CN106693966A - Efficient silver catalyst with regular grain size distribution for epoxyethane preparation and preparation method thereof - Google Patents
Efficient silver catalyst with regular grain size distribution for epoxyethane preparation and preparation method thereof Download PDFInfo
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- CN106693966A CN106693966A CN201611024156.9A CN201611024156A CN106693966A CN 106693966 A CN106693966 A CN 106693966A CN 201611024156 A CN201611024156 A CN 201611024156A CN 106693966 A CN106693966 A CN 106693966A
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- silver
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- 239000003054 catalyst Substances 0.000 title claims abstract description 110
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 48
- 239000004332 silver Substances 0.000 title claims abstract description 48
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000009826 distribution Methods 0.000 title claims abstract description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 36
- 239000005977 Ethylene Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 24
- 239000013078 crystal Substances 0.000 claims description 20
- 238000007598 dipping method Methods 0.000 claims description 15
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 229910052702 rhenium Inorganic materials 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- 238000002803 maceration Methods 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 3
- 239000004480 active ingredient Substances 0.000 abstract 3
- 239000000969 carrier Substances 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000000243 solution Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 229910001868 water Inorganic materials 0.000 description 17
- 238000001035 drying Methods 0.000 description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 238000004898 kneading Methods 0.000 description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 229910052593 corundum Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 238000007493 shaping process Methods 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 6
- 229910001679 gibbsite Inorganic materials 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- 229910019599 ReO2 Inorganic materials 0.000 description 4
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 4
- 239000013081 microcrystal Substances 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910001958 silver carbonate Inorganic materials 0.000 description 3
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 240000005702 Galium aparine Species 0.000 description 1
- 235000014820 Galium aparine Nutrition 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241000612118 Samolus valerandi Species 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 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
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- 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
- B01J35/396—Distribution of the active metal ingredient
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an efficient silver catalyst with regular grain size distribution for epoxyethane preparation. The efficient silver catalyst with regular grain size distribution for epoxyethane preparation consists of three parts, namely a main active ingredient, accessory ingredients and carriers, wherein silver is taken as the main active ingredient and is uniformly distributed in the catalyst, the grain size of silver ranges from 10nm to 100nm, and silver is regularly distributed in a large-to-small manner in the catalyst from inside to outside. According to the preparation method, distribution of active ingredient Ag grains with grain size within 10nm to 100nm in the silver catalyst along the radial direction of the center O of the catalyst can be realized by virtue of performing gas processing during a catalyst preparation process and controlling a gas processing mode without performing too complicated change on an existing preparation process and mode. The method is simple in operation, low in cost and high in controllability, is capable of easily preparing a silver catalyst with optimal grain size distribution, and meets the requirements of improving the selectivity, stability and the like of the silver catalyst.
Description
Technical field
The present invention relates to the high-efficiency silver catalyst for oxidizing ethylene into epoxy ethane and its system of a kind of distribution of grain size rule
Preparation Method, particularly improves the method for preparing catalyst of ethylene epoxy ethane catalyst activity, stability and selectivity,
Belong to catalyst preparation and application field.
Background technology
The ADSORPTION STATE elemental oxygen species on Ag surfaces are only the key species of epoxidation of ethylene, and the selectivity to EO is not deposited
In 85.7% upper limit.According to ADSORPTION STATE elemental oxygen and the power of the interphase interaction of Ag, it is classified as " adsorbing oxygen by force " and " weak
Absorption oxygen "." weakly stable oxygen " generates the reaction of EO beneficial to ethylene epoxidizing；" adsorbing oxygen by force " is easily caused ethene complete oxidation, life
Into CO2And H2O.Every chemical environment beneficial to " weakly stable oxygen " generation is beneficial to the improve of catalyst choice.Fig. 1 gives
Various adsorption form figures of the molecular oxygen in Ag (110) single-crystal surface；Fig. 2 gives elemental oxygen in each of Ag (110) single-crystal surface
Plant adsorption form figure.
Therefore the Ag crystal grain for being close to catalyst surface can be controlled smaller, and it is larger near the Ag crystal grain of catalyst center.
