CN112517080A - Ethylene selective tetramerization catalyst composition and application thereof - Google Patents
Ethylene selective tetramerization catalyst composition and application thereof Download PDFInfo
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- CN112517080A CN112517080A CN202011555873.0A CN202011555873A CN112517080A CN 112517080 A CN112517080 A CN 112517080A CN 202011555873 A CN202011555873 A CN 202011555873A CN 112517080 A CN112517080 A CN 112517080A
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
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- 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
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The 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 which can effectively form a bimetal center in the catalysis process to improve the selectivity of 1-octene and can effectively inhibit the generation of polymer ethylene by-products. When the catalyst is used for catalyzing ethylene oligomerization, the catalyst has the advantages of high activity, easiness in separation from products, high selectivity of 1-octene in the products, few polyethylene byproducts and the like.
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 an important organic monomer, and has wide application in the synthesis of high polymer, high-performance lubricating oil and detergent, and taking synthetic polyethylene as an example, linear low-density polyethylene (LLDPE) synthesized by taking 1-octene as a comonomer can obviously improve the mechanical property, optical property, impact resistance, elasticity and the like of the LLDPE. 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 also be used for the synthesis of plasticizers, fatty acids, detergents, lubricant additives, and the like.
However, the 1-octene used in industry at present is still obtained by non-selective oligomerization of ethylene, the alpha olefin produced by this type of process being C4-C20The product of the mixture (A) meets the Schulz-Flory distribution, so that pure 1-octene can be obtained only by continuous rectification at the end of the process, and a large amount of energy is consumed. The selective oligomerization of ethylene is a process for preparing alpha olefin, which is opposite to non-selective oligomerization, and the process selectively generates one to two kinds of alpha olefin, and the prior art realizes the industrialization of ethylene dimerization to prepare 1-butene and trimerization to prepare 1-hexene. Independent processes are developed by Phillips, Amoco and Japan light extraction company respectively and successfully popularized in the world, wherein the selectivity of 1-hexene in the processes of Phillips and Amoco is generally higher than 90%, and the purity of the 1-hexene is also higher than 92%. However, no truly successful commercial process for the selective oligomerization of ethylene to produce 1-octene is currently available.
There are a number of patents on the selective tetramerisation of ethylene. For example, patents CN102040624B, CN102451759B, CN103100420A, CN105268480B, CN105498840B, CN105562095B, CN105562101B, CN105562102B, CN105562103B, CN105566037B and CN107282128B of China petrochemical application, CN 103285926A of China petroleum, US10539517, US10538088, US11629533 and US11993396 of CN 110801864A, Sasol of Michelle and the like all disclose that the selectivity of 1-octene in the product can be more than 70 percent.
Previous studies [ chem. eur. j. 2010, 16, 7670-.
At present, the production capacity of 2.1 million tons/year alpha olefin is formed globally, but most of the process is non-selective oligomerization of ethylene, and the product is mainly C4-C20And 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 the reaction is mostly homogeneous catalysis reaction, the catalyst is difficult to recover, and the catalyst is difficult to separate when being mixed in the product, thereby increasing the production cost. In addition, a small amount of polyethylene byproducts are accumulated to easily block pipelines and control valves in a reaction system, so that the accumulation of the polyethylene byproducts becomes a main reason for influencing the long-time operation of a catalytic system.
Current catalysts for selective oligomerization of ethylene have chromium as the metal center. A few patents disclose the technology of loading selective oligomerization catalyst for ethylene, for example, patent CN106492880B applied by Tianjin university of science and technology uses molecular sieve as carrier, metal chromium reacts with the catalyst prepared by the action of the molecular sieve to catalyze the selective oligomerization of ethylene after the catalyst is activated by cocatalyst, and C in the product6+C8The selectivity is more than 60 percent; patent CN109865533A uses metal oxide as carrier, metal chromium and catalyst prepared by the action of metal chromium are activated by cocatalyst to catalyze ethylene to selectively oligomerize, C in the product8The selectivity is greater than 40%. It is known from the above patent that the synthesized chromium metal catalyst has improved stability, but the selectivity of 1-octene is lower than about 70% reported for the homogeneous catalyst.
