CN108722382B - Spherical mesoporous composite material, supported catalyst and preparation method thereof - Google Patents
Spherical mesoporous composite material, supported catalyst and preparation method thereof Download PDFInfo
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- CN108722382B CN108722382B CN201710260646.7A CN201710260646A CN108722382B CN 108722382 B CN108722382 B CN 108722382B CN 201710260646 A CN201710260646 A CN 201710260646A CN 108722382 B CN108722382 B CN 108722382B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 239000002131 composite material Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000012065 filter cake Substances 0.000 claims abstract description 96
- 239000012528 membrane Substances 0.000 claims abstract description 70
- 239000013335 mesoporous material Substances 0.000 claims abstract description 70
- 238000002156 mixing Methods 0.000 claims abstract description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000919 ceramic Substances 0.000 claims abstract description 46
- 238000000498 ball milling Methods 0.000 claims abstract description 39
- 239000000741 silica gel Substances 0.000 claims abstract description 37
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 37
- 238000001694 spray drying Methods 0.000 claims abstract description 28
- 239000000047 product Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims description 47
- 239000011148 porous material Substances 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 31
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 150000003608 titanium Chemical class 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 159000000003 magnesium salts Chemical class 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 18
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- 239000011777 magnesium Substances 0.000 claims description 16
- 229910052749 magnesium Inorganic materials 0.000 claims description 16
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 13
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 13
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 150000007522 mineralic acids Chemical class 0.000 claims description 12
- 239000012452 mother liquor Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 235000019353 potassium silicate Nutrition 0.000 claims description 12
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 12
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 239000007974 sodium acetate buffer Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229920000428 triblock copolymer Polymers 0.000 claims description 2
- -1 polyethylene Polymers 0.000 abstract description 23
- 239000004698 Polyethylene Substances 0.000 abstract description 20
- 229920000573 polyethylene Polymers 0.000 abstract description 20
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000011068 loading method Methods 0.000 abstract description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- 238000004876 x-ray fluorescence Methods 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005374 membrane filtration Methods 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000009295 crossflow filtration Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
The invention relates to the field of catalysts, and discloses a spherical mesoporous composite material, a supported catalyst and a preparation method thereof. The preparation method of the spherical mesoporous composite material comprises the following steps: (1) preparing a first mesoporous material filter cake; (2) preparing a second mesoporous material filter cake; (3) preparing a silica gel filter cake; (4) and respectively or after mixing the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake, carrying out ball milling on the ball-milled products by using a ceramic membrane filter, and then carrying out spray drying to obtain the spherical mesoporous composite material. The spherical mesoporous composite material has higher catalytic activity after loading a polyethylene catalyst, and the obtained polyethylene product has lower bulk density and melt index.
Description
Technical Field
The invention relates to the field of mesoporous materials, in particular to a preparation method of a spherical mesoporous composite material, the spherical mesoporous composite material obtained by the method, a supported catalyst, a preparation method of the supported catalyst and the supported catalyst prepared by the method.
Background
The development and application of polyethylene catalysts is a major breakthrough in the field of olefin polymerization catalysts after traditional Ziegler-Natta catalysts, which makes the research of polyethylene catalysts enter a rapidly developing stage. Because the homogeneous polyethylene catalyst needs a large amount of catalyst to reach high activity, the production cost is high, and the obtained polymer has no granular shape and cannot be used in the polymerization process of a slurry method or a gas phase method which is widely applied, the soluble polyethylene catalyst is effectively carried.
At present, common catalyst carriers are mesoporous materials and silica gel carriers. Among them, the mesoporous material has not high enough catalytic activity after loading the polyethylene catalyst, and there is a need to develop a catalyst carrier capable of improving activity to promote further development of the carrier catalyst and polyolefin industry.
Disclosure of Invention
The invention provides a preparation method of a spherical mesoporous composite material and the spherical mesoporous composite material prepared by the method.
At present, silica gel and mesoporous materials are usually removed by using a plate-and-frame filter press, but the catalytic activity of a carrier obtained by using the method after loading a catalyst is low, possibly because the removal of impurities is not thorough. In addition, the plate and frame filter press still has a lot of shortcomings, for example, plate and frame filter press area is great, simultaneously, because the plate and frame filter press is discontinuous operation, inefficiency, the operation room environment is relatively poor, has secondary pollution, and in addition, because use filter cloth, it is relatively poor to get rid of the impurity effect, and waste water can not recycle, wastes the water source very much in the washing process, simultaneously because the exhaust waste water can't be handled, causes environmental pollution and secondary waste again. After intensive research, the inventor of the present invention finds that when the ceramic membrane is used for washing the spherical mesoporous composite material, the obtained spherical mesoporous composite material has high catalytic activity after loading the polyethylene catalyst, and the obtained polyethylene product has low bulk density and low melt index. The present inventors have completed the present invention based on the above findings.
Specifically, in a first aspect, the present invention provides a method for preparing a spherical mesoporous composite material, comprising:
(1) carrying out first mixing contact on a template agent, tetramethoxysilane, ethanol, trimethylpentane and an acid agent, and crystallizing and filtering a mixture obtained by the first mixing contact to obtain a first mesoporous material filter cake;
(2) carrying out second mixing contact on ethyl orthosilicate, hexadecyl trimethyl ammonium bromide and ammonia, and filtering a mixture obtained by the second mixing contact to obtain a second mesoporous material filter cake;
(3) carrying out third mixing contact on water glass and inorganic acid, and filtering a mixture obtained after the third mixing contact to obtain a silica gel filter cake;
(4) respectively or after mixing the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake, carrying out ball milling on the ball-milled products, washing the ball-milled products by using a ceramic membrane filter, and then carrying out spray drying to obtain the spherical mesoporous composite material; or,
and (3) washing the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake respectively or after mixing, and then carrying out ball milling and spray drying to obtain the spherical mesoporous composite material.
In a second aspect, the invention also provides the spherical mesoporous composite material prepared by the method.
In a third aspect, the present invention provides a supported catalyst, which comprises a carrier and a magnesium salt and/or a titanium salt supported on the carrier, wherein the carrier is the spherical mesoporous composite material provided by the present invention.
In a fourth aspect, the present invention provides a method for preparing a supported catalyst, the method comprising: contacting the support with a mother liquor containing magnesium and/or titanium salts in the presence of an inert gas; wherein, the carrier is the spherical mesoporous composite material provided by the invention.
In a fifth aspect, the present invention provides a supported catalyst prepared by the above method.
