Industrial Chemistry

The question is how to make a profit from science?

• Industry sectors and manufacturing industry • The beginning and the history of chemical industry • Industrial chemistry • The scope and the structure of global industrial chemistry • Characteristic and classification of industrial chemicals • Basic organic and inorganic chemicals (BOC & BIC) • Building block • Reactors in industrial chemistry • Batch, semi-batch and continues reactors • Economic considerations • Chemical processes (unit processes and unit operations) • Balancing( materials balance) • Examples of chemical industries

Outlines

Industry sectors • Industry is a general term which is refers to all the economic

activities that deal with the production of goods and services. Goods and services are key words when talking about industry therefore, the industry expect to include the following main sectors:

INDUSTRY

Manufacturing Energy

Transport

Agriculture

etc.

Tourism

Communication Building and construction

Trade

Finance

Education

Manufacturing industry • Manufacturing industry is a part of industry or

economy which is concerned with the production or making of goods out of raw materials by means of a system of organized labor.

• Manufacturing industry can be classified into two major categories namely;

1. Capital-intensive industries (heavy industries) (include those that produce industrial machinery, vehicles and basic chemicals)

2. Labour intensive (light) industries this kind is easier to relocate than heavy industries and require less money investment to build

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Manufacturing industry • The Sub-sectors of Manufacturing industry are;

Food, beverages and tobacco

Textiles, wearing clothes, leather goods

Paper products, printing and publishing

Chemical, petroleum, rubber and plastic products

Basic metal products, machines and equipment

Non-metallic mineral products other than

petroleum products Essa I. Ahmed-PhD

• Ancient man (prehistoric–600 BC) practiced certain chemical arts such as extraction and working of metals, manufacture of leather, production of alcoholic beverages, and the use of vegetable oils, alkaloids, and narcotics.

• In the Dark and Middle Ages, alchemy grown and gradually evolved into an experimental science as the result of the thinking of men such as Roger Bacon (1214–1294), Paracelsus (1493–1541), and Francis Bacon (1561–1626).

• Pre-1600 Alchemists sought to turn base metals (iron, zinc, lead) into gold using the four “elements”— earth, fire, air, and water.

The beginning

• About 1600 the chemical era began • 1600s Robert Boyle worked out scientific

experimental methods and published his findings (the scientific method)

• 1700s Joseph Priestly discovered oxygen and Antoine Lavoisier distinguished between chemical and physical changes (the birth of modern chemistry as an exact science, based on the law of the conservation of mass and on the quantitative study of chemical reactions from the work of Lavoisier

• 1800s Dmitri Mendeleev published the Periodic Table of the Elements

The beginning

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• Pre-1900 Cement, alkali soln., soap, explosives, dyes, paint, fertilizer, chemicals based on coal

• 1920s–30s Cellophane and rayon (based on wood), medicinals, photographic chemicals, nylon, plastics

• 1940s Synthetic rubber, pesticides, plastic films, chemicals based on petroleum

• 1950s Engineering plastics, preservatives, new catalysts

• 1960s Foreign investment, lower prices, performance improvements, pollution awareness

• 1970s Energy and feedstock problems, higher raw materials costs

• 1980s Imports, environment, and health concerns • 1990s Global industry, governmental regulations

The history of chemical industry

Industrial Chemistry

• What does means by industrial chemistry? • Industrial chemistry is concerned with using

chemical and physical processes to transform raw materials into products that are beneficial to humanity.

• This includes the manufacture of basic chemicals to produce products for various industries

• Industrial chemistry can be thought of as an industry that generates synthetic replacements for natural products

• The exploitation of materials and energy in appropriate scale

• Application of science and technology to enable humanity experience the benefits of chemistry in areas such as

• Food production, • Health and cleanness, • Housing, • Protection, • Decoration, • Reformationand entertainment.

