. Adams, M. J. Earle, K. R. Seddon, Chem. Commun., 1999, 1043-1044.

35. N. Winterton, K. R Seddon, Y. Patell, WO 0037400

36. M. J. Earle, P. B. McCormac, K. R. Seddon, Green Chem., 1999, 1,23-25.

37. N. Sun, H. Rodriguez, M. Rahman, and R. D. Rogers, Chem. Commun., 2011, 47, 1405-1421.

38. M. Maase and K. Massonne, American Chemical Society, Washington D. C., 2005, 902, 126-

132.

39. S. N. Falling, S. A. Godlieski, J. R. Monnier, G. W. Phillips, and J. S. Kanel, Book of Abstracts, 1st

International Congress on Ionic Liquids, Salzurg Austria, 2005, 58-59.

40. S. N. Falling, S. A. Godleski, L. W. McGarry, T. R. Nolen, and J. S. Kanel. U.S. Patent 5,238,889,

1993.

41. G. W. Phillips, S. N. Falling, S. A. Godleski, J. R. Monnier, U.S. Patent 5,315,019, 1994.

42. J. S. Kanel, S. N. Falling, G. W. Phillips, J. R. Monnier, S. A. Godlieski, AIChE Annual Meeting, San

Francisco, 2006.

43. M. Serban, J. A. Kocal, U. S. Patent 7,749,377, July 06, 2010.

44. P. Wasserscheid, et al. U.S. Patent 7,553,406 B2, 2010.

45. D.N. Myers et al., US Patent 8,127,938 B2, March 06, 2012, M. Serban et al., US

Patent 8,383,538 B2, February 26, 2013.

46. A. Feller, J. a. Lercher, Adv. Catal, 2004, 48, 229-295.

47. A. Corma and A. Martinez, Catal. Rev. Sci. Eng. 1993, 35,483.

48. P. Kumar, W. Vermeiren, J-P. Dath, and W. F. Hoelderich, Appl. Catal. A: General, 2006, 131,

304.

49. P. Kumar, W. Vermeiren, J-P Dath, W. Hoeldrich, Appl. Catal. A, 2006, 304,131.

50. K. Yoo, V. N. Namboodiri, R. S. Varma, P. G. Smirniotis, J. Catal., 2004, 222, 511-519.

51. T. V. Harris, et al. U. S. Patent 7,531,707, 2009.

52. Honeywell-UOP, U. S. Patent Applications under Preparation, 2011.

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74

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53. M. Armand, F Endres, D. R. MacFarlane, H. Ohno, and B. Scrosati, Nature Materials, 2009, 8,

621-629.

54. Teramoto, R. Yokoyama, H. Kagawa, T. Sada, and N. Ogata, in Molten Salts and Ionic Liquids:

M. G. Escard and K. R. Seddon, Eds., Wiley, New York, 2010, 367-388.

55a. K. Mizuta, T. Kasahara, Y. Arimoto, H. Hashimoto, K. Takei, H. Katsuyama,

WO/2007/055392.

55b. "Ionic Liquids in synthesis" Wassercheid, P. and Welton T. Eds. Volume 2, Chapters 6 and 9,

Wiley-VCH, 2008.

56. P. U. Yauheni, J. Phys. Chem. Ref. Data, 2010, 39, 1-23.

57. R. Adler, Reports on Science and Technology, Wiesbaden, 2006.

58. D. Wei, A. Ivaska, Anal. Chim. Acta, 2008, 607, 126-135.

59. P. Sun, D. W. Armstrong, Anal. Chim. Acta, 2010, 661, 1-16.

60. R. J. Soukup-Hein, M. M. Warnke, D. W. Armstrong, Annu. Rev. Anal. Chem., 2009, 2, 145-168.

61. J. A. Shiddiky, A. J. Torriero, Biosensors and Bioelectronics, 2011, 26, 1775-1787.

62. N. Sun, H. Rodriquez, M Rahman, and R. D. Rogers, Chem. Commun., 2011, 47, 1405-1421.

63. M. Zavrel, D. Bross, M. Funke, J. Buchs, and A. C. Spies, Bioresource Technol,. 2009, 100,

2580-2587.

64. A. Ortiz, L. M. Galan, D. Gurri, A. B. De Haan, and I. Ortiz, Ind. Eng. Chem. Res. 2010, 49, 7227-

7233.

65. F. Agel, F. Pitsch, F. F. Krull, P. Schultz, M. Wessling, T. Melin, and P. Wasserscheid, Phys. Chem.

Chem. Phys., 2011, 13, 725-731.

66. P. Scovazzo, A. Visser, J. Davis, R. Rogers, C. A. Koval, D. DuBois, D. and R. D. Noble,

"Supported Ionic Liquid Membranes (SILMs) and Facilitated Ionic Liquid Membranes

(FILMs)", Ionic Liquids: Industrial Applications to Green Chemistry, American Chemical

Society Symposium Series 818, Robin D. Rogers, Kenneth R. Seddon Eds. 2002, 69-87.

Scope of Fuel Cell Technology in India

Dr. Suddhasatwa Basu, Department of Chemical Engineering, Indian Institute of Technology Delhi

1. Introduction

In recent years, global energy shortage and ecological pollution problems have

created opportunities for fuel cells to replace the existing technologies in variety of

applications. Some common areas of application of fuel cells include power for

Stationary, portable and transport applications. They are used to provide electricity

and heat in large stationary applications. They are also used to provide power in areas

which are difficult to serve by the national grid. In sectors like telecom, they find use in

providing backup power. Another promising area of application is their use in

portable devices like mobile phones. Due to their light weight and higher operating

times they are seen as a good alternative to solid batteries. Their application in

transport finds its roots in their ability to meet the stringent emission norms.

As far as the world fuel cell industry is concerned, most of the activities are

concentrated in regions of North America, Japan and Europe. The areas of expertise

range from R&D to component manufacture and system integration. Fundamental

and applied R&D is carried out in universities as well as by commercial players. A

large number of corporations are involved in component manufacturing and system

integration. The governments in these regions provide strong funding for the

development of fuel cell sector.

India's fuel cell industry is not quite developed as compared to the above mentioned

regions. Even then it can be considered a very important and emerging market. An

economy growing at a fast pace and a country in need of energy to sustain the growth

are the factors that strengthen India's position as a prospective market for fuel cells.

New national energy policies of the country that promote the growth of hydrogen and

fuel cell technologies add to the market potential of fuel cells in India.

India is the second most populous country in the world and the fourth largest

economy by purchasing power parity. India has seen dramatic economic growth

over the past decade with GDP growth rates going as high as 9 percent in the year

2007-08 (fig 1.1). Although due to the global economic slowdown, Indian

economy has also slowed (GDP growth rate of about 6.1 %) down from its high

performance but still it was one of the few economies where impact of this

downturn was minimum. India's growth rate was among the highest in the world

along with China.

1.1 India - a growing economy

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53. M. Armand, F Endres, D. R. MacFarlane, H. Ohno, and B. Scrosati, Nature Materials, 2009, 8,

621-629.

54. Teramoto, R. Yokoyama, H. Kagawa, T. Sada, and N. Ogata, in Molten Salts and Ionic Liquids:

M. G. Escard and K. R. Seddon, Eds., Wiley, New York, 2010, 367-388.

55a. K. Mizuta, T. Kasahara, Y. Arimoto, H. Hashimoto, K. Takei, H. Katsuyama,

WO/2007/055392.

55b. "Ionic Liquids in synthesis" Wassercheid, P. and Welton T. Eds. Volume 2, Chapters 6 and 9,

Wiley-VCH, 2008.

56. P. U. Yauheni, J. Phys. Chem. Ref. Data, 2010, 39, 1-23.

57. R. Adler, Reports on Science and Technology, Wiesbaden, 2006.

58. D. Wei, A. Ivaska, Anal. Chim. Acta, 2008, 607, 126-135.

59. P. Sun, D. W. Armstrong, Anal. Chim. Acta, 2010, 661, 1-16.

60. R. J. Soukup-Hein, M. M. Warnke, D. W. Armstrong, Annu. Rev. Anal. Chem., 2009, 2, 145-168.

61. J. A. Shiddiky, A. J. Torriero, Biosensors and Bioelectronics, 2011, 26, 1775-1787.

62. N. Sun, H. Rodriquez, M Rahman, and R. D. Rogers, Chem. Commun., 2011, 47, 1405-1421.

63. M. Zavrel, D. Bross, M. Funke, J. Buchs, and A. C. Spies, Bioresource Technol,. 2009, 100,

2580-2587.

64. A. Ortiz, L. M. Galan, D. Gurri, A. B. De Haan, and I. Ortiz, Ind. Eng. Chem. Res. 2010, 49, 7227-

7233.

65. F. Agel, F. Pitsch, F. F. Krull, P. Schultz, M. Wessling, T. Melin, and P. Wasserscheid, Phys. Chem.

Chem. Phys., 2011, 13, 725-731.

66. P. Scovazzo, A. Visser, J. Davis, R. Rogers, C. A. Koval, D. DuBois, D. and R. D. Noble,

"Supported Ionic Liquid Membranes (SILMs) and Facilitated Ionic Liquid Membranes

(FILMs)", Ionic Liquids: Industrial Applications to Green Chemistry, American Chemical

Society Symposium Series 818, Robin D. Rogers, Kenneth R. Seddon Eds. 2002, 69-87.

Scope of Fuel Cell Technology in India

Dr. Suddhasatwa Basu, Department of Chemical Engineering, Indian Institute of Technology Delhi

1. Introduction

In recent years, global energy shortage and ecological pollution problems have

created opportunities for fuel cells to replace the existing technologies in variety of

applications. Some common areas of application of fuel cells include power for

Stationary, portable and transport applications. They are used to provide electricity

and heat in large stationary applications. They are also used to provide power in areas

which are difficult to serve by the national grid. In sectors like telecom, they find use in

providing backup power. Another promising area of application is their use in

portable devices like mobile phones. Due to their light weight and higher operating

times they are seen as a good alternative to solid batteries. Their application in

transport finds its roots in their ability to meet the stringent emission norms.

As far as the world fuel cell industry is concerned, most of the activities are

concentrated in regions of North America, Japan and Europe. The areas of expertise

range from R&D to component manufacture and system integration. Fundamental

and applied R&D is carried out in universities as well as by commercial players. A

large number of corporations are involved in component manufacturing and system

integration. The governments in these regions provide strong funding for the

development of fuel cell sector.

India's fuel cell industry is not quite developed as compared to the above mentioned

regions. Even then it can be considered a very important and emerging market. An

economy growing at a fast pace and a country in need of energy to sustain the growth

are the factors that strengthen India's position as a prospective market for fuel cells.

New national energy policies of the country that promote the growth of hydrogen and

fuel cell technologies add to the market potential of fuel cells in India.

India is the second most populous country in the world and the fourth largest

economy by purchasing power parity. India has seen dramatic economic growth

over the past decade with GDP growth rates going as high as 9 percent in the year

2007-08 (fig 1.1). Although due to the global economic slowdown, Indian

economy has also slowed (GDP growth rate of about 6.1 %) down from its high

performance but still it was one of the few economies where impact of this

downturn was minimum. India's growth rate was among the highest in the world

along with China.

1.1 India - a growing economy

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12

10

8

6

4

2

0

2000 2002 2004 2006 2008 2010

Year

GD

P g

row

th r

ate

%

Fig 1.1 India's GDP growth rate over the years

This high growth rate essentially signifies upliftment of large number of population

from poverty to India's growing middle class. This growing middle class is causing a

consumer boom in Indian market which is contributing to India's growth.

Agricultural sector still employs about 60% of population. A growing service industry

is the largest contributor to India's GDP followed by industrial and agricultural sector.

Despite robust economic growth, India continues to face many major problems. One

of the major challenges that India is facing to sustain its high levels of economic

growth is lack of an effective infrastructure that can support its large population. A

provision for reliable power supply and a network for energy supply to India's

industrial and transportation sector are the two key issues that need to be addressed.

India is world's sixth largest energy consumer, accounting for almost 3.4 % of the

global energy consumption. Due to continuous high growth rates seen over the past

few years the demand for energy has been constantly growing in the economy. To

sustain the growth rate for the next 20 years, India needs to increase its primary

energy supply to 3-4 times. By 2030 the power generation capacity must increase to

about 8, 00,000 MW from current levels of about 1, 60,000 MW. (Source: Integrated

Energy Policy Report - 2006).A look at the current energy landscape shows India's

dependence on fossil fuels for its energy needs.

2. Energy Landscape

Fig 2.1 India's fuel cell mix

About 76% of the electricity produced in India is generated by thermal power plants,

21% by hydroelectric power plants and almost 2-3 % by nuclear power plants. India's

fuel mix is heavily dependent on hydrocarbons. Figure 2.1 shows the contribution of

various fuels in supply of energy.

This heavily fossil fuel dependent fuel mix of India raises concerns over energy

security of India, particularly regarding imported oil. The main challenge facing

India's energy sector is to increase and improve the delivery of energy services to

various sections of the economy. A problem of disparity in demand and supply of

energy is another big issue that needs to be addressed.

Despite an ambitious rural electrification program and huge additions in power

generation capacities, millions of Indians still have no access to electricity. While

80 percent of Indian villages have at least an electricity line, just 44 percent of

rural households have access to electricity. The gap between electricity supply

and demand nationwide averages up to 16 percent at peak times, according to

government figures, and 25 percent according to industry estimates. And

according to the Planning Commission of India, around 600 million people -

more than the entire population of the European Union - are not even on the

national grid. In some states, like poverty-hit Jharkhand, 90 percent of rural

households have no electricity and still use oil lamps for light.

India's industry incurs a direct loss of nearly 9 billion USD due to shortage of

power. The loss amounts to 1% of India's GDP. The highest loss is incurred by the

power intensive sectors like manufacturing which accounts for 35 per cent of the

total loss, small and medium enterprises, second highest, at 16 per cent, hospital

and hotel, retail at 12 per cent, real estate and infrastructure at 10 percent.

2.1 Electricity Demand supply situation

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12

10

8

6

4

2

0

2000 2002 2004 2006 2008 2010

Year

GD

P g

row

th r

ate

%

Fig 1.1 India's GDP growth rate over the years

This high growth rate essentially signifies upliftment of large number of population

from poverty to India's growing middle class. This growing middle class is causing a

consumer boom in Indian market which is contributing to India's growth.

Agricultural sector still employs about 60% of population. A growing service industry

is the largest contributor to India's GDP followed by industrial and agricultural sector.

Despite robust economic growth, India continues to face many major problems. One

of the major challenges that India is facing to sustain its high levels of economic

growth is lack of an effective infrastructure that can support its large population. A

provision for reliable power supply and a network for energy supply to India's

industrial and transportation sector are the two key issues that need to be addressed.

India is world's sixth largest energy consumer, accounting for almost 3.4 % of the

global energy consumption. Due to continuous high growth rates seen over the past

few years the demand for energy has been constantly growing in the economy. To

sustain the growth rate for the next 20 years, India needs to increase its primary

energy supply to 3-4 times. By 2030 the power generation capacity must increase to

about 8, 00,000 MW from current levels of about 1, 60,000 MW. (Source: Integrated

Energy Policy Report - 2006).A look at the current energy landscape shows India's

dependence on fossil fuels for its energy needs.

2. Energy Landscape

Fig 2.1 India's fuel cell mix

About 76% of the electricity produced in India is generated by thermal power plants,

21% by hydroelectric power plants and almost 2-3 % by nuclear power plants. India's

fuel mix is heavily dependent on hydrocarbons. Figure 2.1 shows the contribution of

various fuels in supply of energy.

This heavily fossil fuel dependent fuel mix of India raises concerns over energy

security of India, particularly regarding imported oil. The main challenge facing

India's energy sector is to increase and improve the delivery of energy services to

various sections of the economy. A problem of disparity in demand and supply of

energy is another big issue that needs to be addressed.

Despite an ambitious rural electrification program and huge additions in power

generation capacities, millions of Indians still have no access to electricity. While

80 percent of Indian villages have at least an electricity line, just 44 percent of

rural households have access to electricity. The gap between electricity supply

and demand nationwide averages up to 16 percent at peak times, according to

government figures, and 25 percent according to industry estimates. And

according to the Planning Commission of India, around 600 million people -

more than the entire population of the European Union - are not even on the

national grid. In some states, like poverty-hit Jharkhand, 90 percent of rural

households have no electricity and still use oil lamps for light.

India's industry incurs a direct loss of nearly 9 billion USD due to shortage of

power. The loss amounts to 1% of India's GDP. The highest loss is incurred by the

power intensive sectors like manufacturing which accounts for 35 per cent of the

total loss, small and medium enterprises, second highest, at 16 per cent, hospital

and hotel, retail at 12 per cent, real estate and infrastructure at 10 percent.

2.1 Electricity Demand supply situation

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Fig 2.2 Installed capacity requirement for power

350

300

250

200

150

100

50

0

2007 2012 2017

GW

Source: Planning Commission

According to KPMG estimates India will have a rise in demand of power to 90 GW by

2012 (fig 2.2) and only 65 GW increase will be there in the installed capacity. To

sustain the GDP growth rate of 8 % India would need to increase its installed capacity

to 220 GW by 2012 from around 130 GW in 2007.

Apart from high levels of disparity in demand supply situation India has other

challenges in its overall energy landscape. These include pollution and growing

concerns over energy security. Air pollution in particular is a concern in India's some

big cities like New Delhi, Mumbai, Kolkata, Chennai, Bangalore, Hyderabad and some

other urban cities. Measures like restraining the use of gasoline and diesel vehicles

had been taken to address the environmental degradation problems. New Delhi has

converted its public transport system including city buses and 3-whellers to CNG.

This CNG is derived from domestic natural gas, providing energy security. Similarly,

cities of Kolkata and Chandigarh have also converted their large autorickshaw fleets

to run on LPG. Still, measures to build a more sustainable energy infrastructure

should be taken and this has been realized by Indian government.

India's policy regarding fuel cells and hydrogen technology development is largely

governed by Ministry of New and Renewable Energy (MNRE). The authority being

quite active has set up a National Hydrogen Energy Board and a roadmap in 2006.

The board set up five expert groups on hydrogen production, storage, power,

transport and systems integration. It provided an integrated blue print for the long

term public and private efforts required for hydrogen energy development inside

the country. This roadmap was one of the measures taken in a series to improve

energy supply situation in India. The 2003 Electricity Act was responsible for

developing an overall framework for renewable energy. The 2005 National

Electricity Policy recognized renewable as a key option for areas where national grid

is not feasible or cost effective.

3. Policy Landscape

The broad objectives of India's National Hydrogen Energy Program are as follows:

1. Reduce dependence on imported petroleum products

2. Promote use of diverse, domestic and sustainable new and renewable energy sources

3. Provide electricity to remote ,rural and far flung areas

4. Promote hydrogen as a fuel for transport and power generation

5. Reduce carbon emissions from energy production and consumption

6. Increase reliability and efficiency of electricity generation

The National Hydrogen energy Roadmap proposed two major initiatives in its Vision 2020

- Prioritized Action Plan. The Green Initiative for Future Transport (GIFT) aims to develop

hydrogen powered IC engine and fuel cell vehicles ranging from small (cars, 3 wheelers) to

big vehicles through different phases of development and demonstration. The Green

Initiative for Power generation (GIP) was to develop hydrogen powered turbine and fuel

cell based decentralized power generating systems.

National Hydrogen Energy Roadmap: Vision - 2020Source: NHERM(2006) report, Ministry of New and Renewable Energy

Box 3.1 GIFT

Green Initiative for Future Transport (GIFT)

Hydrogen Cost at delivery point at Rs. 60-70 per kg

Hydrogen storage capacity to be 9 weight %

Development of safety regulations, legislations, codes and standards

1, 000, 000 hydrogen fuelled vehicles on road

l750,000 two/three wheelers

l150,000 cars/taxis

l100,000 buses vans

Green Initiative for Power Generation (GIP)

Hydrogen bulk storage methods and pipeline methods to be in place

Support infrastructure including large number of dispensing stations

1000 MW hydrogen based power generating capacity to be setup

l50 MW small IC engine standalone generators

l50 MW standalone fuel cell power packs

l900 MW aggregate capacity centralized plants

Box 3.2 GIP

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Fig 2.2 Installed capacity requirement for power

350

300

250

200

150

100

50

0

2007 2012 2017

GW

Source: Planning Commission

According to KPMG estimates India will have a rise in demand of power to 90 GW by

2012 (fig 2.2) and only 65 GW increase will be there in the installed capacity. To

sustain the GDP growth rate of 8 % India would need to increase its installed capacity

to 220 GW by 2012 from around 130 GW in 2007.