The carrier of the spherical mesoporous composite material prepared by the ceramic membrane filtration method has the following advantages: (1) the separation process is simple, the separation efficiency is high, the number of matched devices is small, the energy consumption is low, and the operation is simple and convenient; (2) the template agent is directly removed by ceramic membrane filtration, and compared with the prior art, the step of removing the template agent by calcination is omitted; (3) the cross-flow filtration is adopted, and the higher membrane surface flow rate is used, so that the accumulation of pollutants on the membrane surface is reduced, and the membrane flux is improved; (4) the ceramic membrane has good chemical stability, acid resistance, alkali resistance, organic solvent resistance and strong regeneration capability, and can be suitable for the preparation process of the carrier; (5) the production of waste liquid is obviously reduced, and the method is green and environment-friendly.
The carrier prepared by the method has large aperture and high specific surface area, and is beneficial to the loading of catalytic components; in addition, the carrier has a spherical geometric shape, and the shape has obvious advantages in the aspects of reducing powder agglomeration, improving fluidity and the like. The supported catalyst prepared by adopting the carrier prepared by the invention has higher catalytic activity in the process of catalyzing ethylene polymerization reaction, and can obtain a polyethylene product with lower bulk density and melt index, and the obtained polyethylene product is spherical and has uniform particle size.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an X-ray diffraction pattern of a spherical mesoporous composite material C1 in example 1;
FIG. 2 is an SEM scanning electron micrograph of a spherical mesoporous composite material C1 in example 1;
fig. 3 is a pore size distribution diagram of the spherical mesoporous composite material C1 in example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein 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, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of a spherical mesoporous composite material, which comprises the following steps:
(1) carrying out first mixing contact on a template agent, tetramethoxysilane, ethanol, trimethylpentane and an acid agent, and crystallizing and filtering a mixture obtained by the first mixing contact to obtain a first mesoporous material filter cake;
(2) carrying out second mixing contact on ethyl orthosilicate, hexadecyl trimethyl ammonium bromide and ammonia, and filtering a mixture obtained by the second mixing contact to obtain a second mesoporous material filter cake;
(3) carrying out third mixing contact on water glass and inorganic acid, and filtering a mixture obtained after the third mixing contact to obtain a silica gel filter cake;
(4) respectively or after mixing the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake, carrying out ball milling on the ball-milled products, washing the ball-milled products by using a ceramic membrane filter, and then carrying out spray drying to obtain the spherical mesoporous composite material; or,
and (3) washing the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake respectively or after mixing, and then carrying out ball milling and spray drying to obtain the spherical mesoporous composite material.
In the invention, the template can be various templates which are conventional in the field as long as the pore structure of the obtained spherical porous mesoporous composite material meets the requirement. For example, the templating agent may be a triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene. Wherein the templating agent is commercially available (e.g., from Aldrich under the trade name P123, formula EO)20PO70EO20And Mn of 5800) or can be prepared by various conventional methods. When the template is polyoxyethylene-polyoxypropylene-polyoxyethylene, the number of moles of the template is calculated from the number average molecular weight of polyoxyethylene-polyoxypropylene-polyoxyethylene.
In the present invention, the acid agent may be various acidic aqueous solutions conventionally used in the art, and preferably, the acid agent is acetic acid and sodium acetate buffer solution having a pH of 1 to 6. The amount of the acid agent is not particularly limited, and may be varied within a wide range, and it is preferable that the pH value in the first mixing contact is 1 to 7.
According to the present invention, the order of the first mixing and contacting is not particularly limited, and the template, tetramethoxysilane, ethanol, trimethylpentane and acid agent may be mixed at the same time, or any two or three of them may be mixed, and the other components may be added and mixed uniformly. According to a preferred embodiment of the present invention, the template agent, ethanol and acid agent are mixed uniformly, then trimethylpentane is added and mixed uniformly, and then tetramethoxysilane is added and mixed uniformly.
In the present invention, the amount of the template, ethanol, trimethylpentane and tetramethoxysilane may vary over a wide range, for example, the molar ratio of template, ethanol, trimethylpentane and tetramethoxysilane may be 1: 100-500: 200-500: 50-200, more preferably 1: 180-400: 250-400: 70-150.
In the present invention, the conditions of the first mixing contact are not particularly limited, and for example, the conditions of the first mixing contact generally include: the temperature can be 10-60 ℃, preferably 10-20 ℃; the time can be 10 to 72 hours, preferably 10 to 30 hours; the pH may be from 1 to 7, preferably from 3 to 6. In order to further facilitate uniform mixing between the substances, according to a preferred embodiment of the invention, the first mixing contact is carried out under stirring conditions.
In the present invention, the conditions for crystallization of the mixture obtained by the first mixing contact include: the temperature can be 30-150 ℃, preferably 40-80 ℃; the time may be 10 to 72 hours, preferably 20 to 30 hours. According to a preferred embodiment, the crystallization is carried out by hydrothermal crystallization.
According to the invention, the amounts of the individual substances used in the second mixed contact can also be selected and adjusted within wide limits, for example the molar ratio of ethyl orthosilicate, cetyltrimethylammonium bromide and ammonia can be 1: 0.1-1: 0.1 to 5, preferably 1: 0.2-0.5: 1.5-3.5.
In the present invention, the ammonia is preferably added in the form of aqueous ammonia. The aqueous ammonia of the present invention may be present in a concentration of 10 to 25% by weight.
In the present invention, the second mixed contacting process of tetraethyl orthosilicate, cetyltrimethylammonium bromide and ammonia is carried out in the presence of water. Preferably, part of the water is introduced in the form of aqueous ammonia and part of the water is added in the form of deionized water. In the second mixed contact system of tetraethoxysilane, hexadecyl trimethyl ammonium bromide and ammonia, the molar ratio of tetraethoxysilane to water can be 1:100-200, and is preferably 1: 120-180.
In the present invention, the conditions of the second mixing contact are not particularly limited, and may include, for example: the contact temperature is 25-100 ℃, preferably 50-90 ℃; the contact time is 2-8 hours, preferably 3-7 hours, and the pH may be 7.5-11, preferably 8-10. Preferably, the second mixing contact is carried out under agitation to facilitate uniform mixing between the substances.
In the present invention, the conditions of the third mixed contact are not particularly limited and may be appropriately determined according to a conventional process for preparing silica gel. For example, the conditions of the third mixing contact include: the temperature can be 10-60 ℃, preferably 20-40 ℃; the time may be 1 to 5 hours, preferably 1 to 3 hours; the pH value is 2-4. In order to facilitate uniform mixing of the materials, the third mixing contact process is preferably performed under stirring conditions.
