CN111408403B - Catalyst composition, preparation method thereof and application thereof in reaction for synthesizing 1-butene through selective dimerization of ethylene - Google Patents
Catalyst composition, preparation method thereof and application thereof in reaction for synthesizing 1-butene through selective dimerization of ethylene Download PDFInfo
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Abstract
The present invention relates to a catalyst composition comprising a titanium compound, an aluminium compound and a lewis base type additive; wherein the Lewis base type additive comprises a sulfur compound A and a sulfur compound B, the sulfur compound A and the sulfur compound B being different. The invention also relates to a preparation method of the catalyst composition, which comprises the step of mixing the titanium compound, the aluminum compound, the sulfur compound A and the sulfur compound B to form the catalyst composition. In addition, the invention also relates to the application of the catalyst composition in the reaction of synthesizing 1-butene by ethylene dimerization. The invention can not only obtain higher 1-butylene selectivity and polyethylene content approaching zero in the product, but also has higher catalyst activity and C4 content in the product, and has rapid reaction, stable operation and good repeatability.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to a catalyst composition, a preparation method thereof and application thereof in reaction for synthesizing 1-butene through selective dimerization of ethylene.
Background
The catalytic systems reported so far for the selective dimerization of ethylene to 1-butene comprise catalytic systems based on vanadium, iron or cobalt, tungsten, tantalum, nickel, titanium. Of these systems, titanium-based catalytic systems are the best. U.S. Pat. No. 2943125 to Ziegler et al discloses a process for dimerizing ethylene to 1-butene using a catalyst obtained by mixing trialkylaluminum with zirconium tetraalkoxide. During this reaction, a certain amount of high molecular weight polymer (i.e., polyethylene) is also formed; this has a rather detrimental effect on the implementation of the method. Patent CN1031364a discloses a process for the preparation of butene-1 comprising dimerization of ethylene in the presence of titanium tetraalkoxide-trialkylaluminum in a hydrocarbon solvent of a catalytic system, followed by distillation of the reactants resulting from the dimerization, in the presence of a compound selected from the group consisting of: mono-and diols, aliphatic and cyclic ethers, aliphatic ketones, carboxamides. The catalyst used in the method is expensive, and in the generated product, the selectivity of the butene-1 is low, only 70 percent, and a large amount of butene-2 is contained.
Therefore, there is a need to develop a catalyst composition with high activity and selectivity and low polyethylene content in the product, a preparation method thereof, and an application thereof in the reaction of ethylene selective dimerization to 1-butene.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a catalyst composition, a preparation method thereof and an application thereof in a reaction for synthesizing 1-butene by selective dimerization of ethylene, aiming at the defects of the prior art. The inventors of the present invention have found through repeated experimental studies that when a mixture of two sulfur-based compounds is used as a lewis base-type additive, a catalyst composition prepared without preparing a pre-prepared mixture with an aluminum compound in advance, i.e., a catalyst composition prepared in situ from components including a titanium compound, an aluminum compound, and a lewis base-type additive, is used in the reaction of selective dimerization of ethylene to 1-butene, the production of polyethylene can be minimized to below the detection limit threshold, while the ethylene dimerization activity and the C4 content in the product are greatly improved.
To this end, the invention provides, in a first aspect, a catalyst composition comprising a titanium compound, an aluminium compound and a lewis base-type additive; wherein the Lewis base type additive comprises a sulfur compound A and a sulfur compound B, the sulfur compound A being different from the sulfur compound B.
In some embodiments, the sulfur compound a and the sulfur compound B are each independently selected from the group consisting of substituted or unsubstituted linear, branched, or cyclic sulfides. The linear sulfide is selected from diethyl sulfide and/or dimethyl disulfide. Preferably, the sulfur compound a and the sulfur compound B are each independently selected from substituted or unsubstituted thiophenes. More preferably, the sulphur compound a and the sulphur compound B are each independently selected from C 1 -C 6 Alkyl or C 1 -C 6 Alkoxy-substituted thiophenes of (a).
