CN111408411B - Catalyst composition, preparation method thereof and application thereof in reaction of synthesizing 1-butene by ethylene selective dimerization - Google Patents

Catalyst composition, preparation method thereof and application thereof in reaction of synthesizing 1-butene by ethylene selective dimerization Download PDF

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CN111408411B
CN111408411B CN201910010180.4A CN201910010180A CN111408411B CN 111408411 B CN111408411 B CN 111408411B CN 201910010180 A CN201910010180 A CN 201910010180A CN 111408411 B CN111408411 B CN 111408411B
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compound
catalyst composition
phosphine
aluminum
ether
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CN111408411A (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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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • B01J35/19—
    • 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
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0204—Ethers
    • 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
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
    • B01J31/0212—Alkoxylates
    • 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
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0257—Phosphorus acids or phosphorus acid esters
    • B01J31/0259—Phosphorus acids or phosphorus acid esters comprising phosphorous acid (-ester) groups ((RO)P(OR')2) or the isomeric phosphonic acid (-ester) groups (R(R'O)2P=O), i.e. R= C, R'= C, H
    • 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
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
    • 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
    • C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
    • 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 aluminum compound and a lewis base additive; wherein the Lewis base type additive comprises an ether compound and a phosphine compound. The invention also relates to a preparation method of the catalyst composition, which comprises the step of mixing a titanium compound, an aluminum compound, an ether compound and a phosphine 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 not only can obtain higher 1-butene selectivity and polyethylene content which tends to 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 of synthesizing 1-butene by ethylene selective dimerization
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 a reaction of synthesizing 1-butene by ethylene selective dimerization.
Background
The catalytic systems reported so far for the selective dimerization of ethylene to 1-butene include catalytic systems based on vanadium, iron or cobalt, tungsten, tantalum, nickel, titanium. Among these systems, titanium-based catalytic systems are most preferred. In patent US 2943125 to ziegler et al a process for dimerizing ethylene to 1-butene using a catalyst obtained by mixing a trialkylaluminum with zirconium tetraalkoxide is disclosed. 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 ethylene dimerization in the presence of titanium tetraalkoxide-trialkyl aluminum in a hydrocarbon solvent of the catalytic system, followed by distillation of the dimerization reactant, the presence of a compound selected from the group consisting of: monohydric and dihydric alcohols, aliphatic and cyclic ethers, aliphatic ketones, carboxamides. The catalyst used in the method is expensive, and the selectivity of butene-1 in the produced product is low and only 70 percent, and contains a large amount of butene-2.
Thus, there is a need for a catalyst composition having high activity and selectivity and a low polyethylene content in the product when used in the reaction for synthesizing 1-butene by the selective dimerization of ethylene, a method for preparing the same, and application thereof in the reaction for synthesizing 1-butene by the selective dimerization of ethylene.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a catalyst composition, a preparation method thereof and application thereof in the reaction of synthesizing 1-butene by ethylene selective dimerization 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 a phosphine compound is used as a lewis base type additive, it is possible to minimize the generation of polyethylene to below a threshold of detection limit while also greatly improving the ethylene dimerization activity and the C4 content in the product, without preparing a pre-prepared mixture with an aluminum compound, i.e., using a catalyst composition prepared in situ from components including a titanium compound, an aluminum compound and a lewis base type additive, for the reaction of ethylene selective dimerization to 1-butene.
To this end, a first aspect of the present invention provides a catalyst composition comprising a titanium compound, an aluminum compound and a lewis base additive; wherein the Lewis base type additive comprises an ether compound and a phosphine 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, di (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, di (2-methoxyethyl) ether, glyme and diglyme.
In other embodiments, the phosphine compound is selected from the group consisting of quilt C 1 -C 6 Alkyl, C of (2) 3 -C 6 Cycloalkyl or C of (C) 6 -C 12 Aryl substituted or unsubstituted phosphines, phosphine oxides, orthophosphates, phosphites and phosphinites.
