CN112517080B - Ethylene selective tetramerization catalyst composition and application thereof - Google Patents
Ethylene selective tetramerization catalyst composition and application thereof Download PDFInfo
- Publication number
- CN112517080B CN112517080B CN202011555873.0A CN202011555873A CN112517080B CN 112517080 B CN112517080 B CN 112517080B CN 202011555873 A CN202011555873 A CN 202011555873A CN 112517080 B CN112517080 B CN 112517080B
- Authority
- CN
- China
- Prior art keywords
- ethylene
- molecular sieve
- tantalum
- mass
- reaction
- 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
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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
-
- 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
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
-
- 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
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
-
- 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
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
- B01J2531/58—Tantalum
-
- 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)
- Inorganic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides an ethylene selective tetramerization catalyst composition and application thereof, wherein the ethylene selective oligomerization catalyst composition comprises a modified molecular sieve, a PNP ligand and a cocatalyst; the catalyst claimed by the invention uses a novel metal center, can effectively form a bimetallic center in the catalytic process, improves the selectivity of 1-octene, and can effectively inhibit the generation of polyethylene byproducts. The catalyst has the advantages of high catalyst activity, easy separation from products, high selectivity of 1-octene in the products, less polyethylene byproducts and the like when catalyzing ethylene oligomerization.
Description
Technical Field
The invention belongs to the technical field of catalyst materials, and particularly relates to an ethylene selective tetramerization catalyst composition and application thereof.
Background
1-octene is used as an important organic monomer, has wide application in the aspects of synthesizing high polymer, high-performance lubricating oil and detergent, and takes synthetic polyethylene as an example, and linear low-density polyethylene (LLDPE) synthesized by taking 1-octene as a comonomer can obviously improve the mechanical property, optical property, shock resistance, elasticity and the like. The polyolefin elastomer (POE) prepared by copolymerizing 1-octene and ethylene has excellent mechanical property, rheological property and ultraviolet light resistance. In addition, 1-octene can be used for synthesizing plasticizers, fatty acids, detergents, lubricating oil additives, etc.
However, the 1-octene used in the industry today is still prepared by non-selective oligomerization of ethylene, and the alpha-olefins produced by such processes are C 4 -C 20 The product is in accordance with Schulz-Flory distribution, so that continuous rectification is required at the end of the process to obtain pure 1-octene, which consumes a great deal of energy. Ethylene selective oligomerization is a process for preparing alpha olefins contrary to non-selective oligomerization, and the process selectively generates one to two alpha olefins, and at present, the preparation of 1-butene by ethylene dimerization and the preparation of 1-hexene by trimerization have all been industrialized. Wherein independent processes are developed by Phillips company, amoco company and Japanese light-emitting company, and the process is successfully popularized worldwide, wherein the selectivity of 1-hexene in the processes of Phillips company and Amoco company is generally higher than 90%, and the purity is also higher than 92%. However, no commercial process for the selective oligomerization of ethylene for the production of 1-octene has been truly successful so far.
There are a number of patents on selective tetramerization of ethylene. As in patent CN102040624B, CN102451759B, CN103100420A, CN105268480B, CN105498840B, CN105562095B, CN105562101B, CN105562102B, CN105562103B, CN105566037B, CN107282128B of the China petrochemical application, CN 103285926A of China petroleum, US10539517, US10538088, US11629533, US11993396 and the like of CN 110801864A, sasol of Michael company all disclose the use of chromium compounds/ligands/auxiliary catalyst systems for ethylene selective oligomerization, and the selectivity of 1-octene in the product can be greater than 70%.
Previous studies [ chem. Eur. J. 2010, 16, 7670-7676] have indicated that the production of alpha-olefins such as 1-octene and 1-decene may follow a bimetallic-centered mechanism different from 1-hexene oligomerization (a single metal-catalyzed mechanism).
At present, the global capacity of 2.1 million tons/year of alpha olefins is formed, but most processes are ethylene nonselective oligomerization, and the products are mainly C 4 -C 20 And thus a large amount of energy is consumed to obtain high purity alpha olefins. The ethylene selective oligomerization effectively solves the problem due to the high selectivity of the product, but most of the reactions are homogeneous catalytic reactions, the catalyst is difficult to recover and the catalyst is difficult to separate when mixed in the product, so that the production cost is increased. In addition, a small amount of polyethylene byproducts are accumulated, so that pipelines and control valves in a reaction system are easy to be blocked, and the accumulated polyethylene byproducts become a main reason for influencing the long-time operation of a catalytic system.
At present, the catalyst for ethylene selective oligomerization mainly uses chromium as a metal center. A small number of patents disclose ethylene selective oligomerization catalyst loading technology, for example, patent CN106492880B filed by Tianjin university of technology takes molecular sieve as carrier, and metal chromium and catalyst prepared after the reaction thereof are activated by cocatalyst to catalyze ethylene selective oligomerization, and C in the product 6 +C 8 Selectivity is greater than 60%; patent CN109865533A takes metal oxide as a carrier, and metal chromium and a catalyst prepared after the metal chromium acts on the catalyst are activated by a cocatalyst to catalyze ethylene to selectively oligomerize, and C in a product 8 The selectivity is greater than 40%. As is evident from the above patents, the chromium metal catalyst after the channels and collaterals has improved stability, but the 1-octene selectivity is lower than about 70% reported by the homogeneous catalyst.
Disclosure of Invention
Based on the problems of the above-mentioned patents, the present invention aims to (1) impregnate tantalum compound and molecular sieve under proper conditions, and after high temperature roasting, make tantalum and molecular sieve form chemical bond, so as to greatly reduce elution rate of tantalum metal; (2) Selecting a proper loading technology to enable tantalum to form a catalyst system with a bimetallic active center with a ligand, an auxiliary agent and the like in a molecular sieve pore canal to prepare 1-octene; (3) The generation of polyethylene byproducts is inhibited by utilizing the nano pore canal limiting effect of the molecular sieve, which is beneficial to long-time continuous operation of the reaction.
