Petrochemical Industries Prof. Dr. Ibtisam Kamal Lec.

Introduction

Petrochemical Industry & Petrochemicals

Petrochemicals are set of very specific chemical compounds derived from petroleum or natural
gas. Petrochemicals constitute a very important segment of world industry today and world
chemicals market, with a share of nearly 40 per cent. Petrochemical industry started 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... and it then
moved to an incredible variety of areas.

Petrochemicals have backward linkages with other industries in petroleum refining, natural gas
processing and forward linkages with industries that deal in a variety of downstream products.
Also, the industry offer alternatives, which serve as substitutes for natural products and hence,
has the capacity to meet the constantly growing demand that would otherwise strain the
natural resources.

Types of Petrochemical Industry

The petrochemical industry is classified into 3 main groups, on the basis of their
Products:
 Upstream Petrochemical Industry
 Intermediate Petrochemical Industry
 Downstream Petrochemical Industry
 Overview of Petrochemical Industry

Upstream Petrochemical Industry

Upstream petrochemical industry is the production of petrochemical products which are feeds
tock for further production of other petrochemical products (intermediate and downstrea
m). It divided to the following 3 groups on the basis of their molecular structure:
 Alkane group, which is methane-based
 Olefin group, which is ethylene-based, propylene-based and Mixed C 4-based
 Aromatic group, which is benzene-based, toluene-based and xylene-base

Intermediate Petrochemical Industry

Intermediate petrochemical industry uses upstream petrochemical products as feedstock and
supplies to downstream petrochemical industry. Its products are grouped on the basis of
their upstream petrochemicals, as follows:
 Alkane Intermediates, namely, products from upstream methane, such as methanol or
methyl alcohol, formaldehyde, ammonia, phosgene, etc.
 Olefin Intermediates, namely, ethylene products such as ethylene dichloride, (EDC),
vinyl chloride monomer (VCM), ethylene oxide (EO), and ethylene glycol (EG),
propylene products such as oxo alcohol and acrylonitrile
 Aromatic Intermediates, namely, benzene products such as ethyl benzene (EB),
 styrene monomer(SM), cyclohexane, carprolactam, and paraxylene products, etc.

Downstream Petrochemical Industry

Downstream Petrochemical Industry uses upstream or intermediate petrochemical produc
ts as
feedstock to manufacture downstream products or end products prior to conversion in other in
dustries. They are categorized by end product, as follows:
 Plastic resins
 Synthetic Fibers
 Synthetic rubbers
 Synthetic coating and Adhesive materials
ดบสาหรบการผลตอตสาหกร

Petrochemical industry Feedstocks

Refineries convert crude oil into oil products part of which is used for petrochemical processing.
Refineries can use different qualities of feedstock oil. Lighter crude oil types are preferred
because of high value end products. Returns from the petrochemical Industry are also used by
the refining industry.
 Petroleum refinery by atmospheric and vacuum distillation

Flow diagram of atmospheric and vacuum distillation units:1 (1,3) heat exchangers; (2) desalter,
(3,4) heater; (5) distillation column, (6) overhead condenser, (7–10) pump around streams, (11)
vacuum distillation heater; (12) vacuum tower.

Distillate Fraction Boiling Point oC Carbom atom

Per molecule
Gases Less than 30 1-4
Gasoline 30-210 5-12
Naphtha 100-200 8-12
Kerosene & Jet fuel 150-250 11-13
Diesel & Jet fuel 160-400 13-17
Atmospheric Gas oil 220-345
Heavy Fuel oil 315-450 20-45
Atmospheric residue More than 450 More than 30
Vacuum residue More than 615 More than 60

Crude Oil refining products- Boiling points and No. of carbon atoms/molecule
Naphtha is the main feedstock in the petrochemical industry around the world. It is used in the
basic petrochemical steam cracking process. Naphtha consists of refinery products in the 30°C
to 210°C distillation range.
Gas oil is the second most important feedstock for the petrochemical steam cracking process.
Gas oil is primarily a medium distillate, distilling between 180°C and 380°C. Gas oil used as
petrochemical feedstock includes also heavy gas oils that distil between 380°C and 540°C.
Liquefied Petroleum Gas (LPG) is the third most important feedstock, LPG consists of light
saturated paraffinic hydrocarbons that are derived from the refinery processes, crude oil
stabilization and natural gas processing plants. They consist mainly of propane and butane or a
combination of the two. Ethane from natural gas is the fourth input for the steam cracking
processes.

The choice of feedstock in petrochemical plants Midterm

Four crucial factors govern the choice of feedstock in petrochemical plants: availability, cost,
power consumption and the product portfolio to be produced. With respect to availability, the
plant owners need to be assured of continuous availability of feedstock. Even though power
accounts for 10 per cent of the cost involved in the cracking of feedstock, an un- interrupted
high quality power is required for the same. Hence, many petrochemical complexes use captive
power. As per the portfolio of products, naphtha is used when a wide range of co-products
(including propylene and butadiene derivatives) is desired while natural gas and NGL are
preferred when the ethylene output of a cracker is to be maximized since they yield a higher
proportion of ethylene.
Petrochemical building blocks
Petrochemical industry is built on small number of basic commodity chemicals, also known as
building blocks such as ethylene, propylene, butadiene, benzene, toluene and xylene. The
basic building blocks are divided to olefins (including ethylene and propylene) and aromatics
(including benzene, toluene and xylene isomers). Oil refineries produce olefins and aromatics
by fluid catalytic cracking of petroleum fractions. Chemical plants produce olefins by steam
cracking of natural gas liquids like ethane and propane. Aromatics are produced by catalytic
reforming of naphtha. Olefins and aromatics are the building-blocks for a wide range of
materials such as solvents, detergents, and adhesives.

The Volume and Growth of Petrochemical Products

The largest petrochemical industries are to be found in the USA and Western Europe, though
the major growth in new production capacity is in the Middle East and Asia. There is a
substantial inter-regional trade in petrochemicals of all kinds. World production of ethylene is
around 110 million tons per year, of propylene 65 million tons, and of aromatic raw materials
70 million tons. Increasing demand for petrochemical products in industries such as
transportation and construction is expected to grow over the next seven years. In the figure
below the expected trend of global petrochemicals capacity up to 2020 is shown below:
The above figure reflect a s growth in Asia but building once in North America.

Petrochemical Products from Hydrocarbons (gas or oil)

Natural gas is treated to remove impurities such as Nitrogen, Carbon dioxide, Hydrogen
Sulphide and the wet gas is separated into its hydrocarbon components: Methane, Ethane,
Propane, Butanes and liquid condensates. Natural gas produced from different gas fields show
large variations in its composition.

Generally the main component is Methane, while Ethane and the other heavier components
are present in far lower proportions. Methane has become the fuel of choice for power
generation for various sectors of manufacturing industry as well as used as a petrochemical
feedstock.

Ethylene is produced by steam cracking in furnaces, either from ethane-rich natural gas (USA
and Middle East) by pyrolysis or by high temperature cracking, or from naphtha (Europe and
Asia). The petrochemicals economy closely depends on the availability and prices of raw
materials (natural gas and crude oil). For natural gas-based production, gas is the largest cost
item and can represent up to 70% of ethylene final price.

The industrial dominance based on petrochemicals from natural gas led the world chemical
activities towards the production of less energy-intensive products with raw materials at lower
cost. So the world industries therefore focused on chemicals derived from naphtha such as
propylene and butadiene.
 Production steps of petrochemical products from hydrocarbons (gas or oil)

The primary petrochemicals are reacted to form secondary petrochemicals, other chemical
products, or polymerized to form synthetic resins.

Petrochemical Products
Basic processes in the petrochemical industry (cracking and reforming)
1. Cracking

Cracking is the name given to breaking up large hydrocarbon molecules into smaller and more
useful bits. This is achieved by using high pressures and temperatures without a catalyst, or
lower temperatures and pressures in the presence of a catalyst.

Steam cracking

Dissociation of raw material such as ethane and propane yielding important petrochemical

products, ethylene and propylene, mixed C4, pyrolysis gasoline. Methane and
hydrogen are also some of major by-products.

Catalytic Cracking
Dissociation of larger, stable molecules requires catalysis. Refinery products such as gasoil
and fuel oil may be passed through catalytic cracker to obtain gasoline and diesel as major
products and by‐product, propylene, which is primary petrochemical product.

The source of the large hydrocarbon molecules are obtained from the distillation process as
liquids, but are re-vaporised before cracking. The hydrocarbons are mixed with a very fine
catalyst powder. These days the catalysts are zeolites (complex aluminosilicates) - these are
more efficient than the older mixtures of aluminium oxide and silicon dioxide.

