Petrochemical Engineering

Course Code: CHE416

Mian Hamood ur Rehman (P.E.)
Lecturer
Chemical Engineering Department
Introduction
• Chemical products made from raw materials of petroleum
(hydrocarbon) origin.
• Petroleum and natural gas are made up of hydrocarbon
molecules which are comprised of one or more carbon atoms
to which hydrogen atoms are attached.
• Currently oil and gas are the main sources of the raw
materials because they are most readily available and can be
processed most easily into primary petrochemicals
• Only about 5% of the oil and gas consumed each year is
needed to make all the petrochemical products.
• Petrochemicals have had a dramatic effect on our food,
clothing and shelter. Some synthetics, tailored for particular
uses actually perform better than products made by nature
because of their unique properties. (pillows)
• Important petrochemicals are alcohols and aldehydes,
ethylene, propylene, butadiene, isoprene, benzene,
toluene, phenol, ethyne, acetic acid, acetic anhydride
and ammonia
• Materials made from gases include polyethylene,
polypropylene, polystyrene
• Two main classes of petrochemical raw materials:
– Olefins (ethylene, propylene) are mainly produced from
hydrocarbons by steam cracking and by catalytic cracking.
– Aromatic hydrocarbons (Benzene and Xylene isomers) are
mainly produced by catalytic reforming.
Primary Petrochemicals
• Include: Olefins (ethylene, propylene and
butadiene), aromatics (benzene, toluene and
xylene) and methanol.
• Olefins are unsaturated hydrocarbons that
appear as short chains of two three or four
carbons in length.
• Aromatics contain a six carbon ring structure.
• The oxygen/hydrogen group in methanol
donates that it is alcohol.
Primary Petrochemicals
Intermediates and Derivatives
• Intermediates 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 and oxygen in the finished derivative
• One of the most important processes is polymerization
used in the production of plastic, fibers and synthetic
rubber
Intermediates and Derivatives
• Some typical derivatives:
– Vinyl acetate for paint paper and textile coatings
– Vinyl chloride for polyvinylchloride (PVC)
– Resin manufacture
– Ethylene glycol for polyester textile fibers
– Styrene which is important in rubber and plastic
manufacturing
Intermediates and Derivatives
Major End Use Products
– Vinyl acetate for paint paper and textile coatings
– Vinyl chloride for polyvinylchloride (PVC)
– Resin manufacture
– Ethylene glycol for polyester textile fibers
– Styrene which is important in rubber and plastic
manufacturing
Major End Use Products
– Vinyl acetate for paint paper and textile coatings
– Vinyl chloride for polyvinylchloride (PVC)
– Resin manufacture
– Ethylene glycol for polyester textile fibers
– Styrene which is important in rubber and plastic
manufacturing
Major End Use Products
Petrochemical Industry
• Petrochemical industry is a large and complex source
which is very difficult to define because its operations
are interwined with the inorganic sector of the
chemical industry, with manufacturing or fabrication
or with the petroleum refining industry
• Chemicals produced in petrochemical industry are
fitted into four categories:
– Basic raw materials
– Key intermediates
– Minor intermediates
– End products
Petrochemical Industry
• Petrochemical industry also includes the treatment of
hydrocarbon streams from the petroleum industry
• Some of the raw materials used in the petrochemical
industry include petroleum, natural gas, ethane,
hydrocarbon, naphtha, etc
• Natural gas and petroleum are the main feed stock of
the petrochemical industry; 65% of petrochemical
facilities are located at or near refineries.
• Approx. 2500 organic chemical products are produced
directly or indirectly from basic petrochemicals
• organic chemicals produced from petrochemical
industries are employed in downstream industries like
plastics, synthetic fibres, elastomers, pharmaceuticals
Process Description
• Main processes conducted in the basic petrochemical
industry are separation and purification
• Some petrochemical conversion processes are
cracking, hydrogenation, isomerization and
disproportionation.
• Six groups of productions are employed by the
petrochemical industry:
– Olefins production
– Butadiene production
– Naphthalene production
– Production of cresols and cresylic acids
– Separation of normal paraffins
Process Description
• 1,3-butadiene is used commercially to produce rubber,
resin and plastic
• 1,3-butadiene is involved in several reactions including
addition, oxidation and substitution reactions; its main
use is for polymerization
• Producers of 1,3-butadiene usually generate feedstock
at the same location as 1,3-butadiene production.
• Most 1,3-butadiene is used in:
– Synthetic elastomer production
– Some is used in adiponitrile production ( the raw material for
Nylon 6,6
• Overall demand of 1,3-butadiene is expected to
increase due to growth of its speciality uses
Process Description
• 1,3-butadiene is produced by one of two processes:
– Recovery from a mixed hydrocarbon stream
– Oxidative dehydrogenation of n-butenes
• In an olefins plant a steam cracking furnace is used to
crack the hydrocarbon feedstock for the
manufacturing of ethylene or other alkenes.
