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Supported catalyst for alpha-olefin oligomerization, and preparation and application thereof

A technology of immobilized catalysts and catalysts, applied in physical/chemical process catalysts, chemical instruments and methods, organic chemistry, etc., can solve problems such as pressure drop, achieve the effect of reducing chlorine content and reducing environmental pollution

Active Publication Date: 2011-11-16
PETROCHINA CO LTD +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, there is an obvious problem of pressure drop in the fixed bed reaction packed with fine particle catalyst

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Spherical γ-alumina carrier is acidified and impregnated: at room temperature, spherical γ-alumina carrier (carrier diameter is 1.3-2.3mm, specific surface area 100-180m 2 / g, total pore volume ≥ 1.0ml / g) was immersed in 1.0M hydrochloric acid solution for 6 hours, and then vacuum dried at 80-100°C for 12 hours.

[0030] Group VIII transition metal salt solution immobilization: at room temperature, immerse the acidified and impregnated spherical γ-alumina support in 0.5M nickel nitrate solution for 6 hours, and then vacuum dry at 100°C for 12 hours. Finally, high-temperature calcination was carried out at 400° C. for 6 hours.

[0031] Solid loading of aluminum trichloride solution: under the protection of argon, make a solution of 5g of anhydrous aluminum trichloride in 100ml of carbon tetrachloride, add it to 10g of activated alumina carrier, and keep it at reflux temperature for 24 hours, the solvent was removed, washed with n-hexane, and vacuum-dried to obtain an al...

Embodiment 2

[0035]The conditions for the preparation of the supported aluminum trichloride catalyst and the step of catalyzing the oligomerization of 1-decene are the same as in Example 1, except that the carrier treatment conditions are as follows: the spherical gamma-alumina carrier is immersed in a 1.5M hydrochloric acid solution for 4 hours, and then heated at 80 Vacuum drying at ~100°C for 12 hours; Group VIII transition metal salt solution immobilization: soak the acidified and impregnated spherical γ-alumina carrier in 2.0M nickel nitrate solution for 6 hours, and then vacuum dry at 100°C for 12 hours.

[0036] Carry out chlorine content measurement to above-mentioned aluminum trichloride loaded catalyst by Volhard titration method, get the chlorine content in the loaded catalyst to be 8.45ω%; Measure metallic nickel, aluminum content with atomic absorption spectrometry, nickel content is 4.27ω%, loaded The aluminum content is 3.45ω%.

[0037] Catalyzes 1-decene oligomerization, th...

Embodiment 3

[0039] The preparation and catalyzed 1-decene oligomerization step conditions of supported aluminum trichloride catalyst are the same as in Example 1, the difference is that the carrier treatment condition is: the spherical gamma-alumina carrier is immersed in 1.0M hydrochloric acid solution for 6 hours, and then heated at 80 Vacuum drying at ~100°C for 12 hours; Group VIII transition metal salt solution immobilization: soak the acidified and impregnated spherical γ-alumina carrier in 1.0M nickel nitrate solution for 6 hours, and then vacuum dry at 100°C for 12 hours.

[0040] Carry out chlorine content measurement to above-mentioned aluminum trichloride loaded catalyst by Volhard titration method, get the chlorine content in the loaded catalyst to be 7.95ω%; Measure metallic nickel, aluminum content with atomic absorption spectrometry, nickel content is 1.53ω%, loaded The aluminum content is 4.57ω%.

[0041] Catalyzed 1-decene oligomerization, the measured 1-decene conversion...

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Abstract

The invention relates to a supported catalyst for alpha-olefin oligomerization, and preparation and application thereof. The catalyst takes gamma-aluminium oxide as a carrier, which is loaded with aluminium trichloride and a VIII group transition metal salt; the catalyst comprises the following components according to weight percentage: 2.5-6.0% of aluminium, 6.0-12.0% of chlorine, 0.5-5.0% of VIII group transition metal salt, and rest being the gamma-aluminium oxide besides SO42- and / or NO3-; and the VIII group transition metal is iron, cobalt, nickel or copper. The supported catalyst exhibits high activity and high stability in catalyzing the oligomerization reaction of 1-decene or 1-octene, overcomes the strong corrosivity of the aluminium trichloride catalyst, and is easy to be separated from the product, and also avoids the problems of a large quantity of sewage and environmental pollution produced by the aluminium trichloride catalyst.

Description

technical field [0001] The invention relates to a gamma-alumina immobilized catalyst suitable for oligomerization of 1-decene or 1-octene, a preparation method and application thereof. Background technique [0002] AlCl 3 The catalyst is a Lewis acid catalyst, which has the characteristics of high polymer yield, narrow molecular weight distribution and good selectivity in catalyzing α-olefin oligomerization; but AlCl 3 The catalyst is highly corrosive, and it is easy to damage the reactor and other devices, which affects the service life of the device, thereby reducing the utilization rate. At the same time, AlCl 3 The catalyst will produce a large amount of sewage, which will seriously pollute the environment if it is not treated in time, and the AlCl after the reaction 3 Catalysts are difficult to recycle and require reprocessing, otherwise large amounts of corrosive waste will be produced. [0003] In order to meet the requirements of green chemistry, in the developmen...

Claims

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Application Information

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IPC IPC(8): B01J27/128B01J27/122C07C2/22C07C11/02
Inventor 黄付玲米普科王斯晗韩雪梅张宝军钱锦华刘敏江玲李建忠张祥良陈谦高飞谷振生卢攀峰王桂芝刑士轩韩云艳王亚丽孙淑坤高宇新于部伟王力搏张德顺郭桂悦王秀绘赵晶莹
Owner PETROCHINA CO LTD
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