Disclosure of Invention
Based on the problems of the patents mentioned above, the present invention aims to (1) utilize tantalum compound and molecular sieve to perform impregnation under proper conditions, and after high temperature roasting, tantalum and molecular sieve form chemical bonds, thereby greatly reducing the elution rate of metallic tantalum; (2) selecting proper loading technology to enable tantalum to form a catalyst system with bimetallic active centers together with ligands, auxiliaries and the like in molecular sieve pore channels to prepare 1-octene; (3) the nano-pore confinement effect of the molecular sieve is utilized to inhibit the generation of polyethylene byproducts, thereby being beneficial to the 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. When the catalyst is used for catalyzing ethylene oligomerization, the catalyst has the advantages of high activity, easiness in separation from products, high selectivity of 1-octene in the products, few polyethylene byproducts and the like.
The catalyst and the preparation technology thereof comprise a carrier, a metal compound, a ligand and an auxiliary agent.
A preparation method of an ethylene selective tetramerization catalyst composition comprises the following steps:
(1) the ethylene selective oligomerization catalyst 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 a tantalum solution, centrifuging, drying and roasting to obtain a tantalum-loaded molecular sieve;
(2) synthesis of PNP (bis (diarylphosphino) -amine) ligand: the PNP ligand was synthesized by reference (A. Bollmann, K. Blann, J.T. Dixon, et al, J. Am. chem. Soc. 126 (2004) 14712-.
The molecular sieve is any one of MCM-41, Y, ZSM-5, ZSM-11, Beta and SAPO-11;
the solvent selected by the tantalum solution is absolute ethyl alcohol, and the concentration of the tantalum in the dipping solution is 0.01-0.5 mol/L;
the loading amount of the metal tantalum on the molecular sieve is 0.5-10 wt%;
the solute used by the tantalum solution is tantalum pentachloride;
the dipping temperature is 30-80 ℃;
the catalyst is matched with an alkyl aluminum 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 preferable load capacity of the metal tantalum on the molecular sieve is 3-8 wt%;
the dipping temperature is preferably 50-70 ℃;
the cocatalyst is an alkyl aluminum cocatalyst, and specifically is one of methylaluminoxane, modified aluminum methyl siloxane, drained methylaluminoxane, triethylaluminum and trimethylaluminum;
the molar ratio of the alkyl aluminum 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 reaction, the kettle body and the lining of the reaction kettle are placed in an oven to be dried overnight at 120 ℃, connected to an evaluation system consisting of the reaction kettle and a vacuum system, sealed, heated to 100 ℃ under the condition of vacuum pumping, kept at the constant temperature for 1h (a tail gas valve is closed), and residual water, oxygen and oxygen-containing impurities are removed. The temperature was then set to the reaction temperature (30-80 ℃) and allowed to cool naturally while the nitrogen was filling, followed by vacuum, repeated three times to ensure that the air had been displaced cleanly. Then the nitrogen gas is pumped out by a vacuum pump, the filling is carried out by ethylene, and the process is repeated for three times, so that the kettle body is ensured to be full of ethylene.
(2) Opening an exhaust valve, injecting cyclohexane solvent and a certain amount of cocatalyst into the reactor sequentially by using an injector under the stirring condition, after the temperature is stabilized to the reaction temperature, injecting the molecular sieve loaded with tantalum and the 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 the PNP ligand, closing ethylene gas after the molar ratio of an alkyl aluminum auxiliary agent to 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, detaching a reaction kettle body, and soaking the reaction kettle body into an ice-water bath to cool the reaction kettle to below 10 ℃.
(3) After the tail gas valve is opened to release pressure, a certain amount of 10% HCl/ethanol solution is injected under the stirring condition to quench the alkyl aluminum cocatalyst, and 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 out to be stored in a refrigerator for 30min, and products are analyzed by GC-FID. Since the nonane mass is determined, the mass of the remaining components can be calculated from the GC results, as well as the selectivity and activity. The remaining sample was filtered, the filter paper weighed in advance to record the mass, then the polymer on the paddle was scraped off with a spoon, washed into a beaker with solvent, the resulting polymer was placed in a vacuum oven to dry overnight at 60 ℃, weighed separately and calculated to obtain the pure mass.