In the present invention, the amounts of the water glass and the inorganic acid may vary within a wide range. For example, the weight ratio of the water glass to the inorganic acid may be 3 to 6: 1.
in the present invention, the water glass is an aqueous solution of sodium silicate, and the concentration thereof may be 3 to 20% by weight, preferably 10 to 20% by weight. The inorganic acid may be various inorganic acids conventionally used in the art, and may be, for example, one or more of sulfuric acid, nitric acid, and hydrochloric acid. The inorganic acids can be used in pure form or in the form of their aqueous solutions, preferably in the form of 3 to 20% by weight aqueous solutions. The inorganic acid is preferably used in such an amount that the pH of the contact reaction system of the water glass and the inorganic acid is 2 to 4.
According to the present invention, in the step (4), the amounts of the first mesoporous material cake, the second mesoporous material cake and the silica gel cake may vary within a wide range, for example, the silica gel cake may be used in an amount of 1 to 200 parts by weight, preferably 20 to 180 parts by weight, and more preferably 50 to 150 parts by weight, relative to 100 parts by weight of the total amount of the first mesoporous material cake and the second mesoporous material cake; the weight ratio of the first mesoporous material filter cake to the second mesoporous material filter cake can be 1:0.1-10, and preferably 1: 0.5-2.
In the invention, the ceramic filter is a gas, liquid and solid separation and purification device which integrates filtration, slag discharge, cleaning and regeneration and takes a ceramic membrane element as a core. The ceramic membrane filter may include a ceramic membrane module and a ceramic membrane element, and the ceramic membrane element may be an inorganic ceramic membrane element (inorganic ceramic membrane for short). The inorganic ceramic membrane is a precise ceramic filter material with a porous structure, which is usually formed by sintering alumina, titanium oxide, zirconium oxide and the like at high temperature, a porous supporting layer, a transition layer and a microporous membrane layer are asymmetrically distributed, and the filtering precision covers micro-filtration, ultra-filtration and nano-filtration. Ceramic membrane filtration is a form of "cross-flow filtration" of fluid separation process: the raw material liquid flows at high speed in the membrane tube, the clarified penetrating fluid containing small molecular components penetrates through the membrane outwards along the direction vertical to the clear penetrating fluid under the drive of pressure, and the turbid concentrated solution containing large molecular components is intercepted by the membrane, so that the purposes of separating, concentrating and purifying the fluid are achieved. The ceramic membrane can be obtained commercially, for example, an inorganic ceramic membrane element obtained from york jiugu high-tech co. The ceramic membrane module may be determined according to the particular circumstances of the ceramic membrane element and the sample to be treated.
According to a specific embodiment, the parameters of the inorganic ceramic membrane elements used in the present invention include: the membrane is made of alumina, and has a shape of multi-channel cylindrical, the number of channels is 19, the diameter of the channel is 4mm, the length is 1016mm, the outer diameter (diameter) is 30mm, and the effective membrane area is 0.24m2。
In the present invention, the conditions for the washing treatment using the ceramic membrane filter include: the operating pressure can be from 2.5 to 3.9bar, preferably from 3 to 3.5 bar; the membrane pressure on the side of the circulation may be from 3 to 5bar, preferably from 3.5 to 4.5 bar; the pressure of the membrane at the circulating side can be 2-2.8bar, preferably 2.2-2.6 bar; the flow rate of the circulating side membrane surface can be 4-5m/s, and is preferably 4-4.5 m/s; the pressure of the permeation side is 0.3-0.5 bar; the temperature may be 10-60 ℃. Wherein the operating pressure is the average of the cycle side membrane inlet pressure and the cycle side membrane outlet pressure.
In the invention, the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake can be washed by using a ceramic membrane filter respectively, or the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake can be mixed and then washed by using a ceramic membrane, and then ball milling and spray drying are carried out, or the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake can be mixed and then ball milling is carried out, and the ball milling product is washed by using the ceramic membrane filter and then spray drying is carried out.
According to a specific embodiment, in the step (4), the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake are respectively washed by using a ceramic membrane filter, and then are mixed, ball-milled and spray-dried to obtain the spherical mesoporous composite material.
According to a specific embodiment, in the step (4), the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake are respectively washed by using a ceramic membrane filter, then are respectively ball-milled, and are mixed and then are spray-dried to obtain the spherical mesoporous composite material.
According to a specific embodiment, in the step (4), the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake are mixed and then washed by using a ceramic membrane filter, and then ball-milled and spray-dried to obtain the spherical mesoporous composite material.
According to a specific embodiment, in the step (4), the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake are respectively ball-milled, then the ball-milled products are respectively washed by using a ceramic membrane filter, and the washed products are mixed and then spray-dried to obtain the spherical mesoporous composite material.
According to a specific embodiment, in the step (4), the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake are respectively ball-milled, and then the ball-milled products are mixed and then are washed and spray-dried by using a ceramic membrane filter, so as to obtain the spherical mesoporous composite material.
According to a specific embodiment, in the step (4), the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake are mixed and then ball-milled, and then the ball-milled product is subjected to washing treatment and spray drying by using a ceramic membrane filter, so as to obtain the spherical mesoporous composite material.
The washing treatment may be performed using water and/or an alcohol (e.g., ethanol). According to a preferred embodiment of the present invention, when the content of sodium ions in the washing liquid of the ceramic membrane filter is detected to be 0.02 wt% or less and the content of the template agent is detected to be less than 1 wt%, the filtration is stopped to obtain a filter cake.
According to the present invention, in the step (4), the conditions and the specific operation method of the ball milling are not particularly limited and may be conventionally selected in the art. For example, the ball milling may be carried out in a ball mill in which the inner walls of the milling bowl are preferably lined with polytetrafluoroethylene and the grinding balls in the ball mill may have a diameter of 2-3 mm; the number of the grinding balls can be reasonably selected according to the size of the ball milling tank, and 1 grinding ball can be generally used for the ball milling tank with the size of 50-150 ml; the material of the grinding ball can be agate, polytetrafluoroethylene and the like, and agate is preferred. The ball milling conditions may include: the rotation speed of the grinding ball can be 300-500r/min, the temperature in the ball milling tank can be 15-100 ℃, and the ball milling time can be 0.1-100 hours.
