CN102240563A - Alpha-olefin oligomerization immobilized catalyst and preparation and application thereof - Google Patents

Alpha-olefin oligomerization immobilized catalyst and preparation and application thereof Download PDF

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CN102240563A
CN102240563A CN201010174749XA CN201010174749A CN102240563A CN 102240563 A CN102240563 A CN 102240563A CN 201010174749X A CN201010174749X A CN 201010174749XA CN 201010174749 A CN201010174749 A CN 201010174749A CN 102240563 A CN102240563 A CN 102240563A
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catalyst
decene
hours
transition metal
gamma
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CN102240563B (en
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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
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East China University of Science and Technology
Petrochina Co Ltd
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East China University of Science and Technology
Petrochina Co Ltd
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    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention relates to an alpha-olefin oligomerization immobilized catalyst and preparation and application thereof; the catalyst takes gamma-alumina as a carrier, and is loaded with aluminum trichloride and VIII-family transition metal salt, and the catalyst comprises the following components in percentage by weight: aluminum: 2.5-6.0%, chlorine: 6.0 to 12.0%, a group VIII transition metal: 0.5-5.0% by weight of SO4 2-And/or NO3 -The rest is gamma-alumina; the group VIII transition metal is iron, cobalt, nickel or copper; the immobilized catalyst has high activity and high stability in catalyzing oligomerization of 1-decene or 1-octene, overcomes the strong corrosivity of aluminum trichloride catalyst, is easy to separate from the product, and avoids the problems of a large amount of sewage and environmental pollution generated by the aluminum trichloride catalyst.

Description

A kind of alpha-olefin oligomerisation solid-carried catalyst and preparation and application
Technical field
The present invention relates to gama-alumina solid-carried catalyst of a kind of 1-of being applicable to decene or the oligomerisation of 1-octene and its production and application.
Background technology
AlCl 3Catalyst is a kind of lewis acid catalyst, has characteristics such as polymer yield height, narrow molecular weight distribution, selectivity be good in catalysis alpha-olefin oligomerisation reaction; But AlCl 3Catalyst has severe corrosive, easily devices such as reactor is damaged, and influences the service life of device, thereby has reduced utilization rate, simultaneously AlCl 3Catalyst can produce large amount of sewage, as untimely processing meeting serious environment pollution, and reacted AlCl 3Catalyst is difficult to reclaim, and needs through post processing, otherwise can produce a large amount of corrosivity waste materials.
In order to reach the requirement of Green Chemistry, replace AlCl at solid acid catalysts such as exploitation load metal oxides 3, BF 3Etc. the traditional catalyst time, also making great efforts research AlCl 3Solid-supported catalyst.Hope can keep AlCl 3Under the prerequisite of good characteristic, problems such as corrosion that solution exists and environmental protection make it change environment amenable catalyst into.Support type AlCl 3Catalyst is a kind of efficient, eco-friendly novel solid acid catalyst, owing to have advantages of high catalytic activity and gentle reaction condition, receives much concern in recent years, is widely used in the research of polymerization and alkylated reaction.
Patent US 2,927, and 087 proposes the earliest, can pass through AlCl 3Steam makes AlCl with refractory oxides reactions such as the aluminium oxide that has surface hydroxyl, silica 3Solid-supported catalyst is emphasized to react the back and is purged with carrier gas being higher than under 300 ℃ the temperature, removes unreacted AlCl 3Necessity.
USP 4,929, and 800 with CCl 4, CH 3Cl or CH 2Cl 2Deng being solvent, the alchlor dissolving wherein, add carriers such as silica or aluminium oxide, at 50~80 ℃ and N 2Protection, lucifuge condition flow a few hours next time to a few days, can make the very high catalyst of alkane isomerization or lytic activity.
Patent USP 6,002, and 060 points out, are catalyst with the support type alchlor, and organo-aluminum compound is an auxiliary agent, can make alpha-olefin generation oligomerisation or copolyreaction.
CN1156338 and CN1939590 utilize the gas phase solid support method under the N2 carrier band, fresh alchlor to be brought into to have mesoporous and reaction tube that the granularity macropore double-pore structure is 20~200 order aluminium oxide in react, prepare AlCl 3Solid-supported catalyst, wherein chlorinty is 6.0~9.0 ω %.This carried catalyst has good catalytic activity and selectivity in isobutene polymerisation, show good stable.But in the fixed bed reaction of filling finely grained catalyst, exist tangible pressure to fall problem.
