CN116003655A - Catalyst carrier for olefin polymerization and preparation method and application thereof - Google Patents
Catalyst carrier for olefin polymerization and preparation method and application thereof Download PDFInfo
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- CN116003655A CN116003655A CN202111230443.6A CN202111230443A CN116003655A CN 116003655 A CN116003655 A CN 116003655A CN 202111230443 A CN202111230443 A CN 202111230443A CN 116003655 A CN116003655 A CN 116003655A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 33
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 30
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- -1 aluminum compound Chemical class 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 238000009826 distribution Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 11
- 229920002492 poly(sulfone) Polymers 0.000 claims description 11
- 229920000098 polyolefin Polymers 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- 238000001694 spray drying Methods 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- 229920005549 butyl rubber Polymers 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 229920006393 polyether sulfone Polymers 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- 229920002379 silicone rubber Polymers 0.000 claims description 5
- 239000004945 silicone rubber Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001350 alkyl halides Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000011068 loading method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 241001391944 Commicarpus scandens Species 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000009718 spray deposition Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
Images
Classifications
-
- 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
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- Polymerization Catalysts (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a catalyst carrier for olefin polymerization, a preparation method and application thereof, wherein the carrier comprises inorganic oxide, polymer and organic aluminum compound. The carrier has good particle morphology and high granularity adjustability, and can adapt to the production requirements of different process devices. And the effective load of the cocatalyst is high, so that the waste can be effectively avoided.
Description
Technical Field
The invention relates to the field of polyolefin catalysts, in particular to a catalyst carrier for olefin polymerization, a preparation method and application thereof.
Background
The polyolefin industry plays a very key role in daily life, and as industry develops, more products with different characteristics are needed to meet the production and living needs, so the development of novel catalysts becomes the core of industry development, and single-site catalysts have great breakthroughs in this aspect. The polyolefin catalyst has a rich structure and high controllability, so that polyolefin products with various different performances can be obtained, and compared with the traditional Ziegler-Natta catalyst, the polyolefin catalyst has unique performances, but the morphology of the product is difficult to control when the unsupported single-site catalyst catalyzes olefin polymerization, and the phenomenon of kettle sticking is serious, so that the application of the polyolefin catalyst in the industrial field is greatly limited. In order to improve the morphology of the polymer, increase the bulk density of the polymer and easily control the particle size distribution of the polymer, the single-site catalyst is suitable for the existing olefin polymerization device and process, and the method which is easy to realize is to load the single-site catalyst system, and the currently mainly used carrier is silica gel, but the activity is lower due to limited load.
In addition to the transition metal compound as the main catalyst, the single-site catalyst also requires lewis acid as a cocatalyst, which has a very important influence on the catalytic performance of the single-site catalyst. The catalyst is not only used for exciting the activity of the main catalyst, but also is very critical to the effective load of the main catalyst, because the main catalyst is difficult to directly and effectively load on the carrier, a large amount of cocatalysts are often required to be treated on the carrier, the activity of the catalyst can meet the production requirement, and the production cost is greatly increased. Therefore, the development of an active carrier for highly effective loading of a cocatalyst is necessary for the research on loading of a single-site catalyst.
Disclosure of Invention
In view of the problem that the existing catalyst carrier in the prior art has low loading rate in the single-site catalyst loading process, so that the catalyst activity is poor, one of the purposes of the invention is to provide a catalyst carrier which has good particle morphology and high granularity adjustability, and can adapt to the production requirements of different process devices. And the effective load of the cocatalyst is high, so that the waste can be effectively avoided.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a catalyst support comprising an inorganic oxide, a polymer, and an organoaluminum compound. Because the catalyst is used with a cocatalyst, namely an organic aluminum compound, the cocatalyst can be directly loaded on the carrier by adding the organic aluminum into the formula, the catalyst preparation step is simplified, and the loading amount of the carrier cocatalyst prepared by the method is larger, so that the catalyst effect is facilitated.
In the above technical solution, the organoaluminum compound is at least one selected from methylaluminoxane, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and diethylaluminum chloride; methylaluminoxane is preferred because it generally gives the best excitation for single-site catalysts.