According to the present invention, in step (4), the spray drying may be carried out according to a conventional method. May be at least one selected from the group consisting of a pressure spray drying method, a centrifugal spray drying method and a pneumatic spray drying method. According to a preferred embodiment of the present invention, the spray drying is a centrifugal spray drying method. The spray drying may be carried out in an atomizer. The conditions of the spray drying may include: the temperature is 100-300 ℃, and the rotating speed is 10000-15000 r/min; preferably, the spray drying conditions include: the temperature is 150-250 ℃, and the rotating speed is 11000-13000 r/min.
The preparation method of the spherical mesoporous composite material in the prior art usually further comprises a step of removing the template agent after spray drying, for example, removing the template agent by a calcination method. Because the method of the invention adopts the ceramic membrane for washing treatment, the method for preparing the spherical mesoporous material of the invention can not comprise the step of calcining to remove the template agent.
The invention also provides the spherical mesoporous composite material prepared by the method.
In the invention, the average particle diameter of the spherical mesoporous composite material is 20-60 μm, and the specific surface area is 150-600m2The pore volume is 0.5-1.8mL/g, the pore diameter is in trimodal distribution, and the trimodal corresponds to the first most probable pore diameter of 5-15nm, the second most probable pore diameter of 20-40nm and the third most probable pore diameter of 45-60nm respectively.
Preferably, the average particle diameter of the spherical mesoporous composite material is 40-50 μm, and the specific surface area is 220-300m2The pore volume is 1.1-1.7mL/g, the pore diameter is in trimodal distribution, and the trimodal corresponds to the first most probable pore diameter of 6-9nm, the second most probable pore diameter of 25-35nm and the third most probable pore diameter of 45-54nm respectively.
In the present invention, the specific surface area, pore volume and pore diameter are measured by a nitrogen adsorption method, and the average particle diameter is measured by a laser particle size distribution instrument. The average particle diameter is the average particle diameter.
The invention also provides a supported catalyst, which comprises a carrier and magnesium salt and/or titanium salt loaded on the carrier, wherein the carrier is the spherical mesoporous composite material provided by the invention.
According to the invention, the content of the support and of the magnesium and/or titanium salt supported on the support in the supported catalyst can vary within wide limits. For example, the carrier may be contained in an amount of 50 to 99% by weight, and the sum of the contents of the magnesium salt and the titanium salt, respectively, in terms of magnesium element and titanium element, may be 1 to 50% by weight, based on the total weight of the catalyst. Preferably, the content of the carrier is 85-99 wt% based on the total weight of the catalyst, and the sum of the contents of the magnesium salt and the titanium salt, calculated as magnesium element and titanium element, is 1-15 wt%.
According to a preferred embodiment of the present invention, the magnesium salt and the titanium salt are used in a weight ratio of 1:0.1 to 2, preferably 1: 0.5-2.
In the present invention, the kind of the magnesium salt and the titanium salt is not particularly limited, and may be conventionally selected in the art. For example, the magnesium salt may be one or more of magnesium chloride, magnesium sulfate, magnesium nitrate and magnesium bromide, preferably magnesium chloride; the titanium salt may be titanium tetrachloride and/or titanium trichloride.
In the invention, the content of each element in the catalyst component can be measured by adopting an X-ray fluorescence spectrum analysis method.
In the present invention, the supported catalyst may be prepared according to various methods conventionally used in the art, as long as a magnesium salt and/or a titanium salt is supported on the carrier.
The invention also provides a preparation method of the supported catalyst, which comprises the following steps: contacting the support with a mother liquor containing magnesium and/or titanium salts in the presence of an inert gas; wherein, the carrier is the spherical mesoporous composite material provided by the invention.
In the present invention, the mother liquor containing magnesium salt and/or titanium salt may be an organic solvent containing magnesium salt and/or titanium salt, the organic solvent may be isopropanol and tetrahydrofuran, and the volume ratio of tetrahydrofuran to isopropanol may be 1: 1-3, preferably 1: 1-1.5.
The magnesium salt and the titanium salt are preferably used in an excess amount relative to the support during the preparation of the catalyst. For example, the magnesium salt, the titanium salt and the carrier may be used in amounts such that the carrier may be contained in an amount of 50 to 99% by weight, and the sum of the contents of the magnesium salt and the titanium salt, respectively, in terms of magnesium element and titanium element, may be 1 to 50% by weight, based on the total weight of the catalyst, in the prepared supported catalyst; preferably, the content of the carrier is 85-99 wt% based on the total weight of the catalyst, and the sum of the contents of the magnesium salt and the titanium salt, calculated as magnesium element and titanium element, is 1-15 wt%.
Preferably, the conditions under which the support is contacted with the mother liquor containing a magnesium salt and/or a titanium salt include: the temperature can be 25-100 ℃, preferably 40-75 ℃; the time can be from 0.1 to 5h, preferably from 1 to 4 h.
In the present invention, the preparation method of the supported catalyst further comprises: after the carrier is contacted with the mother liquor containing a magnesium salt and/or a titanium salt, the carrier loaded with the magnesium salt and/or the titanium salt is filtered and dried. The drying conditions are not particularly limited and may be drying means and conditions which are conventional in the art. Preferably, the preparation of the supported catalyst also comprises a washing process after filtration and before drying, and/or a milling process after drying. The washing and milling conditions can be selected by the person skilled in the art according to the practical circumstances and will not be described in detail here.
In the present invention, the inert gas is a gas which does not react with the raw materials and the product, and may be, for example, nitrogen gas or at least one of group zero element gases in the periodic table, preferably nitrogen gas, which is conventional in the art.
The invention also provides a supported catalyst prepared by the method.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples,
polyoxyethylene-polyoxypropylene-polyoxyethylene, available from Aldrich, abbreviated as P123, having the formula EO20PO70EO20The substance having a number average molecular weight Mn of 5800 is registered with the American chemical Abstract under the accession number 9003-11-6.
The ceramic membrane filter used was an inorganic ceramic membrane element of JWCM19 x 30, available from Kyosu Jiuwu high-tech Co., Ltd., and a packing membrane area of 0.5m2The ceramic membrane module of (a); inorganic ceramic membrane elementThe parameters of the piece include: the shape is a multi-channel cylinder, the number of channels is 19, the diameter of the channels is 4mm, the length is 1016mm, and the outer diameter (diameter) is 30 mm.
Scanning electron microscopy analysis was performed on a scanning electron microscope, model XL-30, available from FEI, USA; pore structure parameter analysis was performed on a nitrogen desorption apparatus model Autosorb-1 available from corna, usa, wherein the sample was degassed at 200 ℃ for 4 hours before testing; the X-ray fluorescence analysis is carried out on an X-ray fluorescence analyzer with the model of Axios-Advanced of the Netherlands company; the particle size distribution curve was measured by a malvern laser particle sizer.
