CN113617353A - Preparation method of silicon carbide-based silver nano catalyst and application of silicon carbide-based silver nano catalyst in synthesis of ethylene oxide - Google Patents
Preparation method of silicon carbide-based silver nano catalyst and application of silicon carbide-based silver nano catalyst in synthesis of ethylene oxide Download PDFInfo
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- CN113617353A CN113617353A CN202110879899.9A CN202110879899A CN113617353A CN 113617353 A CN113617353 A CN 113617353A CN 202110879899 A CN202110879899 A CN 202110879899A CN 113617353 A CN113617353 A CN 113617353A
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- silicon carbide
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 91
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 40
- 239000004332 silver Substances 0.000 title claims abstract description 40
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000005977 Ethylene Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 229910052796 boron Inorganic materials 0.000 claims abstract description 11
- 238000011068 loading method Methods 0.000 claims abstract description 11
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012071 phase Substances 0.000 claims abstract description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 5
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- 238000012986 modification Methods 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 5
- 238000000967 suction filtration Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004472 Lysine Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000012279 sodium borohydride Substances 0.000 claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910000085 borane Inorganic materials 0.000 claims description 2
- 125000005619 boric acid group Chemical group 0.000 claims description 2
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 claims description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 2
- 229940043256 calcium pyrophosphate Drugs 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 235000019821 dicalcium diphosphate Nutrition 0.000 claims description 2
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 235000019820 disodium diphosphate Nutrition 0.000 claims description 2
- GYQBBRRVRKFJRG-UHFFFAOYSA-L disodium pyrophosphate Chemical compound [Na+].[Na+].OP([O-])(=O)OP(O)([O-])=O GYQBBRRVRKFJRG-UHFFFAOYSA-L 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims 3
- 229910003465 moissanite Inorganic materials 0.000 claims 2
- 239000012266 salt solution Substances 0.000 claims 2
- 239000005696 Diammonium phosphate Substances 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000005470 impregnation Methods 0.000 claims 1
- 238000002715 modification method Methods 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 238000011946 reduction process Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 150000003754 zirconium Chemical class 0.000 claims 1
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 abstract description 18
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001961 silver nitrate Inorganic materials 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 description 14
- 238000005406 washing Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 240000006909 Tilia x europaea Species 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
-
- 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
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- 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)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of a silicon carbide-based silver nano catalyst and application thereof in ethylene oxide synthesis, comprising modification of SiC carrier and size regulation of silver nano particles, firstly, in the preparation process of SiC precursor, adding a proper amount of boron source and phosphorus source to carry out B, P bulk phase doping on SiC; then using CeO2、ZrO2、Al2O3Modifying the SiC surface by oxide containing oxygen vacancy; finally, loading metallic silver on the surface of the SiC carrier by using different amounts of silver nitrate as a precursor by adopting a liquid phase reduction method, performing suction filtration,Drying to obtain the supported silicon carbide-based silver nano catalyst. The catalyst prepared by optimizing the property of the catalyst carrier and the metal loading condition has the characteristics of controllable silver particle size, uniform dispersion, good thermal conductivity, good stability and the like. The catalyst is used in the reaction of preparing ethylene oxide by ethylene epoxidation, and can show excellent catalytic activity, product selectivity and stability.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a preparation method of a silicon carbide-based silver nano catalyst and application of the silicon carbide-based silver nano catalyst in synthesis of ethylene oxide.
Background
Ethylene oxide is an important organic chemical raw material and is widely used in washing, pharmacy, printing and dyeing and other industries. Conventional methods for producing ethylene oxide include chlorohydrin processes and oxidation processes. The chlorohydrin method mainly comprises two steps: the first step is that ethylene and chlorine are introduced into water to react to generate 2-chloroethanol; the second step is to react 2-chloroethanol with alkali (common lime milk) to produce ethylene oxide product. However, the ethylene unit consumption is high and the environmental pollution is serious in the production process of the chlorohydrin method, and the ethylene unit consumption is gradually stopped.