The whole mixture is blown rather like a liquid through a reaction chamber at a temperature of
about 500°C. Because the mixture behaves like a liquid, this is known as fluid catalytic cracking
(or fluidised catalytic cracking).

Although the mixture of gas and fine solid behaves as a liquid, this is nevertheless an example
of heterogeneous catalysis - the catalyst is in a different phase from the reactants.

The catalyst is recovered afterwards, and the cracked mixture is separated by cooling and
further fractional distillation.

There isn't any single unique reaction happening in the cracker. The hydrocarbon molecules are
broken up in a fairly random way to produce mixtures of smaller hydrocarbons, some of which
have carbon-carbon double bonds. One possible reaction involving the hydrocarbon
C15H32 might be:
2. Reforming

Reforming of hydrocarbon structure may be accomplished by the use of heat, pressure a

nd/or catalyst in order to obtain desired products. This process converts heavy naphtha t
o aromatics such as benzene, toluene and xylene as well as hydrogen as by-product .
Reforming may be carried out by several methods:

 Dehydrogenation is a process in which hydrogen atoms are being taken away

from saturated hydrocarbons structure leaving product of unsaturated hydrocarbon
s such as the dehydrogenation of cyclohexane to aromatics.
 Dehydrocyclization is a process in which hydrogen atoms are being taken away
from aliphatic hydrocarbons yielding aromatics such as dehydrocyclization
of paraffin.
 Dealkylation is the extraction of alkyl group from toluene and xylene yielding benzene.
 Transalkylation or Disproportionation is the combination process of two
molecules resulting in two new molecules which are bigger and smaller than
precursor ones i.e., catalytic transalkylation of toluene to benzene and xylene.

 Isomerization involves the molecular restructuring of material while retaining the

same number of atoms i.e., isomerization of o-xylene and m-xylene to p-xylene.

Reforming uses a platinum catalyst suspended on aluminium oxide together with various
promoters to make the catalyst more efficient. The original molecules are passed as vapours
over the solid catalyst at a temperature of about 500°C.
The petrochemical products produced from ethylene, propylene and benzene are shown in the
following blocks:
Petrochemical Industries Lec. 2

PRODUCTION OF PETROCHEMICALS

I. OLEFINS PRODUCTION

Introduction

Olefins are major building blocks for petrochemicals. Because of their reactivity and versatility,
olefins especially the light olefins like ethylene, propylene, butenes, butadiene, etc., there has
been tremendous growth in the demand of the olefins. Ethylene itself is basic building block
for large number of petrochemicals and is quoted as king of chemicals. The following table
shows some olefins (monomers), their polymers, properties and uses.

The steam cracker remains the fundamental unit and is the heart of any petrochemical complex
and mother plant and produces large number of products and byproducts such as olefins -
ethylene, propylene, butadiene, butane and butenes, isoprene, etc., and pyrolysis gasoline. The
choice of the feedstock for olefin production depends on the availability of raw materials and the
range of downstream products. Naphtha has made up about 50-55 percent of ethylene feedstock
sources. Although basic steam cracking technology remain same for naphtha, gas oil and natural
gas.
1. ETHYLENE PRODUCTION PROCESS

Ethylene is one of the simplest hydrocarbons. It comes in a gaseous form, and similar to many
other hydrocarbons, it is colorless and flammable. Ethylene is the source material for a variety
of products such as polyethylene resin, ethylene glycol, vinyl chloride resin, acetic acid,
styrene, and alpha olefin which are produced by polymerization, oxidation, alkylation,
hydration, or the addition of halogen.

Ethylene and its derivatives

Ethylene is produced from the cracking of fractions obtained from distillation of natural gas and
oil. The processes are:

a) The steam cracking of ethane and propane (from natural gas and from crude oil)
b) The steam cracking of naphtha from crude oil

c) The catalytic cracking of gas oil from crude oil.

 Lower alkenes from Natural gas

*Amylene: Any of five unsaturated isomeric hydrocarbons having the formula C5H10

Lower alkenes from crude oil

The choice of feedstock depends on availability, price (which can vary considerably), and what
other products from cracking are needed. The vast majority of ethene is produced by steam
cracking. Some crackers are capable of producing more than 3000 tonnes of ethene a day.

d) New plants based on bioethanol produced from sugar cane are in operation around the world.
High yields of ethane are obtained by dehydrating ethanol vapour using a catalyst containing a
mixture of magnesium oxide, alumina and silica at 600-750 K.

The ethylene is used principally to produce polyethylene, which can thus be classified as 'green'.

ETHYLENE PRODUCTION BY NAPHTHA AND GAS CRACKING

NAPHTHA /GAS CRACKING

Requirement of steam will depend upon the type of feedstock; the lighter hydrocarbon requires
less steam as compared to heavier feedstock. Steam cracking relative cost according to feedstock
Steam requirement in steam cracker and Energy requirement pattern for olefin production is
given in below:
Modern ethylene plants incorporate following major process steps : cracking compression and
separation of the cracked gas by low temperature fractionation. The nature of the feed stock and
the level of pyrolysis severity largely determine the operating conditions in the cracking and
quenching section.

STEPS INVOLVED IN THE PYROLYSIS OF NAPHTHA

Hot Section

It consists of convection zone and radiant zone. In the convection zone, hydrocarbon feed stock
is preheated and mixed with steam and heated to high temperature. In the convection zone the
rapid rise in temperature takes place and pyrolysis reaction takes place. The addition of dilution
steam enhances ethylene yield and reduces the coking tendency in the furnace coils. The
production of the pyrolysis reaction consists of a wide range of saturated and unsaturated
hydrocarbons.

In an ethylene plant, the steam cracking furnace has the largest production capacity and,
consequently, the highest energy consumption.

The operation level of the furnace can significantly impact the production costs of the whole
ethylene plant, and thus, even a slight improvement in the operation of the furnace can increase
the economic benefits.

In the practical operation of a steam cracking furnace, there are four key control variables: coil
outlet temperature (COT), steam-to-naphtha ratio, naphtha feed flow rate (FLOW), and coil
outlet pressure (COP). Together, these control variables determine the yield rates of ethylene and
propylene.

The pyrolysis process in a cracking furnace

 Hot section

Quench Section

To avoid subsequent reaction the effluent are fixed in their kinetic development by sudden
quench first by indirect quench by water to 400 – 450 o C in transfer line exchanger or quench
boiler. This is a large heat exchanger that is a bundle of metal tubes through which the gases pass
and around which is circulated water under pressure. The hot water produced is used to generate
steam for use in the plant. In the next step the quench is done by heavy product of pyrolysis.

Cold Section

After compression, caustic scrubbing and drying the light effluents enter the cold section of the
unit which performs the separation of (I) hydrogen to various concentration (ii) ethylene
containing 99.4percent (iii) 95percent propylene (iv) A C4 cut containing 25-50 percent
butadiene (v) pyrolysis gasoline which is rich in aromatic hydrocarbons. The complexity of the
separation section of a cracker increases markedly as the feed changes from ethane.
REACTIONS IN STEAM CRACKING

The reactions involved in thermal cracking of hydrocarbons are quite complex and involve many
radical steps. The thermal cracking reaction proceeds via a free radical mechanism. Two types of
reactions are involved in the thermal cracking (i) primary cracking where the initial formation of
paraffin and olefin takes place (ii) secondary cracking reaction where light products rich in
olefins are formed. The total cracking reactions can be grouped as follows: Initiation reaction ,
Propagation reaction, Addition reaction, Isomerization reaction, Termination reaction, Molecular
cyclization reaction.
 Chemistry of steam cracking

OPERATING VARIABLES OF STEAM CRACKING

The main operating variables in the pyrolysis of hydrocarbon are composition of feed stock,
reaction temperature, residence time, hydrocarbon partial pressure and severity.

1. Composition of Feed Stock

Midterm
Naphtha are mixture of alkane, cycloalkanes, and aromatic hydrocarbons depending on the type
of oil from which the naphtha was derived. The group properties of these components greatly
influence the yield pattern of the pyrolysis products. The steam cracking of the naphtha yields
wide variety of products, ranging from hydrogen to highly aromatic heavy liquid fractions. The
thermal stability of hydrocarbons increases in the following order: parafins, naphthenes,
aromatics.