The bulk density of the polyolefin powder was determined by the method specified in GB/T1636-2008.
Polymer melt index: measured according to ASTM D1238-99.
Example 1
This example is used to illustrate the spherical mesoporous composite material and supported catalyst provided by the present invention and their preparation methods
(1) Preparation of spherical mesoporous composite material
1g (0.00017mol) of template P123 and 1.69g (0.037mol) of ethanol are added into 28mL of acetic acid and sodium acetate buffer solution with pH 4.4, the mixture is stirred at 15 ℃ until the template is completely dissolved, 6g (0.05mol) of trimethylpentane is added into the solution, the solution is stirred at 15 ℃ for 8 hours, 2.13g (0.014mol) of tetramethoxysilane is added into the solution, the solution is stirred at 15 ℃ for 20 hours, the solution is transferred into an agate-lined reaction kettle, oven crystallization is carried out at 60 ℃ for 24 hours, and then suction filtration is carried out to obtain a first mesoporous material filter cake A11.
Adding hexadecyl trimethyl ammonium bromide and ethyl orthosilicate into an ammonia water solution with the concentration of 25 weight percent at the temperature of 80 ℃, and then adding deionized water, wherein the adding amount of the ethyl orthosilicate is 1g, and the mol ratio of ammonia to water in the ethyl orthosilicate, the hexadecyl trimethyl ammonium bromide and the ammonia water is 1: 0.37: 2.8: 142 and stirred at the temperature of 80 ℃ for 4 hours, and then the solution is filtered by suction to obtain a second mesoporous material filter cake a 12.
Mixing 15 wt% water glass and 12 wt% sulfuric acid solution in the weight ratio of 5: 1, and then the mixture was subjected to a contact reaction at 20 ℃ for 1.5 hours, followed by adjusting the pH to 3 with sulfuric acid having a concentration of 98% by weight, and then the resulting reaction mass was subjected to suction filtration to obtain a silica gel cake B1.
5g of the filter cake A11 prepared above, 5g of the filter cake A12 prepared above and 10g of the filter cake B1 prepared above are mixed, and the mixture is washed by a ceramic membrane filter until the content of sodium ions is 0.02 wt% and the content of a template agent is less than 1 wt%, so that the spherical mesoporous composite material filter cake is obtained. Wherein the operating pressure of the membrane module is 3.3bar, the pressure of the membrane at the circulating side is 4bar, the pressure of the membrane at the circulating side is 2.5bar, the flow rate of the membrane surface at the circulating side is 4m/s, the pressure of the permeation side is 0.3bar, and the temperature is 20 ℃.3 parts by weight of water is consumed for preparing one part by weight of the spherical mesoporous composite filter cake.
And (3) putting the spherical mesoporous composite filter cake into a 100mL ball milling tank, wherein the ball milling tank is made of agate, the grinding balls are made of agate, the diameter of each grinding ball is 3mm, the number of the grinding balls is 1, and the rotating speed is 400 r/min. And (3) sealing the ball milling tank, carrying out ball milling for 5h at the temperature of 60 ℃ in the ball milling tank, and carrying out spray drying on the ball-milled slurry at the temperature of 200 ℃ at the rotating speed of 12000r/min to obtain the spherical mesoporous composite material C1.
The spherical mesoporous composite material C1 is characterized by XRD, a scanning electron microscope and a nitrogen adsorption instrument.
Fig. 1 is an X-ray diffraction pattern, wherein a is an XRD pattern of the spherical mesoporous composite material C1, the abscissa is 2 θ, and the ordinate is intensity. As can be seen from a small-angle spectrum peak appearing in an XRD spectrogram, the spherical mesoporous composite material C1 has a 2D hexagonal pore channel structure which is unique to mesoporous materials.
FIG. 2 is an SEM image. As can be seen from the figure, the microscopic morphology of the spherical mesoporous composite material C1 is microspheres with the particle size of 30-60 μm, and the dispersion performance is good.
Fig. 3 is a pore size distribution diagram of the spherical mesoporous composite material C1. As can be seen from the figure, the spherical mesoporous composite material C1 has a porous structure distribution and uniform pore channels.
The pore structure parameters of the spherical mesoporous composite material C1 are shown in table 1 below.
TABLE 1
*: the first most probable aperture, the second most probable aperture, and the third most probable aperture are separated by commas: the first most probable aperture, the second most probable aperture and the third most probable aperture are arranged in the order from left to right.
(2) Preparation of Supported catalysts
0.1g of magnesium chloride and 0.1g of titanium tetrachloride were dissolved in 10mL of a composite solvent of tetrahydrofuran and isopropanol (the volume ratio of tetrahydrofuran to isopropanol was 1: 1.2) to form a catalyst mother liquor. 1g of the spherical mesoporous composite material C1 was added to the mother liquor at 45 ℃ and immersed for 1h, then filtered, and washed with n-hexane for 4 times, dried at 75 ℃ and ground to obtain the catalyst D1.
As a result of X-ray fluorescence analysis, the catalyst D1 obtained in this example had a magnesium element content of 7.0 wt% and a titanium element content of 1.7 wt%, calculated as elements.
Example 2
This example illustrates the preparation of the spherical mesoporous composite material and supported catalyst of the present invention
(1) Preparation of spherical mesoporous composite material
Adding 1g (0.00017mol) of template P123 and 1.4g (0.03mol) of ethanol into 28mL of acetic acid and sodium acetate buffer solution with the pH value of 4.4, stirring at 10 ℃ until the template is completely dissolved, adding 4.56g (0.04mol) of trimethylpentane into the solution, stirring at 10 ℃ for 8 hours, adding 1.83g (0.012mol) of tetramethoxysilane into the solution, stirring at 10 ℃ for 30 hours, transferring the solution into an agate-lined reaction kettle, oven-crystallizing at 80 ℃ for 20 hours, and filtering to obtain a first mesoporous material filter cake A21.
Adding hexadecyl trimethyl ammonium bromide and ethyl orthosilicate into an ammonia water solution with the concentration of 25 weight percent at 50 ℃, and adding deionized water, wherein the adding amount of the ethyl orthosilicate is 1g, and the mol ratio of ammonia to water in the ethyl orthosilicate, the hexadecyl trimethyl ammonium bromide and the ammonia water is 1: 0.5: 1.5: 180 and stirring at 50 ℃ for 7 hours, and then filtering the solution by suction to obtain a second mesoporous material filter cake A22.