Currently, the industrial production of ethylene oxide is mainly carried out by the direct oxidation process, i.e. the epoxidation of ethylene based on oxygen to produce ethylene oxide. The existing ethylene oxide industrial production device mostly adopts an Ag-based nano catalyst, and the Ag-based nano catalyst has certain defects after years of development although the catalytic performance is improved. Firstly, the selectivity of the catalyst is a problem, and one of the main reasons that the selectivity of the product is difficult to improve at present is that oxidation reaction releases a large amount of heat, and the heat removal rate has a bottleneck, and the core factor of the catalyst is that the heat conduction rate of the traditional carrier material alpha-alumina is low; secondly, the specific surface area of the alpha-alumina carrier material adopted by the traditional technology is small, the dispersity of the loaded Ag is poor, and the Ag is easy to agglomerate; to ensure activity, high loadings of Ag are required. In addition, if a material with acid sites on the surface is used as a catalyst carrier, the reaction network is easier to proceed to the route of ethylene oxide isomerization to acetaldehyde, and the EO selectivity is seriously reduced, so that a surface inert material is required as the carrier. Therefore, an inert inorganic material with a high specific surface area and good thermal conductivity is developed to be used as a carrier, so that the selectivity and the stability of the Ag-based catalyst can be effectively improved.
Silicon carbide is a semiconductor material, has high temperature resistance, corrosion resistance, high mechanical strength and good chemical stability, and particularly has good electric conductivity and heat conductivity. In addition, when a metal is loaded on the surface of the SiC, electron transfer can occur between the metal and the SiC carrier, so that the metal and the SiC carrier can show unique activity and selectivity in catalytic reaction. High specific surface area silicon carbide as oneThe novel supports have shown significant advantages in the fields of catalysis, photocatalysis and electrocatalysis. Therefore, SiC is used as the carrier of the ethylene epoxidation catalyst, and the existing Ag/alpha-Al can be broken through2O3The catalytic system faces the technical bottlenecks of low product selectivity and high Ag loading, thereby generating a subversive effect on the epoxidation reaction.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: in order to overcome the defects in the prior art, the invention provides a preparation method of a silicon carbide-based silver nano catalyst and application of the silicon carbide-based silver nano catalyst in ethylene oxide synthesis, so that the nano catalyst with uniform metal dispersion, good stability and good thermal conductivity is obtained and is used for preparing ethylene oxide by ethylene epoxidation.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of silicon carbide based silver nano-catalyst comprises the following steps:
(1) during the preparation of SiC precursor, adding boron source and phosphorus source to carry out B, P bulk phase doping on SiC, and then adopting CeO2、ZrO2、Al2O3And modifying the SiC surface by oxide containing oxygen vacancy or mixture thereof to obtain the modified SiC carrier.
(2) Mixing and stirring a certain amount of silver nitrate solution and the SiC carrier for a period of time, then dropwise adding a quantitative 0.1M lysine solution, continuously stirring, finally dropwise adding a proper amount of 0.1M sodium borohydride solution and a proper amount of 0.1M hydrochloric acid solution into the reaction solution in sequence, continuously stirring for reaction, performing suction filtration, washing and drying to obtain the high-efficiency silicon carbide-based silver catalyst.
Preferably, the content of the bulk phase doping B, P in the carrier is controlled to be B/Si or the molar ratio of P/Si is 0.01-1; surface modification of CeO2、ZrO2、Al2O3The content of the oxygen-containing vacancy oxide is 0.1-20% of the mass fraction of the silicon carbide.
Preferably, the phosphorus source is phosphoric acid, phosphorous acid, sodium phosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, calcium hydrogen phosphate, calcium pyrophosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium acid pyrophosphate, sodium dihydrogen phosphate or sodium pyrophosphate; the boron source is boric acid, borane, boron trichloride or boron trifluoride.
Preferably, the carrier in the metal loading process is an optimally screened SiC carrier.
Preferably, the content of silver in the catalyst is 0.1-80% of the weight fraction of the silicon carbide, and the particle size of the prepared silver nanoparticles is less than 5-50 nm.
Preferably, the added lysine accounts for 0.1-80% of the weight fraction of the silicon carbide.
Preferably, the amount of the sodium borohydride reducing agent added is 0.1-80% of the weight fraction of the silicon carbide.
Preferably, the amount of the added hydrochloric acid solution is controlled to keep the pH value of the reaction solution between 9 and 10.
Preferably, the temperature in the preparation process of the catalyst is controlled to be 20-50 ℃.
