CN115960279A - Catalyst carrier and preparation method and application thereof - Google Patents
Catalyst carrier and preparation method and application thereof Download PDFInfo
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- CN115960279A CN115960279A CN202111171126.1A CN202111171126A CN115960279A CN 115960279 A CN115960279 A CN 115960279A CN 202111171126 A CN202111171126 A CN 202111171126A CN 115960279 A CN115960279 A CN 115960279A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 74
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 150000001336 alkenes Chemical class 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000009826 distribution Methods 0.000 claims description 13
- 238000001694 spray drying Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 229920002492 poly(sulfone) Polymers 0.000 claims description 8
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 7
- 229920000098 polyolefin Polymers 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 150000002170 ethers Chemical class 0.000 claims description 5
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 229920005549 butyl rubber Polymers 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 229920002379 silicone rubber Polymers 0.000 claims description 4
- 229920001971 elastomer Polymers 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
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 abstract description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 12
- 238000006116 polymerization reaction Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 7
- 239000007921 spray Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 230000003287 optical effect Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 230000001788 irregular Effects 0.000 description 6
- 239000002685 polymerization catalyst Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 230000006978 adaptation Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000004945 silicone rubber Substances 0.000 description 3
- 241001391944 Commicarpus scandens Species 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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- 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)
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Abstract
The invention relates to a catalyst carrier, a preparation method and application thereof. The carrier has good particle shape, adjustable particle size, high specific surface area, high pore volume and relatively large pore diameter, and can improve the loading capacity of the catalyst so as to improve the activity of the catalyst in olefin polymerization.
Description
Technical Field
The invention relates to the field of inorganic materials, in particular to a catalyst carrier and a preparation method and application thereof.
Background
Polyolefins are the most productive and versatile synthetic polymers in the world, and catalysts have a decisive influence on the structural properties of the olefin polymer products. Among polyolefin catalysts, single site catalysts have advantages over conventional Ziegler-Natta catalysts, and can produce a variety of polyolefin products with specific structural properties. In order to meet the requirements of most of the current industrial production apparatuses, research on the load of the apparatuses is receiving more and more attention.
The loading mainly solves the problems of the form of a homogeneous single-site catalyst and large consumption of a cocatalyst, and is more beneficial to industrial application. The support is a key component for supporting single-site catalysts, and after a large number of inorganic and organic supports have been studied, silica gel has been found to be the most suitable support. However, the traditional silica gel type catalyst has limited loading capacity, which results in lower catalytic activity. It is difficult to meet the requirements of high-load production. In addition, the particle size of the carrier is also very important for industrial production, and different production processes have different requirements on the morphology and the particle size of the catalyst, so that the adjustability of the particle size shape is also an important parameter for characterizing the carrier.
Therefore, the research and development of the carrier with high loading capacity and adjustable and controllable granularity is of great significance.
Disclosure of Invention
In view of the problem of poor catalyst activity caused by low loading rate of the prior catalyst carrier in the single-site catalyst loading process in the prior art, the invention aims to provide a catalyst carrier which has high specific surface area and relatively large pore volume and pore diameter, and can increase the loading amount of the catalyst so as to improve the activity of the catalyst in olefin polymerization; the carrier has good particle shape and controllable particle size, and is very suitable for the requirements of the polymerization process on the catalyst carrier.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a catalyst support comprising an inorganic oxide and a polymer. The polymer is used in the catalyst carrier because the preparation is convenient and simple, the polymer is cheap and easy to obtain and is easy to dissolve in an organic solvent; the second aspect is that the carrier has good forming effect after the polymer is used, and the obtained carrier has better particle shape; in the third aspect, the polymer has various types, such as polarity, non-polarity and the like, different polymer characteristics have certain adjustment on the catalytic characteristics of the supported catalyst, and the supported catalyst can be used for preparing catalysts with various characteristics.
In the above technical solution, the inorganic oxide is an ultrafine inorganic oxide, preferably a silicon oxide and/or an aluminum oxide, and more preferably silica.
Preferably, the first and second liquid crystal display panels are,
in the above technical solution, the particle size of the ultrafine inorganic oxide is 0.01 to 10 μm, preferably 0.01 to 5 μm, more preferably 0.02 to 2 μm, and most preferably 0.03 to 1 μm.