Yield of ethylene as well as that of propylene is higher if the naphtha feed stock is rich in
paraffins. The relative production of ethylene decreases as the feed stock becomes heavier. The
percentage of pyrolysis gasoline C5-200 o C cut increases. Simultaneously butadiene yield varies
slight with feed stock in the treatment of liquid petroleum fractions.
2. Furnace Run Length

Furnace run length can be calculated from the equation:

Tmd = maximum allowable tube skin temperature

Tm /day= Average rise in tube skin temperature per day

Tmc = maximum metal skin temperature in the clean, un coked condition

For any feedstock the heater section run length depends on the pyrolysis coil selectivity,
cracking severity and transfer line exchanger design. Run length varied between 21 - 60 days for
gas based furnaces and 21-40 days for liquid feed based furnace.

3. Pyrolysis temperature and Residence Time

The effluent exit temperature is generally considered a significant indicator of the operation of a
furnace. As the furnace exit temperature rises, the yield also rises, while the yields of propylene
and pyrolysis gasoline (C5-200 oCcut) decrease. With respect of ethylene yield, each furnace
exit temperature, correspond to an optimum. The highest ethylene are achieved by operating at
high severely, namely, around 850 oC with residence time ranging from 0.2 to 0.4s. However,
operating at high temperature results in high coke formation.

4. Partial Pressure of Hydrocarbon and Steam to Naphtha Ratio

Pyrolysis reaction producing light olefins are more advanced at lower pressure. Decrease into the
partial pressure of hydrocarbons by dilution with steam, reduces the overall rate reaction rate, but
also help to enhance the selectivity of pyrolysis substantially in favour of the light olefins
desired. Other role of steam during pyrolsis is (1) to increase the temperature of feed stock (2)
reduction in the quantity of heat to be furnished per linear meter of tube in the reaction section
(3) to remove partially coke deposits in furnace tubes. The ethylene yield decreases as the partial
pressure of hydrocarbon increases. For economic reason a value of 0.5 to 0.64 of steam per tonne
of naphtha is generally adopted as the upper limit.

5. Severity and Selectivity Concept

Severity is often used to describe the depth of cracking or extent of conversion. The definition
of severity varies with the different manufactures and may differ accordingly to the type of
hydrocarbon treated. In the case of steam cracking of the ethane and propane, it is convenient to
express the severity of the operating conditions in terms of feed conversion. At very high
severities, the methane and ethylene yield level off, while those of propylene and C4 cut reach a
peak and then decline consequently. The ratio of ethylene and propylene yield increases with
severity, which hence favours the formation of ethyelene. The relative production of C5+ cut
passes through a minimum and at the very high severity tends to increase. Modern ethylene
plants are normally designed for near maximum cracking severity because of economic
considerations.
Typical Naphtha Cracker Plant
Petrochemical Industries Lec. 3

2. Vinyl Chloride Monomer (VCM) Production Process

Vinyl chloride monomer (VCM) is a colorless gas with a sweet odor. It is highly toxic,

flammable, and carcinogenic. However, VCM is among the top twenty largest petrochemicals in

world production. VCM is an important industrial chemical chiefly used to produce

the polymer polyvinyl chloride (PVC).

VCM is produced by the thermal cracking of ethylene dichloride (EDC). EDC is produced by

direct chloronation or oxychloronation of ethylene. The chlorine used in the manufacture of

EDC is derived from common salt (NaCl) by electrolysis, so 43 % by weight of PVC originates

from crude oil.

CH2=CH2 + Cl2 → ClCH2CH2Cl

ClCH2CH2Cl → CH2=CHCl + HCl

In the direct chlorination section, ethylene is directly chlorinated to produce ethylene dichloride

(EDC). In the oxychlorination section hydrogen chloride (HCl) is reacted with ethylene and

oxygen to yield EDC and water. Both processes are often effected in separate stand-alone units

to produce high-purity EDC.

The EDC produced by direct chlorination is fed straight into the cracking section without any

further purification.

The crude EDC from the oxychlorination sections passes through a purification stage (EDC

distillation).

In the next process section, the cracking unit, EDC is thermally cracked to yield VCM, HCl and

unreacted EDC.
Pure VCM is then separated from the other pyrolysis products in the VCM distillation section

and these are then recycled to either the oxychlorination (HCl) or the cracking section

(unconverted EDC).

Direct chlorination

C2H4 + Cl2 C2H4Cl2

Oxychlorination

C2H4 + 2 HCl + 1/2 O2 C2H4Cl2 + H2O

EDC cracking

C2H4Cl2 C2H3Cl + HCl

The individual sections, which comprise direct chlorination, oxychlorination and EDC cracking

processes, are combined into the so-called "balanced" process which only produces VCM and

water:

VCM synthesis

2 C2H4 + Cl2 + 1/2 O2 2 C2H3Cl + H2O

VCM could be produced also from Acetylene by reaction with anhydrous hydrogen chloride gas

over a mercuric chloride catalyst :

C2H2 + HCl → CH2=CHCl

Also, VCM could be by direct conversion of ethane.

Various trace impurities do occur in the vinyl chloride, a number of these such as 1.3 butadiene

and mono-vinyl acetylene can have adverse effects upon the polymerization kinetics even at very

low levels (mg per kg) and thus must be stringently controlled. VCM storage can either be under

pressure or refrigerated at approximately atmospheric pressure. A chemical inhibitor, such as a

hindered phenol, is sometimes added to prevent polyperoxide formation.

Midterm
Production process of Vinyl Chloride Monomer (VCM)

3. STYRENE PRODUCTION PROCESS

Styrene is one of the most important monomers in modern petrochemical industry. It is colorless

to yellow oily liquid, its density 0.909 g/cm³ , Boiling point 145 °C, with Penetrating odor.

Styrene is mainly used for the production of many different polymeric materials, the most

important being polystyrene, styrene-acrylonitrile and acrylonitrile-butadiene-styrene (ABS).

Another important application is in producing styrene-butadiene latex.

Styrene is produced by dehydrogenation of ethylbenzene (EB) in presence of superheated steam

over potassium promoted iron oxide catalyst. The accounts for more than 90% of the worldwide

capacity.

The process can be run industrially either adiabatically or isothermally. The energy needed for

the reaction is supplied by superheated steam (at about 720 °C) that is injected into a vertically

mounted fixed bed catalytic reactor with vaporized ethylbenzene. The catalyst is iron oxide

based and contains Cr2O3 and a potassium compound (KOH or K2CO3) which act as reaction

promoters.

Typically, 2.5-3 kg steam are required for each kilogram of ethylbenzene to ensure sufficiently

high temperatures throughout the reactor. The superheated steam supplies the necessary reaction

temperature of 550-620 °C throughout the reactor. Ethylbenzene conversion is typically 60-65%.

The three significant byproducts are toluene, benzene, and hydrogen.

After the reaction, the products are cooled rapidly (perhaps even quenched) to prevent

polymerization. The product stream (containing styrene, toulene, benzene, and unreacted

ethylbenzene) is fractionally condensed after the hydrogen is flashed from the stream. The

hydrogen from the reaction is used as fuel to heat the steam (boiler fuel). After adding a

polymerization inhibitor (usually a phenol), the styrene is vacuum distilled in a series of four

columns (often times packed columns) to reach the required 99.8% purity. The separation is

difficult due to the similar boiling points of styrene and ethylbenzene. Typical capacity per plant

ranges from 70,000 to 100,000 metric tonnes per year in each reactor and most plants contain

multiple reactors or units.

Flow Diagram for Styrene Production DM: Dehydrogenating mixture

4. BUTADIENE PRODUCTION PROCESS

Midterm
Butadiene is a flammable, colorless gas with a mild aromatic odor and it is highly reactive. It’s It

is colorless gas that has a mild gasoline-like odor. Butadiene is soluble in alcohol and ether,

insoluble in water and polymerizes readily, particularly if oxygen is present.

One major use of butadiene has been in the making of synthetic rubber (styrene-butadiene and

nitrile butadiene rubbers. Butadiene is also used extensively for various polymerizations for

plastics manufacturing.
There are two sources of butadiene in world: Extractive distillation from Crude C4 stream

produced as a co-product of ethylene production, and “on-purpose” production by

dehydrogenation o n-Butane or n-Butenes.

Up to 50% of the produced volume of butadiene is taken up by SBR and polybutadiene.

Butadiene is used to manufacture rubber for tires, hoses, gaskets, paints and adhesives. It is also

used in the production of nylon clothing, carpets and engineering plastic parts.