Most preferably, the sulphur compound A is selected from the group consisting of C 1 -C 6 The sulfur compound B is selected from thiophene substituted by C 1 -C 6 Alkyl-substituted thiophenes of (a).
In some specific embodiments, the sulfur compound A is selected from one or more of 2-methoxythiophene, 3-methoxythiophene, 2-ethoxythiophene, 3-ethoxythiophene, 2-propoxythiophene, 3-propoxythiophene, 2-butoxythiophene, 3-butoxythiophene, 2-pentoxythiophene, 3-pentoxythiophene, 2-hexoxythiophene, and 3-hexoxythiophene. The sulfur compound B is selected from one or more of 2-methylthiophene, 3-methylthiophene, 2-ethylthiophene, 3-ethylthiophene, 2-propylthiophene, 3-propylthiophene, 2-butylthiophene, 3-butylthiophene, 2-pentylthiophene, 3-pentylthiophene, 2-hexylthiophene and 3-hexylthiophene.
In some embodiments, the molar ratio of the sulfur compound a to the sulfur compound B is (0.05-20): 1, preferably (0.2-10): 1.
The inventor of the invention researches and discovers that when a mixture of two sulfur compounds is used as a Lewis base additive for selective dimerization of ethylene to synthesize 1-butene, the two sulfur compounds have synergistic effect, so that the activity of the catalyst and the content of C4 in a product are higher, and simultaneously, the content of polyethylene in the product is lower.
In some embodiments, the titanium compound is a compound of formula (I),
Ti(OR) 4 (I)
in the general formula (I), R is selected from C which is substituted or unsubstituted by a substituent containing or not containing a hetero atom 2 -C 30 Straight or branched alkanes or C 6 -C 30 Aryl of (a); preferably the heteroatoms are selected from one or more of nitrogen, phosphorus, sulphur and oxygen atoms.
In some specific embodiments, in formula (I), R is selected from one or more of tetraethyl, tetraisopropyl, tetra-n-butyl, tetra-2-ethylhexyl, phenyl, 2-methylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 4-methylphenyl, 2-phenylphenyl, 2,6-diphenylphenyl, 2,4,6-triphenylphenyl, 4-phenylphenyl, 2-tert-butyl-6-phenylphenyl, 2,4-di-tert-butyl-6-phenylphenyl, 2,6-diisopropylphenyl, 2,6-di-tert-butylphenyl, 4-methyl-2,6-di-tert-butylphenyl, 2,6-dichloro-4-tert-butylphenyl, and 5283 zxft 525283-dibromo-4-tert-butylphenyl, biphenyl, binaphthyl, and 1,8-naphthalene-diyl.
In some embodiments, the aluminum compound is selected from a hydrocarbylaluminum compound and/or an aluminoxane compound. Optionally, the hydrocarbyl group in the hydrocarbylaluminum compound is substituted with a halogen, preferably the halogen is selected from chlorine or bromine. In some more preferred embodiments, the hydrocarbylaluminum compound is a trihydrocarbylaluminum compound. In some further preferred embodiments, the hydrocarbyl aluminum compound is triethylaluminum.
In some embodiments, the ratio of the number of moles of the lewis base additive to the number of moles of aluminum in the aluminum compound is (0.5-20): 1, preferably (0.5-5.3): 1, more preferably (1-5): 1.
In other specific embodiments, the molar ratio of the aluminum compound to the titanium compound, calculated as aluminum to titanium, is (1-100): 1, preferably (1-30): 1, more preferably (1-10): 1.
In a second aspect, the present invention provides a process for preparing a catalyst composition according to the first aspect of the invention, comprising mixing a titanium compound, an aluminium compound, a sulphur compound a and a sulphur compound B to form the catalyst composition.
In some specific embodiments, the sulfur compound a and the sulfur compound B are added separately as a single component, or the sulfur compound a and the sulfur compound B are premixed and then added.
The method adopts the titanium compound, the aluminum compound and the Lewis base type additive containing the sulfur compound A and the sulfur compound B to prepare the catalyst composition in situ, and the catalyst composition prepared in situ has the advantages that: the generation of active species of the catalyst is facilitated; the method is beneficial to reducing the steps of synthesizing the catalyst and reducing the synthesis cost; is beneficial to the smooth initiation of the reaction.
