CHEMICAL PROCESS INDUSTRIES CPI 201T-11 Petrochemical Industry 2012

By

Dr Alex Sofianos
Bsc Chem Eng, Msc, PhD Ind Chem (GERMANY), MBL (UNISA)

Course Contents
1. 2. 3. 4. 5. 6. 7. 8. 9. Introduction Inorganic Bulk Commodity Chemicals Synthesis Gas Processes Petroleum Refining Polymerisation and Petrochemicals Organic Chemical Process Industries Cement, Glass, Dyes Manufacturing Hydrometallurgical Processes Environmental Issues and Green Chemistry
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Inorganic Bulk Chemicals

Sulphuric Acid Contact Process Phosphoric Acid Lurgi- Fisons Process Ammonia Haber-Bosch Process Nitric Acid Ostwald Process Urea and Fertilizers Sodium Hydroxide Chloralkali Process Chlorine Chloralkali Process Soda Ash Solvay Process
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Synthesis Gas Processes

Synthesis Gas Production
Coal Gasification Steam Reforming of Methane

Water Gas Shift Reaction Fischer-Tropsch Process Methanol Synthesis Methanol Conversion to Chemicals
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Petroleum Refining
Petroleum refining processes are those chemical engineering processes and other facilities used in petroleum refineries (also referred to as oil refineries). The purpose is to transform crude oil into useful products such as
liquefied petroleum gas (LPG), gasoline or petrol, kerosene, jet fuel, diesel oil and fuel oils.
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Petrochemistry
Petrochemistry is a science that can readily be applied to fundamental human needs, such as health, hygiene, housing and food. Inventive business sector, constantly adapting to new environments and meeting new challenges. Chemicals derived from petroleum or natural gas petrochemicals - are an essential part of the chemical industry today. Petrochemistry is a fairly young industry; it only started to grow in the 1940s, more than 80 years after the drilling of the first commercial oil well in 1859.
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Petrochemistry (2)
During World War II, the demand for synthetic materials to replace costly and sometimes less efficient products caused the petrochemical industry to develop into a major player in today's economy and society Before then, it used to be a tentative, experimental sector, starting with basic materials: synthetic rubbers in the 1900s, Bakelite, the first petrochemical-derived plastic in 1907, the first petrochemical solvents in the 1920s, polystyrene in the 1930s...

Petrochemistry (3)
Petrochemistry then moved to an incredible variety of areas - from household goods (kitchen appliances, textile, furniture) to medicine (heart pacemakers, transfusion bags), from leisure (running shoes, computers...) to highly specialised fields like archaeology or crime detection. Petrochemicals do not reach the final consumer - the man in the street; they are first sold to customer industries, undergo several transformations, and finally go into products that seem to bear no relation whatsoever to the initial raw material.

Petrochemistry (4)
The result is: few make the connection between the petrochemical industry and their GP's equipment, their CDs, food packaging or computers; few realise the amount of scientific efforts that went into these commonplace objects. Although benefiting daily from end products that have been made thanks to the input of the petrochemical industry, Mostly no obvious connection between these everyday commodities and petrochemistry.
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Petrochemical Industry
Petrochemicals are chemicals made from raw materials with origin mainly crude oil and gas
Only about five percent of the oil and gas consumed each year is needed to make all the petrochemical products. The rest Petrol, Diesel, lubricants etc. Petrochemicals have had a dramatic impact on our food, clothing, shelter and leisure. Some synthetics, tailored for particular uses, actually perform better than products made by nature because of their unique properties, example: natural rubber vs synthetic rubber
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 Gallons per barrel (bbl) of petroleum or related products = 42 Barrels of Crude Oil per Metric Ton = 7.33; 1 bbl = 159 litres 12 U.S. Gallons to litres = 3.785

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Petrochemical Industry
Overview of the Petrochemicals Industry Petrochemicals are chemicals made from raw materials with origin
Petroleum (crude oil) and/or Natural gas Petroleum and natural gas are made up of hydrocarbon molecules, These consist of one or more carbon atoms, to which hydrogen atoms are attached: (C H) n
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Petrochemical Industry
Overview of the Petrochemicals Industry Currently, oil and gas are the main sources of the raw materials: because they are the least expensive, most readily available, and can be processed most easily into the primary petrochemicals

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Petrochemical Industry
Raw Materials & Feedstocks Primary Petrochemicals Petrochemical Intermediates Derivatives End Product - Petrochemicals

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Petrochemical Plant Feedstocks

Major hydrocarbon sources used in producing petrochemicals are:
1. Methane, ethane, propane and butanes: Obtained primarily from natural gas processing plants. 2. Naphtha obtained from petroleum refineries. 3. Benzene, toluene and xylenes, referred to as BTX aromatics obtained from petroleum refineries by extraction from the reformate produced in catalytic reformers. 4. Gas oil obtained from petroleum refineries.