Flow diagram for butadiene plant

Description of the process

The crude C4 and the DMF solvent are fed to 1st extractive distillation column where the C4

stream is separated into the C4 raffinate-1 from top and the bottom stream which contains

Butadiene/acetylene in the DMF solvent. The Butadiene/acetylene rich solvent is fed to 2nd

extractive distillation column where mainly vinyl acetylene is removed. The top stream is sent to
the Butadiene purification section where the remaining acetylene is removed and purified 1,3-

Butadiene is produced using two distillation columns. The lean solvent from two strippers is

cooled via heat recovery prior to being sent back to the extractors.

II. BTX Production

In the petroleum refining and petrochemical industries, BTX refers to mixtures

of benzene, toluene, and the three xylene isomers, all of which are aromatic hydrocarbons. The

xylene isomers are distinguished by the designations ortho – (or o –), meta – (or m –), and para –

(or p –). If ethylbenzene is included, the mixture is sometimes referred to as BTEX.

The BTX aromatics are very important petrochemical materials. Global consumption of BTX

showed an unprecedented growth. Toluene is a valuable petrochemical for use as a solvent and

intermediate in chemical manufacturing processes and as a high octane gasoline component

Benzene, toluene, and xylenes can be made by various processes. However, most BTX

production is based on the recovery of aromatics derived from the catalytic

reforming of naphtha in a petroleum refinery.

Catalytic reforming usually utilizes a feedstock naphtha that contains non-

aromatic hydrocarbons with 6 to 11 or 12 carbon atoms and typically produces

a reformate product containing C6 to C8 aromatics (benzene, toluene, xylenes) as well

as paraffins and heavier aromatics containing 9 to 11 or 12 carbon atoms.

Another process for producing BTX aromatics involves the steam cracking of hydrocarbons

which typically produces acracked naphtha product commonly referred to as pyrolysis

gasoline, pyrolysis gas or pygas. The pyrolysis gasoline typically consists of C6 to C8 aromatics,
heavier aromatics containing 9 to 11 or 12 carbon atoms, and non-aromaticcyclic

hydrocarbons (naphthenes) containing 6 or more carbon atoms. The adjacent table compares the

BTX content of pyrolysis gasoline produced at standard cracking severity or at medium cracking

severity with the BTX content of catalytic reformate produced by either a continuous catalytic

regenerative (CCR) reformer or by a semi-regenerative catalytic reformer. About 70 percent of

the global production of benzene is by extraction from either reformate or pyrolysis gasoline.

BTX content of Pyrolysis Gasoline and Reformate

Pyrolysis Gasoline Reformate

Standard Medium
CCR SR
severity severity

BTX content, wt % 58 42 51 42

Benzene, wt % of BTX 48 44 17 14

Toluene, wt % of BTX 33 31 39 39

Xylenes, wt % of BTX 19 25 44 47

CCR = Continuous catalytic regenerative reformer

SR = Semi-regenerative catalytic reformer

The BTX aromatics can be extracted from catalytic reformate or from pyrolysis gasoline by

many different methods. Most of those methods, but not all, involve the use of a solvent either

for liquid-liquid extraction or extractive distillation. Many different solvents are suitable,

including sulfolane (C4H8O2S), furfural (C5H4O2), tetraethyleneglycol (C8H18O5),

dimethylsulfoxide (C 2H6OS), and N-methyl-2-pyrrolidone(C5H9NO).Below is a schematic flow

diagram of one method, involving extractive distillation, for extraction of the BTX aromatics

from a catalytic reformate.

BTX production Flow diagram

Petrochemicals produced from BTX
Petrochemical Industries Lec. 4

PLASTIC INDUSTRIES: AN OVERVIEW

I. Introduction
Final
Plastics are also called synthetic resins are broadly classified into three categories: thermosetting
resins , thermoplastic resins and elastomers.

Thermosetting resins include phenolic resin and melamine resin, which are thermally hardened
and never become soft again. They are hard and brittle. Thermoplastic resins include PVC,
polyethylene (PE), polystyrene (PS) and polypropylene (PP), which can be re-softened by
heating. They are ductile. Elastomers are polymers that are joined by chemical bonds, acquiring
a final slightly crosslinked structure. They have high elongation and flexibility or elasticity.
Elastomers include rubbers and silicone and polyurethane polymers.

The production of plastics follows the scheme given in below with monomers, comonomers,
catalysts, solvents as well as energy and water on the input side and the product, off-gases, waste
water and wastes on the output side.

Production scheme for plastics

1
Raw Materials

Pure raw materials are needed (a purity of 99.9999 % is required). Thus, side products from
monomer synthesis, impurities from storage containers, oxygen, degradation products or
stabilisers added for transport, have to be removed before use. General purification units like
distillation, extraction or fractionated crystallisation are usually part of the monomer supply.

Energy

Energy is needed for the production of polymers, even in the case of polymerisation systems
where the process itself is exothermic.

II. Polymerisation: The reaction principles

Plastics are formed by three different reaction mechanisms: addition polymerization,

polycondensation and polyaddition.

1. Addition Polymerization

Addition polymerisation is the most important reaction process and produces amongst others the
plastics polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC) and polystyrene (PS).
The reaction principle includes the opening of the double bond of a monomer and linking many
monomeric molecules together forming a saturated long chain macromolecule. The product
retains the same composition as the starting materials and no secondary products are eliminated.
These reactions are usually exothermic, thus producing energy. The actual polymerisation may
be carried out in bulk, in water or in organic solvents or dispersants. The addition polymerization
reaction is initiated by heat, pressure and catalysts. The course of the reaction process is chain
growth polymerization can be generally described as: Start reaction, Growth reaction and
Termination reaction

2
 polycaprolactone

2. Polycondensation (step growth reaction)

The reaction principle includes the reaction of a monomer with two distinctive reactive
functional groups or the combining of two bifunctional monomers forming a polymer and
generating a by-product which is, in many cases, water. The reactive groups may be for instance:

 Alcohol plus acid for polyesters

 Amine plus acid for polyamides

Poly-condensation of diacid and diol to polyester

3
Polycondensation is considered to be a ‘step growth reaction’. The process often (but not always)
needs a catalyst which is usually a metal salt or a combination of metal salts. The degree of
polymerisation is generally lower than in the case of chain polymerisation (between 1000 and
10000) due to inherent process characteristics. The molecule grows step by step at a relatively
slow rate. The growth proceeds slowly from monomer to dimer, trimer, etc. until full sized
macromolecules are formed only at very high conversion rates towards the end of the reaction
time. Generally, polycondensation reactions are carried out either in bulk or in organic solvents.

The Typical features

1. The control of oxygen is important not only for safety reasons, but also for product quality.
Oxygen causes side reactions resulting in products which discolour the end-product and increase
the concentration of low molecular weight products. These parts either remain in the product or
have to be removed and sent for waste treatment, for instance incineration.

2. The high reaction temperature at the end of the reaction may also lead to degradation products,
which also cause discoloration. Localized heat spots have to be avoided.

3. The build-up of solid layers in the inside of the reactors or heat exchangers also occurs in
these reactions

3. Polyaddition

Polyaddition is defined as the joining together of several molecules of different starting materials
with migration of hydrogen atoms, but without secondary products being formed.

4
The characteristic of these processes closely follows those of polycondensation reactions; thus, a
stepwise growth with all the limitations can be observed. An advantage also from an
environmental point of view is that there are no low molecular weight products formed.

III. Production Processes ( Polymerisation Technologies)

Generally, the reaction of monomers to polymers may be carried out discontinously or

continously by one of the following processes:

• Suspension Polymerisation

• Bulk Polymerisation

• Emulsion Polymerisation

• Gas Phase Polymerisation

• Solution Polymerisation.

A. Suspension polymerisation

In suspension polymerisation, the chemical reaction takes places in droplets that are in
suspension in a solvent. Suspension polymerisation is characterised by a good transfer of the
reaction heat, a low dispersion viscosity and low separation costs on the one side but also by the
fact that it is a discontinuous process, and there are relatively high amounts of waste water,
significant reactor wall fouling and suspension agents remaining in the final product and in the
waste streams.

5
Typical products made by suspension processes are: polyvinyl chloride, polymethyl
methacrylate, polystyrene, polytetrafluoroethylene, polyolefins as slurry in mineral oil fractions.