The preset pressure value in the step (2) is 1.0-6.0 MPa.
The invention has the advantages that:
(1) the ethylene is loaded with metal tantalum through a molecular sieve for the first time and then is used for ethylene selective oligomerization reaction with a PNP ligand;
(2) the selectivity of 1-octene in the product is high;
(3) the polyethylene content in the product is very low.
The ring formation mechanism is as follows: the chromium metal center reacts with ethylene molecules to form 9-membered rings, and 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 domain limiting effect of the molecular sieve can reduce the generation of polymer. The trivalent chromium becomes divalent after reacting with the ligand, and the remaining two electron orbitals are just taken as orbitals of a ring forming mechanism. However, in the process of acting with the molecular sieve, the molecular sieve skeleton is electronegative and is easy to act with the electron empty orbit of the chromium metal, and the ring forming mechanism is influenced. The pentavalent tantalum has enough electron empty orbitals, and the sensitivity to electron donor is lower than that of trivalent chromium, so that the activity of the pentavalent tantalum can be maintained for a long time.
Detailed Description
In order to make the aforementioned and other features and advantages of the invention more comprehensible, embodiments accompanied with figures are described in detail below. The method of the present invention is a method which is conventional in the art unless otherwise specified.
And (3) synthesis of a ligand:
the ligand synthesis is completed in a glove box, 80mL of anhydrous and oxygen-free 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 through a syringe under magnetic stirring, a needle is washed through 20mL of dichloromethane, after uniform stirring, the temperature is reduced to 0 ℃, 133mmol of triethylamine (3.64 g, 5.00 mL) is added, after uniform stirring, 18mmol of isopropylamine (1.064 g, 1.54 mL) is added dropwise into the system at 0 ℃, after stirring for 30min, after ice water bath is removed, the reaction is continued to be stirred for 24h, white triethylamine hydrochloride crystals are removed through filtration, the solution is recrystallized after concentration, and is filtered and dried to obtain the PNP ligand.
Example 1:
(1) modification of the molecular sieve:
placing a three-neck flask with a reflux condenser tube into a constant-temperature magnetic stirrer, adding 16.1195g of tantalum pentachloride and 150mL of absolute ethanol (the concentration of a tantalum solution is 0.3 mol/L), stirring to dissolve, adding 8.63g of activated MCM-41 molecular sieve, refluxing at 60 ℃ for 12 h, stopping stirring, and cooling to room temperature. Centrifuging, separating, drying, and roasting the obtained sample at 450 ℃ for 4h in a nitrogen atmosphere to obtain the product. The loading of tantalum on the molecular sieve was 6.23wt% as measured using an ICP spectrometer.
(2) Evaluation reaction:
the ethylene oligomerization reaction was carried out in a 300mL autoclave. Before reaction, the kettle body and the lining of the reaction kettle are placed in an oven to be dried overnight at 120 ℃, connected to an evaluation system, sealed, heated to 100 ℃ under the condition of vacuum pumping and kept at the constant temperature for 1h (the tail gas valve is closed), and residual water, oxygen and oxygen-containing impurities are removed. Then the temperature was set to 60 ℃ to allow it to cool naturally while nitrogen was filling, followed by vacuum pumping and repeating three times to ensure that the air had been displaced cleanly. Then the nitrogen gas is pumped out by a vacuum pump, the filling is carried out by ethylene, and the process is repeated for three times, so that the kettle body is ensured to be full of ethylene. Opening an exhaust valve, injecting 80mL of cyclohexane solvent and 2.25mmol of methylaluminoxane (the methylaluminoxane is a 1.5mol/L toluene solution, and 1.5mL of the solution) in sequence by using an injector under the stirring condition, dispersing the modified molecular sieve in 10mL of cyclohexane after the temperature is stabilized to 60 ℃, injecting the suspension into a reaction kettle by using the injector after the ultrasonic is uniform, and then washing the injector by using 10mL of cyclohexane to ensure that all the modified molecular sieve is 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 flow meter data and 0.0145g of tantalum-loaded molecular sieve and 0.0026g of ligand, closing ethylene gas after 1.0h, recording mass flow meter data, stopping reaction, closing an air inlet valve, dismounting a reaction kettle body, and soaking the reaction kettle body in an ice-water bath to cool the reaction kettle to below 10 ℃. After opening the tail gas valve to depressurize, 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 kettle is opened, a small amount of organic phase is taken out to be stored in a refrigerator for 30min, and products are analyzed by GC-FID. Since the nonane mass is determined, the mass of the remaining components can be calculated from the GC results, as well as the selectivity and activity. The remaining sample was filtered, the filter paper weighed in advance and the mass recorded, then the polymer on the paddle was scraped off with a spoon, washed into a beaker with solvent, all the polymer was dried overnight in a vacuum oven at 60 ℃, weighed separately and calculated to give a pure mass.
