 Outlines

 Historical background
 Modern  petrochemical  industry  and  processes
 Summary
PC development in Pakistan

Dr.Prof. Khadija Qureshi

Chairperson Chemical Engineering department
Mehran UET jamshoro
 • Petrochemical History
• Coal‐derived  chemicals
• acetylene  chemistry  (Walter Reppe  chemistry)
• steam  crackers  and  the  olefin  industry.
• History of petrochemicals
• The  “birth”  of  petrochemicals  goes  back  more  than  150  years,
 when  aniline (A colorless oily liquid, C6H5NH2, present in coal
tar. It is used in the manufacture of dyes, drugs, and plastics, and
was the basis of the earliest synthetic dyes ) and  dyestuffs  were
 first  produced  from coal
• The  petrochemical  industry  was  largely  developed  in  
Germany  and  was  based  on  coal.

• The  first  large  scale  production  of   a  petrochemical  was that  of
acetylene
Historical date of first commercial Production
phenol F rasching (Germany), 1901
Hoffmann-Larochi
(Switzerland)

carbon  tetrachloride Gresheim-Elektro 1903

(Germany)

trichloroethylene Walker (Germany ) 1908

ethylene Gresheim-Elektro 1913

(Germany)
Ammonia BASF (Germany) 1913
Acetic acid Walker (Germany) 1916
Ethylene dioxide BASF (Germany) 1916
Acetaldehyde Hoechst (Germany) 1916
Historical date of first commercial Production
Acetone Hoechst (Germany) 1917
Weitzman (UK)
Standard oil of NJ (US)

Vinyl acetate Shawinigan chemicals 1920

Canada

Methanol BASF (Germany) 1923

Butanol BASF (Germany) 1923

Badische, Aniline, Soda,
Fabrik.

Vinyl Chloride Walker (Germany) 1930

 Petrochemicals
Franz  Fisher  and  Hans  Tropsch  in   1925
demonstrated  that  synthesis  gas  (a  mixture  of
H2and  CO)  can  be  converted  into  a  mixture  of  C2
to  C3carbon  range  oxygenates  and  hydrocarbons;
 later  this  came  to  be  known  as  the   Fischer‐
Tropsch  (FT)technology. Development  of  FT
 technology  led  to  the  development  of  several
 downstream  processes,  among  them  Gas  to  Liquids
 (GTL),  and  hydroformylation  (OXO) processes  for
 the  production  of  alcohols.
•Germany  used  GTL  widely  during  WWII  to  support
the  demand  for  aviation  fuels.
Basic Petrochemicals raw materials
From  these  early  developments,  we  arrive  at  
today’s  petrochemical  industry  

There  are  roughly  three  basic  types  of  raw

 materials  for  petrochemical  derivatives
Synthesis  gas  (syn  gas)  
Aromatics:  benzene,  toluene,  and  xylenes  (BTX)  
Olefins:  ethylene,  propylene,  butenes
 Synthetic gas: Key to conversion natural gas or coal
For  coal  or  natural  gas  to  chemicals  or  fuels,
 synthesis  gas  is  the  key  intermediate
 Electricity LNG

Although with
Coal continuous
N.Gas
Incremental
improvement
Gasificatio Steam
n Reforming, The basic technology
Partial OX
remain unchanged.

Synthesis
gas
 Synthesis gas: Key to conversion of N.gas or coal
Wax
 Hydrogen, CO,
Ammonia, Urea
Linear
paraffin Fischer
Tropsch
GTL
Acetic acid,
Formaldehyde, Synthesis
MTBE chemicals Gas Liquid fuel