• A mixed hydrocarbon stream containing butadiene is
routed to a recovery unit where the butadiene is
separated
• The heavy hydrocarbon are broken into two or more
fragments forming a stream of mixed hydrocarbons
• The flue gas from cracking furnace is vented in to the
atmosphere
Process Description
• After the cracking step, the mixed hydrocarbon stream
is cooled and sent to gasoline fractionator
• The fractionator is used to recover heavy
hydrocarbons (C5 and higher)
• The mixed stream is the compressed prior to removal
of acid gas (hydrogen sulfide) and carbon monoxide
• The mixed hydrocarbon stream then goes through
additional refining steps where it is separated from
Olefins (C3 and lower)
• The mixed C4 stream may be sent directly to
butadiene recovery at the same plant
Process Description
• If this olefins plant does not produce finished
butadiene, use the by-product mixed C4 streams in the
folowing ways:
– Recover the crude butadiene from the stream and sell it to a
butadiene producer
– Recirculate the stream into the front of the ethylene process
– Use the stream to fuel the equipment (eg furnaces) in the
ethylene process
• How to recover butadiene from C4 mixed stream?
• The mixed C4 stream is fed from pressurized storage
tanks into a hydrogen reactor to convert some of the
unsaturated hydrocarbons (acetylene) to olefins
Process Description
• The product C4 stream from hydrogenator is combined
with a solvent (furfural) and fed into an extractive
distillation operation
• In this operation most of the butanes and butenes are
separated from butadiene which is absorbed in the
solvent along with residual impurities
• Stripping operation is used to separate the butadiene
from the solvent
• Some residuals (alkynes) are removed from butadiene
stream by distillation and are usually vented to an
emission control device
Process Description
• The bottom stream from acetylene removal operation
contains butadiene and residuals such as polymer and
2-butene
• The residuals are removed in the butadiene finishing
operation and sent to the waste treatment system
• The finished butadiene is then stored in pressurized
tanks.
Process Description
• In dehydrogenation process, steam and air are
combined with n-butenes and preheated, then passed
through a dehydrogenation reactor.
• Hydrogen is removed from the butenes feed stream
• The stream is compressed and then sent to a
hydrocarbon adsorption and stripping process
• The product is then routed to a light ends column for
further separation
• Finally, distillation and separation takes place with the
finished butadiene sent to storage
Aromatics and Derivative Flow scheme
Feedstocks
• Raw materials that are processed into other
substances and finished products in a petrochemical
plant
Classification of feedstocks
• Classified into three major groups:
– Olefins
– Aromatics
– Third generation mainly conisists of synthesis gas and
inorganic compounds
• Other feed stocks such as alkanes, cycloalkanes and
other organic compounds are also used
Feedstocks
Classification of feedstocks
• Naphtha a mixture of alkanes cycloalkanes and
aromatic compounds with a boiling point in the range
of 20 to 200oC contains 2 to 12 carbon atoms
• Other feedstocks are crackergases used in catalytic
cracking mainly for the production propylene and
butenes
Common feedstocks
• Most important alkenes feedstocks are ethene
propene and butadiene
• Ethene or ethylene is the most common used and
manufactured feedstock (eg plastic based on ethylene)
Feedstocks
Common feedstocks
• Aromatic feedstocks include benzene toluene xylene
and naphthalene
• Benezene to form styrene, a major contributor to
many types of plastics
• C6H6 + C2H4  C6H5C2H5  C6H5CH=CH2 + H2
benzene ethene ethylbenzene Styrene
• One of the most common product of feedstocks is
ammonia
• Ammonia is produced by reforming reactions involving
synthesis gas.
Effects on Environment
Carbonmonoxide poisoning
• Burning of all hydrocarbons is a two way process:
– First carbonmonoxide and water are created
CH4(g) + 2O2(g)  2CO(g) + 2H2O(l)
– Carbonmonoxide is burnt to creat carbondioxide
2CO(g) + O2  2CO2(g)
• CO will be formed if the petrochemical is not burned
properly (temp. is not high enough or constant)
• CO causes problem for humans as lungs will use CO in
the body before it uses O2
• A person can suffocate in a normal room as CO
replaces the O2 in the hemoglobin molecules in
human blood stream
Effects on Environment
Plastics
• Plastics are used in a huge range of products from
household items to industrial machines
• Plastics are durable and long lasting and can be just
molded in to any shape
• Problem is the long lasting part
• Plastics after the end of their use are thrown into the
dump, where they sit and sit and sit
• Take thousands of years to degrade, unlike the other
food items to degrade.
• Foods rot, metals rust but plastic have no really form of
decay in earth’s atmosphere
Effects on Environment
Acid Rain
• Petrochemicals are involved in the production of acid
rain
• All petrochemicals contain some percentage of sulfur
and nitrogen
• On burning they produce sulfur and nitrogen dioxide
that react with rain water and sulphate and nitrate
ions are produced, which cause the formation of an
acid in the rain water:
 SO2 + 2H2O  2H+ + SO42- + H2
 2NO2 + 2H2O  2H+ + 2NO3- + H2
Effects on Environment
Acid Rain
• Acid rain causes many problems both in our society
and natural world:
– Reacts with buildings and statues to slowly erode
the surface
– Fish and other water life could die due to more
acidic conc.