Summary of the invention
The objective of the invention is gama-alumina solid-carried catalyst that discloses a kind of 1-of being applicable to decene or the oligomerisation of 1-octene and its production and application.Supported catalyst catalysis 1-decene of the present invention or 1-octene oligomerisation reaction are active high, and product separates easily, and the recyclable recycling of catalyst reduces environmental pollution; Avoided the corrosion of homogeneous catalyst, also avoided halid existence in the 1-decene oligomerization product simultaneously reactor.
Catalyst component is as follows by weight percentage:
Aluminium: 2.5~6.0%
Chlorine: 6.0~12.0%
VIII group 4 transition metal: 0.5~5.0%
Deduction SO 4 2-Or/and NO 3 -All the other are gama-alumina outward;
The VIII group 4 transition metal is iron, cobalt, nickel or copper.
The preparation method of supported catalyst of the present invention is as follows:
1) gamma-aluminium oxide carrier is carried out the acidifying impregnation process: actual conditions is: under the room temperature, gamma-aluminium oxide carrier was flooded 4~12 hours in hydrochloric acid, sulfuric acid, nitric acid or their mixture solution of 0.5~2.0M, then 80~100 ℃ of vacuum drying 2~12 hours;
2) gamma-aluminium oxide carrier with acidifying carries out VIII group 4 transition metal salt impregnation process: actual conditions is: under the room temperature, the gamma-aluminium oxide carrier of acidifying was soaked 6~12 hours in the sulfate of VIII group 4 transition metal iron, cobalt, nickel or the copper of 0.5-3.0M or nitrate solution, then 80~100 ℃ of vacuum drying 2~12 hours; Under 300~800 ℃, carry out high-temperature roasting 6~16 hours again;
3) it is immobilized alchlor to be carried out solution: will 5~10g aluminum trichloride (anhydrous) add in 100ml carbon tetrachloride, chloroform or the dichloromethane solvent and make solution, join in the gamma-aluminium oxide carrier after 10~20g activates, under reflux temperature, kept 6~24 hours, remove and desolvate, wash with n-hexane, obtaining after the vacuum drying with the gama-alumina is carrier, and load has the catalyst of alchlor and VIII group 4 transition metal salt.
In the preparation of supported catalyst of the present invention, gamma-aluminium oxide carrier is ball-aluminium oxide carrier or bar shaped alumina support; Spherical gamma-aluminium oxide carrier diameter is 1.3~2.3mm, preferred 1.5~2.0mm, specific area 100~180m 2/ g, preferred 120~160m 2/ g, total pore volume 〉=1.0ml/g, strip carrier diameter 3mm, length is 4~10mm, preferred 5~8mm, its specific area is 100~200m 2/ g, preferred 140~180m 2/ g, total pore volume 〉=0.6ml/g.
Optimum acid is hydrochloric acid during the gamma-aluminium oxide carrier acid treatment, and suitable concentration of hydrochloric acid is 0.5~1.5M, and suitable dip time is 4~8 hours; Optimum transition metal salt was nickel nitrate or nickelous sulfate when the gamma-aluminium oxide carrier of acidifying flooded the VIII group 4 transition metal, suitable nickel nitrate solution concentration is 0.5-3.0M, or nickel sulfate solution concentration is 0.25-1.5M, and suitable dip time is 6~12 hours.Then 80~100 ℃ of vacuum drying 2~12 hours; Under 300~800 ℃, carry out high-temperature roasting 6~16 hours again.400 ℃ of optimum calcination temperatures, roasting time 12 hours.
In the preparation of supported catalyst of the present invention, optimum solvent is that carbon tetrachloride or carbon tetrachloride and chloroform volume ratio are 1: 1 mixed solvent during the load aluminum trichloride (anhydrous), best return time 12 hours.
Utilize the preparation method of supported catalyst of the present invention, the chlorinity of the load aluminum trichloride catalyst that finally makes is 6.0~12 ω %, aluminium: 2.5~6.0 ω %, VIII group 4 transition metal (iron, cobalt, nickel, copper): 0.5~5.0 ω %, deduction SO 4 2-, NO 3 -All the other are gama-alumina outward.
In this Preparation of catalysts, all courses of reaction all are to carry out under the inert gas shielding condition, and inert gas is nitrogen or argon gas.