Apart from high levels of disparity in demand supply situation India has other

challenges in its overall energy landscape. These include pollution and growing

concerns over energy security. Air pollution in particular is a concern in India's some

big cities like New Delhi, Mumbai, Kolkata, Chennai, Bangalore, Hyderabad and some

other urban cities. Measures like restraining the use of gasoline and diesel vehicles

had been taken to address the environmental degradation problems. New Delhi has

converted its public transport system including city buses and 3-whellers to CNG.

This CNG is derived from domestic natural gas, providing energy security. Similarly,

cities of Kolkata and Chandigarh have also converted their large autorickshaw fleets

to run on LPG. Still, measures to build a more sustainable energy infrastructure

should be taken and this has been realized by Indian government.

India's policy regarding fuel cells and hydrogen technology development is largely

governed by Ministry of New and Renewable Energy (MNRE). The authority being

quite active has set up a National Hydrogen Energy Board and a roadmap in 2006.

The board set up five expert groups on hydrogen production, storage, power,

transport and systems integration. It provided an integrated blue print for the long

term public and private efforts required for hydrogen energy development inside

the country. This roadmap was one of the measures taken in a series to improve

energy supply situation in India. The 2003 Electricity Act was responsible for

developing an overall framework for renewable energy. The 2005 National

Electricity Policy recognized renewable as a key option for areas where national grid

is not feasible or cost effective.

3. Policy Landscape

The broad objectives of India's National Hydrogen Energy Program are as follows:

1. Reduce dependence on imported petroleum products

2. Promote use of diverse, domestic and sustainable new and renewable energy sources

3. Provide electricity to remote ,rural and far flung areas

4. Promote hydrogen as a fuel for transport and power generation

5. Reduce carbon emissions from energy production and consumption

6. Increase reliability and efficiency of electricity generation

The National Hydrogen energy Roadmap proposed two major initiatives in its Vision 2020

- Prioritized Action Plan. The Green Initiative for Future Transport (GIFT) aims to develop

hydrogen powered IC engine and fuel cell vehicles ranging from small (cars, 3 wheelers) to

big vehicles through different phases of development and demonstration. The Green

Initiative for Power generation (GIP) was to develop hydrogen powered turbine and fuel

cell based decentralized power generating systems.

National Hydrogen Energy Roadmap: Vision - 2020Source: NHERM(2006) report, Ministry of New and Renewable Energy

Box 3.1 GIFT

Green Initiative for Future Transport (GIFT)

Hydrogen Cost at delivery point at Rs. 60-70 per kg

Hydrogen storage capacity to be 9 weight %

Development of safety regulations, legislations, codes and standards

1, 000, 000 hydrogen fuelled vehicles on road

l750,000 two/three wheelers

l150,000 cars/taxis

l100,000 buses vans

Green Initiative for Power Generation (GIP)

Hydrogen bulk storage methods and pipeline methods to be in place

Support infrastructure including large number of dispensing stations

1000 MW hydrogen based power generating capacity to be setup

l50 MW small IC engine standalone generators

l50 MW standalone fuel cell power packs

l900 MW aggregate capacity centralized plants

Box 3.2 GIP

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4. R&d Situation In India

Past few years have seen a considerable activity in the area of fuel cell research in

India. Most of the basic research is done by India's reputed academic institutions and

a very few industrial organizations are involved in research. A vast majority of this

research is funded by government under new energy policies of Ministry of New and

Renewable Energy. These research institutions are involved in more fundamental

research such as catalysis and MEA development. Some institutions are also involved

in more application oriented research such as stack development and BoP related

work. Table 2.1 presents a summary of fuel cell related activities of key R&D

institutions in India.

Although, Indian companies are generally regarded as only manufacturers and

service providers with less emphasis on R&D, some big corporate houses of India

have entered the area of fuel cell research. Most of these industrial houses are

carrying out applied research which concerns with the adaptation of fuel cell

technologies in Indian scenario. Car makers like Tata and Mahindra & Mahindra are

involved in making fuel cells a part of Indian automobile industries.

Apart from these, several foreign companies have also entered the Indian market

since the market is still in nascent stage. Some of these organizations are focusing on

bringing the technologies developed in other countries to India, while some have

focused on using Indian expertise and resources to develop a strong R&D base. Some

local players are also involved in collaborations with these companies.

In the past few years India has seen a steep growth in fuel cell research activities

with several national and international conferences and workshops organized

locally. Both academic institutions and private sector companies are actively

participating to organize these events. These events have provided a good platform

to Indian researchers to interact among themselves and also with researchers from

other countries. This is quite important, as no active network of Indian researchers

exists in the area of fuel cell research.

Most of the organizations involved in fuel cell activities are concentrated in the

areas of Delhi, Tamil Nadu and Maharashtra (fig 4.1). Apart from this, significant fuel

cell research is being done by institutions in Uttar Pradesh, West Bengal and

Karnataka. It is important to note that city of Chennai is home to some of the

important fuel cell research institutions in India.

Fig 4.1 Distribution of fuel cell organization by region in India

Karnataka

Tamil Nadu

Maharashtra

New Delhi

Uttar Pradesh

West Bengal

13%

21%

8%

32%

13%

13%

A large percentage of organizations involved in fuel cell activities are working on

small stationary units (fig 4.2). Power distribution is a big problem in both domestic

and industrial sectors in India and fuel cells are being looked as a good option to

provide stationary backup power. Several programs related to stationary

applications of fuel cells are being promoted by government.

21%

14%

7%7%

51%

Automobile

H- Storage

Large Stationary

Portable

Small Stationary

Fig 4.2 Distribution of fuel cell organization by application type in India

Apart from stationary power, automotive sector is also an important focus area for

fuel cell research institutions in India. Some of the big industrial organizations are

involved in development of fuel cells for automobile applications. Hydrogen storage,

portable and large stationary applications of fuel cells are some other important

areas of fuel cell research in India.

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4. R&d Situation In India

Past few years have seen a considerable activity in the area of fuel cell research in

India. Most of the basic research is done by India's reputed academic institutions and

a very few industrial organizations are involved in research. A vast majority of this

research is funded by government under new energy policies of Ministry of New and

Renewable Energy. These research institutions are involved in more fundamental

research such as catalysis and MEA development. Some institutions are also involved

in more application oriented research such as stack development and BoP related

work. Table 2.1 presents a summary of fuel cell related activities of key R&D

institutions in India.

Although, Indian companies are generally regarded as only manufacturers and

service providers with less emphasis on R&D, some big corporate houses of India

have entered the area of fuel cell research. Most of these industrial houses are

carrying out applied research which concerns with the adaptation of fuel cell

technologies in Indian scenario. Car makers like Tata and Mahindra & Mahindra are

involved in making fuel cells a part of Indian automobile industries.

Apart from these, several foreign companies have also entered the Indian market

since the market is still in nascent stage. Some of these organizations are focusing on

bringing the technologies developed in other countries to India, while some have

focused on using Indian expertise and resources to develop a strong R&D base. Some

local players are also involved in collaborations with these companies.

In the past few years India has seen a steep growth in fuel cell research activities

with several national and international conferences and workshops organized

locally. Both academic institutions and private sector companies are actively

participating to organize these events. These events have provided a good platform

to Indian researchers to interact among themselves and also with researchers from

other countries. This is quite important, as no active network of Indian researchers

exists in the area of fuel cell research.

Most of the organizations involved in fuel cell activities are concentrated in the

areas of Delhi, Tamil Nadu and Maharashtra (fig 4.1). Apart from this, significant fuel

cell research is being done by institutions in Uttar Pradesh, West Bengal and

Karnataka. It is important to note that city of Chennai is home to some of the

important fuel cell research institutions in India.

Fig 4.1 Distribution of fuel cell organization by region in India

Karnataka

Tamil Nadu

Maharashtra

New Delhi

Uttar Pradesh

West Bengal

13%

21%

8%

32%

13%

13%

A large percentage of organizations involved in fuel cell activities are working on

small stationary units (fig 4.2). Power distribution is a big problem in both domestic

and industrial sectors in India and fuel cells are being looked as a good option to

provide stationary backup power. Several programs related to stationary

applications of fuel cells are being promoted by government.

21%

14%

7%7%

51%

Automobile

H- Storage

Large Stationary

Portable

Small Stationary

Fig 4.2 Distribution of fuel cell organization by application type in India

Apart from stationary power, automotive sector is also an important focus area for

fuel cell research institutions in India. Some of the big industrial organizations are

involved in development of fuel cells for automobile applications. Hydrogen storage,

portable and large stationary applications of fuel cells are some other important

areas of fuel cell research in India.

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Table 4.1 Summary of fuel cell R&D Organizations in India

Institute/Organization Main Focus Area(s) Achievements/Remarks

CECRI, Chennai PEMFC,DMFC,DBFC, Hydrogen Generation kW PEMWE

CFCT, Chennai PEMFC, Hydrogen Developed PEMFC stacks up to 5 kW, Grid Generation independent power systems (3 kW), Fuel cell

systems for transport applications withMahindra and Mahindra and Reva

CGCRI, Kolkata SOFC Developed electrode and membrane materialsfor high performance SOFCs and LowTemperature SOFC

SPIC SF, Chennai PEMFC, DMFC, Developed 5 kW PEMFC stacks, 250 W DMFC Hydrogen Generation Stack, PEM based Water and methanol

electrolyzers, fuel cell based stationaryapplications like UPS

IIT Bombay, Mumbai PEMFC, DMFC, IT- Working on HT-PEMFC and IT-SOFC, Hydrogen SOFC, hydrogen storage in complex hydrides generation

IIT Delhi, Delhi PMFC, DAFC, Developed DEFC with power density of 60-70 Hydrogen mW/sq.cm, electrode-catalysts, Working onGeneration, Direct Direct Glucose fuel cells, developed high hydrocarbon SOFC, temperature PEM water electrolyzer for Low temperature SOFC hydrogen generation. Developed anode

material for direct methane and butane SOFC.

IIT Madras, Chennai PEMFC, DMFC,SOFC, Developed a DMFC with non noble cathode Hydrogen Storage catalyst with 340 mA/sq.cm (0.6 V) at 80 oC

NCL, Pune PEMFC Prepared thermally stable PBI membranes,Demonstrated a 350 W (15 cell) PBI basedPEMFC stack.

NMRL, DRDO, Mumbai PAFC, PEMFC, Developed and demonstrated 700-1000 W Hydrogen Storage capacity PAFC based UPS/generators. 1.2 kW

PAFC system integrated in an electric vehicledeveloped under DRDO-REVA joint project

BARC, Mumbai SOFC, PEMFC SOFC material and tubular SOFC underdevelopment

BHU, Varanasi Hydrogen Storage, Developed AB and AB type storage materials 5 2

Hydrogen IC Engines, with improved storage capacity. Converted Hydrogen Production existing petrol driven IC engines to operate

with hydrogen as fuel.

IISc, Bangalore PAFC,DMFC,PEMFC Developed PAFC with power density value ofabout 560 mW/sq.cm.

Mahindra & Mahindra Hydrogen IC engines Developed hydrogen powered Alfa 3 wheelervehicle. Developing battery powered electrichybrid vehicle

TATA Motors Fuel cell technology for Developing a fuel cell based city bus, Projectstransport applications on using hydrogen blends as fuels. TATA

teleservices involved in demonstration of fuelcell technology for mobile tower backup power

Developed a 1 kW PEMFC stack, Developed a 5


Indian Oil Corp. Ltd. Hydrogen Setup hydrogen dispensing stations. HCNGinfrastructure, usage in 3-wheeled vehicles and light dutyhydrogen for transport buses.sector

Reliance Industries Ltd. PEMFC for stationary Joined the NMITLI project for Indigenousapplications, SOFC PEMFC Technology Development as the

industrial partner. Established a fuel cell R&Dlab in Mumbai

REVA Fuel cell based Developed a car with NMRL with 1 kW PAFCsmall cars stack on board. Involved in a similar projectwith CFCT.

BHEL PAFC, PEMFC,SOFC Developed a 50 kW PAFC power plant,developed 1 kW PEMFC modules and a 3 kWPEMFC power pack. Partner institute in thedevelopment of a 5 kW PEMFC system underthe NMITLI project

Nissan India PEMFC technology for Working on membrane development for PEMFCautomobile technology. Studying membrane degradationapplications

ACME Telepower Fuel cells for backup Joint venture with Ballard power systems Inc.power and Ida-Tech to setup a high volume low cost

fuel cell systems for mobile tower back uppower (target 30,000 units by 2013)

Eden Energy hydrogen for transport Involved in production of HYTHANE,(India) Pvt. Ltd. sector agreement was signed with Ashok Leyland for

the supply of Hythane to be used in natural gaspowered buses

Gas Authority of Hydrogen Main player for supply of suitable fuels,India Limited Infrastructure including hydrogen, natural gas, propane,

butane and methanol

Bloom Energy (India) Private Limited SOFCWorking on testing and characterization of SOFC technology

Daimler Research Fuel cell for transport Setup an outsourcing R&D centre inCenter (DMRC), applications Bangalore. Considering launching a commercialBangalore fuel cell vehicle in India

5. Markets For Fuel Cells In India

A fast growing economy, with a large gap in demand and supply of power, makes

India a good potential market for various power generation technologies including

fuel cells. Favourable national energy policies for hydrogen and fuel cell technology

development in stationary power and automotive sectors strengthen India's

position as a future market for fuel cell based applications. This section of the report

describes some of the markets for fuel cells in stationary power and automotive

sectors.

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Table 4.1 Summary of fuel cell R&D Organizations in India


CECRI, Chennai PEMFC,DMFC,DBFC, Hydrogen Generation kW PEMWE

CFCT, Chennai PEMFC, Hydrogen Developed PEMFC stacks up to 5 kW, Grid Generation independent power systems (3 kW), Fuel cell

systems for transport applications withMahindra and Mahindra and Reva

CGCRI, Kolkata SOFC Developed electrode and membrane materialsfor high performance SOFCs and LowTemperature SOFC

SPIC SF, Chennai PEMFC, DMFC, Developed 5 kW PEMFC stacks, 250 W DMFC Hydrogen Generation Stack, PEM based Water and methanol

electrolyzers, fuel cell based stationaryapplications like UPS

IIT Bombay, Mumbai PEMFC, DMFC, IT- Working on HT-PEMFC and IT-SOFC, Hydrogen SOFC, hydrogen storage in complex hydrides generation

IIT Delhi, Delhi PMFC, DAFC, Developed DEFC with power density of 60-70 Hydrogen mW/sq.cm, electrode-catalysts, Working onGeneration, Direct Direct Glucose fuel cells, developed high hydrocarbon SOFC, temperature PEM water electrolyzer for Low temperature SOFC hydrogen generation. Developed anode

material for direct methane and butane SOFC.

IIT Madras, Chennai PEMFC, DMFC,SOFC, Developed a DMFC with non noble cathode Hydrogen Storage catalyst with 340 mA/sq.cm (0.6 V) at 80 oC

NCL, Pune PEMFC Prepared thermally stable PBI membranes,Demonstrated a 350 W (15 cell) PBI basedPEMFC stack.

NMRL, DRDO, Mumbai PAFC, PEMFC, Developed and demonstrated 700-1000 W Hydrogen Storage capacity PAFC based UPS/generators. 1.2 kW

PAFC system integrated in an electric vehicledeveloped under DRDO-REVA joint project

BARC, Mumbai SOFC, PEMFC SOFC material and tubular SOFC underdevelopment

BHU, Varanasi Hydrogen Storage, Developed AB and AB type storage materials 5 2

Hydrogen IC Engines, with improved storage capacity. Converted Hydrogen Production existing petrol driven IC engines to operate

with hydrogen as fuel.

IISc, Bangalore PAFC,DMFC,PEMFC Developed PAFC with power density value ofabout 560 mW/sq.cm.

Mahindra & Mahindra Hydrogen IC engines Developed hydrogen powered Alfa 3 wheelervehicle. Developing battery powered electrichybrid vehicle

TATA Motors Fuel cell technology for Developing a fuel cell based city bus, Projectstransport applications on using hydrogen blends as fuels. TATA

teleservices involved in demonstration of fuelcell technology for mobile tower backup power

Developed a 1 kW PEMFC stack, Developed a 5


Indian Oil Corp. Ltd. Hydrogen Setup hydrogen dispensing stations. HCNGinfrastructure, usage in 3-wheeled vehicles and light dutyhydrogen for transport buses.sector

Reliance Industries Ltd. PEMFC for stationary Joined the NMITLI project for Indigenousapplications, SOFC PEMFC Technology Development as the

industrial partner. Established a fuel cell R&Dlab in Mumbai

REVA Fuel cell based Developed a car with NMRL with 1 kW PAFCsmall cars stack on board. Involved in a similar projectwith CFCT.

BHEL PAFC, PEMFC,SOFC Developed a 50 kW PAFC power plant,developed 1 kW PEMFC modules and a 3 kWPEMFC power pack. Partner institute in thedevelopment of a 5 kW PEMFC system underthe NMITLI project

Nissan India PEMFC technology for Working on membrane development for PEMFCautomobile technology. Studying membrane degradationapplications

ACME Telepower Fuel cells for backup Joint venture with Ballard power systems Inc.power and Ida-Tech to setup a high volume low cost

fuel cell systems for mobile tower back uppower (target 30,000 units by 2013)

Eden Energy hydrogen for transport Involved in production of HYTHANE,(India) Pvt. Ltd. sector agreement was signed with Ashok Leyland for

the supply of Hythane to be used in natural gaspowered buses

Gas Authority of Hydrogen Main player for supply of suitable fuels,India Limited Infrastructure including hydrogen, natural gas, propane,

butane and methanol

Bloom Energy (India) Private Limited SOFCWorking on testing and characterization of SOFC technology

Daimler Research Fuel cell for transport Setup an outsourcing R&D centre inCenter (DMRC), applications Bangalore. Considering launching a commercialBangalore fuel cell vehicle in India

5. Markets For Fuel Cells In India

A fast growing economy, with a large gap in demand and supply of power, makes

India a good potential market for various power generation technologies including

fuel cells. Favourable national energy policies for hydrogen and fuel cell technology

development in stationary power and automotive sectors strengthen India's

position as a future market for fuel cell based applications. This section of the report

describes some of the markets for fuel cells in stationary power and automotive

sectors.

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Stationary power generation sector in India can be considered to have the

most near term potential market for fuel cells. The rapid growth in Indian

economy demands for a growth in infrastructure facilities and energy supply.

Currently, India is suffering from severe power shortages which can affect the

growth levels of economy as it affects both the domestic and industrial sectors.

In India, several industrial and commercial enterprises use some form of

captive power and are potential customers for fuel cell based stationary power

plants. An unreliable grid system and prolonged power black outs in urban

areas in India add to the market potential for fuel cell applications in stationary

power sector. A study conducted by TERI, Delhi, on the market assessment of

fuel cells in India, identified several key markets for fuel cell stationary power

plants in India. These include chlor-alkali industry, luxury hotels, paper and

pulp industry, dairy industry, telecommunication industry and stationary

backup power. Study identified availability of fuel for fuel cell power plant as

one of the key factors in selection of potential consumers. Also, potential use of

waste heat from fuel cell power plant was another important factor considered

in the selection of consumer. Table 5.1 presents some of the key niche areas for

stationary power generation indentified from the study.

Another market application for fuel cell base power plants could be in

distributed power generation in Indian rural areas. Due to the unavailability of

grid connected power supply these areas can be seen as a potential market for

distributed power generation systems. Government incentives and support in

this area can be seen as an advantage for the market players.

