Molecular sieves – new opportunities and services offered ... · Molecular sieves – new opportunities and services offered by BRENNTAG and CECA . Laurentiu GHITA, Oil&Gas BDM

Molecular sieves – new opportunities and services offered by BRENNTAG and CECA

Laurentiu GHITA, Oil&Gas BDM BRENNTAG

SILIPORITE

ROMANIA 2015 - DOWNSTREAM CONFERENCE, 16 September 2015, Bucharest

Agenda

Part I : BRENNTAG and CECA in brief …

Part II : Molecular sieves basics - General and Technical aspects ● What are they like? ● How do they work? ● How to produce Molecular Sieves? Part III : Products for Refining Industry ● Range of products ● Typical application Part IV : CECA solutions for Petrochemical inducstry

Part V CECA solutions for your molecular sieve units

Part VI: CECA references

Part I – BRENNTAG in brief …

Specialty Chemicals app. 30%

Group sales 2012 over € 9 billion

Specialty Chemicals app. 30%

Industrial Chemicals app. 70%

Over 170,000 customers

Brenntag is the leading global distributor of specialties and industrial chemicals...

Europe 49%

North America

33%

Latin America

8%

Asia Pacific 7%

RoW 3%

Figures excluding RoW

North America Warehouse Sites: 138 Employees: ~3,480 Customers: ~35,000

Asia Pacific Warehouse Sites: 41 Employees: ~1,020 Customers: ~9,800

Europe Warehouse Sites: 204 Employees: ~6,118 Customers: ~115,000

Latin America Warehouse Sites: 54 Employees: ~1,234 Customers: ~18,000

…and operates a broad global network of office and warehouse locations

Part I – CECA in brief …

CECA in a snapshot

CECA is a Specialty Chemicals company, 100% Subsidiary of ARKEMA Group (France)

7 businesses with market leader positions

Sales of € 600 M

1000 employees

20 industrial plants

3 research centers

2,5% of revenue allocated to Research & Development

CECA Molecular Sieves Leading positions

N°2 Worldwide, covering all applications

Building

Automotive Petchem &

Refinery

Industrial Gases

Natural Gas

Chemicals

Food & Beverages

Pharmaceuticals

40 years experience in providing solutions…

… from design to after sales services

Our brands

CECA Molecular Sieves A Global presence

HONFLEUR (Fr)

INOWROCLAW (Pl)

PHILADELPHIA (US)

HOUSTON (US) DUBAI (UAE)

PARIS (Fr)

PERTH (Au)

TOKYO (Jp) PAU (Fr)

SAO PAOLO (Br)

BUENOS AIRES (Ar)

SEOUL (SK)

MOSCOW (Ru)

SHANGHAI (Ch)

MARKETING & SALES OFFICES R & D PLANTS 180 employees

worldwide

Part II – Molecular Sieve basics

Molecular Sieves : what are they like ?

The final material

● Powder static application ● Powder + binding clay:

– Granulation Beads – Extrusion pellets

The initial crystal

● Zeolite (alumino-silicate) ● Mainly synthetized and some natural zeolithe ● Chemical formula : (M2+ or M+

2)O•Al2O3•nSiO2•pH20

Synthetized zeolite powder

● SEM photograph

Molecular Sieves : selecting the right one ?

Ratio Si/Al = 1.25

Pore opening: 7.4 Å

13X mol sieve

Ratio Si/Al = 1

Stabilized by Na+ 4A

3A 5A

K+ exchange

Ca2+ exchange

« A » family « X » family

Molecular sieves: how does it work?

● Aluminosilicates with crystalline structure showing channels and cavities (« pores »)

● If they are small enough to enter the pores they are « adsorbed » (captured)

● The other molecules go their way (ex: methane)

● The electronic activity of the large internal surface attracts polar molecules (Van der Wiels

interaction)

Na+

● Adsorption is exothermic: ~ 1000 kcal/kg of water

● Reversible phenomena renegerable process

Which molecules are adsorbed ? Pore size and polarity

Polarity

H2O

Decreasing size

4Å 3Å

5Å

13X (7.4Å)

NH3 MeOH

H2S CO2

Light RSH

Heavy RSH

BTX

In any case : water first !!