The scope of industrial chemistry

Most important segments of chemical industries are;

• Inorganic chemicals • Petrochemicals • Synthetic resins and

plastics • Textile fibres • Synthetic rubber • Pharmaceuticals and

drugs • Soap, detergents, and

cosmetics

• Paint, varnishes, and printing inks

• Fertilizers and other agricultural chemicals

• Adhesives and sealants, • Dyes and pigments, • Paper, • Glass

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The structure of global chemical industry • It is possible to describe the structure of the global

chemical industry as follows; 1. Commodity or industrial Chemicals are defined as low-

valued products produced in large quantities • They are for general purpose including inorganic

chemicals (BIC) and basic organic chemicals (BOC) Together are known as commodity or industrial chemicals

1. Specialty Chemicals also called performance chemicals are High-value added chemical products ( production of small quantities) for specific end uses due to their specific functions such as enzymes and dyes are performance chemicals.

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The structure of global chemical industry

• Other examples of specialty chemicals include medicinal chemicals, agrochemicals, pigments, flavour and fragrances, personal care products, surfactants and adhesives.

3. Fine Chemicals are value-added pure chemical substances produced in relatively low volumes and sold on the basis of exact specifications of purity rather than functional characteristics

• Some examples are research chemicals and pharmaceutical ingredients are examples of this kind of chemicals.

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Characteristic of Industrial Chemicals

KEY SUCCESS FACTORS •cost • technical service

• links with customer

INDUSTRY CHARACTERISTICS

BULK OR COMMODITIES

CHEMICALS

INTERMEDIATES/SPECIALTIES

FINE CHEMICALS

Long >100

>10,000 t/y >1$/kg none Low

high process

Moderate >1,000

<10,000 t/y 1-50$/kg very low

high moderate

process

Short/moderate > 50,000

highly variable 50-1000$/kg

high high

moderate/low application

Product life cycle No. of products Product volumes Product prices Product differentiation Value added Capital intensity R&D focus

BULK OR

- -

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The “chemis-tree” illustrating the origin of organic industrial chemicals

(1) Raw materials that are “activated’ To > 20 BOC By oil processing

(2) Functionalization of base chemicals Into about 300 intermediates

(3) Application of intermediates into many thousands of consumer products

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INDUSTRIAL CHEMISTRY

Industrial Inorganic Chemistry

Extractive metallurgy

Chlor-alkali, ammonia,

sulphuric acid, fertilizer, cement

Chem yyy

Chlor alk

General Industrial Chemistry

Introduction

to industrial chemistry and

chemical industry

Unit operations

and unit processes

Industrial Organic

chemistry

Petroleum,

petrochemicals and polymers

Fermentation, ethanol,

pharmaceuticals, soaps and detergents

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F

Classification of chemical industry • The chemical industry could be classified according to the

type of main raw materials used and/or the type of principal products made as shown below;

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• Organic compounds are either primary building blocks e.g. ethylene, propene, butadiene and benzene and how they are used to make secondary building blocks, such as ethane-1,2-diol, ethanoic acid (Acetic acid) and methanal, useful in their own right or are used to make other useful compounds.

• Inorganic chemicals include compounds such as calcium carbonate, chlorine, hydrogen chloride, nitric acid, sodium hydroxide, sodium carbonate and sulphuric acid, which are used to make other compounds, including plastics, fertilizers, soaps and surfactants, and building materials.

Basic organic and inorganic chemicals (BOC & BIC)

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1850- Plants, Animals 1850+ Coal Tar (side product of “coal gasification“) 1920+ Acetylene from CaC2, (Reppe Chemistry) 1950+ Ethylene (from oil) 1973+ CH4, CO/H2 (syngas) Future

CO/H2 from Coal (exothermic)

CO2 fixation via:

Plants, Animals (endothermic)

CO2 fixation (endothermic)

The history of industrial chemistry is linked to building blocks

What is a Building Block? • A building block is any (organic) chemical that

can be used to synthesize other (organic) chemicals.

• There are very few truly primary, large-volume organic building blocks.