Example 2:
(1) modification of the molecular sieve:
placing a three-neck flask with a reflux condenser tube into a constant-temperature magnetic stirrer, adding 10.7463g of tantalum pentachloride and 150mL of absolute ethanol (the concentration of a tantalum solution is 0.2 mol/L), stirring to dissolve, adding 5.75g of activated NAY molecular sieve, refluxing at 50 ℃ for 12 h, stopping stirring, and cooling to room temperature. Centrifuging, separating, drying, and roasting the obtained sample at 450 ℃ for 4h in a nitrogen atmosphere to obtain the product. The loading of tantalum on the molecular sieve was measured to be 4.31wt% using an ICP spectrometer.
(2) Evaluation reaction:
the ethylene oligomerization reaction was carried out in a 300mL autoclave. Before reaction, the kettle body and the lining of the reaction kettle are placed in an oven to be dried overnight at 120 ℃, connected to an evaluation system, sealed, heated to 100 ℃ under the condition of vacuum pumping and kept at the constant temperature for 1h (the tail gas valve is closed), and residual water, oxygen and oxygen-containing impurities are removed. Then the temperature is set to 50 ℃, so that the air is naturally cooled, the nitrogen is filled at the same time, and then the vacuum pumping is carried out for three times, so as to ensure that the air is completely replaced. Then the nitrogen gas is pumped out by a vacuum pump, the filling is carried out by ethylene, and the process is repeated for three times, so that the kettle body is ensured to be full of ethylene. Opening an exhaust valve, injecting 80mL of cyclohexane solvent and 1.75mmol of methylaluminoxane (the methylaluminoxane is a 1.5mol/L toluene solution, and 1.17mL of the solution) in sequence by using an injector under the stirring condition, dispersing the modified molecular sieve in 10mL of cyclohexane after the temperature is stabilized to 50 ℃, injecting the suspension into a reaction kettle by using the injector after the ultrasonic homogenization, and then washing the injector by using 10mL of cyclohexane to ensure that all the modified molecular sieve is 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 4.0MPa, recording mass flow meter data, 0.0210g of tantalum-loaded molecular sieve and 0.0026g of ligand, closing ethylene gas after the molar ratio of ligand/cocatalyst/tantalum is 240:350:1, 1.0h, recording mass flow meter data, stopping the reaction, closing an air inlet valve, dismounting the reaction kettle body, and soaking the reaction kettle in an ice-water bath to cool the reaction kettle to below 10 ℃. After opening the tail gas valve to depressurize, 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 kettle is opened, a small amount of organic phase is taken out to be stored in a refrigerator for 30min, and products are analyzed by GC-FID. Since the nonane mass is determined, the mass of the remaining components can be calculated from the GC results, as well as the selectivity and activity. The remaining sample was filtered, the filter paper weighed in advance and the mass recorded, then the polymer on the paddle was scraped off with a spoon, washed into a beaker with solvent, all the polymer was dried overnight in a vacuum oven at 60 ℃, weighed separately and calculated to give a pure mass.