Mixing water glass with the concentration of 20 weight percent and sulfuric acid solution with the concentration of 12 weight percent in a weight ratio of 3: 1, and then the mixture is contacted and reacted at 20 ℃ for 3 hours, then the pH value is adjusted to 4 by using sulfuric acid with the concentration of 98 weight percent, and then the obtained reaction material is filtered by suction to obtain a filter cake B2 of silica gel.
6.7g of the filter cake A11, 3.3g of the filter cake A12 and 15g of the filter cake B1 prepared in the above were mixed, and the mixture was washed with a ceramic membrane filter until the sodium ion content was 0.02% by weight and the content of the template agent was less than 1% by weight, to obtain a spherical mesoporous composite filter cake. Wherein the operating pressure of the membrane module is 3bar, the pressure of the membrane at the circulating side is 3.5bar, the pressure of the membrane at the circulating side is 2.5bar, the flow rate of the membrane surface at the circulating side is 4.5m/s, the pressure of the permeation side is 0.4bar, and the temperature is 60 ℃.
And (3) putting the spherical mesoporous composite filter cake into a 100mL ball milling tank, wherein the ball milling tank is made of agate, the grinding balls are made of agate, the diameter of each grinding ball is 3mm, the number of the grinding balls is 1, and the rotating speed is 500 r/min. And (3) sealing the ball milling tank, carrying out ball milling for 20h at the temperature of 35 ℃ in the ball milling tank, and carrying out spray drying on the ball-milled slurry at the temperature of 150 ℃ at the rotating speed of 13000r/min to obtain the spherical mesoporous composite material C2.
The pore structure parameters of the spherical mesoporous composite material C2 are shown in table 2 below.
TABLE 2
*: the first most probable aperture, the second most probable aperture, and the third most probable aperture are separated by commas: the first most probable aperture, the second most probable aperture and the third most probable aperture are arranged in the order from left to right.
(2) Preparation of Supported catalysts
0.1g of magnesium chloride and 0.2g of titanium tetrachloride were dissolved in 10mL of a composite solvent of tetrahydrofuran and isopropanol (the volume ratio of tetrahydrofuran to isopropanol was 1: 1.5) to form a catalyst mother liquor. 1g of the spherical mesoporous composite material C2 was added to the mother liquor at 60 ℃ and immersed for 1h, then filtered, and washed with n-hexane for 4 times, dried at 75 ℃ and ground to obtain the catalyst D2.
As a result of X-ray fluorescence analysis, the catalyst D2 obtained in this example had a magnesium element content of 6.3 wt% and a titanium element content of 1.4 wt%, calculated as elements.
Example 3
This example illustrates the preparation of the spherical mesoporous composite material and supported catalyst of the present invention
(1) Preparation of spherical mesoporous composite material
Adding 1g (0.00017mol) of template P123 and 3.13g (0.068mol) of ethanol into 28mL of acetic acid and sodium acetate buffer solution with the pH value of 4.4, stirring at 20 ℃ until the template is completely dissolved, adding 7.75g (0.068mol) of trimethylpentane into the solution, stirring at 20 ℃ for 8h, adding 3.8g (0.025mol) of tetramethoxysilane into the solution, stirring at 20 ℃ for 10h, transferring the solution into an agate-lined reaction kettle, carrying out oven crystallization at 40 ℃ for 30h, and carrying out suction filtration to obtain a first mesoporous material filter cake A31.
Adding hexadecyl trimethyl ammonium bromide and ethyl orthosilicate into an ammonia water solution with the concentration of 25 weight percent at 90 ℃, and adding deionized water, wherein the adding amount of the ethyl orthosilicate is 1g, and the mol ratio of ammonia to water in the ethyl orthosilicate, the hexadecyl trimethyl ammonium bromide and the ammonia water is 1: 0.2: 3.5: 120 and stirring for 3 hours at the temperature of 90 ℃, and then filtering the solution by suction to obtain a second mesoporous material filter cake A32.
Mixing water glass with the concentration of 10 weight percent and sulfuric acid solution with the concentration of 12 weight percent in a weight ratio of 4: 1, and then the mixture is contacted and reacted for 1.5h at 30 ℃, then the pH value is adjusted to 2 by using sulfuric acid with the concentration of 98 weight percent, and then the obtained reaction material is filtered by suction to obtain a filter cake B3 of silica gel.
Mixing 7g of the filter cake A31, 14g of the filter cake A32 and 10g of the filter cake B3, and washing the mixture by using a ceramic membrane filter until the content of sodium ions is 0.02 wt% and the content of a template agent is less than 1 wt%, thereby obtaining the spherical mesoporous composite filter cake. Wherein the operating pressure of the membrane module is 3.4bar, the pressure of the membrane at the circulating side is 4.5bar, the pressure of the membrane at the circulating side is 2.3bar, the flow rate of the membrane surface at the circulating side is 4.2m/s, the pressure of the permeate side is 0.5bar, and the temperature is 40 ℃.
And (3) putting the spherical mesoporous composite filter cake into a 100mL ball milling tank, wherein the ball milling tank is made of agate, the grinding balls are made of agate, the diameter of each grinding ball is 3mm, the number of the grinding balls is 1, and the rotating speed is 500 r/min. And (3) sealing the ball milling tank, carrying out ball milling for 10h at the temperature of 50 ℃ in the ball milling tank, and carrying out spray drying on the ball-milled slurry at the temperature of 250 ℃ at the rotating speed of 11000r/min to obtain the spherical mesoporous composite material C3.
The pore structure parameters of the spherical mesoporous composite material C3 are shown in table 3 below.
TABLE 3
*: the first most probable aperture, the second most probable aperture, and the third most probable aperture are separated by commas: the first most probable aperture, the second most probable aperture and the third most probable aperture are arranged in the order from left to right.
(2) Preparation of Supported catalysts
0.2g of magnesium chloride and 0.1g of titanium tetrachloride were dissolved in 10mL of a composite solvent of tetrahydrofuran and isopropanol (the volume ratio of tetrahydrofuran to isopropanol was 1: 1) to form a catalyst mother liquor. 1g of the spherical mesoporous composite material C3 was added to the mother liquor at 40 ℃ and immersed for 1h, then filtered, and washed with n-hexane for 4 times, dried at 75 ℃ and ground to obtain the catalyst D3.
As a result of X-ray fluorescence analysis, the catalyst D3 obtained in this example had a magnesium element content of 5.3 wt% and a titanium element content of 1.1 wt%, calculated as elements.