Reactant can thus be improved in the reaction activity near catalyst external surface, reactant is reduced near catalyst center
Reaction activity, so as to control to improve in the reaction selectivity near catalyst external surface while and controlling catalytic inner temperature to prolong
Catalyst life long.The Ag crystal grain near catalyst external surface is controlled for 10~20nm, near the Ag crystal grain of catalyst center
Size is in the range of 40~100nm.
Silver catalyst is by last century the '30s, today is developed into by decades, form two main classes
Type：A kind of is the high activated catalyst of selectivity 75~82%；Another kind is the high-selectivity catalyst of selectivity 82~89%.
The improvement of silver catalyst used carrier and production technology had both been given the credit in these progress, while also giving the credit to silver catalyst preparation method
Progress, the main use including auxiliary agent, the improvement of dipping method and activating process.Patent US2238474 proposes silver catalyst
Middle addition alkaline-earth metal can play effect well, by silver and 2~40% at least one oxidation selected from barium, strontium and lithium
The catalyst of thing, peroxide and hydroxide composition can improve catalyst performance.Patent US4833261, US4761394 is public
Cloth uses rhenium as silver catalyst auxiliary agent, has opened the prelude of modern high selectivity silver catalyst research.Patent
US4766105, US4808738 and US4820675 added in Ag-Re-Cs catalyst 0.2~5mmol selected from S, Mo, W,
The coassist agent of the Re of Cr or its mixture, makes selectivity particularly initial selectivity higher.Patent CN105618047A is disclosed
A kind of method that solvent processes silver catalyst to improve silver catalyst performance.Patent CN1162416C discloses a kind of inert gas
The method that Processing Ag catalyst Precursors carry out modulation silver catalyst performance.Patent CN1142154C has invented a kind of stanniferous carrier,
By by varigrained gibbsite and false water aluminum oxide, tin compound, pore creating material, cosolvent, fluoride, binding agent
Mix with appropriate water, be molded, drying, be calcined be obtained.Silver catalyst activity and selectivity is same obtained in immersion silver and alkali metal
When improved.
The content of the invention
For the Ag/Al currently used for ethylene epoxidizing epoxy ethane2O3Catalyst choice declines very fast, stability
Bad the shortcomings of, the present invention propose a kind of distribution of grain size rule high-efficiency silver catalyst for oxidizing ethylene into epoxy ethane and
Its preparation method, using the catalyst, the reaction of ethylene epoxidizing epoxy ethane has selectivity height, good stability, uses the longevity
The advantages of ordering long.
The invention provides a kind of high-efficiency silver catalyst for oxidizing ethylene into epoxy ethane of grain size rule distribution, by leading
Active component, auxiliary agent and the part of carrier three composition, main active component is silver, and silver content keeps being uniformly distributed in the catalyst, silver
Size of microcrystal between 10~100nm scopes, in the catalyst from inside to outside be in descending regularity distribution.Preferred promoter
One or more in for Na, Cs, Ce, Re, Zr, the weight/mass percentage composition of each component is in catalyst：Silver is 1~30wt%,
The oxide content of auxiliary element is 0.001~10wt%, and remaining is carrier.
The high-efficiency silver catalyst for oxidizing ethylene into epoxy ethane being distributed present invention also offers above-mentioned grain size rule
Preparation method, it is characterized by：1) carrier and maceration extract were carried out into volume mixture, carried out catalyst dipping, the maceration extract was
Containing silver complex；
2) by step 1) in the mixture that obtains carry out the separation of solid-liquid, gained solid phase particles are dried；
3) by step 2) in dried solid phase activated；
Wherein, in 1)~arbitrary steps 3), the operation of gas treatment is added, the gas includes simple substance and/or change
One or more in compound；The gas is inert gas, chlorine, carbon monoxide, oxynitrides gas, monochlorethane gas
One or more in body；The gas treatment temperature is 20~200 DEG C.
In preparation method of the present invention, the gas treatment condition is preferably 2~3MPa of normal pressure or malleation, place
Reason temperature is 60~90 DEG C.