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. Tests have shown that the carriers prepared using the further preferred polymers have a better particle shape.
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 is one or more of chloroform, methylene chloride and tetrahydrofuran. The preferred organic solvents have better solubility for the polymer.
In the 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 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 diameter of the catalyst particles, so the particle diameter is preferably used for realizing the adaptation of the device; the smaller the particle size distribution is, the more concentrated the particle size distribution is, 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 scheme, the catalyst carrier is of a porous structure, and the specific surface area is 200-600m 2/ g range, pore volume of 0.5-6.0cm 3 In the range of/g, the mean pore diameter is from 1 to 100nm, preferably from 5 to 80nm, most preferably from 10 to 40nm.
The invention also aims to provide the preparation method of the catalyst carrier, the carrier obtained by the preparation method has high granularity adjustability, can meet the requirement of different process devices on the adjustability of catalyst diversity, and is not easy to break, thereby being beneficial to avoiding the fine powder problem in the polymerization process.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method of making a catalyst support comprising: mixing, stirring and dissolving a polymer and an organic solvent, adding an inorganic oxide, mixing and stirring to obtain uniformly dispersed slurry; and finally, spray drying the obtained slurry.
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 is one or more of chloroform, methylene chloride and tetrahydrofuran.
In the technical scheme, the mass ratio of the inorganic oxide to the polymer is 1-50, preferably 2-20; the amount of organic solvent used per gram of said inorganic oxide is 5-100mL, preferably 10-30mL.
Preferably, the first and second liquid crystal display panels are,
in the technical scheme, the dissolving temperature of the polymer in the solvent is constant at 20-70 ℃ for 0.5-3h.
In the technical scheme, the superfine inorganic oxide is added at the temperature of 20-60 ℃ and stirred for 2-12h.
In the above technical scheme, the spray drying conditions are as follows: the inlet temperature is 80-240 ℃, preferably 80-200 ℃; the outlet temperature is 50 to 180 ℃ and preferably 50 to 150 ℃. For example, the spray drying inlet temperature can be 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃ or 230 ℃; 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 has certain influence on the carrier forming, and the carrier with better grain shape can be obtained by proper inlet and outlet temperature. The invention also aims to provide a catalyst carrier or an application of the catalyst carrier prepared by the preparation method in olefin polymerization.
The invention has the beneficial effects that: the carrier obtained by using the raw material and the preparation method of the invention has adjustable particle size, good particle morphology, high specific surface area and pore volume, and particularly has relatively larger pore diameter than the traditional carrier, so that the loading capacity of the catalyst can be improved, and the activity of the catalyst in olefin polymerization can be improved.
Drawings
FIG. 1: scanning electron micrograph of the catalyst carrier obtained in example 1.
FIG. 2: scanning electron micrographs of the catalyst carrier obtained in example 2.
FIG. 3: scanning electron micrographs of the catalyst carrier obtained in example 3.
FIG. 4 is a schematic view of: scanning electron micrograph of the catalyst carrier obtained in example 4.
FIG. 5: scanning electron micrographs of the catalyst carrier obtained in example 5.
FIG. 6: scanning electron micrographs of the catalyst carrier obtained in example 6.
FIG. 7: comparative example 1 scanning electron micrograph of catalyst support.
Detailed Description
While the present invention will be described in conjunction with specific embodiments thereof, it is to be understood that the following examples are included merely for purposes of illustration and are not to be construed as limiting the scope of the present invention, as the invention will be further modified and modified by those skilled in the art in light of the present disclosure.
It is to be noted that the various features described in the following detailed description may be combined in any suitable manner without contradiction. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, as long as the idea of the present invention is not violated, and the technical solution formed thereby is part of the original disclosure of the present specification, and also falls into the protection scope of the present invention.
And (3) reagent sources: the reagents are all commercially available; the silica particle size ranges from 0.01 to 5 μm.
Scanning electron microscope: FEI inc, nanoSEM 450;
specific surface and void analyzer: microphone ASAP2460.
