Abstract:
A method for synthesis of 1-decene oligomer is provided, wherein 1-decene is polymerized at 80-120° C., 0.8-1.4 MPa in the presence of aluminum trichloride catalyst supported on gamma-alumina and n-hexane solvent where the volume ratio of 1-decene to n-hexane is 3:8-4:1. The catalyst is treated as follows: impregnating gamma-alumina carrier in 0.5-2.0 mol of hydrochloric acid, sulfuric acid, nitric acid or mixtures thereof, then vacuum drying at 80-100° C. and calcining at 400-800° C.; dissolving 5-10 g of anhydrous aluminum trichloride in 100 ml of tetrachloromethane, trichloromethane or dichloromethane solvent; adding the obtained solution into 10-20 g of activated alumina carrier and obtaining the catalyst after vacuum drying. The conversion rate of 1-decene is 50 wt % or more. The oligomer has a kinematic viscosity at 40° C. of 6.0-25 mm2/s and a viscosity index of 160-262.

Description:
FIELD OF THE INVENTION 
       [0001]    The present invention relates to use of aluminum trichloride catalyst supported on gamma-alumina in catalyzing 1-decene oligomerization. 
       BACKGROUND OF THE INVENTION 
       [0002]    AlCl 3  catalyst used in cationic polymerization is a Lewis acid catalyst, which is one of the important catalysts widely used chemical industry, petroleum refining and pharmaceuticals industry. Due to good catalysis effect, such catalysts have features of high polymer yield, narrow molecular weight distribution and good selectivity etc. in catalyzing α-olefin oligomerization. Although it has very high activity, AlCl 3  catalyst has obvious disadvantages as follows: (1) AlCl 3  catalyst has strong causticity, and easily causes damage to equipments such as reactors and thus reduces service life of equipments leading to less usage; (2) a large number of sewage will be produced while polymerization is taken in the presence of AlCl 3  catalyst, and severe environmental pollution will be caused if such sewage cannot be disposed in time; and (3) AlCl 3  catalyst after reaction cannot be easily recovered, and needs to be after-treated, otherwise numerous corrosive waste will be produced. 
         [0003]    JP 08505888 discloses a method for producing lubricant base oil with cationic polymerization, wherein decene homopolymer is polymerized in the presence of Lewis acid such as AlCl 3 , BF 3  and so on. Since homogeneous system is used in this method and then the amount of halide such as AlCl 3 , BF 3  is high in product, product with low halide cannot be produced in this method. What is more, BF 3  is expensive and may cause a series of environmental problems due to corrosion of F. Such catalysts are difficult to be separated and recovered, produce a number of troublesome industrial waste liquid and thus the cost of production is increased. Meanwhile, α-olefin polymer thus obtained has low molecular weight, and then lubricant has low viscosity, thus cannot meet environmental requirements when used as lubricant. 
         [0004]    In order to satisfy the requirement of green chemistry, solid acid catalysts such as supported metal oxide are developed so as to replace traditional catalysts such as AlCl 3  and BF 3 , meanwhile supported AlCl 3  catalysts are also studied widely. It is desirable to change AlCl 3  catalyst into environmentally friendly catalyst while maintaining its excellent characteristics. Supported AlCl 3  catalyst is a novel, efficient and environmentally friendly solid acid catalyst. In recent years, it receives much concern and is widely used in the research on polymerization and alkylation due to higher catalyst activities and mild reaction conditions. 
         [0005]    U.S. Pat. No. 2,927,087 first put forward the technical solution that supported AlCl 3  catalyst can be produced by the reaction of AlCl 3  steam with infusible oxides such as alumina and silica having surface hydroxyl group. And it emphasizes the necessity to undergo carrier gas purging above 300° C. after reaction and thus remove unreacted AlCl 3 . 
         [0006]    U.S. Pat. No. 4,929,800 discloses a catalyst with high activity in alkanes isomerization and pyrolysis is produced at 50-80° C. under N 2  protection and dark condition refluxing for several hours to days in the presence of aluminum trichloride in CCl 4 , CH 3 Cl or CH 2 Cl 2  solvent and silica or alumina carrier. 
         [0007]    U.S. Pat. No. 6,002,060 indicates that alpha-olefin is oligomerized or copolymerized in the presence of supported aluminum trichloride as catalyst and organic aluminum compound as promoter. 