Supported catalyst of the present invention is applied to catalysis 1-decene or 1-octene oligomerisation reaction, makes 1-decene or 1-octene oligomer.Its principle is according to the cationic oligomer reaction principle, adopts Lewis acid catalyst and promoter to form the complex catalysis system.The present invention is used as 1-decene or 1-octene oligomerisation reaction catalyst; 1-decene or 1-octene oligomerisation reaction are solvent with the n-hexane, and 1-decene or 1-octene and n-hexane volume ratio (3: 8)~(4: 1) are to react under 0.8~1.4MPa condition 5~6 hours in 80 ℃~120 ℃ of temperature, reaction pressure; Stop reaction then, filtering catalyst, air-distillation removes the n-hexane that desolvates, and unreacted monomer 1-decene or 1-suffering and part dimer are removed in decompression distillation, obtain the oligomer of final 1-decene or 1-octene.
1-decene conversion ratio 〉=50 ω %, 100 ℃ of kinematic viscosity 〉=3.46mm 2/ s.
The 1-decylene oligomer that the present invention obtains meets the requirement of lube base oil viscosity, the quality height of oil product.
The present invention can reduce the chlorinity in the product by heterogeneousization of polymerization system, makes catalyst can separate, recycle and reuse with product, reduces environmental pollution.
The specific embodiment
Embodiment 1
Spherical gamma-aluminium oxide carrier carries out the acidifying impregnation process: at room temperature, (the carrier diameter is 1.3~2.3mm, specific area 100~180m with spherical gamma-aluminium oxide carrier 2/ g, total pore volume 〉=1.0ml/g) in the hydrochloric acid solution of 1.0M, flooded 6 hours, again 80~100 ℃ of vacuum drying 12 hours.
VIII group 4 transition metal salting liquid is immobilized: at room temperature, the spherical gamma-aluminium oxide carrier of acidifying impregnation process was flooded 6 hours in the 0.5M nickel nitrate solution, then 100 ℃ of vacuum drying 12 hours.Under 400 ℃, carry out high-temperature roasting 6 hours at last.
Aluminum trichloride solution is immobilized: under argon shield; the 5g aluminum trichloride (anhydrous) is made solution in the 100ml carbon tetrachloride; join in the alumina support after 10g activates; under reflux temperature, kept 24 hours; remove and desolvate; with the n-hexane washing, obtain the alchlor supported catalyst after the vacuum drying.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 6.73 ω %; Survey metallic nickel, aluminium content with atomic absorption spectrum, nickel content is 0.67 ω %, and load aluminium content is 3.46 ω %.
The oligomerisation of catalysis 1-decene: in the 250ml polymerization autoclave, add n-hexane 80ml, above-mentioned supported catalyst 8g, 1-decene 30ml, co-catalyst water 0.0936mol (co-catalyst/-AlCl 2Mol ratio=0.90), under 80 ℃ of reaction temperatures, reaction pressure 1.0MPa condition, carried out 1-decene oligomerisation reaction 5 hours.Stop reaction, filtering catalyst removes the n-hexane that desolvates through the normal pressure distillation, and unreacted monomer 1-decene and part dimer are removed in decompression distillation, obtain final oligomer.1-decene conversion ratio 43.6 ω %, 100 ℃ of kinematic viscosity 3.46mm of oligomer 2/ s.
Embodiment 2
Preparation of load aluminum trichloride catalyst and catalysis 1-decene oligomerisation step condition are with embodiment 1, and difference is that the vehicle treated condition is: spherical gamma-aluminium oxide carrier was flooded 4 hours in the hydrochloric acid solution of 1.5M, again 80~100 ℃ of vacuum drying 12 hours; VIII group 4 transition metal salting liquid is immobilized: the spherical gamma-aluminium oxide carrier of acidifying impregnation process was flooded 6 hours in the 2.0M nickel nitrate solution, then 100 ℃ of vacuum drying 12 hours.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 8.45 ω %; Survey metallic nickel, aluminium content with atomic absorption spectrum, nickel content is 4.27 ω %, and load aluminium content is 3.45 ω %.
The oligomerisation of catalysis 1-decene records 1-decene conversion ratio 58.3 ω %, 100 ℃ of kinematic viscosity 6.64mm of oligomer 2/ s.