In the technical scheme, the mass fraction of the aluminum is 5% -50% based on the total weight of the catalyst carrier; preferably, the mass fraction of the aluminum is between 10% and 30%.
In the above technical solution, the polymer is selected from polymers soluble in organic solvents, preferably at least one of polyolefin, rubber, polysulfone, polyether, polyester, polyether ketone and polyether sulfone, and more preferably at least one of polysulfone, polystyrene, butyl rubber, silicone rubber and polyether ketone.
In the above technical solution, the inorganic oxide is an ultrafine inorganic oxide, preferably a silicon oxide and/or an aluminum oxide, preferably silicon dioxide.
Preferably, the ultrafine inorganic oxide particle size is 0.01 to 10. Mu.m, preferably 0.01 to 5. Mu.m.
More preferably 0.02 to 2. Mu.m, most preferably 0.03 to 1. Mu.m.
In the above technical scheme, the particle size of the ultrafine inorganic oxide is 0.01-10. Mu.m, preferably 0.01-5. Mu.m, more preferably 0.02-2. Mu.m, most preferably 0.03-1. Mu.m.
In the above technical solution, the polymer is selected from polymers soluble in organic solvents, preferably at least one of polyolefin, rubber, polysulfone, polyether, polyester, polyether ketone and polyether sulfone, and more preferably at least one of polysulfone, polystyrene, butyl rubber, silicone rubber and polyether ketone. Experiments prove that the carrier prepared by using the further preferable polymer has better particle shape.
In the above technical scheme, the average particle diameter of the catalyst carrier is 10-100 μm, preferably 20-90 μm; the particle size distribution is less than 1.5, preferably the particle size distribution is less than 1. The diameter of the carrier particles determines the diameter of the catalyst particles, and different production devices have certain requirements on the particle diameter of the catalyst, so that the particle diameter is preferable for realizing the adaptation with the device; the smaller the particle size distribution, the more concentrated the particle size distribution, and the less the catalyst is broken, which can effectively avoid the occurrence of fine powder in the polymerization process, thereby ensuring the stable production of the device.
In the technical proposal, the catalyst carrier has a porous structure, and the specific surface area is 200-600m 2/ g, pore volume of 0.5-6.0cm 3 In the range of/g, the average pore diameter is from 1 to 100nm, preferably from 5 to 80nm, most preferably from 10 to 40nm.
The second purpose of the invention is to provide the preparation method of the catalyst carrier, the carrier granularity obtained by the preparation method is high in adjustability, the method can meet the requirements of different process devices on catalyst diversity adjustability, the prepared carrier is not easy to break, and the method is helpful for avoiding the problem of fine powder in the polymerization process.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method of preparing a catalyst support comprising: mixing and stirring the polymer and the organic solvent for dissolution, and then adding the inorganic oxide and the organic aluminum compound for mixing and stirring to form uniformly dispersed slurry; finally, the slurry obtained is spray dried.
In the above technical solution, the organic solvent is at least one selected from alkanes, halogenated alkanes, aromatic hydrocarbons, heterocyclic compounds, ethers, ketones and esters, preferably at least one selected from pentane, hexane, heptane, dichloromethane, chloroform, benzene, toluene, chlorobenzene, chlorotoluene, tetrahydrofuran, acetone, diethyl ether and ethyl acetate. Further preferred are one or more of chloroform, dichloromethane and tetrahydrofuran. The preferred organic solvents have better solubility for the polymer.
In the technical scheme, the mass ratio of the superfine inorganic oxide to the polymer is 1-50, preferably 5-10; the amount of organic solvent used per gram of the ultrafine inorganic oxide is 5 to 100mL, preferably 10 to 30mL.
Preferably, the aluminium/ultrafine inorganic oxide mass ratio is between 0.1 and 1, preferably between 0.1 and 0.5.
In the technical scheme, the dissolution temperature of the polymer in the solvent is constant for 0.5-3 hours at 20-70 ℃.
In the technical scheme, the superfine inorganic oxide is added at 20-60 ℃ and stirred for 2-12h.