In order to solve the technical problems, the invention discloses an ethylene selective oligomerization catalyst composition and application thereof, and the catalyst claimed by the invention uses a novel metal center which can effectively form a bimetallic center in the catalytic process to improve the selectivity of 1-octene and can effectively inhibit the generation of polyethylene byproducts. The catalyst has the advantages of high catalyst activity, easy separation from products, high selectivity of 1-octene in the products, less polyethylene byproducts and the like when catalyzing ethylene oligomerization.
The invention discloses a catalyst and a preparation technology thereof, wherein the catalyst comprises a carrier, a metal compound, a ligand and an auxiliary agent.
A method for preparing an ethylene selective tetramerization catalyst composition, comprising the following steps:
(1) An ethylene selective oligomerization catalyst composition comprising a modified molecular sieve, a PNP ligand, and a cocatalyst; the modified molecular sieve is prepared by immersing the activated molecular sieve in tantalum solution, centrifuging, drying and roasting to obtain a molecular sieve loaded with tantalum;
(2) Synthesis of PNP (bis (diarylphosphino) -amine) ligand: the PNP ligand is synthesized by reference (A. Bollmann, K. Blann, J.T. Dixon, et al, J. Am. chem. Soc.126 (2004) 14712-14713).
The molecular sieve is any one of MCM-41, Y, ZSM-5, ZSM-11, beta and SAPO-11;
the tantalum solution is prepared from absolute ethyl alcohol, and the concentration of tantalum in the impregnating solution is 0.01-0.5 mol/L;
the loading amount of the metal tantalum on the molecular sieve is 0.5-wt% -10 wt%;
the solute used by the tantalum solution is tantalum pentachloride;
the dipping temperature is 30-80 ℃;
the catalyst is matched with an aluminum alkyl cocatalyst for use;
the molecular sieve is preferably an MCM-41 molecular sieve;
the concentration of the ion exchange tantalum solution is preferably 0.2-0.5 mol/L;
the metal tantalum loading on the molecular sieve is preferably 3-8 wt%;
the dipping temperature is preferably 50-70 ℃;
the cocatalyst is an alkyl aluminum cocatalyst, in particular one of methyl aluminoxane, modified aluminum methyl aluminoxane, pumped-dry methyl aluminoxane, triethyl aluminum and trimethyl aluminum;
the molar ratio of the aluminum alkyl cocatalyst to the metal in the catalyst is 100:1-500:1.
The application (using method) of the ethylene selective oligomerization catalyst composition in ethylene oligomerization reaction comprises the following steps:
(1) Before the reaction, the reaction kettle body and the lining are placed in an oven for drying overnight at 120 ℃, are connected to an evaluation system consisting of the reaction kettle and a vacuum system, are sealed, are heated to 100 ℃ under the condition of vacuum pumping and are kept at the constant temperature for 1h (a tail gas valve is closed), and residual water, oxygen and oxygen-containing impurities are removed. Then the temperature is set as the reaction temperature (30-80 ℃), the temperature is naturally reduced, nitrogen is filled, and then the vacuum pumping is carried out for three times, so that the air is ensured to be replaced completely. Then pumping nitrogen by a vacuum pump, filling with ethylene, repeating for three times, and ensuring that the kettle body is full of ethylene.
(2) Opening an exhaust valve, sequentially injecting cyclohexane solvent and a certain amount of cocatalyst by using an injector under the stirring condition, after the temperature is stabilized to the reaction temperature, injecting a tantalum-loaded molecular sieve and PNP ligand by using the injector, closing the exhaust valve, adjusting a pressure reducing valve, starting timing after the pressure is increased to a preset pressure value, recording mass flowmeter data and the mass of the molecular sieve and PNP ligand, closing ethylene gas after the molar ratio of the aluminum alkyl auxiliary agent to the metal tantalum in the catalyst is 100:1-500:1 and 0.5-4h, recording the mass flowmeter data, stopping the reaction, closing an air inlet valve, removing the reaction kettle body, and soaking in an ice water bath to cool the reaction kettle to below 10 ℃.
(3) After the tail gas valve is opened for pressure relief, a certain amount of 10% HCl/ethanol solution is injected under stirring, so that the aluminum alkyl cocatalyst is quenched, and then nonane with fixed mass is injected as an internal standard. After the reaction vessel was opened, a small amount of the organic phase was cooled in a refrigerator for 30min, and the product was analyzed by GC-FID. Since the nonane mass has been determined, the mass of the remaining components, as well as the selectivity and activity, can be calculated from the GC results. Filtering the residual sample, weighing filter paper in advance to record the quality, scraping the polymer on a stirring paddle by a spoon, cleaning the polymer into a beaker by a solvent, drying the obtained polymer in a vacuum oven at 60 ℃ overnight, weighing the polymer respectively, and calculating to obtain the pure quality.
And (3) the preset pressure value in the step (2) is 1.0-6.0 MPa.
The invention has the advantages that:
(1) The first time through molecular sieve and metal tantalum load and PNP ligand are used for ethylene selective oligomerization reaction;
(2) The selectivity of 1-octene in the product is high;
(3) The polyethylene content in the product is very low.
