WO2011060606A1 - 一种合成1-癸烯齐聚物的方法 - Google Patents

一种合成1-癸烯齐聚物的方法 Download PDF

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WO2011060606A1
WO2011060606A1 PCT/CN2010/001110 CN2010001110W WO2011060606A1 WO 2011060606 A1 WO2011060606 A1 WO 2011060606A1 CN 2010001110 W CN2010001110 W CN 2010001110W WO 2011060606 A1 WO2011060606 A1 WO 2011060606A1
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catalyst
decene
aluminum trichloride
hours
supported
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PCT/CN2010/001110
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English (en)
French (fr)
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黄付玲
米普科
王斯晗
钱锦华
陈谦
许胜�
李建忠
王刚
张宝军
刘敏
王桂芝
韩雪梅
曲家波
卢攀峰
孙淑坤
王秀绘
高宇新
张德顺
江玲
于部伟
王力搏
王亚丽
范玲婷
卫鹏
刘伟
郭桂悦
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中国石油天然气股份有限公司
华东理工大学
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Priority to US13/510,216 priority Critical patent/US9248430B2/en
Publication of WO2011060606A1 publication Critical patent/WO2011060606A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0205—Impregnation in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
    • C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
    • C07C2/22—Metal halides; Complexes thereof with organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/125—Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
    • C07C2527/126—Aluminium chloride

Definitions

  • the invention relates to the use of a ⁇ -alumina supported aluminum trichloride catalyst for catalyzing the oligomerization of 1-decene. Background technique
  • the A1C1 3 catalyst used in the positive ion polymerization is a Lewis acid catalyst and is one of the important catalysts widely used in the chemical, petroleum refining and pharmaceutical industries. Due to its good catalytic effect, such catalysts have the characteristics of high polymer yield, narrow molecular weight distribution and good selectivity in catalyzing the oligomerization of ⁇ -olefins; however, A1C1 3 catalysts have extremely high activity, There are obvious deficiencies: 1 A1C1 3 catalyst is highly corrosive, easily damages the reactor and other devices, affects the service life of the device, thus reducing the utilization rate; 2 using AlC catalyst to produce a large amount of sewage at the same time, can not produce Timely treatment will seriously pollute the environment; 3A1C1 3 catalyst after the reaction is difficult to recover and needs to be post-treated, otherwise it will produce a lot of corrosive waste.
  • Japanese Patent No. JP08505888 discloses a method for preparing a lubricating base oil by cationic polymerization, and using a Lewis acid such as A1C1 3 or BF 3 as a catalyst to prepare a polydecene. Due to the use of a homogeneous system, the method has high content of halogenated products such as A1C1 3 and BF 3 in the product, and it is impossible to produce low halogenated products. BF 3 is not only expensive but also causes a series of environmental problems due to the corrosiveness of fluorine. . Since the catalyst is difficult to separate and cannot be recycled, a large amount of production waste liquid which is difficult to handle is produced, thereby increasing the cost of production. At the same time, the obtained poly- ⁇ -olefin has a low molecular weight, and the obtained lubricating oil has a low viscosity, and does not reach an environmental standard when used as a lubricating oil.
  • a Lewis acid such as A1C
  • a solid acid catalyst such as a supported metal oxide has been developed in place of a conventional catalyst such as A1C1 3 or BF 3 , and an A1C1 3 immobilization catalyst has been studied. It is hoped that the existing problems can be solved while maintaining the excellent characteristics of A1C1 3 , making it an environmentally friendly catalyst.
  • the supported A1C1 3 catalyst is a new type of solid acid catalyst which is highly efficient and environmentally friendly. Due to its high catalytic activity and mild reaction conditions, it has attracted much attention in recent years and is widely used in the research of polymerization and thiolation reactions.
  • Patent US 2, 927, 087 first proposed that A1C1 3 immobilized catalyst can be prepared by reacting A1C1 3 vapor with refractory oxides such as alumina or silica with surface hydroxyl groups, emphasizing that the reaction is higher than 300 ° C.
  • the carrier gas is purged at the temperature to remove the unreacted A1C1 3 necessity.
  • USP 4, 929, 800 is prepared by dissolving aluminum trichloride in a solvent such as CC1 4 , CH 3 C1 or CH 2 C1 2 , adding a carrier such as silica or alumina, and protecting it at 50 to 80 ° C and N 2 . After refluxing for several hours to several days in the dark, a catalyst having a high activity of isomerization or cleavage of hydrazine can be obtained.
  • Patent USP 6, 002, 060 states that organoaluminum compounds are auxiliary agents, using supported aluminum trichloride as a catalyst.
  • the ⁇ -olefin can be oligomerized or copolymerized.
  • CN1156338 and CN1939590 are reacted by a gas phase solid-state method in a reaction tube of 20 to 200 mesh alumina having a mesoporous and macroporous double pore structure under a ruthenium 2 carrier tape to produce A1C1.
  • a supported catalyst having a chlorine content of 6.0 to 9.0 ⁇ %.
  • the supported catalyst has good catalytic activity and selectivity in the low polymerization of isobutylene and exhibits good stability.
  • the object of the present invention is to disclose the use of a ⁇ -alumina-supported aluminum trichloride catalyst for catalyzing the oligomerization of 1-decene.
  • the supported catalyst of the invention catalyzes the high activity of 1-decene oligomerization and the separation of products is easy.
  • the catalyst can be recycled and reused to reduce environmental pollution; the homogeneous catalyst is prevented from corroding the reactor, and the presence of halides in the 1-decene oligomerization product is also avoided.
  • the preparation method of the supported catalyst of the invention is as follows:
  • ⁇ -alumina carrier is subjected to an acid immersion treatment.
  • the specific conditions are as follows: ⁇ -alumina carrier is immersed in a solution of 0.5 to 2.0 Torr of hydrochloric acid or sulfuric acid or nitric acid or a mixture thereof for 4 to 12 hours at room temperature, and then dried under vacuum at 80 to 100 ° C for 2 to 12 hours. Finally, the high temperature baking is carried out at 300 to 800 ° C for 6 to 16 hours.