In some embodiments, the titanium compound or any of the titanium compounds is used as a mixture with a hydrocarbon solvent. Preferably, the volume ratio of hydrocarbon solvent to the titanium compound in the mixture is (1-100): 1, preferably (10-75): 1.
In some preferred embodiments, the hydrocarbon solvent is selected from C substituted or unsubstituted with halogen 1 -C 7 Alkane of C 3 -C 7 Cycloalkane of (2) 6 -C 20 One or more of (a) aromatic hydrocarbons.
In some more preferred embodiments, the hydrocarbon solvent is selected from one or more of n-butane, isobutane, n-hexane, n-heptane, cyclohexane, benzene, toluene, o-xylene, mesitylene, and ethylbenzene.
In a third aspect, the present invention provides the use of a catalyst composition according to the first aspect of the present invention or a process for the preparation of a catalyst composition according to the second aspect of the present invention in a reaction for the selective dimerization of ethylene to 1-butene.
In some embodiments, the dimerization temperature is 20 to 180 ℃, preferably 40 to 140 ℃. The total pressure of the dimerization reaction is 0.5 to 20MPa, preferably 0.5 to 15MPa, more preferably 1 to 10MPa. The dimerization reaction time is 10-120min, preferably 30-60min.
In the present invention, the ethylene dimerization reaction is preferably performed under a lower total pressure, which not only can make the dimerization reaction more controllable, but also can ensure that the content of polyethylene PE in the dimerization reaction product is lower.
Compared with the prior art, the invention has the following beneficial effects:
when the mixture of two sulfur compounds is used as the Lewis base additive, the catalyst composition prepared on the premise of not preparing a prefabricated mixture with an aluminum compound in advance, namely the catalyst composition prepared by mixing components including the titanium compound, the aluminum compound and the Lewis base additive in situ is used for the reaction of synthesizing 1-butene through selective dimerization of ethylene, the generation of polyethylene can be minimized to be lower than the threshold value of a detection limit, and simultaneously, the dimerization activity of the ethylene and the content of C4 in a product are greatly improved. Moreover, the preparation method of the catalyst composition is simple, the ethylene dimerization reaction is rapid, the operation is stable, the repeatability is good, and the catalyst composition is more beneficial to industrial popularization and application.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.
The test method or the calculation method provided by the invention is as follows:
the ethylene dimerization product is firstly qualitatively analyzed by combining gas chromatography and mass spectrometry to determine the peak quality of each product. Samples were routinely made for quantitative analysis by gas chromatography. The gas chromatograph is an Agilent 7890A, SE-54 type chromatographic column with a column length of 30m and an inner diameter of 0.2mm, the carrier gas is high-purity nitrogen, and the FID detector is used. The temperature program of the chromatogram is: the initial temperature is 40 ℃, the mixture stays for 3 minutes, then the temperature is raised to 50 ℃ at the speed of 30 ℃/min, the mixture stays for 1 minute, and then the temperature is raised to 280 ℃ at the speed of 40 ℃/min, and the mixture stays for 15 minutes.
(1) Method for calculating the catalyst activity (in g/gTi. H):
(Note: the molar mass of titanium is 48 g/mol.)
(2) Method for calculating C4 content (%) and 1-butene selectivity (%):
(3) The content of PE was measured by weighing the reaction solution after filtering, drying and drying.
