III B. Tech. I Sem.

Petrochemical Engineering

Petrochemicals
Prof. K. V. Rao
Programme Director
Petroleum Courses
JTNUK

Contents
Chemical industry & Catalysis
Origin of Petrochemicals
Basic / Building block chemicals
Basic chemicals to Petrochemicals
Petrochemical processes & catalysts
Ethylene, Propylene & Butadiene by thermal cracking
Alternative routes for Basic chemicals

Chemical Industry-The Fact Sheet

70000 products
10 Million direct employees
50 Million indirect employees
Wide range of products/processes
/ feed-stocks
Enabling better quality of life
Annual growth rate 2.4 %
Global enterprise valued at $2.2 Trillion and growing

Chemical Industry- Products pattern

Petrochemicals-37%

Chemicals- Intricately woven with our day to day life

Petroleum Refining- The Mother Ind

Transport

%
95

Petroleum
Refining

Energy

E
O

C
R
U
D

Chemicals &
Fertilizers

Petro
chemicals

5-6%

Product Slates
Petroleum
Fuels
Feed-stocks
Hydrogen
Lubricants
Syngas
Sulfur

Petrochemical feedstocks
C2-C3 gas
LPG
C4 stream
Naphtha for light
olefins
Naphtha for aromatics
Kerosene
Gas oil for cracking

Petrochemicals- The Origin

CRUDE OIL
REFINARY
FEEDSTOCKS
Gas, Naphtha, Gas Oil,
Kerosene

PETROCHEMICAL
INDUSTRY
BASIC CHEMICALS
Ethylene, Propylene, 1.3-Butadiene &
BTX,

PETROCHEMICALS
PE,PP,PVC,PS,PBR,MEG,LAB,ACN, AF, PTA, PHA,
MA,CPL

Basic/Building block Chemicals

Ethylene
Propylene
Butadiene (1,3)
Benzene
Toulene
Xylenes

Petrochemicals from Ethylene

Petrochemicals from Propylene

Petrochemicals from B
Butadien
Butadiene
Polybutadiene
Rubber
PBR

Styrene-Butadiene
Rubber SBR

AcrylonitrileButadiene
-Styrene ABS

Adiponitrile
ADN

Specialty
Polymers /
Chemicals

Petrochemicals from Benzene

Petrochemicals from Toluene

Toluene

Benzene

Xylenes

Specialty/
Functionalized
chemicals

Petrochemicals from Xylenes

Xylenes

m-Xylene

p-Xylene

O-Xylene

Iso-phthalic acid

Terephthalic acid
PTA

Phthalic anhydride

PET

Polyesters

Plasticizers

Table.3. Major petrochemical processes &

catalysts
Process

Catalysts/Processes

Aromatics
Naphtha reforming- Production of
Gasoline & BTX

Pt-Re/Al2O3, Pt-Sn/Al2O3,
Semi-regenerative/ CCR
UOP/Axens/Criterion/Chevron/I
PCL/RIL

Xylene Isomerization- Towards

maximization of p-Xylene- EB
Conversion/ EB dealkylation prcesses

ZSM-5 Composite
UOP, Axens, Exxon-Mobil
Zeolyst, IPCL/RIL

C7+C9 Aromatics TransalkylationUpgradation of low value C7& C9

streams, towards maximization of pXylene

ZSM-5 Composite
UOP, Axens, Exxon-Mobil,SK
Corpn

Toluene Disproportionation- Up
gradation of low value C7 streamValue added products- Benzene & pXylene
Alkylation of Toluene/ Ethylbenzne-

ZSM-5 Composite
UOP, Axens, Exxon-Mobil,

Dehydrogenation
C3 ,C4 paraffins to OlefinsMonomers- Propylene, Iso-butene

Cr2 O3/Al2O3, Pt-Sn/Al2O3,

UOP, CATOFIN, Phillips,
Linde

C10-C13 paraffins to Mono

olefins- For alkylation with
Benzene to Linear Alkyl Benzene
(LAB)