Ring forming mechanism: the chromium metal center reacts with ethylene molecules to form 9-membered rings, and then 1-octene is released. In addition, the homogeneous catalyst can reduce the loss of metal center after being loaded on the molecular sieve, and the limit domain effect of the molecular sieve can reduce the generation of polymer. Trivalent chromium becomes positive divalent after reacting with the ligand, and the remaining two electron orbitals act exactly as orbitals of the cyclization mechanism. However, in the process of acting with the molecular sieve, the molecular sieve framework is electronegative, and is easy to act with electron empty orbitals of metal chromium to influence the cyclization mechanism. The tantalum with positive pentavalent has enough electron empty orbit, is less sensitive to electron donor than trivalent chromium, and can keep the activity for a long time.
Detailed Description
The following examples are provided to illustrate the above features and advantages of the present invention. The method of the invention is a conventional method in the art unless specifically stated otherwise.
Synthesis of ligand:
the ligand synthesis is completed in a glove box, 80mL of anhydrous and anaerobic dichloromethane is added into a 250mL three-neck flask which is dried overnight, 36mmol of diphenyl phosphine chloride (7.943 g,6.46 mL) is added dropwise by a syringe under magnetic stirring, a needle is washed by 20mL of dichloromethane, the temperature is reduced to 0 ℃ after uniform stirring, 133mmol of triethylamine (3.64 g,5.00 mL) is added, 18mmol of isopropylamine (1.064 g,1.54 mL) is added dropwise into the system under 0 ℃ after uniform stirring, stirring is continued for 30min after removing an ice water bath, white triethylamine hydrochloride crystals are removed by filtration, the solution is recrystallized after concentration, and PNP ligand is obtained by filtration and drying.
Example 1:
(1) Modification of molecular sieves:
the three-neck flask with the reflux condenser is placed in a constant temperature magnetic stirrer, 16.1195g of tantalum pentachloride and 150mL of absolute ethyl alcohol (the concentration of tantalum solution is 0.3 mol/L) are added, 8.63g of activated MCM-41 molecular sieve is added after stirring and dissolution, after 12 h of reflux at 60 ℃, stirring is stopped, and cooling to room temperature is carried out. Centrifuging, separating, drying, and roasting the obtained sample for 4 hours in a nitrogen atmosphere at 450 ℃ to obtain a product. The tantalum loading on the molecular sieve was measured to be 6.23wt% using an ICP spectrometer.
(2) Evaluation of the reaction:
ethylene oligomerization was carried out in a 300mL autoclave. Before the reaction, the reaction kettle body and the lining are placed in an oven for drying at 120 ℃ overnight, are connected to an evaluation system, are sealed, are heated to 100 ℃ under the condition of vacuum pumping and are kept at constant temperature for 1h (a tail gas valve is closed), and residual water, oxygen and oxygen-containing impurities are removed. Then the temperature is set to 60 ℃ to naturally cool, nitrogen is filled, and then vacuum pumping is carried out, and the process is repeated three times, so that the air is ensured to be replaced completely. Then pumping nitrogen by a vacuum pump, filling with ethylene, repeating for three times, and ensuring that the kettle body is full of ethylene. The gas release valve was opened, 80mL of cyclohexane solvent and 2.25mmol of methylaluminoxane (methylaluminoxane is a toluene solution of 1.5mol/L, 1.5mL of the solution) were sequentially injected under stirring, after the temperature had stabilized to 60 ℃, the modified molecular sieve was dispersed in 10mL of cyclohexane, after the ultrasonic homogenization, the suspension was injected into the reaction vessel with the injector, and then the injector was washed with 10mL of cyclohexane to ensure that all the modified molecular sieve had been injected into the reactor. Then injecting the ligand solution into the reaction kettle, closing an exhaust valve, adjusting a pressure reducing valve, starting timing after the pressure is increased to 5.0MPa, recording mass flowmeter data, 0.0145g of molecular sieve and 0.0026g of ligand after tantalum loading, closing ethylene gas after the molar ratio of ligand to cocatalyst to tantalum is 240:450:1 for 1.0h, recording mass flowmeter data, stopping the reaction, closing an air inlet valve, removing the reaction kettle body, and soaking in an ice water bath to cool the reaction kettle to below 10 ℃. After opening the off-gas valve and depressurizing, 5ml of 10% hcl/ethanol solution was injected under stirring to quench the methylaluminoxane, followed by injection of a fixed mass of nonane as an internal standard. After the reaction vessel was opened, a small amount of the organic phase was cooled in a refrigerator for 30min, and the product was analyzed by GC-FID. Since the nonane mass has been determined, the mass of the remaining components, as well as the selectivity and activity, can be calculated from the GC results. The remaining samples were filtered, the filter paper weighed in advance and the mass was recorded, then the polymer on the stirring paddle was scraped off with a spoon, washed with solvent into a beaker, all the polymer was dried overnight in a vacuum oven at 60 ℃, weighed separately and calculated to obtain pure mass.
Example 2:
(1) Modification of molecular sieves:
the three-neck flask with reflux condenser is placed in a constant temperature magnetic stirrer, 10.7463g of tantalum pentachloride and 150mL of absolute ethyl alcohol (the concentration of tantalum solution is 0.2 mol/L) are added, 5.75g of activated NAY molecular sieve is added after stirring and dissolution, after 12 h of reflux is carried out at 50 ℃, stirring is stopped, and cooling to room temperature is carried out. Centrifuging, separating, drying, and roasting the obtained sample for 4 hours in a nitrogen atmosphere at 450 ℃ to obtain a product. The loading of tantalum on the molecular sieve was measured to be 4.31wt% using an ICP spectrometer.
