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Homogeneous Catalysis HMC-6- 2010. Dr. K.R.Krishnamurthy National Centre for Catalysis Research Indian Institute of Technology,Madras Chennai-600036. DIMERIZATION & OILGOMERIZATION. Homogeneous Catalysis- Major Industrial Processes. Production, MTA.
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Homogeneous CatalysisHMC-6- 2010 Dr. K.R.Krishnamurthy National Centre for Catalysis Research Indian Institute of Technology,Madras Chennai-600036
Homogeneous Catalysis- Major Industrial Processes Production, MTA Oligomerization & Dimerization – Key homogeneous processes
Dimerization & Oligomerization Processes • Dimerization of ethylene to Butene-1- Co-monomer in LLDPE- IFP & SABIC processes • Dimerization of propylene- Methyl pentenes & Hexenes- Gasoline additives- DIMERSOL- IFP Sumitomo & BP processes • Dimerization of Butadiene- 1,5 Cyclo-octadiene-Cyclooctene- (ROP)- Vestenamer-Hulls process • Trimerization of Butadiene-Cyclododecatriene- (ROP)- Vestamid-Hulls process • Butadiene+ Ethylene co-polymerization-EPDM rubber- DuPont-Process • Oligomerization of ethylene to Linear Alpha Olefins- LAO - Chevron-Phillips,(Gulf Oil)-GULFTENE, Ineos (Ethyl), Idemitsu, Conaco, Shell (SHOP), SABIC (-SABLIN) Basis for the production of wide range of useful olefins & monomers
Dimerization of Propylene & Butadiene, Trimerization of Butadiene & Co-polymerization of Butadiene & ethylene to yield EPDM rubber
Alpha Olefins-Applications C4 to C6 Poly butenes, Co-monomers in polyethylene (4-12%) C6 to C10 Plasticizer alcoholsC8 to C10 Trimers, as Synthetic lubricants- C10 to C14 Detergents - Linear Alkyl Benzene (LAB) Alpha Olefin Sulphonates (LAO,AOS) C16 to C18 Lube oils, SurfactantsC20 to C30+ Oil field Chemicals, Wax replacements
Alpha Olefins -Processes • Thermal cracking of wax • Paraffins dehydrogenation • Alcohol dehydration • Ethylene oligomerization • F-T synthesis
Alpha Olefins via Ziegler Process Alfen Process Two steps 100ºC,10 MPa pressure ethylene 300ºC,1 MPa Gulf/Chevron & Ethyl Processes
Gulf/Chevron Process • One step process, with chain growth & elimination occur simultaneously • Solvent—Heptane, 200ºC, 25 MPa ethylene pressure • 0.4 % Al Et3 is used as catalyst • Schulz-Flory distribution of alpha olefins- Broad distribution of carbon No • Ethyl Process • Oligomerization at 160-275ºC, 13-27 MPa pressure • Separation into, C4-C10 & C12 –C18 • Higher Al alkyls produced at 100ºC & 20 MPa • Transalkylation of C4-C10 olefins with higher alkyls at 300º C & 10 Mpa • to get higher olefins • Idemitsu • Zr based catalyst
Shell Higher Olefins Process (SHOP) Involves four processes • Oligomerization of ethylene to C4-C20+α- olefins 80 to 120 °C and 70 to 140 bar (7 to 14 MPa) with a nickel phsophine complex (C6H5)2P(CH2)2COONi- Homogeneous • Isomerization of α-olefins to internal olefins- Heterogeneous • Metathesis of C20+olefins with C4-C8 olefins- Heterogeneous • Isomerization, hydroformylation & hydrogenation to α-alcohols- Homogeneous • Reaction carried out in polar solvents (1.4 Butane diol) in which α-olefins are insoluble • Bi-phasic liquid-liquid reaction with Ni concn.0.001-0.005 mole%, at 80-140ºC, 7-14 Mpa • Exothermic heat removed by exchangers
Shell’s SHOP Process-Stepwise conversions Step. 1- Oligomerization H2C=CH2 -----------→ H (CH2-CH2)n-CH=CH2 n= 1 to 19 Ni complex Step.2- Fractionation of alpha-olefins C4-C10- Olefins C10-C14- Olefins C16-C40- Olefins Step.3 – Hydroformylation of C10-C14 Olefins C10-C14 Olefins ------------→C11-C15 alcohols H2+CO CH3(CH2)7-CH=CH2-------------→CH3(CH2)7-CH2- CH2 –CHO Co(Co)4 ↓ H2 CH3(CH2)7-CH2- CH2 –CH2- OH
