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-600036
INDIA
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 $2.2 Trillion …… and growing
Catalysis in Chemical Industry
Petroleum
Petroleum
refining
refining
EnvironEnvironmental
mental
protection
protection
PetroPetrochemicals
chemicals
Catalysis
Catalysis
Fine
Fine&&
Agro
Agro
chemicals
chemicals
Fertilizer&
Fertilizer&
Inorganic
Inorganic
chemicals
chemicals
PharmaPharmaceutical
ceutical
Catalysts- Motors of Chemical Industry
Chemical Industry-The challenges
Constraints in feedstock with respect to availability,
quality & cost
Eco friendly processes & products: stringent emission
levels- Preserving the environment
Need for conserving energy
Waste minimization/effective treatment
Catalysts with higher efficacy: activity/selectivity/ life /
Max.atom efficiency
Process improvements: milder conditions/fewer steps
Ever-increasing demand for niche /specialty products at
affordable prices
New catalysts /processes: Reduction in discovery &
process development cycle time
Catalysis provides innovative solutions
Catalysis- Key to process innovations
New
processes
New
products
Energy
Catalysis
Feed stock
Environment
Cost of
production
Catalysis: The science behind sustainable energy & chemicals
How Science responds to the technological challenges ?
Production Ultra Low Sulfur Diesel requires ultra high active HDS catalysts
Target ( <10ppm S) achieved through scientific pursuits
Science takes on the demands from the environment
Global Catalyst Market
Global Catalyst Market
Major market segments
14
13
US$ Billion
Petroleum Refining
Polymerization
Petrochemicals /
Chemicals
Environmental
12
11
10
9
8
1999
Market Projections- 2012
Growth rate
Market value
6.3 %
16.5 Bill.US$
2002
2005
2007
Year
Global Catalyst market: $ 12.9 Bill
(up to 2007).
Catalysts for Energy & Environment to grow faster
Chemical Industry- Products pattern
Petrochemicals-37%
Chemicals- Intricately woven with our day to day life
Petroleum Refining- The Mother Industry
Transport
Energy
Petroleum
Refining
Chemicals &
Fertilizers
Petro
chemicals
Product Slates
Petroleum
Fuels
Feed-stocks
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
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
Butadiene
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
Plasticizers
Polyesters
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/
IPCL/RIL
Xylene Isomerization- Towards
ZSM-5 Composite
maximization of p-Xylene- EB Conversion/ UOP, Axens, Exxon-Mobil
EB dealkylation prcesses
Zeolyst , IPCL/RIL
C7+C9 Aromatics TransalkylationUpgradation of low value C7& C9 streams,
towards maximization of p-Xylene
ZSM-5 Composite
UOP, Axens, Exxon-Mobil,SK
Corpn
Toluene Disproportionation- Up gradation
of low value C7 stream- Value added
products- Benzene & p- Xylene
ZSM-5 Composite
UOP, Axens, Exxon-Mobil,
Alkylation of Toluene/ EthylbenzneValue added products- p-Xylene & PDEB
Pore regulated ZSM-5
IPCL/RIL, UOP
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 Pt-Sn/Al2O3,
alkylation with Benzene to Linear
UOP, IFP,IPCL/RIL
Alkyl Benzene (LAB)
Ethyl benzene to Styrene
Fe-K/Al2O3
UOP
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 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 Co-Mn fatty acids
(PTA)
Butane to Maleic anhydride
V-P-O, Ineos
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)
UOP’s 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)
Mobil’s Olefin Inter conversion Process (MOI)