(2) Evaluation of the reaction:
ethylene oligomerization was carried out in a 300mL autoclave. Before the reaction, the reaction kettle body and the lining are placed in an oven for drying at 120 ℃ overnight, are connected to an evaluation system, are sealed, are heated to 100 ℃ under the condition of vacuum pumping and are kept at constant temperature for 1h (a tail gas valve is closed), and residual water, oxygen and oxygen-containing impurities are removed. Then the temperature is set to be 50 ℃, the temperature is naturally reduced, nitrogen is filled, and then the vacuum is pumped for three times, so that the air is ensured to be replaced completely. Then pumping nitrogen by a vacuum pump, filling with ethylene, repeating for three times, and ensuring that the kettle body is full of ethylene. The gas release valve was opened, 80mL of cyclohexane solvent and 1.75mmol of methylaluminoxane (methylaluminoxane is a toluene solution of 1.5mol/L, 1.17mL of the solution) were sequentially injected under stirring, after the temperature had stabilized to 50 ℃, the modified molecular sieve was dispersed in 10mL of cyclohexane, after the homogenization, the suspension was injected into the reaction vessel by means of the injector, and then the injector was washed by means of 10mL of cyclohexane, thereby ensuring that all the modified molecular sieve had been injected into the reactor. Then injecting the ligand solution into a reaction kettle, closing an exhaust valve, adjusting a pressure reducing valve, starting timing after the pressure is increased to 4.0MPa, recording mass flowmeter data, 0.0210g of molecular sieve and 0.0026g of ligand after tantalum is loaded, closing ethylene gas after the molar ratio of ligand to cocatalyst to tantalum is 240:350:1 for 1.0h, recording mass flowmeter data, stopping the reaction, closing an air inlet valve, removing the reaction kettle body, and soaking in an ice water bath to cool the reaction kettle to below 10 ℃. After opening the off-gas valve and depressurizing, 5ml of 10% hcl/ethanol solution was injected under stirring to quench the methylaluminoxane, followed by injection of a fixed mass of nonane as an internal standard. After the reaction vessel was opened, a small amount of the organic phase was cooled in a refrigerator for 30min, and the product was analyzed by GC-FID. Since the nonane mass has been determined, the mass of the remaining components, as well as the selectivity and activity, can be calculated from the GC results. The remaining samples were filtered, the filter paper weighed in advance and the mass was recorded, then the polymer on the stirring paddle was scraped off with a spoon, washed with solvent into a beaker, all the polymer was dried overnight in a vacuum oven at 60 ℃, weighed separately and calculated to obtain pure mass.
Example 3:
(1) Modification of molecular sieves:
the three-neck flask with the reflux condenser is placed in a constant temperature magnetic stirrer, 13.4329g of tantalum pentachloride and 150mL of absolute ethyl alcohol (the concentration of tantalum solution is 0.25 mol/L) are added, 10.44g of activated ZSM-5 molecular sieve is added after stirring and dissolution, after 12 h of reflux is carried out at 30 ℃, stirring is stopped, and cooling to room temperature is carried out. Centrifuging, separating, drying, and roasting the obtained sample for 4 hours in a nitrogen atmosphere at 450 ℃ to obtain a product. The loading of tantalum on the molecular sieve was measured to be 3.25wt% using an ICP spectrometer.
(2) Evaluation of the reaction:
ethylene oligomerization was carried out in a 300mL autoclave. Before the reaction, the reaction kettle body and the lining are placed in an oven for drying at 120 ℃ overnight, are connected to an evaluation system, are sealed, are heated to 100 ℃ under the condition of vacuum pumping and are kept at constant temperature for 1h (a tail gas valve is closed), and residual water, oxygen and oxygen-containing impurities are removed. Then the temperature is set to 80 ℃ to naturally cool, nitrogen is filled, and then vacuum pumping is carried out, and the process is repeated three times, so that the air is ensured to be replaced completely. Then pumping nitrogen by a vacuum pump, filling with ethylene, repeating for three times, and ensuring that the kettle body is full of ethylene. The gas release valve was opened, 80mL of cyclohexane solvent and 1.5mmol of triethylaluminum (triethylaluminum is a 1.0mol/L cyclohexane solution, 1.5mL of the solution) were sequentially injected under stirring, after the temperature had stabilized to 80 ℃, the modified molecular sieve was dispersed in 10mL of cyclohexane, after the ultrasonic homogenization, the suspension was injected into the reaction vessel with the injector, and then the injector was washed with 10mL of cyclohexane to ensure that all the modified molecular sieve had been injected into the reactor. Then injecting the ligand solution into a reaction kettle, closing an exhaust valve, adjusting a pressure reducing valve, starting timing after the pressure is increased to 1.0MPa, recording mass flowmeter data, 0.0278g of molecular sieve and 0.0026g of ligand after tantalum loading, closing ethylene gas after the molar ratio of ligand to cocatalyst to tantalum is 240:300:1 and 0.5h, recording mass flowmeter data, stopping the reaction, closing an air inlet valve, removing the reaction kettle body, and soaking in an ice water bath to cool the reaction kettle to below 10 ℃. After opening the off-gas valve and depressurizing, 5ml of 10% hcl/ethanol solution was injected under stirring to quench the triethylaluminum, followed by injection of a fixed mass of nonane as an internal standard. After the reaction vessel was opened, a small amount of the organic phase was cooled in a refrigerator for 30min, and the product was analyzed by GC-FID. Since the nonane mass has been determined, the mass of the remaining components, as well as the selectivity and activity, can be calculated from the GC results. The remaining samples were filtered, the filter paper weighed in advance and the mass was recorded, then the polymer on the stirring paddle was scraped off with a spoon, washed with solvent into a beaker, all the polymer was dried overnight in a vacuum oven at 60 ℃, weighed separately and calculated to obtain pure mass.