Preferably, after each drop of the solution is added, the stirring is continued for 0.5-2 hours; and stirring and reacting for 1-48 h after all the dropwise adding is finished.
Preferably, the catalyst preparation process agitation is magnetic agitation.
Preferably, the catalyst wash is a wash with deionized water.
Preferably, the drying temperature of the catalyst is 50-80 ℃, and the drying time is 6-18 h.
The silicon carbide-based silver nano-catalyst prepared by the method is applied to the reaction of preparing ethylene oxide by ethylene epoxidation, and the specific reaction conditions are as follows: filling 0.05-50 g of silicon carbide-based silver nano catalyst on a fixed bed reactor, wherein the raw materials comprise ethylene and oxygen, and the balance is nitrogen; the airspeed is 800-10000 h-1The reaction pressure is 0-5 MPa, the reaction temperature is 100-300 ℃, the selectivity of the catalyst to ethylene oxide reaches over 80 percent, and the service life of the catalyst reaches over 800 hours.
The invention has the beneficial effects that: the invention uses silicon carbide as a catalyst carrier and utilizes a liquid phase reduction method to load active silver nano particles. The silicon carbide-based silver nanocatalyst with uniform metal dispersion, good thermal conductivity and high stability is prepared by optimizing the property of the silicon carbide carrier and a metal loading process, the preparation process has universality and simplicity, and the industrial synthesis is easy to realize; the catalyst can show higher activity, selectivity and cycling stability when being applied to the preparation of ethylene oxide by ethylene epoxidation.
Detailed Description
Specific examples of the present invention are described in further detail below. It should be understood that the specific embodiments described herein are only for illustrating and explaining the technical solutions of the present invention, and are not used to limit the technical solutions of the present invention.
Example one
High surface silicon carbide was used directly as support: 1854mL of AgNO3Uniformly mixing and stirring an aqueous solution (0.01M) and 18g of silicon carbide, adding 200mL of 0.1M lysine, stirring for 1h, then adding 100mL of 0.1M sodium borohydride aqueous solution, stirring for 0.5h, finally adding 100mL of 0.1M HCl to keep the pH of the solution between 9 and 10, then continuing stirring for 24h at room temperature, centrifuging, washing and drying to obtain the Ag/SiC catalyst with the loading of 10 wt%, wherein the average particle size of silver particles is about 20 nm.
5g of the catalyst is filled into a fixed bed reactor, and the volume of raw material gas comprises 25 percent of ethylene, 7 percent of oxygen and the balance of nitrogen; the space velocity is 5000h-1The reaction pressure is 1.5MPa, and the reaction temperature is 200 ℃. The gas chromatography quantitative detection of the outlet gas and the feed gas of the reactor shows that the ethylene conversion rate is 5 percent and the selectivity of the ethylene oxide is 82.5 percent.
Example two
Directly using high-surface silicon carbide as a carrier, then using aluminum nitrate as a precursor, and modifying Al on the surface of the silicon carbide2O3The content is 5 percent of the mass fraction of the silicon carbide.
1854mL of AgNO3Mixing and stirring uniformly an aqueous solution (0.01M) and 18g of modified silicon carbide, adding 200mL of 0.1M lysine, stirring for 1h, then adding 100mL of 0.1M sodium borohydride aqueous solution, stirring for 0.5h, finally adding 100mL of 0.1M HCl to keep the pH of the solution between 9 and 10, then continuing stirring for 30h at room temperature, centrifuging, washingWashing and drying to obtain Ag/Al with the loading of 10 wt%2O3-SiC catalyst, in which the silver particles have an average particle size of about 13 nm.
Filling 8g of the catalyst into a fixed bed reactor, wherein the volume of raw material gas comprises 25% of ethylene, 8% of oxygen and the balance of nitrogen; space velocity is 5500h-1The reaction pressure is 1.5MPa, and the reaction temperature is 200 ℃. The gas chromatography quantitative detection of the outlet gas and the feed gas of the reactor shows that the ethylene conversion rate is 5.9 percent and the selectivity of the ethylene oxide is 85 percent.