In the above technical scheme, the spray drying conditions are: the inlet temperature is 80-240 ℃, preferably 80-200 ℃; the outlet temperature is 50-180deg.C, preferably 70-150deg.C. For example, the spray drying inlet temperature may be 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, or 240 ℃; the outlet temperature may be 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, or 180 ℃. The inlet and outlet temperature of spray drying has a certain influence on the carrier formation, and a carrier with better particle shape can be obtained by the proper inlet and outlet temperature.
It is a further object of the present invention to provide a catalyst support or the use of a catalyst support prepared by the method for the polymerization of olefins.
The invention has the beneficial effects that:
the catalyst prepared by the method can adjust the shape and the size of the catalyst by adjusting the spraying condition and the formula, so that the carrier prepared by the method has good particle shape and high granularity adjustability, and can adapt to the production requirements of different process devices. And the method of adding the cocatalyst into the carrier formula for spray forming ensures that the effective load is high, and can effectively avoid waste.
Drawings
Fig. 1: scanning electron micrographs of the catalyst support obtained in example 1.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
One of the purposes of the invention is to provide a catalyst carrier which has good particle morphology and high granularity adjustability and can adapt to the production requirements of different process devices. And the effective load of the cocatalyst is high, so that the waste can be effectively avoided.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a catalyst support comprising an inorganic oxide, a polymer, and an organoaluminum compound. Because the catalyst is used with a cocatalyst, namely an organic aluminum compound, the cocatalyst can be directly loaded on the carrier by adding the organic aluminum into the formula, the catalyst preparation step is simplified, and the loading amount of the carrier cocatalyst prepared by the method is larger, so that the catalyst effect is facilitated.
In a preferred embodiment, the organoaluminum compound is selected from at least one of methylaluminoxane, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and diethylaluminum monochloride; methylaluminoxane is preferred because it generally gives the best excitation for single-site catalysts.
In a preferred embodiment, the aluminum is present in an amount of from 5% to 50% by mass, based on the total weight of the catalyst support; preferably, the mass fraction of the aluminum is between 10% and 30%.
In a preferred embodiment, the polymer is selected from polymers soluble in organic solvents, preferably at least one of polyolefin, rubber, polysulfone, polyether, polyester, polyether ketone and polyether sulfone, further preferably at least one of polysulfone, polystyrene, butyl rubber, silicone rubber and polyether ketone.
In a preferred embodiment, the inorganic oxide is an ultrafine inorganic oxide, preferably a silicon oxide and/or an aluminum oxide, preferably silicon dioxide.
In a preferred embodiment, the ultrafine inorganic oxide particle size is from 0.01 to 10. Mu.m, preferably from 0.01 to 5. Mu.m.
More preferably 0.02 to 2. Mu.m, most preferably 0.03 to 1. Mu.m.
In a preferred embodiment, the ultrafine inorganic oxide particle size is from 0.01 to 10. Mu.m, preferably from 0.01 to 5. Mu.m, more preferably from 0.02 to 2. Mu.m, most preferably from 0.03 to 1. Mu.m.
In a preferred embodiment, the polymer is selected from polymers soluble in organic solvents, preferably at least one of polyolefin, rubber, polysulfone, polyether, polyester, polyether ketone and polyether sulfone, further preferably at least one of polysulfone, polystyrene, butyl rubber, silicone rubber and polyether ketone. Experiments prove that the carrier prepared by using the further preferable polymer has better particle shape.
In a preferred embodiment, the catalyst support has an average particle diameter of from 10 to 100. Mu.m, preferably from 20 to 90. Mu.m; the particle size distribution is less than 1.5, preferably the particle size distribution is less than 1. The diameter of the carrier particles determines the diameter of the catalyst particles, and different production devices have certain requirements on the particle diameter of the catalyst, so that the particle diameter is preferable for realizing the adaptation with the device; the smaller the particle size distribution, the more concentrated the particle size distribution, and the less the catalyst is broken, which can effectively avoid the occurrence of fine powder in the polymerization process, thereby ensuring the stable production of the device.
In a preferred embodiment, the catalyst support has a porous structure and a specific surface area of 200-600m 2/ g range, pore volume of 0.5-6.0cm 3 In the range of/g, the average pore diameter is from 1 to 100nm, preferably from 5 to 80nm, most preferably from 10 to 40nm.