Example 4:
(1) Modification of molecular sieves:
the three-neck flask with the reflux condenser is placed in a constant temperature magnetic stirrer, 0.5373g of tantalum pentachloride and 150mL of absolute ethyl alcohol (the concentration of tantalum solution is 0.01 mol/L) are added, 6.90g of activated SAPO-11 molecular sieve is added after stirring and dissolution, after 12 h of reflux is carried out at 80 ℃, stirring is stopped, and cooling to room temperature is carried out. Centrifuging, separating, drying, and roasting the obtained sample for 4 hours in a nitrogen atmosphere at 450 ℃ to obtain a product. The loading of tantalum on the molecular sieve was measured to be 2.32wt% using an ICP spectrometer.
(2) Evaluation of the reaction:
ethylene oligomerization was carried out in a 300mL autoclave. Before the reaction, the reaction kettle body and the lining are placed in an oven for drying at 120 ℃ overnight, are connected to an evaluation system, are sealed, are heated to 100 ℃ under the condition of vacuum pumping and are kept at constant temperature for 1h (a tail gas valve is closed), and residual water, oxygen and oxygen-containing impurities are removed. Then the temperature is set to 30 ℃, the temperature is naturally reduced, nitrogen is filled, and then the vacuum is pumped for three times, so that the air is ensured to be replaced completely. Then pumping nitrogen by a vacuum pump, filling with ethylene, repeating for three times, and ensuring that the kettle body is full of ethylene. The gas release valve was opened, 80mL of cyclohexane solvent and 2mmol of modified methylaluminoxane (1.5 mol/L of modified methylaluminoxane in toluene solution was obtained by taking 1.33mL of the solution) were sequentially injected under stirring by using an injector, after the temperature had stabilized to 30 ℃, the modified molecular sieve was dispersed in 10mL of cyclohexane, after the ultrasonic homogenization, the suspension was injected into the reaction vessel by using the injector, and then the injector was washed by using 10mL of cyclohexane, thereby ensuring that all the modified molecular sieve had been injected into the reactor. Then injecting the ligand solution into the reaction kettle, closing an exhaust valve, adjusting a pressure reducing valve, starting timing after the pressure is increased to 6.0MPa, recording the data of a mass flowmeter, 0.0390g of a molecular sieve loaded by tantalum and 0.0026g of ligand, closing ethylene gas after the molar ratio of the ligand to the cocatalyst to the tantalum is 240:400:1 for 4.0h, recording the data of the mass flowmeter, stopping the reaction, closing an air inlet valve, removing the reaction kettle body, and soaking in an ice water bath to cool the reaction kettle to below 10 ℃. After opening the tail gas valve and depressurizing, 5ml of 10% HCl/ethanol solution is injected under stirring to quench the modified methylaluminoxane, and then nonane with fixed mass is injected as an internal standard. After the reaction vessel was opened, a small amount of the organic phase was cooled in a refrigerator for 30min, and the product was analyzed by GC-FID. Since the nonane mass has been determined, the mass of the remaining components, as well as the selectivity and activity, can be calculated from the GC results. The remaining samples were filtered, the filter paper was weighed in advance to record the mass, then the polymer on the stirring paddle was scraped off with a spoon, washed with solvent into a beaker, all the polymer was dried overnight in a vacuum oven at 60 ℃, weighed separately, and calculated to obtain pure mass.
Example 5:
(1) Modification of molecular sieves:
the three-neck flask with the reflux condenser is placed in a constant temperature magnetic stirrer, 1.0746g of tantalum pentachloride and 150mL of absolute ethyl alcohol (the concentration of tantalum solution is 0.02 mol/L) are added, 1.3g of activated Beta molecular sieve is added after stirring and dissolution, after 12 h of reflux at 40 ℃, stirring is stopped, and cooling to room temperature is carried out. Centrifuging, separating, drying, and roasting the obtained sample for 4 hours in a nitrogen atmosphere at 450 ℃ to obtain a product. The loading of tantalum on the molecular sieve was 1.35wt% as measured using an ICP spectrometer.
(2) Evaluation of the reaction:
ethylene oligomerization was carried out in a 300mL autoclave. Before the reaction, the reaction kettle body and the lining are placed in an oven for drying at 120 ℃ overnight, are connected to an evaluation system, are sealed, are heated to 100 ℃ under the condition of vacuum pumping and are kept at constant temperature for 1h (a tail gas valve is closed), and residual water, oxygen and oxygen-containing impurities are removed. Then the temperature is set to 45 ℃ to naturally cool, nitrogen is filled, and then vacuum pumping is carried out, and the process is repeated for three times, so that the air is ensured to be replaced completely. Then pumping nitrogen by a vacuum pump, filling with ethylene, repeating for three times, and ensuring that the kettle body is full of ethylene. The gas release valve was opened, 80mL of cyclohexane solvent and 2.5mmol of a pumped methylaluminoxane (1.5 mol/L toluene solution of methylaluminoxane was pumped) were sequentially injected under stirring, after the temperature had stabilized to 45℃and after the modified molecular sieve was dispersed in 10mL of cyclohexane, the suspension was injected into the reaction vessel with the syringe after ultrasonic homogenization, and then the syringe was washed with 10mL of cyclohexane to ensure that all the modified molecular sieve had been injected into the reactor. Then injecting the ligand solution into a reaction kettle, closing an exhaust valve, adjusting a pressure reducing valve, starting timing after the pressure is increased to 3.0MPa, recording mass flowmeter data, 0.0670g of molecular sieve loaded by tantalum and 0.0026g of ligand, closing ethylene gas after the molar ratio of ligand to cocatalyst to tantalum is 240:500:1 and 0.8h, recording mass flowmeter data, stopping the reaction, closing an air inlet valve, removing the reaction kettle body, and soaking in an ice water bath to cool the reaction kettle to below 10 ℃. After opening the tail gas valve and depressurizing, 5ml of 10% HCl/ethanol solution was injected under stirring to quench the pumped methylaluminoxane, and then a fixed mass of nonane was injected as an internal standard. After the reaction vessel was opened, a small amount of the organic phase was cooled in a refrigerator for 30min, and the product was analyzed by GC-FID. Since the nonane mass has been determined, the mass of the remaining components, as well as the selectivity and activity, can be calculated from the GC results. The remaining samples were filtered, the filter paper weighed in advance and the mass was recorded, then the polymer on the stirring paddle was scraped off with a spoon, washed with solvent into a beaker, all the polymer was dried overnight in a vacuum oven at 60 ℃, weighed separately and calculated to obtain pure mass.
