CN111408412B - 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

Info

Publication number
CN111408412B
CN111408412B CN201910014408.7A CN201910014408A CN111408412B CN 111408412 B CN111408412 B CN 111408412B CN 201910014408 A CN201910014408 A CN 201910014408A CN 111408412 B CN111408412 B CN 111408412B
Authority
CN
China
Prior art keywords
compound
catalyst composition
ether
titanium
sulfur
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910014408.7A
Other languages
Chinese (zh)
Other versions
CN111408412A (en
Inventor
郑明芳
张海英
王怀杰
刘珺
项迎春
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to CN201910014408.7A priority Critical patent/CN111408412B/en
Publication of CN111408412A publication Critical patent/CN111408412A/en
Application granted granted Critical
Publication of CN111408412B publication Critical patent/CN111408412B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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 sulfur 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 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 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 sulfur 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 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, 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 sulfur-based compound is selected from a substituted or unsubstituted linear sulfide, branched sulfide, or cyclic sulfide.
Preferably, the sulfur compound is selected from substituted or unsubstituted thiophenes. More preferably, the sulfur compound is selected from the group consisting of C 1 -C 6 Alkyl or C of (2) 1 -C 6 Alkoxy-substituted thiophenes of (a).
In some specific embodiments, the sulfur compound is selected from one or more of diethyl sulfide, dimethyl disulfide, tetrahydrothiophene, 2-methoxythiophene, 3-methoxythiophene, 2-ethoxythiophene, 3-ethoxythiophene, 2-propoxythiophene, 3-propoxythiophene, 2-butoxythiophene, 3-butoxythiophene, 2-pentoxy thiophene, 3-pentoxy thiophene, 2-hexoxy thiophene, 3-hexoxy thiophene, 2-methyl thiophene, 3-methyl thiophene, 2-ethyl thiophene, 3-ethyl thiophene, 2-propyl thiophene, 3-propyl thiophene, 2-butyl thiophene, 3-butyl thiophene, 2-pentyl thiophene, 3-pentyl thiophene, 2-hexyl thiophene, and 3-hexyl thiophene.
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 present invention has found that when a mixture of ether compounds and sulfur compounds is used as a lewis base additive for the selective dimerization of ethylene to synthesize 1-butene, a synergistic effect exists between the two compounds, so that the catalyst activity and the C4 content in the product are higher, and 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 process for preparing a 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 a 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 mixed in advance and then added.
The method adopts titanium compound, aluminum compound and Lewis base type additive containing ether compound and sulfur 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 sulfur 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 in advance, namely the catalyst composition prepared by in-situ mixing of all 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 the polyethylene can be minimized to be lower than a threshold value of a detection limit, and simultaneously, the dimerization activity of the ethylene and the content of C4 in a product are greatly improved. 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):
Figure SMS_1
(Note: the molar mass of titanium was 48 g/mol)
(2) Calculation method of C4 content (%) and 1-butene selectivity (%):
Figure SMS_2
/>
Figure SMS_3
(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 0.51g of 2-methoxythiophene (4.44 mmol) were charged into a reaction vessel, and ethylene was dimerized to 1-butene at 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 the amount of olefins having 4 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 0.17g of 2-methoxythiophene (1.48 mmol) were added so that the molar ratio of 1, 4-dioxane to 2-methoxythiophene 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 a titanium tetrabutoxide compound at 0.085mol/L was added so that the Al/Ti molar ratio was 6, and 0.13g of 1, 4-dioxane (1.48 mmol) and 0.85g of 2-methoxythiophene (7.4 mmol) were added so that the molar ratio of 1, 4-dioxane to 2-methoxythiophene was 0.2:1, while controlling the reaction time to 60 minutes. 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 0.063g of 2-methoxythiophene (0.555 mmol) were added so that the molar ratio of 1, 4-dioxane to 2-methoxythiophene 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 repeated except that "0.39g of 1, 4-dioxane (4.44 mmol) and 0.51g of 2-methoxythiophene (4.44 mmol)" in example 1 was replaced with "0.32g of tetrahydrofuran (4.44 mmol) and 0.44g of 2-methylthiophene (4.44 mmol)" in combination. 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 only 2-methoxythiophene is used as the Lewis base type additive and that the amount of 2-methoxythiophene added is 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 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 55 ℃, the desired amount of route is introduced under ethylene pressureEasy-to-use alkali type additive and AlEt 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. 1.01g of 2-methoxythiophene (8.88 mmol) was further charged into 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 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.
Figure SMS_4
As can be seen from table 1, when the catalyst composition of the present invention comprising the lewis base additive of ether compound and sulfur 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 sulfur 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 (24)