EXAMPLE III
In the preparation process of the silicon carbide precursor, adding a proper amount of boric acid to enable the molar ratio of B/Si to be 0.1, and preparing a B-doped silicon carbide carrier (B-SiC); then with Ce (NO)3)2·6H2O is used as a precursor, and a single-layer CeO is modified on the surface of the B-SiC2(CeO22 percent of the mass fraction of B-SiC) to obtain the modified silicon carbide carrier.
2224.9mL of AgNO3Uniformly mixing and stirring an aqueous solution (0.01M) and 17.6g of modified silicon carbide, adding 250mL of 0.1M lysine, stirring for 1h, then adding 130mL of 0.1M sodium borohydride aqueous solution, stirring for 0.5h, and finally adding 130mL of 0.1M HCl to keep the pH value of the solution between 9 and 10; then continuously stirring for 24 hours at room temperature, centrifuging, washing and drying to obtain Ag/CeO with the load of 12 wt%2-B-SiC catalyst, wherein the silver particles have an average particle size of about 15 nm.
5g of the catalyst is filled into a fixed bed reactor, and the volume of raw material gas comprises 25 percent of ethylene, 8 percent of oxygen and the balance of nitrogen; the space velocity is 5000h-1The reaction pressure is 2MPa, and the reaction temperature is 190 ℃. The gas chromatography quantitative detection of the reactor outlet gas and the feed gas shows that the ethylene conversion rate is 7 percent and the selectivity of the ethylene oxide is 884 percent.
Example four
In the preparation process of the silicon carbide precursor, adding a proper amount of ammonium phosphate to ensure that the molar ratio of P/Si is 0.5, and preparing a P-doped silicon carbide carrier (P-SiC); then, taking zirconium oxychloride as a precursor to modify ZrO on the surface of the P-SiC2(ZrO21 percent of P-SiC mass fraction) to obtain the modified silicon carbide carrier.
927mL of AgNO3Uniformly mixing and stirring an aqueous solution (0.01mol/L) and 19g of silicon carbide, adding 150mL of 0.1M lysine, stirring for 1h, then adding 50mL of 0.1M sodium borohydride aqueous solution, stirring for 0.5h, and finally adding 50mL of 0.1M HCl to keep the pH of the solution between 9 and 10; then continuously stirring for 24 hours at room temperature, centrifuging, washing and drying to obtain Ag/ZrO with the load of 5 wt%2-P-SiC catalyst, in which the silver particles have an average particle size of about 15 nm.
3g of the catalyst is filled into a fixed bed reactor, and the volume of raw material gas comprises 26 percent of ethylene, 8 percent of oxygen and the balance of nitrogen; the space velocity is 4000h-1The reaction pressure is 2.5MPa, and the reaction temperature is 200 ℃. The gas chromatography quantitative detection of the outlet gas and the feed gas of the reactor shows that the ethylene conversion rate is 6.3 percent and the selectivity of the ethylene oxide is 87.4 percent.
After the catalyst is used for 800 hours, the conversion rate of ethylene is 5.9 percent, and the selectivity of ethylene oxide is 80 percent.
EXAMPLE five
In the preparation process of the silicon carbide precursor, a proper amount of boric acid is added to ensure that the molar ratio of B/Si is 0.3, and the B-doped silicon carbide carrier (B-SiC) is prepared. Then cerium nitrate and aluminum nitrate are taken as precursors to modify CeO on the surface of B-SiC2And Al2O3(the content of the oxide is 3 percent of the mass fraction of the B-SiC) to obtain the modified silicon carbide carrier.
1483mL of AgNO3Uniformly mixing and stirring an aqueous solution (0.01mol/L) and 18.4g of silicon carbide, adding 180mL of 0.1M lysine, stirring for 1h, then adding 70mL of 0.1M sodium borohydride aqueous solution, stirring for 0.5h, and finally adding 70mL of 0.1M HCl to keep the pH value of the solution between 9 and 10; then continuously stirring for 24 hours at room temperature, centrifuging, washing and drying to obtain Ag/CeO with the load of 8 wt%2-Al2O3-B-SiC catalyst, wherein the silver particles have an average particle size of about 15 nm.