         [0008]    CN 1156338 and CN 1939590 disclose that AlCl 3  immobilized catalysts are prepared by gas-phase immobilization as follows: fresh aluminum trichloride under N 2  carrier gas is brought into reaction tube having alumina therein with mesopore and macropore double-pore structure and particles sizes of 20-200 mesh, wherein chlorine content is 6.0-9.0 wt %. The catalysts have shown good catalytic activity and selectivity in isobutene polymerization of low degree, and exhibit good stability. However, noticeable pressure drop exists in fixed bed reactor filled with fine particle catalysts. 
       SUMMARY OF THE INVENTION 
       [0009]    The aim of the present application is to disclose use of aluminum trichloride catalyst supported on gamma-alumina in catalyzing 1-decene oligomerization. The supported catalyst has high activity in catalyzing 1-decene oligomerization. The reaction product is easy to be separated. The catalyst can be recovered and reused, thus reducing pollution to environment. And the catalyst can avoid the corrosion to reactor caused by homogenous catalysts, and also avoid the presence of halide in 1-decene oligomerization product. 
         [0010]    The catalyst of the present application is prepared as follows: 
         [0011]    1) a step of acidifying and impregnating gamma-alumina carrier 
         [0012]    In particular, gamma-alumina carrier is first impregnated in 0.5-2.0 mol of hydrochloric acid, sulfuric acid, nitric acid or mixtures thereof at room temperature for 4-12 hours, then is vacuum dried at 80-100° C. for 2-12 hours and finally is calcined at 300-800° C. for 6-16 hours. 
         [0013]    2) a step of solution immobilizing aluminum trichloride 
         [0014]    5-10 g of anhydrous aluminum trichloride is dissolved in 100 ml of tetrachloromethane, trichloromethane or dichloromethane organic solvent to form a solution. The obtained solution is added into 10-20 g of activated alumina carrier, then kept at reflex temperature for 6-24 hours. The solvent is removed. Then washing with n-hexane is taken. The aluminum trichloride catalyst supported on gamma-alumina is finally obtained after vacuum drying. 
         [0015]    In the preparation of the catalyst of the present application, gamma-alumina carrier is in a form of sphere or strip. For gamma-alumina carrier in a form of sphere, it has a diameter of 1.3-2.3 mm, preferably 1.5-2.0 mm, specific surface area of 100-180 m 2 /g, preferably 120-160 m 2 /g, and total pore volume &gt;1.0 ml/g. For gamma-alumina carrier in a form of strip, it has a diameter of 3 mm, length of 4-10 mm, preferably 5-8 mm, specific surface area of 100-200 m 2 /g, preferably 140-180 m 2 /g, and total pore volume ≧0.6 ml/g. 
         [0016]    When acidifying gamma-alumina carrier, most preferably, the acid is hydrochloric acid, the concentration of hydrochloric acid is 1M, the impregnating time is 6 hours, calcination temperature is 400° C., and the calcination lasts for 12 hours. 
         [0017]    In the preparation of the catalyst of the present application, when supporting anhydrous aluminum trichloride, the most suitable solvent is tetrachloromethane or the solvent containing 1:1 tetrachloromethane:trichloromethane (in volume). And the reflux preferably lasts for 12 hours. 
         [0018]    According to the method of the present application using the catalyst as mentioned above, the chlorine content in the final supported aluminum trichloride is 6.0-12 wt %. That is, —AlCl 2  in supported catalyst amounts for 8.28-16.56 wt %. 
         [0019]    When immobilizing aluminum trichloride on alumina, inert atmosphere is taken throughout the process. And nitrogen or argon is used as inert gas. 
         [0020]    1-decene oligomer is obtained when the supported catalyst of the present application is applied to catalyze 1-decene oligomerization. It is based on cationic oligomerization principle, and Lewis acid catalyst and promoter constitute complex catalyst system. In 1-decene oligomerization, n-hexane is used as solvent, volume ratio of 1-decene to n-hexane is 3:8-4:1, reaction is undergone under pressure of 0.8-1.4 MPa at temperature of 80-120° C. for 5-6 hours, then the reaction is stopped, the catalyst is filtered, n-hexane solvent is removed by atmospheric distillation, unreacted monomer 1-decene and part of dimers are removed by reduced pressure distillation, finally 1-decene oligomer is obtained. 