The second purpose of the invention is to provide the preparation method of the catalyst carrier, the carrier granularity obtained by the preparation method is high in adjustability, the method can meet the requirements of different process devices on catalyst diversity adjustability, the prepared carrier is not easy to break, and the method is helpful for avoiding the problem of fine powder in the polymerization process.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method of preparing a catalyst support comprising: mixing and stirring the polymer and the organic solvent for dissolution, and then adding the inorganic oxide and the organic aluminum compound for mixing and stirring to form uniformly dispersed slurry; finally, the slurry obtained is spray dried.
In a preferred embodiment, the organic solvent is selected from at least one of alkanes, halogenated alkanes, aromatic hydrocarbons, heterocyclic compounds, ethers, ketones and esters, preferably at least one of pentane, hexane, heptane, dichloromethane, chloroform, benzene, toluene, chlorobenzene, chlorotoluene, tetrahydrofuran, acetone, diethyl ether and ethyl acetate. Further preferred are one or more of chloroform, dichloromethane and tetrahydrofuran. The preferred organic solvents have better solubility for the polymer.
In a preferred embodiment, the superfine inorganic oxide to polymer mass ratio is from 1 to 50, preferably from 5 to 10; the amount of organic solvent used per gram of the ultrafine inorganic oxide is 5 to 100mL, preferably 10 to 30mL.
In a preferred embodiment, the aluminum/ultrafine inorganic oxide mass ratio is between 0.1 and 1, preferably between 0.1 and 0.5.
In a preferred embodiment, the dissolution temperature of the polymer in the solvent is constant at 20-70℃for 0.5-3h.
In a preferred embodiment, the ultra-fine inorganic oxide is added at 20-60 ℃ and stirred for a period of 2-12 hours.
In a preferred embodiment, the spray drying conditions are: the inlet temperature is 80-240 ℃, preferably 80-200 ℃; the outlet temperature is 50-180deg.C, preferably 70-150deg.C. The inlet and outlet temperature of spray drying has a certain influence on the carrier formation, and a carrier with better particle shape can be obtained by the proper inlet and outlet temperature.
It is a further object of the present invention to provide a catalyst support or the use of a catalyst support prepared by the method for the polymerization of olefins.
The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein. In the following, the individual technical solutions can in principle be combined with one another to give new technical solutions, which should also be regarded as specifically disclosed herein.
The invention has the beneficial effects that:
the catalyst prepared by the method can adjust the shape and the size of the catalyst by adjusting the spraying condition and the formula, so that the carrier prepared by the method has good particle shape and high granularity adjustability, and can adapt to the production requirements of different process devices. And the method of adding the cocatalyst into the carrier formula for spray forming ensures that the effective load is high, and can effectively avoid waste.
Reagent source: the reagents are all commercially available, and the particle size of the silicon dioxide is in the range of 0.01-5 mu m.
The testing method comprises the following steps:
scanning electron microscope: FEI Co., USA, nanoSEM 450;
particle size and particle size distribution: malvern MS3000;
al content: ICP-MS Agilent 7500CX.
Example 1
After 0.5g of polysulfone and 70ml of toluene were stirred at room temperature for 1 hour, 6g of silica and 30ml of a toluene solution of Methylaluminoxane (MAO) having a mass fraction of 10% were added, and the mixture was heated to 50℃with stirring, reacted at constant temperature for 6 hours, and then cooled to room temperature. Spray drying was then carried out with a gas-flow spray dryer, spray conditions: inlet temperature: 140℃and an outlet temperature of 90℃to give 4.2g of a carrier. The morphology of the particles observed by an optical microscope is shown in fig. 1, and it can be seen from the figure that the olefin polymerization catalyst carrier has regular particle morphology, smooth surface, concentrated particle size distribution, basically no abnormal particle and few crushing examples. The physical properties of the support portion are shown in Table 1. And directly testing the sprayed carrier to obtain the carrier aluminum content, wherein the content is determined by the MAO adding proportion, and repeatedly washing the carrier with toluene for three times to obtain the washed Al content. It was found that there was no significant change in the aluminum content, indicating that MAO was effective loaded on silica gel.