Examples
Example 1
Dimerization was carried out in a 300mL jacketed stainless steel reaction kettle of effective volume equipped with mechanically driven paddles with temperature adjusted by water circulation. 50mL of n-heptane, 5mL of n-heptane solution of titanium tetrabutoxide compound with concentration of 0.085mol/L, and 7mL of AlEt with concentration of 0.238mol/L under ethylene atmosphere and at ambient temperature 3 In heptane (1 mL of AlEt having a density of 0.84g/mL 3 Dissolved in 30mL of an n-heptane solution) and a mixture of 0.51g of 2-methoxythiophene (4.44 mmol) and 0.44g of 2-methylthiophene (4.44 mmol) were charged into a reaction vessel, and dimerization of ethylene to 1-butene was carried out at a temperature of 55 ℃ and a pressure of 10MPa. After 30min of reaction, the ethylene feed was stopped and a sample was taken and the gas was analysed by gas chromatography. The liquid phase in the reactor is then weighed, the polymer (if present) recovered, dried and weighed. The specific reaction conditions and the obtained results are shown in table 1. In table 1, the activity is the mass of ethylene consumed per gram of titanium initially introduced per hour. % C 4 Corresponding to the amount of olefin containing 4 carbon atoms in the total product. % C 4 =1 Is shown in C 4 Selectivity to 1-butene in the fraction. The amount of polyethylene (% PE) corresponds to the mass of polyethylene recovered.
Example 2
The same as example 1 except that 3.3mL of a 0.085mol/L n-heptane solution of a titanium tetrabutoxide compound was added so that the Al/Ti molar ratio was 6. Specific reaction conditions and results obtained are shown in table 1.
Example 3
The same as example 1 except that 3.3mL of a 0.085mol/L n-heptane solution of titanium tetrabutoxide compound was added so that the Al/Ti molar ratio was 6 while controlling the reaction time at 60min. Specific reaction conditions and results obtained are shown in table 1.
Example 4
The same as in example 1, except that 3.3mL of a 0.085mol/L n-heptane solution of titanium tetrabutoxide compound was added so that the Al/Ti molar ratio was 6 while controlling the reaction time at 120min. The specific reaction conditions and the obtained results are shown in table 1.
Example 5
The same as example 1 except that 3.3mL of a 0.085mol/L n-heptane solution of titanium tetrabutoxide compound was added so that the Al/Ti molar ratio was 6, and 0.85g of 2-methoxythiophene (7.4 mmol) and 0.15g of 2-methylthiophene (1.48 mmol) were added so that the molar ratio of 2-methoxythiophene to 2-methylthiophene was 5:1 while controlling the reaction time to 60min. Specific reaction conditions and results obtained are shown in table 1.
Example 6
As in example 1, 3.3mL of a 0.085mol/L n-heptane solution of titanium tetrabutoxide compound was added so that the Al/Ti molar ratio was 6, and 0.17g of 2-methoxythiophene (1.48 mmol) and 0.73g of 2-methylthiophene (7.4 mmol) were added so that the molar ratio of 2-methoxythiophene to 2-methylthiophene was 0.2, while controlling the reaction time to 60min. The specific reaction conditions and the obtained results are shown in table 1.
Example 7
The same as example 1 except that 3.3mL of a 0.085mol/L n-heptane solution of a titanium tetrabutoxide compound was added so that the Al/Ti molar ratio was 6, and 0.95g of 2-methoxythiophene (8.325 mmol) and 0.054g of 2-methylthiophene (0.555 mmol) were added so that the molar ratio of 2-methoxythiophene to 2-methylthiophene was 15, while controlling the reaction time to 60min. Specific reaction conditions and results obtained are shown in table 1.
Example 8
The procedure of example 1 was repeated, except that 0.66mL of a 0.085mol/L n-heptane solution of titanium tetrabutoxide was added to give an Al/Ti molar ratio of 30. The specific reaction conditions and the obtained results are shown in table 1.
Comparative example 1
The same as in example 1 except that only 2-methoxythiophene was used as the Lewis base type additive, and that 8.88mmol of 2-methoxythiophene was added. Specific reaction conditions and results obtained are shown in table 1.
Comparative example 2
The same as in example 1 except that only 2-methylthiophene was used as the Lewis base type additive, and that the amount of 2-methylthiophene added was 8.88mmol. Specific reaction conditions and results obtained are shown in table 1.
Comparative example 3
Dissolving 7mL of AlEt with a concentration of 0.238mol/L under an inert atmosphere 3 In heptane (1 mL of AlEt having a density of 0.84 g/mL) 3 Dissolved in 30mL of n-heptane) was introduced into a Schlenk flask. 1.01g of 2-methoxythiophene (8.88 mmol) was added to the Schlenk flask described above, and the solution was stirred for about 1 hour at room temperature under a nitrogen atmosphere to form a Lewis base type additive and AlEt 3 The pre-formed mixture of (1).