  • the aluminum trichloride is solution-fixed. 5 ⁇ 10g of anhydrous aluminum trichloride is prepared in 100ml of organic solvent such as carbon tetrachloride or chloroform or dichloromethane, and added to 10 ⁇ 20g of activated alumina carrier, and kept at reflux temperature. After 6 to 24 hours, the solvent was removed, washed with n-hexane, and dried under vacuum to obtain an aluminum trichloride supported catalyst.
  • organic solvent such as carbon tetrachloride or chloroform or dichloromethane
  • the ⁇ -alumina support is a spherical alumina support or a strip-shaped alumina support; the spherical ⁇ -alumina support has a diameter of 1.3 to 2.3 mm, preferably 1.5 to 2.0 mm, and a specific surface area of 100 to 180 m. 2 / g, preferably 120 to 160 m 2 /g, total pore volume 1.0 ml / g, strip carrier diameter 3 mm, length 4 to 10 mm, preferably 5 to 8 mm, and specific surface area of 100 to 200 m 2 /g, Preferably, it is 140 to 180 m 2 /g, and the total pore volume is 0.6 ml/g.
  • the most suitable acid for the ⁇ -alumina carrier acid treatment is hydrochloric acid.
  • the optimum hydrochloric acid concentration is 1 ⁇
  • the optimum immersion time is 6 hours
  • the optimum calcination temperature is 400 ° C
  • the calcination time is 12 hours.
  • the most suitable solvent for supporting anhydrous aluminum trichloride is carbon tetrachloride or a mixed solvent of carbon tetrachloride and chloroform in a volume ratio of 1:1, and the optimum reflux time is 12 hours.
  • the chlorine content of the finally supported aluminum trichloride catalyst is 6.0 to 12 ⁇ %, that is, the weight of the -A1C1 2 in the supported catalyst is 8.28 to 16.56%.
  • the supported catalyst of the present invention is applied to catalyze the oligomerization of 1-decene to obtain a 1-decene oligomer.
  • the principle is based on the principle of cationic oligomerization, using a Lewis acid catalyst and a promoter to form a complex catalytic system.
  • the 1-decene oligomerization reaction of the present invention uses n-hexane as a solvent, and the volume ratio of 1-decene to n-hexan is 3:8 to 4:1, at a temperature of 80 ° C to 120 ° C, and the reaction pressure is 0.8 to 1.4 MPa.
  • the reaction is carried out for 5 to 6 hours; the reaction is then stopped, the catalyst is filtered, the solvent n-hexane is removed by distillation under normal pressure, and the unreacted monomer 1-terpene and a part of the dimer are distilled off under reduced pressure to obtain a final oligomer.
  • the spherical ⁇ -alumina support is subjected to acidification immersion treatment: at room temperature, a spherical ⁇ -alumina support (carrier diameter: 1.3 to 2.3 mm, specific surface area: 100 to 180 m 2 /g, total pore volume: 1.0 ml/g ;
  • the mixture was immersed in a 1.0 M hydrochloric acid solution for 6 hours, vacuum-dried at 80 to 100 ° C for 12 hours, and then calcined at 400 ° C for 6 hours at a high temperature.
  • Aluminum trichloride solution immobilization Under argon protection, 5 g of anhydrous aluminum trichloride is made into a solution of 100 ml of carbon tetrachloride, added to 10 g of activated alumina carrier, and maintained at reflux temperature. After an hour, the solvent was removed, washed with n-hexane, and dried under vacuum to give an aluminum trichloride supported catalyst.
  • the chlorine content of the above aluminum trichloride supported catalyst was measured by the Fulhard titration method, and the weight of chlorine in the supported catalyst was 8.56%.
  • Catalytic polymerization of 1-decene 80 ml of n-hexane was added to a 250 ml high pressure polymerization reactor, 8 g of the above supported catalyst, 30 ml of 1-decene, and 0.174 ml of cocatalyst water, at a reaction temperature of 8 (TC, reaction pressure of 1.0 MPa)
  • the 1-decene oligomerization reaction was carried out for 5 hours, the reaction was stopped, the catalyst was filtered, the solvent hexamethylene was removed by atmospheric distillation, and the unreacted monomer 1-decene and a partial dimer were distilled off under reduced pressure to obtain a final oligomer.
  • the supported aluminum trichloride catalyst was prepared in the same manner as in Example 1, except that the carrier treatment conditions were such that the spherical ⁇ -alumina support was immersed in a 1.5 M hydrochloric acid solution for 6 hours at room temperature, and then vacuum dried at 80 to 100 ° C. After an hour, it was then calcined at 400 Torr for 6 hours.
  • the chlorine content of the above aluminum trichloride supported catalyst was measured by the Fulhard titration method, and the weight of chlorine in the supported catalyst was 6.82%.
  • Catalyzed 1-decene oligomerization 80 ml of n-hexane was added to a 250 ml high pressure polymerization vessel, 8 g of the above supported catalyst, 30 ml of 1-decene, 0.14 ml of cocatalyst water, and the reaction temperature was 80 Torr, and the reaction pressure was 1.0 MPa. - Terpene oligomerization reaction for 5 hours.
  • the supported aluminum trichloride catalyst was prepared in the same manner as in Example 1, except that the carrier calcination temperature was 800 ° C and the calcination time was 6 hours.
  • the chlorine content of the above aluminum trichloride supported catalyst was measured by the Fulhard titration method to obtain a chlorine weight of 6.42% in the supported catalyst.
  • Catalyzed 1-decene oligomerization 80 ml of n-hexane was added to a 250 ml high pressure polymerization vessel, 8 g of the above supported catalyst, 30 ml of 1-decene, 0.13 ml of cocatalyst water, at a reaction temperature of 80 ° C and a reaction pressure of 1.0 MPa.