Example 2
After stirring 0.5g of polyetherketone and 60ml of toluene at room temperature for 1 hour, 6g of silica and 40ml of MAO toluene solution with mass fraction of 10% were added, and the mixture was heated to 50℃with stirring, reacted at constant temperature for 6 hours, and then cooled to room temperature. Spray drying was then carried out with a gas-flow spray dryer, spray conditions: inlet temperature: 140℃and an outlet temperature of 90℃to give 3.6g of a carrier. The obtained carrier has regular particle morphology, centralized particle size distribution and basically no special-shaped particles. The physical properties of the support portion are shown in Table 1. And directly testing the sprayed carrier to obtain the carrier aluminum content, wherein the content is determined by the MAO adding proportion, and repeatedly washing the carrier with toluene for three times to obtain the washed Al content. It was found that the reduction in aluminum content was not significant, indicating that MAO was on silica gel payload.
Example 3
After stirring 0.5g of butyl rubber and 50ml of toluene at room temperature for 1 hour, 6g of silica and 50ml of MAO toluene solution with a mass fraction of 10% were added, and the mixture was heated to 50℃with stirring, reacted at constant temperature for 6 hours, and then cooled to room temperature. Spray drying was then carried out with a gas-flow spray dryer, spray conditions: inlet temperature: 140℃and an outlet temperature of 90℃to give 4.5g of a carrier. The obtained carrier has regular particle morphology, concentrated particle size distribution and basically no abnormal particle. The physical properties of the support portion are shown in Table 1. And directly testing the sprayed carrier to obtain the carrier aluminum content, wherein the content is determined by the MAO adding proportion, and repeatedly washing the carrier with toluene for three times to obtain the washed Al content. It was found that there was a limited reduction in the aluminum content, indicating that MAO was effective loaded on silica gel.
Comparative example 1
30ml of MAO 10% by mass and 6g 955# silica gel were reacted for 4 hours at 50℃with stirring, filtered, washed three times with toluene and dried in vacuo. And filtering, directly pumping and drying, testing to obtain the Al content, washing with toluene, and testing to obtain the washed Al content.
Comparative example 2
40ml of MAO 10% by mass and 6g 955# silica gel were reacted for 4 hours at 50℃with stirring, filtered, washed three times with toluene and dried in vacuo. And filtering, directly pumping and drying, testing to obtain the Al content, washing with toluene, and testing to obtain the washed Al content.
Comparative example 3
50ml of MAO 10% by mass and 6g 955# silica gel were reacted for 4 hours at 50℃with stirring, filtered, washed three times with toluene and dried in vacuo. And filtering, directly pumping and drying, testing to obtain the Al content, washing with toluene, and testing to obtain the washed Al content.
TABLE 1 physical Properties of Carrier part and Al content
As can be seen from Table 1, the carrier obtained by the preparation method of the invention has adjustable granularity, which can meet different requirements of different production devices on the granularity of the catalyst, and the carrier has good granularity and is basically spherical from an electron microscope. In addition, the effective load of the cocatalyst MAO (expressed by Al content) of the carrier prepared by the method is higher than that of the catalyst in the comparative example, and particularly when the load is increased, the load of the catalyst in the comparative example is obviously increased after washing, which can help to increase the load of the main catalyst in the subsequent catalyst preparation, thereby increasing the activity of the catalyst.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (13)
1. A catalyst support for olefin polymerization, which comprises a polymer, an organoaluminum compound, and an inorganic oxide.
2. The catalyst support according to claim 1, wherein the organoaluminum compound is at least one selected from the group consisting of methylaluminoxane, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and diethylaluminum chloride.
3. The catalyst support according to claim 1, wherein the mass fraction of aluminum is between 5% and 50% based on the total weight of the catalyst support; preferably, the mass fraction of the aluminum is between 10% and 30%.
4. The catalyst support according to claim 1, characterized in that the polymer is selected from polymers soluble in organic solvents, preferably at least one of polyolefin, rubber, polysulfone, polyether, polyester, polyether ketone and polyether sulfone, further preferably at least one of polysulfone, polystyrene, butyl rubber, silicone rubber and polyether ketone.
