Olefin oligomerization catalyst and preparation method and application thereof

A catalyst, olefin technology, applied in chemical instruments and methods, physical/chemical process catalysts, organic compound/hydride/coordination complex catalysts, etc., can solve the problems of low carbon olefins, such as excess, decline, and excessive C activity. , to achieve the effect of high content of high-carbon olefins, improved catalytic activity, and high yield of α-olefins

Active Publication Date: 2013-06-05
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

USP4886933 uses two kinds of alkylaluminum compounds as cocatalysts to carry out ethylene oligomerization to prepare α-olefins. USP4783573 adds a third component on this basis to carry out ethylene oligomerization. The third component is one or more Lewis bases, such as Thiophene, methyl disulfide, thiourea, triphenylphosphine or trioctylphosphine to achieve the purpose of improving the thermal stability of the catalyst itself and improving product distribution, but there are still many deficiencies, such as low carbon olefins in the product Many, most notably C 4 Excessive or decreased activity, etc.

Method used

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  • Olefin oligomerization catalyst and preparation method and application thereof

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preparation example Construction

[0013] The preparation method of the catalyst provided by the invention comprises fully reacting zirconium tetrachloride in an aromatic hydrocarbon medium with an aliphatic alcohol having the general formula ROH, wherein R is C in the ROH 3 ~C 8 The chain alkyl group, the molar ratio of fatty alcohol and zirconium tetrachloride in the reaction is 3~9:1.

[0014] The reaction temperature is the reflux temperature of the aromatic hydrocarbons contained in the system, preferably 70-100°C.

[0015] The aliphatic alcohol reacted with zirconium tetrachloride in the present invention is preferably butanol, propanol or hexanol, and the aromatic hydrocarbon in the reaction medium is preferably benzene or toluene.

[0016] Carrying out the olefin oligomerization method with the catalyst provided by the invention is: Zr(OR) with the general formula of the present invention m Cl 4-m nROH's chlorinated alkoxyzirconium alkoxide as the main catalyst and organoaluminum as the co-catalyst e...

example 1

[0022] The following examples prepare the oligomerization catalysts described in this invention.

[0023] Suspend 10mmol of zirconium tetrachloride in 34.6g of toluene, stir at 70°C for 1 hour, add 30mmol of n-butanol, reflux at 85°C for 4 hours, and measure the generated HCl by quantitative analysis. The composition of butoxy zirconium alkoxide is: Zr(OBu)Cl 3 2C 4 h 9 Oh. After the reaction, the temperature of the system was lowered to 25°C, and 20 grams of toluene was added to prepare Zr(OBu)Cl with a zirconium concentration of 0.2 mol / liter. 3 2C 4 h 9 OH solution in toluene A.

example 2

[0025] Prepare chloroalkoxy zirconium alkoxide by the method for example 1, difference is the n-butanol that adds 40mmol, makes the alcoholate of chloro n-butoxy zirconium, and its composition is: Zr(OBu)Cl 3 ·3C 4 h 9 Oh. After the reaction was completed, the system was cooled down, and 18.9 grams of toluene was added to form Zr(OBu)Cl with a zirconium concentration of 0.2 mol / liter. 3 ·3C 4 h 9 OH solution in toluene B.

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Abstract

The invention relates to an olefin oligomerization catalyst, which comprises an ethylchloride zirconyl alcohol adduct with the general formula of Zr (OR) mCl4-m . nROH, wherein m is an integer from 1 to 3, n is 2 to 8, and R is C3 to C8 chain alkyl. The preparation method of the catalyst is simple, the catalyst has higher oligomerization activity when being matched with an organic aluminum catalyst, the content of oligomer in the oligomerization product is low, the content of C12 to C20 olefin is higher, and the yield of alpha-olefin is high.

Description

technical field [0001] The invention relates to a catalyst for olefin oligomerization, its preparation method and application, specifically, a catalyst for homogeneous olefin oligomerization, its preparation method and the application of the catalyst in olefin oligomerization. Background technique [0002] Olefin oligomerization is an important part of olefin polymerization. With the expansion of demand for specific products in modern production and life, the rise of oligomerization is triggered, especially the use of ethylene oligomerization to prepare alkenes with higher carbon numbers. [0003] Traditional ethylene oligomerization processes, such as Gulf, Ethyl, and SHOP methods, have problems such as harsh operating conditions, low single-pass catalyst activity, wide carbon number distribution of products, difficult separation of products and raw materials, and difficult disposal of waste liquid, especially when the operating pressure is too high , reaching about 20MPa, ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/02B01J31/38C07C2/22
CPCY02P20/52
Inventor 倪静荣峻峰宗明生景振华
Owner CHINA PETROLEUM & CHEM CORP
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