By ethylene epoxy ethane silver catalyst prepared by as above step, with electron probe, ESEM or throwing
The characterization methods such as radio mirror carry out catalyst section grain form and size is characterized, it is possible to find the particle diameter distribution of its crystal grain exists
On catalyst section.By the measurable grain size of above means, can obtain size of microcrystal from catalyst center to edge point
Cloth situation.When carrying out grain size sign, the point from most portionafrom theasurface is defined as catalyst center O, for the rule close to circle
Crystal grain, the size of size of microcrystal is the diameter of crystal grain；For irregular crystal grain, its size of microcrystal is equivalent diameter.For urging
Agent section is circular catalyst, and its central point is its center of circle；It is not circular catalyst for catalyst section, wherein
Heart point is a point or multiple point farthest from catalyst external surface.
Although passing through according to being distributed from the inside to surface according to the catalyst activity component grain size of above-mentioned steps preparation
Scraping different thin layers carries out chemical constituent analysis, as a result shows that silver content keeps being uniformly distributed in the catalyst.What is scraped is thin
Layer is maximum to be no more than 0.5 millimeter, and the thickness for being scraped carries out chemical constituent analysis, shows active component along catalyst section enough
Content distribution of the center of circle to catalyst edge.
When catalyst of the present invention is used for the reaction of ethylene epoxy ethane, typically under 200~300 DEG C of reaction temperature
Carry out, the content of ethene is typically no less than 25% in unstripped gas, and the general condition of reaction is reaction pressure：2~3MPa, reaction temperature
200~300 DEG C of degree, ethylene gas air speed is 1500~3500h-1。
Because ethylene epoxy ethane is a strong exothermal reaction, industrially normally more focus on target in this reaction
The selectivity of product, and reaction is maintained the transform level of relatively low stabilization.
The raw material that catalyst of the present invention is applicable be ethylene contents 25~35%, in 2~3MPa of reaction pressure, reaction temperature
Degree 200~300 DEG C, 1500~3500h of ethylene raw material gas gas space velocity-1Under conditions of, conversion of ethylene is 8~10%, epoxy
Ethane is selectively higher than 88%.Catalyst life more than 20%, achieves gratifying result.
The remarkable advantage of technology of the invention is：(1) it is different using the distribution of Ag crystal grain in gas treatment regulation and control catalyst
Size Ag crystal grain is distributed by rule so that catalyst performance is significantly improved；(2) preferred scheme alkali metal and alkaline earth gold
Category auxiliary agent is modified to carrier so that carrier has suitable surface acidic-basic property, improves the ethylene epoxy of catalyst
The selectivity of ethane.Relative to prior art, the target that catalyst of the present invention has the ethylene epoxy ethane of stabilization is produced
Thing selectivity, long lifespan；The preparation method of catalyst of the present invention is simple and easy to apply.
Brief description of the drawings
Fig. 1 is various adsorption form figures of the molecular oxygen in Ag (110) single-crystal surface；
Fig. 2 is various adsorption form figures of the elemental oxygen in Ag (110) single-crystal surface；
It is the catalysis activity test result of the catalyst A in embodiment 1 that Fig. 3 is, Curve selection 1 is catalyst A in figure
Catalytic performance test result, in figure Curve selection 2 for catalyst O catalytic performance test result.
Specific embodiment
Below will by specific embodiment, the invention will be further described, but the invention is not limited in these implement
Example.
High-efficiency silver catalyst for oxidizing ethylene into epoxy ethane employs conventional mixed with aluminum oxide and silica in embodiment
Compound is carrier, and Ag is the main active component of catalyst, and one or more in Na, Cs, Ce, Re, Zr is auxiliary agent.It is each in catalyst
The weight/mass percentage composition of component is：Active component silver is 1~30wt%, preferably 10~30wt%；The oxide of auxiliary element
Content is 0.001~10wt%, preferably 0.001~1wt%；Remaining is carrier.
