Ethylene oligomerization catalyst composition and oligomerization method
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An ethylene oligomerization and composition technology, applied in the direction of catalysts, hydrocarbons, hydrocarbons, etc., can solve the problems of harsh process requirements and poor repeatability caused by the oligomerization reaction process reaction, and achieve good repeatability, catalytic effect and The effect of cost balancing and cost reduction
Active Publication Date: 2017-10-24
CHINA PETROLEUM & CHEM CORP +1
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[0003] At present, it is generally believed that oxygen is very unfavorable to the ethylene oligomerization 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 process 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
[0028] 1. Catalyst synthesis of chlorinated 2,6-bis(2-benzimidazolyl)pyridine chromium(III) complexes
[0029] According to the preparation method reported in the literature (Organometallics.2006,25,1961-1969), 2,6-bis(2-benzimidazolyl)pyridine chromium(III) chloride was prepared, R 1 -R 5 Both are hydrogen.
[0030] 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 tert-butyl hydroperoxide and toluene solvent in the reaction kettle, add 1.37ml triethylaluminum toluene solution (concentration is 715μmol / ml), add 2ml 2,6-chloride After the toluene solution (concentration is 2.5 μ mol / ml) of two (2-benzimidazolyl) pyridine chromium (III) complexes, the total amount of...
Embodiment 2
[0032] With embodiment 1, difference is that the weight content of tert-butyl hydroperoxide is 100ppm. See Table 1 for the data.
Embodiment 3
[0034] With embodiment 1, difference is that the weight content of tert-butyl hydroperoxide is 250ppm. See Table 1 for the data.
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Abstract
The invention discloses a catalyst composition for an ethylene oligomerization reaction process. The catalyst composition comprises a main catalyst shown in formula I, namely a 2,6-di(2-benzimidazolyl) pyridine chromium (III) complex, an aluminum-containing promoter and tert-butyl hydroperoxide. The catalyst composition disclosed by the invention is applied to the ethylene oligomerization reaction process, is very high in oligomerization reaction activity, high in alpha-olefin selectivity, is rapid in oligomerization reaction initialization speed, stable in operation and good in repeatability, and is still very good in oligomerization reaction activity even in a low aluminum / chromium ratio, so that technical prejudice of operators of the field is overcome, unforeseeable technical effects are achieved, catalysis effects and cost are relatively well balanced, the ethylene oligomerization reaction cost is greatly reduced, and the catalyst composition is good in practicability and wide in industrialization prospect.
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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