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Petrochemical plant feedstock sources

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Petrochemical Plant Feedstocks

Methane and BTX aromatics are used directly as feedstocks for producing petrochemicals. Ethane, propane, butanes, naphtha and gas oil serve as optional feedstocks for steam-assisted thermal cracking plants referred to as steam crackers that produce these intermediate petrochemical feedstocks: ethylene propylene n-butenes and butadiene (C4 fraction) Benzene

In 2007, the amounts of ethylene and propylene produced in steam crackers were about 115 Mt (megatonnes) and 70 Mt, respectively.

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Primary Petrochemicals
"Primary Petrochemicals" include: olefins (ethylene, propylene and butadiene) aromatics (benzene, toluene, and xylenes); and methanol.
Olefins are unsaturated molecules of carbon (C) and hydrogen (H) that appear as short chains, of two, three or four carbons in length. Aromatics contain a six carbon ring structure. The oxygen/hydrogen (OH) group in methanol denotes that it is an alcohol.
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Petrochemical Intermediates & Derivatives

Petrochemical intermediates:
generally produced by chemical conversion of primary petrochemicals to form more complicated derivative products Petrochemical derivative products can be made in a variety of ways: directly from primary petrochemicals; through intermediate products which still contain only carbon and hydrogen; through intermediates which incorporate chlorine, nitrogen or oxygen in the finished derivative.
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Petrochemical Intermediates & Derivatives

Petrochemical intermediates: In some cases, they are finished products; in others, more steps are needed to arrive at the desired composition. Of all the processes used, one of the most important is Polymerization. It is used in the production of plastics, fibers and synthetic rubber; the main finished petrochemical derivatives.

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Petrochemical Intermediates & Derivatives

Typical Petrochemical intermediates:
vinyl acetate for paint (PVA), paper and textile coatings vinyl chloride for polyvinyl chloride (PVC) - plastics resin manufacture ethylene glycol for polyester textile fibers styrene which is important in rubber and plastic manufacturing Formaldehyde (from methanol); Phenol-formaldehyde polymers (resins) for glue

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Petrochemicals Produced from Ethylene

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Petrochemicals Produced from Propylene

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Petrochemicals Produced from Benzene

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Petrochemicals Produced from Toluene

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Petrochemicals Produced from Xylenes

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Petrochemicals Produced from Benzene

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Example 1

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Introduction to Polymerization
Polymers are a large class of materials consisting of many small molecules (called monomers) that can be linked together to form long chains, thus they are known as macromolecules. The picture below is a short section of such a chain. A typical polymer may include tens of thousands of monomers. Because of their large size, polymers are classified as macromolecules.

Humans have used polymers for centuries in a variety of applications, in the form of oils, tars, resins, and gums.

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Introduction to Polymerization
During the industrial revolution modern polymer industry began to develop. In the late 1830s, Charles Goodyear succeeded in producing a useful form of natural rubber through a process known as "vulcanization." Some 40 years later, Celluloid (a hard plastic formed from nitrocellulose) was successfully commercialized. In the 1930s, new materials such as vinyl, neoprene, polystyrene, and nylon were developed. The introduction of these revolutionary materials began an explosion in polymer research that is still going on today.

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Introduction to Polymerization
Unmatched in the diversity of their properties, polymers such as cotton, wool, rubber, Teflon(tm), and all plastics are used in nearly every industry. Natural and synthetic polymers can be produced with a wide range of stiffness, strength, heat resistance, density, and even price. With continued research into the science and applications of polymers, they are playing an ever increasing role in society. The following sections provide an introduction to the science of macromolecules.

