CN113663669A - Hydrosilylation catalyst, preparation method and application thereof - Google Patents
Hydrosilylation catalyst, preparation method and application thereof Download PDFInfo
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- CN113663669A CN113663669A CN202111018951.8A CN202111018951A CN113663669A CN 113663669 A CN113663669 A CN 113663669A CN 202111018951 A CN202111018951 A CN 202111018951A CN 113663669 A CN113663669 A CN 113663669A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 110
- 238000006459 hydrosilylation reaction Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 39
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 238000001354 calcination Methods 0.000 claims abstract description 27
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000000465 moulding Methods 0.000 claims abstract description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005977 Ethylene Substances 0.000 claims abstract description 15
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 15
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000009467 reduction Effects 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims description 58
- 239000000843 powder Substances 0.000 claims description 42
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000012298 atmosphere Substances 0.000 claims description 21
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- KRBSYIOFFXEHQK-UHFFFAOYSA-K ruthenium(3+);trichloride;dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cl-].[Ru+3] KRBSYIOFFXEHQK-UHFFFAOYSA-K 0.000 claims description 5
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 claims description 5
- ZTWIEIFKPFJRLV-UHFFFAOYSA-K trichlororuthenium;trihydrate Chemical compound O.O.O.Cl[Ru](Cl)Cl ZTWIEIFKPFJRLV-UHFFFAOYSA-K 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 abstract description 13
- 239000002815 homogeneous catalyst Substances 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 9
- 230000002194 synthesizing effect Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000000376 reactant Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 20
- 238000005303 weighing Methods 0.000 description 19
- 238000003756 stirring Methods 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
- 239000008185 minitablet Substances 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 14
- 229910001928 zirconium oxide Inorganic materials 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 229910019891 RuCl3 Inorganic materials 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000007809 chemical reaction catalyst Substances 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- -1 alicyclic amine Chemical class 0.000 description 2
- 230000004075 alteration Effects 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
- 238000005119 centrifugation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000003921 particle size analysis Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910018084 Al-Fe Inorganic materials 0.000 description 1
- 229910018192 Al—Fe Inorganic materials 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical group NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- UNPLRYRWJLTVAE-UHFFFAOYSA-N Cloperastine hydrochloride Chemical compound Cl.C1=CC(Cl)=CC=C1C(C=1C=CC=CC=1)OCCN1CCCCC1 UNPLRYRWJLTVAE-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 229960003493 octyltriethoxysilane Drugs 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007652 sheet-forming process Methods 0.000 description 1
- 150000004756 silanes Chemical group 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
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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
-
- 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
- Y02P20/584—Recycling of catalysts
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Abstract
The invention provides a hydrosilylation catalyst, a preparation method and application thereof. The preparation method comprises the following steps: and mixing a ruthenium source, a solvent and a carrier, and then sequentially carrying out calcination treatment, molding treatment and reduction treatment to obtain the catalyst. The catalyst has excellent selectivity in the reaction of synthesizing ethyl triethoxysilane from ethylene and triethoxysilane, has performance obviously higher than that of a ruthenium trichloride homogeneous catalyst, is easy to separate from liquid reactants and products, is convenient to recover, and can be recycled. Meanwhile, the preparation method of the catalyst has the advantages of simple process, low cost and easy implementation.
Description
Technical Field
The invention belongs to the field of catalysts, and relates to a hydrosilylation catalyst, and a preparation method and application thereof.
Background
Ethyltriethoxysilane is an important organosilicon chemical reagent, can be used as a raw material of silicone resin, a silica gel cross-linking agent, a silane coupling agent, a silicon-based aerogel, a surfactant, a release coating, a lubricant, an adhesive and the like, and can also be used for synthesizing organosilicon intermediates and high molecular polymers. In addition, the method has important application in the production of dielectric materials and insulating materials, and also has important significance in the design of novel catalysts, defense materials and life science products.
