Catalyst composition for ethylene oligomerization, and oligomerization method
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A technology of ethylene oligomerization and catalyst, which is applied in the direction of hydrocarbons, hydrocarbons, chemical instruments and methods, etc., can solve the problems of poor repeatability of oligomerization process reaction, high production cost, harsh process requirements, etc. High performance, stable operation and good repeatability
Active Publication Date: 2016-05-11
CHINA PETROLEUM & CHEM CORP +1
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[0003] The Institute of Chemistry, Chinese Academy of Sciences reported a catalyst for ethylene oligomerization and polymerization (Eur.J.Inorg.Chem.2009,4149–4156), which is 2-benzoxazolyl-6-acetylcondensate Amine Fe 2+ Chloride, under the action of co-catalyst methyl aluminoxane, when the molar ratio of the metal aluminum in the co-catalyst to the central metal in the main catalyst is 200-2000, and the reaction temperature is 30-50 ° C, oligomerization and Polymerization activity up to 10 7 g mol(Fe) -1 h -1 ; and whether methylalumoxane or modified methylalumoxane is used as a cocatalyst, the cost is too high and the consumption is too large. When the cocatalyst is used in large-scale ethylene oligomerization, it will inevitably lead to high cost
[0004] At present, it is generally believed that water is very unfavorable to the ethylene oligomerization reaction process. CN200810111717.8 discloses a method for ethylene oligomerization, which is strictly controlled in an anhydrous and oxygen-free environment. Therefore, the current ethylene oligomerization reaction is harmful to the process. The requirements are very demanding, resulting in very poor reaction initiation and repeatability of the oligomerization process
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Embodiment 1
[0029] 1. Synthesis of Catalyst Chlorinated 2-Benzoxazolyl-6-Acetyl 2,6-Diethylanilinate Iron(II) Complex
[0030] According to the preparation method reported in the literature (Eur.J.Inorg.Chem.2009,4149–4156), 2-benzoxazolyl-6-acetyl acetal 2,6-diethylanilinate iron(II) chloride was prepared ) complexes.
[0031] 2. Ethylene oligomerization reaction, which specifically includes the following steps: (1) replace the reaction system by high temperature drying, vacuum replacement and other operations to ensure that there is no water and oxygen in the reaction system; (2) use ethylene to replace the reaction system, Make the reaction system in an ethylene environment; (3) add water and toluene solvent in the reaction kettle, add 1.37ml triethylaluminum toluene solution (concentration is 715 μ mol / ml), add 2ml chloride 2-benzoxazolyl-6 -After the toluene solution (concentration is 2.5 μ mol / ml) of acetylated 2,6-diethylaniline iron (II), make the composition total amount be 100m...
Embodiment 2
[0033] Same as Example 1, the difference is that the weight content of water is 20ppm. See Table 1 for the data.
Embodiment 3
[0035] Same as Example 1, the difference is that the weight content of water is 50ppm. See Table 1 for the data.
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Abstract
The invention discloses a catalyst composition used for an ethylene oligomerization reaction technology. The composition comprises a main catalyst 2-benzoxazolyl-6-acetylaminochloro iron (II) complex represented by formula (I), an aluminum-containing cocatalyst, water and an organic solvent. The catalyst composition prepared in the invention is used in the ethylene oligomerization reaction technology, has the advantages of very high oligomerization reaction activity, high selectivity of alpha-olefin, rapid initiation of the oligomerization reaction, stable running and good repeatability, still has very good oligomerization reaction activity even if the aluminum/iron ratio is low, so the technical prejudice of technical personnel in the field is overcome, an unexpected technical effect is achieved, and the catalysis effect and the cost are well balanced, thereby the ethylene oligomerization reaction cost is greatly reduced, the practicality is strong, and the industrial prospect is wide.
Description
technical field [0001] The invention relates to the field of ethylene oligomerization, in particular to a catalyst composition used in an ethylene oligomerization process. Background technique [0002] Linear α-olefins are widely used in the fields of ethylene comonomers, surfactant synthesis intermediates, plasticizer alcohols, synthetic lubricating oils and oil additives. In recent years, with the continuous development of the polyolefin industry, the worldwide demand for α-olefins has grown rapidly. At present, the vast majority of α-olefins are prepared by ethylene oligomerization. The used catalyst of ethylene oligomerization mainly contains nickel series, chromium series, zirconium series and aluminum series etc., in recent years, Brookhart group (Brookhart, the people such as M, J.Am.Chem.Soc.,1998,120,7143-7144 ; WO99 / 02472,1999), Gibson group (Gibson, V.C. et al., Chem.Commun., 1998,849-850; Chem.Eur.J., 2000,2221-2231) found that some Fe(II) and Co The tridentat...
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