Methanol DME

MT
gasoline MTO ,Ethylene, Fuel
Propylene
Fuel
Methanol Production

iC4 = + CH3OH Estrification MTBE

CH3OH + CO Carbonylation Acetic acid
CH3OH Light olefins and gasoline
CH3OH Light olefins
2 CH3OH DME + water
Aromatic: Raw material For many Petrochemical
Derivative
• BTX
• Before  ~1950  petrochemicals  were  based  on coal
• In  1955,  the  US  benzene  production  was  70%
 based  on  coal  and  30%  on  petroleum
• With  the  increase  in  refining  capacity  and  the
 development  of  catalytic  reforming  technology,
 naphtha  became  the  primary  feedstock
• There  are  two  main  ways  of  generating  aromatics
 from  naphtha:
• naphtha  reforming
• naphtha  pyrolysis
Aromatics BXT: raw material and technology
1950’s:  The  development  of  liquid‐liquid  solvent
 extraction  technology  accelerated  the  production
 and  use of  BTX.
1952extraction  with  ethylene  glycols   Dow  Chemical
 (later  also  Union Carbide)
1960’sextraction  with  sulfolane shell
 Aromatics BXT: raw material and technology

 Benzene
Xylene
Toluene
Naphtha reforming

Raffinate
Solvents
Tetra ethyl glycol∽1952
Sulfolane∽ 1960
NMP∽ 2000
others
 Para -Xylene raw material for poly ester
1960’s:  the  adsorptive  separation  of  components
 was  developed,  employing  molecular  sieves,  by
 class  and  molecular  shape
1964:the  separation  of  normal  paraffin's  from
 kerosene   was  developed  using  molecular  sieves;
 this  led  to  the  production  of  linear  alkyl
benzene  (LAB)  biodegradable  detergent
 intermediates
1970’s:until  1970  all  the  p‐xylene  was  produced
 via  crystallization;  in  1971  the  adsorptive  
separation  of  p‐xylene  using  molecular  sieves  
was  commercialized  (UOP  ParexTM  process)
Para-xylene - both methyl groups can be oxidized to form
terephthalic acid dimethyl terephthalate - can be copolymerized
to form certain polyesters
Polyesters - although there can be many types, polyethylene
terephthalate is made from petrochemical products and is
very widely used.
Purified terephthalic acid - often copolymerized to form
polyethylene terephthalate
polyesters
Meta-xylene iso-phthalic acid
alkyd resins
Polyamide Resins
Unsaturated Polyesters
• Benzene Derivatives:
benzene - the simplest aromatic hydrocarbon
Ethyl benzene - made from benzene and ethylene
 styrene made by dehydrogenation of ethyl benzene; used as a
monomer
 polystyrenes - polymers with styrene as a monomer

cumene- isopropyl benzene; a feedstock in the cumene

process
 phenol- hydroxybenzene; often made by the cumene process
 acetone - dimethyl ketone; also often made by the cumene process

 bisphenol A - a type of "double" phenol used in polymerization in

epoxy resins and making a common type of polycarbonate

 epoxy resins - a type of polymerizing glue from bisphenol A,

epichlorohydrin, and some amine.

 polycarbonate - a plastic polymer made from bisphenol A
and phosgene (carbonyl dichloride)
 solvents - liquids used for dissolving materials; examples
often made from petrochemicals include ethanol, isopropyl
alcohol, acetone, benzene, toluene, xylenes
Cyclo-hexane - a 6-carbon aliphatic cyclic hydrocarbon
sometimes used as a non-polar solvent
 Adipic acid - a 6-carbon dicarboxylic acid which can be a
precursor used as a co-monomer together with a di-amine to
form an alternating copolymer form of nylon.
 Nylons - types of polyamides, some are alternating

copolymers formed from copolymerizing dicarboxylic acid

or derivatives with di-amines
 caprolactam - a 6-carbon cyclic amide
 nylons - types of polyamides, some are from polymerizing

caprolactam
nitrobenzene - can be made by single nitration of benzene
 aniline- amino benzene
 Methylene ,biphenyl, di-isocyanate (MDI) - used as a co-

monomer with diols or polyols to form polyurethanes or

with di- or polyamines to form polyureas
 polyurethanes

Alkyl benzene - a general type of aromatic hydrocarbon

which can be used as a presursor for a sulfonate
surfactant(detergent)
 detergents - often include surfactants types such as

alkylbenzene sulfonates and nonyl-phenol -ethoxylates

chlorobenzene
 Toluene derivative
Toluene - methylbenzene; can be a solvent or
precursor for other chemicals
benzene
toluene di-Iso cyanate (TDI) - used as co-
monomers with diols or polyols to form
polyurethanes or with di- or polyamines to form
polyureas
polyurethanes - a polymer formed from di-
isocyanates and diols or polyols
benzoic acid - carboxybenzene
caprolactam
nylon
Olefins: Main raw material for many Pertochemical derivatives