     
    
     DETAILED DESCRIPTION OF THE INVENTION 
       [0021]    The present application will be further described based on the following examples. 
       Example 1 
       [0022]    Acidifying and Impregnating Gamma-Alumina Carrier in a Form of Sphere: 
         [0023]    Gamma-alumina carrier in a form of sphere is impregnated in 1.0M hydrochloric acid solution for 6 hours at room temperature, then vacuum dried at 80-100° C. for 12 hours and finally calcined at 400° C. for 6 hours, in which gamma-alumina carrier in a form of sphere has a diameter of 1.3-2.3 mm, specific surface area of 100-180 m 2 /g and total pore volume of 1.0 ml/g or more. 
         [0024]    Solution Immobilizing Aluminum Trichloride: 
         [0025]    5 g of anhydrous aluminum trichloride is dissolved in 100 ml of tetrachloromethane to form a solution. Then the obtained solution is added into 10 g of activated alumina carrier, kept at reflex temperature for 24 hours. The solvent is removed. Washing is taken with n-hexane. Then the catalyst is obtained after vacuum drying. 
         [0026]    The chlorine content in the aluminum trichloride supported catalyst is assayed to be  8 . 56  wt % by Volhard titration. 
         [0027]    Catalyzing 1-Decene Oligomerization: 
         [0028]    To 250 ml high pressure polymerizer is added 80 m1 of n-hexane, 8 g of catalyst obtained as above, 30 ml of 1-decene and 0.174 ml of water as promoter. 1-decene oligomerization is carried out at 80° C. under pressure of 1.0 MPa for 5 hours. Then the reaction is stopped, the catalyst is filtered, n-hexane solvent is removed by atmospheric distillation, unreacted monomer 1-decene and part of dimers are removed by reduced pressure distillation. 1-decene oligomer is finally obtained. The conversion rate of 1-decene is 54.1 wt %. The oligomer has a kinematic viscosity at 40° C. of 16.51 mm 2 /s, a kinematic viscosity at 100° C. of 5.81 mm 2 /s and a viscosity index of 208.80. 
       Example 2 
       [0029]    Aluminum trichloride supported catalyst is prepared the same as Example 1, except that gamma-alumina carrier in a form of sphere is impregnated in 1.5M hydrochloric acid solution for 6 hours at room temperature, then vacuum dried at 80-100° C. for 12 hours and finally calcined at 400° C. for 6 hours. 
         [0030]    The chlorine content in the aluminum trichloride supported catalyst is assayed to be 6.82 wt % by Volhard titration. 
         [0031]    Catalyzing 1-decene oligomerization: 
         [0032]    To 250 ml high pressure polymerizer is added 80 ml of n-hexane, 8 g of catalyst obtained as above, 30 ml of 1-decene and 0.14 ml of water as promoter. 1-decene oligomerization is carried out at 80° C. under pressure of 1.0 MPa for 5 hours. Then the reaction is stopped, the catalyst is filtered, n-hexane solvent is removed by atmospheric distillation, unreacted monomer 1-decene and part of dimers are removed by reduced pressure distillation. 1-decene oligomer is finally obtained. The conversion rate of 1-decene is 57.1 wt %. The oligomer has a kinematic viscosity at 100° C. of 6.04 mm 2 /s and a viscosity index of 202.80. 
       Example 3 
       [0033]    Aluminum trichloride supported catalyst is prepared the same as Example 1, except that gamma-alumina carrier in a form of sphere is calcined at 800° C. for 6 hours. 
         [0034]    The chlorine content in the aluminum trichloride supported catalyst is assayed to be 6.42 wt % by Volhard titration. 
         [0035]    Catalyzing 1-Decene Oligomerization: 
         [0036]    To 250 ml high pressure polymerizer is added 80 ml of n-hexane, 8 g of catalyst obtained as above, 30 ml of 1-decene and 0.13 ml of water as promoter. 1-decene oligomerization is carried out at 80° C. under pressure of 1.0 MPa for 5 hours. Then the reaction is stopped, the catalyst is filtered, n-hexane solvent is removed by atmospheric distillation, unreacted monomer 1-decene and part of dimers are removed by reduced pressure distillation. 1-decene oligomer is finally obtained. The conversion rate of 1-decene is 57.4 wt %. The oligomer has a kinematic viscosity at 40° C. of 16.14 mm 2 /s, a kinematic viscosity at 100° C. of 6.66 mm 2 /s and a viscosity index of 212.58. 