Pt-Sn/Al2O3,
UOP, IFP,IPCL/RIL

Ethyl benzene to Styrene

Fe-K/Al2O3
UOP

Hydrogenation
Acetylenics in C2/C3/C4
hydrocarbon streamsPurification of monomers

Pd/Ni supported on
alumina with promoters
Axens, Sud-Chemie, BASF

Benzene to Cyclohexane- For

caprolactum production

Ni/Alumina, Pt/Alumina
Axens, SC,UOP

Hydrogenation of Oils/Fats

Ni/Alumina

Purification of PTA- removal of 4CBA

Pd/Carbon
BASF, Sud-Chemie,Chemit

Hydrogenation of unsaturated
organic compounds

Supported Ni/Pd with

promoters

Oxidation /Epoxidation /Oxychlrination /

Ammoxidation
Ethylene to Ethylene oxide

Promoted Ag/Alumina,
DOW,Shell,Sci.Design

Ethylene to Acetic acid

Supported Pd

Ethylene+ HCl to Ethylene

dichloride

CuCl2- KCl/Alumina
BASF, KNF, Oxyvinyl

Propylene to Acrylonitrile

Molybdates of
Bi,Fe,Ni/Silica
Ineos

Propylene to Acrylic acid

V-P-O,Ineos

Propylene to Propylene oxide

Supported Mo Oxides/Au

O-Xylene to Phthalic anhydride

Vanadia/TiO2

P-Xylene to Purified Terephthalic

acid
(PTA)

Co-Mn fatty acids

Syngas conversions
CO+2H2 CH3OH

ZnO-CuO-Chromia

CO+H2 n-Paraffins (FischerTropsch)

Supported Co/Fe with

promoters

CO + CH3OH Acetic acid

Rh-,Ir-Iodide promoted

Polymer
Processes

Ethylene to
Polyethylene
LDPE, LLDPE, HDPE

High pressure tubular process (LDPE)

Chevron-Phillips slurry process
Basell Spherilene process
( LLDPE/HDPE)
NOVA- Sclairtech process
( LLDPE/HDPE)

Propylene to
Polypropylene
PP, PE Copolymers

Basell Spheripol PP process

Dow UNIPOL PP process
Borstar PP process

Vinyl chloride to
Polyvinyl chloride
PVC

Innovyl Suspension PVC

UHDE, Goodrich process

Polymer
Processes

Ethylene to
Polyethylene
LDPE, LLDPE, HDPE

High pressure tubular process (LDPE)

Chevron-Phillips slurry process
Basell Spherilene process
( LLDPE/HDPE)
NOVA- Sclairtech process
( LLDPE/HDPE)

Propylene to
Polypropylene
PP, PE Copolymers

Basell Spheripol PP process

Dow UNIPOL PP process
Borstar PP process

Vinyl chloride to
Polyvinyl chloride
PVC

Innovyl Suspension PVC

UHDE, Goodrich process

(SRT-Heaters)

S as DMDS is injected to control CO & Coke

Selective hydrogenation of C2,C3 & C4 acetylenes in olefinic

streams are the critical processes to get pure C2,C3 & C4 olefins

Propylene: Supply-Demand gap

Olefin metathesis
C2H4 + C4H8 2 C3H6
Can be a stand alone unit or integrated with cracker/FCC unit
Low investment, less energy intensive, attractive returns
High propylene/ethylene yield ratios, varying from 0.5 to 1.1
Use of low cost C4 stream
Process technologies
META-4 (Axens IFP Group Technologies)
OCT Olefins Conversion Technology (ABB Lummus)
UOPs process
Depends on relative costs of ethylene & propylene

Metathesis- Catalysts & Process

conditions

Alternative routes to Propylene

Olefin Inter conversion Processes

Catalytic cracking of C4- C5 streams or the light naphtha

streams in a fixed or fluidized bed reactor
Compatible with crackers and FCC units
Unlike metathesis, do not consume ethylene.

Process technologies

Olefin Cracking Process (UOP-ATOFINA)

Propylur (Lurgi)
PCC process (Exxon Mobil)
SUPERFLEX (Lyondell/Kellogg)
Mobils Olefin Inter conversion Process (MOI)