CN111408408B - 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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- 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
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- C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
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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 contains a phosphine compound and a sulfur compound. 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 phosphine compound and the sulfur compound 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 into 1-butene include catalytic systems based on vanadium, iron or cobalt, tungsten, tantalum, nickel, titanium. Of these systems, titanium-based catalytic systems are the best. Patent US 2943125 to ziegler et al discloses a process for the dimerization of ethylene to 1-butene using a catalyst obtained by mixing a trialkylaluminum with a 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 preparing butene-1, which comprises 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 a phosphine-based compound and a sulfur-based compound 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 a threshold value below the detection limit, while the dimerization activity of ethylene and the C4 content in the product are greatly improved.
To this end, a first aspect of the invention provides a catalyst composition comprising a titanium compound, an aluminum compound and a lewis base-type additive; wherein the Lewis base type additive comprises a phosphine compound and a sulfur compound.
In some embodiments, the phosphine is selected from the group consisting of C 1 -C 6 Alkyl of (C) 3 -C 6 Cycloalkyl or C 6 -C 12 Aryl substituted or unsubstituted phosphines, phosphine oxides, orthophosphoric acid esters, phosphorous acid esters and hypophosphorous acid esters.
Preferably, the phosphine is selected from one or more of triisopropylphosphine, tributylphosphine, tricyclohexylphosphine, triphenylphosphine, tri (o-tolyl) phosphine, and bis (diphenylphosphino) ethane. The phosphine oxide is selected from trioctylphosphine oxide and/or triphenylphosphine oxide. The phosphite ester is one or more selected from triphenyl phosphite, triisopropylphosphine phosphite, tributylphosphine phosphite and tricyclohexylphosphine phosphite. The orthophosphoric acid ester is one or more selected from triphenyl phosphate, triisopropyl phosphine phosphate, tributylphosphine phosphate and tricyclohexyl phosphine phosphate. The hypophosphite is selected from one or more of triphenyl hypophosphite, triisopropyl phosphine hypophosphite, tributylphosphine hypophosphite and tricyclohexylphosphine hypophosphite.
In other embodiments, the sulfur-based compound is selected from substituted or unsubstituted linear, branched, or cyclic sulfides.
Preferably, the sulfur compound is selected from substituted or unsubstituted thiophenes. More preferably, the sulphur compound is selected from the group consisting of 1 -C 6 Alkyl or C 1 -C 6 Alkoxy-substituted thiophenes of (a).
In some specific embodiments, the sulfur-based compound is selected from one or more of diethylsulfide, dimethyldisulfide, tetrahydrothiophene, 2-methoxythiophene, 3-methoxythiophene, 2-ethoxythiophene, 3-ethoxythiophene, 2-propoxythiophene, 3-propoxythiophene, 2-butoxythiophene, 3-butoxythiophene, 2-pentoxythiophene, 3-pentoxythiophene, 2-hexoxythiophene, 3-hexyloxythiophene, 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 phosphine compound to the sulfur compound is (0.05-20): 1, preferably (0.2-10): 1.
The inventor of the invention researches and discovers that when a mixture of a phosphine compound and a sulfur compound is used as a Lewis base additive for selective dimerization of ethylene to synthesize 1-butene, the two compounds have synergistic effect, so that the activity of the catalyst and the content of C4 in a product are higher, and 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 Of a straight or branched alkane 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 2, 6-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 of 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 method for preparing a catalyst composition according to the first aspect of the present invention, which comprises mixing a titanium compound, an aluminum compound, a phosphine compound and a sulfur compound to form the catalyst composition.
In some specific embodiments, the phosphine compound and the sulfur compound are added separately as a single component, or the phosphine compound and the sulfur compound are premixed and then added.