       Example 4 
       [0037]    Aluminum trichloride supported catalyst is prepared the same as Example 1, except that 10 g of anhydrous aluminum trichloride is dissolved in 100 ml of tetrachloromethane to form a solution. Then the obtained solution is added into 10 g of activated alumina carrier, kept at reflex temperature for 24 hours. The solvent is removed. Washing is taken with n-hexane. Then the catalyst is obtained after vacuum drying. 
         [0038]    The chlorine content in the aluminum trichloride supported catalyst is assayed to be 8.24 wt % by Volhard titration. 
         [0039]    Catalyzing 1-Decene Oligomerization: 
         [0040]    To 250 ml high pressure polymerizer is added 80 ml of n-hexane, 8 g of catalyst obtained as above, 30 ml of 1-decene and 0.167 ml of water as promoter. 1-decene oligomerization is carried out at 80° C. under pressure of 1.0 MPa for 5 hours. Then the reaction is stopped, the catalyst is filtered, n-hexane solvent is removed by atmospheric distillation, unreacted monomer 1-decene and part of dimers are removed by reduced pressure distillation. 1-decene oligomer is finally obtained. The conversion rate of 1-decene is 58.6 wt %. The oligomer has a kinematic viscosity at 40° C. of 18.94 mm 2 /s, a kinematic viscosity at 100° C. of 5.97 mm 2 /s and a viscosity index of 197.07. 
       Example 5 
       [0041]    Aluminum trichloride supported catalyst is prepared the same as Example 1, except that gamma-alumina carrier in a form of sphere is calcined at 600° C. for 6 hours. 
         [0042]    The chlorine content in the aluminum trichloride supported catalyst is assayed to be 7.83 wt % by Volhard titration. 
         [0043]    Catalyzing 1-Decene Oligomerization: 
         [0044]    To 250 ml high pressure polymerizer is added 80 ml of n-hexane, 8 g of catalyst obtained as above, 30 ml of 1-decene and 0.159 ml of water as promoter. 1-decene oligomerization is carried out at 80° C. under pressure of 1.0 MPa for 5 hours. Then the reaction is stopped, the catalyst is filtered, n-hexane solvent is removed by atmospheric distillation, unreacted monomer 1-decene and part of dimers are removed by reduced pressure distillation. 1-decene oligomer is finally obtained. The conversion rate of 1-decene is 52.4 wt %. The oligomer has a kinematic viscosity at 40° C. of 16.09 mm 2 /s, a kinematic viscosity at 100° C. of 5.38 mm 2 /s and a viscosity index of 208.85. 
       Example 6 
       [0045]    Aluminum trichloride supported catalyst is prepared the same as Example 1, except that gamma-alumina carrier in a form of sphere is calcined at 600° C. for 12 hours. 
         [0046]    The chlorine content in the aluminum trichloride supported catalyst is assayed to be 7.77 wt % by Volhard titration. 
         [0047]    Catalyzing 1-Decene Oligomerization: 
         [0048]    To 250 ml high pressure polymerizer is added 80 ml of n-hexane, 8 g of catalyst obtained as above, 30 ml of 1-decene and 0.159 ml of water as promoter. 1-decene oligomerization is carried out at 80° C. under pressure of 1.0 MPa for 5 hours. Then the reaction is stopped, the catalyst is filtered, n-hexane solvent is removed by atmospheric distillation, unreacted monomer 1-decene and part of dimers are removed by reduced pressure distillation. 1-decene oligomer is finally obtained. The conversion rate of 1-decene is 57.8 wt %. The oligomer has a kinematic viscosity at 40° C. of 19.21 mm 2 /s, a kinematic viscosity at 100° C. of 6.69 mm 2 /s and a viscosity index of 200.61. 
       Example 7 
       [0049]    Aluminum trichloride supported catalyst is prepared the same as Example 1, except that the supported time for aluminum trichloride lasts for 12 hours. 
         [0050]    The chlorine content in the aluminum trichloride supported catalyst is assayed to be 7.92 wt % by Volhard titration. 