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; the ether compound is selected from monoethers and/or polyether; the sulfur compound is selected from substituted or unsubstituted thiophene;
the molar ratio of the aluminum compound to the titanium compound is calculated as aluminum: titanium meter (1-30): 1, a step of;
the molar ratio of the ether compound to the sulfur compound is (0.2-10): 1, a step of;
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.
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 1 wherein the sulfur compound is selected from the group consisting of a sulfur compound and a sulfur compound 1 -C 6 Alkyl or C of (2) 1 -C 6 Alkoxy-substituted thiophenes of (a).
4. The catalyst composition according to any one of claims 1 to 3, wherein the titanium compound is a compound represented by 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-chain or branched alkanes or C 6 -C 30 Aryl groups of (a).
5. The catalyst composition of claim 4 wherein the heteroatom is selected from one or more of nitrogen, phosphorus, sulfur and oxygen atoms.
6. 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.
7. A catalyst composition according to any of claims 1-3, characterized in that the aluminium compound is selected from hydrocarbylaluminum compounds and/or alumoxane compounds; optionally, the hydrocarbyl groups in the hydrocarbylaluminum compound are substituted with halogen.
8. The catalyst composition of claim 7 wherein the halogen is selected from chlorine or bromine.
9. The catalyst composition of claim 7 wherein the hydrocarbylaluminum compound is a trihydrocarbylaluminum compound.
10. The catalyst composition of claim 7 wherein the hydrocarbylaluminum compound is triethylaluminum.
11. A catalyst composition according to any of claims 1 to 3, 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 (1-5): 1.
12. A catalyst composition according to any of claims 1-3, characterized in that the molar ratio of the aluminium compound to the titanium compound is in aluminium: the titanium meter is (1-10): 1.
13. A method of preparing the catalyst composition of any one of claims 1-12, comprising mixing a titanium compound, an aluminum compound, an ether compound, and a sulfur compound to form the catalyst composition.
14. The production method according to claim 13, wherein the ether compound and the sulfur compound are added separately as a single component, or the ether compound and the sulfur compound are mixed in advance and then added.
15. The production method according to claim 13, wherein any one of the titanium compound and the aluminum compound is used as a mixture with a hydrocarbon solvent.
16. The process according to claim 13, wherein the volume ratio of hydrocarbon solvent to titanium compound in the mixture is (1-100): 1.
17. The process according to claim 16, wherein the volume ratio of hydrocarbon solvent to titanium compound in the mixture is (10-75): 1.
18. The process according to claim 16, 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).
19. The process of claim 18, wherein the hydrocarbon solvent is selected from one or more of n-butane, isobutane, n-hexane, n-heptane, cyclohexane, benzene, toluene, o-xylene, mesitylene, and ethylbenzene.
20. Use of the catalyst composition according to any one of claims 1-12 or the method of preparing the catalyst composition according to any one of claims 13-19 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.
21. The use according to claim 20, wherein the dimerization reaction temperature is 40-140 ℃.
22. The use according to claim 20, wherein the total pressure of the dimerization reaction is 0.5-15MPa.
23. The use according to claim 20, wherein the total pressure of the dimerization reaction is between 1 and 10MPa.
24. The use according to claim 20, wherein the dimerization reaction takes from 30 to 60 minutes.
CN201910014408.7A 2019-01-04 2019-01-04 Catalyst composition, preparation method thereof and application thereof in reaction of synthesizing 1-butene by ethylene selective dimerization Active CN111408412B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910014408.7A CN111408412B (en) 2019-01-04 2019-01-04 Catalyst composition, preparation method thereof and application thereof in reaction of synthesizing 1-butene by ethylene selective dimerization

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910014408.7A CN111408412B (en) 2019-01-04 2019-01-04 Catalyst composition, preparation method thereof and application thereof in reaction of synthesizing 1-butene by ethylene selective dimerization

Publications (2)

Publication Number Publication Date
CN111408412A CN111408412A (en) 2020-07-14
CN111408412B true CN111408412B (en) 2023-05-09

Family

ID=71487519

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910014408.7A Active CN111408412B (en) 2019-01-04 2019-01-04 Catalyst composition, preparation method thereof and application thereof in reaction of synthesizing 1-butene by ethylene selective dimerization

Country Status (1)

Country Link
CN (1) CN111408412B (en)

