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Ethene oligomerization continuous reaction method

A technology for ethylene oligomerization and reaction, which is applied in the direction of chemical instruments and methods, hydrocarbons, organic compounds/hydrides/coordination complex catalysts, etc., and can solve the problem of poor repeatability of oligomerization reaction process and harsh ethylene process conditions , process requirements and other issues, to achieve high selectivity, good oligomerization reactivity, and good repeatability

Active Publication Date: 2016-05-11
CHINA PETROLEUM & CHEM CORP +1
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[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
[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

Method used

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Examples

Experimental program
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Effect test

Embodiment 1

[0029] 1. Synthesis of main catalyst chloride 2-benzoxazolyl-6-acetyl condensed 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 2′,6′-diethylaniline iron chloride was prepared (II) Complexes.

[0031] 2. The continuous reaction of ethylene oligomerization specifically comprises the following steps: (1) in a 100ml continuous reaction device, aqueous ethylene, solvent toluene, main catalyst solution (concentration is 2.5 μ mol / ml, solvent is toluene) and cocatalyst solution (concentration is 715 μ mol / ml, and solvent is toluene) enters reactor respectively, and flow rate is respectively 80g / h, 168.26g / h, 3.40g / h and 2.34g / h, and Al / Fe is 196.8 in the reaction system, keeps the reaction mass in The residence time in the reactor is 30min; (2) reaction pressure is 1MPa and reaction temperature is 30 ℃, wherein, take ethylene as calculation basis, the mass co...

Embodiment 2

[0033] Same as Example 1, the difference is that the mass content of water is 60ppm. See Table 1 for the data.

Embodiment 3

[0035] Same as Example 1, the difference is that the mass content of water is 150ppm. See Table 1 for the data.

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Abstract

The invention discloses an ethene oligomerization continuous reaction method. The method comprises that a main catalyst 2-benzoxazolyl-6-acetyl(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 method for continuous 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 pyridine imine c...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C2/22C07C11/02C07C11/08B01J31/22
CPCY02P20/52
Inventor 刘珺郑明芳张海英王怀杰栗同林李维真吴红飞祁彦平
Owner CHINA PETROLEUM & CHEM CORP
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