Dimerization was carried out in a 300mL jacketed stainless steel reaction kettle of effective volume equipped with mechanically driven paddles with temperature adjusted by water circulation. 50mL of n-heptane and 5mL of a 0.085mol/L solution of titanium tetrabutoxide in n-heptane were added to the reactor under an ethylene atmosphere at ambient temperature. Once the reactor temperature reached 55 ℃, the desired amount of Lewis base additive and AlEt was introduced under ethylene pressure 3 The pre-formed mixture of (1). The ethylene pressure was maintained at 10MPa and the temperature at 55 ℃. After 30min of reaction, the ethylene feed was stopped and a sample was taken and analyzed by gas chromatography for this gas. Then the liquid in the reaction kettle is mixedPhase weighing, recovery of the polymer (if present), drying and weighing. Specific reaction conditions and results obtained are shown in table 1.
Comparative example 4
Dissolving 7mL of AlEt with a concentration of 0.238mol/L under an inert atmosphere 3 In heptane (1 mL of AlEt having a density of 0.84g/mL 3 Dissolved in 30mL of n-heptane) was introduced into a Schlenk flask. 0.87g of 2-methylthiophene (8.88 mmol) was added to the Schlenk flask, and the solution was stirred under a nitrogen atmosphere at room temperature for about 1 hour to form a Lewis base type additive and AlEt 3 The pre-formed mixture of (1).
Dimerization was carried out in a 300mL jacketed stainless steel reaction kettle of effective volume equipped with mechanically driven paddles with temperature adjusted by water circulation. 50mL of n-heptane and 5mL of a 0.085mol/L solution of titanium tetrabutoxide in n-heptane were added to the reactor under an ethylene atmosphere at ambient temperature. Once the reactor temperature reached 55 ℃, the desired amount of Lewis base additive and AlEt was introduced under ethylene pressure 3 The pre-formed mixture of (1). The ethylene pressure was maintained at 10MPa and the temperature at 55 ℃. After 30min of reaction, the ethylene feed was stopped and a sample was taken and analyzed by gas chromatography for this gas. The liquid phase in the reactor is then weighed, the polymer (if present) recovered, dried and weighed. Specific reaction conditions and results obtained are shown in table 1.
As can be seen from table 1, the catalyst composition employing the lewis base additive comprising the sulfur compound a and the sulfur compound B according to the present invention allows higher catalyst activity and C4 content in the product when used in the selective dimerization synthesis of 1-butene of ethylene, while ensuring that the production of polyethylene is minimized to below the threshold of detection limit, compared to the catalyst composition employing a single sulfur compound as the lewis base additive. In addition, compared with the prior art, the method of the invention omits the step of premixing the aluminum compound and the Lewis base type additive, is more beneficial to the generation of catalyst active species and the smooth initiation of reaction, further improves the catalyst activity and obtains better effect.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined within the scope of the claims and modifications may be made without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (22)
1. A catalyst composition for the selective dimerization of ethylene to 1-butene, characterized in that it comprises a titanium compound, an aluminum compound and a lewis base type additive; wherein the Lewis base type additive comprises a sulfur compound A and a sulfur compound B, the sulfur compound A being different from the sulfur compound B;
the sulfur compound A is selected from C 1 -C 6 The sulfur compound B is selected from thiophene substituted by C 1 -C 6 Alkyl-substituted thiophenes of (a).
2. The catalyst composition of claim 1, wherein the molar ratio of the sulfur compound a to the sulfur compound B is (0.05-20): 1.
3. The catalyst composition of claim 2, wherein the molar ratio of the sulfur compound a to the sulfur compound B is (0.2-10): 1.
4. The catalyst composition according to claim 1, characterized in that the titanium compound is a compound of formula (I),
Ti(OR) 4 (I)
in the general formula (I), R is selected from C which is substituted or unsubstituted by a substituent containing or not containing a hetero atom 2 -C 30 Straight or branched alkanes or C 6 -C 30 Aryl group of (1).