5. The catalyst support according to claim 1, characterized in that the inorganic oxide is an ultrafine inorganic oxide, preferably a silicon oxide and/or an aluminum oxide, preferably silica; and/or the number of the groups of groups,
the ultrafine inorganic oxide particle size is 0.01 to 10. Mu.m, preferably 0.01 to 5. Mu.m.
6. The catalyst support of claim 1, wherein the catalyst support is a multicatalystPore structure with specific surface area of 200-600m 2/ g, pore volume of 0.5-6.0cm 3 And/g, the average pore diameter is 1 to 100nm, preferably 5 to 80nm.
7. The catalyst support according to claim 1, characterized in that the average particle diameter of the catalyst support is 10-100 μm, preferably 20-90 μm; the particle size distribution is less than 1.5, preferably the particle size distribution is less than 1.
8. A method of preparing the catalyst support of any one of claims 1 to 7, comprising: mixing and stirring the polymer and the organic solvent for dissolution, and then adding the inorganic oxide and the organic aluminum compound for mixing and stirring to form uniformly dispersed slurry; finally, the slurry obtained is spray dried.
9. The method according to claim 8, wherein the organic solvent is selected from at least one of alkanes, haloalkanes, aromatic hydrocarbons, heterocyclic compounds, ethers, ketones and esters, preferably at least one of pentane, hexane, heptane, dichloromethane, chloroform, benzene, toluene, chlorobenzene, chlorotoluene, tetrahydrofuran, acetone, diethyl ether and ethyl acetate.
10. The method according to claim 8, characterized in that the ultra-fine inorganic oxide to polymer mass ratio is 1-50, preferably 5-10; and/or the number of the groups of groups,
the dosage of the organic solvent used per gram of the superfine inorganic oxide is 5-100mL, preferably 10-30mL; and/or the number of the groups of groups,
the mass ratio of aluminum to ultrafine inorganic oxide is 0.1-1, preferably 0.1-0.5.
11. The method according to claim 8, wherein the dissolution temperature of the polymer in the solvent is constant at 20-70 ℃ for 0.5-3h; and/or the number of the groups of groups,
the superfine inorganic oxide is added at 20-60 ℃ and stirred for 2-12h.
12. The method of claim 8, wherein the spray drying conditions are: the inlet temperature is 80-240 ℃, preferably 80-200 ℃; the outlet temperature is 50-180deg.C, preferably 70-150deg.C.
13. Use of a catalyst support according to any one of claims 1 to 7 or a catalyst support prepared by a method of preparation according to any one of claims 8 to 12 in the polymerisation of olefins.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120130034A1 (en) * | 2009-05-18 | 2012-05-24 | Yongrong Yang | Catalyst support used for olefin polymerization and preparing method and application thereof |
| DE102012209262A1 (en) * | 2012-06-01 | 2013-12-05 | BSH Bosch und Siemens Hausgeräte GmbH | Preparing supported catalyst useful for decomposition of substances e.g. ozone, comprises providing carrier comprising polymer, dissolving carrier surface using solvent, applying catalyst to dissolved carrier surface, and removing solvent |
| CN104511312A (en) * | 2013-09-30 | 2015-04-15 | 中国石油化工股份有限公司 | Catalyst used for catalytic rectification selective hydrogenation, preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120130034A1 (en) * | 2009-05-18 | 2012-05-24 | Yongrong Yang | Catalyst support used for olefin polymerization and preparing method and application thereof |
| DE102012209262A1 (en) * | 2012-06-01 | 2013-12-05 | BSH Bosch und Siemens Hausgeräte GmbH | Preparing supported catalyst useful for decomposition of substances e.g. ozone, comprises providing carrier comprising polymer, dissolving carrier surface using solvent, applying catalyst to dissolved carrier surface, and removing solvent |
| CN104511312A (en) * | 2013-09-30 | 2015-04-15 | 中国石油化工股份有限公司 | Catalyst used for catalytic rectification selective hydrogenation, preparation method and application thereof |
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| 谢宝军等: "有机/ 无机复合载体负载茂金属催化剂的制备和乙烯聚合", 《应用化学》, vol. 16, no. 5, pages 1 - 4 * |
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