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 is selected from one or more of triphenyl phosphite, triisopropyl phosphine phosphite, tributyl phosphine phosphite and tricyclohexyl phosphine phosphite. The orthophosphoric acid ester is selected from one or more of triphenyl phosphate, triisopropyl phosphine phosphate, tributyl phosphine phosphate and tricyclohexyl phosphine phosphate. The phosphinate is selected from one or more of triphenyl hypophosphite, triisopropyl phosphinate, tributyl phosphinate and tricyclohexyl phosphinate.
In some embodiments, the molar ratio of the ether compound to the phosphine compound is (0.05-20): 1, preferably (0.2-10): 1.
The inventor of the invention researches and discovers that when a mixture of ether compounds and phosphine compounds is used as a Lewis base additive for synthesizing 1-butene by ethylene selective dimerization, a synergistic effect exists between the two compounds, so that the catalyst activity and the C4 content in a product are higher, and meanwhile, the polyethylene content 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-chain or branched alkanes or C 6 -C 30 Aryl of (a); preferably the heteroatom is 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 groups in the hydrocarbylaluminum compound are 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 hydrocarbylaluminum compound is triethylaluminum.
In some embodiments, the ratio of the moles of the Lewis base type additive to the 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 is (1-100): 1, preferably (1-30): 1, more preferably (1-10): 1, calculated as aluminum to titanium.
In a second aspect, the present invention provides a method of preparing a catalyst composition according to the first aspect of the present invention, comprising mixing a titanium compound, an aluminum compound, an ether compound, and a phosphine compound to form a catalyst composition.
In some embodiments, the ether compound and the phosphine compound are added separately as a single component, or the ether compound and the phosphine compound are mixed in advance and then added.
The method adopts titanium compound, aluminum compound and Lewis base type additive containing ether compound and phosphine compound to prepare catalyst composition by in situ mixing, and the in situ preparation of catalyst composition has the advantages that: is beneficial to the generation of catalyst active species; the method is beneficial to reducing steps of synthesizing the catalyst and reducing the synthesis cost; is favorable for the smooth initiation of the reaction.
In some specific 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, C 3 -C 7 Naphthenes and C of (C) 6 -C 20 One or more of the aromatic hydrocarbons of (a).
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 invention or a method of preparing a catalyst composition according to the second aspect of the invention in a reaction for the selective dimerization of ethylene to 1-butene.
In some embodiments, the dimerization reaction temperature is 20 to 180 ℃, preferably 40 to 140 ℃. The total pressure of the dimerization reaction is 0.5 to 20MPa, preferably 0.5 to 15MPa, more preferably 1 to 10MPa. The dimerization reaction time is 10-120min, preferably 30-60min.
In the present invention, it is preferable to carry out the ethylene dimerization reaction at a lower total pressure, not only making the controllability of the dimerization reaction stronger, but also ensuring a lower polyethylene PE content in the dimerization reaction product.
Compared with the prior art, the invention has the following beneficial effects:
when the mixture of the ether compound and the phosphine compound is used as the Lewis base additive, the catalyst composition prepared on the premise that the pre-prepared mixture is not required to be prepared with the aluminum compound, namely the catalyst composition prepared by in-situ mixing of the components comprising the titanium compound, the aluminum compound and the Lewis base additive is used for the reaction of synthesizing the 1-butene by selectively dimerization of ethylene, the generation of polyethylene can be minimized to be lower than a threshold value of a detection limit, and simultaneously, the dimerization activity of ethylene and the C4 content in a product are greatly improved. In addition, 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 invention may be more readily understood, the invention will be described in detail below with reference to the following examples, which are given by way of illustration only and are not limiting of the scope of application of the invention.
The test method or the calculation method provided by the invention is as follows:
the ethylene dimerization products are subjected to qualitative analysis by gas chromatography and mass spectrometry, and the peaks of the products are qualitative. The samples taken daily were quantitatively analyzed by gas chromatography. The gas chromatograph is Agilent 7890A, SE-54 type chromatographic column with column length of 30m and inner diameter of 0.2mm, and the carrier gas is high purity nitrogen, and is FID detector. The temperature program of the chromatograph is: the initial temperature was 40℃for 3 minutes, then at 30℃per minute to 50℃for 1 minute, and then at 40℃per minute to 280℃for 15 minutes.
(1) The method for calculating the catalyst activity (unit g/gTi.h):
(Note: the molar mass of titanium was 48 g/mol)
(2) Calculation method of C4 content (%) and 1-butene selectivity (%):
(3) The PE content was measured by filtering the reaction solution, drying, and weighing.
Examples
Example 1
Dimerization was carried out in a 300mL effective volume jacketed stainless steel reactor equipped with mechanically driven paddles, the temperature of which was regulated by water circulation. 50mL of n-heptane, 5mL of an n-heptane solution of titanium tetrabutoxide compound having a concentration of 0.085mol/L, 7mL of AlEt having a concentration of 0.238mol/L were mixed under an ethylene atmosphere and at ambient temperature 3 (1 mL of AlEt having a density of 0.84 g/mL) 3 Dissolved in 30mL of n-heptane) and a mixture of 0.39g of 1, 4-dioxane (4.44 mmol) and 1.16g of triphenylphosphine (4.44 mmol) were added to the reaction vessel and ethylene dimerization 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. The liquid phase in the reaction vessel is then weighed, and the polymer (if present) is recovered, dried and weighed. The specific reaction conditions and the 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 containing 4The amount of olefins of carbon atoms in the total product. % C 4 ＝1 Represented 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 procedure of example 1 was followed except that 3.3mL of an n-heptane solution of 0.085mol/L of titanium tetrabutoxide compound was added so that the Al/Ti molar ratio was 6. The specific reaction conditions and the results obtained are shown in Table 1.
Example 3
The same as in example 1 was conducted except that 3.3mL of an n-heptane solution of 0.085mol/L of titanium tetrabutoxide compound was added so that the Al/Ti molar ratio was 6, while controlling the reaction time to be 60 minutes. The specific reaction conditions and the results obtained are shown in Table 1.
Example 4
The same as in example 1 was conducted except that 3.3mL of an n-heptane solution of 0.085mol/L of titanium tetrabutoxide compound was added so that the Al/Ti molar ratio was 6, while controlling the reaction time to 120 minutes. The specific reaction conditions and the results obtained are shown in Table 1.
Example 5
The same as in example 1 was conducted except that 3.3mL of an n-heptane solution of 0.085mol/L of a 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 0.39g of triphenylphosphine (1.48 mmol) were added so that the molar ratio of 1, 4-dioxane to triphenylphosphine was 5:1, while controlling the reaction time to 60 minutes. The specific reaction conditions and the results obtained are shown in Table 1.
Example 6
As in example 1, 3.3mL of an n-heptane solution of 0.085mol/L 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 1.94g of triphenylphosphine (7.4 mmol) were added so that the molar ratio of 1, 4-dioxane to triphenylphosphine was 0.2:1, while controlling the reaction time to 60min. The specific reaction conditions and the results obtained are shown in Table 1.
Example 7
The same as in example 1 was conducted except that 3.3mL of an n-heptane solution of 0.085mol/L of a titanium tetrabutoxide compound was added so that the Al/Ti molar ratio was 6, and 0.73g of 1, 4-dioxane (8.325 mmol) and 0.15g of triphenylphosphine (0.555 mmol) were added so that the molar ratio of 1, 4-dioxane to triphenylphosphine was 15:1, while controlling the reaction time to 60 minutes. The specific reaction conditions and the results obtained are shown in Table 1.
Example 8
The same as in example 1 was conducted except that 0.66mL of an n-heptane solution of 0.085mol/L of titanium tetrabutoxide compound was added so that the Al/Ti molar ratio was 30. The specific reaction conditions and the results obtained are shown in Table 1.
Example 9
The same as in example 1 was conducted except that "a mixture of 0.39g of 1, 4-dioxane (4.44 mmol) and 1.16g of triphenylphosphine (4.44 mmol)" in example 1 was replaced with "a mixture of 0.32g of tetrahydrofuran (4.44 mmol) and 1.38g of triphenyl phosphite (4.44 mmol)". The specific reaction conditions and the results obtained are shown in Table 1.
Comparative example 1
The difference from example 1 is that only 1, 4-dioxane was used as the Lewis base type additive and that the amount of 1, 4-dioxane added was 8.88mmol. The specific reaction conditions and the results obtained are shown in Table 1.
Comparative example 2
The difference from example 1 is that triphenylphosphine alone is used as the Lewis base type additive and that triphenylphosphine is added in an amount of 8.88mmol. The specific reaction conditions and the results obtained are shown in Table 1.
Comparative example 3
Under inert atmosphere, 7mL of AlEt with concentration of 0.238mol/L is dissolved 3 (1 mL of AlEt having a density of 0.84 g/mL) 3 Dissolved in 30mL of n-heptane) was introduced into the Schlenk flask. Then 0.78g of 1, 4-dioxane (8.88 mmol) was added to the above Schlenk flask, and the solution was stirred under a nitrogen atmosphere at room temperature for about 1 hour to form a Lewis base type additive and AlEt 3 Is a mixture of the above components.
Dimerization was carried out in a 300mL effective volume jacketed stainless steel reactor equipped with mechanically driven paddles, the temperature of which was regulated by water circulation. 50mL of n-heptane was run under an ethylene atmosphere at ambient temperatureAnd 5mL of a 0.085mol/L n-heptane solution of titanium tetrabutoxide compound were added to the reaction vessel. Once the reactor temperature reaches 55deg.C, the desired amounts of Lewis base type additive and AlEt are introduced under ethylene pressure 3 Is a mixture of the above components. The ethylene pressure was maintained at 10MPa and the temperature was maintained at 55 ℃. After 30min of reaction, the ethylene feed was stopped and a sample was taken and analyzed by gas chromatography. The liquid phase in the reaction vessel is then weighed, and the polymer (if present) is recovered, dried and weighed. The specific reaction conditions and the results obtained are shown in Table 1.
Comparative example 4
Under inert atmosphere, 7mL of AlEt with concentration of 0.238mol/L is dissolved 3 (1 mL of AlEt having a density of 0.84 g/mL) 3 Dissolved in 30mL of n-heptane) was introduced into the Schlenk flask. 2.33g of triphenylphosphine (8.88 mmol) was then added to the Schlenk flask described above and the solution was stirred under nitrogen at ambient temperature for about 1 hour to form a Lewis base additive and AlEt 3 Is a mixture of the above components.
Dimerization was carried out in a 300mL effective volume jacketed stainless steel reactor equipped with mechanically driven paddles, the temperature of which was regulated by water circulation. 50mL of n-heptane and 5mL of a 0.085mol/L n-heptane solution of titanium tetrabutoxide compound were added to the reaction vessel under an ethylene atmosphere and at ambient temperature. Once the reactor temperature reaches 55deg.C, the desired amounts of Lewis base type additive and AlEt are introduced under ethylene pressure 3 Is a mixture of the above components. The ethylene pressure was maintained at 10MPa and the temperature was maintained at 55 ℃. After 30min of reaction, the ethylene feed was stopped and a sample was taken and analyzed by gas chromatography. The liquid phase in the reaction vessel is then weighed, and the polymer (if present) is recovered, dried and weighed. The specific reaction conditions and the results obtained are shown in Table 1.
As can be seen from table 1, when the catalyst composition of the present invention comprising the lewis base additive of ether compound and phosphine compound is used for the reaction of ethylene selective dimerization to 1-butene, the catalyst activity and the C4 content in the product are both high while ensuring that the production of polyethylene is minimized below the threshold of the detection limit, compared to the catalyst composition using the single ether compound or the single phosphine compound as the lewis base additive. In addition, compared with the prior art, the method omits the step of premixing the aluminum compound and the Lewis base additive, is more beneficial to the generation of the active species of the catalyst and the smooth initiation of the reaction, further improves the activity of the catalyst and achieves better effect.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.