Example 6:
(1) Modification of molecular sieves:
the three-neck flask with the reflux condenser is placed in a constant temperature magnetic stirrer, 26.8658g of tantalum pentachloride and 150mL of absolute ethyl alcohol (the concentration of tantalum solution is 0.5 mol/L) are added, 14.38g of activated ZSM-11 molecular sieve is added after stirring and dissolution, after 12 h of reflux at 80 ℃, stirring is stopped, and cooling to room temperature is carried out. Centrifuging, separating, drying, and roasting the obtained sample for 4 hours in a nitrogen atmosphere at 450 ℃ to obtain a product. The tantalum loading on the molecular sieve was measured to be 9.25wt% using an ICP spectrometer.
(2) Evaluation of the reaction:
ethylene oligomerization was carried out in a 300mL autoclave. Before the reaction, the reaction kettle body and the lining are placed in an oven for drying at 120 ℃ overnight, are connected to an evaluation system, are sealed, are heated to 100 ℃ under the condition of vacuum pumping and are kept at constant temperature for 1h (a tail gas valve is closed), and residual water, oxygen and oxygen-containing impurities are removed. Then the temperature is set as the reaction temperature, so that the reaction temperature is naturally reduced, nitrogen is filled, and then the vacuum pumping is carried out for three times, so that the air is ensured to be replaced completely. Then pumping nitrogen by a vacuum pump, filling with ethylene, repeating for three times, and ensuring that the kettle body is full of ethylene. The gas release valve was opened, 80mL of cyclohexane solvent and 0.5mmol of trimethylaluminum (trimethylaluminum is a toluene solution of 2mol/L, 0.25mL of the solution) were sequentially injected under stirring, after the temperature had stabilized to 60 ℃, the modified molecular sieve was dispersed in 10mL of cyclohexane, after the ultrasonic homogenization, the suspension was injected into the reaction vessel with the injector, and then the injector was washed with 10mL of cyclohexane to ensure that all the modified molecular sieve had been injected into the reactor. Then injecting the ligand solution into a reaction kettle, closing an exhaust valve, adjusting a pressure reducing valve, starting timing after the pressure is increased to 2.0MPa, recording mass flowmeter data, 0.0098g of molecular sieve and 0.0026g of ligand after tantalum loading, closing ethylene gas after the molar ratio of ligand to cocatalyst to tantalum is 240:100:1 and 0.5h, recording mass flowmeter data, stopping the reaction, closing an air inlet valve, removing the reaction kettle body, and soaking in an ice water bath to cool the reaction kettle to below 10 ℃. After opening the off-gas valve and depressurizing, 5ml of 10% hcl/ethanol solution was injected under stirring to quench the trimethylaluminum, followed by injection of nonane of fixed mass as an internal standard. After the reaction vessel was opened, a small amount of the organic phase was cooled in a refrigerator for 30min, and the product was analyzed by GC-FID. Since the nonane mass has been determined, the mass of the remaining components, as well as the selectivity and activity, can be calculated from the GC results. The remaining samples were filtered, the filter paper was weighed in advance to record the mass, then the polymer on the stirring paddle was scraped off with a spoon, washed with solvent into a beaker, all the polymer was dried overnight in a vacuum oven at 60 ℃, weighed separately, and calculated to obtain pure mass.
The ethylene oligomerization activity and product distribution of the examples of the present invention.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (6)
1. An ethylene selective tetramerisation catalyst composition, characterised in that the composition comprises a modified molecular sieve, a PNP ligand and a cocatalyst; the modified molecular sieve is prepared by immersing the activated molecular sieve in tantalum solution, centrifuging, drying and roasting to obtain a molecular sieve loaded with tantalum;
the molecular sieve is any one of MCM-41, Y, ZSM-5, ZSM-11, beta and SAPO-11;
the loading amount of the metal tantalum on the molecular sieve is 0.5-wt% -10 wt%;
the cocatalyst is an alkyl aluminum cocatalyst, and comprises one of methyl aluminoxane, modified methyl aluminoxane, pumped methyl aluminoxane, triethyl aluminum and trimethyl aluminum;
the molar ratio of the aluminum alkyl cocatalyst to the metal tantalum in the catalyst is 100:1-500:1.
2. The ethylene selective tetramerisation catalyst composition according to claim 1, characterized in that: the tantalum solution is prepared from absolute ethyl alcohol, and the concentration of tantalum in the impregnating solution is 0.01-0.5 mol/L.
3. The ethylene selective tetramerisation catalyst composition according to claim 1, characterized in that: the solute used in the tantalum solution is tantalum pentachloride.
4. The ethylene selective tetramerisation catalyst composition according to claim 1, characterized in that: the dipping temperature is 30-80 ℃.
5. Use of the ethylene selective tetramerisation catalyst composition according to claim 1 in ethylene oligomerization reactions, characterized in that: the specific method comprises the following steps:
(1) Before the reaction, firstly placing the reaction kettle body and the lining in an oven at 120 ℃ for drying overnight, connecting the reaction kettle body and the lining to an evaluation system, sealing, closing an exhaust valve, heating to 100 ℃ under the vacuumizing condition, keeping the temperature for 1h, removing residual water, oxygen and oxygen-containing impurities, setting the temperature to be 30-80 ℃ for naturally cooling the reaction kettle body and the lining, simultaneously filling nitrogen, vacuumizing the reaction kettle body and the lining for three times, ensuring that air is replaced completely, pumping nitrogen by a vacuum pump, filling the nitrogen by ethylene, repeating the steps for three times, and ensuring that the kettle body is full of ethylene;
(2) Opening an exhaust valve, sequentially injecting cyclohexane solvent and a certain amount of cocatalyst by using an injector under the stirring condition, after the temperature is stabilized to the reaction temperature, injecting a tantalum-loaded molecular sieve and PNP ligand by using the injector, closing the exhaust valve, adjusting a pressure reducing valve, starting timing after the pressure is increased to a preset pressure value, recording mass flowmeter data and the mass of the molecular sieve and PNP ligand, closing ethylene gas after 0.5-4h, recording mass flowmeter data, stopping the reaction, closing an air inlet valve, unloading a reaction kettle body, and soaking in an ice water bath to cool the reaction kettle to below 10 ℃;
(3) After the tail gas valve is opened and depressurized, a certain amount of 10% HCl/ethanol solution is injected under stirring condition to quench the cocatalyst, then nonane with fixed mass is injected as an internal standard, after the reaction kettle is opened, a small amount of organic phase is taken to cool in a refrigerator for 30min, the product is analyzed by GC-FID, the mass of the rest components, the selectivity and the activity can be calculated according to the GC result because the mass of the nonane is determined, the rest samples are filtered, the filter paper is used for weighing and recording the mass in advance, then the polymer on the stirring paddle is scraped off by a spoon, the solvent is used for cleaning the polymer into a beaker, the obtained polymer is placed in a vacuum oven for drying at 60 ℃ for overnight, and the pure mass is obtained through calculation.
6. The use of claim 5, wherein the predetermined pressure value in step (2) is 1.0mpa to 6.0mpa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011555873.0A CN112517080B (en) | 2020-12-25 | 2020-12-25 | Ethylene selective tetramerization catalyst composition and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011555873.0A CN112517080B (en) | 2020-12-25 | 2020-12-25 | Ethylene selective tetramerization catalyst composition and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112517080A CN112517080A (en) | 2021-03-19 |
| CN112517080B true CN112517080B (en) | 2023-06-23 |
Family
ID=74976340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011555873.0A Active CN112517080B (en) | 2020-12-25 | 2020-12-25 | Ethylene selective tetramerization catalyst composition and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112517080B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113880881B (en) * | 2021-10-20 | 2023-11-17 | 中化泉州石化有限公司 | Synthesis of rigid organic phosphine ligand and application of rigid organic phosphine ligand in ethylene oligomerization |
| CN113996343A (en) * | 2021-11-19 | 2022-02-01 | 中化泉州石化有限公司 | Catalyst composition for preparing 1-octene |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4371457A (en) * | 1980-10-29 | 1983-02-01 | Mobil Oil Corporation | Zeolites modified with group VA metals |
| CN101291733A (en) * | 2005-08-19 | 2008-10-22 | 切夫里昂菲利普化学有限责任公司 | Methods of preparation of an olefin oligomerization catalyst |
| CN101605605A (en) * | 2007-01-18 | 2009-12-16 | Sk能源株式会社 | Ethene four gathers catalyst systems and uses this catalyst system to prepare the method for 1-octene |
| CN105008313A (en) * | 2012-12-21 | 2015-10-28 | 诺瓦化学品(国际)股份有限公司 | Continuous ethylene tetramerization process |
| CN105418812A (en) * | 2015-11-19 | 2016-03-23 | 华东理工大学 | Supported vanadium alkene polymerization catalyst, preparation method and applications thereof |
| CN106492880A (en) * | 2016-09-20 | 2017-03-15 | 天津科技大学 | A kind of catalyst for ethylene oligomerization and preparation method thereof |
| CN106582851A (en) * | 2016-10-17 | 2017-04-26 | 天津科技大学 | Catalyst component for selective oligomerization of ethylene and catalyst thereof |
| CN109174191A (en) * | 2018-09-17 | 2019-01-11 | 天津科技大学 | A kind of catalyst of ethylene selectivity oligomerisation reaction |
| CN109475850A (en) * | 2016-05-24 | 2019-03-15 | 埃克森美孚化学专利公司 | Synthetic zeolite comprising catalytic metal |
| CN109865533A (en) * | 2017-12-05 | 2019-06-11 | 天津科技大学 | A kind of solid catalyst and preparation method thereof for ethylene oligomerization |
| CN111094308A (en) * | 2018-02-27 | 2020-05-01 | Sk新技术株式会社 | Ligand, oligomerization catalyst comprising the same, and method for preparing ethylene oligomer using the oligomerization catalyst |
| CN111841646A (en) * | 2019-04-24 | 2020-10-30 | 万华化学集团股份有限公司 | Ethylene oligomerization catalyst, preparation method and application thereof |
| CN111889142A (en) * | 2020-07-23 | 2020-11-06 | 天津科技大学 | Catalyst system for selective oligomerization of ethylene, reaction method and application thereof |