Comparative example 1
Comparative example to illustrate a reference Carrier and Supported catalyst and Process for making the same
(1) Preparation of the support
Mixing 15 wt% water glass and 12 wt% sulfuric acid solution in the weight ratio of 5: 1 at 20 c, followed by adjustment of the pH to 3 with 98% by weight sulfuric acid, and then treatment of the resulting reaction mass with a plate and frame filter press, followed by washing with water to a sodium ion content of 0.02% by weight, to give a silica gel filter cake. Eleven parts by weight of water were consumed to prepare one part by weight of the silica gel filter cake.
And (3) putting 10g of the silica gel filter cake into a 100ml ball milling tank, wherein the ball milling tank is made of polytetrafluoroethylene, grinding balls are made of agate, the diameter of each grinding ball is 3mm, the number of the grinding balls is 1, and the rotating speed is 400 r/min. And (3) sealing the ball milling tank, carrying out ball milling for 5h at the temperature of 60 ℃ in the ball milling tank, carrying out spray drying on the ball-milled slurry at the temperature of 200 ℃ at the rotating speed of 12000r/min, and calcining the spray-dried product in a muffle furnace at the temperature of 400 ℃ for 10h in a nitrogen atmosphere to remove hydroxyl and residual moisture, thereby obtaining the silica gel carrier DA 1.
(2) Preparation of Supported catalysts
The procedure was followed as in example 1, except that the spherical mesoporous composite material C1 was replaced with the silica gel carrier DA1 to obtain a supported catalyst DD 1.
As a result of X-ray fluorescence analysis, the obtained catalyst DD1 contained 1.1 wt% of magnesium, 1.7 wt% of titanium, and 18.32 wt% of chlorine.
Comparative example 2
Comparative example to illustrate a reference Carrier and Supported catalyst and Process for making the same
(1) Preparation of the support
The procedure of example 1 was followed, except that the washing was not carried out using a ceramic membrane filter, but a mixture of the first mesoporous material cake, the second mesoporous material cake, and the silica gel cake was washed using distilled water, and only the mixture was mixed with distilled water and then subjected to suction filtration, and the washing was repeated until the sodium ion content was 0.02% by weight, to obtain a spherical mesoporous composite filter cake. Eleven parts by weight of water consumed by preparing one part by weight of the spherical mesoporous composite filter cake. Followed by ball milling and spray drying according to the method of example 1, to obtain a spherical mesoporous composite material DC 1.
(2) Preparation of Supported catalysts
The procedure was followed as in example 1, except that the spherical mesoporous composite material C1 was replaced with the spherical mesoporous composite material DC1, to obtain a supported catalyst DD 2.
Comparative example 3
Comparative example to illustrate a reference Carrier and Supported catalyst and Process for making the same
The preparation of the support and supported catalyst was carried out according to the method of comparative example 2, except that the following steps were added after spray drying: and calcining the spray-dried product in a muffle furnace at 400 ℃ for 24h in a nitrogen atmosphere, and removing the template agent to obtain the spherical mesoporous composite material DC2 and the supported catalyst DD 3.
Experimental example 1
This experimental example is used to illustrate the application of the supported catalyst provided by the present invention.
In a 2L stainless steel high pressure polymerization reactor, nitrogen and ethylene were each replaced three times, then 200mL of hexane was added, the reactor was warmed to 80 ℃ and 800mL of hexane was added, 2mL of a 1mol/L Triethylaluminum (TEA) solution in hexane was added with the addition of hexane, then 0.5g of catalyst component D1 was added, ethylene gas was introduced, the pressure was raised to 1.0MPa and maintained at 1.0MPa, and after 1 hour of reaction at 70 ℃, separation by suction filtration was carried out to obtain a polyethylene pellet powder. Bulk Density (BD) and melt index MI of the obtained polyethylene granular powder2.16And the catalyst efficiencies are listed in table 4.
Experimental example 2
This experimental example is used to illustrate the application of the supported catalyst provided by the present invention.
In a 2L stainless steel autoclave, nitrogen and ethylene were each replaced three times, then 200mL of hexane were added, the autoclave was warmed to 75 ℃ and 900mL of hexane were added, followed by 2mL of 1mol/L hexaneA hexane solution of Triethylaluminum (TEA), followed by addition of 0.1g of catalyst component D2, passing ethylene gas through, increasing the pressure to 1MPa and maintaining it at 1MPa, reaction at 75 ℃ for 1.5 hours and separation by suction filtration gave polyethylene granular powder. Bulk Density (BD) and melt index MI of the obtained polyethylene granular powder2.16And the catalyst efficiencies are listed in table 4.
Experimental example 3
This experimental example is used to illustrate the application of the supported catalyst provided by the present invention.
In a 2L stainless steel high pressure polymerization reactor, nitrogen and ethylene were each replaced three times, then 200mL of hexane was added, the reactor was warmed to 85 ℃ and 700mL of hexane was added, 2mL of a 1mol/L Triethylaluminum (TEA) solution in hexane was added with the addition of hexane, then 1g of catalyst component D3 was added, ethylene gas was introduced, the pressure was raised to 1MPa and maintained at 1MPa, and after reacting at 85 ℃ for 2 hours, separation by suction filtration, a polyethylene pellet powder was obtained. Bulk Density (BD) and melt index MI of the obtained polyethylene granular powder2.16And the catalyst efficiencies are listed in table 4.
Experimental comparative examples 1 to 3
This experimental comparative example serves to illustrate the use of a reference supported catalyst
Polymerization of ethylene was carried out in the same manner as in experimental example 1, except that the catalysts D1 prepared in example 1 were replaced with the same parts by weight of comparative catalysts DD1, DD2 and DD3 prepared in comparative examples 1-3, respectively. Bulk Density (BD) and melt index MI of the obtained polyethylene granular powder2.16And the catalyst efficiencies are listed in table 4.
