Composite catalyst, preparation process thereof, and process for catalyzing the trimerization of butadiene using the composite catalyst

Abstract

The present invention relates to a composite catalyst, preparation process thereof, and process for catalyzing the trimerization of butadiene using the composite catalyst. The composite catalyst comprises: (A) a titanium compound catalyst active component, (B) an organometallic compound co-catalyst component, (C) a sulfoxide compound catalyst-modifying component, (D) a monoester compound catalyst-modifying component, and (E) a solvent component. The composite catalyst has advantages of excellent selectivity, high catalytic activity, easy preparation and so on.

Claims

1. A composite catalyst trimerization of butadiene to 1,5,9-cyclododecatriene consisting of (A) a titanium compound catalyst active component, wherein the titanium compound is one or more selected from TiCl.sub.4, TiCl.sub.2R.sub.4-z or TiCl.sub.z(OR).sub.4-z, wherein Z=1, 2 or 3, OR is alkoxy, R is alkyl having 1-20 carbons, (B) an organometallic compound co-catalyst component selected from one or more of methyl lithium, n-butyl lithium, n-hexyl lithium, sec-butyl lithium, (C) a sulfoxide compound catalyst-modifying component selected from one or more of dimethyl sulfoxide, thionyl chloride, diphenyl sulfoxide, and trimethylsulfoxonium iodide, (D) a monoester compound catalyst-modifying component selected from one or more of the group consisting of methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, butyl p-hydroxybenzoate, methyl aminobenzoate, ethyl aminobenzoate, butyl aminobenzoate, methyl p-benzenesulfonate, ethyl p-benzenesulfonate, butyl p-benzenesulfonate, methyl salicylate, ethyl salicylate and butyl salicylate, and (E) a solvent component selected from one or more of propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, cyclohexane, n-heptane, n-octane, benzene, toluene, xylene, 1,5,9-cyclododecatriene.

2. The composite catalyst according to claim 1, wherein: the molar ratio of the organometallic compound co-catalyst component (B) to the titanium compound catalyst active component (A) is 1-1000:1; the molar ratio of the sulfoxide compound catalyst-modifying component (C) to the titanium compound catalyst active component (A) is 1-30:1; the molar ratio of the monoester compound catalyst-modifying component (D) to the titanium compound catalyst active component (A) is 0.1-50:1; the molar ratio of the solvent component (E) to the titanium compound catalyst active component (A) is 5000-30000:1.

3. The composite catalyst according to claim 2, wherein: the molar ratio of the organometallic compound co-catalyst component (B) to the titanium compound catalyst active component (A) is 20-500:1; and the molar ratio of the monoester compound catalyst-modifying component (D) to the titanium compound catalyst active component (A) is 1-30:1.

4. The composite catalyst according to claim 1, wherein the titanium compound catalyst active component (A) comprises one or more of titanium tetrachloride, titanium tetraethoxide, and triethoxytitanium chloride.

5. A process for preparing the composite catalyst according to claim 1, wherein said process comprises: adjusting a temperature of an oxygen-free and water-free reaction system for preparing the composite catalyst to a preparation temperature of the catalyst, and adding to the reaction system the titanium compound catalyst active component (A), the organometallic compound co-catalyst component (B), the sulfoxide compound catalyst-modifying component (C), the monoester compound catalyst-modifying component (D), and the solvent component (E) in a specified proportion under stirring, wherein a time needed for preparing the composite catalyst is 15-600 minutes, timing from an end of addition of all the components, a temperature of preparing the composite catalyst is 20-120 C., and nitrogen or helium or argon is continuously introduced during the preparation.

6. The process for preparing the composite catalyst according to claim 5, wherein: the time needed for preparing the composite catalyst is 20-300 minutes, timing from the end of addition of all the components; and the temperature of preparing the composite catalyst is 25-80 C.

7. A catalyzation process comprising adding the composite catalyst according to claim 1 to a butadiene to 1,5,9-cyclododecatriene trimerization reaction system, introducing butadiene to the trimerization reaction system and catalyzing the trimerization of butadiene to 1,5,9-cyclododecatriene.