The method adopts the titanium compound, the aluminum compound and the Lewis base additive containing the phosphine compound and the sulfur compound 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, and 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 the phosphine compound and the sulfur compound 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 the 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 the detection limit, and simultaneously, the dimerization activity of ethylene and the content of C4 in the 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 taken daily 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 filtration, 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 n-heptane solution) And a mixture of 1.16g of triphenylphosphine (4.44 mmol) and 0.51g of 2-methoxythiophene (4.44 mmol) were added to the 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 analyzed by gas chromatography for this gas. The liquid phase in the reactor is then weighed, the polymer (if present) is recovered, dried and weighed. Specific reaction conditions and results obtained 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 1.94g of triphenylphosphine (7.4 mmol) and 0.17g of 2-methoxythiophene (1.48 mmol) were added so that the molar ratio of triphenylphosphine to 2-methoxythiophene was 5, 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 0.39g of triphenylphosphine (1.48 mmol) and 0.85g of 2-methoxythiophene (7.4 mmol) were added so that the molar ratio of triphenylphosphine to 2-methoxythiophene was 0.2. 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 titanium tetrabutoxide compound was added so that the Al/Ti molar ratio was 6, and 2.18g of triphenylphosphine (8.325 mmol) and 0.063g of 2-methoxythiophene (0.555 mmol) were added so that the molar ratio of triphenylphosphine to 2-methoxythiophene was 15, while controlling the reaction time to 60min. Specific reaction conditions and results obtained are shown in table 1.
Example 8
The same as example 1 except that 0.66mL of a 0.085mol/L n-heptane solution of titanium tetrabutoxide compound was added so that the Al/Ti molar ratio was 30. The specific reaction conditions and the obtained results are shown in table 1.
Example 9
The same as in example 1, except that "a mixture of 1.16g of triphenylphosphine (4.44 mmol) and 0.51g of 2-methoxythiophene (4.44 mmol)" in example 1 was replaced with "a mixture of 1.38g of triphenyl phosphite (4.44 mmol) and 0.44g of 2-methylthiophene (4.44 mmol)". Specific reaction conditions and results obtained are shown in table 1.
Comparative example 1
The same as in example 1 except that triphenylphosphine was used as the Lewis base type additive, and that the amount of triphenylphosphine added was 8.88mmol. Specific reaction conditions and results obtained are shown in table 1.
Comparative example 2
The same as in example 1, except that the Lewis base type additive was 2-methoxythiophene alone and that 2-methoxythiophene was added in an amount of 8.88mmol. Specific reaction conditions and results obtained are shown in table 1.
Comparative example 3
Dissolving 7mL of the solution with the concentration of 0.238mol under inert atmosphereAlEt of/L 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. 2.33g of triphenylphosphine (8.88 mmol) were 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 with 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 (a). 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. The specific reaction conditions and the obtained results are shown in table 1.
Comparative example 4
7mL of AlEt with a concentration of 0.238mol/L dissolved therein were added 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 with an effective volume, equipped with mechanically driven paddles, and temperature regulated 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, stopEthylene was taken and the gas was analyzed by gas chromatography. 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, when the catalyst composition using the lewis base additive comprising the phosphine compound and the sulfur compound of the present invention is used in the reaction of selective dimerization of ethylene to 1-butene, the catalyst activity and the C4 content in the product are made higher while ensuring that the production of polyethylene is minimized to below the threshold of detection limit, as compared to the catalyst composition using a single phosphine compound or 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. The invention can be modified, as prescribed, within the scope of the claims and 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 (24)
1. A catalyst composition for the selective dimerization of ethylene to 1-butene comprising a titanium compound, an aluminum compound and a lewis base type additive; wherein the Lewis base type additive comprises a phosphine-based compound and a sulfur-based compound;
the phosphine compound is selected from C 1 -C 6 Alkyl of (C) 3 -C 6 Cycloalkyl or C 6 -C 12 Aryl substituted or unsubstituted phosphines and phosphites;
the sulfur compound is selected from substituted or unsubstituted thiophene.
2. The catalyst composition of claim 1, wherein the phosphine is selected from one or more of triisopropylphosphine, tributylphosphine, tricyclohexylphosphine, triphenylphosphine, tri (o-tolyl) phosphine, and bis (diphenylphosphino) ethane; the phosphite ester is selected from one or more of triphenyl phosphite, triisopropylphosphine phosphite, tributylphosphine phosphite and tricyclohexylphosphine phosphite.
