Catalyst composition for ethylene oligomerization and application thereof
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A technology for ethylene oligomerization and catalysts, which is applied in the direction of hydrocarbons, hydrocarbons, physical/chemical process catalysts, etc., can solve the problems of poor repeatability of oligomerization process reactions, harsh process requirements, and high production costs, etc., to achieve The effect of high selectivity, good repeatability and smooth operation
Active Publication Date: 2018-11-02
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 (Organometallics2006, 25, 1961–1969), which was 2,6-bis(2-benzimidazolyl)pyridine chromium chloride ( III) The complex, under the action of the cocatalyst methylaluminoxane, when the molar ratio of the metal aluminum in the cocatalyst to the central metal in the main catalyst is 100 to 1500, and the reaction temperature is 0 to 80 ° C, oligomerization and polymerization activity up to 10 6 g mol(Cr) -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. Catalyst synthesis of chlorinated 2,6-bis(2-benzimidazolyl)pyridine chromium(III) complexes
[0030] According to the preparation method reported in literature (Organometallics.2006, 25, 1961-1969), 2,6-bis(2-benzimidazolyl)pyridine chromium(III) chloride complex was prepared.
[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 2,6-di(2-benzene After the toluene solution (concentration is 2.5 μ mol / ml) of imidazolyl) pyridine chromium (III) complex, make the composition total amount be 100ml, wherein, take the weight ...
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 for an ethylene oligomerization reaction process. The catalyst composition contains a main catalyst represented by a formula I shown in the description, i.e., a chlorinated 2,6-di(2-benzimidazoyl)pyridine chromium (III) complex, an aluminiferous cocatalyst, water and an organic solvent. According to the catalyst composition, the catalyst composition disclosed by the invention is applied to the ethylene oligomerization reaction process and has very high oligomerization reaction activity and high alpha-olefin selectivity, and the oligomerization reaction is high in initiating speed, stable in operation and good in repeatability; even if the Al / Cr ratio is low, the catalyst composition has very good oligomerization reaction activity; and thus, the technical prejudice of those skilled in the art are overcome, an unexpected technical effect is achieved, and the catalysis effect and the cost are better balanced, so that the cost of ethylene oligomerization reaction is reduced greatly, the practicability is high, and the industrialization prospect is broad.
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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