         [0051]    Catalyzing 1-Decene Oligomerization: 
         [0052]    To 250 ml high pressure polymerizer is added 80 ml of n-hexane, 8 g of catalyst obtained as above, 30 ml of 1-decene and 0.16 ml of water as promoter. 1-decene oligomerization is carried out at 80° C. under pressure of 1.0 MPa for 5 hours. Then the reaction is stopped, the catalyst is filtered, n-hexane solvent is removed by atmospheric distillation, unreacted monomer 1-decene and part of dimers are removed by reduced pressure distillation. 1-decene oligomer is finally obtained. The conversion rate of 1-decene is 52.2 wt %. The oligomer has a kinematic viscosity at 40° C. of 15.17 mm 2 /s. 
       Example 8 
       [0053]    Aluminum trichloride supported catalyst is prepared the same as Example 1, except that gamma-alumina carrier is in a form of strip, which has a diameter of 3 mm, length of 4-10 mm, specific surface area of 100-200 m 2 /g and total pore volume ≧0.6 ml/g. The carrier is calcined at 600° C. for 9 hours. 
         [0054]    The chlorine content in the aluminum trichloride supported catalyst is assayed to be 7.87 wt % by Volhard titration. 
         [0055]    Catalyzing 1-Decene Oligomerization: 
         [0056]    To 250 ml high pressure polymerizer is added 80 ml of n-hexane, 8 g of catalyst obtained as above, 30 ml of 1-decene and 0.16 ml of water as promoter. 1-decene oligomerization is carried out at 80° C. under pressure of 1.0 MPa for 4 hours. Then the reaction is stopped, the catalyst is filtered, n-hexane solvent is removed by atmospheric distillation, unreacted monomer 1-decene and part of dimers are removed by reduced pressure distillation. 1-decene oligomer is finally obtained. The conversion rate of 1-decene is 54.2 wt %. The oligomer has a kinematic viscosity at 100° C. of 4.95 mm 2 /s and a viscosity index of 222.14. 
       Example 9 
       [0057]    Aluminum trichloride supported catalyst is prepared the same as Example 1, except that gamma-alumina carrier is in a form of strip, which has a diameter of 3 mm, length of 4-10 mm, specific surface area of 100-200 m 2 /g and total pore volume ≧0.6 ml/g, and the supported time for aluminum trichloride lasts for 12 hours. 
         [0058]    The chlorine content in the aluminum trichloride supported catalyst is assayed to be 7.65 wt % by Volhard titration. 
         [0059]    Catalyzing 1-Decene Oligomerization: 
         [0060]    To 250 ml high pressure polymerizer is added 80 ml of n-hexane, 8 g of catalyst obtained as above, 30 ml of 1-decene and 0.144 ml of water as promoter. 1-decene oligomerization is carried out at 80° C. under pressure of 1.0 MPa for 5 hours. Then the reaction is stopped, the catalyst is filtered, n-hexane solvent is removed by atmospheric distillation, unreacted monomer 1-decene and part of dimers are removed by reduced pressure distillation. 1-decene oligomer is finally obtained. The conversion rate of 1-decene is 58.8 wt %. The oligomer has a kinematic viscosity at 40° C. of 14.82 mm 2 /s. 
       Example 10 
       [0061]    Aluminum trichloride supported catalyst is prepared the same as Example 1, except that the solvent used is a mixed solvent containing 1:1 tetrachloromethane : trichloromethane (in volume). And the supported time lasts for 12 hours. 
         [0062]    The chlorine content in the aluminum trichloride supported catalyst is assayed to be 8.11 wt % by Volhard titration. 
         [0063]    Catalyzing 1-Decene Oligomerization: 
         [0064]    To 250 ml high pressure polymerizer is added 80 ml of n-hexane, 8 g of catalyst obtained as above, 30 ml of 1-decene and 0.165 ml of water as promoter. 1-decene oligomerization is carried out at 80° C. under pressure of 1.0 MPa for 5 hours. Then the reaction is stopped, the catalyst is filtered, n-hexane solvent is removed by atmospheric distillation, unreacted monomer 1-decene and part of dimers are removed by reduced pressure distillation. 1-decene oligomer is finally obtained. The conversion rate of 1-decene is 52.2 wt %. The oligomer has a kinematic viscosity at 40° C. of 16.87 mm 2 /s. 