| CN112047808A (en) * | 2019-06-05 | 2020-12-08 | 中国石油化工股份有限公司 | Method for liquid-phase catalytic selective hydrogenation of crotonaldehyde |
| CN112264106A (en) * | 2020-11-20 | 2021-01-26 | 中化泉州石化有限公司 | Ethylene selective oligomerization catalyst composition and application thereof |
-
2020
- 2020-12-25 CN CN202011555873.0A patent/CN112517080B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4371457A (en) * | 1980-10-29 | 1983-02-01 | Mobil Oil Corporation | Zeolites modified with group VA metals |
| CN101291733A (en) * | 2005-08-19 | 2008-10-22 | 切夫里昂菲利普化学有限责任公司 | Methods of preparation of an olefin oligomerization catalyst |
| CN101605605A (en) * | 2007-01-18 | 2009-12-16 | Sk能源株式会社 | Ethene four gathers catalyst systems and uses this catalyst system to prepare the method for 1-octene |
| CN105008313A (en) * | 2012-12-21 | 2015-10-28 | 诺瓦化学品(国际)股份有限公司 | Continuous ethylene tetramerization process |
| CN105418812A (en) * | 2015-11-19 | 2016-03-23 | 华东理工大学 | Supported vanadium alkene polymerization catalyst, preparation method and applications thereof |
| CN109475850A (en) * | 2016-05-24 | 2019-03-15 | 埃克森美孚化学专利公司 | Synthetic zeolite comprising catalytic metal |
| CN106492880A (en) * | 2016-09-20 | 2017-03-15 | 天津科技大学 | A kind of catalyst for ethylene oligomerization and preparation method thereof |
| CN106582851A (en) * | 2016-10-17 | 2017-04-26 | 天津科技大学 | Catalyst component for selective oligomerization of ethylene and catalyst thereof |
| CN109865533A (en) * | 2017-12-05 | 2019-06-11 | 天津科技大学 | A kind of solid catalyst and preparation method thereof for ethylene oligomerization |
| CN111094308A (en) * | 2018-02-27 | 2020-05-01 | Sk新技术株式会社 | Ligand, oligomerization catalyst comprising the same, and method for preparing ethylene oligomer using the oligomerization catalyst |
| CN109174191A (en) * | 2018-09-17 | 2019-01-11 | 天津科技大学 | A kind of catalyst of ethylene selectivity oligomerisation reaction |
| CN111841646A (en) * | 2019-04-24 | 2020-10-30 | 万华化学集团股份有限公司 | Ethylene oligomerization catalyst, preparation method and application thereof |
| CN112047808A (en) * | 2019-06-05 | 2020-12-08 | 中国石油化工股份有限公司 | Method for liquid-phase catalytic selective hydrogenation of crotonaldehyde |
| CN111889142A (en) * | 2020-07-23 | 2020-11-06 | 天津科技大学 | Catalyst system for selective oligomerization of ethylene, reaction method and application thereof |
| CN112264106A (en) * | 2020-11-20 | 2021-01-26 | 中化泉州石化有限公司 | Ethylene selective oligomerization catalyst composition and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| "Microporous zeolite supported Cr(acac)3/PNP catalysts for ethylene tetramerization: Influence of supported patterns and confinement onreaction performance";Huaiqi Shao, et al.;《Journal of Molecular Catalysis A: Chemical》;20140330;第390卷;第152-158页 * |
| "乙烯选择性齐聚催化体系的研究进展";毛国梁等;《化工科技》;20151225;第23卷(第6期);第75-81页 * |
| 汪多仁等.《增塑剂配方工艺与应用实例》.《增塑剂配方工艺与应用实例》.北京：印刷工业出版社,2013,第5页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112517080A (en) | 2021-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112517080B (en) | Ethylene selective tetramerization catalyst composition and application thereof | |
| EP1299189B1 (en) | Olefin trimerisation using a catalyst comprising a source of chromium and a ligand containing phosphorous bound to organic groups | |
| US7829749B2 (en) | Tetramerization | |
| KR101719221B1 (en) | Method for oligomerization of ethylene | |
| JP5372327B2 (en) | Catalytic trimerization of olefin monomers | |
| EP2139906B2 (en) | Amino phosphine | |
| US20070185363A1 (en) | Transition metal catalysts | |
| CN112264106A (en) | Ethylene selective oligomerization catalyst composition and application thereof | |
| CN114789067B (en) | Ethylene selective oligomerization catalyst composition and preparation method thereof | |
| CN113880881B (en) | Synthesis of rigid organic phosphine ligand and application of rigid organic phosphine ligand in ethylene oligomerization | |
| CN111349115A (en) | PNNP structural ligand, preparation method thereof, ethylene oligomerization catalyst system and application thereof | |
| CN111349116A (en) | Bipyridine structure ligand, preparation method thereof, catalytic system based on bipyridine structure and application of catalytic system in ethylene oligomerization | |
| FR2942230A1 (en) | New metal complex useful in oligomerization and polymerization process of olefins, preferably ethylene, propylene or butene | |
| CN112920227B (en) | Indenoindole structure-containing metallocene compound, preparation method and application thereof, and preparation method of alpha-olefin | |
| CN114011469A (en) | Catalyst composition for ethylene oligomerization | |
| CN116917040A (en) | Catalyst system | |
| KR100493926B1 (en) | Catalytic Composition and Reaction Methods for Ethylene Oligomerization | |
| JP6647320B2 (en) | Olefin oligomerization method | |
| CN116713038A (en) | Ethylene selective tetramerization catalyst composition and preparation method thereof | |
| CN116174040A (en) | Ethylene trimerization catalyst composition and application thereof | |
| CN113004327B (en) | Ligand based on pyridine structure and preparation method thereof, supported catalyst based on pyridine structure, preparation method and application thereof | |
| EP3214087B1 (en) | Ligand compound, catalyst system for olefin oligomerization, and olefin oligomerization method using same | |
| CN117046522A (en) | Synthesis and application of ethylene selective oligomerization catalyst | |
| CN114933613A (en) | Preparation of PNNP ligand, ethylene oligomerization catalyst and application thereof | |
| CN115501913A (en) | Catalyst containing rigid structure compound and application thereof in ethylene oligomerization |
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 |