Ethylene: Raw material and technology

Raw materials Technology
Ethane, propane, Thermal pyrolysis
Naphtha, gas oil
Incremental innovations in thermal cracking and
furnace design technology have allowed single
train ethylene capacity to exceed 1 mm MT/Yr
Natural gas based or coal based Methanol to
Olefins (MTO) technology is on the horizon.
• Steam Cracker and olefins industry
ethane  ⇾ethylene
LPG  ⇾ethylene,  propylene,  etc.
naphtha  ⇾ ethylene,  propylene,  C4S  (butadiene,  etc.),
 producer  gas,  BTX  aromatics
Steam Cracking
Main  products  (depending  on  feedstock,  severity,  and
 recovey  scheme)
ethylene
propylene
1,3‐butadiene
isobutylene
1‐butene  (2‐butene)
Pyroducer  gas  (pyrolysis  gasoline)  and  aromatics
Ethylene Derivatives
Ethylene - the simplest olefin; used as a chemical
feedstock and ripening hormone
Polyethylene (LDPE, HDPE, LLDPE) – polymerized
ethylene
Ethanol - via ethylene hydration (chemical reaction
adding water) of ethylene
ethylene oxide - via ethylene oxidation
ethylene glycol - via ethylene oxide hydration

engine coolant - ethylene glycol, water and inhibitor

mixture
polyesters- any of several polymers with ester

linkages in the backbone chain

 glycol ethers - via glycol condensation
ethoxylates

vinyl acetate
1,2-dichloroethane
trichloroethylene

Tetra, chloroethylene - also called

per-chloro ethylene; used as a dry cleaning

solvent and degreaser

vinyl chloride - monomer for polyvinyl chloride

polyvinyl chloride (PVC) - type of plastic used

for piping, tubing, other things.

Propylene: Raw material and tecnology
Until  1990  propylene  was  produced  from  the
 following  two  sources:
Steam  cracking  provided  about  2/3  of  the
propylene demand:  Propylene  is  a   byproduct  when
 propane  and  heavier  feed  stocks  are  used  for
 ethylene production    
The  remaining  1/3  came  from  refinery  FCC:
 Propylene  is  a  byproduct  of  refinery  FCC
   operation  for  the  production  of  gasoline  and
 diesel
Due  to  increasing  use  of  lighter  ethane
 feedstock  for   ethylene  production,  a  gap
 developed  between  propylene  supply  and
 demand  promoting  on‐purpose  propylene
 production

 Catalytic dehydrogenation of propane to

propylene (PDH) began in 1990
 Metathesis (C2= + C4= to 2 C3=)
Higher olefins ( C4-C8olefins) cracking technology
came on stream during the late 1990s
 Propylene Derivative
 Propylene - used as a monomer and a chemical feedstock isopropyl
alcohol - 2-propanol; often used as a solvent or rubbing alcohol
 Acrylonitrile - useful as a monomer in forming Orlon, ABS
 polypropylene - polymerized propylene
 propylene oxide
 Polyol - used in the production of polyurethanes
 propylene glycol - used in engine coolant and aircraft deicer fluid
 glycol ethers - from condensation of glycols
 acrylic acid
 acrylic polymers
 Allyl chloride -
 epichlorohydrin - chloro-oxirane; used in epoxy resin formation
 epoxy resins - a type of polymerizing glue from bisphenol A,

epichlorohydrin, and some amine.