Molecular Sieves : how are they produced ? Experience makes good products

Synthesis

Extrusion / Granulation

Sodium Silicate

Caustic Soda

Sodium Aluminate

Ion Exchange

Zeolite Powder

Drying

Activation

Activated Powder

Pellets 1.6 mm 3.2 mm 6.4 mm

Beads 0.5 to 5 mm

Zeolite

● Type ● Cation ● Crystal size

+ Binder

● Clay ● Quantity

+ Process

= Molecular Sieve

● Shape & Size ● Porosity distribution ● Adsorption capacity ● Physical properties ● Chemical properties

Binding Clay

Mixing

Part III – Products for Refining industry

CECA Products for Refining

A full range of dedicated adsorbents… ● SILIPORITE ® Molecular Sieves ● SILIPORITE ® Activated Aluminas ● ACTICARBONE ® Activated Carbons

… for various purposes : ● Drying / Purification of gas / liquid streams ● Catalyst protection ● Protection of equipments against freezing in cryogenic processes ● Protection against corrosion ● Hydrocarbons separation

Molecular Sieves in a Refinery : where ?

FCC

Alkylation

Reforming

Isomerisation

MTBE unit

Hydrotreating

Finishing sections

Hydrotreating

Hydrotreating

Isomerisation

CECA Products in Refinery Units - 1

Alkylation Section

Application Purpose of the unit Main concerns CECA adsorbents

Drying of FCC C4 cut feed for HF alkylation

Protection of catalyst &

equipments Get an extra-dry

feed SILIPORITE® NK30COS

FCC Section

Application Purpose of the unit Main concerns CECA adsorbents

Drying of C3/C3= cut before

cryogenic separation Avoid freezing in Turbo-Expander

Olefin coadsorption SILIPORITE® NK30COS


MTBE Section

Application Purpose of the unit

Main concerns CECA adsorbents

I-C4 purification (feed to reactor)


equipments Clean product

SILIPORITE® G5

SILIPORITE® OXY30

MTBE reactor effluent purification (drying, sulphur)



SILIPORITE® OPX

SILIPORITE® SCOS

Oxygenate Removal (ORU) on i-C4 after reactor



SILIPORITE® OXY30

SILIPORITE® G5

SILIPORITE® NK30

Chloride trap Protection of

catalyst & equipments

SILIPORITE® NK10Cl


Reforming section



HCl / H2O Removal from CCR Naphtha / CCR Overhead

streams Protection of equipments

Green Oil formation

SILIPORITE® NK10Cl

SILIPORITE© RA

H2O / HCl / H2S Removal from H2 recycle streams in cyclic or semi-regenerative reformers

Prevent deactivation / fast stripping of chloride off

cata.

Decrease of capacity with ageing of bed

SILIPORITE® NK10Cl

SILIPORITE® RA


Isomerisation Sections



Liquid C5/C6 purification – only at PENEX ® unit

Drying /Purification, sulphur and oxygenates removal of

paraffin cut /

Pt Catalyst protection

Nature & content of inlet impurities are

difficult to check

Bed coking

SILIPORITE® NK10

/ SILIPORITE® G5

C4 cut drying / purification BUTAMER

SILIPORITE® G5

H2 Make-up Drying (injected for isomerization reactions/ not in all units)

Trace contaminant

Removal

Operation of downstream

hydrosections

SILIPORITE® NK10

MOLEX®/ ELUPAR® & ISOSIV®/ TIP/ IPSORB® units

N/Iso paraffins separation in Gas or Liquid

phase

Separation efficiency

Pollution by aromatics

Lifetime of adsorbent

SILIPORITE® NPL50

SILIPORITE® NPG50


Aromatic & Finishing Sections


Main concerns

CECA adsorbents

Benzene / Toluene Drying Purity of end product

Bed coking SILIPORITE ® NK10

LPG Drying / Sweetening

Pass 1A Copper Strip /

HD-5 tests

End products without smell

Sulfur pick-up

SILIPORITE ® NK10

SILIPORITE ® NK20C

SILIPORITE® G5

SILIPORITE © SCOS Fuel Gas Drying Re-use clean

gas SILIPORITE ® NK30COS

Other Hydrocarbon Drying and Mild Purification

Pass 1A Copper Strip /

HD-5 tests

Bed coking SILIPORITE ® SCOS

SILIPORITE ® OXY30

SILIPORITE ® CO2


Hydrotreatment Section



PSA H2 High purity H2 for hydrogenation

sections

Units able to remove a wide

range of impurities

SILIPORITE ® PHYG1

SILIPORITE ® PHYG3

Kerosene Sweetening Purity of the end

product Fouling ACTICARBONE ® BGP

MEROX ®, MERICHEM ®, SULFREX ® units

Conversion of mercaptans

Activated Carbon = good support for

catalyst. advantages size

distribution, density, purity

ACTICARBONE ® BGP

Hydrogen production, PSA unit

Those Molecular Sieves are perfectly suitable for PSA H2 unit :