8. The process of claim 7, comprising: adding the composite catalyst and a solvent for trimerization to the trimerization reaction system, wherein the molar ratio of the solvent for trimerization to the titanium compound catalyst active component (A) is 10000-50000:1; introducing the butadiene continuously to start the reaction, wherein the temperature for the trimerization is 20-200C; the pressure for the trimerization is 0.1-1 MPa; and time for the trimerization is 10-600 minutes; and adding the termination agent to terminate the reaction, wherein a molar ratio of the termination agent to the titanium compound catalyst active component (A) of the composite catalyst is 0.1-5:1, the solvent for trimerization comprises one or more selected from the group consisting of propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, cyclohexane, n heptane, n-octane, benzene, toluene, xylene, and 1,5,9-cyclododecatriene, the termination agent comprises water, monohydroxy alcohol, or the mixture of water and monohydroxy alcohol in any proportion, wherein the monohydroxy alcohol is one or more selected from the group consisting of methanol, ethanol and n-butanol.

9. The process of claim 8, wherein: the molar ratio of the solvent for trimerization to the titanium compound catalyst active component (A) is 18000-30000:1; the temperature for the trimerization is 25-120 C.; the pressure for the trimerization is 0.2-0.7 MPa; and the time for the trimerization is 15-300 minutes; and the solvent for trimerization comprises one or more selected from the group consisting of propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, cyclohexane, n-heptane, n-octane, benzene, toluene, xylene, 1,5,9-cyclododecatriene.

Description

THE MODE OF CARRYING OUT THE INVENTION

(1) The present invention will be described in greater detail in conjunction with the following specific examples, but the present invention should not be interpreted to be limited to these examples.

(2) The following instruments and measuring conditions are used in the present invention. The amount of CDT contained in a reaction liquid is measured by gas chromatography internal standard method using GC-2060 gas chromatograph (manufactured by Shanghai Ruimin Instrument Co., Ltd.). The testing conditions of the gas chromatography are as follows: the type of chromatographic column: SE-54, 30 ml0.25 ml0.25 ml; the detector used: hydrogen flame detector. The temperature settings of the gas chromatograph: the detector temperature is 250 C., the sample chamber temperature is 200 C., the temperature programmed steps of the column temperature is set to maintain at 50 C. for 3 min, rise to 250 C. at the rate of 25 C./min, and then maintain at 250 C. for 5 min. The gas feeding conditions are as follows: air 250 cm.sup.3/min, hydrogen gas 35 cm.sup.3/min, carrier gas (nitrogen) 0.7 cm.sup.3/min.

(3) The reaction products of the present invention are detected by the gas chromatography internal standard method. The detection method comprises the preparation of a standard curve and the detection of the reaction products.

(4) The preparation of the standard curve: n-dodecane is used as the internal standard of detecting the amount of CDT. Firstly, the standard solutions having CDT/dodecane mass ratio of 0.1, 0.3, 0.5, 0.7, 0.9, 1.1, 1.3, 1.5 are prepared, respectively, and the standard solutions are introduced respectively into the chromatographic column according to the above-said chromatographic conditions to obtain the chromatograms. Secondly, the peak area ratio of CDT and dodecane is calculated according to the chromatograms obtained in the first step, and a standard curve is plotted with area ratio as abscissa and mass ratio as ordinate.

(5) The detection of the reaction products: after the reaction is completed, a small amount of the reaction liquid is weighed, in which a specified amount of dodecane is added and mixed well, and then the resulting mixture is introduced into the chromatographic column, in order to obtain the chromatograms. After calculating the area ratio according to chromatograms, the mass ratio is determined from the above-described standard curve, and the mass of CDT contained in the small amount of weighed reaction liquid is obtained. Further, total mass of CDT contained in all the reaction liquid is obtained, and from this the activity of the catalyst and CDT selectivity of the reaction product are calculated.