  • the 1-decene oligomerization reaction was carried out for 5 hours. The reaction was stopped, the catalyst was filtered, and the solvent was gradually distilled to remove n-hexane. The unreacted monomer 1-decene and a part of the dimer were distilled off under reduced pressure to obtain a final oligomer.
  • the supported aluminum trichloride catalyst was prepared in the same manner as in Example 1, except that when the aluminum trichloride solution was supported, 10 g of anhydrous aluminum trichloride was made into a solution of 100 ml of carbon tetrachloride, and 10 g of activated alumina was added. The carrier was kept at reflux temperature for 24 hours, the solvent was removed, and the mixture was washed with n-hexane. After vacuum drying, an aluminum trichloride supported catalyst was obtained.
  • the chlorine content of the above aluminum trichloride supported catalyst was measured by the Fulhard titration method, and the weight of chlorine in the supported catalyst was 8.24%.
  • Catalyzed 1-decene oligomerization 80 ml of n-hexane was added to a 250 ml high pressure polymerization vessel, the above supported catalyst 8 g, 1-decene 30 ml, cocatalyst water 0.167 ml, at a reaction temperature of 80 ° C, a reaction pressure of 1.0 MPa
  • the 1-decene oligomerization reaction was carried out for 5 hours. The reaction was stopped, the catalyst was filtered, the solvent was distilled off by constant pressure distillation, and the unreacted monomer 1-decene and a part of the dimer were distilled off under reduced pressure to obtain a final oligomer.
  • the supported aluminum trichloride catalyst was prepared in the same manner as in Example 1 except that the carrier calcination temperature was 600 ° C and the calcination time was 6 hours.
  • the chlorine content of the above aluminum trichloride supported catalyst was measured by the Fulhard titration method, and the weight of chlorine in the supported catalyst was 7.83 %.
  • Catalytic polymerization of 1-decene 80 ml of n-hexane was added to a 250 ml high pressure polymerization reactor, 8 g of the above supported catalyst, 30 ml of 1-decene, 0.159 ml of cocatalyst water, at a reaction temperature of 80 ° C and a reaction pressure of 1.0 MPa.
  • the 1-decene oligomerization reaction was carried out for 5 hours. The reaction was stopped, the catalyst was filtered, the solvent n-hexane was removed by atmospheric distillation, and the unreacted monomer 1-decene and a partial dimer were distilled off under reduced pressure to obtain a final oligomer.
  • the supported aluminum trichloride catalyst was prepared in the same manner as in Example 1, except that the carrier was calcined at a temperature of 600 ° C and the calcination time was 12 hours.
  • the chlorine content of the above aluminum trichloride supported catalyst was measured by the Fulhard titration method, and the weight of chlorine in the supported catalyst was 7.77%.
  • Catalytic polymerization of 1-decene 80 ml of n-hexane was added to a 250 ml high pressure polymerization reactor, 8 g of the above supported catalyst, 30 ml of 1-decene, 0.159 ml of cocatalyst water, at a reaction temperature of 80 ° C and a reaction pressure of 1.0 MPa.
  • the 1-decene oligomerization reaction was carried out for 5 hours. The reaction was stopped, the catalyst was filtered, the solvent n-hexane was removed by atmospheric distillation, and the unreacted monomer 1-decene and a partial dimer were distilled off under reduced pressure to obtain a final oligomer.
  • the spherical gamma-alumina supported aluminum trichloride catalyst was prepared in the same manner as in Example 1, except that the aluminum trichloride loading time was 12 hours.
  • the chlorine content of the above aluminum trichloride supported catalyst was measured by the Fulhard titration method, and the weight of chlorine in the supported catalyst was 7.92%.
  • Catalyzed 1-decene oligomerization 'In a 250 ml high pressure polymerizer, 80 ml of n-hexane was added, the above supported catalyst 8 g, 1-decene 30 ml, cocatalyst water 0.16 ml, at a reaction temperature of 80 ° C, a reaction pressure of 1.0 MPa The 1-decene oligomerization reaction was carried out for 5 hours. The reaction was stopped, the catalyst was filtered, the solvent n-hexane was removed by atmospheric distillation, and the unreacted monomer 1-decene and a partial dimer were distilled off under reduced pressure to obtain a final oligomer.
  • 1-decene conversion rate 52.2 (0%, oligomer 40 ° C kinematic viscosity 15.17 mm 2 / s.
  • the supported aluminum trichloride catalyst was prepared in the same manner as in Example 1, except that the ⁇ -alumina carrier was strip-shaped (diameter 3 mm, length 4 to 10 mm, specific surface area of 100 to 200 m 2 /g, total pore volume 0.6 ml). /g), carrier baking The firing temperature was 600 ° C and the baking time was 9 hours.
  • the chlorine content of the above-mentioned aluminum trichloride supported catalyst was measured by the Fulhard titration method, and the weight of chlorine in the supported catalyst was 7.87%.
  • Catalyzed 1-decene oligomerization 80 ml of n-hexane was added to a 250 ml high pressure polymerization vessel, 8 g of the above supported catalyst, 30 ml of 1-decene, and 0.16 ml of cocatalyst water, at a reaction temperature of 80 ° C and a reaction pressure of 1.0 MPa.
  • the 1-decene oligomerization reaction was carried out for 4 hours. The reaction was stopped, the catalyst was filtered, the solvent was distilled off by constant pressure distillation, and the unreacted monomer 1-decene and a part of the dimer were distilled off under reduced pressure to obtain a final oligomer.
  • the conversion of 1-decene is 54.2 ⁇ %
  • the kinematic viscosity at 100 ° C of the oligomer is 4.95 mm 2 /s
  • the viscosity index is 222.14.
  • the supported aluminum trichloride catalyst was prepared in the same manner as in Example 1, except that the ⁇ -alumina carrier was strip-shaped (diameter 3 mm, length 41 to 10 mm, specific surface area of 100 to 200 m 2 /g, total pore volume 0.6 ml). /g), aluminum trichloride loading time is 12 hours.