These are all currently obtained from:

Petroleum Refining Natural Gas Coal Ammonia Carbon Dioxide Renewable Resources

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Classification of building blocks (BBs) Primary

BBs Secondary

BBs

Tertiary

BBs

Ethylene Ethylene Dichloride , Ethylene Oxide , Ethyl Benzene

Vinyl Chloride , Ethylene Glycol , Vinyl Acetate

Propylene Propylene Oxide , Acrylonitrile , Isopropyl Alcohol , Cumene,

N-butyl Alcohol

Acetone

Benzene Ethyl Benzene, Isopropylbenzezne (Cumene)

Styrene , Phenol , Acetone,

Bisphenol A Methanol Acetic Acid , Formaldehyde , MTBE Vinyl Acetate Toluene Xylenes

Terephthalic Acid Polyester

• In the top ten BIC, almost all the time, sulphuric acid, nitrogen, oxygen, ammonia, lime, sodium hydroxide, phosphoric acid and chlorine dominate

• The reason why sulphuric acid is always number one is because it is used in the manufacture of fertilizers, polymers, drugs, paints, detergents and paper. It is also used in petroleum refining, metallurgy and in many other processes.

• The top ranking of oxygen is to do with its use in the steel industry

• Ethylene and propylene are usually among the top ten BOC

• They are used in the production of many organic chemicals including polymers

Most important basic chemicals

The first building block: the age of acetylene

• Reppe Chemistry: Make everything from acetylene some examples are;

important industrial

products from ethylene

• Raw materials, are either; • Non-living e.g. minerals, or • Living, e.g. plants and micro-organisms. (collectively

known as biomass). • A chemical plant produces the desired products. • The process operated either in batch or continuous

sequences.

• Both in research and in industrial practice, different configurations of chemical and biotechnological reactors exist,

• Each reactor is designed and optimized for a specific chemical or biological task.

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Reactors in industrial chemistry

• The reasons for the existing of various reactors may due to the following:

1. The reaction parameters are differ strongly, for example, the

• Residence time (ranging from ms to days), • The pressure (up to 3000 bar), and • Temperature (typical ranges from 0 to 2000°C) 2. Cooling and heating due to (exothermic or endothermic

reactions) 3. The reaction may be single, bi-, or multi-phasic 4. The mode of operation may be (batchwise) or continuous 5. The reaction is homogeneous or a catalyst may be needed 6. The temperature limitation by thermodynamic constraints

Variety of reactors

Most important cases are, a) The uniformly mixed batch reactor, b) The plug flow reactor (PFR), c) The continuous stirred tank reactor (CSTR), and d) A cascade of CSTRs. • Real reactors are arbitrarily complicated, but can be

regarded as composed of elements of ideal reactors.

Ideal reactors against real reactors

c) b) a)

• A “batch” of reactants is introduced into the reactor operated at the desired conditions until the target conversion is reached.

• Stirring always done using • internal impellers, • Bubblings, or • a pump around loop • Temperature is regulated via internal cooling surfaces

using coils or tubes, jackets, reflux condensers, or pump-around loop

• Features • Small production rates, • To long reaction times, • Desired selectivity, and • Flexibility in campaigning different products

Batch reactors

Batch reactor systems • Types of stirred batch reactors with heat transfer. 1. Jacket, 2. Internal coils.,

3. External heat exchanger. 4. External reflux condenser.

Continuous reactors • Reactants are added and products removed continuously

at a constant mass flow rate • A continuous stirred tank reactor (CSTR) is a vessel to

which reactants are added and products removed while the contents within the vessel are vigorously stirred using internal agitation or by internally (or externally) recycling the contents.

• Advantages of continuous processes are; 1. A far-reaching automatization, 2. A reduced volume of equipment at the same production

rate compared to a batch reactor as the plant never runs idle, and

3. Large daily production and constant product quality as the operating conditions are constant Essa I. Ahmed-PhD

Batch versus continuous manufacturing in the chemical industry

BATCH CONTINUOUS

For (Advantages)

• OK for up to 100 tonnes per annum.

• More versatile. • Good for multi-step

reactions.

• OK for over 1000 tonnes per annum.

• Good for fast single step processes.

• Easy to automate.

Against (Disadvantages)

• Contamination of product is more likely.

• At times, no product is made.

• Safety more of an issue.

• Capital cost is high. • Less flexible. • Need to run at full

capacity to make a profit.

