process for the production of a mixture of straight chain monoolefinen with a geradzahligen and ungeradzahligen number of carbon atoms in molecule via multiple catalytic disproportionierungen

摘要

1357632 Disproportionating olefins SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ NV 6 March 1972 [22 Feb 1971] 5107/71 Heading C5E Process for the manufacture of a mixture of normal mono-olefins having a number of carbon atoms per molecule in the range of from m + 1 to 2(m - 1), m being an integer of at least 4, which process comprises the following steps: step 1: disproportionation of a starting mixture comprising n substantially normal-alpha mono-olefins with m carbon atoms per molecule, m being an integer as hereinbefore defined and different for each olefin present in the starting mixture and n being an integer of at least 2, with 2-butene in the presence of a first disproportionation catalyst into propene and a mixture substantially comprising normal betamono-olefins having (m+1) carbon atoms per molecule; step 2: separating the reaction mixture formed in step 1 into at least one lower normal mono-olefin fraction, an intermediate normal mono-olefin fraction of a selected range of carbon atoms per molecule, which fraction is recovered as product, and optionally a higher normal mono-olefin fraction; step 3: substantial mutual disproportionation of normal mono-olefins present in the lower normal mono-olefin fraction(s) separated in step 2 in the presence of a second disproportionation catalyst into 2-butene and a mixture substantially comprising internal normal mono-olefins; step 4: separating the reaction mixture formed in step 3 into a lower normal internal mono-olefin fraction, an intermediate substantially normal internal mono-olefin fraction of a selected range of carbon atoms per molecule, which fraction is recovered as product, and optionally a higher internal normal mono-olefin fraction. A mixture of C 6 , C 8 , C 10 and C 12 normal α- olefins may be converted into C 11 and C 13 normal #-olefins (separated in step 2) and C 12 and C 14 internal normal olefins (separated in step 4). The disproportionation catalysts may be homogeneous such as combinations of a transition metal compound and an organometallic compound, promoted with O 2 or a carboxylic acid (e.g. NCl 6 /EtAlCl 2 /acetic acid) or a solid alumina supported catalyst containing Co, Mo, W or Re compounds. The normal α-olefin feed may be prepared by oligomerizing ethylene, and the 2- butene by dimerizing ethylene and isomerizing the butene-1 product.