Example 1

(6) The preparation of composite catalyst 1: A 500 ml water-free and oxygen-free flask with four necks is immersed in a thermostatic oil bath at the temperature of 50 C. 5.2710.sup.2 mmol of TiCl.sub.2(OEt).sub.2, 5.27 mmol of triethyl aluminium, 110 ml of toluene, 1.32 mmol of dimethyl sulfoxide, and 1.32 mmol of methyl benzoate are added into the flask in order, nitrogen gas is introduced into the flask continuously, and the reaction is conducted at 50 C. for 20 min. The composite catalyst 1 is obtained.

(7) The trimerization process: After 78 ml of n-heptane is added to the flask, butadiene is introduced such that the pressure in the flask is maintained at 0.1 MPa, the temperature is raised to 70 C., and the reaction is conducted for 60 min. After that, 5.2710.sup.2 mmol of water is added to terminate the reaction. The reaction liquid is weighed and then filtered, and the resulting filtrate is determined by gas chromatography.

(8) As a result, the composite catalyst 1 has the activity of 20423.7 g CDT/g .sub.Ti/h and CDT selectivity of 95.27%.

Example 2

(9) The preparation of composite catalyst 2: A 500 ml water-free and oxygen-free flask with four necks is immersed in a thermostatic oil bath at the temperature of 70 C. 55 ml of toluene, 5.2710.sup.2 mmol of TiCl(OEt).sub.3, 2.64 mmol of triethyl aluminium, 0.264 mmol of trimethylsulfoxonium iodide, and 5.2710.sup.2 mmol of methyl formate are added into the flask in order, nitrogen gas is introduced into the flask continuously, and the reaction is conducted at 70 C. for 20 min. The composite catalyst 2 is obtained.

(10) The trimerization process: After 78 ml of n-heptane is added to the flask, butadiene is introduced such that the pressure in the flask is maintained at 0.1 MPa, and the reaction is conducted at the temperature of 70 C. for 120 min. After that, 5.2710.sup.2 mmol of ethanol is added to terminate the reaction. The reaction liquid is weighed and then filtered, and the resulting filtrate is determined by gas chromatography.

(11) As a result, the composite catalyst 2 has the activity of 20323.5 g CDT/g .sub.Ti/h and CDT selectivity of 95.48%.

Example 3

(12) The preparation of composite catalyst 3: The preparation of the composite catalyst 2 in example 2 is repeated using Ti(OEt).sub.3 in place of TiCl(OEt).sub.3.

(13) The trimerization process: According to the trimerization process of example 2.

(14) As a result, the composite catalyst 3 has the activity of 20497.9 g CDT/g .sub.Ti/h and CDT selectivity of 96.25%.

Example 4

(15) The preparation of composite catalyst 4: A 500 ml water-free and oxygen-free flask with four necks is immersed in a thermostatic oil bath at the temperature of 20 C. 165 ml of toluene, 5.2710.sup.2 mmol of TiCl.sub.4, 1.32 mmol of dimethyl sulfoxide, 52.7 mmol of n-butyl lithium, and 2.63 mmol of butyl salicylate are added into the flask in order, nitrogen gas is introduced into the flask continuously, and the reaction is conducted at 20 C. for 300 min. The composite catalyst 4 is obtained.

(16) The trimerization process: After 165 ml of toluene is added to the flask, butadiene is introduced such that the pressure in the flask is maintained at 1 MPa, the temperature is raised to 80 C., and the reaction is conducted for 15 min After that, 5.2710.sup.2 mmol of water is added to terminate the reaction. The reaction liquid is weighed and then filtered, and the resulting filtrate is determined by gas chromatography.

(17) As a result, the composite catalyst 4 has the activity of 24347.4 g CDT/g .sub.Ti/h and CDT selectivity of 96.34%.

Example 5

(18) The preparation of composite catalyst 5: A 500 ml water-free and oxygen-free flask with four necks is immersed in a thermostatic oil bath at the temperature of 120 C. 1.05 mmol of sesquiethyl aluminum chloride, 380 ml of n-heptane, 5.2710.sup.2 mmol of TiCl.sub.4, 1.32 mmol of the mixture (molar ratio 1:1) of thionyl chloride and dimethyl sulfoxide, and 1.32 mmol of ethyl p-hydroxybenzoate are added into the flask in order, nitrogen gas is introduced into the flask continuously, and the reaction is conducted at 120 C. for 600 min. The composite catalyst 5 is obtained.