Butene Derivative
 C4 hydrocarbons - a mixture consisting of butanes, butylenes and
butadienes isomers of butylene - useful as monomers or co-monomers
 isobutylene - feed for making methyl ter-butyl ether (MTBE) or
monomer for copolymerization with a low percentage of isoprene to
make butyl rubber.
 1,3-butadiene (or buta-1,3-diene) - a di-ene often used as a monomer or
co-monomer for polymerization to elastomers such as polybutadiene,
styrene-butadiene rubber, or a plastic such as Acrylonitrile-butadiene-
styrene (ABS)
 synthetic rubbers - synthetic elastomers made of any one or more of
several petrochemical (usually) monomers such as 1,3-butadiene,
styrene, isobutylene, isoprene, chloroprene; elastomeric polymers are
often made with a high percentage of conjugated di-ene monomers
such as 1,3-butadiene, isoprene, or chloroprene
Higher olefins
higher olefins poly olefins such, poly-alpha-
olefins which are used as lubricants
alpha-olefins - used as monomers, co-
monomers, and other chemical precursors. For
example, a small amount of 1-hexene can be
copolymerized with ethylene into a more flexible
form of polyethylene.
other higher olefins
detergent alcohols
Ethylene-Propylene summary
The  Middle  East  has  become  a  major  player;
 China,  India  are  growing  as  well  
Coal  or  natural  gas  based  methanol  will  be  a  new
raw  material  source  for  ethylene  and  propylene  
Naphtha  crackers  and  refinery  FCC  units  will
continue  to  be  a  major  source  of  propylene
Advantaged  propane  feed  stock  will  promote  PDH
at  selective  locations
In  the  future,  natural  gas  based  MTO  projects  at
 advantaged  NG  locations  (ME,  FSU)  may  give  tough
competition  to  naphtha  based  projects.
Over all summary
Time  and  time  again,  technology
 breakthroughs  make  major  impacts  on
 industry.
Industry  always  looks  at  the  availability
 of  lower  cost  raw  materials  or  relocates
 to  where  they  are  
No  near  term  major  changes  are
 expected  in  BTX  or  LAB  production
technologies
New  technologies  for  the  production  of  light  olefins
 will  accelerate  growth
ME  is  becoming  a  key  player  due  to  low  cost  ethane
 feed  stock
As  happened  to  the  methanol  industry,  the  olefins
industry  is  poised  for  another  change  to  come  
Methanol  will  become  a  bigger  and  more
 important industry
Natural  gas  or  coal  based  methanol  will
 promote MTO
We  have  only  covered  aromatics  and  olefins  as  main
 petrochemical  intermediates.
The  downstream  industry  of  polymers,  plastics,  fibers,
 resins  is  vast,  continuously  innovating,  and  coming  up
 with  new  engineered  materials.\
http://www.engineeringpakistan.com/ChemicalVision.pdf
Petrochemical development in Pakistan
Pakistan Scenario:-
Historical Background
The development of the chemical industry in Pakistan
started in the early 1950’s. Since Pakistan did not have
an industrial base, governments gave preference to
import substitution over export-oriented policies in their
strategic plans for future development.
In spite of rather poor available resources, Pakistan
made a significant start and was considered a promising
developing country in 1960’s. Pakistan continued to
follow an inward-oriented import-substitution policy
until the end of 1990’s, which hampered the
development of export-oriented industries.
Continue:-
Pakistan did not appreciate the advantages
associated with trade liberalization until late in
1990s and supported highly protectionist trade
policies. It delayed trade liberalization and tariff
rationalization until the end of 1990’s. The
chemical and the manufacturing sectors have
also been adversely affected by various factors,
such as acute energy shortages and poor
structural policies. Their present share in
2008/09 GDP is estimated at 18.4%, compared
with a contribution of 23% in 2006-07.
Existing Status Of PC in Pakistan
 Chemical industry in Pakistan is widespread, in
organized & unorganized sector. It is not
possible to have an exact figure for investment in
this sector; however a close approximation of
investment in chemical sectors ranges between
Rs. 550 - 600 billion. The chemical related
imports constitute about 17% of the total import
bill. There are three general classes of products
in this Sector:
Continue:

 Basic chemicals both inorganic and organic such as

acids, alkalies, salts, ethylene, propylene, benzene,
toluene, Xylene etc.;

 Chemical products used in further manufacturing i.e.

