Ethene oligomerization continuous reaction method

Abstract

The invention discloses an ethene oligomerization continuous reaction method. The method comprises that a main catalyst 2-acetyl-6-(1H-benzimidazolyl)(anil)FeCl2 shown in the formula (I), an aluminum-containing cocatalyst and an organic solvent are added into aqueous ethene as a raw material. The catalyst is used for an ethene oligomerization reaction process, has very high oligomerization reaction activity and high alpha-ethene selectivity, realizes fast oligomerization reaction initiation, stable reaction process and good repeatability and still has very good oligomerization reaction activity at a low aluminum / iron ratio. The ethene oligomerization continuous reaction method overcomes technology biases of the technicist in the field, produces unforeseeable technical effects, realizes good balance of catalysis effects and a cost, greatly reduces an ethene oligomerization reaction cost and has good practicality and a wide industrial application prospect.

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 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 tridentate pyridin...

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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 (Organometallics2009, 28, 2225–2233), which was Fe of 2-benzimidazolyl-6-acetylamide 2+ Chloride, under the action of cocatalyst methylaluminoxane or modified methylaluminoxane, when the molar ratio of the metal aluminum in the cocatalyst to the central metal in the main catalyst is 500-1500, and the reaction temperature is 20 At ~60°C, the oligomerization and polymerization activities reached a maximum of 10 6 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

[0005] 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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