Suspension polymerisation produces latex particles in the size range from 1 to 1000 Wm. This
process comprises monomer + initiator + solvent (usually water) + surfactant. The monomer and
the initiator are both insoluble in the solvent (water), e.g. styrene and benzoyl peroxide; hence
the monomer is dispersed as droplets (as in emulsion polymerisation), but the initiator is present
in these droplets (and not in the aqueous phase). The role of the surfactant is purely to stabilise
these droplets. There are no micelles in the aqueous phase. The focus of polymerisation is now
totally inside the monomer droplets. Hence, the polymerisation resembles a (micro-) bulk
polymerisation, but confined to each monomer droplet separately. Heat transfer problems are
greatly diminished, compared to an actual bulk polymerisation, because the aqueous phase can
conduct away most of the heat generated. The size distribution of the final particles should
closely follow that of the initial monomer emulsion droplets (provided coalescence is avoided).

b. Bulk polymerisation

In bulk polymerisation, the polymer is produced in a reactor where only the monomer and a
small amount of an initiator are present. Bulk polymerisation processes are characterised by high
product purity, high reactor performances and low separation costs, but also by high viscosities
in the reactors. Bulk processes cause reactor fouling, and in the case of polycondensation
products, a high vacuum is required. Typical products made by bulk processes are: polyolefins,
polystyrene , polyvinyl chloride , polymethyl methacrylate, polyamides , polyesters.

6
This is the usual method for step-growth (condensation) polymerisation. The reaction is often
carried out at a high temperature, but there are no real problems with heat transfer out of the
reaction vessel (i.e. temperature build-up). The degree of polymerisation increases linearly with
time, so that the viscosity of the reaction mixture only increases relatively slowly; this allows for
efficient gas (e.g. water vapour) bubble transfer out of the system as well.

This method can be used for chain-growth polymerisation, but only on a small scale, preferably
at low temperature. Heat and bubble transfer may give problems, since the degree of
polymerisation (and hence, also the viscosity of the reaction mixture) increases very rapidly from
the beginning of the reaction. For certain monomers (e.g. vinyl chloride), the polymer is
insoluble in its own monomer (above some critical molar mass). Hence, in these cases, the
polymer precipitates (as aggregated, swollen particles) from the monomer after a while.
Eventually all the monomer is converted to polymer.

c. Emulsion polymerisation

In emulsion polymerisation, the chemical reaction takes places in droplets that are in suspension
in a solvent – like in the case of suspension polymerisation – but also in emulsion structures
called micelles, and in the solvent. Emulsion processes typically show a low dispersion viscosity,
good heat transfer, high conversion rates and are suitable for the production of high molar mass
polymers. They are also characterised by high separation costs, reactor wall fouling and
emulsifiers remaining in the product and in the waste streams. Typical products made by
emulsion processes are: ABS, polyvinyl chloride , PTFE , SBR, NBR, PVA, PMMA,
polyacrylates for paints.

7
 Emulsion polymerization

Emulsion polymerisation produces latex particles in the size range from 0.03 to 0.1 Wm. The
process comprises monomer + initiator + solvent (usually water) + surfactant (usually anionic,
e.g. sodium dodecyl sulphate). The monomer has only a very limited (but finite) solubility in the
solvent (e.g. styrene in water). Most of it is present initially in dispersed droplets (hence the term
emulsion polymerisation); one role of the (anionic) surfactant is to help stabilise these droplets,
by adsorbing at the droplet/water interface. However, some of the monomer is present in the
water phase. Most of the surfactant is present as micelles, again in the water phase, and some of
the monomer will be solubilised in the micelles. Thus, the monomer is actually distributed in
three locations: droplets, aqueous solution (small amount) and micelles. The initiator is soluble
(and therefore present) in the water phase. The initial locus of polymerisation is, therefore, again
in the aqueous solution (as in dispersion polymerisation), i.e. that is the first monomer to
polymerise. The growing, oligomeric free-radical chains will co-micellise in with the existing
micelles from the added anionic surfactant. The primary locus of polymerisation now switches to
the micelles, where the solubilised monomer can now begin to polymerise. As polymerisation (in
the micelles) continues, particles form, as in dispersion polymerisation, and the distribution of
monomer, is gradually pulled to the right. Polymerisation continues in the growing particles until
all the monomer in the droplets and free solution is exhausted. The size of the final particles is
controlled by the number of micelles present (i.e. the initial surfactant concentration)

d. Gas phase polymerisation

Midterm
In gas phase polymerisation, the monomer is introduced in the gaseous phase and put in contact
with a catalyst deposited on a solid structure. Gas phase processes allow an easy removal of the
reaction heat, they are low in emissions and waste and no additional solvents are needed.

8
Gas phase processes are not applicable for all end-products and the investment costs are
relatively high, partially caused by the high pressure equipment needed for most of the processes.
Currently, gas phase processes are only applied to the polyolefins: polyethylene , polypropylene.
This process is often used, e.g. in Ziegler-Natta type polymerisations of ethylene and propylene
where the catalyst is supported on inert silica particles so the reaction therefore takes place at the
surface. This helps control the stereochemistry (especially for isotactic polypropylene). A typical
gas phase polymerization of olefins takes place at 80 to 100 °C and 30 - 35 bar reactor pressure.

E. Solution polymerisation

In solution polymerisation, the chemical reaction takes place in a solution of the monomer in a
solvent. Solution polymerisation processes are characterised by a good transfer of the reaction
heat, a low dispersion viscosity and little reactor wall fouling, but also by the low reactor
capacities, high separation costs, often the use of inflammable and/or toxic solvents and traces of
solvent contaminating the final product. Typical products made by solution processes are:
polyacrylonitrile , polyvinyl alcohol , SBR , BR , EPDM , polyethylene.

Solution polymerisation comprises (monomer + initiator + solvent). This is the preferred method
to use for chain-growth polymerisation. The solvent helps heat dispersal and reduces the rapid
build-up in viscosity in the reaction mixture. The polymer may or may not be soluble in the
solvent; in the latter case (e.g. styrene + methanol) the polymer precipitates from solution (above
some critical molar mass).

9
Free radical Polymerization technologies: Advantages and limitations

10
Petrochemical Industries Lec. 5

II. POLYOLEFINS INDUSTRY

1. Polyethylene Industry

Polyethylene is the most widely produced polymer worldwide and everyone comes into contact
with it daily. Polyethylene can be made into soft and flexible, as well as tough, hard and sturdy
products. It is found in objects of all dimensions with simple and complicated designs. Among
others, it can also be turned into everyday objects, packaging, pipes and toys.

a. Low density polyethylene (LDPE)

Low density polyethylene is the oldest type of polyethylene. It is produced in a high pressure
process. It is a soft, tough and flexible kind of polyethylene due to its highly branched molecular
structure. The typical density of LDPE lies between 915 and 935 kg/m3 . When it is deformed, it
can recover its original shape due to its natural elasticity. The „high pressure‟ polyethylene
shows a higher melt flow index (MFI) and therefore, processes easier than most other types of
polyethylene.

It is used for strong, supple items like lids. It has been used as an insulation material for a long
time. Nowadays, the most popular application is film, some examples being carrier bags,
packaging material and agricultural film covers.

b. High density polyethylene (HDPE)

Caused by its high crystallinity, high density polyethylene is the most rigid and least bendable
amongst the different types of polyethylene. HDPE has hardly any side branches. Therefore, the
density is always higher than 940 kg/m 3 . The rigid and somewhat hard character is useful for a
wide range of applications. The narrow molecular mass distribution polymer , is used to make,
for example, the crates for fruits, vegetables or drinks. Broader molecular mass distribution
polyethylenes , can be found in non transparent bottles, containers and pipes. Although HDPE is
quite rigid, it also can be used to make very thin films which are very light and can crackle.
 c. Linear low density polyethylene (LLDPE)

This is the youngest of all the PE types. It looks similar to HDPE but has lower crystallinity due
to a larger number of short chain branches. Therefore, it also has a lower density (normally lower
than 940 kg/m3 ). However, PE with densities between 930 and 940 kg/m 3 is often called MDPE
or medium density polyethylene.

LLDPE is used to make flexible as well as rigid products.. It is also used in packaging made up
of multilayer films. LLDPE is very tough and keeps its shape. These properties are useful for the
manufacture of larger objects like lids.

Low density polyethylene processes

The high pressure LDPE process is very generic and the basic design does not change from
company to company. The major variation is in reactor type, tubular versus autoclave. In
principle, the tubular process is preferred to make resins with good optical properties, while only
the autoclave process can make good extrusion coating resins and more homogeneous copolymer
products.
General purpose products can be manufactured from both technologies. The ethylene conversion
level achieved in the tubular process is typically higher than for the autoclave process, however,
due to the typical lower operating pressure level in the autoclave process, the final energy
consumption per tonne polyethylene produced can be the same for both processes.