• very high N2 and CO adsorption capacity • Strong mechanical strength

Product Name PHYG-1 PHYG-3

Avalibale Shape 1/16” Pellets (1.6 mm)

1/16” Beads (1.6 -2.5 mm)

Breakthrough capacity, mini

CO: 8.2 NL/kg MS N2: 2.1 NL/kg MS

CO: 11.0 NL/kg MS N2: 2.8 NL/kg MS

Typical applications Standard Units Debottleneckings

Compact new units

Reforming: Chloride Traps Removal

26

Chlorinated compounds are injected in Reforming sections to control activity & Pt dispersion on the catalyst. Due to continues stripping – mainly HCl migrates to downstream process.

CECA Molecular Sieves SILIPORITE® NK 10CL in Beads is a special 4A dedicated to HCl removal in both gas and liquid streams :

• maximum chloride adsorption capacity : in gases the chloride capacity is around 17% wt on molecular sieves compared to 8% wt on activated alumina and 12% on promoted activated alumina

• longest life: for a fixed volume of adsorbent and fixed concentration of HCl in the feed gas, lifetime of molecular sieves is 1.4 times lifetime of promoted activated alumina and 2.1 times lifetime of plain activated alumina

• no green oil formation : green oil is formed by oligomerisation and cyclisation of unsaturated hydrocarbons . These reactions are catalyzed by the acidic sites of the adsorbent, especially in the macropores. Molecular sieves will minimise green oil formation because of its controlled acidity and pore size distribution.

• very slow pressure drop build-up

Bigger molecules (organic chlorides) are captured on 5A and 13X Siliporite® grades

Cl

Part IV – Products for Petrochemical Industry

CECA

GLOBAL

OFFER

FOR

PETRO-

CHEMICAL

INDUSTRY:

Molecular sieves

Silicagel

Activated Aluminas

Ceramic Balls

CECA – Products for Petrochemistry (1)

Drying Purification

>> Design of mix beds for multi-component removal <<


Choice of material depends on the gas composition :

Cracked gas drying : 3A

Olefin cut drying : 3A

Hydrogen drying : 3A or 4A

Different types of Activated Aluminas or Molsieves depending on impurities to be removed :

Sulphur cpnds / COS removal : 5A, 13X, AA

For Oxygenates removal : promoted AA, 13X

For Chloride Traps : 4A


Product Characteristics Shape

OPX K High adsorption Kinetic properties Pellets or beads

OPX R Improved Resistance to aggressive feedstocks Pellets or beads

OPX T Low pressure drop ¼” Trilob (extrudate)

OPX M Very low olefin co-adsorption Efficiency of Methanol removal Pellets


Feed : Naphta

Western Europe

525 000 tpy C2=

System: 2+1

Adsorption: 48hrs

Lifetime: 5 years

OPX R for EZ

OPX K for MTZ

CB 1”

CB ½”

150 mm

75 mm

ID = 3 400 mm

1 000 mm

75 mmCB ¼ “

OPX R P3.2mm25 T

OPX K P1.6mm6 T

3 900 mm

OPX K pellets OPX R pellets

Feed : Ethane

Asia

1 100 000 tpy C2=

System: 2+1

Adsorption: 36+6hrs

Lifetime: 4 years

Regeneration with high content of C2=

OPX R for EZ & for MTZ

High resistance to aggressive feed

CB 1”

CB ½”

150 mm

75 mm

ID = 4 000 mm

2 700 mm

75 mmCB ¼ “

OPX R P3.2mm18 T

OPX R P1.6mm23 T

2 000 mm

Part V – CECA solutions for your molecular sieve units

CECA solutions

Optimized design ● Process and Vessels drawing review (including internals) ● Operating parameters optimization leading to cost reduction

Plant support ● Performance evaluation ● Breakthrough tests ● Molecular sieve sample analyses ● Troubleshooting

Services ● Operators seminar and training assistance ● Operation procedure review and assistance ● Loading assistance and on-site vessel / equipment inspection ● Start-up assistance

FOR THE SAME ADSORPTION TIME AND THE SAME LIFETIME :

7 680 mm

1/8 inch d=650kg/m3

62 750 kg

1/8 inch d=700kg/m3

62 750 kg

7 130 mm 6 170 mm

1/8 & 1/16 inch

53 570 kg

1/8 & 1/16 inch

46 330 kg

5 335 mm

density split bed

regeneration optimization

- 26% mass* - 31% volume*

Conservative design

CECA optimized

design

* in this example (may vary depending on the regeneration possibilities, the feed characteristics, the pressure drop limit....)