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3652705A (en) * 1968-10-03 1972-03-28 Mitsui Petrochemical Ind Process for the oligomerization of ethylene
US3962130A (en) * 1973-08-30 1976-06-08 Exxon Research And Engineering Company Butadiene polymerization catalyst
NO750225L (en) * 1974-02-12 1975-08-13 Ici Ltd
US4422956A (en) * 1982-05-14 1983-12-27 Standard Oil Company (Indiana) Activation of complexed reduced titanium halide olefin polymerization catalyst with haloalkylchlorosilanes
US7534842B2 (en) * 2005-11-16 2009-05-19 Chevron Phillips Chemical Company, Lp Catalysts for olefin polymerization
WO2008085657A1 (en) * 2007-01-08 2008-07-17 Exxonmobil Chemical Patents Inc. Chromium complexes of pyridine bis (oxazoline)- ligands for ethylene dimeri zation
FR2937262B1 (en) * 2008-10-17 2010-11-05 Inst Francais Du Petrole PROCESS FOR THE PREPARATION OF A CATALYTIC COMPOSITION FOR DIMERISATION, CO-DIMERIZATION AND OLIGOMERIZATION OF OLEFINS
FR2960234B1 (en) * 2010-05-18 2013-11-01 Inst Francais Du Petrole A METHOD FOR DIMERIZING ETHYLENE TO BUTENE-1 USING A COMPOSITION COMPRISING A TITANIUM-BASED COMPLEX AND A HETEROATOMY-FUNCTIONALIZED ALCOXY LIGAND
FR3008697B1 (en) * 2013-07-19 2015-07-31 IFP Energies Nouvelles METHOD FOR SELECTIVELY DIMERIZING ETHYLENE TO BUTENE-1 USING A CATALYTIC COMPOSITION COMPRISING AN ADDITIVE TITANIUM COMPLEX IN ASSOCIATION WITH A HETERO-ATOMIC FUNCTIONALIZED ALCOXY LIGAND
FR3023183A1 (en) * 2014-07-04 2016-01-08 IFP Energies Nouvelles CATALYTIC COMPOSITION AND METHOD FOR SELECTIVE DIMERIZATION OF ETHYLENE TO BUTENE-1
FR3023285B1 (en) * 2014-07-04 2017-10-27 Ifp Energies Now IMPROVED METHOD FOR SELECTIVE DIMERIZATION OF ETHYLENE TO BUTENE-1

Also Published As

Publication number Publication date
CN111408412A (en) 2020-07-14

Similar Documents

Publication Publication Date Title
US9499455B2 (en) Process for the selective dimerisation of ethylene to 1-butene
FR3023183A1 (en) CATALYTIC COMPOSITION AND METHOD FOR SELECTIVE DIMERIZATION OF ETHYLENE TO BUTENE-1
EP2388069A1 (en) Method for dimerisation of ethylene into butene-1 using a composition including a titanium complex and an alcoxy ligand functionalised by a heteroatom
TWI434733B (en) Catalyst composition and process for preparing linear alpha-olefins
CN102451758A (en) Catalyst for ethylene tetramerization and preparation and application thereof
CN111408412B (en) Catalyst composition, preparation method thereof and application thereof in reaction of synthesizing 1-butene by ethylene selective dimerization
CN111408407B (en) Catalyst composition, preparation method thereof and application thereof in reaction of synthesizing 1-butene by ethylene selective dimerization
CN111408403B (en) Catalyst composition, preparation method thereof and application thereof in reaction for synthesizing 1-butene through selective dimerization of ethylene
CN111408408B (en) Catalyst composition, preparation method thereof and application thereof in reaction for synthesizing 1-butene through selective dimerization of ethylene
CN111408411B (en) Catalyst composition, preparation method thereof and application thereof in reaction of synthesizing 1-butene by ethylene selective dimerization
CN111408406A (en) Catalyst composition, preparation method thereof and application thereof in reaction for synthesizing 1-butene through selective dimerization of ethylene
CN103100419B (en) Mixed decene oligomerization catalyst
CN111408404B (en) Catalyst composition, preparation method thereof and application thereof in reaction for synthesizing 1-butene through selective dimerization of ethylene
US20060129010A1 (en) Method for selective hydrogenation of polyunsaturated compounds into monounsaturated compounds using a homogeneous catalyst
CN111408410B (en) Catalyst composition, preparation method thereof and application thereof in reaction for synthesizing 1-butene through selective dimerization of ethylene
Gomes et al. First examples of neutral and cationic indenyl nickel (II) complexes bearing arsine or stibine ligands: highly active catalysts for the oligomerisation of styrene
CN111408409B (en) Catalyst composition, preparation method thereof and application thereof in reaction for synthesizing 1-butene through selective dimerization of ethylene
RU2818194C1 (en) CATALYST COMPOSITION FOR POLYMERIZATION OF α-OLEFINS, PREPARATION AND USE THEREOF
US20230374169A1 (en) CATALYST COMPOSITION FOR POLYMERIZATION OF a-OLEFIN AND PREPARATION AND USE THEREOF
CN106927988B (en) Preparation method of decene
CN111408405B (en) Catalyst composition, preparation method thereof and application thereof in reaction for synthesizing 1-butene through selective dimerization of ethylene
WO2019105844A1 (en) New catalytic composition based on nickel and a phosphonium, and use thereof for the oligomerisation of olefins
RU2423371C2 (en) Method of producing 1-ethyl-2,3-dialkyl(phenyl)aluminacyclopent-2-enes
JP2023076813A (en) PROCESS AND CATALYST COMPOSITION FOR PRODUCING LINEAR α-OLEFINS IN HIGH YIELD BY ETHYLENE OLIGOMERIZATION
KR100403090B1 (en) A process for preparation of high 1,4-cis polybutadiene

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant