CN111408404B - 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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CN111408404B
CN111408404B CN201910007609.4A CN201910007609A CN111408404B CN 111408404 B CN111408404 B CN 111408404B CN 201910007609 A CN201910007609 A CN 201910007609A CN 111408404 B CN111408404 B CN 111408404B
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catalyst composition
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CN111408404A (en
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张海英
郑明芳
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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Abstract

The invention relates to a catalyst composition, a preparation method thereof and application thereof in the reaction of synthesizing 1-butene by ethylene selective dimerization, wherein the catalyst composition comprises a titanium compound, an aluminum compound and a Lewis base type additive; wherein the Lewis base type additive comprises an ether compound and an amine 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 amine 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 zero polyethylene content 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 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 selective dimerization of ethylene to 1-butene, 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 compound and an amine 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 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 an amine 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 still other embodiments of the present invention, the amine compound is selected from C 1 -C 5 Alkyl of (C) 1 -C 5 Alkoxy, halogen, C 6 -C 12 Aryl substituted or unsubstituted monoamines, polyamines, imines, pyridines, bipyridines, quinolines, imidazoles, pyrroles and pyrazoles.
Preferably, the substituted monoamine is selected from trimethylamine and/or triethylamine. The substituted polyamine is selected from propane diamine and/or butane diamine. The substituted imine is selected from the group consisting of benzoylimine, N ' -dimethyl-ethane-1, 2-diimine, N ' -diphenyl-butane-2, 3-diimine, N ' -di-tert-butyl-butane-2, 3-diimine, N, one or more of N ' -bis- (dimethyl-2, 6-diphenyl) ethane-1, 2-diimine, N ' -bis- (diisopropyl-2, 6-diphenyl) ethane-1, 2-diimine, N ' -bis- (dimethyl-2, 6-diphenyl) -butane-2, 3-diimine, and N, N ' -bis- (diisopropyl-2, 6-diphenyl) -butane-2, 3-diimine. The substituted pyridine is selected from one or more of 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, 2-fluoropyridine, 3-trifluoromethylpyridine, 2-phenylpyridine, 3-phenylpyridine, 2-benzylpyridine, 3, 5-dimethylpyridine, 2, 6-di-tert-butylpyridine and 2, 6-diphenylpyridine. The unsubstituted bipyridine is selected from one or more of 1,1' -bipyridine, 2' -bipyridine and 3,3' -bipyridine. The substituted quinoline is selected from 2-methylquinoline and/or 8-hydroxyquinoline. The substituted imidazole is selected from N-methylimidazole and/or N-butylimidazole. The substituted pyrroles are selected from N-methyl pyrrole and/or N-butyl pyrrole. The substituted pyrazole is N-methylpyrazole.
In some embodiments, the molar ratio of the ether compound to the amine 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 an amine compound is used as a Lewis base additive for selective dimerization of ethylene to 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 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 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 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, which comprises mixing a titanium compound, an aluminum compound, an ether compound and an amine compound to form the catalyst composition.
In some embodiments, the ether compound and the amine compound are added separately as a single component, or the ether compound and the amine compound are premixed and then added.
The method adopts the titanium compound, the aluminum compound and the Lewis base additive containing the ether compound and the amine 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 favorable for 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 the 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, 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 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 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 the ether compound and the amine compound is used as the Lewis base type 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 type 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 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, and the carrier gas is high-purity nitrogen and an FID detector. The temperature program of the chromatogram is: the initial temperature is 40 ℃, the temperature is kept for 3 minutes, then the temperature is increased to 50 ℃ at 30 ℃/min, the temperature is kept for 1 minute, and then the temperature is increased to 280 ℃ at 40 ℃/min, and the temperature is kept for 15 minutes.
(1) Method for calculating catalyst activity (unit g/gTi. Multidot.h):
Figure BDA0001936066740000051
(Note: the molar mass of titanium is 48 g/mol)
(2) Method for calculating C4 content (%) and 1-butene selectivity (%):
Figure BDA0001936066740000052
Figure BDA0001936066740000053
(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 with an effective volume, equipped with mechanically driven paddles, and temperature regulated by water circulation. Titanium tetrabutylate with the concentration of 0.085mol/L is added into 50mL of n-heptane and 5mL of titanium tetrachloride under the atmosphere of ethylene and at the ambient temperatureThe product was in n-heptane solution, 7mL of AlEt with a concentration of 0.238mol/L 3 In heptane (1 mL of AlEt having a density of 0.84 g/mL) 3 Dissolved in 30mL of an n-heptane solution) and a mixture of 0.39g of 1, 4-dioxane (4.44 mmol) and 1.03g of 2, 6-diphenylpyridine (4.44 mmol) were charged into a reaction vessel, and a dimerization reaction 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) 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 at 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. Specific reaction conditions and results obtained 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 0.65g of 1, 4-dioxane (7.4 mmol) and 0.34g of 2, 6-diphenylpyridine (1.48 mmol) were added so that the molar ratio of 1, 4-dioxane to 2, 6-diphenylpyridine was 5. 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 0.13g of 1, 4-dioxane (1.48 mmol) and 1.71g of 2, 6-diphenylpyridine (7.4 mmol) were added so that the molar ratio of 1, 4-dioxane to 2, 6-diphenylpyridine was 0.2. Specific reaction conditions and results obtained 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 tetrabutantitanium compound was added so that the Al/Ti molar ratio was 6, and 0.73g of 1, 4-dioxane (8.325 mmol) and 0.13g of 2, 6-diphenylpyridine (0.555 mmol) were added so that the molar ratio of 1, 4-dioxane to 2, 6-diphenylpyridine 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. 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 (4.44 mmol) and 1.03g of 2, 6-diphenylpyridine (4.44 mmol)" in example 1 was replaced with "a mixture of 0.32g of tetrahydrofuran (4.44 mmol) and 0.36g of N-methylpyrrole (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 8.88mmol. Specific reaction conditions and results obtained are shown in table 1.
Comparative example 2
The same as in example 1, except that only 2, 6-diphenylpyridine was used as the Lewis base type additive, and that the amount of 2, 6-diphenylpyridine 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 0.84g/mL 3 Dissolved in 30mL of n-heptane) was introduced into a Schlenk flask. 0.78g of 1, 4-dioxane (8.88 mmol) was then added to the Schlenk flask described above and the solution was stirred for about 1 hour at ambient temperature under a nitrogen atmosphere to form the Lewis base type additive with AlEt 3 The pre-formed mixture of (a).
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 required 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 the gas was analysed by gas chromatography. 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.
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 0.84g/mL 3 Dissolved in 30mL of n-heptane) was introduced into a Schlenk flask. 2.05g of 2, 6-diphenylpyridine (8.88 mmol) were further added to the Schlenk flask mentioned above, and the solution was stirred under a nitrogen atmosphere at ordinary 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 temperature of the reaction kettle reaches 55 DEG CBy introducing the desired amount of Lewis base additive with AlEt 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 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 BDA0001936066740000091
As can be seen from table 1, when the catalyst composition using the lewis base additive comprising the ether compound and the amine compound according to the present invention is used in the reaction for selective dimerization of ethylene to 1-butene, the catalyst activity and the C4 content in the product are both made higher while ensuring that the production of polyethylene is minimized to be below the threshold of detection limit, compared to the catalyst composition using a single ether compound or a single amine 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 (19)