• In the semicontinuous reactors some reactants are supplied batchwise while others are supplied continuously

• Here some or one of the reactants are loaded into the reactor, and the rest of the reactants are fed gradually

• Once the reactor is full, it may be operated in a batch mode to complete the reaction

• Semibatch reactors are especially favoured when there are large heat effects and heat-transfer capability is limited

• Exothermic reactions may be slowed down and endothermic reactions controlled by limiting reactant concentration

Semibatch reactors

Economic considerations

Consideration has to be given to: • Operating conditions • Costs (capital, fixed and variable) • Use of energy • Location of the chemical industry • Safety and the environment

REACTION Temp, pressure, catalyst

Recycle loop

Feedstock preparation Fep

Energy in or out

Separation

products

By-products

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Cost considerations

1- Capital costs: The one-off cost of constructing the plant and all the associated costs of all buildings.

2- Variable costs: The cost that changes throughout the year and is dependant on how much product is sold. e.g. Buying raw materials, treating waste and despatching the product.

3- Fixed costs: The annual cost of the staff, local rates, advertising and utility bills.

There are three kind of costs which must be considered for investment in chemical industries

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1. Cost, availability of feedstocks 2. Yield of the reaction 3. Can un-reacted materials be recycled? 4. Can by-products be sold? 5. Cost of waste disposal 6. Energy consumption, generating your own, conservation, use of catalysts, recycling of heat, (heat exchangers), 7. Environmental issues

• Value added, eg increasing the value of the products from crude oil

£’s per tonne 1x£’s per tonne 3x£’s per tonne 8x£’s per tonne 20x£’s per tonne

Choices to be made

• The different order of energy involved in the various aspects of chemical processing operations is illustrated below:

1. Chemical energy: Burning 1 tonne of octane releases (45000MJ)

2. Thermal energy: Conversion of 1 tonne of octane from liquid to vapour at the boiling point requires (400MJ)

3. Gravitational energy: Raising 1 tonne of octane through 100 m requires (1MJ)

4. Frictional resistance: Pumping 1 tonne of octane 1 km horizontally through typical pipework (0.01 MJ)

• Kinetic energy: tonne of octane flowing at 1 m s-1 (0.001 MJ) • In addition most heat exchangers in the petrochemical

industry can transfer 1 to 5MJs-1

Energy consumption examples

An example; costs consideration of phenol production

Research and development (R&D) R&D activities: 1. Basic chemical research (by trained chemists); much of

this is done in universities 2. Improve existing products (e.g., better quality) 3. Improve existing processes (by chemists and engineers),

including cost reductions 4. By-product disposal and utilization 5. Solution of environmental problems • Important base for chemical industry: 1. R&D spending for 2000 was over $250 billion. 2. Most of the R&D in the U.S. was funded and carried out

by the chemical industry. 3. High investment facilities required with modern (state-of-

the-art) scientific equipment.

• Balancing is a condition guide to describing the interaction between the reaction and transport processes for mass, energy, and impulse taking place simultaneously.

• For this reasons it is important to take considerations for; 1. Equations for the rate of chemical transformations; 2. The law of conservation of mass with the variable

concentration; 3. The law of conservation of energy (enthalpy) with the

variable temperature; 4. Equations for the physical transport processes of mass and

heat; 5. The law of conservation of impulse with the variable total

pressure. 6. Depending on the specific case, not all of these equations

are needed or have at least a different relevance:

Balancing

• Every industrial process is designed to produce a desired product from raw materials using treatment steps either physical or chemical in nature.

Chemical Processes

Input Material Process (transformation) Output product

A typical industrial process

The layout of a chemical process areas are: o Pretreatment of Raw materials o Conversion o Separation of products from by-products is carried out o Refining/purification o Entry and exit points of services such as cooling water and

steam

• These are the physical treatment steps, which are required 1. To put the raw materials in a form in which they can be

reacted chemically 2. To put the product in a form which is suitable for the market • Some common unit operations are given in below table,

Unit operations

Examples of unit operations.

Agitation Dispersion Heat transfer

Atomization Distillation Humidification

Centrifuging Evaporation Mixing

Classification Filtration Pumping

Crushing Flotation Settling

Decanting Gas absorption Size reduction

• Unit operations are very many and include; A. Size reduction, this refers to all the ways in which particles

are cut or broken into smaller pieces for any of the following reasons:

• To reduce chunks of raw materials or to reduce the bulk of fibrous materials for easier handling

• To meet standard specifications on size and shape • To increase particles in number to increase surface area

and for selling purposes • To improve blending efficiency of formulations,

composites

Unit operations

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• An example of an industrial equipment that is based on compression is a jaw crusher shown below;

Size Reduction

• An example of an industrial equipment that is based on impact is a ball mill shown below.