Embodiment 3
Preparation of load aluminum trichloride catalyst and catalysis 1-decene oligomerisation step condition are with embodiment 1, and difference is that the vehicle treated condition is: spherical gamma-aluminium oxide carrier was flooded 6 hours in the hydrochloric acid solution of 1.0M, again 80~100 ℃ of vacuum drying 12 hours; VIII group 4 transition metal salting liquid is immobilized: the spherical gamma-aluminium oxide carrier of acidifying impregnation process was flooded 6 hours in the 1.0M nickel nitrate solution, then 100 ℃ of vacuum drying 12 hours.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 7.95 ω %; Survey metallic nickel, aluminium content with atomic absorption spectrum, nickel content is 1.53 ω %, and load aluminium content is 4.57 ω %.
The oligomerisation of catalysis 1-decene records 1-decene conversion ratio 52.7 ω %, 100 ℃ of kinematic viscosity 5.29mm of oligomer 2/ s.
Embodiment 4
Preparation of load aluminum trichloride catalyst and catalysis 1-decene oligomerisation step condition are with embodiment 3, and difference is that VIII group 4 transition metal salting liquid is immobilized: replace nickel nitrate solution with nickelous sulfate.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 8.28 ω %; Survey metallic nickel, aluminium content with atomic absorption spectrum, nickel content is 3.21 ω %, and load aluminium content is 4.31 ω %.
The oligomerisation of catalysis 1-decene records 1-decene conversion ratio 59.1 ω %, 100 ℃ of kinematic viscosity 6.13mm of oligomer 2/ s.
Embodiment 5
Preparation of load aluminum trichloride catalyst and catalysis 1-decene oligomerisation step condition are with embodiment 4, and difference is that VIII group 4 transition metal salting liquid is immobilized: replace nickel sulfate solution with copper sulphate.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 10.68 ω %; Survey metallic copper, aluminium content with atomic absorption spectrum, copper content is 2.57 ω %, and load aluminium content is 4.04 ω %.
The oligomerisation of catalysis 1-decene records 1-decene conversion ratio 57.7 ω %, 100 ℃ of kinematic viscosity 9.85mm of oligomer 2/ s.
Embodiment 6
Preparation of load aluminum trichloride catalyst and catalysis 1-decene oligomerisation step condition are with embodiment 4, and difference is that VIII group 4 transition metal salting liquid is immobilized: replace nickel sulfate solution with ferric sulfate.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 6.51 ω %; Survey metallic iron, aluminium content with atomic absorption spectrum, iron content is 0.59 ω %, and load aluminium content is 3.13 ω %.
The oligomerisation of catalysis 1-decene records 1-decene conversion ratio 58.6 ω %, 100 ℃ of kinematic viscosity 6.99mm of oligomer 2/ s.
Embodiment 7
Preparation of load aluminum trichloride catalyst and catalysis 1-decene oligomerisation step condition are with embodiment 3, and difference is that VIII group 4 transition metal salting liquid is immobilized: dipping is 12 hours in the 1.0M nickel nitrate solution.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 9.00 ω %; Survey metallic nickel, aluminium content with atomic absorption spectrum, nickel content is 2.25 ω %, and load aluminium content is 4.38 ω %.The oligomerisation of catalysis 1-decene records 1-decene conversion ratio 55.4 ω %, 100 ℃ of kinematic viscosity 5.25mm of oligomer 2/ s.
Embodiment 8
Preparation of load aluminum trichloride catalyst and catalysis 1-decene oligomerisation step condition are with embodiment 7, and difference is that VIII group 4 transition metal salting liquid is immobilized: transition metal salt solution is the mixture of 1: 1 1.0M nickel nitrate solution of volume ratio and 1.0M copper-bath.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 8.30 ω %; Survey metallic nickel, copper, aluminium content with atomic absorption spectrum, nickel content is 1.15 ω %, and copper content is 1.08 ω %, and load aluminium content is 4.54 ω %.The oligomerisation of catalysis 1-decene records 1-decene conversion ratio 56.0 ω %, 100 ℃ of kinematic viscosity 6.45mm of oligomer 2/ s.
Embodiment 9
Load aluminum trichloride catalyst preparation process condition is with embodiment 3; difference is that aluminum trichloride solution is immobilized: under argon shield; the 10g aluminum trichloride (anhydrous) is made solution in the 100ml carbon tetrachloride; join in the alumina support after 10g activates; under reflux temperature, kept 24 hours; remove and desolvate,, obtain the alchlor supported catalyst after the vacuum drying with the n-hexane washing.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 8.24 ω %; Survey metallic nickel, aluminium content with atomic absorption spectrum, nickel content is 1.75 ω %, and load aluminium content is 3.84 ω %.