6g of the catalyst is filled into a fixed bed reactor, and the volume composition of raw material gas is 28 percent of ethylene and oxygen9 percent of nitrogen and the balance of nitrogen; the space velocity is 8000h-1The reaction pressure is 2MPa, and the reaction temperature is 210 ℃. The gas chromatography quantitative detection of the outlet gas and the feed gas of the reactor shows that the ethylene conversion rate is 7.2 percent and the selectivity of the ethylene oxide is 84.0 percent.
After the catalyst is used for 500 hours, the conversion rate of ethylene is 6.8 percent, and the selectivity of ethylene oxide is 80 percent.
EXAMPLE six
In the preparation process of the silicon carbide precursor, adding a proper amount of boric acid to enable the molar ratio of B/Si to be 0.25, and preparing a B-doped silicon carbide carrier (B-SiC); then cerium nitrate and zirconium nitrate are used as precursors to modify CeO on the surface of B-SiC2And ZrO2(the content of the oxide is 4 percent of the mass fraction of the B-SiC) to obtain the modified silicon carbide carrier.
742mL of AgNO3Uniformly mixing and stirring an aqueous solution (0.01M) and 19.2g of silicon carbide, adding 100mL of 0.1M lysine, stirring for 2h, then adding 50mL of 0.1M sodium borohydride aqueous solution, stirring for 1h, and finally adding 30mL of 0.1M HCl to keep the pH of the solution between 9 and 10; then continuously stirring for 48 hours at room temperature, centrifuging, washing and drying to obtain Ag/CeO with the load of 4 wt%2-ZrO2-B-SiC catalyst, wherein the silver particles have an average particle size of about 10 nm.
10g of the catalyst is filled into a fixed bed reactor, and the volume of raw material gas comprises 28 percent of ethylene, 8 percent of oxygen and the balance of nitrogen; space velocity of 7000h-1The reaction pressure is 2.3MPa, and the reaction temperature is 200 ℃. The gas chromatography quantitative detection of the outlet gas and the feed gas of the reactor shows that the ethylene conversion rate is 6.5 percent and the selectivity of the ethylene oxide is 88 percent.
After the catalyst is used for 200 hours, the conversion rate of ethylene is 6.1 percent, and the selectivity of ethylene oxide is 80 percent.
EXAMPLE seven
Adding a proper amount of phosphoric acid in the preparation process of the silicon carbide precursor to enable the molar ratio of P/Si to be 0.19, and preparing a P-doped silicon carbide carrier (P-SiC); then, cerium nitrate and zirconium nitrate are used as precursors to modify CeO on the surface of P-SiC2And ZrO2(the oxide content is B-SiC by mass)Fraction 10%) to yield a modified silicon carbide support.
5562mL of AgNO3Uniformly mixing and stirring an aqueous solution (0.0mol/L) and 34g of silicon carbide, adding 600mL of 0.1M lysine, stirring for 1h, then adding 350mL of 0.1M sodium borohydride aqueous solution, stirring for 2h, and finally adding 350mL of 0.1M HCl to keep the pH of the solution between 9 and 10; then continuously stirring for 48 hours at room temperature, centrifuging, washing and drying to obtain Ag/CeO with 15 wt% of loading capacity2-ZrO2-B-SiC catalyst, wherein the silver particles have an average particle size of about 25 nm.
Filling 30g of the catalyst into a fixed bed reactor, wherein the volume of raw material gas comprises 30% of ethylene, 9% of oxygen and the balance of nitrogen; space velocity of 10000h-1The reaction pressure is 1.5MPa, and the reaction temperature is 180 ℃. The gas chromatography quantitative detection of the outlet gas and the feed gas of the reactor shows that the ethylene conversion rate is 6.8 percent and the selectivity of the ethylene oxide is 85.3 percent.
After 800h of use, the catalyst had an ethylene conversion of 6.5% and an ethylene oxide selectivity of 82%.