Example 3:
(1) modification of the molecular sieve:
placing a three-neck flask with a reflux condenser tube into a constant-temperature magnetic stirrer, adding 13.4329g of tantalum pentachloride and 150mL of absolute ethanol (the concentration of a tantalum solution is 0.25 mol/L), stirring to dissolve, adding 10.44g of activated ZSM-5 molecular sieve, refluxing at 30 ℃ for 12 h, stopping stirring, and cooling to room temperature. Centrifuging, separating, drying, and roasting the obtained sample at 450 ℃ for 4h in a nitrogen atmosphere to obtain the product. The loading of tantalum on the molecular sieve was 3.25wt% as measured using an ICP spectrometer.
(2) Evaluation reaction:
the ethylene oligomerization reaction was carried out in a 300mL autoclave. Before reaction, the kettle body and the lining of the reaction kettle are placed in an oven to be dried overnight at 120 ℃, connected to an evaluation system, sealed, heated to 100 ℃ under the condition of vacuum pumping and kept at the constant temperature for 1h (the tail gas valve is closed), and residual water, oxygen and oxygen-containing impurities are removed. Then the temperature is set to 80 ℃, so that the air is naturally cooled, the nitrogen is filled at the same time, and then the vacuum pumping is carried out for three times, so as to ensure that the air is completely replaced. Then the nitrogen gas is pumped out by a vacuum pump, the filling is carried out by ethylene, and the process is repeated for three times, so that the kettle body is ensured to be full of ethylene. Opening an exhaust valve, injecting 80mL of cyclohexane solvent and 1.5mmol of triethylaluminum (the triethylaluminum is 1.0mol/L of cyclohexane solution, taking 1.5mL of the solution) in turn by using a syringe under the stirring condition, dispersing the modified molecular sieve in 10mL of cyclohexane after the temperature is stabilized to 80 ℃, injecting the suspension into a reaction kettle by using the syringe after the ultrasonic is uniform, and then washing the syringe by using 10mL of cyclohexane to ensure that all the modified molecular sieve is 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 1.0MPa, recording mass flow meter data, 0.0278g of tantalum-loaded molecular sieve and 0.0026g of ligand, closing ethylene gas after the molar ratio of ligand/cocatalyst/tantalum is 240:300:1, and 0.5h, recording mass flow meter data, stopping the reaction, closing a gas inlet valve, dismounting the reaction kettle body, and soaking the reaction kettle in an ice-water bath to cool the reaction kettle to below 10 ℃. After opening the tail gas valve to depressurize, 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 kettle is opened, a small amount of organic phase is taken out to be stored in a refrigerator for 30min, and products are analyzed by GC-FID. Since the nonane mass is determined, the mass of the remaining components can be calculated from the GC results, as well as the selectivity and activity. The remaining sample was filtered, the filter paper weighed in advance and the mass recorded, then the polymer on the paddle was scraped off with a spoon, washed into a beaker with solvent, all the polymer was dried overnight in a vacuum oven at 60 ℃, weighed separately and calculated to give a pure mass.
Example 4:
(1) modification of the molecular sieve:
placing a three-neck flask with a reflux condenser tube into a constant-temperature magnetic stirrer, adding 0.5373g of tantalum pentachloride and 150mL of absolute ethanol (the concentration of a tantalum solution is 0.01 mol/L), stirring to dissolve, adding 6.90g of activated SAPO-11 molecular sieve, refluxing at 80 ℃ for 12 h, stopping stirring, and cooling to room temperature. Centrifuging, separating, drying, and roasting the obtained sample at 450 ℃ for 4h in a nitrogen atmosphere to obtain the product. The loading of tantalum on the molecular sieve was 2.32wt% as measured using an ICP spectrometer.