5.1. Stationary Power

























Potential Markets Power Requirement Potential fuel

MW cell types

Remarks

Luxury Hotels 0.5 -5 PAFC,SOFC,MCFC Availability of natural gas

or LPG a big advantage

Chlor alkali 5-45 SOFC,MCFC Hydrogen available as a by

product

Pulp and Paper 2-50 SOFC,MCFC Availability of natural gas is

required

Dairy Industry <5 AFC,PAFC,PEMFC Use of biogas from rural

areas will be economical

Telecom & IT <5 AFC,PAFC,PEMFC Fuel availability a big issue

Table 5.1 Summary of key niche markets for stationary power generation in India

5.1.1 Telecommunication Industry

India has emerged as one of the fastest growing telecom markets in

world. Mobile services in telecom industry have been growing at a much

faster pace mainly in urban areas with an all India subscriber base of

around 525,147,922. Still, the total wireless tele-density remains at

around 40.3 % which shows a huge untapped potential for market

growth. The main future market for these services lies in non-urban

areas where penetration of these services remains low.

A growing telecom industry presents itself as a potential market in

mobile towers backup power. Currently there are around 2,50,000

mobile telecom sites and it is estimated that about 5,00,000 sites will be

required by 2011. One of the main infrastructure requirements for

mobile towers is the provision of backup power which is a necessity due

to frequent power cuts in both urban and rural areas. The issue of

irregular power supply is more pronounced in the rural sector, where a

number of Indian villages either do not have an electricity grid

connection or face limited power availability. Mobile towers use backup

power in the form of diesel powered generators. Although the start-up

costs for diesel based power generators are low, the operating costs are

quite high due to high costs of crude oil in recent times. It is estimated

that over 35% of rural cell site's network operating expenses are due to

costs associated with electricity and diesel.

Fuel cells are being offered as a viable option to telecom customers in

place of diesel generators. Telecom infrastructure companies are willing

to pay a premium for reliable power especially in remote rural areas. Fuel

cells offer clean, noise free and most importantly they can be run on a

variety of fuels. These fuels can be cheap bio-gas which is available in

remote rural areas and thus can provide a solution to telecom companies

looking for a replacement to diesel based generators.

In May 2008, agreement between Ballard Power systems and ACME Telepower for supply

of fuel cell stacks for telecoms backup power.

A development and supply agreement between ACME, Ballard and IdaTech for supply of 5

kW natural gas PEMFC stack - 30,000 systems to be delivered by 2013

A minimum order of 10,000 systems to be completed by 2010, rest order after evaluation of

these units

In august 2008, Plug Power demonstrated a LPG fuelled telecom power backup unit in

partnership with Hindustan Petroleum Corp. Ltd. and Tata Teleservices

Box 5.1 Recent fuel cell activities in Indian Telecom market

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Potential Markets Power Requirement Potential fuel

MW cell types

Remarks

Luxury Hotels 0.5 -5 PAFC,SOFC,MCFC Availability of natural gas

or LPG a big advantage

Chlor alkali 5-45 SOFC,MCFC Hydrogen available as a by

product

Pulp and Paper 2-50 SOFC,MCFC Availability of natural gas is

required

Dairy Industry <5 AFC,PAFC,PEMFC Use of biogas from rural

areas will be economical

Telecom & IT <5 AFC,PAFC,PEMFC Fuel availability a big issue

Table 5.1 Summary of key niche markets for stationary power generation in India

5.1.1 Telecommunication Industry

India has emerged as one of the fastest growing telecom markets in

world. Mobile services in telecom industry have been growing at a much

faster pace mainly in urban areas with an all India subscriber base of

around 525,147,922. Still, the total wireless tele-density remains at

around 40.3 % which shows a huge untapped potential for market

growth. The main future market for these services lies in non-urban

areas where penetration of these services remains low.

A growing telecom industry presents itself as a potential market in

mobile towers backup power. Currently there are around 2,50,000

mobile telecom sites and it is estimated that about 5,00,000 sites will be

required by 2011. One of the main infrastructure requirements for

mobile towers is the provision of backup power which is a necessity due

to frequent power cuts in both urban and rural areas. The issue of

irregular power supply is more pronounced in the rural sector, where a

number of Indian villages either do not have an electricity grid

connection or face limited power availability. Mobile towers use backup

power in the form of diesel powered generators. Although the start-up

costs for diesel based power generators are low, the operating costs are

quite high due to high costs of crude oil in recent times. It is estimated

that over 35% of rural cell site's network operating expenses are due to

costs associated with electricity and diesel.

Fuel cells are being offered as a viable option to telecom customers in

place of diesel generators. Telecom infrastructure companies are willing

to pay a premium for reliable power especially in remote rural areas. Fuel

cells offer clean, noise free and most importantly they can be run on a

variety of fuels. These fuels can be cheap bio-gas which is available in

remote rural areas and thus can provide a solution to telecom companies

looking for a replacement to diesel based generators.

In May 2008, agreement between Ballard Power systems and ACME Telepower for supply

of fuel cell stacks for telecoms backup power.

A development and supply agreement between ACME, Ballard and IdaTech for supply of 5

kW natural gas PEMFC stack - 30,000 systems to be delivered by 2013

A minimum order of 10,000 systems to be completed by 2010, rest order after evaluation of

these units

In august 2008, Plug Power demonstrated a LPG fuelled telecom power backup unit in

partnership with Hindustan Petroleum Corp. Ltd. and Tata Teleservices

Box 5.1 Recent fuel cell activities in Indian Telecom market

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5.1.2 Chlor alkali Industry

Chlor alkali industry in India mainly comprises manufacturers of caustic

soda and soda ash. In the process of manufacturing caustic soda, some

valuable by products are produced. A tonne of caustic soda produces 860

kg of chlorine and 25 kg of hydrogen. Chlorine and hydrogen produced

can be combined to make hydrochloric acid. These basic chemicals are

used by many industries. Table 5.2 shows the hydrogen producing

capacity of various chlor alkali plants in India

The manufacturing process of caustic soda is quite energy intensive

(load 5-45 MW). The load requirements are met by grid supply as well as

captive power plants.

Hydrogen as a major by product of the manufacturing process finds little

usage in chemical industry. Although some hydrogen is used in the

manufacturing of HCl and some is sold after compression and storage in

bottles, a significant amount doesn't find any use. Compression of

hydrogen and storage into cylinders is a labour and energy intensive

process. Also, market for HCL is limited so conversion of hydrogen to HCl

is restricted by demand.

Caustic soda is transported to long distances after it is converted to

caustic flakes by an evaporation process, which consumes fuel. Use of

hydrogen in this process is also difficult as it requires sophisticated

burners and controls. It has been also estimated that all the hydrogen

produced as by product in the plant cannot meet the energy

requirements of the flaking process. So, use of additional fuel is

necessary in any case.

Due to above mentioned factors use of hydrogen in fuel cells presents

itself as a promising option. In recent times due to liberal import policies

of Govt. of India, domestic chlor alkali industry is facing stiff competition

from overseas manufacturers which sell caustic soda at significantly

lower price. So, domestic manufactures are looking for technologies

which can give them an advantage in terms of overall cost reduction

inside the plant. Several domestic manufacturers have switched to more

efficient technologies of production namely membrane cell processes

and are incurring large capital investments.

For fuel cell technology adoption in this market economics of fuel cell

power plant and particularly the capital investment would be of utmost

importance. Thus, fuel cells which also generate waste heat in the form of

steam can be thought of as a good option as they can satisfy some of the

energy needs of the plant. SOFC and MCFC power plants could be the

ideal fit in these cases. The steam from the fuel cell power plants can be

used in the flaking process of the caustic soda. Benefits of the fuel

cell power plants depend on how effectively the waste heat is

utilized in the plant.

Manufacturer, State H2 ,Nm3/day Excess H2 ,Nm3/day

Century Rayon, Maharashtra 11000 11000

Hukumchand Jute Inds Ltd, M.P. 23100 11100

DCW Ltd. , Tamilnadu 48160 16800

Indian Petrochemicals Corpn Ltd., Gujarat 120000 50000

Grasim Ind. Ltd. 112000 50000

Tata Chemicals, Gujarat 29500 4720

Punjab Alkalies & Chemicals 84000 11866

Table 5.2 Hydrogen producing capacity of some chlor alkali plants in India

5.1.3 Luxury hotels

There is a need of reliable primary and backup power in large

commercial premises. The five star hotels of India can be viewed as a

prime candidate for the adoption of fuel cell technology in stationary

power generation. The load requirements range from 500 kW to 5 MW

depending upon the capacity of hotels. The load is distributed lighting

requirements, kitchen load, operation of lifts and mainly space

conditioning.

These hotels require heat for various purposes which include hot water

for guests, kitchen, and laundry. Some hotels also have sauna baths and

health clubs which also require steam.

The hotels are well connected by grid but due to frequent power cuts

they also maintain some form of captive power generation which can

meet the energy requirements. Most commonly diesel based generators

are used as captive power plants in the hotels.

Fig 5.1 Two 750 kVA diesel generators at Taj Palace hotel, Rajasthan

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5.1.2 Chlor alkali Industry

Chlor alkali industry in India mainly comprises manufacturers of caustic

soda and soda ash. In the process of manufacturing caustic soda, some

valuable by products are produced. A tonne of caustic soda produces 860

kg of chlorine and 25 kg of hydrogen. Chlorine and hydrogen produced

can be combined to make hydrochloric acid. These basic chemicals are

used by many industries. Table 5.2 shows the hydrogen producing

capacity of various chlor alkali plants in India

The manufacturing process of caustic soda is quite energy intensive

(load 5-45 MW). The load requirements are met by grid supply as well as

captive power plants.

Hydrogen as a major by product of the manufacturing process finds little

usage in chemical industry. Although some hydrogen is used in the

manufacturing of HCl and some is sold after compression and storage in

bottles, a significant amount doesn't find any use. Compression of

hydrogen and storage into cylinders is a labour and energy intensive

process. Also, market for HCL is limited so conversion of hydrogen to HCl

is restricted by demand.

Caustic soda is transported to long distances after it is converted to

caustic flakes by an evaporation process, which consumes fuel. Use of

hydrogen in this process is also difficult as it requires sophisticated

burners and controls. It has been also estimated that all the hydrogen

produced as by product in the plant cannot meet the energy

requirements of the flaking process. So, use of additional fuel is

necessary in any case.

Due to above mentioned factors use of hydrogen in fuel cells presents

itself as a promising option. In recent times due to liberal import policies

of Govt. of India, domestic chlor alkali industry is facing stiff competition

from overseas manufacturers which sell caustic soda at significantly

lower price. So, domestic manufactures are looking for technologies

which can give them an advantage in terms of overall cost reduction

inside the plant. Several domestic manufacturers have switched to more

efficient technologies of production namely membrane cell processes

and are incurring large capital investments.

For fuel cell technology adoption in this market economics of fuel cell

power plant and particularly the capital investment would be of utmost

importance. Thus, fuel cells which also generate waste heat in the form of

steam can be thought of as a good option as they can satisfy some of the

energy needs of the plant. SOFC and MCFC power plants could be the

ideal fit in these cases. The steam from the fuel cell power plants can be

used in the flaking process of the caustic soda. Benefits of the fuel

cell power plants depend on how effectively the waste heat is

utilized in the plant.

Manufacturer, State H2 ,Nm3/day Excess H2 ,Nm3/day

Century Rayon, Maharashtra 11000 11000

Hukumchand Jute Inds Ltd, M.P. 23100 11100

DCW Ltd. , Tamilnadu 48160 16800

Indian Petrochemicals Corpn Ltd., Gujarat 120000 50000

Grasim Ind. Ltd. 112000 50000

Tata Chemicals, Gujarat 29500 4720

Punjab Alkalies & Chemicals 84000 11866

Table 5.2 Hydrogen producing capacity of some chlor alkali plants in India

5.1.3 Luxury hotels

There is a need of reliable primary and backup power in large

commercial premises. The five star hotels of India can be viewed as a

prime candidate for the adoption of fuel cell technology in stationary

power generation. The load requirements range from 500 kW to 5 MW

depending upon the capacity of hotels. The load is distributed lighting

requirements, kitchen load, operation of lifts and mainly space

conditioning.

These hotels require heat for various purposes which include hot water

for guests, kitchen, and laundry. Some hotels also have sauna baths and

health clubs which also require steam.

The hotels are well connected by grid but due to frequent power cuts

they also maintain some form of captive power generation which can

meet the energy requirements. Most commonly diesel based generators

are used as captive power plants in the hotels.

Fig 5.1 Two 750 kVA diesel generators at Taj Palace hotel, Rajasthan

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Fuel cells which can simultaneously supply electricity, steam and hot

water will be an attractive option to hotel owners. PAFC, MCFC and SOFC

power plants are best suited for this case. A clean and noise free energy

generation process with ease of operation can be considered as factors

which will drive fuel cells entry in this market.

Availability of fuel for such plants will be another important factor in this

market. Some of the cities in India, mainly metropolitan cities like Delhi

and Mumbai have a good infrastructure of natural gas distribution. This

infrastructure is being extended to commercial hotels in these cities.

These large hotels also have a good supply of LPG gas for their cooking

requirements. So, availability of fuels is another advantageous factor for

the adoption of fuel cell technology in this market.

5.1.4 Other stationary power generation markets for fuel cells

The pulp and paper industry in India have the electricity requirement in

the range 2-50 MW. The industry also requires low and medium

pressure steam in the chemical processes of cooking raw material for

making pulp, for drying of paper and evaporation processes. The

bleaching plants also require saturated steam at around 200 oC. The

industry uses captive power generation systems mainly in the form of

diesel generators. Sometimes gas turbines or steam turbines are used

for power generation.

Fuel cell system with the capacity to produce heat (PAFC, SOFC and

MCFC) can be useful in the industry. Again the capital cost of the fuel cell

systems would be critical in their entry into this market.

Another area of fuel cell application in stationary power sector is in the

dairy industries most of which are in the western and north-western

parts of the country. These industries currently use diesel generators or

gas turbine based captive power generation systems. These dairy

industries in western India have easy access to natural gas. Other fuels

such as biomass and biogas are also available in these areas. Thus, fuel

availability is a major advantage for fuel cell applications in these

industries.

Power cuts in the urban area have created a market for standby/back up

power generation systems used by domestic users. The backup power

load ranges from 0.3 kW to 5 kW depending upon the requirements of

the domestic user. Diesel, petrol and kerosene generators and battery

banks (DC to AC inverters) are the most commonly adopted power

generation systems used by domestic users. The problem with diesel,

petrol and kerosene based generators lie in the pollution and noise

caused by these systems. The inverts are also not very efficient while

charging and discharging cycles. PEMFC based systems can be good

alternative for domestic users but they face a stiff competition from

conventional generators in terms of their costs.

The automobile industry in India is one of the India's fastest growing industrial

sectors. Still, the penetration in this sector is quite low which indicates towards

a huge potential for growth. The Indian automobile industry can be classified

as follows:

lLight duty 2- and 3-wheeled vehicles, passenger car

lHeavy duty vehicles including buses and trucks

The following section discusses the market potential of fuel cells and recent

market developments in both of these categories.

5.2.1 Light Duty Vehicles

Majority of light duty vehicles in India belong to 2- and 3-whelled

vehicles category. Two wheeled scooters and motor-cycles are the main

mode of transport for the Indian middle class homes which constitute a

large market. As per the NHERM, activities related to adoption of

hydrogen based technologies in this vehicle segment have already

started. Currently the focus is on the development of hydrogen powered

IC engines rather than adoption of fuel cells.

Domestic manufacturers such as Mahindra & Mahindra have developed

a hydrogen IC engine based vehicle 'HyAlfa' (as described in the earlier

part of the report). Bajaj have developed hydrogen powered three

wheeler vehicle. Companies are involved in developing hybrid versions

of 2- and 3-wheeled vehicles. But lack of hydrogen infrastructure in

majority of Indian cities has kept these vehicles from coming into the

market. Most of such vehicles are in the demonstration stages in Delhi,

where they have developed a hydrogen/CNG infrastructure. Fuel cell

application in this area would not be possible in the near term. This is due

to high capital costs associated with fuel cell systems, which makes it

hard for the consumers in this category to adapt this technology. Indian

middle class consumers would find it hard to invest a substantial amount

on a two wheeler where the gasoline based vehicles are available at

substantially cheap prices. Similarly, fuel cell costs may be prohibitively

high for an Indian autorickshaw operator. With huge skilled labour force

in India for maintenance, it is possible that the fuel cell applications in

India may not need be as sophisticated as that of developed world, where

labour force is dwindling and costly. This may bring down the cost of fuel

cell and may become competitive with the IC engine based vehicles.

5.2 Fuel cell markets in automotive sector

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Fuel cells which can simultaneously supply electricity, steam and hot

water will be an attractive option to hotel owners. PAFC, MCFC and SOFC

power plants are best suited for this case. A clean and noise free energy

generation process with ease of operation can be considered as factors

which will drive fuel cells entry in this market.

Availability of fuel for such plants will be another important factor in this

market. Some of the cities in India, mainly metropolitan cities like Delhi

and Mumbai have a good infrastructure of natural gas distribution. This

infrastructure is being extended to commercial hotels in these cities.

These large hotels also have a good supply of LPG gas for their cooking

requirements. So, availability of fuels is another advantageous factor for

the adoption of fuel cell technology in this market.

5.1.4 Other stationary power generation markets for fuel cells

The pulp and paper industry in India have the electricity requirement in

the range 2-50 MW. The industry also requires low and medium

pressure steam in the chemical processes of cooking raw material for

making pulp, for drying of paper and evaporation processes. The

bleaching plants also require saturated steam at around 200 oC. The

industry uses captive power generation systems mainly in the form of

diesel generators. Sometimes gas turbines or steam turbines are used

for power generation.

Fuel cell system with the capacity to produce heat (PAFC, SOFC and

MCFC) can be useful in the industry. Again the capital cost of the fuel cell

systems would be critical in their entry into this market.

Another area of fuel cell application in stationary power sector is in the

dairy industries most of which are in the western and north-western

parts of the country. These industries currently use diesel generators or

gas turbine based captive power generation systems. These dairy

industries in western India have easy access to natural gas. Other fuels

such as biomass and biogas are also available in these areas. Thus, fuel

availability is a major advantage for fuel cell applications in these

industries.

Power cuts in the urban area have created a market for standby/back up

power generation systems used by domestic users. The backup power

load ranges from 0.3 kW to 5 kW depending upon the requirements of

the domestic user. Diesel, petrol and kerosene generators and battery

banks (DC to AC inverters) are the most commonly adopted power

generation systems used by domestic users. The problem with diesel,

petrol and kerosene based generators lie in the pollution and noise

caused by these systems. The inverts are also not very efficient while

charging and discharging cycles. PEMFC based systems can be good

alternative for domestic users but they face a stiff competition from

conventional generators in terms of their costs.

The automobile industry in India is one of the India's fastest growing industrial

sectors. Still, the penetration in this sector is quite low which indicates towards

a huge potential for growth. The Indian automobile industry can be classified

as follows:

lLight duty 2- and 3-wheeled vehicles, passenger car

lHeavy duty vehicles including buses and trucks

The following section discusses the market potential of fuel cells and recent

market developments in both of these categories.

5.2.1 Light Duty Vehicles

Majority of light duty vehicles in India belong to 2- and 3-whelled

vehicles category. Two wheeled scooters and motor-cycles are the main

mode of transport for the Indian middle class homes which constitute a

large market. As per the NHERM, activities related to adoption of

hydrogen based technologies in this vehicle segment have already

started. Currently the focus is on the development of hydrogen powered

IC engines rather than adoption of fuel cells.

Domestic manufacturers such as Mahindra & Mahindra have developed

a hydrogen IC engine based vehicle 'HyAlfa' (as described in the earlier

part of the report). Bajaj have developed hydrogen powered three

wheeler vehicle. Companies are involved in developing hybrid versions

of 2- and 3-wheeled vehicles. But lack of hydrogen infrastructure in

majority of Indian cities has kept these vehicles from coming into the

market. Most of such vehicles are in the demonstration stages in Delhi,

where they have developed a hydrogen/CNG infrastructure. Fuel cell

application in this area would not be possible in the near term. This is due

to high capital costs associated with fuel cell systems, which makes it

hard for the consumers in this category to adapt this technology. Indian

middle class consumers would find it hard to invest a substantial amount

on a two wheeler where the gasoline based vehicles are available at

substantially cheap prices. Similarly, fuel cell costs may be prohibitively

high for an Indian autorickshaw operator. With huge skilled labour force

in India for maintenance, it is possible that the fuel cell applications in

India may not need be as sophisticated as that of developed world, where

labour force is dwindling and costly. This may bring down the cost of fuel

cell and may become competitive with the IC engine based vehicles.

