1. Catalysts & Catalytic Processes in Petrochemical Industry
Part-1 Basic chemicals
10 th Orientation Course in Catalysis for Research Scholars
28 th November to 16 th December,2009
Dr.K.R.Krishnamurthy
National Centre for Catalysis Research (NCCR)
Indian Institute of Technology
Chennai
INDIA

2. 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

3. 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

4. Catalysis in Chemical Industry
Catalysts- Motors of Chemical Industry

5. Chemical Industry-The challenges
Constraints in feedstock with respect to availability, quality & cost
Eco friendly processes & products: stringent emission levels- Preserving the environment
Need for conserving energy
Waste minimization/effective treatment
Catalysts with higher efficacy: activity/selectivity/ life / Max.atom efficiency
Process improvements: milder conditions/fewer steps
Ever-increasing demand for niche /specialty products at affordable prices
New catalysts /processes: Reduction in discovery & process development cycle time
Catalysis provides innovative solutions

6. Catalysis- Key to process innovations
Catalysis: The science behind sustainable energy & chemicals

7. Target ( <10ppm S) achieved through scientific pursuits
How Science responds to the technological challenges ?
Production Ultra Low Sulfur Diesel requires ultra high active HDS catalysts
Target ( <10ppm S) achieved through scientific pursuits
Science takes on the demands from the environment

8. Global Catalyst Market
Major market segments
Petroleum Refining
Polymerization
Petrochemicals / Chemicals
Environmental
Market Projections- 2012
Growth rate %
Market value Bill.US$
Global Catalyst market: $ 12.9 Bill
(up to 2007).
Catalysts for Energy & Environment to grow faster

9. Chemical Industry- Products pattern
Petrochemicals-37%
Chemicals- Intricately woven with our day to day life

11. Petroleum Refining- The Mother IndustryC R U D E O I L
5-6%

12. Product Slates Petrochemical feed-stocks Petroleum Fuels C2-C3 gas
Hydrogen
Lubricants
Syngas
Sulfur
Petrochemical feed-stocks
C2-C3 gas
LPG
C4 stream
Naphtha for light olefins
Naphtha for aromatics
Kerosene
Gas oil for cracking

13. Ethylene, Propylene, 1.3-Butadiene & BTX,
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

14. Basic/Building block Chemicals
Ethylene
Propylene
Butadiene (1,3)
Benzene
Toulene
Xylenes

15. Petrochemicals from Ethylene

16. Petrochemicals from Propylene

17. Petrochemicals from Butadiene
Polybutadiene
Rubber
PBR
Styrene-Butadiene
Rubber SBR
Acrylonitrile-
Butadiene
-Styrene ABS
Adiponitrile
ADN
Specialty
Polymers /
Chemicals

18. Petrochemicals from Benzene

19. Petrochemicals from Toluene
Benzene
Xylenes
Specialty/
Functionalized
chemicals

20. Petrochemicals from Xylenes
O-Xylene
m-Xylene
p-Xylene
Phthalic anhydride
Terephthalic acid
PTA
Iso-phthalic acid
Plasticizers
PET
Polyesters

21. Table.3. Major petrochemical processes & catalysts
Catalysts/Processes
Aromatics
Naphtha reforming- Production of Gasoline & BTX
Pt-Re/Al2O3, Pt-Sn/Al2O3,
Semi-regenerative/ CCR
UOP/Axens/Criterion/Chevron/IPCL/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 Transalkylation- Upgradation of low value C7& C9 streams, towards maximization of p-Xylene
UOP, Axens, Exxon-Mobil,SK Corpn 
Toluene Disproportionation- Up gradation of low value C7 stream- Value added products- Benzene & p- Xylene
UOP, Axens, Exxon-Mobil, 
Alkylation of Toluene/ Ethylbenzne- Value added products- p-Xylene & PDEB
Pore regulated ZSM-5
 IPCL/RIL, UOP

22. 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 Styrene
Fe-K/Al2O3
UOP

23. Hydrogenation
Acetylenics in C2/C3/C4 hydrocarbon streams- Purification 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 4-CBA
Pd/Carbon
BASF, Sud-Chemie,Chemit
Hydrogenation of unsaturated organic compounds
Supported Ni/Pd with promoters

24. 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
Butane to Maleic anhydride
V-P-O, Ineos

25. Syngas conversions CO+2H2→ CH3OH ZnO-CuO-Chromia
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

26. Polymer Processes Ethylene to Polyethylene LDPE, LLDPE, HDPE
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

27. Polymer Processes Ethylene to Polyethylene LDPE, LLDPE, HDPE
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

44. (SRT-Heaters)
S as DMDS is injected to control CO & Coke

47. Selective hydrogenation of C2,C3 & C4 acetylenes in olefinic
streams are the critical processes to get pure C2,C3 & C4 olefins

50. Propylene: Supply-Demand gap

51. Depends on relative costs of ethylene & propylene
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)
UOP’s process
Depends on relative costs of ethylene & propylene

54. Metathesis- Catalysts & Process conditions

55. 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)
Mobil’s Olefin Inter conversion Process (MOI)