(2) Evaluation reaction:
the ethylene oligomerization reaction was carried out in a 300mL autoclave. Before reaction, the kettle body and the lining of the reaction kettle are placed in an oven to be dried overnight at 120 ℃, connected to an evaluation system, sealed, heated to 100 ℃ under the condition of vacuum pumping and kept at the constant temperature for 1h (the tail gas valve is closed), and residual water, oxygen and oxygen-containing impurities are removed. Then the temperature is set to 30 ℃, so that the air is naturally cooled, the nitrogen is filled at the same time, and then the vacuum pumping is carried out for three times, so as to ensure that the air is completely replaced. Then the nitrogen gas is pumped out by a vacuum pump, the filling is carried out by ethylene, and the process is repeated for three times, so that the kettle body is ensured to be full of ethylene. Opening an exhaust valve, injecting 80mL of cyclohexane solvent and 2mmol of modified methylaluminoxane (the modified methylaluminoxane is 1.5mol/L of toluene solution, taking 1.33mL of the solution) in sequence by using an injector under the stirring condition, dispersing the modified molecular sieve in 10mL of cyclohexane after the temperature is stabilized to 30 ℃, injecting the suspension into a reaction kettle by using the injector after the ultrasonic is uniform, and then washing the injector by using 10mL of cyclohexane to ensure that all the modified molecular sieve is 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 mass flow meter data, 0.0390g of the tantalum-loaded molecular sieve and 0.0026g of the ligand, closing ethylene gas after the molar ratio of the ligand/cocatalyst/tantalum is 240:400:1 and 4.0h, recording the mass flow meter data, stopping the reaction, closing an air inlet valve, unloading the reaction kettle body, and soaking the reaction kettle in an ice-water bath to cool the reaction kettle to below 10 ℃. The tail gas valve was opened to allow pressure to escape and 5mL of 10% HCl/ethanol solution was injected under stirring to quench the modified methylaluminoxane followed by injection of a fixed mass of nonane as an internal standard. After the reaction kettle is opened, a small amount of organic phase is taken out to be stored in a refrigerator for 30min, and products are analyzed by GC-FID. Since the nonane mass is determined, the mass of the remaining components can be calculated from the GC results, as well as the selectivity and activity. The remaining sample was filtered, the filter paper weighed in advance to record the mass, then the polymer on the paddle was scraped off with a spoon, washed into a beaker with solvent, all the polymer was dried overnight in a vacuum oven at 60 ℃, weighed separately and calculated to obtain the pure mass.
Example 5:
(1) modification of the molecular sieve:
placing a three-neck flask with a reflux condenser tube into a constant-temperature magnetic stirrer, adding 1.0746g of tantalum pentachloride and 150mL of absolute ethanol (the concentration of a tantalum solution is 0.02 mol/L), stirring to dissolve, adding 1.3g of activated Beta molecular sieve, refluxing at 40 ℃ for 12 h, stopping stirring, and cooling to room temperature. Centrifuging, separating, drying, and roasting the obtained sample at 450 ℃ for 4h in a nitrogen atmosphere to obtain the product. The loading of tantalum on the molecular sieve was 1.35wt% as measured using an ICP spectrometer.