5. The catalyst composition of claim 4, wherein the heteroatoms are selected from one or more of nitrogen, phosphorus, sulfur, and oxygen atoms.
6. The catalyst composition of claim 4, wherein in formula (I), R is selected from one or more of tetraethyl, tetraisopropyl, tetra-n-butyl, tetra-2-ethylhexyl, phenyl, 2-methylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 4-methylphenyl, 2,6-diisopropylphenyl, 2,6-di-tert-butylphenyl, 4-methyl-2,6-di-tert-butylphenyl, 2,6-dichloro-4-tert-butylphenyl, 2,6-dibromo-4-tert-butylphenyl, biphenyl, and binaphthyl.
7. The catalyst composition according to claim 1, characterized in that the aluminum compound is selected from hydrocarbylaluminum compounds and/or aluminoxane compounds; the hydrocarbyl group in the hydrocarbylaluminum compound is substituted with a halogen.
8. The catalyst composition of claim 7, wherein the halogen is selected from chlorine or bromine.
9. The catalyst composition according to claim 7, characterized in that the hydrocarbylaluminum compound is a trihydrocarbylaluminum compound.
10. The catalyst composition according to claim 9, characterized in that the aluminum hydrocarbyl compound is triethylaluminum.
11. The catalyst composition according to claim 1, characterized in that the ratio of the number of moles of Lewis base type additive to the number of moles of aluminum in the aluminum compound is (0.5-20): 1; and/or
The molar ratio of the aluminum compound to the titanium compound is (1-100): 1 in terms of aluminum to titanium.
12. The catalyst composition of claim 11, wherein the ratio of the number of moles of the lewis base additive to the number of moles of aluminum in the aluminum compound is (0.5-5.3): 1; and/or
The molar ratio of the aluminum compound to the titanium compound is (1-30): 1 in terms of aluminum to titanium.
13. The catalyst composition of claim 12, wherein the ratio of the number of moles of the lewis base additive to the number of moles of aluminum in the aluminum compound is (1-5): 1; and/or
The molar ratio of the aluminum compound to the titanium compound is (1-10): 1 in terms of aluminum: titanium.
14. A process for the preparation of a catalyst composition according to any one of claims 1 to 13, characterized in that a titanium compound, an aluminium compound, a sulphur compound a and a sulphur compound B are mixed to form the catalyst composition.
15. The production method according to claim 14, characterized in that the sulfur compound a and the sulfur compound B are added separately as a single component, or the sulfur compound a and the sulfur compound B are added after being mixed in advance; and/or
Any one of the titanium compound and the aluminum compound is used as a mixture with a hydrocarbon solvent.
16. The method according to claim 15, wherein the volume ratio of the hydrocarbon solvent to the titanium compound in the mixture is (1-100): 1.
17. The method according to claim 16, wherein the volume ratio of the hydrocarbon solvent to the titanium compound in the mixture is (10-75): 1.
18. The method according to claim 15, wherein the hydrocarbon solvent is selected from C substituted or unsubstituted with halogen 1 -C 7 Alkane of C 3 -C 7 Cycloalkane of (2) 6 -C 20 One or more of (a) aromatic hydrocarbons.
19. The method of claim 18, wherein the hydrocarbon solvent is selected from one or more of n-butane, isobutane, n-hexane, n-heptane, cyclohexane, benzene, toluene, o-xylene, mesitylene, and ethylbenzene.
20. Use of a catalyst composition according to any one of claims 1 to 13 or a method for preparing a catalyst composition according to any one of claims 14 to 19 in a reaction for the selective dimerization of ethylene to 1-butene, characterized in that the temperature of the dimerization reaction is 20 to 180 ℃; the total pressure of dimerization reaction is 0.5-20MPa; the dimerization reaction time is 10-120min.
21. The use according to claim 20, wherein the dimerization temperature is 40-140 ℃; and/or
The total pressure of the dimerization reaction is 0.5-15MPa; and/or
The dimerization reaction time is 30-60min.
22. Use according to claim 21, wherein the total pressure of the dimerization reaction is 1-10MPa.
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