The industrial traditional method for producing ethyltriethoxysilane mainly uses ethylene and triethoxysilane as raw materials, adopts noble metal compound as homogeneous catalyst, and is synthesized by hydrosilylation reaction, and the reaction equation is as follows:
CH2＝CH2+HSi(OC2H5)3→CH3CH2Si(OC2H5)3+Si(OC2H5)4+ minor amounts of other products
Seki et al (Journal of Organic Chemistry,1986,51(21):3890-5) reported a method for synthesizing ethyltriethoxysilane by using triethoxysilane and ethylene as raw materials and benzene as a solvent and using a catalyst of ruthenium dodecacarbonyl, but the product obtained by the method contains a large amount of vinyltriethoxysilane, and is poor in selectivity, difficult in separation of the solvent, product and catalyst, and easily causes environmental pollution by using a large amount of highly toxic benzene solvent. Chernyshev et al (Russian Journal of General Chemistry,2006,76(2):225-228) report a process for the preparation of ethyltriethoxysilane by homogeneous catalysis with a vinyl complex of platinum (Karstedt catalyst) starting from triethoxysilane and ethylene. CN101735263A reports that iodine-doped RuCl was selected3·3H2O as a homogeneous catalytic system shows higher catalytic activity and selectivity, but iodine is easy to sublimate, thereby polluting the environment. CN102898458A reports RuCl3·3H2O is used as a main catalyst, CuCl is used as a cocatalyst, and triethoxysilane and ethylene are used as raw materials to synthesize the ethyltriethoxysilane. From the technical background, the problem of difficult separation and recycling of different noble metal homogeneous catalysts is solved. Therefore, it is necessary to develop a supported heterogeneous catalyst which can be used for hydrosilylation of triethoxysilane and ethylene, and has high activity, high selectivity and recycle.
Recent studies have shown that certain noble metal monatomic catalysts can be used as alternatives to hydrosilylationA homogeneous catalyst. Cui et Al (ACS Central Science,2017,3,580-585) reported that Al is loaded on2O3The above monatomic Pt catalyst can be used for hydrosilylation reactions of 1-octene with various tertiary silanes. Chen et al (Journal of the American Chemical Society,2018,140,7407-7410) reported a support on TiO2The single atom Pt catalyst can be used for preparing octyl triethoxysilane by hydrosilylation of 1-octene and triethoxysilane. In addition, numerous patents report the preparation and other uses of various noble metal monoatomic atoms. CN107649124B discloses a preparation method and application of a metal rhodium (Rh), ruthenium (Ru), platinum (Pt), iridium (Ir), palladium (Pd) and titanium oxide bi-component catalyst. CN112774707A discloses that Ru-N-C monatomic catalyst can be used for the reaction of preparing sorbitol by glucose hydrogenation. CN112973751A discloses a Ru monoatomic compound and g-C3N4A preparation method of a composite photocatalyst. CN111036291A discloses g-C modified with anilines3N4And loading ruthenium salt as a carrier, and then reducing, washing and drying to obtain the monoatomic Ru-based Fischer-Tropsch synthesis catalyst. CN 112387295A discloses that a nitrogen-doped carbon-supported Ru monatomic catalyst can be used for the reaction of preparing alicyclic amine by one-step hydrogenation of nitroaromatic compounds. CN111715235B discloses a high-temperature anti-loss Mg-Al-Fe spinel loaded Ru monatomic catalyst and a preparation method thereof. CN109234756A discloses a hydrotalcite-supported Ru monatomic catalyst and a preparation method thereof. CN111001426B discloses a Ru monatomic catalyst supported on the surface of transition metal nitride or transition metal carbide and a preparation method thereof.
CN108940274A and CN111269086A disclose Ru monatomic catalysts supported on the surface of metal oxide and methods for preparing the same, respectively. Therefore, it is possible to develop a monatomic Ru catalyst instead of a Ru homogeneous catalyst for the hydrosilylation reaction of ethylene and triethoxysilane to synthesize ethyltriethoxysilane.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a hydrosilylation catalyst, a preparation method and an application thereof, wherein the catalyst has excellent selectivity in the reaction of synthesizing ethyl triethoxysilane from ethylene and triethoxysilane, has performance obviously higher than that of a ruthenium trichloride homogeneous catalyst, is easy to separate from liquid reactants and products, is convenient to recover and can be recycled. Meanwhile, the preparation method of the catalyst has the advantages of simple process, low cost and easy implementation.
In order to achieve the technical effect, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide a hydrosilylation reaction catalyst, which consists of a carrier and monatomic ruthenium loaded on the carrier.
In the invention, Ru is dispersed on the surface of the carrier in an atomic-level dispersion mode, the utilization rate of Ru atoms can reach 100 percent, the catalyst can replace the traditional homogeneous catalyst and is used for selectively synthesizing the ethyltriethoxysilane by taking ethylene and triethoxysilane as raw materials through hydrosilylation.
In a preferred embodiment of the present invention, the ruthenium content in the catalyst is 0.1 to 1.0% by mass, for example, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, or 0.9%, but the catalyst is not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
As a preferred embodiment of the present invention, the carrier comprises zirconium dioxide.
