ContentsContents

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

Chemicals- Intricately woven with our day to day life

Petrochemicals-37%Petrochemicals-37%

Energy

Chemicals & Fertilizers

Petrochemicals

Transport

Petroleum Refining

95%

Petroleum Refining- The Mother IndustryPetroleum Refining- The Mother Industry

5-6%

CR

UD

E OI

L

Product SlatesProduct Slates

Petroleum Petroleum FuelsFeed-stocksHydrogenLubricantsSyngasSulfur

Petrochemical feed-Petrochemical feed-stocksstocks

CC22-C-C33 gas gas

LPGLPG

CC44 stream stream

Naphtha for light Naphtha for light olefinsolefins

Naphtha for Naphtha for aromaticsaromatics

KeroseneKerosene

Gas oil for crackingGas oil for cracking

CRUDE OIL

REFINARY

FEEDSTOCKSGas, Naphtha, Gas Oil, Kerosene

PETROCHEMICAL INDUSTRY

BASIC CHEMICALSEthylene, Propylene, 1.3-Butadiene &

BTX,

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

Petrochemicals- The OriginPetrochemicals- The Origin

Basic/Building block Chemicals

Ethylene

Propylene

Butadiene (1,3)

Benzene

Toulene

Xylenes

Petrochemicals from EthylenePetrochemicals from Ethylene

Petrochemicals from PropylenePetrochemicals from Propylene

AdiponitrileADN

PolybutadieneRubber

PBR

Styrene-ButadieneRubber SBR

Acrylonitrile-Butadiene

-Styrene ABS

Butadiene

Petrochemicals from ButadienePetrochemicals from ButadienePetrochemicals from BPetrochemicals from B

Specialty Polymers /Chemicals

Petrochemicals from BenzenePetrochemicals from Benzene

Toluene

Specialty/Functionalized

chemicals

XylenesBenzene

Petrochemicals from ToluenePetrochemicals from Toluene

Xylenes

O-Xylenep-Xylenem-Xylene

Phthalic anhydrideTerephthalic acidPTA

Iso-phthalic acid

PlasticizersPolyestersPET

Petrochemicals from XylenesPetrochemicals from Xylenes

Table.3. Major petrochemical processes & Table.3. Major petrochemical processes & catalystscatalysts

Process Catalysts/Processes

Aromatics

Naphtha reforming- Production of Gasoline & BTX

Pt-Re/Al2O3, Pt-Sn/Al2O3,Semi-regenerative/ CCRUOP/Axens/Criterion/Chevron/IPCL/RIL

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

ZSM-5 CompositeUOP, Axens, Exxon-MobilZeolyst , IPCL/RIL

C7+C9 Aromatics Transalkylation- Upgradation of low value C7& C9 streams, towards maximization of p-Xylene

ZSM-5 CompositeUOP, Axens, Exxon-Mobil,SK Corpn 

Toluene Disproportionation- Up gradation of low value C7 stream- Value added products- Benzene & p- Xylene

ZSM-5 CompositeUOP, Axens, Exxon-Mobil, 

Alkylation of Toluene/ Ethylbenzne- Value added products- p-Xylene & PDEB

Pore regulated ZSM-5 IPCL/RIL, UOP

Dehydrogenation

C3 ,C4 paraffins to Olefins- Monomers- 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 StyreneFe-K/Al2O3

UOP 

Hydrogenation

Acetylenics in C2/C3/C4 hydrocarbon streams- Purification of monomers

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

Benzene to Cyclohexane- For caprolactum production

Ni/Alumina, Pt/AluminaAxens, SC,UOP

Hydrogenation of Oils/Fats Ni/Alumina

Purification of PTA- removal of 4-CBA

Pd/CarbonBASF, Sud-Chemie,Chemit

Hydrogenation of unsaturated organic compounds

Supported Ni/Pd with promoters

Oxidation /Epoxidation /Oxychlrination / Oxidation /Epoxidation /Oxychlrination / AmmoxidationAmmoxidation

Ethylene to Ethylene oxidePromoted 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 

Butane to Maleic anhydride V-P-O, Ineos

Syngas conversionsSyngas conversions 

CO+2H2→ CH3OH ZnO-CuO-Chromia

CO+H2→ n-Paraffins (Fischer-Tropsch)

Supported Co/Fe with promoters 

CO + CH3OH→ Acetic acid Rh-,Ir-Iodide promoted

Polymer Processes

 

Ethylene to PolyethyleneLDPE, LLDPE, HDPE

High pressure tubular process (LDPE)Chevron-Phillips slurry processBasell Spherilene process ( LLDPE/HDPE)NOVA- Sclairtech process ( LLDPE/HDPE)

Propylene to PolypropylenePP, PE Copolymers

Basell Spheripol PP processDow UNIPOL PP processBorstar PP process

Vinyl chloride to Polyvinyl chloride PVC

Innovyl Suspension PVCUHDE, Goodrich process

Polymer Processes

 

Ethylene to PolyethyleneLDPE, LLDPE, HDPE

High pressure tubular process (LDPE)Chevron-Phillips slurry processBasell Spherilene process ( LLDPE/HDPE)NOVA- Sclairtech process ( LLDPE/HDPE)

Propylene to PolypropylenePP, PE Copolymers

Basell Spheripol PP processDow UNIPOL PP processBorstar PP process

Vinyl chloride to Polyvinyl chloride PVC

Innovyl Suspension PVCUHDE, 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

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)

UOP’s process

Olefin metathesis

Depends on relative costs of ethylene & propyleneDepends on relative costs of ethylene & propylene

Metathesis- Catalysts & Process Metathesis- Catalysts & Process conditionsconditions

Alternative routes to PropyleneAlternative 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)• Mobil’s Olefin Inter conversion Process (MOI)