       Comparative Example 1 
       [0065]    Aluminum trichloride supported catalyst is prepared the same as Example 1, except that the carrier is not treated with hydrochloric acid impregnation. 
         [0066]    The chlorine content in the aluminum trichloride supported catalyst is assayed to be 6.33 wt % by Volhard titration. 
         [0067]    The process and conditions for 1-decene oligomerization are the same as Example 1. 
         [0068]    The conversion rate of 1-decene is 35.0 wt %. The oligomer has a kinematic viscosity at 100° C. of 2.66 mm 2 /s. 
       Comparative Example 2 
       [0069]    Aluminum trichloride supported catalyst is prepared the same as Example 1, except that the carrier is impregnated with 0.5M hydrochloric acid for 2 hours. 
         [0070]    The chlorine content in the aluminum trichloride supported catalyst is assayed to be 6.88 wt % by Volhard titration. 
         [0071]    The process and conditions for 1-decene oligomerization are the same as Example 1. 
         [0072]    The conversion rate of 1-decene is 37.8 wt %. The oligomer has a kinematic viscosity at 100° C. of 2.46 mm 2 /s. 
       Comparative Example 3 
       [0073]    Aluminum trichloride supported catalyst is prepared the same as Example 1, except that the gamma-alumina carrier in a form of sphere is impregnated in 0.5M hydrochloric acid solution for 16 hours at room temperature, then vacuum dried at 80-100° C. for 12 hours and finally calcined at 400° C. for 6 hours. 
         [0074]    The chlorine content in the aluminum trichloride supported catalyst is assayed to be 7.45 wt % by Volhard titration. 
         [0075]    The process and conditions for 1-decene oligomerization are the same as Example 1. 
         [0076]    The conversion rate of 1-decene is 52.11 wt %. The oligomer has a kinematic viscosity at 100° C. of 6.08 mm 2 /s and a viscosity index of 172.00. 
       Comparative Example 4 
       [0077]    Aluminum trichloride supported catalyst is prepared the same as Example 1, except that the carrier is calcined at 200° C. 
         [0078]    The chlorine content in the aluminum trichloride supported catalyst is assayed to be 10.75 wt % by Volhard titration. 
         [0079]    The process and conditions for 1-decene oligomerization are the same as Example 1, except that the amount of water as promoter is 0.218 ml. 
         [0080]    The conversion rate of 1-decene is 45.7 wt %. The oligomer has a kinematic viscosity at 100° C. of 4.13 mm 2 /s. 
       Comparative Example 5 
       [0081]    Aluminum trichloride supported catalyst is prepared the same as Example 1, except that the carrier is calcined at 400° C. for 4 hours. 
         [0082]    The chlorine content in the aluminum trichloride supported catalyst is assayed to be 7.26 wt % by Volhard titration. 
         [0083]    The process and conditions for 1-decene oligomerization are the same as Example 1, except that the amount of water as promoter is 0.147 ml. 
         [0084]    The conversion rate of 1-decene is 47.7 wt %. The oligomer has a kinematic viscosity at 100° C. of 4.24 mm 2 /s. 
       PRACTICAL APPLICABILITY 
       [0085]    1-decene oligomer is obtained when the supported catalyst of the present application is applied to catalyze 1-decene oligomerization. It is based on cationic oligomerization principle, and Lewis acid catalyst and promoter constitute complex catalyst system. In 1-decene oligomerization, n-hexane is used as solvent, volume ratio of 1-decene to n-hexane is 3:8-4:1, reaction is undergone under pressure of 0.8-1.4 MPa at temperature of 80-120° C. for 5-6 hours, then the reaction is stopped, the catalyst is filtered, n-hexane solvent is removed by atmospheric distillation, unreacted monomer 1-decene and part of dimers are removed by reduced pressure distillation, finally 1-decene oligomer is obtained. The conversion rate of 1-decene is 50 wt % or more. The oligomer has a kinematic viscosity at 40° C. of 6.0-25 mm2/s and a viscosity index of 160-262. 
         [0086]    The 1-decene oligomer produced by the method of the present application meets the requirement for viscosity of lubricant base oil and the oil product has good quality. 
         [0087]    The heterogeneous reaction of polymerization system in the present application can reduce the chlorine content in the product, allow the catalyst to be separated and recovered from product and then reduce pollution to environment.