CN111408412A - 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 PDF

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CN111408412A
CN111408412A CN201910014408.7A CN201910014408A CN111408412A CN 111408412 A CN111408412 A CN 111408412A CN 201910014408 A CN201910014408 A CN 201910014408A CN 111408412 A CN111408412 A CN 111408412A
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catalyst composition
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titanium
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CN111408412B (en
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郑明芳
张海英
王怀杰
刘珺
项迎春
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/30—Catalytic processes with hydrides or organic compounds containing metal-to-carbon bond; Metal hydrides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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 an ether 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 ether 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-butene 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

Catalyst composition, preparation method thereof and application thereof in reaction for synthesizing 1-butene through selective dimerization of ethylene
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. Patent US2943125 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 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 an ether-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 an ether compound and a sulfur compound.
In some embodiments, the ether compound is selected from the group consisting of monoethers and polyethers.
Preferably, the monoether is selected from one or more of diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, 2-methoxy-2-methylpropane, 2-methoxy-2-methylbutane, 2-methoxy-2, 2 propane, bis (ethyl-2-hexyloxy) -2,2 propane, 2, 5-dihydrofuran, tetrahydrofuran, 2-methoxytetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2, 3-dihydropyran, tetrahydropyran, and benzofuran. The polyether is selected from one or more of 1, 3-dioxane, 1, 4-dioxane, dimethoxyethane, bis (2-methoxyethyl) ether, glyme, and diglyme.
In other embodiments, the sulfur based compound is selected from a substituted or unsubstituted linear, branched, or cyclic sulfide.
Preferably, the sulphur compound is selected from substituted or unsubstituted thiophenes. More preferably, the sulphur compound is selected from the group consisting of1-C6Alkyl or C1-C6Alkoxy-substituted thiophenes of (a).
In some specific embodiments, the sulfur compound is selected from the group consisting 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-hexyloxythiophene, 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 ether 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 an ether 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 a 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 atom2-C30Straight or branched alkanes or C6-C30Aryl 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 the group consisting 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, One or more of 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 method for preparing the catalyst composition according to the first aspect of the present invention, which comprises mixing a titanium compound, an aluminum compound, an ether compound and a sulfur compound to form the catalyst composition.
In some embodiments, the ether compound and the sulfur compound are added separately as a single component, or the ether compound and the sulfur compound are premixed and then added.
The method adopts the titanium compound, the aluminum compound and the Lewis base type additive containing the ether 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 preferredIn an embodiment of (1), the hydrocarbon solvent is selected from C substituted or unsubstituted with halogen1-C7Alkane, C3-C7Cycloalkane of (2)6-C20One 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 10 MPa. The dimerization reaction time is 10-120min, preferably 30-60 min.
In the present invention, the ethylene dimerization reaction is preferably performed under a lower total pressure, so that not only is the controllability of the dimerization reaction stronger, but also the content of polyethylene PE in the dimerization reaction product is ensured to be lower.
Compared with the prior art, the invention has the following beneficial effects:
when the mixture of the ether 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 the 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 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 adopted. 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):
Figure BDA0001936221580000051
(Note: the molar mass of titanium is 48g/mol)
(2) Method for calculating C4 content (%) and 1-butene selectivity (%):
Figure BDA0001936221580000052
Figure BDA0001936221580000053
(3) the content of PE was measured by weighing the reaction solution after filtration, drying and drying.
Examples
Example 1
The dimerization reaction was carried out in a stainless steel reaction vessel of effective volume 300m L, equipped with mechanically driven stirring paddles, jacketed by water circulation to adjust the temperature, under an ethylene atmosphere and at ambient temperature, 50m L n-heptane and a concentration of 5m LA solution of titanium tetrabutoxide in n-heptane of 0.085 mol/L, AlEt L at a concentration of 7m L of 0.238 mol/L3In heptane (1m L AlEt with a density of 0.84g/m L3Dissolved in 30m L n-heptane) and a mixture of 0.39g 1, 4-dioxane (4.44mmol) and 0.51g 2-methoxythiophene (4.44mmol) were added to the reaction vessel and the 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 reaction vessel was then weighed, the polymer (if present) was recovered, dried and weighed specific reaction conditions and results obtained are shown in table 1, the activity being in mass.% C of ethylene consumed per hour per gram of the titanium initially introduced4Corresponding to the amount of olefin containing 4 carbon atoms in the total product. % C4 ＝1Is shown in C4Selectivity to 1-butene in the fraction. The amount of polyethylene (% PE) corresponds to the mass of polyethylene recovered.