In a preferred embodiment of the present invention, the particle size distribution of the catalyst is in the range of 1.0 to 5.0mm, such as 1.5mm, 2mm, 2.5mm, 3mm, 3.5mm, 4mm or 4.5mm, but the catalyst is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Another object of the present invention is to provide a method for preparing the above hydrosilylation catalyst, the method comprising:
and mixing a ruthenium source, a solvent and a carrier, and then sequentially carrying out calcination treatment, molding treatment and reduction treatment to obtain the catalyst.
As a preferred embodiment of the invention, the ruthenium source comprises any one of ruthenium chloride monohydrate, ruthenium chloride dihydrate or ruthenium chloride trihydrate, or a combination of at least two of these, typical but non-limiting examples being: a combination of ruthenium chloride monohydrate and ruthenium chloride dihydrate, a combination of ruthenium chloride dihydrate and ruthenium chloride trihydrate, a combination of ruthenium chloride trihydrate and ruthenium chloride monohydrate, or a combination of ruthenium chloride monohydrate, ruthenium chloride dihydrate, and ruthenium chloride trihydrate, and the like.
Preferably, the solvent comprises any one of water, ethanol, isopropanol or acetone, or a combination of at least two of these, typical but non-limiting examples being: a combination of water and ethanol, a combination of ethanol and isopropanol, a combination of isopropanol and acetone, or a combination of water, ethanol and isopropanol, etc., preferably water.
Preferably, the ratio of the mass of ruthenium in the ruthenium source to the volume of the solvent is 3 to 6g/L, such as 3.5g/L, 4g/L, 4.5g/L, 5g/L, or 5.5g/L, but not limited to the recited values, and other values not recited in this range are equally applicable.
Preferably, the carrier is zirconia powder.
Preferably, the zirconia powder is monoclinic zirconia.
Preferably, the particle size of the zirconia powder is 30 to 1000nm, such as 50nm, 100nm, 150nm, 200nm, 250nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, etc., but not limited to the recited values, and other values not recited in the range of the values are also applicable.
In a preferred embodiment of the present invention, the temperature of the calcination treatment is 300 to 600 ℃, for example, 350 ℃, 400 ℃, 450 ℃, 500 ℃ or 550 ℃, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are also applicable, and preferably 400 to 500 ℃.
Preferably, the time of the calcination treatment is 0.5 to 4.0 hours, such as 1.0 hour, 1.5 hours, 2.0 hours, 2.5 hours, 3.0 hours, or 3.5 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 1.0 to 3.0 hours.
Preferably, the solvent is removed by evaporation and/or drying before the calcination.
In the present invention, the calcination treatment may be carried out in a tube furnace, a box furnace or a rotary furnace.
In a preferred embodiment of the present invention, the molding process includes any one or a combination of at least two of a sheet forming process, a strip extruding process, and a spray granulation process.
In a preferred embodiment of the present invention, the reduction treatment is performed in a reducing atmosphere.
Preferably, the reducing atmosphere comprises hydrogen or a mixture of hydrogen and nitrogen.
Preferably, the temperature of the reduction treatment is 140 to 230 ℃, such as 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃,200 ℃, 210 ℃ or 220 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 160 to 200 ℃.
Preferably, the time of the reduction treatment is 0.5 to 4.0 hours, such as 1.0 hour, 1.5 hours, 2.0 hours, 2.5 hours, 3.0 hours, or 3.5 hours, but is not limited to the recited values, and other values not recited in the range of the values are also applicable, and more preferably 1.0 to 3.0 hours.
In the present invention, the reduction treatment may be carried out in a tube furnace, a box furnace or a rotary furnace.
The invention also aims to provide the application of the hydrosilylation catalyst, and the catalyst is used for selectively synthesizing the ethyltriethoxysilane by the hydrosilylation reaction of ethylene and triethoxysilane.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the invention provides a hydrosilylation catalyst, wherein Ru in the catalyst is distributed in an atomic form, the dispersity is high, the utilization rate of catalyst atoms is high and can almost reach 100%;
(2) the invention provides a hydrosilylation catalyst, which has obviously higher performance than a ruthenium trichloride homogeneous catalyst in the reaction of preparing ethyltriethoxysilane by the addition of ethylene and triethoxysilane, is easy to separate from liquid reactants and products, is convenient to recover and can be recycled, and has obvious economic benefit;
(3) the invention provides a preparation method of a hydrosilylation catalyst, which has the advantages of simple process, low cost and easy implementation.
