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A kind of olefin oligomerization catalyst and its preparation and use method

A catalyst and co-catalyst technology, applied in chemical instruments and methods, physical/chemical process catalysts, organic compounds/hydrides/coordination complex catalysts, etc., can solve the problems of low product yield, harsh reaction conditions, and raw material production efficiency Low-level problems, to achieve the effect of simple and efficient preparation and operation, simplification of steps and costs, and improvement of raw material utilization

Active Publication Date: 2016-09-28
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] To sum up, the industrial ethylene oligomerization catalysts currently have problems such as harsh reaction conditions, insufficient catalytic activity, and poor product distribution, which seriously restrict the development of the oligomerization industry, and cause industrial production to face great safety hazards. The production efficiency is low, and the product income is not high
At present, it is difficult to effectively adjust the catalyst to obtain products under different requirements, and it is difficult to guarantee the activity and product distribution at the same time

Method used

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  • A kind of olefin oligomerization catalyst and its preparation and use method

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preparation example Construction

[0028] The steps of the preparation method of olefin oligomerization catalyst are as follows:

[0029] 1) 1-10 mmol of zirconium tetrachloride is placed in the reactor, 40-100 ml of reaction medium is added under the protection of nitrogen, the stirring is started, and the temperature is raised in a water bath, the reaction temperature is 50-90°C, preferably 60-80°C 0.5-2h, obtain the suspension of zirconium tetrachloride;

[0030] 2) Quickly add ArOH compounds with a syringe, the molar ratio of ArOH to zirconium tetrachloride is 1-12:1, heat up, the reaction temperature is 80-120°C, preferably 80-90°C, and at the same time cool to reflux and continue to stir , Keep for 2-6h to obtain olefin oligomerization catalyst, which can be used directly without separation.

[0031] The reaction medium is one or both of aromatic hydrocarbons and halogenated aromatic hydrocarbons. Benzene or toluene is preferred.

[0032] The method of using the olefin oligomerization catalyst: under a...

Embodiment 1

[0041] The following examples prepare oligomerization catalyst systems described in the present invention.

[0042] Accurately weigh 5 mmol ZrCl in the glove box 4 Place in a preparation reactor, add 20ml of toluene as a reaction medium under the protection of nitrogen, start stirring, heat with a water bath to 70°C and keep for 1h to obtain a suspension of zirconium tetrachloride in toluene. Quickly add 10mmol of phenol with a syringe, that is, the Zr:phenol molar ratio is 1:2, heat up to 85°C while cooling to reflux and keep stirring for 4h. According to the elemental analysis results, it is determined that the structure of the generated aryloxy zirconium compound is Zr(OC 6 h 5 ) 2 Cl, cooled to room temperature to obtain Zr(OC 6 h 5 ) 2 Cl solution in toluene A.

Embodiment 2

[0044] Add reaction system with 20mmol phenol, i.e. Zr: the phenol molar ratio is 1:4, and all the other operations are identical with embodiment 1, obtain aryloxy zirconium phenoxide compound structure as Zr(OC 6 h 5 ) 3 Cl·C 6 h 5 OH, Zr(OC 6 h 5 ) 3 Cl·C 6 h 5 OH solution in toluene B.

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Abstract

The invention discloses an olefin oligomerization catalyst and its preparation and use method. The composition of the olefin oligomerization catalyst is Zr(OAr) n Cl 4‑n •mArOH, in the general formula, n is an integer of 1~4, m is 0~8, and Ar is an aromatic group; its preparation method is that ZrCl 4 and ligands are added to the synthesis reactor containing the reaction medium, and the appropriate temperature is controlled to synthesize a homogeneous catalytic system; the zirconium-based catalyst and co-catalyst are added to the oligomerization reactor containing the reaction medium, the appropriate reaction temperature is controlled, and the introduction The olefin monomer is subjected to reaction pressure to undergo oligomerization; the ligand is selected from one or more of phenols, aldehydes, acids and condensed ring aromatic compounds. The invention is easy to operate, has high activity of ethylene oligomerization, strong modifiability of ligands, can regulate product distribution in a wide range, and there is no high polymer product in the product, which is beneficial to the utilization of raw materials, the safety of industrial production and the high yield economic benefits.

Description

technical field [0001] The invention relates to the field of preparation of higher alpha-olefins by oligomerization of low-carbon olefins, in particular to an olefin oligomerization catalyst and its preparation and use method. Background technique [0002] Linear α-olefins are important chemical raw materials in great demand. where C 4 ~C 24 The linear α-olefins are especially concerned, and have important applications in the preparation of low-density polyethylene, high-density polyethylene, plasticizers, synthetic lubricants, detergents, fragrances and papermaking. With the expansion of demand for related products in industry and life, the production of linear α-olefins has been widely valued. At present, the oligomerization of lower olefins, especially ethylene, to produce alkenes with higher carbon numbers is the most important and also the most promising method for preparing linear α-olefins. [0003] Traditional ethylene oligomerization processes such as the Gulf m...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/22B01J31/02B01J31/14C07C2/30C07C2/32C07C11/02C07C11/08C07C11/107
Inventor 蒋斌波秦一超叶健王靖岱阳永荣黄正梁廖祖维
Owner ZHEJIANG UNIV
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