Shell higher olefin process

The Shell higher olefin process is a chemical process for the production of linear alpha olefins via ethene oligomerization and olefin metathesis invented and exploited by Royal Dutch Shell ^[1].

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The first step in this process is the ethylene oligomerization at 80 to 120 °C and 70 to 140 bar (7 to 14 MPa) with a phosphine ligand nickel complex (C₆H₅)₂P(CH₂)₂COONi to a mixture of even-numbered α-olefins. The process and its mechanism was intensively studied by the group of Professor Wilhelm Keim at the RWTH Aachen, who is also regarded as one of the key figures in the development of the procecss.

The fraction containing C₆ to C₁₈ olefins has commercial value and is removed. The remaining higher and lower olefins next undergo isomerization reactions leading to internal double bonds and then to olefin metathesis which causes the internal double bond to break up into new internal double bonds in olefins of intermediate molecular weight. The process was commercialized in 1977 and in 1993 global annual production capacity was ten million tons.

In another olefin application of Shell cyclododecatriene is partially hydrogenated to cyclododecene and then subjected to ethenolysis to the terminal linear open-chain diene. The process is no longer in use.