(19) The trimerization process: Butadiene is introduced to the flask such that the pressure in the flask is maintained at 0.5 MPa, the temperature is raised to 180 C., and the reaction is conducted for 600 min. After that, 5.2710.sup.2 mmol of water is added to terminate the reaction. The reaction liquid is weighed and then filtered, and the resulting filtrate is determined by gas chromatography.

(20) As a result, the composite catalyst 5 has the activity of 20324.4 g CDT/g .sub.Ti/h and CDT selectivity of 98.01%.

Example 6

(21) The preparation of composite catalyst 6: A 500 ml water-free and oxygen-free flask with four necks is immersed in a thermostatic oil bath at the temperature of 70 C. 1.05 mmol of sesquiethyl aluminum chloride, 5.2710.sup.2 mmol of TiCl.sub.4, 28 ml of toluene, 5.2710.sup.2 mmol of dimethyl sulfoxide, and 2.6410.sup.2 mmol of ethyl benzoate are added into the flask in order, nitrogen gas is introduced into the flask continuously, and the reaction is conducted at 70 C. for 300 min. The composite catalyst 6 is obtained.

(22) The trimerization process: After 275 ml of toluene is added to the flask, butadiene is introduced such that the pressure in the flask is maintained at 0.1 MPa, the temperature is raised to 100 C., and the reaction is conducted for 300 min. After that, 0.263 mmol of n-butanol is added to terminate the reaction. The reaction liquid is weighed and then filtered, and the resulting filtrate is determined by gas chromatography.

(23) As a result, the composite catalyst 6 has the activity of 20342.1 g CDT/g .sub.Ti/h and CDT selectivity of 97.83%.

Example 7

(24) The preparation of composite catalyst 7: The preparation of the composite catalyst 6 in example 6 is repeated using ethyl acetate in place of ethyl benzoate.

(25) The trimerization process: According to the trimerization process of example 6.

(26) As a result, the composite catalyst 7 has the activity of 20124.4 g CDT/g .sub.Ti/h and CDT selectivity of 96.17%.

Example 8

(27) The preparation of composite catalyst 8: A 500 ml water-free and oxygen-free flask with four necks is immersed in a thermostatic oil bath at the temperature of 80 C. 26.35 mmol of triethyl boron, 5.2710.sup.2 mmol of TiCl.sub.4, 65 ml of xylene, 5.2710.sup.2 mmol of dimethyl sulfoxide, and 2.6410.sup.2 mmol of the mixture (molar ratio 1:1) of methyl benzoate and ethyl p-hydroxybenzoate are added into the flask in order, nitrogen gas is introduced into the flask continuously, and the reaction is conducted at 80 C. for 20 min. The composite catalyst 8 is obtained.

(28) The trimerization process: After 100 ml of CDT is added to the flask, butadiene is introduced to the flask such that the pressure in the flask is maintained at 0.3 MPa, and the reaction is conducted at the temperature of 80 C. for 60 min. After that, 5.2710.sup.2 mmol of water is added to terminate the reaction. The reaction liquid is weighed and then filtered, and the resulting filtrate is determined by gas chromatography.

(29) As a result, the composite catalyst 8 has the activity of 26635.8 g CDT/g .sub.Ti/h and CDT selectivity of 96.73%.

Example 9

(30) The preparation of composite catalyst 9: The preparation of the composite catalyst 8 in example 8 is repeated using 69 ml of n-hexane in place of 68 ml of xylene.

(31) The trimerization process: According to the trimerization process of example 8.

(32) As a result, the composite catalyst 9 has the activity of 25432.7 g CDT/g .sub.Ti/h and CDT selectivity of 98.29%.