The preparation method of the carrier that the embodiment of the present invention is used is：By a certain amount of gibbsite powder, a water oxygen
It is that 1~20% graphite powder and 0.1~10% calcium carbonate are well mixed with total alumina powder mass fraction is accounted for change aluminium powder body,
Mass concentration is added for 1~30% dust technology carries out kneading, kneading time is 0.1~2h, finally enterprising in forming machine again
Row shaping, after room temperature dries 1~12h, then at 80~150 DEG C of 1~8h of drying, the carrier of drying finally exists the carrier after shaping
800~1800 DEG C of 1~12h of roasting, obtain final carrier in Muffle furnace.
The machine of carrier shaping includes tablet press machine, moulding machine, kneader, banded extruder, rolling granulators, pellet processing machine etc..Into
The shape of type rear oxidation aluminium mixture is including single-orifice type, porous type, honeycomb briquet type, cylinder, bunge bedstraw herb type etc..
The preparation of the ethylene epoxidizing epoxy ethane catalyst can be using co-impregnation is come supported active metals and helps
Agent, prepares the dipping complex solution containing main active component and auxiliary agent, immersion or spray saturation impregnated carrier, then dry, roasting
Fire to obtain ethylene epoxidizing epoxy ethane silver catalyst.
Processed using gas in some of catalyst preparation process step, some described steps are dipping
When, dipping after dry before ageing process, dry roasting before in one or multi-step.
The dipping complex solution containing silver element and adjuvant component in catalyst preparation process is usually molten soluble-salt
Liquid complexing is formed, including nitrate, hydrochloride or acylate etc..
The salt that occurred complex reaction of the silver element added in catalyst preparation process from silver is dissolved in the water, including
One or more in silver nitrate, silver oxalate, silver carbonate.
In catalyst preparation process add Na, Cs, Ce, Re, Zr auxiliary element, be also its it is water-soluble in salt, bag
Include nitrate, hydrochloride or acylate etc..
Catalyst is dried at 90~150 DEG C, is activated in 200~400 DEG C of moving air.Moving air flow
It is 50~200L/h, 1~600min of soak time.
Embodiment 1
Carrier Al2O3Preparation.By a certain amount of gibbsite：One water aluminum oxide is 2:1 mixed powder mixes with accounting for
Powder quality fraction is that 10% graphite powder is well mixed, and adds calcium carbonate that mass fraction is 5% and mass concentration is
10% dust technology carries out kneading, and the kneading time is 30min, is finally molded on forming machine again, and the carrier after shaping exists
After room temperature dries 8h, then at 120 DEG C of drying 4h, the last 1400 DEG C of roasting 6h in Muffle furnace of carrier of drying, obtain final
Carrier A, its water absorption rate is 100%.
Weigh silver nitrate 46.0g, ammonium oxalate 20.2g is dissolved in 224.0g and is heated to 50 DEG C of deionized water to be made into ammonium oxalate molten
Liquid, the silver nitrate that will be weighed up is slowly dissolved in ammonium oxalate solution, produces white silver oxalate precipitate.Precipitation is leached and is dissolved in second two
In the mixed solution of amine, monoethanolamine and water, the brown complex solution of clarification is obtained.Weigh cesium nitrate 0.08g, zirconyl nitrate 2.1g
2ml solution is made into respectively to pour into above-mentioned complex solution, measures the liquid 5.0ml that Re element weight/mass percentage compositions are 0.5% same
Sample is injected in above-mentioned solution.Weigh the carrier A40g of above-mentioned preparation carries out supersaturation dipping 0.5h under vacuumized conditions, then
Then atmospheric pressure environment leaches the carrier after dipping to monochlorethane gas treatment 2h is constantly roused in solution, and 2h is aged in room temperature,
Then at 120 DEG C of drying 2h, 5min is calcined under 350 DEG C of air atmospheres, obtains finished catalyst A.