Drawings
FIG. 1 is an electron microscope image of spherical aberration of a zirconia-supported Ru monatomic catalyst prepared in example 1 of the present invention;
FIG. 2 is an appearance diagram of a zirconia-supported Ru monatomic catalyst prepared in example 1 of the present invention;
FIG. 3 is a graph comparing the color of the filtered zirconia-supported Ru monatomic catalyst reaction product prepared in example 1 of the present invention with the color of the homogeneous catalyst reaction product.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
This embodiment provides a preparation method of a hydrosilylation catalyst, including:
weighing technical grade 0.112g RuCl3·H2And adding 25mL of deionized water into the O to dissolve the O, mixing the O with 10.0g of monoclinic commercial zirconium oxide powder (the particle size is 30-50 nm), and heating and stirring the mixed solution until the solvent is evaporated to dryness. Calcining the rest of the dried powder in air at 400 deg.C for 2H, molding with a laboratory mini-tablet machine, and placing in a tube furnace H2Reducing for 2h at 170 ℃ in the atmosphere to obtain the zirconia-supported Ru monatomic catalyst, wherein the supported Ru amount is 0.5%, the particle diameter is 5mm, the thickness is 3-5 mm, and the total particle size distribution range is 3-5 mm.
The monoatomic and particle size analysis of the prepared zirconia-supported Ru monoatomic catalyst specifically comprises the following steps:
(1) single atom test analysis: the Ru monatomic catalyst prepared above was characterized by using a transmission electron microscope for spherical aberration correction of the FeI-Titan cube Themis G2300, the Netherlands, as shown in FIG. 1. As can be seen from fig. 1, no Ru nanoparticles or Ru clusters are shown on the zirconia surface, and the bright spots of the individual Ru atoms marked by black circles are uniformly dispersed, confirming that Ru exists as isolated individual atoms.
(2) And (3) particle size analysis: the photograph analysis using a general camera is shown in FIG. 2. As can be seen from FIG. 2, the particle diameter of the prepared zirconia-supported Ru monatomic catalyst is 5mm, the thickness of the catalyst is 3-5 mm, and the total particle size distribution range is 4-5 mm.
(3) Color analysis of the product: the reaction product of the zirconium oxide supported Ru monatomic catalyst and the filtered product was photographed with a general camera, as shown in fig. 3. It can be seen from fig. 3 that the ethyl triethoxysilane product after the reaction of the zirconia-supported Ru monatomic catalyst and the particulate catalyst can be separated by simple filtration, the product is a transparent liquid, and the reaction product after the use of the homogeneous catalyst is miscible with the homogeneous catalyst, cannot be separated, and is brown in color.
Example 2
This embodiment provides a preparation method of a hydrosilylation catalyst, including:
weighing 0.022g of RuCl of industrial grade3·H2And adding 25.0mL of deionized water to dissolve O, mixing with 10.0g of monoclinic commercial zirconium oxide powder (the particle size is 30-50 nm), and heating and stirring the mixed solution until the solvent is evaporated to dryness. Calcining the rest of the dried powder in air at 400 deg.C for 2H, molding with a laboratory mini-tablet machine, and placing in a tube furnace H2Reducing for 2h at 170 ℃ in the atmosphere to obtain the zirconia-supported Ru monatomic catalyst, wherein the supported Ru amount is 0.1%, the particle diameter is 5mm, the thickness is 3-5 mm, and the total particle size range is 3-5 mm.
Example 3
This embodiment provides a preparation method of a hydrosilylation catalyst, including:
weighing industrial-grade 0.225 gGluCl3·H2Adding 25mL of deionized water into O for dissolving, and mixing with 10.0g of monoclinic commercial zirconium oxide powder (the particle size is 30-50 n)m), mixing, heating and stirring the mixed solution until the solvent is evaporated to dryness. Calcining the rest of the dried powder in air at 400 deg.C for 2H, molding with a laboratory mini-tablet machine, and placing in a tube furnace H2Reducing for 2h at 170 ℃ in the atmosphere to obtain the zirconia-supported Ru monatomic catalyst, wherein the supported Ru amount is 1.0%, the particle diameter is 5mm, the thickness is 3-5 mm, and the total particle size range is 3-5 mm.