The oligomerisation of catalysis 1-decene records 1-decene conversion ratio 58.6 ω %, 40 ℃ of kinematic viscosity 18.94mm of oligomer 2/ s, 100 ℃ of kinematic viscosity 5.97mm 2/ s.
Embodiment 10
Preparation of load aluminum trichloride catalyst and catalysis 1-decene oligomerisation step condition are with embodiment 9, and difference is that aluminum trichloride solution is immobilized: reflux temperature kept 12 hours down.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 8.74 ω %; Survey metallic nickel, aluminium content with atomic absorption spectrum, nickel content is 2.02 ω %, and load aluminium content is 4.12 ω %.
The oligomerisation of catalysis 1-decene records 1-decene conversion ratio 61.24 ω %, 100 ℃ of kinematic viscosity 5.23mm of oligomer 2/ s.
Embodiment 11
Preparation of load aluminum trichloride catalyst and catalysis 1-decene oligomerisation step condition are with embodiment 9, and difference is that aluminum trichloride solution is immobilized: reflux temperature kept 6 hours down.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 8.20 ω %; Survey metallic nickel, aluminium content with atomic absorption spectrum, nickel content is 1.85 ω %, and load aluminium content is 3.91 ω %.
The oligomerisation of catalysis 1-decene records 1-decene conversion ratio 57.14 ω %, 100 ℃ of kinematic viscosity 460mm of oligomer 2/ s.
Embodiment 12
Preparation of load aluminum trichloride catalyst and catalysis 1-decene oligomerisation step condition are with embodiment 3, and it is the 1-octene that difference is to urge the oligomerisation monomer.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 7.95 ω %; Survey metallic nickel, aluminium content with atomic absorption spectrum, nickel content is 1.53 ω %, and load aluminium content is 4.57 ω %.
The catalyzed 1-octylene oligomerisation records 1-octene conversion ratio 67.0 ω %, 100 ℃ of kinematic viscosity 3.12mm of oligomer 2/ s.
Comparative example 1
Spherical gamma-alumina load aluminum trichloride catalyst preparation and catalysis 1-decene oligomerisation step condition are with embodiment 3, and difference is that carrier carried out impregnation process 2 hours with 0.5M hydrochloric acid, did not have the immobilized step of VIII group 4 transition metal salting liquid.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 6.88 ω %.
Products obtained therefrom 1-decene conversion ratio 37.8 ω %, 100 ℃ of kinematic viscosity 2.46mm of oligomer 2/ s.
Comparative example 2
Spherical gamma-alumina load aluminum trichloride catalyst preparation and catalysis 1-decene oligomerisation step condition are with embodiment 3, difference is not carry out carrier acidifying impregnation process and the immobilized step of VIII group 4 transition metal salting liquid, and carrier directly carries out aluminum trichloride solution through 400 ℃ of roastings after 6 hours immobilized.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 6.93 ω %.
Products obtained therefrom 1-decene conversion ratio is 30.30 ω %, 100 ℃ of kinematic viscosity 2.45mm of oligomer 2/ s.
Comparative example 3
Load aluminum trichloride catalyst preparation and catalysis 1-decene oligomerisation step condition be with embodiment 3,, difference is 200 ℃ of supported catalyst sintering temperatures.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 9.47 ω %.
Products obtained therefrom 1-decene conversion ratio 43.0 ω %, 100 ℃ of kinematic viscosity 4.24mm of oligomer 2/ s.

Claims (3)

1. alpha-olefin oligomerisation solid-carried catalyst, it is characterized in that: this catalyst is carrier with the gama-alumina, and load has alchlor and VIII group 4 transition metal salt, and catalyst component is as follows by weight percentage:
Aluminium: 2.5~6.0%,
Chlorine: 6.0~12.0%,
VIII group 4 transition metal: 0.5~5.0%,
Deduction SO 4 2-And/or NO 3 -All the other are gama-alumina outward;
The VIII group 4 transition metal is iron, cobalt, nickel or copper.