1. 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 an amine compound,
wherein the ether compound is selected from monoethers and/or polyethers; the amine compound is selected from C 1 -C 5 Alkyl of (C) 1 -C 5 Alkoxy, halogen, C 6 -C 12 Aryl substituted or unsubstituted monoamines, polyamines, imines, pyridines, bipyridines, quinolines, imidazoles, pyrroles, and pyrazoles;
the molar ratio of the ether compound to the amine compound is (0.05-20) to 1;
the ratio of the number of moles of the Lewis base type additive to the number of moles of aluminum in the aluminum compound is (0.5-20): 1; the molar ratio of the aluminum compound to the titanium compound is (1-100) to 1 in terms of aluminum to titanium;
the preparation method of the catalyst composition comprises the following steps:
mixing a titanium compound, an aluminum compound, an ether compound and an amine compound to form a catalyst composition;
wherein the ether compound and the amine compound are respectively added as a single component, or the ether compound and the amine 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, wherein the volume ratio of the hydrocarbon solvent to the titanium compound in the mixture is (1-100): 1.
2. The catalyst composition of claim 1, wherein 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.
3. Catalyst composition according to claim 1, characterized in that the substituted monoamine is selected from trimethylamine and/or triethylamine; the substituted polyamine is selected from propane diamine and/or butane diamine; the substituted imine is selected from the group consisting of benzoylimine, N ' -dimethyl-ethane-1, 2-diimine, N ' -diphenyl-butane-2, 3-diimine, N ' -di-tert-butyl-butane-2, 3-diimine, N, one or more of N ' -bis- (dimethyl-2, 6-diphenyl) ethane-1, 2-diimine, N ' -bis- (diisopropyl-2, 6-diphenyl) ethane-1, 2-diimine, N ' -bis- (dimethyl-2, 6-diphenyl) -butane-2, 3-diimine, and N, N ' -bis- (diisopropyl-2, 6-diphenyl) -butane-2, 3-diimine; the substituted pyridine is selected from one or more of 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, 2-fluoropyridine, 3-trifluoromethylpyridine, 2-phenylpyridine, 3-phenylpyridine, 2-benzylpyridine, 3, 5-dimethylpyridine, 2, 6-di-tert-butylpyridine and 2, 6-diphenylpyridine; the unsubstituted bipyridine is selected from one or more of 1,1' -bipyridine, 2' -bipyridine and 3,3' -bipyridine; the substituted quinoline is selected from 2-methylquinoline and/or 8-hydroxyquinoline; the substituted imidazole is selected from N-methylimidazole and/or N-butylimidazole; the substituted pyrrole is selected from N-methyl pyrrole and/or N-butyl pyrrole; the substituted pyrazole is N-methylpyrazole.
4. The catalyst composition according to claim 1, wherein the molar ratio of the ether compound to the amine compound is (0.2-10): 1.
5. The catalyst composition according to any of claims 1 to 4, 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 (1).
6. The catalyst composition of claim 5, wherein the heteroatoms are selected from one or more of nitrogen, phosphorus, sulfur, and oxygen atoms.
7. The catalyst composition according to claim 5, 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.
8. The catalyst composition according to any one of claims 1 to 4, 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.
9. The catalyst composition of claim 8, wherein the halogen is selected from chlorine or bromine.
10. The catalyst composition according to claim 8, characterized in that the hydrocarbylaluminum compound is a trihydrocarbylaluminum compound.
11. The catalyst composition of claim 10, wherein the hydrocarbyl aluminum compound is triethylaluminum.
12. The catalyst composition of claim 1 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. The catalyst composition of claim 1, wherein the volume ratio of hydrocarbon solvent to the titanium compound in the mixture is (10-75): 1.
15. The catalyst composition according to claim 1, wherein the hydrocarbon solvent is selected from C substituted or unsubstituted with halogen 1 -C 7 Alkane, C 3 -C 7 Cycloalkane of (2) 6 -C 20 One or more of (a) aromatic hydrocarbons.
16. The catalyst composition of claim 15, 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.
17. Use of a catalyst composition according to any one of claims 1 to 16 in the selective dimerization of ethylene to 1-butene, wherein the dimerization temperature is 20 to 180 ℃; the total pressure of dimerization reaction is 0.5-20MPa; the dimerization reaction time is 10-120min.
18. The use according to claim 17, 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.
19. Use according to claim 18, wherein the dimerization reaction is carried out at a total pressure of 1 to 10MPa.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG64584G (en) * 1980-05-30 1985-03-15 Millar John Uk Ltd Microprocessor controlled valve flow indicator
CN104119463A (en) * 2014-07-16 2014-10-29 任丘市利和科技发展有限公司 Catalyst component for vinyl polymerization and preparation method and application of catalyst component
CN105233868A (en) * 2014-07-04 2016-01-13 Ifp新能源公司 Catalytic composition and process for the dimerisation of ethylene to 1-butene
CN105562087A (en) * 2014-10-11 2016-05-11 中国石油化工股份有限公司 Catalyst composition for ethylene oligomerization and application thereof
CN105828942A (en) * 2013-12-13 2016-08-03 沙特基础工业公司 Catalyst compositions for selective dimerization of ethylene
CN105980053A (en) * 2014-02-06 2016-09-28 沙特基础工业全球技术有限公司 Modifying organoaluminum co-catalysts for improved performance