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Chain-Growth Polymerization
Chain-growth (or Addition) polymerization is a polymerization technique where unsaturated monomer molecules add on to a growing polymer chain one at a time It can be represented with the chemical equation: n.M (monomer) (-M-)n (polymer) where n is the degree of polymerization. Example: n CH2 = CH2 - (CH2 - CH2 )n 38

Chain-Growth Polymerization
The most common type of addition polymerization is free radical polymerization. A free radical is simply a molecule with an unpaired electron. The tendency for this free radical to gain an additional electron in order to form a pair makes it highly reactive so that it breaks the bond on another molecule by stealing an electron, leaving that molecule with an unpaired election (which is another free radical). Free radicals are often created by the division of a molecule (known as an initiator) into two fragments along a single bond. The following diagram shows the formation of a radical from its initiator, in this case benzoyl peroxide.
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Polymerization
A polymerization process takes place in three distinct steps: 1. chain initiation, usually by means of an initiator which starts the chemical process. Typical initiators include any organic compound with a labile group: e.g. azo (-N=N-), disulfide (-S-S-), or peroxide (-O-O-). Two examples are benzoyl peroxide and AIBN. 2. Chain propagation 3. Chain termination, which occurs either by combination or disproportionation. Termination, in radical polymerization, is when the free radicals combine and is the end of the polymerization process.
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Polymerization - Initiation

benzoyl peroxide Benzoyl peroxide is usually prepared by treating hydrogen peroxide with benzoyl chloride. The oxygen-oxygen bond in peroxides is weak. Thus benzoyl peroxide readily undergoes homolysis (symmetrical scission), forming free radicals: *C6H5C(O)+2O2 2 C6H5CO2
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Polymerization - Initiation

*C6H5C(O)+2O2 2 C6H5CO2 The symbol indicates that the products are radicals; i.e., they contain at least one unpaired electron. Such species are highly reactive. The homolysis is usually induced by heating. The half-life of benzoyl peroxide is one hour at 920C. At 131 C, the half-life is one minute. The stability of a radical refers to the molecule's tendency to react with other compounds. An unstable radical will readily combine with many different molecules. However a stable radical will not easily interact with other chemical substances.
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Polymerization - Initiation
The stability of free radicals can vary widely depending on the properties of the molecule. The active center is the location of the unpaired electron on the radical because this is where the reaction takes place. In free radical polymerization, the radical attacks one monomer, and the electron migrates to another part of the molecule. This newly formed radical attacks another monomer and the process is repeated. Thus the active center moves down the chain as the polymerization occurs.
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Propagation Reaction

After a synthesis reaction has been initiated, the propagation reaction takes over. In the propagation stage, the process of electron transfer and consequent motion of the active center down the chain proceeds. In this diagram, (chain) refers to a chain of connected monomers, and X refers to a substituent group (a molecular fragment) specific to the monomer.

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Propagation Reaction
For example, if X were a methyl group, the monomer would be propylene and the polymer, polypropylene. In free radical polymerization, the entire propagation reaction usually takes place within a fraction of a second. Thousands of monomers are added to the chain within this time. The entire process stops when the termination reaction occurs.

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Termination Reaction
In theory, the propagation reaction could continue until the supply of monomers is exhausted! However, this outcome is very unlikely. Most often the growth of a polymer chain is halted by the termination reaction. Termination typically occurs in two ways: combination and disproportionation.
Combination occurs when the polymer's growth is stopped by free electrons from two growing chains that join and form a single chain.
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Termination Reaction

The following diagram depicts combination, with the symbol (R) representing the rest of the chain. For example, if X were a methyl group, the monomer would be propylene and the polymer, polypropylene. Disproportionation halts the propagation reaction when a free radical strips a hydrogen atom from an active chain. A carbon-carbon double bond takes the place of the missing hydrogen. Termination by disproportionation is shown in the diagram. 47

Termination Reaction

Termination by disproportionation is shown in the diagram above. Disproportionation can also occur when the radical reacts with an impurity. This is why it is so important that polymerization be carried out under very clean conditions.

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Other types of Polymerization

The new monomer adds on the growing polymer chain via the reactive active centre which can be a: free radical in radical polymerization carbocation in cationic polymerization carbanion in anionic polymerization organometallic complex in coordination polymerization. the monomer molecule can be a: unsaturated compound like ethylene or acetylene, see vinyl polymer Alicyclic compound, see ring-opening polymerization
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Cationic Polymerization
In carbo-cationic polymerization the active site is a carbocation with a counter-ion in close proximity. 1. Initiation A+B- + H2C=CHR A-CH2-RHC + -B2. Chain propagation: A-CH2-RHC+-B- + H2C=CHR A-(CH2-RHC)n-CH2-RHC+-B3. Chain termination: A-(CH2-RHC)n-CH2-RHC+-B- A-(CH2-RHC)n-CH2-RHC-B 4. Chain transfer: A-(CH2-RHC)n-CH2-RHC+-B- A-(CH2-RHC)n-CH2=CR H+-B50