5.2 Fuel cell markets in automotive sector

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The other kind of heavy vehicles in India, trucks show very little scope for

fuel cell adoption. These trucks are mostly operated by private owners.

Fuel cell operated trucks should be affordable and operation wise less

expensive so that the owners do not incur loss. These owners would not

be willing to invest in this technology unless the capital costs become

low. Also, the operation of these trucks is very rough and runs for long

hours. The fuel cell systems in such vehicles should be rugged and

reliable with low maintenance costs. These factors impose further

restrictions for the fuel cell technology to be implemented in such

vehicles. The only option is to run fuel cell for auxiliary power unit

required in truck with the present state-of-art of FC technology.

There is a small window for the entry of fuel cells in the niche vehicles

market. These vehicles can be forklift trucks in the warehouses of the

industries like food processing and microelectronics manufacturing.

Such industries require zero emissions vehicles and mostly use battery

run electric vehicles to which fuel cell based vehicles will be a good

alternative. Also, some airports in the country can switch to fuel cell

operated vehicle fleet to decrease the noise and air pollution inside the

airport premise. Some monumental sites like Taj Mahal in city of Agra

impose severe restrictions on the use of fossil fuel based vehicles near

the premise. Sites like these can be a good market for fuel cell operated

vehicles as they are already using electric vehicles.

Another important issue will be the durability of fuel cell based vehicles

given the near continuous operation of 3 wheelers and bad condition of

Indian roads which are often filled with potholes. So, market potential

for fuel cell based 2- and 3- wheelers in quite limited in India.

Passenger car market in India presents an interesting picture. This

sector is growing at a very rapid pace which has led to many

international automobile manufacturers to enter the Indian market.

Apart from a number of large domestic players, Indian automobile sector

now has several world known automobile manufacturers, which sell

their products in the premium segment of the market.

The domestic manufacturers in this market are looking for alternate

fuelling options. Various activities regarding the development of

alternate fuelled vehicles are being carried out by these car companies.

Details of these activities have been covered in the previous section of

the report.

Again a look at the hydrogen fuel infrastructure condition in India tells us

that commercialization of fuel cell based passenger cars in not an

immediate term option. Also the capital costs related with these systems

make it hard to commercialize such vehicles in Indian markets. Although,

fuel cell based vehicles can be a good option to battery based electric

vehicles as range extenders which have a very small market in India at

present. Delhi government gives tax sops to manufacturer and users of

battery operated vehicles, which is a good sign to start with. Such

benefits may be extended to fuel cell operated vehicles in future during

implementation stage.

5.2.2 Heavy Duty Vehicles

Buses in India show a promising future for the adoption of fuel cell

technology. A number of manufacturers in this industry in India are

showing a lot of interest for the development of fuel cell based

demonstration units. Operation of buses in many cities is by state run

enterprises. Also, in many metro cities government is planning to impose

some environmental constraints on public transport systems of which

buses are an integral part. A good example of this is the conversion of city

buses in Delhi to CNG fueled buses in 2001. In near future buses seem to

be the most promising option for fuel cell technology implementation.

Although, high capital costs will still hinder this technology to come in

the market, but fuel cell buses for demonstration purposes have

sufficient scope.

Two of the biggest manufacturers (TATA and Ashok Leyland) in this

sector have started developing buses based on hydrogen technologies.

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The other kind of heavy vehicles in India, trucks show very little scope for

fuel cell adoption. These trucks are mostly operated by private owners.

Fuel cell operated trucks should be affordable and operation wise less

expensive so that the owners do not incur loss. These owners would not

be willing to invest in this technology unless the capital costs become

low. Also, the operation of these trucks is very rough and runs for long

hours. The fuel cell systems in such vehicles should be rugged and

reliable with low maintenance costs. These factors impose further

restrictions for the fuel cell technology to be implemented in such

vehicles. The only option is to run fuel cell for auxiliary power unit

required in truck with the present state-of-art of FC technology.

There is a small window for the entry of fuel cells in the niche vehicles

market. These vehicles can be forklift trucks in the warehouses of the

industries like food processing and microelectronics manufacturing.

Such industries require zero emissions vehicles and mostly use battery

run electric vehicles to which fuel cell based vehicles will be a good

alternative. Also, some airports in the country can switch to fuel cell

operated vehicle fleet to decrease the noise and air pollution inside the

airport premise. Some monumental sites like Taj Mahal in city of Agra

impose severe restrictions on the use of fossil fuel based vehicles near

the premise. Sites like these can be a good market for fuel cell operated

vehicles as they are already using electric vehicles.

Another important issue will be the durability of fuel cell based vehicles

given the near continuous operation of 3 wheelers and bad condition of

Indian roads which are often filled with potholes. So, market potential

for fuel cell based 2- and 3- wheelers in quite limited in India.

Passenger car market in India presents an interesting picture. This

sector is growing at a very rapid pace which has led to many

international automobile manufacturers to enter the Indian market.

Apart from a number of large domestic players, Indian automobile sector

now has several world known automobile manufacturers, which sell

their products in the premium segment of the market.

The domestic manufacturers in this market are looking for alternate

fuelling options. Various activities regarding the development of

alternate fuelled vehicles are being carried out by these car companies.

Details of these activities have been covered in the previous section of

the report.

Again a look at the hydrogen fuel infrastructure condition in India tells us

that commercialization of fuel cell based passenger cars in not an

immediate term option. Also the capital costs related with these systems

make it hard to commercialize such vehicles in Indian markets. Although,

fuel cell based vehicles can be a good option to battery based electric

vehicles as range extenders which have a very small market in India at

present. Delhi government gives tax sops to manufacturer and users of

battery operated vehicles, which is a good sign to start with. Such

benefits may be extended to fuel cell operated vehicles in future during

implementation stage.

5.2.2 Heavy Duty Vehicles

Buses in India show a promising future for the adoption of fuel cell

technology. A number of manufacturers in this industry in India are

showing a lot of interest for the development of fuel cell based

demonstration units. Operation of buses in many cities is by state run

enterprises. Also, in many metro cities government is planning to impose

some environmental constraints on public transport systems of which

buses are an integral part. A good example of this is the conversion of city

buses in Delhi to CNG fueled buses in 2001. In near future buses seem to

be the most promising option for fuel cell technology implementation.

Although, high capital costs will still hinder this technology to come in

the market, but fuel cell buses for demonstration purposes have

sufficient scope.

Two of the biggest manufacturers (TATA and Ashok Leyland) in this

sector have started developing buses based on hydrogen technologies.

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Electrocoagulation for the treatment of industry effluent

Dr. Anil. K. SarohaDepartment of Chemical Engineering

Indian Institute of Technology, Delhi

Electrocoagulation has recently attracted attention as a potential technique for treating

industrial wastewaters due to its versatility and environmental compatibility. This method

uses direct current source between metal electrodes immersed in the effluent, which causes

the dissolution of electrode plates into the effluent. The metal ions, at an appropriate pH, can

form wide range of coagulated species and metal hydroxides that destabilize and aggregate

particles or precipitate and adsorb the dissolved contaminants. Therefore, the objective of

the present manuscript is to review the potential of electrocoagulation for the treatment of

industrial effluent generated from different type of industries.

Electrocoagulation (EC) involves many chemical and physical phenomena that make use

of consumable electrodes to generate ions into the pollutant system. In an

electrocoagulation process the coagulating ions are produced in situ and it involves the

following successive stages:

lAnode dissolution,

lFormation of OH- ions and H2 at the cathode

lElectrolytic reactions at electrode surfaces,

lAdsorption of coagulant on colloidal pollutants, and

lRemoval of colloids by sedimentation or flotation.

In electrocoagulation process, the electrode or electrode assembly is usually connected to

an external DC source and the important parameter is the selection of the electrode

material and the mode of combination of anode and cathode. The electrode material

should be non-toxic to human health and environment. The most common electrode

materials used for electrocoagulation are aluminum, iron and steel as they are cheap,

readily available, non-toxic and very effective. The different combinations (Al/Al, Al/Fe,

Fe/Al, Fe/Fe) of electrodes for wastewater treatment have also been used. When

aluminum and iron are used as anode material, metal ions are released from anode and

many ionic monomeric hydrolysis species are formed, depending on the pH of the solution.

The main reactions occurring for aluminum and iron electrodes are as follows:

For Aluminum electrodes

Oxidation reaction takes place at the anode

3+ -Al → Al (aq) + 3e (1)(s)

Reduction reaction takes place at the cathode

- -3 H O + 3e → (3/2) H + 3 OH (2) 2 2

Overall reaction during electrolysis

3+ (3-n) 4+ 5+Al →Al (OH) →Al (OH) →Al (OH) →Al complex→ Al (OH) (3)n 2 2 3 4 13 3

For Iron electrodes


2+ -Fe → Fe + 2 e (4)(s) (aq)

3+ -Fe → Fe + 3 e (5)(s) (aq)


-2 H O + 2 e → H + 2 OH- (6)2 2(g)

- -3 H O + 3e → (3/2) H + 3 OH (7)2 2


2+ -Fe + 2 OH→ Fe(OH) (8)(aq) 2(s)

3+ -Fe + 3 OH → Fe(OH) (9)(aq) 3(s)

Electrocoagulation is an efficient technique because adsorption of hydroxide on mineral

surfaces is 100 times greater on in 'situ' rather than on pre-precipitated hydroxides when

metal hydroxides are used as coagulant. Since the flocs formed by EC are relatively large,

which contain less bound water and are more stable, therefore, they can be easily removed

by filtration. It is cost-effective, and easily operable. EC needs simple equipments and can

be designed for any capacity of effluent treatment plant. Since no chemical addition is

required in this process, it reduces the possibility of generation of secondary pollutants. It

needs low current, and therefore, can be operated by green processes, such as, solar,

windmills and fuel cells. It is an environment-friendly technique since the 'electron' is the

main reagent and does not require addition of the reagents/chemicals. This will minimize

the sludge generation to a great extent and eventually eliminate some of the harmful

chemicals used as coagulants in the conventional effluent treatment methods.

Electrocoagulation can effectively destabilize small colloidal particles and generates lower

quantity of sludge compared to other processes.

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Electrocoagulation for the treatment of industry effluent

Dr. Anil. K. SarohaDepartment of Chemical Engineering

Indian Institute of Technology, Delhi

Electrocoagulation has recently attracted attention as a potential technique for treating

industrial wastewaters due to its versatility and environmental compatibility. This method

uses direct current source between metal electrodes immersed in the effluent, which causes

the dissolution of electrode plates into the effluent. The metal ions, at an appropriate pH, can

form wide range of coagulated species and metal hydroxides that destabilize and aggregate

particles or precipitate and adsorb the dissolved contaminants. Therefore, the objective of

the present manuscript is to review the potential of electrocoagulation for the treatment of

industrial effluent generated from different type of industries.

Electrocoagulation (EC) involves many chemical and physical phenomena that make use

of consumable electrodes to generate ions into the pollutant system. In an

electrocoagulation process the coagulating ions are produced in situ and it involves the

following successive stages:

lAnode dissolution,

lFormation of OH- ions and H2 at the cathode

lElectrolytic reactions at electrode surfaces,

lAdsorption of coagulant on colloidal pollutants, and

lRemoval of colloids by sedimentation or flotation.

In electrocoagulation process, the electrode or electrode assembly is usually connected to

an external DC source and the important parameter is the selection of the electrode

material and the mode of combination of anode and cathode. The electrode material

should be non-toxic to human health and environment. The most common electrode

materials used for electrocoagulation are aluminum, iron and steel as they are cheap,

readily available, non-toxic and very effective. The different combinations (Al/Al, Al/Fe,

Fe/Al, Fe/Fe) of electrodes for wastewater treatment have also been used. When

aluminum and iron are used as anode material, metal ions are released from anode and

many ionic monomeric hydrolysis species are formed, depending on the pH of the solution.

The main reactions occurring for aluminum and iron electrodes are as follows:

For Aluminum electrodes


3+ -Al → Al (aq) + 3e (1)(s)


- -3 H O + 3e → (3/2) H + 3 OH (2) 2 2


3+ (3-n) 4+ 5+Al →Al (OH) →Al (OH) →Al (OH) →Al complex→ Al (OH) (3)n 2 2 3 4 13 3

For Iron electrodes


2+ -Fe → Fe + 2 e (4)(s) (aq)

3+ -Fe → Fe + 3 e (5)(s) (aq)


-2 H O + 2 e → H + 2 OH- (6)2 2(g)

- -3 H O + 3e → (3/2) H + 3 OH (7)2 2


2+ -Fe + 2 OH→ Fe(OH) (8)(aq) 2(s)

3+ -Fe + 3 OH → Fe(OH) (9)(aq) 3(s)

Electrocoagulation is an efficient technique because adsorption of hydroxide on mineral

surfaces is 100 times greater on in 'situ' rather than on pre-precipitated hydroxides when

metal hydroxides are used as coagulant. Since the flocs formed by EC are relatively large,

which contain less bound water and are more stable, therefore, they can be easily removed

by filtration. It is cost-effective, and easily operable. EC needs simple equipments and can

be designed for any capacity of effluent treatment plant. Since no chemical addition is

required in this process, it reduces the possibility of generation of secondary pollutants. It

needs low current, and therefore, can be operated by green processes, such as, solar,

windmills and fuel cells. It is an environment-friendly technique since the 'electron' is the

main reagent and does not require addition of the reagents/chemicals. This will minimize

the sludge generation to a great extent and eventually eliminate some of the harmful

chemicals used as coagulants in the conventional effluent treatment methods.

Electrocoagulation can effectively destabilize small colloidal particles and generates lower

quantity of sludge compared to other processes.

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The advantages of electrocoagulation as compared to chemical coagulation are as follows:

l EC requires no addition of chemicals and provides better removal capabilities for the

same species than chemical coagulation

l EC removes many species that chemical coagulation cannot remove

l EC produces less sludge, thus lowering the sludge disposal cost

l EC sludge is more readily filterable and can be utilized as a soil additive.

l EC sludge contains metal oxides that pass the leachability test.

l EC technique needs minimal startup time; the process can be started by turning on the

switch

Some of the limitations of the electrochemical coagulation are as follows:

1. The sacrificial anodes need to be replaced periodically.

2. Electrocoagulation requires a minimum conductivity depending on reactor

design, limiting its use with water containing low dissolved solids.

3. In case of the removal of organic compounds, there is a possibility of formation

of toxic chlorinated organic compounds if chlorides are also present.

Wastewater with high humic and fluvic acid content may be amenable to

the formation of trihalomethanes. If phenols and algal metabolic and

decomposition products are present, chlorine may lead to bad taste and odor.

4. An impermeable oxide film may be formed on the cathode that may interfere

with the performance of the EC cell. However, changing polarity may help reduce

this interference.

5. The cost of operating EC may be high in those areas where the cost of electricity

is high.

Electrocoagulation can be used for the removal of a wide range of pollutants using batch

and continuous mode of operation. A continuous system operates under steady state

conditions, specially a fixed pollutant loading and flow rate. By contrast, a batch reactor's

dynamic nature enables to study the range of conditions and is more suited for research

work. Continuous systems are better suited to industrial processes for large effluent

quantities whereas the batch reactors are suited to laboratory scale applications. The

continuous mode of operation is preferred due to its better control than the batch mode of

operation. The typical schematic diagram for continuous mode of operation is shown in

the figure.

The efficiency of the electrocoagulation depends on many operational parameters such as

conductivity of the solution, arrangement of electrode, electrode shape, type of power

supply, pH of the solution, current density, distance between the electrodes, agitation

speed, electrolysis time, initial pollutant concentration, electrolyte concentration,

retention time and passivation of the electrode.

Cost analysis plays an important role in industrial wastewater treatment technique as the

waste water treatment technique should be cost attractive. The operating cost can be

calculated by the following equations:

Electrode consumption

3Electrode consumption ELC (kg/m ) = (10)

Energy consumption

3Energy consumption ENC (kwh/m ) = (11)

Chemical consumption

3Chemical consumption CC (kg of chemical /m ) = (12)

Operating cost

where

a =Cost of electricity/ kwh; b =Cost of electrode /kg electrode;

c = Cost of chemical /kg of chemical I = Applied current (A)

3t = Electrolysis time (h) U = Applied voltage (volt) V= Volume of treated effluent (m )

Sum of all chemical used in kgsm of treated effluent

kg of electrode dissolved3m of treated effluent

UxIxt

V

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The advantages of electrocoagulation as compared to chemical coagulation are as follows:

l EC requires no addition of chemicals and provides better removal capabilities for the

same species than chemical coagulation

l EC removes many species that chemical coagulation cannot remove

l EC produces less sludge, thus lowering the sludge disposal cost

l EC sludge is more readily filterable and can be utilized as a soil additive.

l EC sludge contains metal oxides that pass the leachability test.

l EC technique needs minimal startup time; the process can be started by turning on the

switch

Some of the limitations of the electrochemical coagulation are as follows:

1. The sacrificial anodes need to be replaced periodically.

2. Electrocoagulation requires a minimum conductivity depending on reactor

design, limiting its use with water containing low dissolved solids.

3. In case of the removal of organic compounds, there is a possibility of formation

of toxic chlorinated organic compounds if chlorides are also present.

Wastewater with high humic and fluvic acid content may be amenable to

the formation of trihalomethanes. If phenols and algal metabolic and

decomposition products are present, chlorine may lead to bad taste and odor.

4. An impermeable oxide film may be formed on the cathode that may interfere

with the performance of the EC cell. However, changing polarity may help reduce

this interference.

5. The cost of operating EC may be high in those areas where the cost of electricity

is high.

Electrocoagulation can be used for the removal of a wide range of pollutants using batch

and continuous mode of operation. A continuous system operates under steady state

conditions, specially a fixed pollutant loading and flow rate. By contrast, a batch reactor's

dynamic nature enables to study the range of conditions and is more suited for research

work. Continuous systems are better suited to industrial processes for large effluent

quantities whereas the batch reactors are suited to laboratory scale applications. The

continuous mode of operation is preferred due to its better control than the batch mode of

operation. The typical schematic diagram for continuous mode of operation is shown in

the figure.

The efficiency of the electrocoagulation depends on many operational parameters such as

conductivity of the solution, arrangement of electrode, electrode shape, type of power

supply, pH of the solution, current density, distance between the electrodes, agitation

speed, electrolysis time, initial pollutant concentration, electrolyte concentration,

retention time and passivation of the electrode.

Cost analysis plays an important role in industrial wastewater treatment technique as the

waste water treatment technique should be cost attractive. The operating cost can be

calculated by the following equations:

Electrode consumption

3Electrode consumption ELC (kg/m ) = (10)

Energy consumption

3Energy consumption ENC (kwh/m ) = (11)

Chemical consumption

3Chemical consumption CC (kg of chemical /m ) = (12)

Operating cost

where

a =Cost of electricity/ kwh; b =Cost of electrode /kg electrode;

c = Cost of chemical /kg of chemical I = Applied current (A)

3t = Electrolysis time (h) U = Applied voltage (volt) V= Volume of treated effluent (m )

Sum of all chemical used in kgsm of treated effluent

kg of electrode dissolved3m of treated effluent

UxIxt

V

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Experiments were performed at the laboratory scale to explore the potential of

electrocoagulation for the treatment of effluent generated from various industries such as

electroplating industry, distillery and textile dye industry. The following observations

were made:

Electroplating Industry: The permissible limits in industrial effluent discharge for

hexavalent chromium and total chromium (trivalent and hexavalent) are 0.1 mg/L and 2

mg/L respectively. The real electroplating industry effluent containing Cr (III) and Cr (VI)

was characterized using the standard Diphenylcarbazide (DPC) method. A 100 %

chromium removal efficiency was obtained for both, trivalent and hexavalent chromium,

for an electrolysis time of 45 min. at 4 pH. It was found that Cr (VI) is initially reduced to Cr

(III) in the acidic medium. An increase in the pH of the effluent was also noticed in the

acidic medium due to the generation of hydroxyl ions. Experiments were performed for

the removal of chromium using ferric chloride as the coagulant and it was found that

electrocoagulation is more efficient and relatively faster compared to chemical

coagulation.