intermediates such as pure Terephthalic acid, phthalic
anhydride,

 Finished chemical products for end use or ultimate

consumption; synthetic fibers i.e. polyester, PVC,
polyethylene, polypropylene, polystyrene etc.
Continue:-
Pakistan made a considerable progress in basic
inorganic chemicals like Soda Ash, Caustic Soda,
Sulphuric Acid & Chlorine and sufficient production
capacity of these chemicals is available not only to cater
the needs of the local industry while surplus is being
exported, imports of these products are negligible.
However Pakistan’s organic chemical industry could not
flourish due to unavailability of basic building blocks
such as Ethylene, Propylene, Butylenes & BTX
(Benzene, Toluene, Xylene) used for the production of
most of the organic chemicals that are employed as a
raw material for a number of chemical sub-sectors such
as;
Pharmaceuticals , Pesticides , Dyes & Pigments ,Soaps & Detergents ,
Paints & Varnishes , Synthetic Fiber , Plastics & Resins , Rubber Tyres
& Tubes, Textiles Auxiliaries , Essential Oils & Perfumes .

 These petrochemical building blocks can be derived from a

Petrochemical complex, which generally consist of a Naphtha Cracker,
whereas naphtha is a product of oil refineries and currently its
production in the country is around 1,000, 000 M.Ton per annum which
is being exported. The investors have remained shy away from this
project due to the following reasons;
 Highly Cost Intensive project
 Sophisticated technology involved
 Export market limitations
 Insufficient current tariff spread
Pakistan Industrial Development Company (PIDC) has
recently developed feasibility study of this mega project
through an international firm of Singapore.
However there are some alternate routes to produce basic
petrochemical building blocks, these are;

 Gasification of Coal

 Dehydrogenation of Associated Gases

 Cracking of Natural Gas

 Each route has its own limitation, however recently some
developments are taking place to produce synthesis gas and
ethylene from natural gas cracking. This project surely opens the
gateway for the development of Petrochemical industry in
Pakistan, which will support the local chemical & allied products
industries in meeting their raw materials requirements and to save
the valuable foreign exchange.
Besides the imports of most of the raw material & intermediate for
these sectors, Pakistan succeeded to develop the downstream allied
chemical industries to meet most of the local demands. The
example of this development is obvious in synthetic fibres, soaps
& detergent, dyes & pigments, Paints & Varnishes, while amongst
intermediates Pakistan has sufficient capacity for Pure
Terephathalic Acid (PTA) and Poly Vinyl Chloride (PVC).
However still the imports of chemicals and allied industries stood
around 20%, which is significant for a small economy of Pakistan
Petrochemicals development in Regional Scenario
By comparison, economic growth in Southeast Asia
started in Japan in the 1960s and was followed by newly
developing countries, such as South Korea, Singapore,
Hong Kong and Taiwan. The “four little dragons” grew
rapidly, owing to their export-orientated
industrialization policies. These countries provided
export incentives, such as subsidized export credits,
duty free imports for feedstock's of manufactured export
products, encouraged foreign direct investment (FDI),
and also developed their science, technology and
engineering infrastructure to support their industrial
base.
Trailing behind the “four little dragons” are four
ASEAN countries--Indonesia, Malaysia, Thailand and
the Philippines. These four countries have also been
successfully increased their exports of high value-added
goods by following a policy of trade liberalization and
technology development.
However, the most spectacular developments in the
production and export of manufactured products
consisting of primary as well secondary chemicals have
taken place in China and India. China’s GDP has grown
at an annual average rate of 9-11% over the past two
decades.
China simultaneously developed a technology and
engineering infrastructure, by virtue of which it is now
exporting its chemical and manufactured products to
developed countries, as well as its process and project
engineering systems to Asia and Africa.
There is widespread understanding that economies with
liberal trade policies and openness have higher economic
growth rates. Trade liberalization, together with
complimentary policies and structural reforms, results in
substantial improvements to the business environment,
fosters market competition and helps technology
improvement and upgrading. These strategies boost
productivity and the optimum utilization of resources which
are absolutely essential for increasing exports and supporting
economic performance.
References:
vhttp://www.aiche.org/uploadedFiles/Conferences/Dep
artmentUploads/PDF/2008_Midwest_Regional_Pujado_
Introduction_Petrochemical_Industry.pdf
www.wikipedia.com

http://www.engineeringpakistan.com/ChemicalVision.p
df
www.google.com