∆P 0.19 bar ∆P 0.16 bar

CECA Optimized design Case study

CECA solutions




Technical support

Breakthrough curves

Troubleshooting

On-site analysis: water, RSH

Troubleshooting example case 3 : Gas dryer showing fast increasing ∆P and early breakthrough

Plant support - troubleshooting Case story 3

Solution : Slower water desorption (ramp, heating step), silica-gel protection layer.

Diagnosis : The T°C inflexion reveals a change of state : desorbed vapor is condensed to liquid water when arriving on vessel colder parts. When liquid water meets the high temperature front, it boils and leads to dusting and agglomeration

CECA solutions




Loading assistance

Complete procedure provided with material

CECA supervision: ● Control of material before loading ● Check internals ● Control respect of loading plan: heights, levelling… ● Report and CECA certificate

Part VI – CECA references

Our References Petrochemistry and Refining

Cracked Gas Drying : ● Main worldwide references

Country

Nb of units

France

3

Iran

3

Germany

2

Croatia

1

Czech rep.

1

India

2

Qatar

1

Poland

1

Russia

3

Sth Africa

2

Algeria

1

USA

1

Korea

4

Israel

1

Malaysia

2

~2/3 from Naphta feed and 1/3 from Ethane 40% have plant capacity > 0.5 MTPA Ethylene

Olefins Drying : ● Ethylene & Propylene

Country

Nb of units

France

13

Netherlands

6

Japan

3

Sth Africa

1

Qatar

2

Korea

1

Germany

1

Italy

2

Malaysia

1

Portugal

1

Greece

1

Liquid sweetening : ● LPG / C3 / C4

Country

Nb of units

France

5

UK

4

Qatar

3

USA

2

Iran

2

Libya

1

Finland

1

Canada

1

~3/4 use 13X type product 50% involve more than 15 tons of MS

Isomer separation : ● CECA exclusive partner of Axens for providing mole sieves to

the Elupar® and Eluxyl® licenses.

Others : ● H2 drying, Cl traps, etc.

Our References Refinery – Chloride traps

Selected Reference List for NK10 CL : Country Customer Unit type Quantity installed

Finland Neste Oil CCR Reformer - Hydrogen gas 50 T

France Total CCR Reformer - Hydrogen recycle gas & Fuel Gas 4 T

France Petroplus Reformer – Hydrogen Net gas 1.2 T

Italy ENI CCR Reformer – Liquid feed to Stabilizer 26.4 T

Czech Republic Ceska Rafinerska CCR reformer Hydrogen gas 4.8 T

Oman ORPC Reduction gas treaters – Hydrogen gas 10.2 T

Poland PKN Orlen CCR reformer – Hydrogen gas & Liquid Reformate 12.6 T

Sweden Preem Semi-regenerative Reformer – Hydrogen rich Net gas & Fuel Gas 15.7 t

United Kingdom ConocoPhillips Reformer – Liquid reformate 25 T

Our References Refinery - Isomerisation

Selected Reference List for Isomerisation :

Country Company Location Licence MS qty (Tons)

France Total Le Havre PENEX liquid 15

France Total Le Havre PENEX gaz 7

Czech Republic Ceska Rafinerska Litvinov PENEX liquid 5.1

Czech Republic Ceska Rafinerska Litvinov PENEX gaz 2.5

Saudi Arabia Ibn Sina Al Jubail Butamer liquid 21

Slovakia Slovnaft Bratislava PENEX liquid 5.8

Slovakia Slovnaft Bratislava PENEX gaz 2.1

Russia LukOil Perm PENEX liqiud 10

United Kingdom Valero Pembroke Butamer gaz 1.2

United Kingdom Valero Pembroke Butamer gaz 1.2

Conclusions Why Choosing CECA ?

DESIGN OPTIMIZATION

Done by process engineer

35 years experience

MOLECULAR SIEVE

European quality (Iso 9001)

N°2 worldwide producer

PLANT SUPPORT

Check performances

Troubleshooting

SERVICES

Loading assistance

BT test

Thank you ! Do you have question ?

Documents

Molecular sieves – new opportunities and services offered ... · Molecular sieves – new opportunities and services offered by BRENNTAG and CECA . Laurentiu GHITA, Oil&Gas BDM