Nickel ethylene oligomerization with

P-17 - Ethylene oligomerization with nickel-containing NaX zeolite... 

Scheme 3-8 Schematic of ethylene oligomerization with nickel complex catalysts [9]...

Ethylene Oligomerization with Metals Other than Nickel... 

Butene. Commercial production of 1-butene, as well as the manufacture of other linear a-olefins with even carbon atom numbers, is based on the ethylene oligomerization reaction. The reaction can be catalyzed by triethyl aluminum at 180—280°C and 15—30 MPa ( 150 300 atm) pressure (6) or by nickel-based catalysts at 80—120°C and 7—15 MPa pressure (7—9). Another commercially developed method includes ethylene dimerization with the Ziegler dimerization catalysts, (OR) —AIR, where R represents small alkyl groups (10). In addition, several processes are used to manufacture 1-butene from mixed butylene streams in refineries (11) (see BuTYLENEs). 

Shell Higher Olefins Process (SHOP). In the Shell ethylene oligomerization process (7), a nickel ligand catalyst is dissolved in a solvent such as 1,4-butanediol (Eig. 4). Ethylene is oligomerized on the catalyst to form a-olefins. Because a-olefins have low solubiUty in the solvent, they form a second Hquid phase. Once formed, olefins can have Htfle further reaction because most of them are no longer in contact with the catalyst. Three continuously stirred reactors operate at ca 120°C and ca 14 MPa (140 atm). Reactor conditions and catalyst addition rates allow Shell to vary the carbon distribution. 

Coordination-catalyzed ethylene oligomerization into n-a-olefins. The synthesis of homologous, even-numbered, linear a-olefins can also be performed by oligomerization of ethylene with the aid of homogeneous transition metal complex catalysts [26]. Such a soluble complex catalyst is formed by reaction of, say, a zero-valent nickel compound with a tertiary phosphine ligand. A typical Ni catalyst for the ethylene oligomerization is manufactured from cyclo-octadienyl nickel(O) and diphenylphosphinoacetic ester ... 

Nickel containing MCM-36 zeolite was used as new catalyst in the ethylene oligomerization reaction performed in slurry semi-batch mode. This catalyst, with micro-mesoporous structure, mild acidity and well balanced Ni2+/acid sites ratio, showed good activity (46 g of oligomers/gcataLh) and selectivity (100% olefins with even number of carbon atoms). The NiMCM-36 behaviour was compared to those obtained with NiMCM-22, NiY, NiMCM-41 and NiMCM-48 catalysts. 

These data clearly indicate that the NiMCM-36 catalyst exhibits very interesting properties for ethylene oligomerization, by comparison with the microporous NiMCM-22 zeolite at both reaction temperatures (70 and 150°C, respectively). Compared with other catalysts, the NiMCM-36 behaviour is intermediate between Ni-exchanged dealuminated Y zeolite and Ni-exchanged mesoporous materials. Taking into account that the amount of Ni2+ sites is near the same for all samples (Table 1), in order to explain these differences in catalytic behaviors, two mains categories of properties could be considered (i) the concentration and strength of acid and nickel sites and (ii) the diffusional properties (determined by the size and the architecture of pores). 

The production of 1-alkenes from ethylene oligomerization was carried out with high selectivity in ionic liquids in the presence of a cationic nickel complex catalyst (ri -methallyl)-[bis(diphenylphosphino)methane-monoxide-K -P,0]nickel(II) hexafluoroantimonate, [(mall)-Ni(dppmo)]Sbp6 (240). The overall reaction rate of... 

Alkenes. At present alkene isomerization is an important step in the production of detergent alkylates (Shell higher olefin process see Sections 12.3 and 13.1.3).264 265 Ethylene oligomerization in the presence of a nickel(O) catalyst yields terminal olefins with a broad distribution range. C4-C6 and C2o+ alkenes, which are not suitable for direct alkylate production, are isomerized and subsequently undergo metathesis. Isomerization is presumably carried out over a MgO catalyst. 

A reasonable mechanism for the co-oligomerization of butadiene with ethylene on a naked-nickel catalyst is shown in Eq. (49). Interaction of an ethylene molecule with the bis(7r-allyl) C8 chain produces a C,0 chain, containing both an alkyl- and a 7r-allylnickel group (XLVI). Coupling of the alkyl bond with the terminal atom of a m-Tr-allyl group or the terminal... 

Shell manufactures a-olefins from ethylene by oligomerization with a nickel catalyst in a polar solvent such as ethylene glycol, under the conditions specified in Equation 27. This corresponds to the first part of the SHOP process (Shell Higher Olefin Process) described in Section 6.2.2. The world production is estimated to be over 1 Mt/a. 

The starting material in our synthesis was cyclododecyne whose oligomerization with two moles of butadiene gave the bicyclic triene 44, which in turn was converted into the cis doubly bridged ethylene 46 by partial catalytic hydrogenation with Raney nickel. Irradiation of 46 with a low-pressure mercury lamp in cyclohexane led to a 1 2 cis-trans mature, from which the trans isomer48, m.p. 37-38°C, was isolated after removal of the unchanged cis isomer as a dichlo-rocarbene adduct. 

Variants of this ethylene oligomerization technique have been developed by Esso and Mitsui Petrochemical, which use titanium base catalysts, and Shell, which uses a complex of nickel with phosphines. 

Perfluormated oligoethers with the acetylacetonate group at the end of the polymer formed complexes 56 with nickel(I), which catalyzed ethylene oligomerization. The turnover number in the reaction reached 2460 in a perfluorinated ether-toluene two-phase system, and the catalyst, which was in the fluorine-containing phase, was readily separable [169]. 

Polymerization Studies. Stereospecific Polymerization of Buta-1,3-diene by Perfluoro-carboxylato Nickel Salts . Oligomerizing Ethylene using a Nickel-containing Catalyst [polymerization catalyst prepared by treating bi (cycio-octa-l,5-diene)nickel(0) with CF, CO,H, CF, CO CHj CO CF (CF,>8C(OH) CH COjH, Or CF, CF CF,). Polymerizing Butadiene to Equal Amounts of CIj-1,4- and 7roRS-l,4-polybutadiene Units (the diene is polymerized in the presence of -altylnickel trifluoroacetate and trifluoroacetic acid). ... 

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