Example 10

(33) The preparation of composite catalyst 10: A 500 ml water-free and oxygen-free flask with four necks is immersed in a thermostatic oil bath at the temperature of 40 C. 55 ml of toluene, 2.64 mmol of aluminium diethyl monochloride, 1.32 ml of thionyl chloride, 5.2710.sup.2 mmol of TiCl.sub.4, and 0.105 mmol of methyl benzoate are added into the flask in order, nitrogen gas is introduced into the flask continuously, and the reaction is conducted at 40 C. for 300 min. The composite catalyst 10 is obtained.

(34) The trimerization process: After 192 ml of CDT is added to the flask, butadiene is introduced to the flask such that the pressure in the flask is maintained at 0.7 MPa, the temperature is raised to 70 C., and the reaction is conducted for 120 min. After that, 0.132 mmol of water is added to terminate the reaction. The reaction liquid is weighed and then filtered, and the resulting filtrate is determined by gas chromatography.

(35) As a result, the composite catalyst 10 has the activity of 20241.0 g CDT/g .sub.Ti/h and CDT selectivity of 98.65%.

Example 11

(36) The preparation of composite catalyst 11: A 500 ml water-free and oxygen-free flask with four necks is immersed in a thermostatic oil bath at the temperature of 40 C. 110 ml of toluene, 0.88 mmol of aluminium diethyl monochloride, 1.32 ml of thionyl chloride, 5.2710.sup.2 mmol of TiCl.sub.4, and 0.105 mmol of methyl benzoate are added into the flask in order, nitrogen gas is introduced into the flask continuously, and the reaction is conducted at 40 C. for 300 min. The composite catalyst 11 is obtained.

(37) The trimerization process: According to the trimerization process of example 10.

(38) As a result, the composite catalyst 11 has the activity of 22762.5 g CDT/g .sub.Ti/h and CDT selectivity of 96.37%.

Example 12

(39) The preparation of composite catalyst 12: A 500 ml water-free and oxygen-free flask with four necks is immersed in a thermostatic oil bath at the temperature of 40 C. 110 ml of toluene, 5.2710.sup.2 mmol of methyl benzoate, 2.64 mmol of aluminium diethyl monochloride, 1.32 ml of thionyl chloride, and 5.2710.sup.2 mmol of TiCl.sub.4 are added into the flask in order, nitrogen gas is introduced into the flask continuously, and the reaction is conducted at 40 C. for 300 min. The composite catalyst 12 is obtained.

(40) As a result, the composite catalyst 12 has the activity of 25535.1 g CDT/g .sub.Ti/h and CDT selectivity of 96.41%.

Example 13

(41) The preparation of composite catalyst 13: A 500 ml water-free and oxygen-free flask with four necks is immersed in a thermostatic oil bath at the temperature of 40 C. 110 ml of toluene, 5.27 mmol of aluminium ethyl dichloride, 0.105 mmol of dimethyl sulfoxide, 5.2710.sup.2 mmol of TiCl.sub.4, and 1.32 mmol of ethyl formate are added into the flask in order, nitrogen gas is introduced into the flask continuously, and the reaction is conducted at 40 C. for 15 min. The composite catalyst 13 is obtained.

(42) The trimerization process: After 58 ml of toluene is added to the flask, butadiene is introduced such that the pressure in the flask is maintained at 0.1 MPa, the temperature is raised to 70 C., and the reaction is conducted for 60 min. After that, 5.2710.sup.2 mmol of ethanol is added to terminate the reaction. The reaction liquid is weighed and then filtered, and the resulting filtrate is determined by gas chromatography.

(43) As a result, the composite catalyst 13 has the activity of 20324.5 g CDT/g .sub.Ti/h and CDT selectivity of 95.43%.

Comparative Example 1

(44) The preparation of comparative catalyst 1: A 500 ml water-free and oxygen-free flask with four necks is immersed in a thermostatic oil bath at the temperature of 120 C. 1.05 mmol of sesquiethyl aluminum chloride, 380 ml of n-heptane, 5.2710.sup.2 mmol of TiCl.sub.4, and 1.32 mmol of the mixture (molar ratio 1:1) of thionyl chloride and dimethyl sulfoxide are added into the flask in order, nitrogen gas is introduced into the flask continuously, and the reaction is conducted at 120 C. for 600 min. The comparative catalyst 1 is obtained.