  • the chlorine content of the above aluminum trichloride supported catalyst was measured by the Fulhard titration method to obtain a weight of chlorine of 7.65% in the supported catalyst.
  • Catalyzed 1-decene oligomerization 80 ml of n-hexane was added to a 250 ml high pressure polymerization vessel, the above supported catalyst 8 g, 1-decene 30 ml, cocatalyst water 0.144 ml, at a reaction temperature of 80 ° C, a reaction pressure of 1.0 MPa
  • the 1-decene oligomerization reaction was carried out for 5 hours. The reaction was stopped, the catalyst was filtered, the solvent was distilled off by constant pressure distillation, and the unreacted monomer 1-decene and a part of the dimer were distilled off under reduced pressure to obtain a final oligomer.
  • the 1-decene conversion rate was 58.8 G>%, and the oligomer 40 ⁇ kinematic viscosity was 14.82 mm 2 /s.
  • the spherical ⁇ -alumina supported aluminum trichloride catalyst was prepared in the same manner as in Example 1, except that the solvent used for the aluminum trichloride loading was a mixed solvent of carbon tetrachloride and chloroform in a volume ratio of 1:1, and the loading time was 12 hours.
  • the chlorine content of the above aluminum trichloride supported catalyst was measured by the Fulhard titration method, and the weight of chlorine in the supported catalyst was 8.11%.
  • Catalyzed 1-decene oligomerization 80 ml of n-hexane was added to a 250 ml high pressure polymerization vessel, 8 g of the above supported catalyst, 30 ml of 1-decene, and 0.165 ml of cocatalyst water, at a reaction temperature of 80 ° C and a reaction pressure of 1.0 MPa.
  • the 1-decene oligomerization reaction was carried out for 5 hours. The reaction was stopped, the catalyst was filtered, the solvent was distilled off by constant pressure distillation, and the unreacted monomer 1-decene and a part of the dimer were distilled off under reduced pressure to obtain a final oligomer.
  • the conversion of 1-decene was 52.2 ⁇ %, and the kinematic viscosity of the oligomer at 40 °C was 16.87 mm 2 /s.
  • Comparative example 1 A spherical gamma-alumina supported aluminum trichloride catalyst was prepared as in Example 1, except that the carrier was not subjected to hydrochloric acid immersion treatment.
  • the chlorine content of the above aluminum trichloride supported catalyst was measured by the Fulhard titration method, and the weight of chlorine in the supported catalyst was 6.33%.
  • the 1-decene oligomerization process and conditions are the same as in the first embodiment.
  • the obtained product 1-decene conversion rate was 35.0 ⁇ %, and the oligomer 100 ° C kinematic viscosity was 2.66 mm 2 /s.
  • the spherical ⁇ -alumina supported aluminum trichloride catalyst was prepared in the same manner as in Example 1.
  • the carrier was immersed in 0.5 Torr hydrochloric acid for 2 hours.
  • the chlorine content of the above-mentioned aluminum trichloride supported catalyst was measured by the Fulhard titration method, and the weight of chlorine in the supported catalyst was 6.88%.
  • the 1-decene oligomerization process and conditions are the same as in the first embodiment.
  • the obtained product 1-decene conversion rate was 37.8 ⁇ %, and the oligomer 100 ⁇ kinematic viscosity was 2.46 mm 2 /s.
  • the supported aluminum trichloride catalyst was prepared in the same manner as in Example 1, except that the carrier treatment conditions were such that the spherical ⁇ -alumina support was immersed in a 0.5 Torr hydrochloric acid solution at room temperature for 16 hours, and then at 80 to 10 (TC vacuum dried 12). After an hour, it was then calcined at 400 Torr for 6 hours.
  • the chlorine content of the above-mentioned aluminum trichloride supported catalyst was measured by the Fulhard titration method, and the weight of chlorine in the supported catalyst was 7.45%.
  • the 1-decene oligomerization process and conditions are the same as in the first embodiment.
  • the obtained product 1-decene conversion was 52.11 ⁇ %, the oligomer had a kinematic viscosity at 100 ° C of 6.08 mm 2 /s, and a viscosity index of 172.00.
  • the supported aluminum trichloride catalyst was prepared in the same manner as in Example 1, except that the supported catalyst was calcined at a temperature of 200 Torr.
  • the chlorine content of the above-mentioned aluminum trichloride supported catalyst was measured by the Fulhard titration method, and the weight of chlorine in the supported catalyst was 10.75%.
  • the 1-decene oligomerization process and conditions were the same as in Example 1, except that the amount of the promoter water was 0.218 ml.
  • the supported aluminum trichloride catalyst was prepared in the same manner as in Example 1, except that the supported catalyst was calcined at a temperature of 400 Torr and baked. The burning time is 4 hours.
  • the chlorine content of the above aluminum trichloride supported catalyst was measured by the Fulhard titration method, and the weight of chlorine in the supported catalyst was 7.26%.
  • the 1-decene oligomerization process and conditions were the same as in Example 1, except that the amount of cocatalyst water was 0.147 ml.
  • the obtained product 1-decene conversion rate was 47.7 ⁇ %, and the oligomer 100 ° C kinematic viscosity was 4.24 mm 2 /s.
  • the supported catalyst of the present invention is applied to catalyze the oligomerization of 1-decene to obtain a 1-decene oligomer.
  • the principle is to form a complex catalytic system by using Lewis acid catalyst and accelerator according to the principle of cationic oligomerization reaction.
  • the 1-decene oligomerization reaction of the present invention uses n-hexane as a solvent, and the volume ratio of 1-decene to n-hexan is 3:8 to 4:1, at a temperature of 80 ° C to 120 ° C, and the reaction pressure is 0.8 to 1.4 MPa.