According to the invention, P, B is doped in the silicon carbide carrier to increase the thermal conductivity of the carrier, accelerate the heat removal rate of the catalyst and effectively improve the selectivity of ethylene epoxidation to ethylene oxide; the oxygen vacancy on the surface of the catalyst is increased by modifying the oxide on the surface of the catalyst, so that the loaded silver nano particles are effectively stabilized, and the stability of the catalyst is improved; the catalyst prepared by optimizing the properties of the silicon carbide carrier and the metal loading process has the advantages of uniform metal dispersion, good thermal conductivity and good stability; the preparation process of the catalyst has universality and simplicity and is easy for industrial synthesis; the prepared silicon carbide-based silver nano-catalyst has higher activity, selectivity and cycling stability for preparing ethylene oxide by ethylene epoxidation.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. A preparation method of silicon carbide based silver nano catalyst is characterized by comprising the following steps: the preparation method comprises the following steps: and (3) taking SiC/modified SiC as a carrier and silver salt as a metal precursor, loading metal silver by adopting a low-temperature liquid phase reduction method, and performing suction filtration and drying to obtain the silicon carbide-based silver nano catalyst.
2. The method for preparing silicon carbide-based silver nanocatalyst according to claim 1, wherein: the SiC is high-surface-area SiC with the specific surface area of 30-200 m2(ii)/g; the SiC carrier is pure SiC or SiC which is subjected to surface modification or bulk phase doping treatment.
3. The method for preparing silicon carbide-based silver nanocatalyst according to claim 2, wherein: the surface modification of SiC adopts oxide CeO with oxygen-containing vacancy2、ZrO2Or Al2O3Or the mixture of the oxides and the mixture modifies the surface of the SiC, and the content of the oxides or the mixture is 0.1 to 20 percent of the weight fraction of the silicon carbide.
4. The method for preparing silicon carbide-based silver nanocatalyst according to claim 3, wherein: the SiC modification method of the oxide is characterized by adopting an impregnation method for preparation, adding a proper amount of SiC powder into a solution of which the precursor is cerium salt, zirconium salt or mixed salt, stirring for a certain time, drying at 110 ℃ for 12-24h, and calcining at 400-600 ℃ in a muffle furnace for 4-10 h to obtain the oxide-modified SiC.
5. The method for preparing silicon carbide-based silver nanocatalyst according to claim 2, wherein: and in the bulk phase doping, a boron source and a phosphorus source are added to carry out B, P bulk phase doping on SiC in the preparation process of the SiC precursor, wherein the molar ratio of B/Si or P/Si is 0.01-1, and then the bulk phase B, P doped SiC is obtained through carbothermal reduction.
6. The method for preparing silicon carbide-based silver nanocatalyst according to claim 5, wherein: the phosphorus source is phosphoric acid, phosphorous acid, sodium phosphate, ammonium phosphate, diammonium phosphate, ammonium dihydrogen phosphate, calcium hydrogen phosphate, calcium pyrophosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium acid pyrophosphate, sodium dihydrogen phosphate or sodium pyrophosphate; the boron source is boric acid, borane, boron trichloride or boron trifluoride.
7. The method for preparing silicon carbide-based silver nanocatalyst according to claim 1, wherein: the liquid phase reduction comprises the following steps: mixing a certain amount of silver salt solution and SiC/modified SiC carrier, stirring for 0.5-2 h, then dropwise adding 0.1M lysine solution into the reaction solution, continuously stirring for 0.5-2 h, finally dropwise adding a proper amount of 0.1M sodium borohydride solution and 0.1M hydrochloric acid solution into the reaction solution in sequence, and continuously stirring for 1-48 h.
8. The method for preparing silicon carbide-based silver nanocatalyst according to claim 7, wherein: in the liquid phase reduction process, the amount of the added silver salt solution is controlled as follows: the content of silver is 0.1-30% of the mass fraction of silicon carbide, and the particle size range of the prepared silver nanoparticles is 5-50 nanometers.
9. The use of the silicon carbide-based silver nanocatalyst prepared by the preparation method of claim 1 in ethylene oxide synthesis, which is characterized in that: the catalyst is applied to the reaction of preparing ethylene oxide by ethylene epoxidation, and the specific reaction conditions are as follows: 1-200 g of silicon carbide-based silver nano catalyst is filled into a fixed bed reactor, and the raw material gas comprises the following components: 25-30% of ethylene, 6-9% of oxygen and the balance of nitrogen; the airspeed is 800-10000 h-1The reaction pressure is 0-5 MPa, and the reaction temperature is 150-250 ℃.
10. The use of the silicon carbide-based silver nanocatalyst of claim 9 in ethylene oxide synthesis, wherein: the selectivity of the ethylene oxide reaches more than 80 percent.
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