It is an object of the present invention to provide a catalyst support comprising an inorganic oxide and a polymer. The polymer is used in the catalyst carrier in the invention because the preparation is convenient and simple, the polymer is cheap and easy to obtain and is easy to dissolve in an organic solvent; the second aspect is that the carrier has good forming effect after the polymer is used, and the obtained carrier has better particle shape; in the third aspect, the polymer has various types, such as polarity, non-polarity and the like, different polymer characteristics have certain adjustment on the catalytic characteristics of the supported catalyst, and the supported catalyst can be used for preparing catalysts with various characteristics.
In a preferred embodiment, the inorganic oxide is an ultrafine inorganic oxide, preferably a silicon oxide and/or aluminum oxide, more preferably silica.
In a preferred embodiment, the ultrafine inorganic oxide particles have a particle size of 0.01 to 10 μm, preferably 0.01 to 5 μm, more preferably 0.02 to 2 μm, and most preferably 0.03 to 1 μm.
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, for example, one or two of them are selected. Tests have shown that the use of the further preferred polymers leads to carriers with better particle shape.
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 is one or more of chloroform, methylene chloride and tetrahydrofuran, and for example, one or two of them are selected. The preferred organic solvents have better solubility for the polymer.
In a preferred embodiment, the catalyst support has an average particle diameter of 10 to 100. Mu.m, preferably 20 to 90 μm; the particle size distribution is less than 1.5, preferably 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 diameter of the catalyst particles, so the particle diameter is preferably used for realizing the adaptation of the device; the smaller the particle size distribution is, the more concentrated the particle size distribution is, the less the catalyst is broken, and therefore fine powder can be effectively prevented from appearing in the polymerization process, and stable production of the device is guaranteed.
In a preferred embodiment, the catalyst support has a porous structure and a specific surface area of 200 to 600m 2/ g range, pore volume of 0.5-6.0cm 3 In the range of/g, the mean pore diameter is from 1 to 100nm, preferably from 5 to 80nm, most preferably from 10 to 40nm.
The invention also aims to provide the preparation method of the catalyst carrier, the carrier obtained by the preparation method has high granularity adjustability, can meet the requirement of different process devices on the adjustability of catalyst diversity, and is not easy to break, thereby being beneficial to avoiding the fine powder problem in the polymerization process.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method of making a catalyst support comprising: mixing, stirring and dissolving a polymer and an organic solvent, adding an inorganic oxide, mixing and stirring to obtain uniformly dispersed slurry; and finally, spray drying the obtained slurry.
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 is one or more of chloroform, methylene chloride and tetrahydrofuran, and for example, one or two of them are selected.
In a preferred embodiment, the inorganic oxide to polymer mass ratio is from 1 to 50, preferably from 2 to 20; the amount of organic solvent used per gram of said inorganic oxide is 5-100mL, preferably 10-30mL.
In a preferred embodiment, the polymer is dissolved in the solvent at a constant temperature of 20 to 70 ℃ for 0.5 to 3 hours.
In a preferred embodiment, the ultrafine inorganic oxide is added at 20-60 ℃ with stirring for 2-12h.
In a preferred embodiment, the spray drying conditions are: the inlet temperature is 80-240 ℃, preferably 80-200 ℃; the outlet temperature is 50 to 180 ℃ and preferably 50 to 150 ℃. The inlet and outlet temperature has certain influence on the carrier forming, and the carrier with better grain shape can be obtained by proper inlet and outlet temperature.
The invention also aims to provide a catalyst carrier or an application of the catalyst carrier prepared by the preparation method in olefin polymerization.
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein. In the following, various technical solutions can in principle be combined with each other to obtain new technical solutions, which should also be regarded as specifically disclosed herein.
The invention has the beneficial effects that: the carrier obtained by using the raw material and the preparation method of the invention has adjustable particle size, good particle morphology, high specific surface area and pore volume, and particularly has relatively larger pore diameter than the traditional carrier, so that the loading capacity of the catalyst can be improved, and the activity of the catalyst in olefin polymerization can be improved.