  • the reaction was carried out for 5 to 6 hours; then, the reaction was stopped, the catalyst was filtered, the solvent was distilled under normal pressure, and the unreacted monomer, 1-decene and a part of the dimer, were distilled off under reduced pressure to obtain a final oligomer.
  • the 1-decene conversion rate is 50% by weight
  • the oligomer 40 ⁇ kinematic viscosity is 6.0 to 25 mm 2 /s
  • the viscosity index is 160 to 262.
  • the 1-decene oligomer obtained by the present invention meets the viscosity requirements of the lubricating base oil, and the quality of the oil is high.
  • the invention can reduce the chlorine content in the product through the heterogeneous polymerization system, so that the catalyst and the product can be separated, recycled and reused, and environmental pollution is reduced.

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Description

一种合成 1-癸烯齐聚物的方法 技术领域
本发明涉及一种 γ-氧化铝负载三氯化铝催化剂在催化 1-癸烯齐聚中的应用。 背景技术
正离子聚合反应使用的 A1C13催化剂是一种路易斯酸催化剂， 是化工、 石油炼制 和制药工业中广泛应用的重要催化剂之一。由于其良好的催化效果，这类催化剂在催 化 α -烯烃齐聚反应中具有聚合物收率高、分子量分布窄、选择性好等特点；但是 A1C13 催化剂在具有极高的活性的同时， 也存在明显的不足之处： ① A1C13催化剂具有强腐 蚀性， 容易将反应釜等装置损坏， 影响装置的使用寿命， 从而降低了使用率； ②运用 AlC 催化剂聚合生产的同时会产生大量污水， 不能及时处理会严重污染环境； ③反 应后的 A1C13催化剂很难回收， 需要经过后处理， 否则会产生大量的腐蚀性废料。
如日本专利 JP08505888 公开了一种阳离子聚合制备润滑油基础油的方法， 以 A1C13、 BF3等 Lewis酸作为催化剂， 制备聚癸烯。 该方法由于采用均相体系， 使得产 品中 A1C13、 BF3等卤代物的含量较高， 无法生产低卤代物的产品， BF3不但很贵而 且由于氟的腐蚀性， 引起一系列的环境问题。 由于催化剂难于分离， 无法回收使用， 产生了大量难以处理的生产废液， 因此提高了生产的成本。 同时， 所获得的聚 α -烯 烃分子量低， 所得到的润滑油的粘度也较低， 作为润滑油使用时达不到环境标准。
因此，为了达到绿色化学的要求，在开发负载型金属氧化物等固体酸催化剂代替 A1C13、 BF3等传统催化剂的同时， 也在努力研究 A1C13固载化催化剂。 希望能在保持 A1C13优良特性的前提下， 解决存在的问题， 使其转变为对环境友好的催化剂。 负载 型 A1C13催化剂是一种高效、 环境友好的新型固体酸催化剂， 由于具有较高的催化活 性和温和的反应条件近年来备受关注， 广泛应用于聚合及垸基化反应的研究中。
专利 US 2, 927, 087最早提出， 可通过 A1C13蒸汽与带有表面羟基的氧化铝、 氧化硅等难熔氧化物反应制得 A1C13固载化催化剂， 强调反应后在高于 300°C的温度 下用载气吹扫， 除去未反应 A1C13的必要性。
USP 4, 929, 800以 CC14、 CH3C1或 CH2C12等为溶剂， 把三氯化铝溶解其中， 加入氧化硅或氧化铝等载体， 在 50〜80°C和 N2保护、 避光条件下回流数小时至数日 后， 可制得垸烃异构化或裂解活性很高的催化剂。
专利 USP 6, 002， 060指出， 以负载型三氯化铝为催化剂，有机铝化合物为助剂， 可使 α -烯烃发生齐聚或共聚反应。
CN1156338及 CN1939590利用气相固载方法在 Ν2载带下将新鲜的三氯化铝带入 具有介孔和大孔双孔结构的粒度为 20〜200目氧化铝的反应管中反应，制造出 A1C13 固载化催化剂， 其中含氯量为 6.0〜9.0ω%。 该载体催化剂在异丁烯低度聚合中具有 良好的催化活性和选择性，表现出良好的稳定性。但在填充细颗粒催化剂的固定床反 应中存在明显的压力降问题。
发明内容
本发明的目的是公开一种 γ-氧化铝负载三氯化铝催化剂在催化 1-癸烯齐聚中的 应用，本发明的负载催化剂催化 1-癸烯齐聚反应活性高，产物分离容易，催化剂可回 收重复利用， 减少环境污染； 避免了均相催化剂对反应器的腐蚀， 同时也避免了 1- 癸烯齐聚产物中卤化物的存在。