Claims (19)

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 phosphine compound; the ether compound is selected from monoethers and/or polyether;
the phosphine compound is selected from quilt C 1 -C 6 Alkyl, C of (2) 3 -C 6 Cycloalkyl or C of (C) 6 -C 12 Aryl substituted or unsubstituted phosphines, phosphine oxides, orthophosphates, phosphites and phosphinites;
the molar ratio of the ether compound to the phosphine compound is (1-5): 1;
the titanium compound is a compound shown in a 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-chain or branched alkanes or C 6 -C 30 Aryl of (a);
the aluminum compound is selected from alkyl aluminum compounds and/or aluminoxane compounds;
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 (1-6) 1 in terms of aluminum to titanium;
the preparation method of the catalyst composition comprises the following steps: which comprises mixing a titanium compound, an aluminum compound, an ether compound and a phosphine compound to form a catalyst composition.
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, di (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, di (2-methoxyethyl) ether, glyme and diglyme.
3. The catalyst composition of claim 2, wherein the phosphine is selected from one or more of triisopropylphosphine, tributylphosphine, tricyclohexylphosphine, triphenylphosphine, tris (o-tolyl) phosphine, and bis (diphenylphosphino) ethane; the phosphine oxide is selected from trioctylphosphine oxide and/or triphenylphosphine oxide; the phosphite is selected from one or more of triphenyl phosphite, triisopropyl phosphine phosphite, tributyl phosphine phosphite and tricyclohexyl phosphine phosphite; the orthophosphoric acid ester is selected from one or more of triphenyl phosphate, triisopropyl phosphine phosphate, tributyl phosphine phosphate and tricyclohexyl phosphine phosphate; the phosphinate is selected from one or more of triphenyl hypophosphite, triisopropyl phosphinate, tributyl phosphinate and tricyclohexyl phosphinate.
4. A catalyst composition according to claim 3, wherein the heteroatom is selected from one or more of nitrogen, phosphorus, sulphur and oxygen atoms.
5. The catalyst composition according to claim 4, wherein in the general formula (I), R is one or more 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, 2, 6-dibromo-4-tert-butylphenyl, biphenyl, binaphthyl and 1, 8-naphthalene-diyl.
6. The catalyst composition of any of claims 1-5, wherein the hydrocarbyl group in the hydrocarbylaluminum compound is substituted with a halogen.
7. The catalyst composition of claim 6 wherein the halogen is selected from chlorine or bromine.
8. The catalyst composition of claim 7 wherein the hydrocarbylaluminum compound is a trihydrocarbylaluminum compound.
9. The catalyst composition of claim 8 wherein the hydrocarbylaluminum compound is triethylaluminum.
10. The catalyst composition of claim 9 wherein the ratio of the moles of lewis base additive to the moles of aluminum in the aluminum compound is from (0.5 to 5.3): 1.
11. The catalyst composition of claim 10 wherein the ratio of the moles of lewis base additive to the moles of aluminum in the aluminum compound is (1-5): 1.
12. The catalyst composition according to claim 11, wherein the ether compound and the phosphine compound are added separately as a single component, or the ether compound and the phosphine compound are added after being mixed in advance; any one of the titanium compound and the aluminum compound is used as a mixture with a hydrocarbon solvent.
13. The catalyst composition of claim 12 wherein the volume ratio of hydrocarbon solvent to titanium compound in the mixture is (1-100): 1.
14. The catalyst composition of claim 13 wherein the volume ratio of hydrocarbon solvent to the titanium compound in the mixture is (10-75): 1.
15. The catalyst composition of claim 14 wherein the hydrocarbon solvent is selected from the group consisting of C substituted or unsubstituted with halogen 1 -C 7 Alkane, C 3 -C 7 Naphthenes and C of (C) 6 -C 20 One or more of the aromatic hydrocarbons of (a).
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 the catalyst composition according to any one of claims 1-16 in a reaction for the selective dimerization of ethylene to 1-butene, wherein the dimerization reaction has a temperature of 20-180 ℃; the total pressure of the dimerization reaction is 0.5-20MPa; the dimerization reaction time is 10-120min.
18. The use according to claim 17, wherein the dimerization reaction 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. The use according to claim 18, wherein the total pressure of the dimerization reaction is between 1 and 10MPa.
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