Example 2
The same as in example 1 except that 3.3m L0.085.085 mol/L of an n-heptane solution of 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 in example 1, except that 3.3m L0.085.085 mol/L of an n-heptane solution of titanium tetrabutoxide compound was added so that the Al/Ti molar ratio was 6 while controlling the reaction time to 60 min.
Example 4
The same as in example 1, except that 3.3m L0.085.085 mol/L mol of an n-heptane solution of titanium tetrabutoxide compound was added so that the Al/Ti molar ratio was 6 while controlling the reaction time to 120 min.
Example 5
The same as example 1 except that 3.3m L0.085.085 mol/L of an n-heptane solution of a tetrabutantitanium compound was added so that the Al/Ti molar ratio was 6, and 0.65g of 1, 4-dioxane (7.4mmol) and 0.17g of 2-methoxythiophene (1.48mmol) were added so that the molar ratio of 1, 4-dioxane to 2-methoxythiophene was 5:1 while controlling the reaction time to 60min, the specific reaction conditions and the results obtained are shown in table 1.
Example 6
As in example 1, 3.3m L0.085.085 mol/L of an n-heptane solution of titanium tetrabutoxide compound was added so that the Al/Ti molar ratio was 6, and 0.13g 1, 4-dioxane (1.48mmol) and 0.85g 2-methoxythiophene (7.4mmol) were added so that the molar ratio of 1, 4-dioxane to 2-methoxythiophene was 0.2:1, while controlling the reaction time to 60min specific reaction conditions and results obtained are shown in table 1.
Example 7
The same as example 1 except that 3.3m L0.085 mol/L of an n-heptane solution of titanium tetrabutoxide compound was added so that the Al/Ti molar ratio was 6, and 0.73g of 1, 4-dioxane (8.325mmol) and 0.063g of 2-methoxythiophene (0.555mmol) were added so that the molar ratio of 1, 4-dioxane to 2-methoxythiophene was 15:1 while controlling the reaction time to 60min the specific reaction conditions and results obtained are shown in table 1.
Example 8
The same as in example 1 except that 0.66m L0.085 of a 0.085 mol/L n-heptane solution of titanium tetrabutoxide compound was added so that the Al/Ti molar ratio was 30 specific reaction conditions and results obtained are shown in Table 1.
Example 9
The same as in example 1 except that "a mixture of 0.39g of 1, 4-dioxane (4.44mmol) and 0.51g of 2-methoxythiophene (4.44 mmol)" in example 1 was replaced with "a mixture of 0.32g of tetrahydrofuran (4.44mmol) 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 the Lewis base type additive used was 1, 4-dioxane only, and the amount of 1, 4-dioxane added was 8.88 mmol. Specific reaction conditions and results obtained are shown in table 1.
Comparative example 2
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 3
AlEt having dissolved a concentration of 0.238 mol/L of 7m L was added under an inert atmosphere3In heptane (1m L AlEt with a density of 0.84g/m L3Dissolved in 30m L n-heptane) was introduced into a Schlenk flask, 0.78g of 1, 4-dioxane (8.88mmol) was added to the Schlenk flask described above, and the solution was stirred under a nitrogen atmosphere at room temperature for about 1 hour to form a lewis base additive with AlEt3The pre-formed mixture of (1).
The dimerization reaction was carried out in a stainless steel reaction vessel of effective volume 300m L, equipped with mechanically driven stirring paddles, jacketed by water circulation to adjust the temperature, 50m L n-heptane and 5m L0.085 mol/L of titanium tetrabutoxide in n-heptane were added to the reaction vessel under an ethylene atmosphere and at ambient temperature, the required amounts of Lewis base type additive and AlEt were introduced under ethylene pressure once the temperature of the reaction vessel reached 55 deg.C3The 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 the gas was analysed 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.
Comparative example 4
AlEt having dissolved a concentration of 0.238 mol/L of 7m L was added under an inert atmosphere3In heptane (1m L AlEt with a density of 0.84g/m L3Dissolved in 30m L n-heptane) was introduced into a Schlenk flask, 1.01g of 2-methoxythiophene (8.88mmol) was further added to the above Schlenk flask, and the solution was stirred under a nitrogen atmosphere at ordinary temperature for about 1 hour to form a Lewis base type additive and AlEt3The pre-formed mixture of (1).
The dimerization reaction was carried out in a stainless steel reaction vessel of effective volume 300m L, equipped with mechanically driven stirring paddles, jacketed by water circulation to adjust the temperature, 50m L n-heptane and 5m L0.085 mol/L of an n-heptane solution of titanium tetrabutoxide compound were added to the reaction vessel under an ethylene atmosphere and at ambient temperature, once reverseThe temperature of the kettle is up to 55 ℃, namely, the required amount of Lewis base additive and AlEt are introduced under the pressure of ethylene3The 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 the gas was analysed 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.