Example 1
2g of polysulfone and 100mL of tetrahydrofuran were stirred at room temperature for 1 hour, 5.8g of silica was added, the temperature was raised to 65 ℃ with stirring, and the mixture was reacted at a constant temperature for 2 hours, and then cooled to room temperature. Subsequently spray drying was carried out with an air-flow spray dryer, the spray conditions: inlet temperature: 140 ℃ C, exit temperature 90 ℃ C, to obtain 4.0g of the carrier. The particle morphology observed by an optical microscope is shown in figure 1, and it can be seen from the figure that the particle morphology of the olefin polymerization catalyst carrier is regular, the surface is smooth, the particle is basically spherical, the particle size distribution is concentrated, and no irregular particles exist basically. Physical characteristic parameters of the support part are shown in Table 1.
Example 2
1g of polystyrene and 100mL of tetrahydrofuran are stirred at room temperature for 1 hour, 5.8g of silicon dioxide is added, the temperature is raised to 65 ℃ while stirring, the reaction is carried out at constant temperature for 2 hours, and then the temperature is reduced to room temperature. Subsequently spray drying was carried out with a gas flow spray dryer, the spray conditions: inlet temperature: 140 ℃ and an outlet temperature of 90 ℃ to obtain 3.0g of the carrier. The morphology of the particles observed by an optical microscope is shown in FIG. 2, and it can be seen from the figure that the olefin polymerization catalyst carrier has regular particle morphology, smooth surface, substantially spherical shape, relatively concentrated particle size distribution, and substantially no irregular particles. Physical characteristic parameters of the support part are shown in Table 1.
Example 3
1g of polyether ketone and 100mL of chloroform are stirred at room temperature for 1 hour, 5.8g of silicon dioxide is added, the temperature is raised to 55 ℃ under stirring, the reaction is carried out at constant temperature for 2 hours, and then the temperature is reduced to room temperature. Subsequently spray drying was carried out with a gas flow spray dryer, the spray conditions: inlet temperature: 120 ℃ C, exit temperature 85 ℃ C, obtained 3.1g of support. The morphology of the particles observed by an optical microscope is shown in fig. 3, and it can be seen from the figure that the olefin polymerization catalyst carrier has regular particle morphology, smooth surface, substantially spherical shape, relatively concentrated particle size distribution, and substantially no irregular particles. The physical properties of the support part are shown in Table 1.
Example 4
1g of silicone rubber and 100mL of hexane were stirred at room temperature for 1 hour, 5.8g of silica was added, the temperature was raised to 65 ℃ with stirring, the reaction was carried out at a constant temperature for 2 hours, and then the temperature was lowered to room temperature. Subsequently spray drying was carried out with an air-flow spray dryer, the spray conditions: inlet temperature: 140 ℃ C, exit temperature 90 ℃ C, 3.5g of support were obtained. The particle morphology observed by an optical microscope is shown in fig. 4, and it can be seen from the figure that the olefin polymerization catalyst carrier has regular particle morphology, smooth surface, and is substantially spherical, the particle size distribution is relatively concentrated, and substantially no irregular particles exist. Physical characteristic parameters of the support part are shown in Table 1.
Example 5
1g of butyl rubber and 100mL of tetrahydrofuran were stirred at room temperature for 1 hour, 5.8g of silica was added, the temperature was raised to 65 ℃ with stirring, and the reaction was carried out at a constant temperature for 2 hours, followed by cooling to room temperature. Subsequently spray drying was carried out with a gas flow spray dryer, the spray conditions: inlet temperature: 140 ℃ and an outlet temperature of 90 ℃ to obtain 3.2g of the carrier. The morphology of the particles observed by an optical microscope is shown in FIG. 5, from which it can be seen that the olefin polymerization catalyst carrier has a regular particle morphology, a smooth surface, a substantially spherical shape, a relatively concentrated particle size distribution, and substantially no irregular particles. Physical characteristic parameters of the support part are shown in Table 1.
Example 6
0.5g of polysulfone and 100mL of chloroform were stirred at room temperature for 1 hour, then 5.8g of silica was added, the temperature was raised to 55 ℃ with stirring, and the reaction was carried out at a constant temperature for 2 hours, after which the temperature was lowered to room temperature. Subsequently spray drying was carried out with an air-flow spray dryer, spray conditions: inlet temperature: 130 ℃ and an outlet temperature of 95 ℃. 3.5g of the carrier was obtained. The morphology of the particles observed by an optical microscope is shown in FIG. 6, from which it can be seen that the olefin polymerization catalyst carrier has a more regular particle morphology, a smooth surface, a substantially spherical shape, a more concentrated particle size distribution, and substantially no presence of irregular particles. Physical characteristic parameters of the support part are shown in Table 1.