3. The catalyst composition of claim 1, wherein the sulfur-based compound is selected from the group consisting of sulfur-based compounds and sulfur-based compounds 1 -C 6 Alkyl or C of 1 -C 6 Alkoxy-substituted thiophenes of (a).
4. The catalyst composition according to any one of claims 1 to 3, wherein the molar ratio of the phosphine compound to the sulfur compound is (0.05 to 20): 1.
5. The catalyst composition according to claim 4, wherein the molar ratio of the phosphine compound to the sulfur compound is (0.2-10): 1.
6. The catalyst composition according to any of claims 1 to 3, characterized in that the titanium compound is a compound of the general 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 (2).
7. The catalyst composition of claim 6, wherein the heteroatoms are selected from one or more of nitrogen, phosphorus, sulfur, and oxygen atoms.
8. The catalyst composition according to claim 6, wherein in the general formula (I), R is selected from one or more of tetraethyl group, tetraisopropyl group, tetra-n-butyl group, tetra-2-ethylhexyl group, phenyl group, 2-methylphenyl group, 2, 6-dimethylphenyl group, 2,4, 6-trimethylphenyl group, 4-methylphenyl group, 2, 6-diisopropylphenyl group, 2, 6-di-tert-butylphenyl group, 4-methyl-2, 6-di-tert-butylphenyl group, 2, 6-dichloro-4-tert-butylphenyl group, 2, 6-dibromo-4-tert-butylphenyl group, biphenyl group and binaphthyl group.
9. The catalyst composition according to any one of claims 1 to 3, characterized in that the aluminium compound is selected from hydrocarbylaluminium compounds and/or aluminoxane compounds; optionally, the hydrocarbyl group in the hydrocarbyl aluminum compound is substituted with a halogen.
10. The catalyst composition of claim 9, wherein the halogen is selected from chlorine or bromine.
11. The catalyst composition of claim 9, wherein the hydrocarbylaluminum compound is a trihydrocarbylaluminum compound.
12. The catalyst composition of claim 11, wherein the hydrocarbyl aluminum compound is triethylaluminum.
13. The catalyst composition according to any one of claims 1 to 3, 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.
14. The catalyst composition according to claim 13, 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 (0.5-5.3): 1; and/or
The molar ratio of the aluminum compound to the titanium compound is (1-30): 1 in terms of aluminum to titanium.
15. The catalyst composition of claim 14, 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.
16. A method of preparing the catalyst composition of any of claims 1-15, comprising mixing a titanium compound, an aluminum compound, a phosphine compound, and a sulfur compound to form the catalyst composition.
17. The production method according to claim 16, wherein the phosphine compound and the sulfur compound are added separately as a single component, or the phosphine compound and the sulfur compound are previously mixed and then added; and/or
Any one of the titanium compound and the aluminum compound is used as a mixture with a hydrocarbon solvent.
18. The method according to claim 17, wherein the volume ratio of the hydrocarbon solvent to the titanium compound in the mixture is (1-100): 1.
19. The method according to claim 18, wherein the volume ratio of the hydrocarbon solvent to the titanium compound in the mixture is (10-75): 1.
20. The process according to claim 17, wherein the hydrocarbon solvent is selected from C substituted or unsubstituted with halogen 1 -C 7 Alkane, C 3 -C 7 Cycloalkane of (2) and C 6 -C 20 One or more of (a) aromatic hydrocarbons.
21. The method of claim 20, 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.
22. Use of a catalyst composition according to any one of claims 1-15 or a catalyst composition obtained by a method for the preparation of a catalyst composition according to any one of claims 16-21 in the selective dimerization of ethylene to 1-butene, wherein the dimerization reaction is carried out at a temperature of 20-180 ℃; the total pressure of dimerization reaction is 0.5-20MPa; the dimerization reaction time is 10-120min.
23. The use according to claim 22, 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.
24. Use according to claim 23, wherein the total pressure of the dimerization reaction is 1-10MPa.
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