Distillery Spent Wash: Distillery spent wash is a potential source of water pollution as it

contains high content of organic & volatile matter. The characteristics of distillery spent

wash depend on the quality of the feed stocks and the various aspects of the ethanol

production process. The spent wash is generally dark brown liquid with an unbearable

odor. It is acidic in nature with high biological oxygen demand (BOD), chemical oxygen

demand (COD) and high concentration of mineral salts.

Although it does not contain toxic substances, its discharge without proper treatment will

impart color and lead to the depletion of dissolved oxygen of the receiving water stream.

Various physical, chemical and biological techniques are used for the treatment of

distillery spent wash before its discharge to the aqueous ecosystem. Bio-methanation of

distillery spent wash followed by aerobic treatment is the commonly used technique for

the treatment of distillery spent wash. Electrochemical treatment of distillery spent wash

was carried out using different combinations of aluminum and iron electrodes in batch

mode of operation. The spent wash was characterized for various parameters as per

standard method of analysis and the treatment results were analyzed in terms of chemical

oxygen demand (COD) removal efficiency of the spent wash. It was observed that

aluminum electrodes were more suitable for treatment of distillery spent wash as

compared to iron electrodes. The maximum COD removal efficiency of 81.3% was

obtained with Al- Al electrodes at the current density of 0.187 A/cm2 and pH 3 for an

electrolysis time of 2 h.

Textile Dyeing Industry: The textile industry has high impact on the environment as it

uses large volumes of water and chemicals in the textile chemical processing.

The large consumption of water results in generation of huge amounts of effluent, which

needs to be treated before discharging into the aqueous ecosystem. The effluent generally

contains a number of contaminants including acids, bases, total dissolved solids (TDS),

heavy metals, toxic compounds, and colored materials (dyes and pigments) which are

clearly visible even if they are present in very low concentrations. Coloring matter is the

major contaminant in the textile effluent and has to be removed before discharging it into

the aqueous ecosystem. Without proper treatment, the colored effluent creates an

aesthetic problem and its color discourages the downstream use of wastewater. Aesthetic

merit, gas solubility and water transparencies are affected by the presence of dyes even in

small amount or concentrations. The removal of colored material from wastewater has

been rated to be relatively more important than the removal of soluble colorless organic

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Experiments were performed at the laboratory scale to explore the potential of

electrocoagulation for the treatment of effluent generated from various industries such as

electroplating industry, distillery and textile dye industry. The following observations

were made:

Electroplating Industry: The permissible limits in industrial effluent discharge for

hexavalent chromium and total chromium (trivalent and hexavalent) are 0.1 mg/L and 2

mg/L respectively. The real electroplating industry effluent containing Cr (III) and Cr (VI)

was characterized using the standard Diphenylcarbazide (DPC) method. A 100 %

chromium removal efficiency was obtained for both, trivalent and hexavalent chromium,

for an electrolysis time of 45 min. at 4 pH. It was found that Cr (VI) is initially reduced to Cr

(III) in the acidic medium. An increase in the pH of the effluent was also noticed in the

acidic medium due to the generation of hydroxyl ions. Experiments were performed for

the removal of chromium using ferric chloride as the coagulant and it was found that

electrocoagulation is more efficient and relatively faster compared to chemical

coagulation.

Distillery Spent Wash: Distillery spent wash is a potential source of water pollution as it

contains high content of organic & volatile matter. The characteristics of distillery spent

wash depend on the quality of the feed stocks and the various aspects of the ethanol

production process. The spent wash is generally dark brown liquid with an unbearable

odor. It is acidic in nature with high biological oxygen demand (BOD), chemical oxygen

demand (COD) and high concentration of mineral salts.

Although it does not contain toxic substances, its discharge without proper treatment will

impart color and lead to the depletion of dissolved oxygen of the receiving water stream.

Various physical, chemical and biological techniques are used for the treatment of

distillery spent wash before its discharge to the aqueous ecosystem. Bio-methanation of

distillery spent wash followed by aerobic treatment is the commonly used technique for

the treatment of distillery spent wash. Electrochemical treatment of distillery spent wash

was carried out using different combinations of aluminum and iron electrodes in batch

mode of operation. The spent wash was characterized for various parameters as per

standard method of analysis and the treatment results were analyzed in terms of chemical

oxygen demand (COD) removal efficiency of the spent wash. It was observed that

aluminum electrodes were more suitable for treatment of distillery spent wash as

compared to iron electrodes. The maximum COD removal efficiency of 81.3% was

obtained with Al- Al electrodes at the current density of 0.187 A/cm2 and pH 3 for an

electrolysis time of 2 h.

Textile Dyeing Industry: The textile industry has high impact on the environment as it

uses large volumes of water and chemicals in the textile chemical processing.

The large consumption of water results in generation of huge amounts of effluent, which

needs to be treated before discharging into the aqueous ecosystem. The effluent generally

contains a number of contaminants including acids, bases, total dissolved solids (TDS),

heavy metals, toxic compounds, and colored materials (dyes and pigments) which are

clearly visible even if they are present in very low concentrations. Coloring matter is the

major contaminant in the textile effluent and has to be removed before discharging it into

the aqueous ecosystem. Without proper treatment, the colored effluent creates an

aesthetic problem and its color discourages the downstream use of wastewater. Aesthetic

merit, gas solubility and water transparencies are affected by the presence of dyes even in

small amount or concentrations. The removal of colored material from wastewater has

been rated to be relatively more important than the removal of soluble colorless organic

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substances, which usually contribute the major fraction of biochemical oxygen demand.

Electrolysis experiments were conducted for the treatment of real effluent collected from

a textile industry containing Reactive Black B, Orange 3R and Yellow GR dye. The inter-

electrode distance was kept at 3 cm. for a constant density of 0.0625A/cm2. The

electrolysis was carried out for 120 min and a color removal efficiency of 93.5 %, 92 % and

91.2 % was obtained for Reactive Black B, Orange 3R and Yellow GR dye respectively. The

real textile effluent was also treated using aluminum sulphate as a chemical coagulant. No

significant color removal efficiency (< 5 %) was obtained using the chemical coagulation

as chemical coagulation is not effective with azo, reactive, acid and basic dyes. The reactive

dye coagulates but does not sediment.

Experiments were conducted to treat the effluent collected from a small scale textile

dyeing unit in a local market using electrocoagulation. The effluent contained four

different dyes (Reactive Yellow 86, Indanthrene Blue RS, Basic GR 4 and Reactive Yellow

145 dyes). A color removal efficiency of more than 97 % was obtained for all the four dyes

for the electrolysis duration of 90 min. A comparison of the color removal efficiency

obtained using electrocoagulation was made with the color removal efficiency obtained

using chemical coagulation and electrochemical treatment was found to be superior. The

conventional biological treatment may be inadequate since one of the dyes is toxic in

nature. Therefore, it can be concluded that electrochemical treatment can be used for the

treatment of the small scale textile dyeing unit effluent.

The rapid urbanization and industrialization in the developing countries is creating high

levels of water pollution due to harmful industrial effects and sewage discharges. The

characteristics of industrial effluents in terms of nature of contaminates, their

concentrations, treatment technique and required disposal method vary significantly

depending on the type of industry. Further, the choice an effluent treatment technique is

governed by various parameters such as the contaminates, their concentration, volume

to be treated and toxicity to microbes. Electrocoagulation is an attractive method for

the treatment of various kinds of wastewater, by virtue of various benefits including

environmental capability, versatility, energy efficiency, safety, selectivity and cost

effectiveness. The process is characterized by simple equipment, easy operation, a

shortened reactive retention period, a reduction or absorbance of equipment for

adding chemicals and decreased amount of precipitate on sludge which sediments

rapidly and retain less water.

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substances, which usually contribute the major fraction of biochemical oxygen demand.

Electrolysis experiments were conducted for the treatment of real effluent collected from

a textile industry containing Reactive Black B, Orange 3R and Yellow GR dye. The inter-

electrode distance was kept at 3 cm. for a constant density of 0.0625A/cm2. The

electrolysis was carried out for 120 min and a color removal efficiency of 93.5 %, 92 % and

91.2 % was obtained for Reactive Black B, Orange 3R and Yellow GR dye respectively. The

real textile effluent was also treated using aluminum sulphate as a chemical coagulant. No

significant color removal efficiency (< 5 %) was obtained using the chemical coagulation

as chemical coagulation is not effective with azo, reactive, acid and basic dyes. The reactive

dye coagulates but does not sediment.

Experiments were conducted to treat the effluent collected from a small scale textile

dyeing unit in a local market using electrocoagulation. The effluent contained four

different dyes (Reactive Yellow 86, Indanthrene Blue RS, Basic GR 4 and Reactive Yellow

145 dyes). A color removal efficiency of more than 97 % was obtained for all the four dyes

for the electrolysis duration of 90 min. A comparison of the color removal efficiency

obtained using electrocoagulation was made with the color removal efficiency obtained

using chemical coagulation and electrochemical treatment was found to be superior. The

conventional biological treatment may be inadequate since one of the dyes is toxic in

nature. Therefore, it can be concluded that electrochemical treatment can be used for the

treatment of the small scale textile dyeing unit effluent.

The rapid urbanization and industrialization in the developing countries is creating high

levels of water pollution due to harmful industrial effects and sewage discharges. The

characteristics of industrial effluents in terms of nature of contaminates, their

concentrations, treatment technique and required disposal method vary significantly

depending on the type of industry. Further, the choice an effluent treatment technique is

governed by various parameters such as the contaminates, their concentration, volume

to be treated and toxicity to microbes. Electrocoagulation is an attractive method for

the treatment of various kinds of wastewater, by virtue of various benefits including

environmental capability, versatility, energy efficiency, safety, selectivity and cost

effectiveness. The process is characterized by simple equipment, easy operation, a

shortened reactive retention period, a reduction or absorbance of equipment for

adding chemicals and decreased amount of precipitate on sludge which sediments

rapidly and retain less water.

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Strengthening of Mithi River Bridge Under N1 Taxiway at Mumbai International Airport

Dr. Gopal L. Rai, CEOR&M International Group

Abstract

I. Introduction

In the present paper we present a case of a bridge which is a part of the Taxiway in the

airport. The Mithi River in Mumbai goes below it. With the increase in plane sizes and also

increase in safety standards it was found that the bridge had to be strengthened as per the

present requirement.

The bridge was a typical multi cell structure with a bottom and a top slab in between we

had girders which were to be strengthened. The only way to reach those webs were to

puncture the bottom slab and also being a very closed and narrow tunnel like structure. It

had boasted many technical, operational and safety problems. We present in this paper the

method statement and the efforts to complete the project within time. It also shows that it

was only due to FRP composites it was possible to achieve the required deadline and also

maintaining the quality and the standard of work.

Keywords: Airport, Bridge, Strengthening, Mithi river, Fiber Wrapping, Carbon Laminate

Strengthening of RCC structural elements is a common task for maintenance now

days. For the purpose of strengthening, several materials and methods are

available such as sprayed concrete, ferro-cement, steel plate and fibre reinforced

polymer (FRP). Sprayed concrete is the oldest materials amongst the group and is

the most common method of repairing and strengthening of reinforced concrete

structures. Among all of the strengthening materials, steel plate and FRP laminate

are the most common and effective materials due to their several advantages.

FRP for civil engineering structures are being increasingly studied in recent years.

These materials are being used in the aerospace, automotive and shipbuilding

industries for almost two decades. In general, FRP offer excellent resistance to

corrosion, good fatigue resistance (with the possible exception of some glass-

based FRP), low density, high stiffness and strength, and a very low coefficient of

thermal expansion in the fibre orientation. FRP materials as having superior

mechanical and physical properties than steel, particularly with respect to tensile

and fatigue strengths. The FRP is usually considered only for special applications,

such as in non magnetic structures, or for use in aggressive corrosive

environments. However, the usage of FRP can be more economical than using steel

plates. This is because the material costs in a rehabilitation project rarely exceed

20 percent of the total cost of the repair. Several fibre reinforced polymer (FRP)

systems are now commercially available for the external strengthening of concrete

structures. The fibre materials commonly used in these systems include glass,

aramid, and carbon.

Mumbai international airport [1].

Chhatrapati Shivaji International Airport , formerly Sahar International Airport, is

the primary international airport in Mumbai, India, and is named after the 17th

century Maratha Emperor, Chhatrapati Shivaji Bhosle.

The airport is South Asia's second busiest airport in terms of passenger traffic and

the busiest airport in India in terms of international passenger traffic and the

second busiest in terms of overall passenger traffic. The airport is one amongst a

few airports in the world to be located within the city's municipal limits. The mithi

river flows below the runway and the taxiways of the airport.

The strengthening of Mithi River bridges was done twice including the present

bridge. The previous strengthening of runway bridge is briefly described below

and then the phase 2 of the project i.e. the Taxiway bridge.

In the first Phase, the bridge under the runway was strengthened. The bridge

structure is a reinforced concrete structure, earlier designed for smaller aircrafts.

But the bridge won't be sufficient to carry the loads of the current design of

aircrafts. Hence a need for strengthening the bridge arose and considering all the

available techniques, FRP laminate bonding was suggested.

The bridge in this case was a T-beam type bridge with two main beams running

through the length of the bridge. Fig 1 shows the application of Fiber and

Laminates for strengthening of structural members.:

II. Strengthening of the Bridge Under Runway [2]

Fig. 1 Application of FRP laminates to the T-Beam at the site

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Strengthening of Mithi River Bridge Under N1 Taxiway at Mumbai International Airport

Dr. Gopal L. Rai, CEOR&M International Group

Abstract

I. Introduction

In the present paper we present a case of a bridge which is a part of the Taxiway in the

airport. The Mithi River in Mumbai goes below it. With the increase in plane sizes and also

increase in safety standards it was found that the bridge had to be strengthened as per the

present requirement.

The bridge was a typical multi cell structure with a bottom and a top slab in between we

had girders which were to be strengthened. The only way to reach those webs were to

puncture the bottom slab and also being a very closed and narrow tunnel like structure. It

had boasted many technical, operational and safety problems. We present in this paper the

method statement and the efforts to complete the project within time. It also shows that it

was only due to FRP composites it was possible to achieve the required deadline and also

maintaining the quality and the standard of work.

Keywords: Airport, Bridge, Strengthening, Mithi river, Fiber Wrapping, Carbon Laminate

Strengthening of RCC structural elements is a common task for maintenance now

days. For the purpose of strengthening, several materials and methods are

available such as sprayed concrete, ferro-cement, steel plate and fibre reinforced

polymer (FRP). Sprayed concrete is the oldest materials amongst the group and is

the most common method of repairing and strengthening of reinforced concrete

structures. Among all of the strengthening materials, steel plate and FRP laminate

are the most common and effective materials due to their several advantages.

FRP for civil engineering structures are being increasingly studied in recent years.

These materials are being used in the aerospace, automotive and shipbuilding

industries for almost two decades. In general, FRP offer excellent resistance to

corrosion, good fatigue resistance (with the possible exception of some glass-

based FRP), low density, high stiffness and strength, and a very low coefficient of

thermal expansion in the fibre orientation. FRP materials as having superior

mechanical and physical properties than steel, particularly with respect to tensile

and fatigue strengths. The FRP is usually considered only for special applications,

such as in non magnetic structures, or for use in aggressive corrosive

environments. However, the usage of FRP can be more economical than using steel

plates. This is because the material costs in a rehabilitation project rarely exceed

20 percent of the total cost of the repair. Several fibre reinforced polymer (FRP)

systems are now commercially available for the external strengthening of concrete

structures. The fibre materials commonly used in these systems include glass,

aramid, and carbon.

Mumbai international airport [1].

Chhatrapati Shivaji International Airport , formerly Sahar International Airport, is

the primary international airport in Mumbai, India, and is named after the 17th

century Maratha Emperor, Chhatrapati Shivaji Bhosle.

The airport is South Asia's second busiest airport in terms of passenger traffic and

the busiest airport in India in terms of international passenger traffic and the

second busiest in terms of overall passenger traffic. The airport is one amongst a

few airports in the world to be located within the city's municipal limits. The mithi

river flows below the runway and the taxiways of the airport.

The strengthening of Mithi River bridges was done twice including the present

bridge. The previous strengthening of runway bridge is briefly described below

and then the phase 2 of the project i.e. the Taxiway bridge.

In the first Phase, the bridge under the runway was strengthened. The bridge

structure is a reinforced concrete structure, earlier designed for smaller aircrafts.

But the bridge won't be sufficient to carry the loads of the current design of

aircrafts. Hence a need for strengthening the bridge arose and considering all the

available techniques, FRP laminate bonding was suggested.

The bridge in this case was a T-beam type bridge with two main beams running

through the length of the bridge. Fig 1 shows the application of Fiber and

Laminates for strengthening of structural members.:

II. Strengthening of the Bridge Under Runway [2]

Fig. 1 Application of FRP laminates to the T-Beam at the site

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III. Strengthening of bridge under the Taxiway

Phase II

After successful completion of the Mithi River Bridge below the Runway. A few

years later in 2012 it was also found that the bridge under the taxiway N1 (Fig 2)

was also to be strengthened. The bridge under consideration was important as it

has movement of Planes over it.

Fig 2: Bridge no 2 over the N1 Taxiway to be strengthened

The structure is a multi cell box girder type structure whose cross-section is shown in

Fig 3.

Fig 3: The cross section of the bridge superstructure.

The bridge consisted of 3 main areas.

1. The taxiway portion

2. The Shoulder area

3. And the Service area

These portions/Areas are joined by expansion Joints.

The deficiencies were found by doing analysis using STAAD-Pro.

It was found that the Shoulder and the Main Taxiway portions are safe for using in the

existing loads over them. But the service portion was found to be deficient.

The main deficiencies found in the service portions were as follows.

1. The Webs were deficient in flexure at the Mid-span as well as at the Junction.

2. The Webs were also found to be deficient in shear.

3. The Cantilever Portion was also found deficient for the existing Loads.

4. The Top slab was deficient in flexure as well as shear

Numerous modelling and analytical tools were used to find out the present status of the

bridge. The area to be strengthened was decided and the methodology was finalized for

strengthening.

Fig 4: Side view of the bridge and the area where scaffolding is erected is the area to be strengthened.

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III. Strengthening of bridge under the Taxiway

Phase II

After successful completion of the Mithi River Bridge below the Runway. A few

years later in 2012 it was also found that the bridge under the taxiway N1 (Fig 2)

was also to be strengthened. The bridge under consideration was important as it

has movement of Planes over it.

Fig 2: Bridge no 2 over the N1 Taxiway to be strengthened

The structure is a multi cell box girder type structure whose cross-section is shown in

Fig 3.

Fig 3: The cross section of the bridge superstructure.

The bridge consisted of 3 main areas.

1. The taxiway portion

2. The Shoulder area

3. And the Service area

These portions/Areas are joined by expansion Joints.

The deficiencies were found by doing analysis using STAAD-Pro.

It was found that the Shoulder and the Main Taxiway portions are safe for using in the

existing loads over them. But the service portion was found to be deficient.

The main deficiencies found in the service portions were as follows.

1. The Webs were deficient in flexure at the Mid-span as well as at the Junction.

2. The Webs were also found to be deficient in shear.

3. The Cantilever Portion was also found deficient for the existing Loads.

4. The Top slab was deficient in flexure as well as shear

Numerous modelling and analytical tools were used to find out the present status of the

bridge. The area to be strengthened was decided and the methodology was finalized for

strengthening.

Fig 4: Side view of the bridge and the area where scaffolding is erected is the area to be strengthened.

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The Strengthening Methodology had the following proposals

1. For treatment of girders at mid-span for flexure Pre-Cured Carbon Fibre Laminate

100x1.4mm were proposed to be provided so as to increase flexure capacity

according to revised loadings after casting the new RCC slab at top. It is shown in Fig 5.