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06329562A (en) * 1993-05-21 1994-11-29 Idemitsu Kosan Co Ltd Production of olefin oligomer
FR3023285B1 (en) * 2014-07-04 2017-10-27 Ifp Energies Now IMPROVED METHOD FOR SELECTIVE DIMERIZATION OF ETHYLENE TO BUTENE-1
EP3310476B1 (en) * 2015-06-19 2019-09-18 Saudi Arabian Oil Company Antifouling oligomerization catalyst systems

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG64584G (en) * 1980-05-30 1985-03-15 Millar John Uk Ltd Microprocessor controlled valve flow indicator
CN105828942A (en) * 2013-12-13 2016-08-03 沙特基础工业公司 Catalyst compositions for selective dimerization of ethylene
CN105980053A (en) * 2014-02-06 2016-09-28 沙特基础工业全球技术有限公司 Modifying organoaluminum co-catalysts for improved performance
CN105233868A (en) * 2014-07-04 2016-01-13 Ifp新能源公司 Catalytic composition and process for the dimerisation of ethylene to 1-butene
CN104119463A (en) * 2014-07-16 2014-10-29 任丘市利和科技发展有限公司 Catalyst component for vinyl polymerization and preparation method and application of catalyst component
CN105562087A (en) * 2014-10-11 2016-05-11 中国石油化工股份有限公司 Catalyst composition for ethylene oligomerization and application thereof

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