Final
Important factors which influence the conversion level and also the consumption of energy
are:

• The molecular weight distribution (MWD) of the polyethylene resin to be produced: broader
MWD products are produced at higher ethylene conversion levels than narrow MWD products.
• Heat transfer: for the tubular process, ethylene conversion can be further increased while
maintaining the desired product quality (5 to 15 % conversion increase), through extending the
heat transfer capability (increasing the heat exchange area through lengthening the reactor and/or
improving the heat transfer coefficient).

• Initiation system: Optimization of the initiation system can lead to a higher conversion level for
the same product properties. The autoclave process is typically operated with organic initiators.
The tubular plants can be operated with oxygen only, peroxides/oxygen or peroxide only as the
initiation system. Tubular reactors operating with peroxides as the initiator typically reach a
higher conversion level than reactors using an oxygen only initiation system. The introduction of
an organic initiator will require the usage of hydrocarbon solvents as the peroxide carrier for the
injection of the initiator.

Thus, reactor selection (tubular or autoclave) and the state of technology applied will
influence the conversion level, the required operating pressure and also the energy consumption;
however, product design and quality requirements for the application can have an even
stronger impact on these parameters. The difference in target applications and MWD quality
requirements could easily lead to a difference of 20 % in conversion level and also in energy
requirements among produced resins. Differences in product mix and quality targets could easily
explain a 10 % deviation in energy consumption for plants using the same technology and
hardware.

The autoclave reactor has an agitator to obtain good quality mixing and performs as an adiabatic CSTR
(continuous stirred tank reactor). In the high pressure polymerization of ethylene, the fresh ethylene is
used as the heat sink for the heat generated by the exothermic polymerization reaction.

Autoclave reactor Tubular reactor

 Flow Diagram for LDPE production

The Technical Parameters For LDPE Production Process

Besides LDPE, there are some more plastics produced using the same high pressure technology, such as:
ethylene-vinyl acetate copolymers (EVA), ethylene-acrylic acid copolymers (EAA) , ethylene ethacrylic
acid copolymers (EMA), most grades of linear low density polyethylene (LLDPE), very low density
polyethylene (VLDPE) , ultra low density polyethylene (ULDPE).
These families of resin are produced in commercial scale high pressure processes. To produce these types
of polymers, additional investment is needed, e.g. in corrosion protection, refrigeration capacity, extrusion
equipment and process units to recycle the co-monomers after purification back into the process.

High density polyethylene production process

There are two main types of processes used for the production of high density polyethylene
(HDPE). Both type 1 (narrow molecular weight distribution) and type 2 (broad molecular weight
distribution) HDPE can be produced by these processes:

• Suspension (slurry) process

• Gas phase process.
Besides these two processes, HDPE type 1 can also be produced by a solution process.

The HDPE processes normally use either a Ziegler type (titanium-based) or a Philips type
(chromium-based) supported catalyst which is prepared by impregnating chromium(VI)
oxide on silica followed activation in dry air at high temperatures. Recently, metallocene
catalysts have also been introduced. In general, the Ziegler catalyst can be used in all these
processes to produce type 1 HDPE. The loop reactor which uses isobutane as a diluent, and the
gas phase reactor can be operated at higher temperatures than STR suspension processes using a
higher boiling solvent and the first two processes are, therefore, more suitable for the production
of type 2 HDPE by using chromium catalysts.

Conventional Ziegler-Natta Catalysts

The loop reactor processes and the gas phase reactor processes normally have only one reactor,
while the STR processes typically have two or more reactors to reach a reasonable plant capacity
and to have the flexibility to produce type 2 HDPE using a Ziegler catalyst.

A co-monomer (butene-1, hexene-1) is used to control the polymer density and hydrogen is
used for molecular weight control. Compared to the gas phase process, the slurry processes are
limited in their capability of producing lower density polyethylene, because the solubility of the
polyethylene in the diluent increases with decreasing density of the polymer. Dissolved polymer
in the diluent causes high viscosity and an increased risk of fouling of the reactor and
downstream equipment. The solubility in hexane is higher than in isobutane. The gas phase
process does not have the problem with dissolved polymers and can, therefore, produce both
HDPE and LLDPE by applying different types of catalysts.
An overview and parameters of HDPE Production processes

Suspension Processes
1. Stirred Tank Reactors

Over the years, several suspension process variants have been developed based on the use of
Ziegler catalysts. The modern stirred tank slurry plants usually use hexane as the diluent. Some
old plants use heavier hydrocarbons, which often require steam stripping for removal of the
diluent from the polymer.
The pressure in the reactors is between 0.5 and 1 MPa, permitting the construction of large
reactors with up to 100 m 3 volume. The reaction temperature is between 80 and 90 °C, and
hexane is used as the diluent.
The main feed to the reactor consists of recycled diluent. The ethylene and co-monomer feed
streams are run through purification beds to remove traces of catalyst poisons. A controlled
amount of ethylene monomer, a co-monomer and hydrogen as well as a suspension of a
catalyst/co-catalyst (alkyl Aluminum) mixture is fed to the reactor. In the subsequent „run-down‟
reactor, the dissolved ethylene is almost completely consumed. The remaining ethylene can be
recovered and sent back to a nearby cracker or used as fuel gas.

The polymer concentration in the slurry is an important process parameter. A high concentration
permits a high production rate for a given reactor volume, but the heat transfer to the reactor
cooling jacket and the operation of the stirrer in the reactor become more difficult. The
maximum polymer slurry concentration is dependent on many factors, for example the type of
solvent, grain size and shape, but basically on the cluster density of the polymer particles. The
concentration of the polymer slurry may range between 15 and 45 % by weight, but is mostly
between 30 and 35 % by weight.
 A process flow diagram of a typical modern STR suspension process for HDPE

2. Loop Reactor Processes

The loop reactor consists of a long pipe equipped with a cooling water jacket and arranged into a
closed loop, in which the slurry is pumped around at a high velocity (6 - 10 m/s) with an inline
axial pump.
The loop reactor was originally developed to avoid deposits which had proven troublesome in
the stirred tank reactor. The reactor has a high surface to volume ratio, which facilitates heat
transfer and permits Short residence times.
The loop reactor usually consists of four or six vertical pipes with a height of up to 50 metres.
Some producers have chosen to arrange the loop pipe in a horizontal position.

Typical reaction conditions are 90 – 110 °C and 3 – 4.5 MPa. The diluent used is normally
isobutane, which facilitates the separation by vaporization in a low pressure flash tank and
permits higher operating temperatures than longer chained organic solvents. After treatment in
purification beds to remove catalyst poisons, the ethylene monomer, co-monomer and recycled
diluent are fed to the loop reactor. The catalyst is flushed out of the feed container into the loop
reactor by the diluent. The polymer concentration in the reactor slurry may range from 30 to 50
wt. %. The slurry from the reactor is passed through a sedimentation zone, where the polymer
concentration increases up to 55 – 65 wt. %, and the slurry is then fed to the flash tank, where the
hydrocarbons evaporate at a low pressure of about 0.15 MPa.

The evaporated gases from the flash tank are filtered, compressed and fed to a distillation
column, where the unreacted ethylene is separated from the diluent and co-monomer. Due to the
high conversion of ethylene in the loop reactor (96 – 98 %) the amount of separated ethylene
rich stream is quite small and can be partly recycled back into the loop reactor, but a small purge
stream is needed to control the accumulation of light inert material. The diluent and the co-
monomer from the distillation are recycled back into the reactor after having poisons such as
water in an alumina or molecular sieve bed removed.

The polymer powder from the flash tank bottom falls by gravity into a heated rotary dryer and
then to a purge column to remove a maximum amount of hydrocarbons in the polymer powder.
After that, the powder can be sent either by gravity to a purge bin with nitrogen sweeping or
directly transferred by a conveying system to a fluff silo. This pneumatic conveying system can
be either a positive conveying system with nitrogen or a vacuum conveying system with air. In
the purge column and in the purge bin, residual hydrocarbons are reduced to a very low level by
nitrogen sweeping. The small amounts of hydrocarbons in the nitrogen rich purge gas can be
recovered or the stream is sent to a flare.

From the purge bin, the powder, with a low residual hydrocarbon level, is fed to the extruder
feed bins, from where the powder is fed to the extruder together with necessary stabilizers and
additives. The powder is melted and homogenized and cut to pellets in an underwater pelletizer.
The pelletizer water is recycled and a small side-stream has to be discharged. This waste water
contains small amounts of hydrocarbons due to the direct contact with the pellets.