Fig 5: Proposed Strengthening from below of the webs for flexure.

2. Flexure Deficiency at support for Inner girders were proposed to be addressed by the

New RCC slab being casted at the top. The reinforcements of slab will be taking care of

the flexure deficiency at support.

3. For Shear enhancement of the Inner Webs. Shear Deficiency at the inner Webs and the

Outer Webs were proposed to be retrofitted with One Ply of 430 GSM Carbon Fiber

Wrap in 0 Degree Direction. On top of this One ply of 990 GSM Glass fiber in 90 Degree

Direction Wraps.

Fig 6: Cross Section, Fiber wrapping

4. For cantilever spans Structural Steel has to be put at a uniform spacing to support the

deficiency and transfer the load properly to the girders which are already

strengthened.

5. The Deficiencies in flexure and shear of the top slab will be taken care by the New RCC

slab which is to be casted above the top slab.

6. For Slab deficiency in shear in the cantilever slab we will have to provide two Box MC

100 made by welding 2 ISMC 100 together as shown in fig 7. The sections will be pre-

fabricated and will be coated with anti-corrosive PU- Aliphatic Coating which is also

UV Resistant.

Fig 7: Cantilever slab enhancement

Step by Step Process and various Actions taken

Following was the step by step sequence of strengthening procedures

1. Creating a way to reach the site: As the Mithi River has moving water the Bunds have to

be prepared and the diversion has to be made so that the area in which strengthening

has to be done is accessible.

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The Strengthening Methodology had the following proposals

1. For treatment of girders at mid-span for flexure Pre-Cured Carbon Fibre Laminate

100x1.4mm were proposed to be provided so as to increase flexure capacity

according to revised loadings after casting the new RCC slab at top. It is shown in Fig 5.

Fig 5: Proposed Strengthening from below of the webs for flexure.

2. Flexure Deficiency at support for Inner girders were proposed to be addressed by the

New RCC slab being casted at the top. The reinforcements of slab will be taking care of

the flexure deficiency at support.

3. For Shear enhancement of the Inner Webs. Shear Deficiency at the inner Webs and the

Outer Webs were proposed to be retrofitted with One Ply of 430 GSM Carbon Fiber

Wrap in 0 Degree Direction. On top of this One ply of 990 GSM Glass fiber in 90 Degree

Direction Wraps.

Fig 6: Cross Section, Fiber wrapping

4. For cantilever spans Structural Steel has to be put at a uniform spacing to support the

deficiency and transfer the load properly to the girders which are already

strengthened.

5. The Deficiencies in flexure and shear of the top slab will be taken care by the New RCC

slab which is to be casted above the top slab.

6. For Slab deficiency in shear in the cantilever slab we will have to provide two Box MC

100 made by welding 2 ISMC 100 together as shown in fig 7. The sections will be pre-

fabricated and will be coated with anti-corrosive PU- Aliphatic Coating which is also

UV Resistant.

Fig 7: Cantilever slab enhancement

Step by Step Process and various Actions taken

Following was the step by step sequence of strengthening procedures

1. Creating a way to reach the site: As the Mithi River has moving water the Bunds have to

be prepared and the diversion has to be made so that the area in which strengthening

has to be done is accessible.

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2. After making the proper access all sludge was removed scaffolding was erected for

creating a proper working platform at the site. The whole area was also tested with

pesticides for having a disease free environment at the site.

Fig 8: The approach for going below the girders

Fig 9: The way after stopping and diverting the Mithi River and Pest control in progress.

Fig 10: Cleaning all the sludge and application of pesticides at the site

3. It was required to make holes for access inside the webs for strengthening the webs.

Inside it was required to ventilate the whole area properly so that while working on

the webs inside it is a safe place to work in.

Fig 11: The access holes made for getting to webs and the duct view from inside

4. After the access was done the surface where work has to be carried out has to be

grinded and well cleaned.

As it is a closed space ventilation was done by designing a ventilation system. Air

blowers and exhaust fans were provided in all working bays. The air quality was

checked everyday for making sure the work is safely done without any complications.

Fig 12: Ventilation with Blowers and holes for exhaust of air during works

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2. After making the proper access all sludge was removed scaffolding was erected for

creating a proper working platform at the site. The whole area was also tested with

pesticides for having a disease free environment at the site.

Fig 8: The approach for going below the girders

Fig 9: The way after stopping and diverting the Mithi River and Pest control in progress.

Fig 10: Cleaning all the sludge and application of pesticides at the site

3. It was required to make holes for access inside the webs for strengthening the webs.

Inside it was required to ventilate the whole area properly so that while working on

the webs inside it is a safe place to work in.

Fig 11: The access holes made for getting to webs and the duct view from inside

4. After the access was done the surface where work has to be carried out has to be

grinded and well cleaned.

As it is a closed space ventilation was done by designing a ventilation system. Air

blowers and exhaust fans were provided in all working bays. The air quality was

checked everyday for making sure the work is safely done without any complications.

Fig 12: Ventilation with Blowers and holes for exhaust of air during works

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Fig 13: measurement of various gas levels for maintaining healthy environment and detecting any of the anomalies before accident.

5. After the access was done the Webs were strngthened and repaired by using Low

Viscosity grouts and Polymer Modified Concrete.

Fig 15: Repair Work under Progress a) b) Low Viscosity Grouting c) Grinding and Resurfacing.

Polymer Modified Mortar

6. The Strengthening of webs in flexure is carried out using 100x1.4mm Carbon

Composite Laminates below the web and above the top slab.

Fig 16: The Cross-sectional positions of laminates for Flexural enhancement in the middle bay.

Fig 17: Flexural Strengthening by Carbon Laminates which were also PU Coated.

7. Fiber wrapping with Glass and carbon over the webs were done. The purpose of

applying fiber wrap system as discussed was to enhance the shear deficiency. The

process of fiber wrapping is fast and due to which the target of completing the whole

project in 30 Days was achieved. It also allowed a better working space without any

accidents.

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Fig 13: measurement of various gas levels for maintaining healthy environment and detecting any of the anomalies before accident.

5. After the access was done the Webs were strngthened and repaired by using Low

Viscosity grouts and Polymer Modified Concrete.

Fig 15: Repair Work under Progress a) b) Low Viscosity Grouting c) Grinding and Resurfacing.

Polymer Modified Mortar

6. The Strengthening of webs in flexure is carried out using 100x1.4mm Carbon

Composite Laminates below the web and above the top slab.

Fig 16: The Cross-sectional positions of laminates for Flexural enhancement in the middle bay.

Fig 17: Flexural Strengthening by Carbon Laminates which were also PU Coated.

7. Fiber wrapping with Glass and carbon over the webs were done. The purpose of

applying fiber wrap system as discussed was to enhance the shear deficiency. The

process of fiber wrapping is fast and due to which the target of completing the whole

project in 30 Days was achieved. It also allowed a better working space without any

accidents.

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Fig 18: Fiber wrapping of all 11 Bays with 1st layer of Carbon Wrap and 2nd Layer of Glass fiber wrap.

8. Steel sections were put for enhancing the end cantilever portions in flexure and shear.

Fig 19: Steel Trusses for strengthening the cantilever portion

Fig 20: Fixed Structural Steel trusses at the cantilever portion.

9. The manholes present in the cells were also required to be strengthened and it was

done by using carbon laminate system for there better workability and spped of

application.

Fig 21:Strengthened opening by means of Carbon Composite Laminates.

10. Completion of Work: After doing all the strengthening work the Manholes made for

doing work were closed. For closing the holes Cured Glass Fibre Composite sheet was

used with fiber anchors fastened at the ends.

The holes will be drilled around the holes as shown in the Fig. Then the Pre-Cured

fiber composite sheet is applied and fiber anchors are put at various positions as

shown.

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Fig 18: Fiber wrapping of all 11 Bays with 1st layer of Carbon Wrap and 2nd Layer of Glass fiber wrap.

8. Steel sections were put for enhancing the end cantilever portions in flexure and shear.

Fig 19: Steel Trusses for strengthening the cantilever portion

Fig 20: Fixed Structural Steel trusses at the cantilever portion.

9. The manholes present in the cells were also required to be strengthened and it was

done by using carbon laminate system for there better workability and spped of

application.

Fig 21:Strengthened opening by means of Carbon Composite Laminates.

10. Completion of Work: After doing all the strengthening work the Manholes made for

doing work were closed. For closing the holes Cured Glass Fibre Composite sheet was

used with fiber anchors fastened at the ends.

The holes will be drilled around the holes as shown in the Fig. Then the Pre-Cured

fiber composite sheet is applied and fiber anchors are put at various positions as

shown.

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Fig 22: Closing of Man holes with pre-cured Fibre Sheet.

Fig 23: Closing of Ventilation Holes with Pre-Cured Fibre Sheet.

Fig 24 : Final View of Completed Strengthening and the water being released in Mithi River.

This project is one of the difficult sites to be handeld as there are lot of safety and working

issues which were taken care and addressed properly for the site to be finished on time.

The time line and

The bridge shown here was one of the very important bridges in day to day functioning of

the bridge. Strengthening it within the time frame and cost was a challenging job. Right

from stopping the river to closing all the holes involved a coordinated and well qualified

people working in sync from all the agencies from the client to the main contractor to the

specialized agencies. The tests carried out subsequently gave satisfactorily results and the

bridge commenced in the operations of the airport.

The high strength, high fatigue resistance, lightweight, and corrosion resistance of

composites are highly desirable characteristics for bridge applications. Currently, these

new materials are a direct technology transfer from the aerospace industry, and they are

far more advanced than those required by civil applications. Most of the advanced

composite materials that are cured at high temperature produce high quality components

and possess excellent characteristics. In bridge applications, resins as the binders for the

fibre and adhesives for joints and connections that can adequately cure at ambient

temperature and still offer comparable quality and characteristics are more desirable and

practical. More research is needed to develop the most effective and durable resin

formulations. More efficient manufacturing and effective production methods for large

volume panels and higher modulus materials are needed to make it more cost effective for

composites to compete in the civil infrastructure. At the present time, the direct use of

fibre composites from the aerospace industry is not cost effective as compared to

conventional materials in bridge applications.

If the cost constraint is kept aside, the fiber wrapping system has been proved to be a

system which has many added advantages over conventional strengthening processes. It

has been proved in laboratory as well in real civil projects that this system is effective and is

useful in real life. As the economy is moving ahead and infrastructure development is

catching its pace, demand for fiber reinforced polymer in civil construction is slowly

increasing and becoming acceptable.

1. http://en.wikipedia.org/wiki/Chhatrapati_Shivaji_International_Airport

2. Singh A.K., Rai G., Jangid R.S. , Strengthening of runway bridge at mumbai airport using

frp.

3. ACI Committee 440. State-of-the-Art Report on FRP for Concrete Structures. ACI

440R-96, Manual of Concrete Practice, ACI, Farmington Hills, MI, 1996, 68 pp.

Summary and Conclusions

References:

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Fig 22: Closing of Man holes with pre-cured Fibre Sheet.

Fig 23: Closing of Ventilation Holes with Pre-Cured Fibre Sheet.

Fig 24 : Final View of Completed Strengthening and the water being released in Mithi River.

This project is one of the difficult sites to be handeld as there are lot of safety and working

issues which were taken care and addressed properly for the site to be finished on time.

The time line and

The bridge shown here was one of the very important bridges in day to day functioning of

the bridge. Strengthening it within the time frame and cost was a challenging job. Right

from stopping the river to closing all the holes involved a coordinated and well qualified

people working in sync from all the agencies from the client to the main contractor to the

specialized agencies. The tests carried out subsequently gave satisfactorily results and the

bridge commenced in the operations of the airport.

The high strength, high fatigue resistance, lightweight, and corrosion resistance of

composites are highly desirable characteristics for bridge applications. Currently, these

new materials are a direct technology transfer from the aerospace industry, and they are

far more advanced than those required by civil applications. Most of the advanced

composite materials that are cured at high temperature produce high quality components

and possess excellent characteristics. In bridge applications, resins as the binders for the

fibre and adhesives for joints and connections that can adequately cure at ambient

temperature and still offer comparable quality and characteristics are more desirable and

practical. More research is needed to develop the most effective and durable resin

formulations. More efficient manufacturing and effective production methods for large

volume panels and higher modulus materials are needed to make it more cost effective for

composites to compete in the civil infrastructure. At the present time, the direct use of

fibre composites from the aerospace industry is not cost effective as compared to

conventional materials in bridge applications.

If the cost constraint is kept aside, the fiber wrapping system has been proved to be a

system which has many added advantages over conventional strengthening processes. It

has been proved in laboratory as well in real civil projects that this system is effective and is

useful in real life. As the economy is moving ahead and infrastructure development is

catching its pace, demand for fiber reinforced polymer in civil construction is slowly

increasing and becoming acceptable.

1. http://en.wikipedia.org/wiki/Chhatrapati_Shivaji_International_Airport

2. Singh A.K., Rai G., Jangid R.S. , Strengthening of runway bridge at mumbai airport using

frp.

3. ACI Committee 440. State-of-the-Art Report on FRP for Concrete Structures. ACI

440R-96, Manual of Concrete Practice, ACI, Farmington Hills, MI, 1996, 68 pp.

Summary and Conclusions

References:

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Technical Paper- Introduction to Poly Tetra Fluoroethylene ( PTFE ) & Its Applications

Kapil Malhotra, Vice President Marketing and

Rajeev Chauhan, Sr. General ManagerR & D, Gujarat Fluoro Chemicals Limited

1. PTFE

1.1. Introduction

1.2. Raw Materials

Polytetrafluoroethylene (PTFE) is one of a class of plastics known as

fluoropolymers. A polymer is a compound formed by a chemical reaction which

combines molecules into groups of repeating unit to form large molecules.

Many common synthetic fibers are polymers, such as polyester and nylon.

PTFE is the polymerized form of tetrafluoroethylene (TFE). PTFE has many

unique properties, which make it valuable in scores of applications. It has a

very high melting point, and is also stable at very low temperatures. It can be

dissolved by nothing but hot fluorine gas or certain molten metals, so it is

extremely resistant to corrosion. It is also very slick and slippery. This makes it

an excellent material for coating machine parts which are subjected to heat,

wear, and friction, for laboratory equipment which must resist corrosive

chemicals, and as a coating for cookware and utensils. PTFE is used to impart

stain-resistance to fabrics, carpets, and wall coverings, and as weatherproofing

on outdoor signs. PTFE has low electrical conductivity, so it makes a good

electrical insulator. It is used to insulate high performance wire and cable, and

it is essential to the manufacture of semi-conductors. PTFE is also found in a

variety of medical applications, such as in vascular grafts. A fiberglass fabric

with PTFE coating serves to protect the roofs of airports and stadiums. PTFE

can even be incorporated into fiber for weaving socks. The low friction of the

PTFE makes the socks exceptionally smooth, protecting feet from blisters.

PTFE is polymerized from of the chemical compound tetrafluoroethylene, or

TFE. A non-stick pan is composed of varying non-stick layers.

TFE is synthesized from fluorspar, hydrofluoric acid, and chloroform. These

ingredients are combined under high heat, an action known as pyrolosis. TFE is

a colorless, odorless, nontoxic gas which is, however, extremely flammable. It is

stored as a liquid, at low temperature and pressure. Because of the difficulty of

transporting the flammable TFE, PTFE manufacturers also manufacture their

own TFE on site. The polymerization process uses a very small amount of other

chemicals as initiators. Various initiators can be used, including ammonium

persulfate or disuccinic acid peroxide. The other essential ingredient of the

polymerization process is water.

PTFE can be produced in a number of ways, depending on the particular traits

desired for the end product. Many specifics of the process are proprietary

secrets of the manufacturers. There are two main methods of producing PTFE.

One is suspension polymerization and other is dispersion polymerization. In

the suspension method, the TFE is polymerized in water, resulting in grains of

PTFE. The grains can be further processed into pellets which can be molded. In

the dispersion method, the resulting PTFE is a milky paste which can be further

processed into two forms wet dispersion and fine powder (coagulated fine

dispersion) also commonly known as paste extrusion grade. Wet PTFE

dispersion can be formulated by addition of various organic and inorganic

additives and converted into coatings. Fine powders are used in articles

processed by special technique known as paste extrusion or calendering

Manufacturing of PTFE begin by synthesizing TFE. The three ingredients of

TFE, fluorspar, hydrofluoric acid, and chloroform are combined in a chemical

reaction chamber heated to between 1094-1652°F (590-900°C). The resultant

gas is then cooled, and distilled to remove any impurities to obtain highly pure

TFE gas.

1.4.2. Suspension Polymerization

The reaction chamber is filled with purified water and a reaction agent

or initiator, a chemical that will set off the formation of the polymer. The

TFE is piped into the reaction chamber. As the TFE meets the initiator, it

begins to polymerize. The resulting PTFE forms solid grains that float to

the surface of the water. As this is happening, the reaction chamber is

mechanically shaken. The chemical reaction inside the chamber gives

off heat, so the chamber is cooled by the circulation of cold water or

another coolant in a jacket around its outsides. Controls automatically

shut off the supply of TFE after a certain weight inside the chamber is

reached. The water is drained out of the chamber, leaving a mess of

stringy PTFE which looks somewhat like grated coconut.

Next, the PTFE is dried and fed into a mill. The mill pulverizes the PTFE

with rotating blades, producing a material with the consistency of wheat

1.3. The Manufacturing Process

1.4.1. Making the TFE

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Technical Paper- Introduction to Poly Tetra Fluoroethylene ( PTFE ) & Its Applications

Kapil Malhotra, Vice President Marketing and

Rajeev Chauhan, Sr. General ManagerR & D, Gujarat Fluoro Chemicals Limited

1. PTFE

1.1. Introduction

1.2. Raw Materials

Polytetrafluoroethylene (PTFE) is one of a class of plastics known as

fluoropolymers. A polymer is a compound formed by a chemical reaction which

combines molecules into groups of repeating unit to form large molecules.

Many common synthetic fibers are polymers, such as polyester and nylon.

PTFE is the polymerized form of tetrafluoroethylene (TFE). PTFE has many

unique properties, which make it valuable in scores of applications. It has a

very high melting point, and is also stable at very low temperatures. It can be

dissolved by nothing but hot fluorine gas or certain molten metals, so it is

extremely resistant to corrosion. It is also very slick and slippery. This makes it

an excellent material for coating machine parts which are subjected to heat,

wear, and friction, for laboratory equipment which must resist corrosive

chemicals, and as a coating for cookware and utensils. PTFE is used to impart

stain-resistance to fabrics, carpets, and wall coverings, and as weatherproofing

on outdoor signs. PTFE has low electrical conductivity, so it makes a good

electrical insulator. It is used to insulate high performance wire and cable, and

it is essential to the manufacture of semi-conductors. PTFE is also found in a

variety of medical applications, such as in vascular grafts. A fiberglass fabric

with PTFE coating serves to protect the roofs of airports and stadiums. PTFE

can even be incorporated into fiber for weaving socks. The low friction of the

PTFE makes the socks exceptionally smooth, protecting feet from blisters.

PTFE is polymerized from of the chemical compound tetrafluoroethylene, or

TFE. A non-stick pan is composed of varying non-stick layers.

TFE is synthesized from fluorspar, hydrofluoric acid, and chloroform. These

ingredients are combined under high heat, an action known as pyrolosis. TFE is

a colorless, odorless, nontoxic gas which is, however, extremely flammable. It is

stored as a liquid, at low temperature and pressure. Because of the difficulty of

transporting the flammable TFE, PTFE manufacturers also manufacture their

own TFE on site. The polymerization process uses a very small amount of other

chemicals as initiators. Various initiators can be used, including ammonium

persulfate or disuccinic acid peroxide. The other essential ingredient of the

polymerization process is water.

PTFE can be produced in a number of ways, depending on the particular traits

desired for the end product. Many specifics of the process are proprietary

secrets of the manufacturers. There are two main methods of producing PTFE.