本发明负载催化剂的制备方法如下：
1)将 γ-氧化铝载体进行酸化浸渍处理。 具体条件为： 室温下， 将 γ-氧化铝载体 在 0.5〜2.0Μ的盐酸或硫酸或硝酸或它们的混合物溶液中浸渍 4〜12小时， 然后在 80〜100°C真空干燥 2〜12小时， 最后再在 300〜800°C下进行高温焙烧 6〜16小时。
2)将三氯化铝进行溶液固载。将 5〜10g无水三氯化铝在 100ml四氯化碳或三氯 甲烷或二氯甲烷等有机溶剂中制成溶液，加入到 10〜20g活化后的氧化铝载体中，在 回流温度下保持 6〜24小时， 除去溶剂， 以正己垸洗涤， 真空干燥后得到三氯化铝负 载催化剂。
本发明负载催化剂的制备中， γ-氧化铝载体为球形氧化铝载体或条形氧化铝载 体；球形 γ-氧化铝载体直径为 1.3〜2.3mm，优选 1.5〜2.0mm，比表面积 100〜180 m2/g, 优选 120〜160 m2/g， 总孔容 1.0ml/g， 条状载体直径 3mm， 长度为 4〜 10mm，优选 5〜8mm， 其比表面积为 100〜200 m2/g, 优选 140〜180 m2/g， 总孔容 0.6ml/g。
γ-氧化铝载体酸处理时最适宜的酸为盐酸， 最佳盐酸浓度为 1Μ， 最佳浸渍时间 为 6小时， 最佳焙烧温度 400°C， 焙烧时间 12小时。
本发明负载催化剂的制备中，负载无水三氯化铝时最适宜的溶剂为四氯化碳或四 氯化碳与三氯甲烷体积比为 1 :1的混合溶剂， 最佳回流时间 12小时。
利用本发明负载催化剂的制备方法，最终制得的负载三氯化铝催化剂的氯含量为 6.0〜12ω%， 即负载催化剂中 -A1C12重量为 8.28〜 16.56%。
在氧化铝固载三氯化铝催化剂的制备中，所有反应过程均是在惰性气体保护条件 下进行， 惰性气体为氮气或氩气。
本发明负载催化剂应用于催化 1-癸烯齐聚反应， 制得 1-癸烯齐聚物。 其原理是 根据阳离子齐聚反应原理，采用 Lewis酸类催化剂及促进剂形成络合催化体系。本发 明 1-癸烯齐聚反应以正己垸为溶剂， 1-癸烯与正己垸体积比 3:8〜4:1， 在温度 80°C〜- 120°C、 反应压力为 0.8〜1.4MPa条件下反应 5〜6小时； 然后停止反应， 过滤催化 剂， 常压蒸熘除去溶剂正己烷， 减压蒸馏除去未反应单体 1一癸烯及部分二聚体， 得 到最终齐聚物。
具体实施方式
现通过下述实施例对本发明作进一步的描述。
实施例 1
球形 γ-氧化铝载体进行酸化浸渍处理：在室温下，将球形 γ-氧化铝载体（载体直 径为 1.3〜2.3mm、 比表面积 100〜180m2/g、 总孔容 1.0ml/g; )在 1.0M的盐酸溶液 中浸渍 6小时， 再在 80〜100°C真空干燥 12小时， 然后在 400°C下进行高温焙烧 6 小时。
三氯化铝溶液固载： 在氩气保护下， 将 5g无水三氯化铝在 100ml四氯化碳中制 成溶液，加入到 10g活化后的氧化铝载体中， 在回流温度下保持 24小时， 除去溶剂， 以正己垸洗涤， 真空干燥后得到三氯化铝负载催化剂。
通过佛尔哈德滴定法对上述三氯化铝负载催化剂进行氯含量测定，得负载催化剂 中氯重量为 8.56%。
催化 1-癸烯齐聚：在 250ml高压聚合釜中加入正己烷 80ml，上述载体催化剂 8g， 1-癸烯 30ml， 助催化剂水 0.174ml， 在反应温度 8(TC、 反应压力 l.OMPa条件下进行 1-癸烯齐聚反应 5小时。停止反应， 过滤催化剂， 经常压蒸馏除去溶剂正己垸， 减压 蒸馏除去未反应单体 1-癸烯及部分二聚体， 得到最终齐聚物。 1-癸烯转化率 54.1ω%， 齐聚物 40°C运动粘度 16.51mm2/s， 100°C运动粘度 5.81mm2/s， 粘度指数 208.80。 实施例 2
负载三氯化铝催化剂制备同实施例 1， 区别在于载体处理条件为在室温下， 将球 形 γ-氧化铝载体在 1.5M的盐酸溶液中浸渍 6小时,再在 80〜100°C真空干燥 12小时， 然后在 400Ό下进行高温焙烧 6小时。
通过佛尔哈德滴定法对上述三氯化铝负载催化剂进行氯含量测定，得负载催化剂 中氯重量为 6.82%。 催化 1-癸烯齐聚：在 250ml高压聚合釜中加入正己垸 80ml，上述载体催化剂 8g， 1-癸烯 30ml， 助催化剂水 0.14ml， 在反应温度 80Ό、 反应压力 l.OMPa条件下进行 1-癸烯齐聚反应 5小时。停止反应， 过滤催化剂， 经常压蒸馏除去溶剂正己垸， 减压 蒸馏除去未反应单体 1-癸烯及部分二聚体， 得到最终齐聚物。 1-癸烯转化率 57.1ω%， 齐聚物 100Ό运动粘度 6.04mm2/s， 粘度指数 202.80。
实施例 3
负载三氯化铝催化剂制备同实施例 1， 区别在于载体焙烧温度为 800'C， 焙烧时 间 6小时。
通过佛尔哈德滴定法对上述三氯化铝负载催化剂进行氯含量测定，得负载催化剂 中氯重量为 6.42%。
催化 1-癸烯齐聚：在 250ml高压聚合釜中加入正己烷 80ml，上述载体催化剂 8g， 1-癸烯 30ml， 助催化剂水 0.13ml, 在反应温度 80°C、 反应压力 l.OMPa条件下进行 1-癸烯齐聚反应 5小时。停止反应， 过滤催化剂， 经常压蒸熘除去溶剂正己垸， 减压 蒸馏除去未反应单体 1-癸烯及部分二聚体， 得到最终齐聚物。 1-癸烯转化率 57.4ω%， 齐聚物 40°C运动粘度 16.14mm2/s， 100°C运动粘度 6.66mm2/s， 粘度指数 212.58。 实施例 4