(2) Evaluation reaction:
the ethylene oligomerization reaction was carried out in a 300mL autoclave. Before reaction, the kettle body and the lining of the reaction kettle are placed in an oven to be dried overnight at 120 ℃, connected to an evaluation system, sealed, heated to 100 ℃ under the condition of vacuum pumping and kept at the constant temperature for 1h (the tail gas valve is closed), and residual water, oxygen and oxygen-containing impurities are removed. Then the temperature was set to 45 ℃ to allow it to cool naturally while nitrogen was filling, followed by vacuum pumping and repeating three times to ensure that the air had been displaced cleanly. Then the nitrogen gas is pumped out by a vacuum pump, the filling is carried out by ethylene, and the process is repeated for three times, so that the kettle body is ensured to be full of ethylene. Opening an exhaust valve, injecting 80mL of cyclohexane solvent and 2.5mmol of drained methylaluminoxane (1.5 mol/L of toluene solution of the drained methylaluminoxane is taken as 1.67mL of the solution) in sequence by using an injector under the stirring condition, dispersing the modified molecular sieve in 10mL of cyclohexane after the temperature is stabilized to 45 ℃, injecting the suspension into a reaction kettle by using the injector after the ultrasonic homogenization, and then washing the injector by using 10mL of cyclohexane to ensure that all the modified molecular sieve is 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 3.0MPa, recording mass flow meter data and 0.0670g of molecular sieve and 0.0026g of ligand after tantalum loading, closing ethylene gas after the molar ratio of the ligand/cocatalyst/tantalum is 240:500:1 and 0.8h, recording the mass flow meter data, stopping the reaction, closing an air inlet valve, unloading the reaction kettle body, and soaking the reaction kettle body in an ice-water bath to cool the reaction kettle to below 10 ℃. After opening the tail gas valve to depressurize, 5mL of 10% HCl/ethanol solution was injected under stirring to quench the drained methylaluminoxane, followed by injection of a fixed mass of nonane as an internal standard. After the reaction kettle is opened, a small amount of organic phase is taken out to be stored in a refrigerator for 30min, and products are analyzed by GC-FID. Since the nonane mass is determined, the mass of the remaining components can be calculated from the GC results, as well as the selectivity and activity. The remaining sample was filtered, the filter paper weighed in advance and the mass recorded, then the polymer on the paddle was scraped off with a spoon, washed into a beaker with solvent, all the polymer was dried overnight in a vacuum oven at 60 ℃, weighed separately and calculated to give a pure mass.
Example 6:
(1) modification of the molecular sieve:
placing a three-neck flask with a reflux condenser tube into a constant-temperature magnetic stirrer, adding 26.8658g of tantalum pentachloride and 150mL of absolute ethanol (the concentration of a tantalum solution is 0.5 mol/L), stirring to dissolve, adding 14.38g of activated ZSM-11 molecular sieve, refluxing at 80 ℃ for 12 h, stopping stirring, and cooling to room temperature. Centrifuging, separating, drying, and roasting the obtained sample at 450 ℃ for 4h in a nitrogen atmosphere to obtain the product. The loading of tantalum on the molecular sieve was measured to be 9.25wt% using an ICP spectrometer.
(2) Evaluation reaction:
the ethylene oligomerization reaction was carried out in a 300mL autoclave. Before reaction, the kettle body and the lining of the reaction kettle are placed in an oven to be dried overnight at 120 ℃, connected to an evaluation system, sealed, heated to 100 ℃ under the condition of vacuum pumping and kept at the constant temperature for 1h (the 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 at the same time, and then the reaction is vacuumized and repeated for three times to ensure that the air is completely replaced. Then the nitrogen gas is pumped out by a vacuum pump, the filling is carried out by ethylene, and the process is repeated for three times, so that the kettle body is ensured to be full of ethylene. Opening an exhaust valve, injecting 80mL of cyclohexane solvent and 0.5mmol of trimethylaluminum (the trimethylaluminum is 2mol/L of toluene solution, taking 0.25mL of the solution) in sequence by using an injector under the stirring condition, dispersing the modified molecular sieve in 10mL of cyclohexane after the temperature is stabilized to 60 ℃, injecting the suspension into a reaction kettle by using the injector after the ultrasonic homogenization, and then washing the injector by using 10mL of cyclohexane to ensure that all the modified molecular sieve is 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 2.0MPa, recording mass flow meter data, 0.0098g of the molecular sieve and 0.0026g of the ligand after the tantalum load, closing ethylene gas after the molar ratio of the ligand to the cocatalyst to the tantalum is 240:100:1, and 0.5h, recording the mass flow meter data, stopping the reaction, closing an air inlet valve, dismounting the reaction kettle body, and soaking the reaction kettle in an ice-water bath to cool the reaction kettle to below 10 ℃. After opening the tail gas valve to depressurize, 5mL of 10% HCl/ethanol solution was injected under stirring to quench the trimethylaluminum, followed by injection of a fixed mass of nonane as an internal standard. After the reaction kettle is opened, a small amount of organic phase is taken out to be stored in a refrigerator for 30min, and products are analyzed by GC-FID. Since the nonane mass is determined, the mass of the remaining components can be calculated from the GC results, as well as the selectivity and activity. The remaining sample was filtered, the filter paper weighed in advance to record the mass, then the polymer on the paddle was scraped off with a spoon, washed into a beaker with solvent, all the polymer was dried overnight in a vacuum oven at 60 ℃, weighed separately and calculated to obtain the pure mass.