The wet pellets are then dried in an air dryer and pneumatically conveyed to intermediate storage
silos. During the intermediate storage, the product can be further degassed by air to remove the
last residual hydrocarbons. The air from the dryer, the air from the silos and the pneumatic
conveying system are discharged directly to the air. After final degassing, quality control and
blending, the product is pneumatically conveyed into storage silos or directly sent to the
packaging or bulk loading areas.

HDPE Slurry Process in loop reactor

 HDPE loop production process

Gas Phase Processes

The cleaned feed ethylene is then compressed to the required reaction pressure and enters the
reactor loop at the bottom of the reactor. The fluidized bed reactor is a vertical pressure vessel
with a total height of up to 40 m. A fluidized bed of polymer particles in gaseous ethylene is
maintained by a recycle compressor. The ethylene recycling gas enters the reactor through a
distributor plate at the bottom to achieve an even gas flow over the entire cross-section and to
hold the particles when the gas flow is turned off. In the characteristically conical upper part of
the reactor, the gas velocity decreases with the increasing diameter of the reactor to keep the
particles in the fluidized bed. The gas leaves the reactor at the top. It is cleaned from entrained
particles by a cyclone, the reaction heat is removed by a recycle gas cooler and the gas is then
routed back to the bottom reactor inlet.

A metal oxide catalyst, aluminum alkyl in hydrocarbon as a co-catalyst, lower olefins as co-
monomers and other auxiliary chemicals are fed directly into the reactor loop. Typically,
different product types can be produced by selecting the catalyst system, the co-monomers and
the reaction conditions.

The reaction temperature is 80 to 105 °C and the reaction pressure of 0.7 to 2 MPa is controlled
by the ethylene feed compressor. Polymer and gas are extracted from the fluidized bed by valves
at the bottom section of the reactor and expanded to a lower pressure of approx. 0.15 MPa in a
degassing vessel to separate polymer particles from monomers.

The gaseous monomers from the degassing vessel are filtered, cooled and recompressed by the
monomer recovery compressor to the reaction pressure. The recovery gas is cooled by a series of
heat exchangers and finally by a cooling medium from a cold box. Condensing liquid
hydrocarbons are delivered back to the solvent supply system; the remaining gas is recycled to
the reactor loop. A small side gas stream has to be separated from the recycling gas to limit the
build-up of impurities. It mainly contains ethylene and can be used as fuel gas or can be fed back
to a cracker. The technology is in continuous development with a number of processes cooling
the recycling gas stream sufficiently to condense some of the co-monomers (known as super
condensing). The co-monomer is recycled back into the reactor as combined feed and coolant.
The latest development is the introduction of a solvent in the circulating stream to improve heat
transfer through condensation.
The product granules are pneumatically conveyed to a purge hopper. By purging with a nitrogen
steam mixture, monomers are further removed from the granules. The purge and conveyor gas
streams are recycled. To limit the build-up of impurities, a side-stream is sent to a dedicated
treatment unit to reduce its VOC content before being discharged into the air.

The degassed polymer granules are fed to a melting extruder and pelletized in an underwater
pelletizer. If required, additives can be added to the melted polymer. The pelletizer water is
recycled; a small side-stream has to be discharged. The resulting waste water contains a small
amount of hydrocarbons due to the direct contact with the pellets.

The wet pellets are sent to an air dryer and pneumatically conveyed to intermediate storage silos.
During intermediate storage, the product can be further conditioned by air to remove the last
residual ethylene. The air from the dryer and the air from the silos and the pneumatic conveying
system are discharged directly into the air. After final degassing, quality control and blending,
the product is pneumatically conveyed into storage silos or directly sent to the packaging or bulk
loading areas.
HDPE Gas Phase Process
Petrochemical Industries Lec. 6

2. Polystyrene industry

Polystyrene belongs to the group of standard thermoplastics that also includes polyethylene,
polypropylene, and polyvinyl chloride. Because of its special properties, polystyrene can be used in an
extremely wide range of applications.
In practice, three different types of polystyrene are distinguished. The transparent and brittle polymer is
called general purpose polystyrene (GPPS), the white, non-shiny but relatively flexible, rubber modified
polystyrene is called (high) impact polystyrene (IPS or HIPS). Expandable or foam polystyrene (EPS) is
the third group to distinguish here due to its different production techniques.

General purpose polystyrene (GPPS) process

Process Description
Final
Raw materials like styrene (potentially purified), and processing aid are fed into the reactor(s). The
reactor train usually includes continuous stirred tank reactors (CSTR) and/or plug flow reactors (PFR).

Styrene itself acts as the solvent of the reaction. Moreover, up to 10 % ethyl benzene may be added to
ensure better reaction control. The reactors‟ temperatures are controlled at between 110 and 180 oC. The
reaction pressure is up to 1 MPa in the case of a PFR and at atmospheric or sub-atmospheric pressure in
the case of a CSTR.

Additional chemicals are added into the feed stream or into the reactors. At the end of the reactor train,
the styrene monomer conversion reaches 60 – 90 % of solid polystyrene product. The process flow then
goes through a devolatilisation section where it faces one or two flashes (one or two devolatilisation
vessels) to separate the polymer from the unreacted species. The devolatilisers are operated at high
temperatures (220 – 260 °C) and under high vacuums (<40 mbar).

Between the two devolatilisation steps, an injection of water (stripping) can be added to improve
monomer removal. After condensation, unreacted styrene and ethyl benzene are recycled to the feed line,
either directly using a recycle loop or through a storage tank. A purge of undesirable components is
carried out on this stream.

The melted polymer is then transferred through a dye head to obtain strands that are cut (dry or
underwater) by pelletizers. After drying, the pellets are discharged in a pneumatic conveyor and
then stored in silos for packaging and/or shipping in bulk.
A flow diagram of the GPPS process

Technical Parameters of GPPS Process

3. Rubber industry

Rubbers are flexible at room temperature. Most of them are amorphous materials and do not
show a melting point. They have a glass transition point instead which is well below room
temperature. Below this glass transition temperature they are rigid. The monomers, polymers,
properties and uses of the most important rubbers are shown below:
1. Polybutadiene Rubber: Properties and Applications

Butadiene is a flammable, colorless gas with a mild aromatic odor and it is highly reactive. Its
molecular weight 54.1 Boiling/Melting Point 24ºF / -164ºF. Butadiene is soluble in alcohol and
ether, insoluble in water and polymerizes readily, particularly if oxygen is present.

One major use of butadiene has been in the making of synthetic rubber (butadiene, styrene-
butadiene and nitrile butadiene rubbers. There are two sources of butadiene in world: Extractive
distillation from Crude C4 stream produced as a co-product of ethylene production, and “on-
purpose” production by dehydrogenation of n-Butane or n-Butenes.

Polybutadiene (BR) is the second largest volume synthetic rubber produced, next to styrene-
butadiene rubber (SBR). The polymer is noted for its high resistance to abrasion, low heat
buildup, and resistance to cracking.
The major polybutadiene is used in tyres with over 70% of the polymer produced going into
treads and sidewalls. Cured BR imparts excellent abrasion resistance (good tread wear), and low
rolling resistance (good fuel economy) due to its low glass transition temperature (Tg). The low
Tg, typically <–90C, is a result of the low “vinyl” content of polybutadiene, polybutadiene is
usually blended with other elastomers like polystyrene and acrylonitrile-butadiene-styrene resin
(ABS) with about 25% of the total volume going into these applications. Also, about 20,000
metric tons worldwide of “high cis” polybutadiene is used each year in golf ball cores due to its
outstanding resiliency.

Polybutadiene Manufacturing Process

Polybutadiene is a homopolymer (only one monomer) of 1,3 butadiene, a monomer containing
four carbon atoms, and six hydrogen atoms (C4H6). The four carbon atoms are in a straight chain
containing two “double bonds” as follows:

1,3 butadiene

It is the double bonds that are the key to polymer formation. They are attacked by catalysts to
maintain a repetitive chain growth process which continues until something is added to terminate
the reaction at the desired molecular weight. For a typical polybutadiene, molecular weight
(Mn = number average) is usually >100,000 grams per mole. This represents a chain that contains
over 2,000 butadiene units.

Most polybutadienes are made by a solution process, using either a transition metal (Nd, Ni, or
Co) complex or an alkyl metal, like butyl lithium, as catalyst. Since the reaction is very
exothermic, and can be explosive, particularly with alkyl lithium catalysts, the reaction is
normally carried out in solvents like hexane, cyclohexane, benzene or toluene. The solvents are
used to reduce the rate of reaction, control the heat generated by the polymerization and to lower
the viscosity of the polymer solution in the reactor. A typical polybutadiene polymerization
would be run at about 20% monomer and 80% solvent.