Comparative example 1
Comparative example 1 is a commercial catalyst support silica gel, and some of the physical properties are shown in Table 1. The particle morphology observed by optical microscope is shown in fig. 7, and it can be seen that the particle morphology of the commercial catalyst carrier silica gel is not as regular as the carrier morphology obtained by the present invention.
TABLE 1 partial physical Properties of the support
Compared with the comparative example, the embodiment of the invention has larger pore volume, larger average pore diameter and easier loading for a single-site catalyst with larger volume, thereby realizing the increase of the loading amount.
It can be seen from the figure that the particle surface of the commercial catalyst carrier silica gel of comparative example 1 was not smooth, and the morphology was not as regular as the catalyst carrier of the present invention. The catalyst carrier obtained by the invention has regular particle shape and smooth surface, is basically spherical and presents good particle shape; the particle size of the catalyst carrier obtained by the method is controllable, namely the particle size of the catalyst carrier obtained after loading is controllable, and the particle size of the catalyst is required to be different when different production devices or the same device are used for producing different types of products, so that the adjustable particle size is very important for the adaptation of the production devices. However, in any device, stable production is required, the flow property of the powder is required, the flow property depends on the powder form, and the powder form is the copy of the catalyst form, so that the catalyst form is required to be more regular and more spherical, and the better. Therefore, the spherical catalyst carrier with regular particle shape, smooth surface and good particle shape, which is obtained by the invention, has more advantages in the industrial polymerization process.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made in the technical solution of the present invention and the embodiments thereof without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (11)
1. A catalyst support comprising an inorganic oxide and a polymer.
2. The catalyst carrier according to claim 1, characterized in that the inorganic oxide is an ultrafine inorganic oxide, preferably a silicon oxide and/or an aluminum oxide, further preferably silica; and/or the presence of a gas in the atmosphere,
the particle size of the inorganic oxide is 0.01-10 μm, preferably 0.01-5 μm.
3. The catalyst carrier according to claim 1, wherein the polymer is selected from polymers soluble in organic solvents, preferably at least one of polyolefins, rubbers, polysulfones, polyethers, polyesters, polyether ketones and polyether sulfones, further preferably at least one of polysulfones, polystyrenes, butyl rubbers, silicone rubbers and polyether ketones.
4. The catalyst carrier according to claim 1, characterized in that the average particle diameter of the catalyst carrier is 10-100 μ ι η, preferably 20-90 μ ι η; the particle size distribution is less than 1.5, preferably less than 1.
5. The catalyst carrier according to claim 1, wherein the catalyst carrier has a porous structure and a specific surface area of 200 to 600m 2/ g range, pore volume of 0.5-6.0cm 3 In the range/g, the mean pore diameter is from 1 to 100nm, preferably from 5 to 80nm.
6. A method for preparing the catalyst carrier of any one of claims 1 to 5, comprising: mixing, stirring and dissolving a polymer and an organic solvent, adding an inorganic oxide, mixing and stirring to obtain uniformly dispersed slurry; and finally, spray drying the obtained slurry.
7. The method according to claim 6, wherein 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.
8. The process according to claim 6, characterized in that the inorganic oxide to polymer mass ratio is between 1 and 50, preferably between 2 and 20; the amount of the organic solvent used per gram of the inorganic oxide is 5 to 100mL, preferably 10 to 30mL.
9. The method according to claim 6, wherein the polymer is dissolved in the solvent at a constant temperature of 20-70 ℃ for 0.5-3h; and/or the presence of a gas in the gas,
the superfine inorganic oxide is added at the temperature of 20-60 ℃ and stirred for 2-12h.
10. The method of claim 6, wherein the spray drying conditions are: the inlet temperature is 80-240 ℃, preferably 80-200 ℃; the outlet temperature is 50 to 180 ℃ and preferably 50 to 150 ℃.
11. Use of a catalyst support according to any one of claims 1 to 5 or a catalyst support prepared by a method according to any one of claims 6 to 10 in the polymerisation of olefins.
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