The ethylene oligomerization activity and the product distribution in the examples of the invention.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (10)
1. An ethylene selective tetramerisation catalyst composition, wherein 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 a tantalum solution, centrifuging, drying and roasting.
2. The ethylene selective tetramerisation catalyst composition according to claim 1, wherein: the molecular sieve is any one of MCM-41, Y, ZSM-5, ZSM-11, Beta and SAPO-11.
3. The ethylene selective tetramerisation catalyst composition according to claim 1, wherein: the solvent selected by the tantalum solution is absolute ethyl alcohol, and the concentration of the tantalum in the dipping solution is 0.01-0.5 mol/L.
4. The ethylene selective tetramerisation catalyst composition according to claim 1, wherein: the loading amount of the metal tantalum on the molecular sieve is 0.5-10 wt%.
5. The ethylene selective tetramerisation catalyst composition according to claim 1, wherein: the solute used by the tantalum solution is tantalum pentachloride.
6. The ethylene selective tetramerisation catalyst composition according to claim 1, wherein: the dipping temperature is 30-80 ℃.
7. The ethylene selective tetramerisation catalyst composition according to claim 1, wherein: the cocatalyst is an alkyl aluminum cocatalyst and comprises one of methylaluminoxane, modified aluminum methyl siloxane, drained methylaluminoxane, triethylaluminum and trimethylaluminum.
8. The ethylene selective tetramerisation catalyst composition according to claim 7, wherein: the molar ratio of the alkyl aluminum cocatalyst to the metal tantalum in the catalyst is 100: 1-500: 1.
9. The use of the ethylene-selective tetramerization catalyst composition of claim 1 in an ethylene oligomerization reaction, wherein: the method comprises the following steps:
(1) before reaction, firstly placing a reaction kettle body and a lining in an oven at 120 ℃ for drying overnight, connecting to an evaluation system, sealing, closing an exhaust valve, heating to 100 ℃ under a vacuum-pumping condition, keeping the temperature for 1h, removing residual water, oxygen and oxygen-containing impurities, setting the temperature to be 30-80 ℃ for natural cooling, filling nitrogen, vacuumizing, repeating for three times, ensuring that air is completely replaced, then pumping the nitrogen by using a vacuum pump, filling with ethylene, repeating for three times, and ensuring that the kettle body is filled with ethylene;
(2) opening a tail gas valve, sequentially injecting a 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 a PNP ligand by using the injector, closing the tail gas valve, adjusting a pressure reducing valve, starting timing after the pressure is increased to a preset pressure value, recording mass flow meter data and the mass of the molecular sieve and the PNP ligand, closing ethylene gas after 0.5-4h, recording the mass flow meter data, stopping the reaction, closing a gas inlet valve, dismounting a reaction kettle body, and soaking the reaction kettle body in an ice-water bath to cool the reaction kettle to below 10 ℃;
(3) opening a tail gas valve to release pressure, injecting a certain amount of 10% HCl/ethanol solution under the stirring condition to quench a cocatalyst, then injecting nonane with fixed mass as an internal standard, opening a reaction kettle, taking a small amount of organic phase, refrigerating for 30min in a refrigerator, analyzing a product by GC-FID (gas chromatography-flame ionization Detector), calculating the mass, selectivity and activity of the rest components according to the GC result, filtering the rest sample, weighing and recording the mass by using filter paper in advance, scraping off a polymer on a stirring paddle by using a spoon, cleaning the polymer into a beaker by using a solvent, drying the obtained polymer in a vacuum oven at 60 ℃ overnight, weighing the polymer respectively, and calculating to obtain pure mass.
10. The use of claim 9, wherein the predetermined pressure value in step (2) is 1.0 MPa-6.0 MPa.
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