One is suspension polymerization and other is dispersion polymerization. In

the suspension method, the TFE is polymerized in water, resulting in grains of

PTFE. The grains can be further processed into pellets which can be molded. In

the dispersion method, the resulting PTFE is a milky paste which can be further

processed into two forms wet dispersion and fine powder (coagulated fine

dispersion) also commonly known as paste extrusion grade. Wet PTFE

dispersion can be formulated by addition of various organic and inorganic

additives and converted into coatings. Fine powders are used in articles

processed by special technique known as paste extrusion or calendering

Manufacturing of PTFE begin by synthesizing TFE. The three ingredients of

TFE, fluorspar, hydrofluoric acid, and chloroform are combined in a chemical

reaction chamber heated to between 1094-1652°F (590-900°C). The resultant

gas is then cooled, and distilled to remove any impurities to obtain highly pure

TFE gas.

1.4.2. Suspension Polymerization

The reaction chamber is filled with purified water and a reaction agent

or initiator, a chemical that will set off the formation of the polymer. The

TFE is piped into the reaction chamber. As the TFE meets the initiator, it

begins to polymerize. The resulting PTFE forms solid grains that float to

the surface of the water. As this is happening, the reaction chamber is

mechanically shaken. The chemical reaction inside the chamber gives

off heat, so the chamber is cooled by the circulation of cold water or

another coolant in a jacket around its outsides. Controls automatically

shut off the supply of TFE after a certain weight inside the chamber is

reached. The water is drained out of the chamber, leaving a mess of

stringy PTFE which looks somewhat like grated coconut.

Next, the PTFE is dried and fed into a mill. The mill pulverizes the PTFE

with rotating blades, producing a material with the consistency of wheat

1.3. The Manufacturing Process

1.4.1. Making the TFE

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flour. This fine powder is difficult to mold. It has "poor flow," meaning it

cannot be processed easily in automatic equipment. Like wheat flour, it

might have both lumps and air pockets. So manufacturers convert this

fine powder into larger granules by a process called agglomeration. This

can be done in several ways. One method is to mix the PTFE powder with

a solvent such as acetone and tumble it in a rotating drum. The PTFE

grains stick together, forming small pellets. The pellets are then dried in

an oven.

The PTFE pellets can be molded into parts using a variety of techniques.

However, PTFE may be sold in bulk already pre-molded into so-called

billets, which are solid cylinders of PTFE. The billets may be 5 ft (1.5 m)

tall. These can be machined into sheets or desired final shape. To form

the billet, PTFE pellets are poured into a cylindrical stainless steel mold.

The mold is loaded onto a hydraulic press, which is something like a

large cabinet equipped with weighted ram. The ram drops down into the

mold and exerts required force on the PTFE. After a certain time period,

the mold is removed from the press and the PTFE is unmolded, this step

is called preforming. After preforming preform is allowed to rest for

stress relaxation, and then placed in an oven for a final step called

sintering. Sintering is the process of controlled heating and cooling of

PTFE preform.

The molded PTFE is heated in the sintering oven for several hours, until

it gradually reaches a temperature of around 707°F (375°C). This is

above the melting point of PTFE. The PTFE particles coalesce and the

material becomes gel-like. Then the PTFE is gradually cooled. The

finished billet can be shipped to customers, who will slice or shave it into

smaller pieces into desired final shape.

1.4.3. Dispersion polymerization

Polymerization of PTFE by the dispersion method leads to either fine

powder or a paste-like substance, which is more useful for coatings and

finishes. TFE is introduced into a water-filled reactor along with the

initiating chemical. Instead of being vigorously shaken, as in the

suspension process, the reaction chamber is only agitated gently. The

PTFE forms into tiny beads. Some of the water is removed, by filtering or

by adding chemicals which cause the PTFE beads to settle. The result is a

milky substance called PTFE dispersion. It can be used as a liquid,

especially in applications like fabric finishes or metal coating. Or it may

be dried into a fine powder used to produce extruded articles.

1.5. Quality Control

Quality control measures take place both at the primary PTFE manufacturing

facility and at plants where further processing steps, such as coatings and

molding are done. In the primary manufacturing facility, standard industrial

procedures are followed to determine purity of ingredients, accuracy of

temperatures, etc. End products are tested for conformance to international

standards like ASTM or ISO. For PTFE specific gravity, bulk density, particle size

and mechanical properties are tested for every lot as per instruction given in

standards.

2. PTFE - PRODUCT INFORMATION

Polytetrafluoroethylene (PTFE) is a synthetic fluoropolymer of tetrafluoroethylene

that finds numerous applications. PTFE is most well known by the DuPont brand

name Teflon.

PTFE is a fluorocarbon solid, as it is a high-molecular-weight compound consisting

wholly of carbon and fluorine. PTFE is hydrophobic: neither water nor water-

containing substances are wet by PTFE, as fluorocarbons demonstrate mitigated

London dispersion forces due to the high electronegativity of fluorine. PTFE has one

of the lowest coefficients of friction against any solid.

PTFE is used as a non-stick coating for pans and other cookware. It is very non-

reactive, partly because of the strength of carbon-fluorine bonds, and so it is often

used in containers and pipework for reactive and corrosive chemicals. Where used as

a lubricant, PTFE reduces friction, wear, and energy consumption of machinery.

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flour. This fine powder is difficult to mold. It has "poor flow," meaning it

cannot be processed easily in automatic equipment. Like wheat flour, it

might have both lumps and air pockets. So manufacturers convert this

fine powder into larger granules by a process called agglomeration. This

can be done in several ways. One method is to mix the PTFE powder with

a solvent such as acetone and tumble it in a rotating drum. The PTFE

grains stick together, forming small pellets. The pellets are then dried in

an oven.

The PTFE pellets can be molded into parts using a variety of techniques.

However, PTFE may be sold in bulk already pre-molded into so-called

billets, which are solid cylinders of PTFE. The billets may be 5 ft (1.5 m)

tall. These can be machined into sheets or desired final shape. To form

the billet, PTFE pellets are poured into a cylindrical stainless steel mold.

The mold is loaded onto a hydraulic press, which is something like a

large cabinet equipped with weighted ram. The ram drops down into the

mold and exerts required force on the PTFE. After a certain time period,

the mold is removed from the press and the PTFE is unmolded, this step

is called preforming. After preforming preform is allowed to rest for

stress relaxation, and then placed in an oven for a final step called

sintering. Sintering is the process of controlled heating and cooling of

PTFE preform.

The molded PTFE is heated in the sintering oven for several hours, until

it gradually reaches a temperature of around 707°F (375°C). This is

above the melting point of PTFE. The PTFE particles coalesce and the

material becomes gel-like. Then the PTFE is gradually cooled. The

finished billet can be shipped to customers, who will slice or shave it into

smaller pieces into desired final shape.

1.4.3. Dispersion polymerization

Polymerization of PTFE by the dispersion method leads to either fine

powder or a paste-like substance, which is more useful for coatings and

finishes. TFE is introduced into a water-filled reactor along with the

initiating chemical. Instead of being vigorously shaken, as in the

suspension process, the reaction chamber is only agitated gently. The

PTFE forms into tiny beads. Some of the water is removed, by filtering or

by adding chemicals which cause the PTFE beads to settle. The result is a

milky substance called PTFE dispersion. It can be used as a liquid,

especially in applications like fabric finishes or metal coating. Or it may

be dried into a fine powder used to produce extruded articles.

1.5. Quality Control

Quality control measures take place both at the primary PTFE manufacturing

facility and at plants where further processing steps, such as coatings and

molding are done. In the primary manufacturing facility, standard industrial

procedures are followed to determine purity of ingredients, accuracy of

temperatures, etc. End products are tested for conformance to international

standards like ASTM or ISO. For PTFE specific gravity, bulk density, particle size

and mechanical properties are tested for every lot as per instruction given in

standards.

2. PTFE - PRODUCT INFORMATION

Polytetrafluoroethylene (PTFE) is a synthetic fluoropolymer of tetrafluoroethylene

that finds numerous applications. PTFE is most well known by the DuPont brand

name Teflon.

PTFE is a fluorocarbon solid, as it is a high-molecular-weight compound consisting

wholly of carbon and fluorine. PTFE is hydrophobic: neither water nor water-

containing substances are wet by PTFE, as fluorocarbons demonstrate mitigated

London dispersion forces due to the high electronegativity of fluorine. PTFE has one

of the lowest coefficients of friction against any solid.

PTFE is used as a non-stick coating for pans and other cookware. It is very non-

reactive, partly because of the strength of carbon-fluorine bonds, and so it is often

used in containers and pipework for reactive and corrosive chemicals. Where used as

a lubricant, PTFE reduces friction, wear, and energy consumption of machinery.

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2.1. Form

2.2. Function

PTFE is a completely fluorinated polymer manufactured when the monomer

tetrafluoroethylene (TFE) undergoes free radical vinyl polymerization. As a

monomer, TFE is made up of a pair of double-bonded carbon atoms, both of

which have two fluorine atoms covalently bonded to them. Thus the name:

"tetra" means there are four atoms bonded to the carbons; "fluoro" means those

bonded atoms are fluorine, and "ethylene" means the carbons are joined by a

double bond as in the classic ethylene structure. (Ethylene has hydrogen atoms

attached to the carbons), but TFE has fluorine in place of the hydrogen. When

TFE polymerizes into PTFE, the carbon-to-carbon double bond becomes a

single bond and a long chain of carbon atoms is formed, this chain is the

polymer's backbone, as shown in above figure.

With a ratio of four fluorine atoms to every two carbon atoms, the backbone is

essentially shielded from contact. It's almost impossible for any other chemical

structure to gain access to the carbon atoms. This gives PTFE extraordinary

chemical resistance. It's tough for a solvent or other agent to degrade the

backbone if the carbon is "out of reach." Even if an agent could gain access, the

carbon-to-fluorine bonds have high bond disassociation energy, making them

almost unbreakable.

What makes PTFE so slippery? By its very nature, the fluorine in PTFE repels

everything. As part of a molecule, fluorine is decidedly "anti-social." It wants to

get as far away from other molecules as possible. Anything getting close is

automatically repelled, and repelled molecules can't stick to the PTFE surface.

The inability of other materials to stick to PTFE makes it perfect for applications

requiring a low coefficient of friction. The only thing slicker than PTFE is ice!

Because they are essentially self-lubricating, PTFE parts are ideal for

applications in which external lubricants (such as oils and greases) can't be

used.

As the most chemically resistant thermoplastic polymer available, PTFE is inert

to almost all chemicals and solvents, allowing PTFE parts to function well in

acids, alcohols, alkalis, esters, ketones, and hydrocarbons. There are only a few

substances harmful to PTFE, notably fluorine, chlorine trifluoride, and molten

alkali metal solutions at high pressures.

PTFE can also withstand a wide range of temperatures -500° to 500° F (-260° to

260° C). Because it's non-flammable and doesn't dissipate heat, PTFE is often

used as a thermal insulator (as in welding equipment). At the other extreme,

PTFE is widely used in very cold environments (such as space). Other important

properties include resistance to both weathering and water absorption. PTFE

can also act as an electrical insulator.

Because of its chemical inertness, PTFE cannot be cross-linked like an

elastomer. Therefore it has no memory and is subject to creep (also known as

cold flow). Creep is the increasing deformation of a material under a constant

compressive load. This can be both good and bad. A little bit of creep allows

PTFE seals to conform to mating surfaces better than most other plastic seals.

Too much creep, however, and the seal is compromised. Compounding fillers are

used to control unwanted creep, as well as to improve wear, friction, and other

properties.

lExceptionally wide range of thermal applications from minus

260°C to plus 260°C

lVirtually universal chemical resistance

lLight- and weather-resistant

lResistant against hot water vapor

lVery low coefficient of friction (Excellent sliding properties)

lNon stick behavior

lNon-combustible

lGood electric and dielectric properties (Low dielectric constant,

2.1 and loss factor (0.0001)

lNo absorption of water

lPhysiologically harmless (FDA-approved for use in food industry

applications)

2.3. Characteristics of PTFE

2.4. Classification of PTFE

PTFE

Suspension Grade

Granular PTFE Modified PTFE Compounded PTFE Dry Dispersion Wet Dispersion

Dispersion Grade

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2.1. Form

2.2. Function

PTFE is a completely fluorinated polymer manufactured when the monomer

tetrafluoroethylene (TFE) undergoes free radical vinyl polymerization. As a

monomer, TFE is made up of a pair of double-bonded carbon atoms, both of

which have two fluorine atoms covalently bonded to them. Thus the name:

"tetra" means there are four atoms bonded to the carbons; "fluoro" means those

bonded atoms are fluorine, and "ethylene" means the carbons are joined by a

double bond as in the classic ethylene structure. (Ethylene has hydrogen atoms

attached to the carbons), but TFE has fluorine in place of the hydrogen. When

TFE polymerizes into PTFE, the carbon-to-carbon double bond becomes a

single bond and a long chain of carbon atoms is formed, this chain is the

polymer's backbone, as shown in above figure.

With a ratio of four fluorine atoms to every two carbon atoms, the backbone is

essentially shielded from contact. It's almost impossible for any other chemical

structure to gain access to the carbon atoms. This gives PTFE extraordinary

chemical resistance. It's tough for a solvent or other agent to degrade the

backbone if the carbon is "out of reach." Even if an agent could gain access, the

carbon-to-fluorine bonds have high bond disassociation energy, making them

almost unbreakable.

What makes PTFE so slippery? By its very nature, the fluorine in PTFE repels

everything. As part of a molecule, fluorine is decidedly "anti-social." It wants to

get as far away from other molecules as possible. Anything getting close is

automatically repelled, and repelled molecules can't stick to the PTFE surface.

The inability of other materials to stick to PTFE makes it perfect for applications

requiring a low coefficient of friction. The only thing slicker than PTFE is ice!

Because they are essentially self-lubricating, PTFE parts are ideal for

applications in which external lubricants (such as oils and greases) can't be

used.

As the most chemically resistant thermoplastic polymer available, PTFE is inert

to almost all chemicals and solvents, allowing PTFE parts to function well in

acids, alcohols, alkalis, esters, ketones, and hydrocarbons. There are only a few

substances harmful to PTFE, notably fluorine, chlorine trifluoride, and molten

alkali metal solutions at high pressures.

PTFE can also withstand a wide range of temperatures -500° to 500° F (-260° to

260° C). Because it's non-flammable and doesn't dissipate heat, PTFE is often

used as a thermal insulator (as in welding equipment). At the other extreme,

PTFE is widely used in very cold environments (such as space). Other important

properties include resistance to both weathering and water absorption. PTFE

can also act as an electrical insulator.

Because of its chemical inertness, PTFE cannot be cross-linked like an

elastomer. Therefore it has no memory and is subject to creep (also known as

cold flow). Creep is the increasing deformation of a material under a constant

compressive load. This can be both good and bad. A little bit of creep allows

PTFE seals to conform to mating surfaces better than most other plastic seals.

Too much creep, however, and the seal is compromised. Compounding fillers are

used to control unwanted creep, as well as to improve wear, friction, and other

properties.

lExceptionally wide range of thermal applications from minus

260°C to plus 260°C

lVirtually universal chemical resistance

lLight- and weather-resistant

lResistant against hot water vapor

lVery low coefficient of friction (Excellent sliding properties)

lNon stick behavior

lNon-combustible

lGood electric and dielectric properties (Low dielectric constant,

2.1 and loss factor (0.0001)

lNo absorption of water

lPhysiologically harmless (FDA-approved for use in food industry

applications)

2.3. Characteristics of PTFE

2.4. Classification of PTFE

PTFE

Suspension Grade

Granular PTFE Modified PTFE Compounded PTFE Dry Dispersion Wet Dispersion

Dispersion Grade

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2.4.1. Suspension Grade

2.4.1.1. Granular PTFE

Granular resins are made by polymerizing TFE alone by

suspension polymerization technique. The various types of

suspension grade granular PTFE are:

lGeneral molding grades: - Also known as mother grade.

PTFE obtained by crushing of polymerized reactor bead.

Average Particle Size between 150-250 µm

lFine cut grades: - Also known as non free flow grades. Post

treated PTFE obtained by milling of mother grade. Further

classified on basis of average particle size (15-50 µm)

lFree flow grades: - Obtained by agglomeration of fine cut

resin. Further Classified on basis of average particle size

(500-800 µm) and flowability

lPre-Sintered Grades: - Also known as ram extrusion grade.

Obtained by pressing and baking of fine cut resin

2.4.1.2. Modified PTFE

Granular resins are made by polymerizing TFE in the presence

of trace amounts of comonomers (less than 1%) by suspension

polymerization technique. Most general comonomer used is

Perfluoropropylvinyl Ether (PPVE). The types of modifies

PTFE are similar as of granular grade. Modified PTFE has some

advantage over conventional PTFE.

lIncreased stiffness & improved creep resistance

lWeldability (Utilizing various heat welding techniques

with moderate pressure)

lHigher dielectric strength yields - superior high-voltage

insulation

lLow micro-void content yields- improved permeation

resistance

lLonger flex life than PTFE

lPart surfaces are smoother, and less porous - components

stay clean since they are less likely to trap contaminants

lHigher transparency

2.4.1.3. Compounded PTFE

In spite of its remarkable properties, pure or 'unfilled' PTFE

was inadequate for a number of more demanding engineering

uses. In particular, its cold flow or creep kept PTFE out of

mechanical applications such as those involving very heavy

loads. In the sixties, Du Pont discovered that the physical

properties of PTFE could be improved by the addition of fillers.

A range of filled granular compounds were found to be highly

suitable for gaskets, valve seats, shaft seals piston rings, high-

voltage switches, bearings, pipe linings etc. It turned out that

through a proper combination of base resin and one or more

fillers, compounds could be tailor-made for many end-uses.

In general, the fillers were found to give:

lImproved resistance to cold flow or 'creep'

lReduced wear and friction

lIncreased stiffness

lIncreased thermal conductivity

lIncreased thermal dimensional stability

lIncreased surface hardness

lIncreased electrical conductivity

2.4.2. Dispersion Grade

2.4.2.1. Wet Dispersion

Dispersion PTFE is produced by polymerization of TFE in an

aqueous medium in the presence of an initiator and surfactant.

The polymerization does not follow a conventional emulsion

mechanism but some of the principles, which apply. The

stability of the dispersion during the polymerization, to avoid

premature coagulation, is balanced against the need to break

the emulsion to recover the PTFE. Low shear rate agitation is

maintained during the polymerization using surfactant levels

below the critical micelle concentration. The rate of

polymerization and particle shape and size are affected by the

concentration of the surfactant. Majority of the particles is

generated in the early part of polymerization and grows as the

cycle proceeds. Molecular weight and composition of within

the particle can be controlled using the polymerization

ingredients and conditions. This wet dispersion grades is used

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2.4.1. Suspension Grade

2.4.1.1. Granular PTFE

Granular resins are made by polymerizing TFE alone by

suspension polymerization technique. The various types of

suspension grade granular PTFE are:

lGeneral molding grades: - Also known as mother grade.

PTFE obtained by crushing of polymerized reactor bead.

Average Particle Size between 150-250 µm

lFine cut grades: - Also known as non free flow grades. Post

treated PTFE obtained by milling of mother grade. Further

classified on basis of average particle size (15-50 µm)

lFree flow grades: - Obtained by agglomeration of fine cut

resin. Further Classified on basis of average particle size

(500-800 µm) and flowability

lPre-Sintered Grades: - Also known as ram extrusion grade.

Obtained by pressing and baking of fine cut resin

2.4.1.2. Modified PTFE

Granular resins are made by polymerizing TFE in the presence

of trace amounts of comonomers (less than 1%) by suspension

polymerization technique. Most general comonomer used is

Perfluoropropylvinyl Ether (PPVE). The types of modifies

PTFE are similar as of granular grade. Modified PTFE has some

advantage over conventional PTFE.

lIncreased stiffness & improved creep resistance

lWeldability (Utilizing various heat welding techniques

with moderate pressure)

lHigher dielectric strength yields - superior high-voltage

insulation

lLow micro-void content yields- improved permeation

resistance

lLonger flex life than PTFE

lPart surfaces are smoother, and less porous - components

stay clean since they are less likely to trap contaminants

lHigher transparency

2.4.1.3. Compounded PTFE

In spite of its remarkable properties, pure or 'unfilled' PTFE

was inadequate for a number of more demanding engineering

uses. In particular, its cold flow or creep kept PTFE out of

mechanical applications such as those involving very heavy

loads. In the sixties, Du Pont discovered that the physical

properties of PTFE could be improved by the addition of fillers.