(45) The trimerization process: Butadiene is introduced to the flask such that the pressure in the flask is maintained at 0.5 MPa, the temperature is raised to 180 C., and the reaction is conducted for 600 min. After that, 5.2710.sup.2 mmol of water is added to terminate the reaction. The reaction liquid is weighed and then filtered, and the resulting filtrate is determined by gas chromatography.

(46) As a result, the comparative catalyst 1 has the activity of 18002 g CDT/g .sub.Ti/h and CDT selectivity of 92.81%.

Comparative Example 2

(47) The preparation of comparative catalyst 2: A 500 ml water-free and oxygen-free flask with four necks is immersed in a thermostatic oil bath at the temperature of 80 C. 26.35 mmol of triethyl boron, 5.2710.sup.2 mmol of TiCl.sub.4, 68 ml of xylene, and 5.2710.sup.2 mmol of dimethyl sulfoxide are added into the flask in order, nitrogen gas is introduced into the flask continuously, and the reaction is conducted at 80 C. for 20 min. The comparative catalyst 2 is obtained.

(48) The trimerization process: After 100 ml of CDT is added to the flask, butadiene is introduced to the flask such that the pressure in the flask is maintained at 0.3 MPa, and the reaction is conducted at the temperature of 80 C. for 60 min. After that, 1.3210.sup.2 mmol of n-butanol is added to terminate the reaction. The reaction liquid is weighed and then filtered, and the resulting filtrate is determined by gas chromatography.

(49) As a result, the comparative catalyst 2 has the activity of 18101.2 g CDT/g .sub.Ti/h and CDT selectivity of 93.6%.

Comparative Example 3

(50) The preparation of comparative catalyst 3: A 500 ml water-free and oxygen-free flask with four necks is immersed in a thermostatic oil bath at the temperature of 40 C. 55 ml of toluene, 2.64 mmol of aluminium diethyl monochloride, 1.32 ml of thionyl chloride, and 5.2710.sup.2 mmol of TiCl.sub.4 are added into the flask in order, nitrogen gas is introduced into the flask continuously, and the reaction is conducted at 40 C. for 300 min. The comparative catalyst 3 is obtained.

(51) The trimerization process: After 192 ml of CDT is added to the flask, butadiene is introduced to the flask such that the pressure in the flask is maintained at 0.7 MPa, the temperature is raised to 70 C., and the reaction is conducted for 120 min. After that, 5.2710.sup.2 mmol of water is added to terminate the reaction. The reaction liquid is weighed and then filtered, and the resulting filtrate is determined by gas chromatography.

(52) As a result, the comparative catalyst 3 has the activity of 18060.3 g CDT/g .sub.Ti/h and CDT selectivity of 93.1%.

Comparative Example 4

(53) The preparation of comparative catalyst 4: A 500 ml water-free and oxygen-free flask with four necks is immersed in a thermostatic oil bath at the temperature of 20 C. 165 ml of toluene, 5.2710.sup.2 mmol of TiCl.sub.4, 1.32 mmol of dimethyl sulfoxide, and 52.7 mmol of n-butyl lithium are added into the flask in order, nitrogen gas is introduced into the flask continuously, and the reaction is conducted at 20 C. for 300 min. The comparative catalyst 4 is obtained.

(54) The trimerization process: After 165 ml of toluene is added to the flask, butadiene is introduced such that the pressure in the flask is maintained at 1 MPa, the temperature is raised to 80 C., and the reaction is conducted for 15 min. After that, 5.2710.sup.2 mmol of water is added to terminate the reaction. The reaction liquid is weighed and then filtered, and the resulting filtrate is determined by gas chromatography.

(55) As a result, the comparative catalyst 4 has the activity of 18156.5 g CDT/g .sub.Ti/h and CDT selectivity of 93.8%.

(56) As seen from comparison of the invention examples and comparative examples, when used for the trimerization of butadiene to CDT, the catalysts of the present invention exhibit a higher catalytic activity and CDT selectivity than those of the comparative examples.