负载三氯化铝催化剂制备同实施例 1， 区别在于三氯化铝溶液固载时， 将 10g无 水三氯化铝在 100ml四氯化碳中制成溶液，加入到 10g活化后的氧化铝载体中，在回 流温度下保持 24小时， 除去溶剂， 以正己垸洗涤， 真空千燥后得到三氯化铝负载催 化剂。
通过佛尔哈德滴定法对上述三氯化铝负载催化剂进行氯含量测定，得负载催化剂 中氯重量为 8.24%。
催化 1-癸烯齐聚：在 250ml高压聚合釜中加入正己垸 80ml，上述载体催化剂 8g， 1-癸烯 30ml， 助催化剂水 0.167ml， 在反应温度 80°C、 反应压力 l.OMPa条件下进行 1-癸烯齐聚反应 5小时。停止反应， 过滤催化剂， 经常压蒸馏除去溶剂正己垸， 减压 蒸馏除去未反应单体 1-癸烯及部分二聚体， 得到最终齐聚物。 1-癸烯转化率 58.6G> %， 齐聚物 40°C运动粘度 18.94mm2/s， 100°C运动粘度 5.97mm2/s， 粘度指数 197.07。 实施例 5
负载三氯化铝催化剂制备同实施例 1，区别在于载体焙烧温度为 600°C，焙烧时 间 6小时。 通过佛尔哈德滴定法对上述三氯化铝负载催化剂进行氯含量测定，得负载催化剂 中氯重量为 7.83 %。
催化 1-癸烯齐聚：在 250ml高压聚合釜中加入正己烷 80ml，上述载体催化剂 8g， 1-癸烯 30ml， 助催化剂水 0.159 ml， 在反应温度 80°C、 反应压力 l.OMPa条件下进行 1-癸烯齐聚反应 5小时。 停止反应， 过滤催化剂， 经常压蒸馏除去溶剂正己烷， 减压 蒸馏除去未反应单体 1-癸烯及部分二聚体， 得到最终齐聚物。 1-癸烯转化率 52.4ω%， 齐聚物 40°C运动粘度 16.09mm2/s， 100°C运动粘度 5.38mm2/s, 粘度指数 208.85。 实施例 6
负载三氯化铝催化剂制备同实施例 1，区别在于载体焙烧温度为 600°C，焙烧时 间 12小时。
通过佛尔哈德滴定法对上述三氯化铝负载催化剂进行氯含量测定，得负载催化剂 中氯重量为 7.77%。
催化 1-癸烯齐聚：在 250ml高压聚合釜中加入正己烷 80ml，上述载体催化剂 8g， 1-癸烯 30ml， 助催化剂水 0.159 ml, 在反应温度 80°C、 反应压力 l.OMPa条件下进行 1-癸烯齐聚反应 5小时。 停止反应， 过滤催化剂， 经常压蒸馏除去溶剂正己烷， 减压 蒸馏除去未反应单体 1-癸烯及部分二聚体， 得到最终齐聚物。 1-癸烯转化率 57.8«%， 齐聚物 40°C运动粘度 19.21mm2/s， 100°C运动粘度 6.69mm2/s, 粘度指数 200.61。 实施例 7
球形 γ-氧化铝负载三氯化铝催化剂制备同实施例 1， 区别在于三氯化铝负载时 间为 12小时。
通过佛尔哈德滴定法对上述三氯化铝负载催化剂进行氯含量测定， 得负载催化 剂中氯重量为 7.92%。
催化 1-癸烯齐聚:'在 250ml高压聚合釜中加入正己垸 80ml， 上述载体催化剂 8g， 1-癸烯 30ml， 助催化剂水 0.16 ml, 在反应温度 80°C、 反应压力 l.OMPa条件下 进行 1-癸烯齐聚反应 5小时。 停止反应， 过滤催化剂， 经常压蒸馏除去溶剂正己烷， 减压蒸馏除去未反应单体 1-癸烯及部分二聚体，得到最终齐聚物。 1-癸烯转化率 52.2(0 % , 齐聚物 40°C运动粘度 15.17mm2/s。
实施例 8
负载三氯化铝催化剂制备同实施例 1， 区别在于 γ-氧化铝载体为条形 （直径为 3mm、 长度为 4〜10mm、 其比表面积为 100〜200 m2/g、 总孔容 0.6ml/g)， 载体焙 烧温度为 600°C , 焙烧时间 9小时。
通过佛尔哈德滴定法对上述三氯化铝负载催化剂进行氯含量测定， 得负载催化 剂中氯重量为 7.87%。
催化 1-癸烯齐聚： 在 250ml高压聚合釜中加入正己烷 80ml， 上述载体催化剂 8g， 1-癸烯 30ml， 助催化剂水 0.16ml， 在反应温度 80°C、反应压力 l.OMPa条件下进 行 1-癸烯齐聚反应 4小时。停止反应， 过滤催化剂， 经常压蒸馏除去溶剂正己垸， 减 压蒸馏除去未反应单体 1-癸烯及部分二聚体， 得到最终齐聚物。 1-癸烯转化率 54.2ω % , 齐聚物 100°C运动粘度 4.95mm2/s, 粘度指数 222. 14。
实施例 9
负载三氯化铝催化剂制备同实施例 1， 区别在于 γ-氧化铝载体为条形（直径为 3mm、 长度为 41〜10mm、 其比表面积为 100〜200 m2/g、 总孔容 0.6ml/g)， 三氯化 铝负载时间为 12小时。
通过佛尔哈德滴定法对上述三氯化铝负载催化剂进行氯含量测定，得负载催化剂 中氯重量为 7.65%。
催化 1-癸烯齐聚：在 250ml高压聚合釜中加入正己垸 80ml，上述载体催化剂 8g， 1-癸烯 30ml， 助催化剂水 0.144 ml， 在反应温度 80°C、 反应压力 l.OMPa条件下进行 1-癸烯齐聚反应 5小时。停止反应， 过滤催化剂， 经常压蒸馏除去溶剂正己垸， 减压 蒸馏除去未反应单体 1-癸烯及部分二聚体， 得到最终齐聚物。 1-癸烯转化率 58.8G> %， 齐聚物 40Ό运动粘度 14.82mm2/s。