A range of filled granular compounds were found to be highly

suitable for gaskets, valve seats, shaft seals piston rings, high-

voltage switches, bearings, pipe linings etc. It turned out that

through a proper combination of base resin and one or more

fillers, compounds could be tailor-made for many end-uses.

In general, the fillers were found to give:

lImproved resistance to cold flow or 'creep'

lReduced wear and friction

lIncreased stiffness

lIncreased thermal conductivity

lIncreased thermal dimensional stability

lIncreased surface hardness

lIncreased electrical conductivity

2.4.2. Dispersion Grade

2.4.2.1. Wet Dispersion

Dispersion PTFE is produced by polymerization of TFE in an

aqueous medium in the presence of an initiator and surfactant.

The polymerization does not follow a conventional emulsion

mechanism but some of the principles, which apply. The

stability of the dispersion during the polymerization, to avoid

premature coagulation, is balanced against the need to break

the emulsion to recover the PTFE. Low shear rate agitation is

maintained during the polymerization using surfactant levels

below the critical micelle concentration. The rate of

polymerization and particle shape and size are affected by the

concentration of the surfactant. Majority of the particles is

generated in the early part of polymerization and grows as the

cycle proceeds. Molecular weight and composition of within

the particle can be controlled using the polymerization

ingredients and conditions. This wet dispersion grades is used

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for coating application. Wet dispersion grade are classified on

the basis of solid content.

2.4.2.2. Dry Dispersion

Dry Dispersion is also known as fine powder or coagulated

dispersion powder. The same polymerization process as

mentioned in wet dispersion makes aqueous dispersions of

PTFE as fine powder. The dispersion is concentrated and

stabilized using a variety of ionic and non-ionic surfactants or

emulsifying agents. Several concentration methods have been

reported including electrodecantation, evaporation and

thermal concentration. Emulsifying agents keep the

dispersion sufficiently stable throughout the polymerization

process so that it does not coagulate prematurely, but unstable

enough so that it can be subsequently coagulated into fine

powder. These dry powder processed by special technique

known as paste extrusion and further classification of dry

dispersion based on:

lReduction ratio (ratio of the cross-sectional area of the

preform to the cross-sectional area of the die)

lStandard specific gravity (SSG)

lStretching void index (SVI)

lExtrusion pressure

The basic advantages of Dispersion PTFE over Conventional

PTFE are:

lBetter gloss

lLow friction and antistick surface

lChemically inert to all industrial chemical and solvent

lExcellent wetting properties

lBetter surface finishing

lExcellent weldability of fabrics

lSuperior film building behavior

lImproved weatherability

2.5.Fillers for Coumpounded PTFE

2.5.1.Choice of filler

Over time, the fillers which gained popularity amongst processors and end-

users alike were glass, bronze, carbon, graphite and molybdenum disulphide.

In addition, compounds with other fillers, or combinations of fillers, or

compounds with standard fillers in non-standard percentages, have also been

developed. The percentage of filler is usually between 5 and 40% by volume.

Below 5%, the impact of the filler on most properties is insignificant and above

40 volume percent most physical properties drop sharply.

Table below shows a number of PTFE compounds generally used.

Type Filler Type % Filler

by Wt. by Vol. Gravity

% Filler Standard Specific

Glass 15% Glass 15 13.2 2.20

Glass 20% Glass 20 17.8 2.21

Glass 25% Glass 25 22.4 2.22

Glass 40% Glass 40 36.5 2.22

Moly 5% MoS2 5 2.3 2.22

Graphite 15% Graphite 15 14.5 2.12

Bronze 40% Bronze 40 14.0 3.05


Glass 20%/ Glass/ 20/5 22.7 2.20

Graphite 5% graphite

Glass 10%/ Glass/ 10/10 18.5 2.17


Glass 15%/ Glass/ MoS2 15/5 15.9 2.26

Moly 5%

Carbon 23%/ Carbon/ 23/2 28.4 2.05


Carbon 29%/ Carbon/ 29/3 35.2 2.00


Unfilled Unfilled - - 2.16

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for coating application. Wet dispersion grade are classified on

the basis of solid content.

2.4.2.2. Dry Dispersion

Dry Dispersion is also known as fine powder or coagulated

dispersion powder. The same polymerization process as

mentioned in wet dispersion makes aqueous dispersions of

PTFE as fine powder. The dispersion is concentrated and

stabilized using a variety of ionic and non-ionic surfactants or

emulsifying agents. Several concentration methods have been

reported including electrodecantation, evaporation and

thermal concentration. Emulsifying agents keep the

dispersion sufficiently stable throughout the polymerization

process so that it does not coagulate prematurely, but unstable

enough so that it can be subsequently coagulated into fine

powder. These dry powder processed by special technique

known as paste extrusion and further classification of dry

dispersion based on:

lReduction ratio (ratio of the cross-sectional area of the

preform to the cross-sectional area of the die)

lStandard specific gravity (SSG)

lStretching void index (SVI)

lExtrusion pressure

The basic advantages of Dispersion PTFE over Conventional

PTFE are:

lBetter gloss

lLow friction and antistick surface

lChemically inert to all industrial chemical and solvent

lExcellent wetting properties

lBetter surface finishing

lExcellent weldability of fabrics

lSuperior film building behavior

lImproved weatherability

2.5.Fillers for Coumpounded PTFE

2.5.1.Choice of filler

Over time, the fillers which gained popularity amongst processors and end-

users alike were glass, bronze, carbon, graphite and molybdenum disulphide.

In addition, compounds with other fillers, or combinations of fillers, or

compounds with standard fillers in non-standard percentages, have also been

developed. The percentage of filler is usually between 5 and 40% by volume.

Below 5%, the impact of the filler on most properties is insignificant and above

40 volume percent most physical properties drop sharply.

Table below shows a number of PTFE compounds generally used.

Type Filler Type % Filler

by Wt. by Vol. Gravity

% Filler Standard Specific

Glass 15% Glass 15 13.2 2.20

Glass 20% Glass 20 17.8 2.21

Glass 25% Glass 25 22.4 2.22

Glass 40% Glass 40 36.5 2.22

Moly 5% MoS2 5 2.3 2.22

Graphite 15% Graphite 15 14.5 2.12



Glass 20%/ Glass/ 20/5 22.7 2.20


Glass 10%/ Glass/ 10/10 18.5 2.17


Glass 15%/ Glass/ MoS2 15/5 15.9 2.26

Moly 5%

Carbon 23%/ Carbon/ 23/2 28.4 2.05


Carbon 29%/ Carbon/ 29/3 35.2 2.00


Unfilled Unfilled - - 2.16

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combined with graphite. The combination of the above properties makes

carbon/graphite compounds the preferred material for non-lubricated piston

rings. The use of a softer carbon has the additional advantage that it lowers tool

wear during machining, thus allowing machining to very close tolerances.

Carbon-containing compounds have some electrical conductivity and are

therefore antistatic

Base: Amorphous petroleum coke

Purity: > 99% C

Particle Size: < 75 um

Density: 4.8C

ARBON FIBRE : Addition of carbon fibre to PTFE changes its physical

properties in the same way as glass fibre does: Lower deformation under load,

higher compressive and flex modulus and increased hardness.

In general, it requires less carbon fibre than glass fibre to achieve the same

effect on PTFE. Carbon fibre is chemically inert and can be used in strong alkali

and in HF, where glass-filled compounds fail. Compounds of PTFE with carbon

fibre have the advantage of higher thermal conductivity and lower thermal

expansion coefficients than glass-filled ones with the same filler percentages,

and they are lighter.

They wear less in contract with most metals, and are also less abrasive on the

mating surface. The wear in water is particularly low. This makes carbon-fibre-

filled PTFE an excellent bearing material, especially when lubricated with

water. It is widely used in the automotive industry for bearings and seal rings,

for example in water pumps and in shock absorbers.

GRAPHITE: Graphite is a crystalline modification of high purity carbon. Its

flaky structure imparts excellent lubricity and decreased wear. Graphite is

often combined with other fillers (especially carbon and glass)

Graphite-filled PTFE has one of the lowest coefficients of friction. It has

excellent wear properties, in particular against soft metals, displays high load-

carrying capability in high-speed contact applications and is chemically inert. It

is often used in combination with other fillers.

Source: synthetic

Purity: > 99%C

Irregular shaped

Particle size: < 75 um

Density: 2.26

2.5.2.About Filler

Practically any material that can withstand the sintering temperature of PTFE

can be used as filler. Characteristics such as particle shape and size and the

chemical composition of the filler greatly affect the properties of the

compound. Also crucial is the blending process. PTFE must be blended with the

appropriate fillers (and any pigment additives which the end-user may want)

using specialised equipment to ensure that the blend is fully uniform. Improper

blending will result in a final product with poor physical properties and can also

be visually displeasing.

Listed below are some of the key fillers and their contribution to the properties

of PTFE:

GLASS : Glass fibre is the most widely used filler. It improves the creep

resistance of PTFE both at low and high temperature.

Widely used in hydraulic piston rings, glass gives good wear resistance, low

creep, and good compressive strength.

It is chemically stable and compatible to most of the fluids (except to strong

alkalis and hydrofluoric acid-HF). It has little effect on the electrical properties

of PTFE and improves its wear and friction behaviour.

An often cited problem with glass-filled PTFE is discoloration of the finished

parts, in particular on the inside of large billets. The other major disadvantage

is that glass-filled PTFE compounds are abrasive to mating surfaces, especially

in rotary applications.

Type: E-glass

Milled fibres, nominal diameter 13 um

Nominal length 0.8 mm

Aspect ratio: min. 10

Density: 2.5

CARBON : (powder or fiber) imparts excellent compression (low deformation

under load) and wear resistance, good thermal conductivity (heat dissipation),

and low permeability. Carbon-filled PTFE compounds are not as abrasive as

glass-filled compounds, but they are still more abrasive than polymer-filled

compounds. Carbon-filled compounds have excellent wear and friction

properties when combined with graphite. Carbon fiber lends better creep

resistance than carbon powder, but fiber is more expensive.

Amorphous carbon is one of the most inert fillers, except in oxidizing

environments where glass performs better. Carbon adds to the creep

resistance, increases the hardness and raises the thermal conductivity of PTFE.

Carbon-filled compounds have excellent wear properties, in particular when

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combined with graphite. The combination of the above properties makes

carbon/graphite compounds the preferred material for non-lubricated piston

rings. The use of a softer carbon has the additional advantage that it lowers tool

wear during machining, thus allowing machining to very close tolerances.

Carbon-containing compounds have some electrical conductivity and are

therefore antistatic

Base: Amorphous petroleum coke

Purity: > 99% C

Particle Size: < 75 um

Density: 4.8C

ARBON FIBRE : Addition of carbon fibre to PTFE changes its physical

properties in the same way as glass fibre does: Lower deformation under load,

higher compressive and flex modulus and increased hardness.

In general, it requires less carbon fibre than glass fibre to achieve the same

effect on PTFE. Carbon fibre is chemically inert and can be used in strong alkali

and in HF, where glass-filled compounds fail. Compounds of PTFE with carbon

fibre have the advantage of higher thermal conductivity and lower thermal

expansion coefficients than glass-filled ones with the same filler percentages,

and they are lighter.

They wear less in contract with most metals, and are also less abrasive on the

mating surface. The wear in water is particularly low. This makes carbon-fibre-

filled PTFE an excellent bearing material, especially when lubricated with

water. It is widely used in the automotive industry for bearings and seal rings,

for example in water pumps and in shock absorbers.

GRAPHITE: Graphite is a crystalline modification of high purity carbon. Its

flaky structure imparts excellent lubricity and decreased wear. Graphite is

often combined with other fillers (especially carbon and glass)

Graphite-filled PTFE has one of the lowest coefficients of friction. It has

excellent wear properties, in particular against soft metals, displays high load-

carrying capability in high-speed contact applications and is chemically inert. It

is often used in combination with other fillers.

Source: synthetic

Purity: > 99%C

Irregular shaped

Particle size: < 75 um

Density: 2.26

2.5.2.About Filler

Practically any material that can withstand the sintering temperature of PTFE

can be used as filler. Characteristics such as particle shape and size and the

chemical composition of the filler greatly affect the properties of the

compound. Also crucial is the blending process. PTFE must be blended with the

appropriate fillers (and any pigment additives which the end-user may want)

using specialised equipment to ensure that the blend is fully uniform. Improper

blending will result in a final product with poor physical properties and can also

be visually displeasing.

Listed below are some of the key fillers and their contribution to the properties

of PTFE:

GLASS : Glass fibre is the most widely used filler. It improves the creep

resistance of PTFE both at low and high temperature.

Widely used in hydraulic piston rings, glass gives good wear resistance, low

creep, and good compressive strength.

It is chemically stable and compatible to most of the fluids (except to strong

alkalis and hydrofluoric acid-HF). It has little effect on the electrical properties

of PTFE and improves its wear and friction behaviour.

An often cited problem with glass-filled PTFE is discoloration of the finished

parts, in particular on the inside of large billets. The other major disadvantage

is that glass-filled PTFE compounds are abrasive to mating surfaces, especially

in rotary applications.

Type: E-glass

Milled fibres, nominal diameter 13 um

Nominal length 0.8 mm

Aspect ratio: min. 10

Density: 2.5

CARBON : (powder or fiber) imparts excellent compression (low deformation

under load) and wear resistance, good thermal conductivity (heat dissipation),

and low permeability. Carbon-filled PTFE compounds are not as abrasive as

glass-filled compounds, but they are still more abrasive than polymer-filled

compounds. Carbon-filled compounds have excellent wear and friction

properties when combined with graphite. Carbon fiber lends better creep

resistance than carbon powder, but fiber is more expensive.

Amorphous carbon is one of the most inert fillers, except in oxidizing

environments where glass performs better. Carbon adds to the creep

resistance, increases the hardness and raises the thermal conductivity of PTFE.

Carbon-filled compounds have excellent wear properties, in particular when

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BRONZE: Bronze is an alloy of copper and tin. Addition of high percentages of

bronze powder to PTFE results in a compound having high thermal

conductivity and better creep resistance than most other compounds.

Bronze-filled materials have higher friction than other filled PTFE compounds,

but that can be improved by adding moly or graphite. Bearing and piston ring

applications often use compounds containing 55% bronze - 5% moly.

Bronze-filled PTFE is often used for components in hydraulic systems, but is not

suited for electrical applications and is attacked by certain chemicals. Bronze-

filled compounds have poorer chemical resistance than other PTFE

compounds.

Bronze has tendency to oxidise: bronze-filled compounds should therefore be

used fresh and containers should always be kept closed. Some discoloration of

the finished part during the sintering cycle is normal and has no impact on its

quality.

Cu/Sn: 9/1

Low in phosphorus/ Particle size: < 60um/ Particle shape: Spherical (Bronze

60%)

Irregular (2146-N) / Density: 8.95

MOLYBDENUM DISULFIDE (MoS2): Molybdenum disulfide adds to the

hardness and stiffness of PTFE and reduces friction. It has little effect on its

electrical properties. It improves wear resistance and further lowers the

coefficient of friction.

It is quite inert chemically and dissolves only in strongly oxidising acids. "Moly"

is typically combined with other fillers (such as glass and bronze). It is normally

used in low percentages and together with other fillers. Compounds containing

molybdenum disulfide need special attention during performing and sintering.

Source: mineral

Purity: > 98%

Particle size: < 65um

Density: 4.9

PTFE compounds have a long and ever-lengthening list of uses. The major

application industries are as given below:

lChemical industries

lPetrochemical Industries

lPharmaceutical Industries

lMechanical Industries

lAutomotive Industries

lSemiconductor Industries

lElectronics Industries

lElectrical Industries

lConstruction Industries

lAerospace Industries

2.6. Applications of PTFE

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BRONZE: Bronze is an alloy of copper and tin. Addition of high percentages of

bronze powder to PTFE results in a compound having high thermal

conductivity and better creep resistance than most other compounds.

Bronze-filled materials have higher friction than other filled PTFE compounds,

but that can be improved by adding moly or graphite. Bearing and piston ring

applications often use compounds containing 55% bronze - 5% moly.

Bronze-filled PTFE is often used for components in hydraulic systems, but is not

suited for electrical applications and is attacked by certain chemicals. Bronze-

filled compounds have poorer chemical resistance than other PTFE

compounds.

Bronze has tendency to oxidise: bronze-filled compounds should therefore be

used fresh and containers should always be kept closed. Some discoloration of

the finished part during the sintering cycle is normal and has no impact on its

quality.

Cu/Sn: 9/1

Low in phosphorus/ Particle size: < 60um/ Particle shape: Spherical (Bronze

60%)

Irregular (2146-N) / Density: 8.95

MOLYBDENUM DISULFIDE (MoS2): Molybdenum disulfide adds to the

hardness and stiffness of PTFE and reduces friction. It has little effect on its

electrical properties. It improves wear resistance and further lowers the

coefficient of friction.

It is quite inert chemically and dissolves only in strongly oxidising acids. "Moly"

is typically combined with other fillers (such as glass and bronze). It is normally

used in low percentages and together with other fillers. Compounds containing

molybdenum disulfide need special attention during performing and sintering.

Source: mineral

Purity: > 98%

Particle size: < 65um

Density: 4.9

PTFE compounds have a long and ever-lengthening list of uses. The major

application industries are as given below:

lChemical industries

lPetrochemical Industries

lPharmaceutical Industries

lMechanical Industries

lAutomotive Industries

lSemiconductor Industries

lElectronics Industries

lElectrical Industries

lConstruction Industries

lAerospace Industries

2.6. Applications of PTFE

Sem

ina

r o

n T

ech

no

log

y U

pg

rad

ati

on

in

CH

EMIC

AL

PET

RO

CH

EMIC

AL

IND

UST

RY&

Know

ledge P

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128

About Indian Institute of Technology : Delhi

About Engineers India Ltd

About IIChE

Indian Institute of Technology Delhi is one of the fifteen Institutes of Technology created as

centres of excellence for training, research and development in science, engineering and

technology in India. It has been declared as an Institution of National Importance under

the "Institutes of Technology (Amendment) Act, 1963" and has been accorded the status

of a deemed university. The Institute is engaged in research and promotion of academic

growth by offering state-of-the-art undergraduate, postgraduate and doctoral programs.

The institute undertakes collaborative projects which offer opportunities for long-term

interaction with academia and industry.

Engineers India Limited (EIL) is a public sector undertaking under th e Ministry of

Petroleum and Natural Gas, Government of India. It has emerged as Asia's leading design,

engineering and turnkey contracting Company in Petroleum, Chemicals, Petrochemicals

and Fertilizers industry. Engineers India Limited has one of the largest multi-disciplinary

engineering work forces with over 4.5 million engineering man-hours available in its

design offices along with 1.9 million man-hours of construction management services

annually.

Indian Institute of Chemical Engineers is the apex professional society of Chemical

Engineers in India, popularly abbreviated as IIChE. IIChE is a confluence of streams of

professionals from academia, research institutes and industry. It provides them the

appropriate forum for joint endeavors, hand in hand, to work for human well being

through application of chemical engineering and allied sciences. The institute is pursuing

its objective of promoting the cause of Chemical Engineering through education and

training activities. The IIChE has more than 30 regional centers operating in the country


IIT - Delhi EIL


April 2013New Delhi


&

For further details please contact...

Mr P. S. SinghHead-Chemicals Division, FICCI


Tel: +91-11-2331 6540 (Dir)

EPBX: +91-11-23738760-70 (Extn 395)

Fax: +91-11-2332 0714/2372 1504


Ms Charu SmitaAssistant Director-Chemicals Division, FICCI


Tel: +91-112335 7350 (Dir)

EPBX: +91-1123738760-70 (Extn 474)

Fax: +91-112332 0714/2372 1504


R.P. LuthraDirector Administration

Indian Institute of Chemical Engineers (Northern Regional Center)C-27, Qutab Institutional Area, New Delhi-110016

Tel. .: 011-26532060, 26533539, E-Mail : [email protected] : www.iichenrc.org

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