Figure BDA0001936221580000091
As can be seen from table 1, the catalyst composition using the lewis base additive comprising the ether compound and the sulfur compound according to the present invention, when used in the reaction for selective dimerization of ethylene to 1-butene, allows higher catalyst activity and higher C4 content in the product, while ensuring that the production of polyethylene is minimized to below the threshold of detection limit, as compared to the catalyst composition using the ether compound alone or the sulfur compound alone 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 (10)

1. A catalyst composition comprising a titanium compound, an aluminum compound, and a lewis base type additive; wherein the Lewis base type additive comprises an ether compound and a sulfur compound.
2. The catalyst composition according to claim 1, wherein the ether compound is selected from monoethers and/or polyethers;
preferably, the monoether is selected from one or more of diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, 2-methoxy-2-methylpropane, 2-methoxy-2-methylbutane, 2-methoxy-2, 2 propane, bis (ethyl-2-hexyloxy) -2,2 propane, 2, 5-dihydrofuran, tetrahydrofuran, 2-methoxytetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2, 3-dihydropyran, tetrahydropyran, and benzofuran; the polyether is selected from one or more of 1, 3-dioxane, 1, 4-dioxane, dimethoxyethane, bis (2-methoxyethyl) ether, glyme and diglyme;
the sulfur compound is selected from substituted or unsubstituted straight chain sulfide, branched chain sulfide or cyclic sulfide, preferably selected from substituted or unsubstituted thiophene; more preferably selected from C1-C6Alkyl or C1-C6Alkoxy-substituted thiophenes of (a).
3. The catalyst composition according to claim 1 or 2, wherein the molar ratio of the ether compound to the sulfur compound is (0.05-20):1, preferably (0.2-10): 1.
4. 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 atom2-C30Straight or branched alkanes or C6-C30Aryl of (a); preferably, the heteroatom is selected from nitrogen, phosphorus, sulfurAnd an oxygen atom.
5. The catalyst composition according to claim 4, wherein in the general formula (I), R is selected from the group consisting 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-phenylphenyl group, 2, 6-diphenylphenyl group, 2,4, 6-triphenylphenyl group, 4-phenylphenyl group, 2-tert-butyl-6-phenylphenyl group, 2, 4-di-tert-butyl-6-phenylphenyl 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, biphenyl, binaphthyl and 1, 8-naphthalene-diyl.
6. The catalyst composition according to any one of claims 1 to 5, characterized in that the aluminium compound is selected from hydrocarbylaluminium compounds and/or aluminoxane compounds; optionally, the hydrocarbyl group in the hydrocarbylaluminum compound is substituted with a halogen, preferably the halogen is selected from chlorine or bromine; more preferably, the hydrocarbylaluminum compound is a trihydrocarbylaluminum compound; further preferably, the hydrocarbyl aluminum compound is triethylaluminum.
7. The catalyst composition according to any one of claims 1 to 6, characterized in that the ratio of the number of moles of Lewis base additive to the number of moles of aluminium in the aluminium compound is (0.5-20) to 1, preferably (0.5-5.3) to 1, more preferably (1-5) to 1; and/or
The molar ratio of the aluminum compound to the titanium compound is (1-100):1, preferably (1-30):1, more preferably (1-10):1, in terms of aluminum: titanium.
8. A method of preparing the catalyst composition of any one of claims 1-7, comprising mixing a titanium compound, an aluminum compound, an ether compound, and a sulfur compound to form the catalyst composition.
9. The production method according to claim 8, characterized in that the ether compound and the sulfur compound are added separately as a single component, or the ether compound and the sulfur compound are premixed and then added; and/or
Any one of the titanium compound and the aluminum compound 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) to 1, preferably (10-75) to 1;
preferably, the hydrocarbon solvent is selected from C substituted or unsubstituted by halogen1-C7Alkane, C3-C7Cycloalkane of (2)6-C20One or more of the aromatic hydrocarbons of (a); preferably, 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.
10. Use of a catalyst composition according to any one of claims 1 to 7 or a method for preparing a catalyst composition according to claim 8 or 9 in a reaction for the selective dimerization of ethylene to 1-butene, wherein the dimerization reaction is carried out at a temperature of 20 to 180 ℃, preferably 40 to 140 ℃; the total pressure of the dimerization reaction is 0.5-20MPa, preferably 0.5-15MPa, and more preferably 1-10 MPa; the dimerization reaction time is 10-120min, preferably 30-60 min.
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