Ethylene oligomerization continuous reaction method

Abstract

The invention discloses an ethylene oligomerization reaction method; with adopting of water-containing ethylene as a raw material, and under the action of a main catalyst chloro-2-(1H-2-benzoimidazole)-8-acetanilide quinoline chromium (III) complex represented by the formula (I), an aluminum-containing co-catalyst and an organic solvent, an ethylene oligomerization reaction is performed; according to the method, the method is used for the ethylene oligomerization reaction process, the oligomerization reaction activity is high, the selectivity of alpha-olefin is high, the oligomerization reaction is fast to initiate, the operation is smooth and steady, and the repeatability is good; even when the aluminum / chromium ratio is low, the catalyst still has good oligomerization reaction activity; therefore, the technical prejudice of technical personnel in the field is overcome, unexpected technical effects are obtained, and the catalytic effect and cost are better balanced, so that the cost of the ethylene oligomerization reaction is significantly decreased, the practicality is high, and the prospects for industrialization are broad.

Description

technical field [0001] The invention relates to the field of ethylene oligomerization, in particular to a continuous reaction method for ethylene oligomerization. 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 catalysts used in ethylene oligomerization mainly include nickel-based, chromium-based, zirconium-based and aluminum-based catalysts. In recent years, Brookhart group (Brookhart, M et al., 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 tridentate pyridine imine complexes of Fe(II) an...

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Problems solved by technology

[0003] The Institute of Chemistry, Chinese Academy of Sciences reported a catalyst for ethylene oligomerization and polymerization (Organometallics2011, 30, 3001–3009), which was 2-(1H-2-benzimidazolyl)-8-acetanilide chloride Quinoline chromium (III), 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 200 to 2500, and the reaction temperature is 30 to 60°C When , the oligomerization and polymerization activities reached a maximum of 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

In addition, the water content of polymer grade ethylene is required to be below 5ppm, which makes the process conditions for producing ethylene more stringent

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