2. the preparation method of the described alpha-olefin oligomerisation of claim 1 solid-carried catalyst is characterized in that:
1) gamma-aluminium oxide carrier is carried out the acidifying impregnation process: actual conditions is: under the room temperature, gamma-aluminium oxide carrier was flooded 4~12 hours in hydrochloric acid, sulfuric acid, nitric acid or their mixture solution of 0.5~2.0M, then 80~100 ℃ of vacuum drying 2~12 hours;
2) gamma-aluminium oxide carrier with acidifying carries out VIII group 4 transition metal salt impregnation process: actual conditions is: under the room temperature, the gamma-aluminium oxide carrier of acidifying was soaked 6~12 hours in the sulfate of VIII group 4 transition metal iron, cobalt, nickel or the copper of 0.5-3.0M or nitrate solution, then 80~100 ℃ of vacuum drying 2~12 hours; Under 300~800 ℃, carry out high-temperature roasting 6~16 hours again;
3) it is immobilized alchlor to be carried out solution: will 5~10g aluminum trichloride (anhydrous) add in 100ml carbon tetrachloride, chloroform or the dichloromethane solvent and make solution, join in the gamma-aluminium oxide carrier after 10~20g activates, under reflux temperature, kept 6~24 hours, remove and desolvate, wash with n-hexane, obtaining after the vacuum drying with the gama-alumina is carrier, and load has the catalyst of alchlor and VIII group 4 transition metal salt.
3. the application of the described alpha-olefin oligomerisation of claim 1 solid-carried catalyst is characterized in that: be used for 1-decene or 1-octene oligomerisation reaction catalyst; 1-decene or 1-octene oligomerisation reaction are solvent with the n-hexane, and 1-decene or 1-octene and n-hexane volume ratio (3: 8)~(4: 1) are to react under 0.8~1.4MPa condition 5~6 hours in 80 ℃~120 ℃ of temperature, reaction pressure; Stop reaction then, filtering catalyst, air-distillation removes the n-hexane that desolvates, and unreacted monomer 1-decene or 1-suffering and part dimer are removed in decompression distillation, obtain the oligomer of final 1-decene or 1-octene.
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CN102728396A (en) * 2012-06-04 2012-10-17 华东理工大学 Preparation method and application of gamma-alumina supported aluminum trichloride catalyst
CN102921437A (en) * 2012-11-02 2013-02-13 华东理工大学 Alpha-olefin oligomerization immobilized catalyst, preparation method and application thereof
CN103666552A (en) * 2012-09-04 2014-03-26 中国石油天然气股份有限公司 Preparation method of medium-viscosity poly-alpha-olefin base oil
CN104324734A (en) * 2014-09-26 2015-02-04 沈阳化工大学 Preparation method of catalyst suitable for synthesizing C8 and C12 through oligomerization of 1-butene
CN108187697A (en) * 2017-12-28 2018-06-22 之江(四川)高新材料应用技术研究院有限公司 Synthesize the method and used catalyst of 2- morpholine ethanols
CN108772099A (en) * 2018-04-03 2018-11-09 山东大学 A kind of preparation method and application of porous Teflon load aluminum trichloride catalyst
CN116023561A (en) * 2021-10-25 2023-04-28 中国石油化工股份有限公司 Supported polyolefin catalyst and preparation method and application thereof

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CN103666552A (en) * 2012-09-04 2014-03-26 中国石油天然气股份有限公司 Preparation method of medium-viscosity poly-alpha-olefin base oil
CN103666552B (en) * 2012-09-04 2016-04-06 中国石油天然气股份有限公司 Preparation method of medium-viscosity poly-alpha-olefin base oil
CN102921437A (en) * 2012-11-02 2013-02-13 华东理工大学 Alpha-olefin oligomerization immobilized catalyst, preparation method and application thereof
CN102921437B (en) * 2012-11-02 2015-04-22 华东理工大学 Alpha-olefin oligomerization immobilized catalyst, preparation method and application thereof
CN104324734A (en) * 2014-09-26 2015-02-04 沈阳化工大学 Preparation method of catalyst suitable for synthesizing C8 and C12 through oligomerization of 1-butene
CN108187697A (en) * 2017-12-28 2018-06-22 之江(四川)高新材料应用技术研究院有限公司 Synthesize the method and used catalyst of 2- morpholine ethanols
CN108772099A (en) * 2018-04-03 2018-11-09 山东大学 A kind of preparation method and application of porous Teflon load aluminum trichloride catalyst
CN116023561A (en) * 2021-10-25 2023-04-28 中国石油化工股份有限公司 Supported polyolefin catalyst and preparation method and application thereof

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