Example 4
This embodiment provides a preparation method of a hydrosilylation catalyst, including:
weighing industrial grade 0.112 gGluCl3·H2And adding 19.0mL of deionized water into the O to dissolve the O, mixing with 10.0g of monoclinic commercial zirconium oxide powder (the particle size is 30-50 nm), and heating and stirring the mixed solution until the solvent is evaporated to dryness. Calcining the rest of the dried powder in air at 400 ℃ for 2H, then forming by using a laboratory spray granulator, and putting the mixture in a tube furnace H2Reducing at 170 ℃ for 2h in the atmosphere to obtain the zirconia supported Ru monatomic catalyst, wherein the supported Ru amount is 0.5%, the average particle diameter is about 1.5mm, and the total particle size range is 1-2 mm.
Example 5
This embodiment provides a preparation method of a hydrosilylation catalyst, including:
weighing industrial grade 0.112 gGluCl3·H2And adding 37.0mL of deionized water into the O to dissolve the O, mixing the O with 10.0g of monoclinic commercial zirconium oxide powder (the particle size is 30-50 nm), and heating and stirring the mixed solution until the solvent is evaporated to dryness. Calcining the rest dry powder in air at 400 deg.C for 2H, shaping with a laboratory plodder, and placing in a tube furnace H2Reducing for 2h at 170 ℃ in the atmosphere to obtain the zirconia supported Ru monatomic catalyst, wherein the supported Ru amount is 0.5%, the particle diameter is 2mm, the length is 1-5mm, and the total particle size range is 1-5 mm.
Example 6
This embodiment provides a preparation method of a hydrosilylation catalyst, including:
weighing industrial grade 0.112 gGluCl3·H2Adding 25.0mL of ethanol into the O to dissolve,and mixing with 10.0g of monoclinic commercial zirconia powder (the particle size is 30-50 nm), and heating and stirring the mixed solution until the solvent is evaporated to dryness. Calcining the rest of the dried powder in air at 400 deg.C for 2H, molding with a laboratory mini-tablet machine, and placing in a tube furnace H2Reducing for 2h at 170 ℃ in the atmosphere to obtain the zirconia-supported Ru monatomic catalyst, wherein the supported Ru amount is 0.5%, the particle diameter is 5mm, the thickness is 3-5 mm, and the total particle size range is 3-5 mm.
Example 7
This embodiment provides a preparation method of a hydrosilylation catalyst, including:
weighing industrial grade 0.112 gGluCl3·H2Adding 25.0mL of isopropanol into O, mixing with 10.0g of monoclinic commercial zirconia powder (the particle size is 30-50 nm), and heating and stirring the mixed solution until the solvent is evaporated to dryness. Calcining the rest of the dried powder in air at 400 deg.C for 2H, molding with a laboratory mini-tablet machine, and placing in a tube furnace H2Reducing for 2h at 170 ℃ in the atmosphere to obtain the zirconia-supported Ru monatomic catalyst, wherein the supported Ru amount is 0.5%, the particle diameter is 5mm, the thickness is 3-5 mm, and the total particle size range is 3-5 mm.
Example 8
This embodiment provides a preparation method of a hydrosilylation catalyst, including:
weighing industrial grade 0.112 gGluCl3·H2And adding 20.0mL of acetone into the O to dissolve the O, mixing the O with 10.0g of monoclinic commercial zirconia powder (the particle size is 30-50 nm), and heating and stirring the mixed solution until the solvent is evaporated to dryness. Calcining the rest of the dried powder in air at 400 deg.C for 2H, molding with a laboratory mini-tablet machine, and placing in a tube furnace H2Reducing for 2h at 170 ℃ in the atmosphere to obtain the zirconia-supported Ru monatomic catalyst, wherein the supported Ru amount is 0.5%, the particle diameter is 5mm, the thickness is 3-5 mm, and the total particle size range is 3-5 mm.
Example 9
This embodiment provides a preparation method of a hydrosilylation catalyst, including:
weighing toolTechnical grade 0.112 gCuCl3·H2And adding 20.0mL of deionized water to dissolve O, mixing with 10.0g of monoclinic commercial zirconium oxide powder (the particle size is 100-500 nm), and heating and stirring the mixed solution until the solvent is evaporated to dryness. The remaining dry powder was calcined in air at 400 ℃ for 2H, then shaped using a laboratory bench-top tablet machine and placed in a tube furnace at 50% H2/N2Reducing for 4 hours at 170 ℃ in the atmosphere to obtain the zirconia-loaded Ru monatomic catalyst, wherein the loaded Ru amount is 0.5%, the particle diameter is 5mm, the thickness is 3-5 mm, and the total particle size range is 3-5 mm.
