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SHOP hell Higher igher Olefins lefins Process rocess Shell By Kamila Stefańska, 2009. Basic info on the SHOP: •Based on the homogenous catalysis •Comprises 3 steps: - oligomerization - isomerization - methathesis •Used for production of linear a – olefins and internal olefins •Designed by the Royal Dutch Shell • Oligomerization – The process of converting a monomer or a mixture of monomers into an oligomer (consists of limitted nb of monomers) •Isomerization – rearrangement reaction that occurs when compounds with the same formula exhibit different structures (e.g. 1 – butene and 2 – butene) •Metathesis – catalytic reaction in which alkenes are converted into new products by breaking - up and reformation of C-C double bonds. Linear a – olefins (LAO) •Olefins = Alekenes CnH2n • Linear Alpha Olefins (LAO) or Normal Alpha Olefins (NAO) • Internal olefins Overview of SHOP Oligomerization of ethylene • Catalyst : Ni complex (usually includes a phosphorous – oxygen chelate and organic part) Examples: • catalyst is dissolved in 1,4 - butanediol (polar) Catalytic cycle for the SHOP oligomerization step Products of oligomerization: Linear even numbered a – olefins ranging from C4 to C40 They are separated by the means of distillation : • C10 – C14 a – olefins • C4 – C8 a – olefins • C16+ a – olefins Linear hydroformylation of C10 – C14 a - olefins C10 – C14 a – olefins C11 – C15 alcohols Isomerization of C4 – C8 and C16 – C40 a - olefins •heterogenous catalyst: Na/K on Al2O3 or a MgO in the liquid phase C4 – C8 a – olefins C4 – C8 internal olefins C16 – C40 a – olefins C16 – C40 internal olefins Metathesis of C4 – C8 and C16 – C40 internal olefins • Short and long chain internal olefins disproportionate CH3CH=CHCH3 + CH3(CH2)8CH=CH(CH2)8CH3 C4 Internal olefin C20 internal olefin 2 CH3CH=CH(CH2)8CH3 C12 internal olefin * Noble Prize 2005 for Development of the Olefin Metathesis Method in Organic Synthesis Catalytic cycle of alkene metathesis Fractionation of internal olefins • C10 – C14 internal olefins • C4 – C8 internal olefins • C16 – C40 internal olefins C4 – C8 and C16 – C40 are again subjected to metathesis Linear hydroformylation of C10 – C14 internal olefins CH3(CH2)8CH=CH-CH3 C12 internal olefin CH3(CH2)8CH2CH2CH2CHO CH3(CH2)11CH2CH2OH C14 alcohol Flexibility of SHOP process •At each step we can decide to stop further „processing” of olefins, adjusting production to present needs. Example Applications of linear olefins • Drilling liquid – C14 – C18 a - olefins Suitable physical properties: High purity Viscosity Pour point Flash point •Drilling muds – C15 – C18 internal olefins • Monomers – C4 – C10 a – olefins For the production of polymers •Plasticizers – C6 – C10 a – olefins for plastics, cement, concrete, wallboard and clay bodies. •Biodegradable detergents – C12 – C20 a – olefins And many others... Other ways for a – olefins production THE OLDEST: - Thermal cracking of waxes (1970’) - Chlorination PROCESSES THAT USE OLIGOMERIZATION: 1. Giving wide range of alpha olefin: - ethyl corporation, Ineos, Gulf, SHOP 2. Giving only kind of olefin: - Pilips, IFP References: 1. D. D. Eley, Bruce C. Gates, Werner O. Haag, Helmut Knözinger; Advances in Catalysis 2. Harold A. Wittcoff, Bryan G. Reuben, Jeffrey S. Plotkin; Industrial organic chemicals 3. Handzlik J. ; Metateza olefin 4. G. Rothenberg; Catalysis: concepts and green applications 5. Catalysis from A to Z; red.: Cornils 6. http://scienzechimiche.unipr.it/didattica/att/bfe8.9521.file.pdf J.C. Mol „Industrial application of olefin metathesis” 7.http://chem.ncue.edu.tw/leehm/teaching/92.1/92.1.PG1%20organometallic%20chemistry/C h7.doc 8. http:// www.shell.com