Shell’s SHOP Process-Stepwise Conversions Step.4 – Isomerization Catalyst Na/K on Al2O3 or MgO C4-C10- Olefins ------------→ C4-C10 Internal olefins C16 –C40- Olefins ------------→ C16 –C40Internal olefins CH3-CH2-CH=CH2------------→ CH3-CH=CH-CH3 CH3 (CH2)17 -CH=CH2-------------→ CH3-(CH2)8-CH=CH-(CH2)8-CH3 Step.5- Metathesis of C4-C10and C16-C40 internal olefins Catalyst Mo/W/Re onAl2O3 CH3-CH=CH-CH3 + CH3-(CH2)8-CH=CH-(CH2)8-CH3 (i-C4) ↓ (iC20) 2 CH3-CH=CH –(CH2)8-CH3 Step.6 – Fractionation of internal olefins C10-C14 Internal Olefins C4-C10 Internal Olefins C16-C40 Internal Olefins Separation of C10-C14 olefins & Hydroformylation to alcohols
Shell’s SHOP Process- Stepwise conversions Step.7 – Hydroformylation of C10-C14 Olefins C10-C14 Olefins ------------→C11-C15 alcohols H2+CO CH3(CH2)7-CH=CH2-------------→CH3(CH2)7-CH2- CH2 –CHO Co(Co)6 ↓ H2 CH3(CH2)7-CH2- CH2 –CH2- OH Step.8 – Repeat of steps 5,6 & 7 to exhaustion
SHOP Process- Isomerization & Metathesis Isomerization Metathesis
SHOP Process Scheme & Catalyst
Oligomerization-Addition of ethylene Initiation- Formation of Ni hydride- active centre for ethylene co-ordination Model compound
SHOP Process- Chain growth & Termination • Process parameters /control • the temperature; note that the reaction is highly exothermic, • • ethene concentration • • but-1-ene concentration • • composition of the medium • • catalyst activity • • process operation; e.g. mixing, settling of the two phases, pressure release, • cooling. • Ethylene pressure to be maintained high so as to promote chain growth • and avoid insertion of butene, which ends up in branched products • The catalyst odes not display any isomerization activity
SHOP Process- Chain growth & Termination Growth factor –γ – Concn. of each alkene is a certain fraction of the preceding alkene Product distribution determined by rate of growth kg and rate of termination, kt Rate constants are the same for all intermediate Ni alkyls, except for the first 2 or 3 members
SHOP Process- Chain growth Schultz Flory distribution Vs Growth factor K K= n(Cn+2 /n(Cn) . K adjusted at 0.75- 0.80
A,B,C &D four different pathways A,B &C- Chain termination Pathways D- Chain propagation pathway
Metathesis Bimolecular process involving exchange /redistribution of bonds in the reactants Yves Chauvin, Richard R. Schrock & R.H Grubbs, awarded Nobel prize in 2005 for pioneering work on metathesis Metathesis – Grubbs illustration as Dancing partners- Exchanging of partners AX +BY → BX +AY Olefin metathesis- Exchange of double bonds Alkane metathesis- Higher alkane to shorter and longer alkane Alkyne metathesis- Redistribution of triple bonds Intra-molecular metathesis of 4 -methyl 1,7 Octadiene
Olefin metathesis-Process steps Step.1 Formation of metal alkylidene complexes Step.2 Formation of metallocyclobutanes Step.3 Opening of metallocyclobutane to form products • Majority of metathesis reactions involve heterogeneous catalysis, Mo/W/Re supported on alumina • Homogeneous systems are also known
Topics for assignment –September 2012 Heterogenized homogeneous catalysts Applications of ionic liquids in homogeneous catalysis Challenges in catalytic processes for manufacture of pharmaceuticals Developments in olefins epoxidation processes in homogeneous phase Heterogeneous catalytic routes for oxidation of p-Xylene to PTA Continuous homogeneous catalytic processes
Assignments in Homogeneous catalysis Green processes for conversion of cyclohexane to adipic acid P- Xylene oxidation without Bromide as the initiator Alternative routes for methyl methacrylate production Homogeneous process for epoxidation of ethylene Alternative processes for propylene oxide