Example 10
This embodiment provides a preparation method of a hydrosilylation catalyst, including:
weighing industrial grade 0.112 gGluCl3·H2And adding 25.0mL of deionized water to dissolve O, mixing with 10.0g of monoclinic commercial zirconium oxide powder (the particle size is 500-1000 nm), and heating and stirring the mixed solution until the solvent is evaporated to dryness. Calcining the remaining dry powder in air at 300 deg.C for 4H, then forming with a laboratory mini-tablet machine, and in a tube furnace H2Reducing for 2h at 170 ℃ in the atmosphere to obtain the zirconia-supported Ru monatomic catalyst, wherein the supported Ru amount is 0.5%, the particle diameter is 5mm, the thickness is 3-5 mm, and the total particle size range is 3-5 mm.
Example 11
This embodiment provides a preparation method of a hydrosilylation catalyst, including:
weighing industrial grade 0.112 gGluCl3·H2And adding 25.0mL of deionized water to dissolve O, mixing with 10.0g of monoclinic commercial zirconium oxide powder (the particle size is 30-50 nm), and heating and stirring the mixed solution until the solvent is evaporated to dryness. Calcining the remaining dry powder in air at 500 deg.C for 2H, then forming with a laboratory mini-tablet machine, and in a tube furnace H2Reducing for 2h at 170 ℃ in the atmosphere to obtain the zirconia-loaded Ru monatomic catalyst, wherein the loaded Ru amount is 0.5%, the particle diameter is 5mm, the thickness is 3-5 mm, and the total particle size is 3-5 mm.
Example 12
This embodiment provides a preparation method of a hydrosilylation catalyst, including:
weighing industrial-grade 0.120 gGluCl3·2H2And adding 25.0mL of deionized water to dissolve O, mixing with 10.0g of monoclinic commercial zirconium oxide powder (the particle size is 30-50 nm), and heating and stirring the mixed solution until the solvent is evaporated to dryness. The remaining dry powder was calcined in air at 500 ℃ for 2H, then shaped using a laboratory minitablet machine and placed in a tube furnace H2Reducing the zirconium oxide loaded Ru for 1h in an atmosphere at 230 ℃ to obtain the zirconium oxide loaded Ru monatomic catalyst, wherein the loaded Ru amount is 0.5%, the particle diameter is 5mm, the thickness is 3-5 mm, and the total particle size range is 3-5 mm.
Example 13
This embodiment provides a preparation method of a hydrosilylation catalyst, including:
weighing industrial grade 0.129 gGluCl3·3H2And adding 25.0mL of deionized water to dissolve O, mixing with 10.0g of monoclinic commercial zirconium oxide powder (the particle size is 30-50 nm), and heating and stirring the mixed solution until the solvent is evaporated to dryness. Calcining the remaining dry powder in air at 600 deg.C for 1H, molding with a laboratory mini-tablet machine, and placing in a tube furnace H2Reducing for 2h at 170 ℃ in the atmosphere to obtain the zirconia-supported Ru monatomic catalyst, wherein the supported Ru amount is 0.5%, the particle diameter is 5mm, the thickness is 3-5 mm, and the total particle size range is 3-5 mm.
Example 14
The temperature of the calcination treatment in this example was 300 ℃ and the time was 4 hours; the temperature of the reduction treatment was 130 ℃ and the time was 4 hours, and the other conditions were the same as in example 1.
Comparative example 1
The present comparative example provides a preparation method of a hydrosilylation reaction catalyst, the preparation method comprising:
weighing technical grade 0.112g RuCl3·H2O was dissolved in 25mL of deionized water and mixed with 10.0g of commercial cerium oxide powder, and the mixture was heated and stirred until the solvent was evaporated to dryness. Calcining the rest dry powder in air at 400 deg.C for 2h, molding with a laboratory mini-tablet machine, and placing in a tubeIn a furnace H2Reducing at 170 ℃ for 2h in the atmosphere to obtain the cerium oxide supported Ru catalyst, wherein the supported Ru content is 0.5%, the particle diameter is 5mm, the thickness is 3-5 mm, and the total particle size range is 3-5 mm.
Comparative example 2
The present comparative example provides a preparation method of a hydrosilylation reaction catalyst, the preparation method comprising:
weighing technical grade 0.112g RuCl3·H2O was dissolved in 25mL of deionized water and mixed with 10.0g of commercial alumina powder and the mixture was heated and stirred until the solvent was evaporated to dryness. Calcining the rest of the dried powder in air at 400 deg.C for 2H, molding with a laboratory mini-tablet machine, and placing in a tube furnace H2Reducing the mixture for 2 hours at 170 ℃ in the atmosphere to obtain the aluminum oxide supported Ru catalyst, wherein the supported Ru amount is 0.5%, the particle diameter is 5mm, the thickness is 3-5 mm, and the total particle size range is 3-5 mm.