• A ball mill is a tumbling mill generally used for previously crushed materials

Ball mill Jaw crusher

Most machines are based on mechanical compression or impact

• This carried out when particles are too small for use in a later stage of the process. For example in metal extraction, some particles may be too fine to be fed into a blast furnace

• In size enlargement, small particles are gathered into larger, relatively permanent masses in which the original particles can still be identified

• The products of size enlargement are either regular shapes e.g. bricks, tiles, tablets, pellets or irregular shapes such as sintered ore

• There are two basic types of agglomerators; A. compaction and B. non-compaction agglomerators

Size enlargement

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A. Compaction agglomeration • The pellet mill belongs to this type which uses mechanical

pressure (and often very high pressures) to "press" the powders together

• Pellet mills shown below is an example of compaction agglomerators

The pellet mill

Photograph of a pelletizer in operation that converts wood planings and saw dust into fuel pellets

Size enlargement

B. Tumbling agglomerators • The common action of most non-compaction agglomerators is to

keep the powders in motion by tumbling, vibrating or shaking, while spraying a correct amount of liquid binder

• After the particles stick together to form a nucleus or germ, then follows the layering or deposition of layers of the raw materials into previously formed nucleus shown below

• Inclined pan agglomerator and drum agglomerator are two examples of this type

• Illustration of the powder layering process

Size enlargement

• This deals with how differences in the physical properties of materials are used to separate mixtures in the chemical industries such as;

Separation of Mixtures

1. Magnetic Separation • If a mixture containing

magnetic materials and non-magnetic materials is subjected to a magnetic field, there is competition for the particles between several forces namely, magnetic, inertia, gravitational and interparticle forces Illustration of the principle of dry

magnetic separation

2. Froth Flotation • This is a process in solids-liquids separation technology

that uses differences in wettability of various materials such as mineral ores

• Although these materials are generally hydrophilic, the surface properties of components they contain may vary within a very narrow range

• These small differences can be amplified by selective adsorption that makes some of the particles hydrophobic. Such hydrophobic particles in a water suspension are floated by attaching them to air bubbles

A flotation cell

Separation of Mixtures

Unit Processes

• Unit processes are defined as chemical transformations or conversions. Unit processes are the core of industrial synthetic chemistry and are dominant in organic processes such as;

• Polymerization, • Alkylation, • Hydrolysis, • Sulphonation, • Esterification, • Hydrogenation, • Halogenation and • Nitration

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Flow Diagrams “A picture says more than a thousand words”

• Some chemical processes are quite simple; others such as oil refineries and petrochemical plants can be very complex. The process description of some processes could take a lot of text and time to read and still not yield 100% comprehension. Errors resulting from misunderstanding processes can be extremely costly

• To simplify process description, flow diagrams also known as flow sheets are used

• “A flow diagram is a road map of the process, which gives a great deal of information in a small space”

• Two types of flow diagrams are in common use, namely, 1. The block diagrams and 2. The process flow diagrams

Block Diagrams

A block diagram for a sulphuric acid plant

This is a schematic diagram, which shows: • What is to be done rather

than how it is to be done. Details of unit operations/ processes are not given

• Flow by means of lines and arrows

• Unit operations and processes by figures such as rectangles and circles

• Raw materials, intermediate and final products

Process flow diagram / flow sheet • Chemical plants are built from process flow drawings or

flow sheets drawn by chemical engineers to communicate concepts and designs

• Communication is improved if accepted symbols are used. Flow sheet symbols are pictorial quick-to-draw, easy-to-understand symbols that transcend language barriers

• Some have already been accepted as national standards while others are symbols commonly used in chemical process industries, which have been proven to be effective

• Below is a cement process flow diagram illustrating the use of equipment symbols Essa I. Ahmed-PhD

A process flow diagram for the manufacture of cement

Process flow diagram / flow sheet