TABLE 4
From the results of experimental examples 1 to 3 and experimental comparative examples 1 to 3, it can be seen that the polyethylene catalyst prepared by using the spherical mesoporous composite material prepared by the method as the carrier has high catalytic activity, and can obtain a spherical polyethylene product with lower bulk density and lower melt index. In addition, the carrier of the supported catalyst prepared by the method of the invention has less water consumption and less generated waste water. The catalyst can be directly loaded after spray drying without calcining, thereby simplifying the preparation process.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (25)
1. A preparation method of a spherical mesoporous composite material is characterized by comprising the following steps:
(1) carrying out first mixing contact on a template agent, tetramethoxysilane, ethanol, trimethylpentane and an acid agent, and crystallizing and filtering a mixture obtained by the first mixing contact to obtain a first mesoporous material filter cake;
(2) carrying out second mixing contact on ethyl orthosilicate, hexadecyl trimethyl ammonium bromide and ammonia, and filtering a mixture obtained by the second mixing contact to obtain a second mesoporous material filter cake;
(3) carrying out third mixing contact on water glass and inorganic acid, and filtering a mixture obtained after the third mixing contact to obtain a silica gel filter cake;
(4) respectively or after mixing the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake, carrying out ball milling on the ball-milled products, washing the ball-milled products by using a ceramic membrane filter, and then carrying out spray drying to obtain the spherical mesoporous composite material; or,
respectively or after mixing the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake, washing the mixture by using a ceramic membrane filter, and then carrying out ball milling and spray drying to obtain a spherical mesoporous composite material;
wherein, the washing treatment conditions using the ceramic membrane filter include: the operating pressure is 2.5-3.9bar, the pressure of the circulating side inlet membrane is 3-5bar, the pressure of the circulating side outlet membrane is 2-2.8bar, and the flow rate of the circulating side membrane surface is 4-5 m/s; the pressure of the permeation side is 0.3-0.5 bar; the temperature is 10-60 ℃.
2. The preparation method according to claim 1, wherein, in the step (4), the silica gel cake is used in an amount of 1 to 200 parts by weight relative to 100 parts by weight of the total amount of the first mesoporous material cake and the second mesoporous material cake; the weight ratio of the first mesoporous material filter cake to the second mesoporous material filter cake is 1: 0.1-10.
3. The preparation method according to claim 2, wherein the silica gel cake is used in an amount of 20 to 180 parts by weight, relative to 100 parts by weight of the total amount of the first mesoporous material cake and the second mesoporous material cake; the weight ratio of the first mesoporous material filter cake to the second mesoporous material filter cake is 1: 0.5-2.
4. The preparation method according to claim 3, wherein the silica gel cake is used in an amount of 50 to 150 parts by weight, relative to 100 parts by weight of the total amount of the first mesoporous material cake and the second mesoporous material cake.
5. The preparation method according to claim 1, wherein, in step (1), the template is a triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene; the acid agent is acetic acid and sodium acetate buffer solution with pH value of 1-6.
6. The production method according to claim 1, wherein, in step (1), the molar ratio of the template, ethanol, trimethylpentane and tetramethoxysilane is 1: 100-500: 200-500: 50-200.
7. The preparation method according to claim 6, wherein the molar ratio of the template, ethanol, trimethylpentane and tetramethoxysilane is 1: 180-400: 250-400: 70-150.
8. The production method according to claim 1, wherein, in step (1), the conditions of the first mixing contact include: the temperature is 10-60 ℃, the time is 10-72 hours, and the pH value is 1-7; the conditions for crystallization of the mixture obtained by the first mixing contact include: the temperature is 30-150 ℃ and the time is 10-72 hours.
9. The production method according to claim 1, wherein in step (2), the molar ratio of ethyl orthosilicate, cetyltrimethylammonium bromide and ammonia is 1: 0.1-1: 0.1-5.
10. The method of claim 9, wherein the molar ratio of ethyl orthosilicate, cetyltrimethylammonium bromide and ammonia is 1: 0.2-0.5: 1.5-3.5.
11. The production method according to claim 1, wherein, in step (2), the conditions of the second mixing contact include: the temperature is 25-100 ℃ and the time is 2-8 hours.
12. The production method according to claim 1, wherein in step (3), the weight ratio of the water glass to the inorganic acid is 3-6:1, and the inorganic acid is one or more of sulfuric acid, nitric acid and hydrochloric acid.
13. The method of claim 1, wherein the third mixing contact conditions comprise: the temperature is 10-60 deg.C, the time is 1-5 hr, and the pH value is 2-4.
14. The preparation method of claim 1, wherein, in the step (4), the ball milling conditions include: the rotation speed of the grinding ball is 300-.
15. The production method according to claim 1, wherein, in the step (4), the conditions of the spray-drying include: the temperature is 100-300 ℃, and the rotating speed is 10000-15000 r/min.
16. The spherical mesoporous composite material prepared by the preparation method of any one of claims 1 to 15.
17. The spherical mesoporous composite material as claimed in claim 16, wherein the average particle diameter of the spherical mesoporous composite material is 20-60 μm, and the specific surface area is 150-600m2The pore volume is 0.5-1.8mL/g, the pore diameter is in trimodal distribution, and the trimodal corresponds to the first most probable pore diameter of 5-15nm, the second most probable pore diameter of 20-40nm and the third most probable pore diameter of 45-60nm respectively.
18. The spherical mesoporous composite material as claimed in claim 17, wherein the average particle diameter of the spherical mesoporous composite material is 40-50 μm, and the specific surface area is 220-300m2The pore volume is 1.1-1.7mL/g, the pore diameter is in trimodal distribution, and the trimodal corresponds to the first most probable pore diameter of 6-9nm, the second most probable pore diameter of 25-35nm and the third most probable pore diameter of 45-54nm respectively.
19. A supported catalyst comprising a carrier and a magnesium salt and/or a titanium salt supported on the carrier, wherein the carrier is the spherical mesoporous composite material according to any one of claims 16 to 18.
20. The supported catalyst of claim 19, wherein the support is present in an amount of 50 to 99 wt.%, and the sum of the amounts of the magnesium salt and the titanium salt, calculated as magnesium and titanium, respectively, is 1 to 50 wt.%, based on the total weight of the catalyst.
21. The supported catalyst of claim 20, wherein the support is present in an amount of 85 to 99 wt.%, and the sum of the amounts of the magnesium salt and the titanium salt, calculated as magnesium and titanium, respectively, is 1 to 15 wt.%, based on the total weight of the catalyst.
22. A method of preparing a supported catalyst, the method comprising: contacting the support with a mother liquor containing magnesium and/or titanium salts in the presence of an inert gas; wherein the carrier is the spherical mesoporous composite material according to any one of claims 16 to 18.
23. The process of claim 22 wherein the magnesium salt, the titanium salt and the support are present in amounts such that in the prepared supported catalyst the support is present in an amount of from 50 to 99 wt%, and the sum of the amounts of the magnesium salt and the titanium salt, as magnesium and titanium, respectively, is from 1 to 50 wt%, based on the total weight of the catalyst.
24. The process of claim 23 wherein the support is present in an amount of 85 to 99 wt.%, and the sum of the amounts of the magnesium salt and the titanium salt, calculated as magnesium and titanium, respectively, is 1 to 15 wt.%, based on the total weight of the catalyst.
25. A supported catalyst prepared by the process of any one of claims 22-24.
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