Comparative example 3
The present comparative example provides a preparation method of a hydrosilylation reaction catalyst, the preparation method comprising:
weighing technical grade 0.112g RuCl3·H2O is dissolved in 25mL of deionized water and mixed with 10.0g of commercial activated carbon powder, and the mixture is heated and stirred until the solvent is evaporated to dryness. Calcining the rest of the dried powder in air at 400 deg.C for 2H, molding with a laboratory mini-tablet machine, and placing in a tube furnace H2Reducing at 170 ℃ for 2h in the atmosphere to obtain the active carbon supported Ru catalyst, wherein the supported Ru content is 0.5%, the particle diameter is 5mm, the thickness is 3-5 mm, and the total particle size range is 3-5 mm.
Comparative example 4
The present comparative example provides a preparation method of a hydrosilylation reaction catalyst, the preparation method comprising:
weighing technical grade 0.112g RuCl3·H2O was dissolved in 25mL of deionized water and mixed with 10.0g of commercial silica powder, and the mixture was heated with stirring until the solvent was evaporated to dryness. Calcining the rest of the dried powder in air at 400 deg.C for 2H, molding with a laboratory mini-tablet machine, and placing in a tube furnace H2170 ℃ in an atmosphereAnd reducing for 2 hours to obtain the silica supported Ru catalyst, wherein the supported Ru amount is 0.5%, the particle diameter is 5mm, the thickness is 3-5 mm, and the total particle size range is 3-5 mm.
Comparative example 5
The present comparative example provides a preparation method of a hydrosilylation reaction catalyst, the preparation method comprising:
weighing 0.100g of PdCl2·2H2And adding 25mL of deionized water into the O to dissolve the O, mixing the O with 10.0g of monoclinic commercial zirconium oxide powder (the particle size is 30-50 nm), and heating and stirring the mixed solution until the solvent is evaporated to dryness. Calcining the rest of the dried powder in air at 400 deg.C for 2H, molding with a laboratory mini-tablet machine, and placing in a tube furnace H2Reducing for 2h at 170 ℃ in the atmosphere to obtain the zirconium dioxide loaded Pd catalyst, wherein the amount of the loaded Pd is 0.5%, the particle diameter is 5mm, the thickness is 3-5 mm, and the total particle size range is 3-5 mm.
Comparative example 6
The comparative example was carried out under the same conditions as in example 1 except that the reduction treatment was not carried out, and finally, zirconium dioxide-supported RuO was obtained2Catalyst, Supported RuO2The amount is 0.6%, the particle diameter is 5mm, the thickness is 3-5 mm, and the total particle size range is 3-5 mm.
In order to examine the catalytic performance of the zirconia-supported Ru monatomic catalyst in the hydrosilylation reaction of ethylene and triethoxysilane to synthesize ethyltriethoxysilane, the zirconia-supported Ru monatomic catalyst obtained in examples 1-14, the Ru catalysts obtained in example 1 with 5 cycles, the Ru catalysts obtained in comparative examples 1-6 with different carriers, and the commonly used Ru homogeneous catalyst (RuCl)3·H2O、RuCl3·2H2O and RuCl3·3H2O) carrying out a catalytic activity test, which specifically comprises the following steps: weighing 25mL of triethoxysilane, adding the triethoxysilane into a dry 100mL high-pressure reaction kettle, attaching a magnetic stirrer, a gas bottom-inserting tube, a contact thermometer and a snake-shaped stainless steel circulating condensation pipeline in the kettle, adding a certain mass of catalyst (20-40 meshes of powder is sieved out for experiments after the catalyst prepared by the invention is crushed), and controlling the Ru content and the triethoxysilane content in the catalystThe molar ratio is 1.1X 10-4. Before the reaction, replacing the air in the reaction kettle with nitrogen, then starting heating and continuously introducing ethylene gas (60mL/min), controlling the pressure in the reaction kettle to be 0.35MPa, the reaction temperature to be 60 ℃, the stirring speed to be 200rpm, stopping the reaction after reacting for 4h, dismantling the reaction device, analyzing and determining the conversion rate of triethoxysilane by GC (Agilent 7890B, HP-5 chromatographic column and TCD detector), and determining the selectivity of the product according to the quantitative analysis result. The catalyst recycling process comprises the following steps: after the single reaction is finished, transferring the product mixed with the heterogeneous catalyst into a centrifuge tube for centrifugation, wherein the conditions of the centrifugation process are 2500rpm and 10min, mixing the catalyst obtained by centrifugal separation with 25mL of triethoxysilane raw material, and then reintroducing the mixture into the reaction system for the next reaction. The results of the reaction are shown in table 1.