实施例 10
球形 γ-氧化铝负载三氯化铝催化剂制备同实施例 1， 区别在于三氯化铝负载时使 用的溶剂为体积比为 1:1的四氯化碳与三氯甲烷混合溶剂， 负载时间为 12小时。
通过佛尔哈德滴定法对上述三氯化铝负载催化剂进行氯含量测定，得负载催化剂 中氯重量为 8.11 %。
催化 1-癸烯齐聚：在 250ml高压聚合釜中加入正己烷 80ml，上述载体催化剂 8g， 1-癸烯 30ml， 助催化剂水 0.165ml， 在反应温度 80°C、 反应压力 l.OMPa条件下进行 1-癸烯齐聚反应 5小时。停止反应， 过滤催化剂， 经常压蒸馏除去溶剂正己垸， 减压 蒸馏除去未反应单体 1-癸烯及部分二聚体， 得到最终齐聚物。 1-癸烯转化率 52.2ω%， 齐聚物 40 °C运动粘度 16.87mm2/s。
比较例 1 球形 γ-氧化铝负载三氯化铝催化剂制备同实施例 1， 区别在于载体不进行盐酸 浸渍处理。
通过佛尔哈德滴定法对上述三氯化铝负载催化剂进行氯含量测定， 得负载催化 剂中氯重量为 6.33 %。
1-癸烯齐聚过程及条件同实施例 1。
所得产品 1-癸烯转化率 35.0ω%， 齐聚物 100°C运动粘度 2.66mm2/s。
比较例 2
球形 γ-氧化铝负载三氯化铝催化剂制备同实施例 1，区别在于载体以 0.5Μ盐酸 进行浸渍处理 2小时。
通过佛尔哈德滴定法对上述三氯化铝负载催化剂进行氯含量测定， 得负载催化 剂中氯重量为 6.88 %。
1-癸烯齐聚过程及条件同实施例 1。
所得产品 1-癸烯转化率 37.8ω%， 齐聚物 100Ό运动粘度 2.46mm2/s。
比较例 3
负载三氯化铝催化剂制备同实施例 1， 区别在于载体处理条件为在室温下， 将 球形 γ-氧化铝载体在 0.5Μ的盐酸溶液中浸渍 16小时， 再在 80〜10(TC真空干燥 12 小时， 然后在 400Ό下进行高温焙烧 6小时。
通过佛尔哈德滴定法对上述三氯化铝负载催化剂进行氯含量测定， 得负载催化 剂中氯重量为 7.45 %。
1-癸烯齐聚过程及条件同实施例 1。
所得产品 1-癸烯转化率为 52.11ω%， 齐聚物 100°C运动粘度 6.08mm2/s， 粘度指 数 172.00。
比较例 3
负载三氯化铝催化剂制备同实施例 1，， 区别在于负载催化剂焙烧温度 200Ό。 通过佛尔哈德滴定法对上述三氯化铝负载催化剂进行氯含量测定， 得负载催化 剂中氯重量为 10.75 %。
1-癸烯齐聚过程及条件同实施例 1， 区别在于助催化剂水用量 0.218ml。
所得产品 1-癸烯转化率 45.7G) %， 齐聚物 100°C运动粘度 4.13mm2/s。 比较例 4
负载三氯化铝催化剂制备同实施例 1，区别在于负载催化剂焙烧温度 400Ό ,焙 烧时间为 4小时。
通过佛尔哈德滴定法对上述三氯化铝负载催化剂进行氯含量测定， 得负载催化 剂中氯重量为 7.26%。
1-癸烯齐聚过程及条件同实施例 1， 区别在于助催化剂水用量 0.147ml。
所得产品 1-癸烯转化率 47.7ω%， 齐聚物 100°C运动粘度 4.24mm2/s。
工业实用性
本发明负载催化剂应用于催化 1-癸烯齐聚反应， 制得 1-癸烯齐聚物。 其原理是 根据阳离子齐聚反应原理，采用 Lewis酸类催化剂及促进剂形成络合催化体系。本发 明 1-癸烯齐聚反应以正己垸为溶剂， 1-癸烯与正己垸体积比 3:8〜4:1， 在温度 80°C〜 120°C、 反应压力为 0.8〜1.4MPa条件下反应 5〜6小时； 然后停止反应， 过滤催化 剂， 常压蒸馏除去溶剂正己垸， 减压蒸馏除去未反应单体 1一癸烯及部分二聚体， 得 到最终齐聚物。 1-癸烯转化率 50%重量， 齐聚物 40Ό运动粘度 6.0〜25mm2/s， 粘度 指数 160〜262。
本发明得到的 1-癸烯齐聚物符合润滑油基础油粘度要求， 油品的品质高。
本发明通过聚合体系的非均相化，能降低产品中的氯含量，使催化剂与产品能分 离、 回收重复利用， 减少环境污染。

Claims

权利要求
1、 一种合成 1-癸烯齐聚物的方法， 其特征在于： 以 γ-氧化铝载体负载三氯化铝 为催化剂， 正己烷为溶剂， 1-癸烯与正己垸按体积比 3 : 8〜4 : 1， 在温度 80〜120°C、 反应压力 0. 8〜1. 4MPa条件下反应 5〜6小时， 然后停止反应， 过滤催化剂， 常压蒸 馏除去溶剂正己垸， 减压蒸馏除去未反应单体 1一癸烯及部分二聚体， 得到最终 1 - 癸烯齐聚物； 催化剂与 1-癸烯重量比为 1 : 3;
γ-氧化铝载体负载三氯化铝催化剂经如下处理：
先将球形或条形 γ-氧化铝载体在 0.5-2.0摩尔的盐酸或硫酸或硝酸或它们的混合 物溶液中浸渍 4〜12小时， 然后在 80〜100°C真空干燥 2〜12小时， 最后再在 400〜 800 °C下进行高温焙烧 6〜16小时；
将 5〜10g无水三氯化铝在 100ml四氯化碳或三氯甲垸或二氯甲烷有机溶剂中制 成溶液， 加入到 10〜20g活化后的氧化铝载体中，在回流温度下保持 6〜24小时， 除 去溶剂， 用正己垸洗涤， 真空干燥后得到三氯化铝负载催化剂。
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