Statistical Analysis of Polymers

When dealing with millions of molecules in a tiny droplet, statistical methods must be employed to make generalizations about the characteristics of the polymer. It can be assumed in polymer synthesis that each chain reacts independently. Therefore, the bulk polymer is characterized by a wide distribution of molecular weights and chain lengths. The degree of polymerization (DP) refers to the number of repeat units in the chain, and gives a measure of molecular weight. Many important properties of the final result are determined primarily from the distribution of lengths and the degree of polymerization.
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Statistical Analysis of Polymers

In order to characterize the distribution of polymer lengths in a sample, two parameters are defined: number average and weight average molecular weight. The number average is just the sum of individual molecular weights divided by the number of polymers. The weight average is proportional to the square of the molecular weight.
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Statistical Analysis of Polymers

Therefore, the weight average is always larger than the number average. The graph in previous slide shows a typical distribution of polymers including the weight and number average molecular weights. The molecular weight of a polymer can also be represented by the viscosity average molecular weight. This form of the molecular weight is found as a function of the viscosity of the polymer in solution (viscosity determines the rate at which the solution flows - the slower a solution moves, the more viscous it is said to be - and the polymer molecular weight influences the viscosity).
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Statistical Analysis of Polymers

It is possible by measuring the viscosity of a polymer solution to use the data you find to produce the viscosity average molecular weight. The degree of polymerization has a dramatic effect on the mechanical properties of a polymer. As chain length increases, mechanical properties such as ductility, tensile strength, and hardness rise sharply and eventually level off. This is schematically illustrated by the blue curve in the figure below.

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Statistical Analysis of Polymers

However, in polymer melts, for example, the flow viscosity at a given temperature rises rapidly with increasing DP for all polymers, as shown by the red curve in the diagram. A fundamental property of bulk polymers is the degree of polymerization, The physical structure of the chain is also an important factor that determines the macroscopic properties
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Physical Structure of Polymers

The physical structure of the chain is also an important factor that determines the macroscopic properties Terms configuration and conformation are used to describe the geometric structure of a polymer and are often confused: Configuration: The geometrical arrangement in polymers arising from the order of atoms determined by chemical bonds. Conformation: The geometrical arrangement in polymers arising from rotation about adjacent carboncarbon single bonds.
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Polymer Configuration
Two types of polymer configurations are cis and trans.
These structures can not be changed by physical means (e.g. rotation). The cis configuration arises when substituent groups are on the same side of a carbon-carbon double bond.

Trans refers to the substituents on opposite sides of the double bond.

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Polymer Configuration
Stereoregularity is the term used to describe the configuration of polymer chains; Three distinct structures: Isotactic is an arrangement where all substituents are on the same side of the polymer chain. A syndiotactic polymer chain is composed of alternating groups and atactic is a random combination of the groups. The following diagram shows two of the three stereoisomers of polymer chain.

.
Isotactic Syndiotactic
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Other Definitions in Polymers

Conformation: The geometrical arrangement in polymers arising from rotation about adjacent carbon-carbon single bonds. Anti (Trans), Eclipsed (Cis), and Gauche (+ or -).

Branched polymers: when there are "side chains" attached to a main chain.
.
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Other Definitions in Polymers

Conformation: The geometrical arrangement in polymers arising from rotation about adjacent carbon-carbon single bonds. Anti (Trans), Eclipsed (Cis), and Gauche (+ or -).

Branched polymers: when there are "side chains" attached to a main chain.
.
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Co-Polymers
A separate kind of chain structure arises when more that one type of monomer is involved in the synthesis reaction. These polymers that incorporate more than one kind of monomer into their chain are called copolymers. There are three important types of copolymers. A random copolymer contains a random arrangement of the multiple monomers. A block copolymer contains blocks of monomers of the same type. A graft copolymer contains a main chain polymer consisting of one type of monomer with branches made up of other monomers.
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Co-Polymers
There are three important types of copolymers. A random copolymer contains a random arrangement of the multiple monomers. A block copolymer contains blocks of monomers of the same type. A graft copolymer contains a main chain polymer consisting of one type of monomer with branches made up of other monomers.

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Co-Polymers

Block Copolymer

Graft Copolymer

Random Copolymer

Nylon is an alternating copolymer with 2 monomers, a 6 carbon diacid and a 6 carbon diamine;One monomer of the diacid combined with one monomer of the diamine

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PetroChemical Industry

THANK YOU

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