TABLE 1
As can be seen from the performance evaluation results in Table 1, the selectivity of the target product ethyltriethoxysilane and the conversion rate of the triethoxysilane as the reaction raw material in the hydrosilylation reaction of ethylene and triethoxysilane by using the zirconia-supported Ru monatomic catalyst (examples 1-14) prepared by the present invention are significantly higher than those of the different-carrier-supported Ru catalysts and homogeneous Ru catalysts (RuCl) obtained by the comparative examples 1-63·H2O、RuCl3·2H2O and RuCl3·3H2O). After 5 cycles of the catalyst prepared in example 1, the selectivity was almost unchanged, but the conversion was slightly reduced, indicating that the zirconia-supported Ru monatomic catalyst could be recycled. Comparative example 1 (cerium oxide carrier), comparative example 2 (alumina carrier), comparative example 3 (activated carbon carrier), comparative example 4 (silica carrier), comparative example 5 (Pd-supported), and comparative example 6 (RuO-supported) were compared2) The zirconia supports selected for use in examples 1-14 have unique advantages and exhibit excellent catalytic performance. The zirconia-supported Ru monogens provided by the present invention are comparable to commercial homogeneous catalystsThe sub-catalyst has better catalytic performance. This is mainly due to the fact that in the catalyst according to the process of the invention the Ru is dispersed in the form of an atomic dispersion on the support ZrO2The utilization rate of Ru atoms on the surface can reach 100 percent, and the Ru atoms and the carrier ZrO2The catalyst has a synergistic catalytic action, so that more excellent catalytic performance is obtained.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A hydrosilylation catalyst, characterized in that the catalyst consists of a carrier and monatomic ruthenium loaded on the carrier.
2. The catalyst according to claim 1, wherein the ruthenium content in the catalyst is 0.1 to 1.0% by mass.
3. The catalyst of claim 1 or 2, wherein the support comprises zirconium dioxide.
4. The catalyst according to any one of claims 1 to 3, wherein the catalyst has a particle size distribution in the range of 1.0 to 5.0 mm.
5. A method for preparing the catalyst of any one of claims 1 to 4, comprising:
and mixing a ruthenium source, a solvent and a carrier, and then sequentially carrying out calcination treatment, molding treatment and reduction treatment to obtain the catalyst.
6. The production method according to claim 5, wherein the ruthenium source comprises any one of ruthenium chloride monohydrate, ruthenium chloride dihydrate or ruthenium chloride trihydrate, or a combination of at least two of them;
preferably, the solvent comprises any one of water, ethanol, isopropanol or acetone or a combination of at least two thereof, preferably water;
preferably, the ratio of the mass of ruthenium in the ruthenium source to the volume of the solvent is 3-6 g/L;
preferably, the carrier is zirconia powder;
preferably, the zirconia powder is monoclinic zirconia;
preferably, the particle diameter of the zirconia powder is 30-1000 nm.
7. The method according to claim 5 or 6, wherein the temperature of the calcination treatment is 300 to 600 ℃, preferably 400 to 500 ℃;
preferably, the time of the calcination treatment is 0.5-4.0 h, preferably 1.0-3.0 h;
preferably, the solvent is removed by evaporation and/or drying before the calcination.
8. The production method according to any one of claims 5 to 7, wherein the molding treatment includes any one of a sheet forming treatment, a bar extruding treatment, or a spray granulation treatment or a combination of at least two thereof.
9. The production method according to any one of claims 5 to 8, characterized in that the reduction treatment is performed in a reducing atmosphere;
preferably, the reducing atmosphere comprises hydrogen or a mixture of hydrogen and nitrogen;
preferably, the temperature of the reduction treatment is 140-230 ℃, and preferably 160-200 ℃;
preferably, the time of the reduction treatment is 0.5-4.0 h, preferably 1.0-3.0 h.
10. Use of a catalyst as claimed in any one of claims 1 to 4 for the selective synthesis of ethyltriethoxysilane by the hydrosilylation reaction of ethylene with triethoxysilane.
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