The polymerization can either be a batch process or a continuous process. In batch mode,
monomer, solvent and catalyst are charged to the reactor, heated to initiate the process, and then
allowed to continue to completion. The polymer solution is then transferred to another vessel or
process unit to remove the solvent.

In continuous mode, monomer, solvent and catalyst are continuously fed into the bottom of the
first of a series of reactors at a temperature suitable for polymerization. The polymerization
progresses as the solution flows through the reactors and polymer solution is taken off at the top
of the last reactor without stopping the process. The continuous process is the most economical.
In both processes, the finished product is usually in the form of bales which weigh from 50 to 75
pounds each.

Commercially, polybutadienes are obtained by anionic polymerization initiated by lithium alkyls

in aliphatic/cycloaliphatic media (n-hexane or cyclopentane) as solvent. The lithium alkyl
initiated polymerization of dienes belongs to the class of anionic living polymerization whose
typical feature is the absence of any termination reactions (living polymerization); this gives a
polybutadiene with vinyl content < 10%, trans and cis being quite of the same quantity, with a
narrow molecular weight distribution (Mw/Mn < 2,2). The reaction is carried out using one
agitated continuous reactors. Due to the features of anionic polymerization in continuous reactors
the use of an antifouling agent is necessary in order to prevent any gel formation during the
polymerization. Antifouling is an hydrocarbon which is continuously fed in reaction in a fixed
ratio with initiator. Modern ionic catalysts are so effective that removal of the catalyst after
polymerization is not required for most of the applications. Only one gram of transition metal,
for instance, produces more than 200 tones of final products. Thus, the residual concentration of
the transition metal is no more than a few parts per million

Continuous polybutadiene Plant

LPS: Low Pressure Separator, MPS: Medium Pressure Separator
Types of Polybutadiene
Polybutadienes are made either with high cis content (95 to 97 percent) or with only 35
percent cis content along with 55 percent trans and 10 percent side vinyl. The properties of the
two polymers are quite different.
a. High Cis Polybutadiene
The alkyllithium and transition metal catalysts make very different products. The transition
metal, or so called Ziegler catalysts produce very “stereoregular” polybutadienes with one type
having the main polymer chain on the same side of the carbon-carbon double bond contained in
the polybutadiene backbone. This is called the cis configuration.

High cis polybutadiene will usually have cis content >95% which gives rise to better “green
strength” and increased cut growth resistance in the cured product. The neodymium catalyst
system produces the highest cis content of about 99% and also makes the most linear chain
structure (no branching) producing a polymer with the best tensile and hysteresis (low heat build-
up) properties of all the high cis types. The cobalt system produces a highly branched BR with a
low solution viscosity that makes a good polystyrene and acrylonitrile-butadiene-styrene
modifier. The nickel catalyst makes polybutadiene with an intermediate level of branching.

Lithium-based Polybutadiene
The alkyllithium or “anionic” catalyst system produces a polymer with about 40% cis,
50% trans and 10% vinyl when no special polar modifiers are used in the process. The
alkyllithium process is probably the most versatile, because the growing chain end contains a
“living” anion (negative charge) which can be further reacted with coupling agents or functional
groups to make a variety of modified polybutadienes.

b. High Trans Polybutadiene

High trans polybutadiene is a crystalline plastic material which was used in golf ball covers.
Trans polybutadiene has a melting point of about 80°C. It is made with transition metal catalysts
similar to the high cis process (La, Nd, and Ni). These catalysts can make polymers with >90%
trans again using the solution process.
2. Styrene-butadiene rubber
Styrene-butadiene rubber is an addition polymer formed by addition reactions between butadiene
and styrene.

SBR Production Process

SBR can be produced by two basically different processes: from solution (S-SBR) or as emulsion
(E-SBR). In the first instance the reaction is ionic polymerisation, in the emulsion
polymerization case the reaction is via free radical polymerization. In that process; Low pressure
reaction vessels are required and usually charged with styrene and butadiene, the two monomers,
a free radical generator and a chain transfer agent such as an alkyl mercaptan and water.
Mercaptans controls molecular weight and high viscosity product from forming. The anionic
polymerization process is initiated by alkyl lithium and water not involved. High styrene content
rubbers are harder but less rubbery.
Petrochemical Industries Lec. 7

Polyvinyl Chloride (PVC) Industry

PVC is a thermoplastic made of 57% chlorine (derived from industrial grade salt) and 43%
carbon (derived predominantly from oil / gas via ethylene). It is less dependent than other
polymers on crude oil or natural gas, which are nonrenewable, and hence can be regarded as a
natural resource saving plastic, in contrast to plastics such as PE, PP, PET and PS, which are
totally dependent on oil or gas. This chlorine gives to PVC excellent fire resistance. The bulk of
world production is currently manufactured using the chemical compound ethylene which is a
product of the oil & gas industry.

At the start of the ethylene-based PVC production process, the ethylene is combined with
chlorine to produce an intermediate chemical known as EDC (ethylene dichloride or 1,2-
dichloroethane), which is then thermally cracked to produce the vinyl chloride monomer VCM.
The VCM gas is polymerized in an aqueous medium for both emulsion and suspension PVC
processes.

The Polymerization Process

At the beginning of any polymerization, the reactor is charged with water and some other
additives. If the gaseous phase contains atmospheric air, this has to be vented to the air.
A vacuum pump is often used to ensure residual oxygen levels are low. The gas head space may
also be purged with an inert gas (nitrogen). Thereafter the monomer is added to the reactor.

Polymerization reactions are exothermic, thus the reactors must be equipped with cooling
facilities. The pressure in the reactor is usually in the range of 0.4 – 1.2 MPa and the reaction
temperature is in the range of 35 – 70 °C. At the end of the reaction, 85 – 95 % of the VCM is
converted into PVC. The unconverted VCM is vented-off to a gas-holder or straight to a VCM
recovery unit, before stripping operations.

Suspension PVC process

In the suspension PVC (S-PVC) process, the monomer is dispersed in demineralized water by
the combination of mechanical stirring and surfactants. Partially hydrolyzed polyvinyl acetates
are the most widely used type of suspension agent. The polymerization takes place inside the
VCM droplets under the influence of VCM soluble initiators such as peroxides. A phase of solid
PVC primary particles builds up. The PVC particles present at the end of the polymerization
process, result from the complex aggregation of such primary particles, giving S-PVC its
characteristic.
A suspension of PVC particles having a mean particle size of between 50 and 200 µm is
produced. Besides particle size, the essential differences between S-PVC grades result from the
average length of polymer chains and from the porosity of the particles. Suspension PVC is
always produced batch wise in a stirred vessel.

Emulsion PVC Process

a. Batch Emulsion Process

In the batch emulsion process, the VCM is dispersed using an emulsifier, usually a sodium alkyl
or aryl sulphonate or alkyl sulphate. The polymerization takes place at the VCM water interface
using a water soluble initiator, such as an alkali metal persulphate. A redox system involving
copper and a reducing agent is often used. This type of process produces narrow width
unimodal latex of a small size (approximately 0.2 µm). Such latex, if dried close to its glass
transition temperature to produce a hard free flowing powder, is excellent for general purpose
use and battery separator polymers.

b. Continuous Emulsion Process

The process can be operated continuously, in which fresh VCM, emulsifiers and an initiator are
fed into the reactor and PVC latex is withdrawn continuously. Such processes tend to require
greater quantities of emulsifiers than the batch process. They produce latexes with a wide
particle size distribution and thus low plastisol viscosities suitable for a wide range of
applications, but the higher levels of emulsifier will preclude them from applications where
water absorption or clarity of the final coating is important.
d. Microsuspension PVC Process

An alternative approach for producing latex is microsuspension polymerization. In this process,

an initiator such as lauroyl peroxide is used, which is highly soluble in the VCM, but is
essentially insoluble in water. Thus, polymerization takes place within the dispersed VCM
droplets. The water insolubility of the initiator also helps to stabilize the VCM droplet, and it
may be possible to use lower levels of emulsifier compared with the batch emulsion and
continuous emulsion processes. Lower levels of emulsifier can be advantageous, for example for
applications coming into contact with food, where water absorption or clarity is important, and
also for the environmental impact of the process. Such latexes produce polymers are with a wide
particle size distribution.

Final
Features for PVC Emulsion Processes