The composition of catalyst A is：Ag-Cs-Re-Zr/Al2O3, wherein weight/mass percentage composition of each component in terms of oxide
For：Ag2O：21.3%, Cs2O：0.03%, ReO2：0.04%, ZrO2：0.23% remaining be aluminum oxide.Leaned on by characterizing discovery
The Ag crystal grain of nearly outer surface is 10~20nm, is 40~80nm by paracentral Ag grain sizes.Other processes and technique are identical,
The silver catalyst not processed by ammonia is catalyst 0, and the Ag of catalyst 0 is distributed in uniform type, is 30-50nm.
The catalysis activity test of catalyst A is at twice：Using 10ml fixed bed minisize reaction evaluation systems, take 10 milliliters and grind
Being milled to during the catalyst A of 20~40 mesh is fitted into the stainless steel reactor that internal diameter is 5mm carries out epoxidation of ethylene performance test.
Reaction condition is：Unstripped gas contains ethene 28%, and the cumulative volume air speed of unstripped gas is 7000h-1, reaction pressure is 2.1MPa, reaction
Temperature is 220 DEG C, carries out the successive reaction of ethylene.A chromatogram sampling analysis is carried out per 10h.The catalysis of catalyst A is lived
The Curve selection 1 that property test result is shown in Fig. 3.When oxirane is selectively less than 50%, it is believed that catalyst has been inactivated
Terminate evaluation response.
In Fig. 3, the evaluation result of the curve catalyst A of selectivity 1, the curve of selectivity 2 is the evaluation knot of catalyst 0
Really.Since figure two curves can be seen that epoxidation of ethylene just when, the target product selectivity of catalyst is basic
Unanimously, but with the carrying out of reaction, the evaluation result of selectivity 1 is more stable, because different size of Ag crystal grain is by rule
Rule distribution, slow down the decline of ethylene target product oxirane selectivity, extend catalyst life.
Embodiment 2
Carrier Al2O3Preparation.By a certain amount of gibbsite：One water aluminum oxide is 5:1 mixed powder mixes with accounting for
Powder quality fraction is that 15% graphite powder is well mixed, and adds calcium carbonate that mass concentration is 3% and mass concentration is
20% dust technology carries out kneading, and kneading time is 30min, is finally molded on forming machine again, and the carrier after shaping exists
Room temperature is dried in the air after 8h, and then at 120 DEG C of drying 4h, the carrier of drying is last in 1300 DEG C of Muffle kiln roasting 12h, obtains final load
Body B, its water absorption rate is 89.1%.
Silver oxalate 35.0g is weighed, alleged silver oxalate is dissolved in the mixed solution of ethylenediamine, monoethanolamine and water, be obtained deep
Black-and-blue complex solution.Weigh cesium nitrate 0.083g, zirconium oxychloride 2.1g and be made into 2ml solution respectively and pour into above-mentioned complex solution
In, measure the liquid 4.12ml that Re element weight/mass percentage compositions are 0.5% and equally inject in above-mentioned solution.Weigh above-mentioned preparation
Carrier B 20g carries out supersaturation dipping 1.0h under vacuumized conditions, then leaches the carrier after dipping, afterwards in an oxidation
Under nitrogen point, 2MPa treatment 4h, filtering is aged 4h, then at 130 DEG C of drying 4h, is calcined under 300 DEG C of air atmospheres in room temperature
10min, obtains finished catalyst B.
The composition of catalyst B is：Ag-Cs-Re-Zr/Al2O3, wherein weight/mass percentage composition of each component in terms of oxide
For：Ag2O：20.4%, Cs2O：0.035%, ReO2：0.059%, ZrO2：0.41% remaining be aluminum oxide.Found by characterizing
Ag crystal grain near outer surface is 15~25nm, is 50~100nm by paracentral Ag grain sizes.
Evaluating catalyst condition is with embodiment 1
With embodiment 1, experimental result is shown in Table 1 to comparative evaluation's experiment condition.
Embodiment 3
Carrier Al2O3Preparation.By a certain amount of gibbsite：One water aluminum oxide is 3:1 mixed powder mixes with accounting for
Powder quality fraction is that 6% graphite powder is well mixed, and it is 15% to add calcium carbonate that mass concentration is 8% and mass concentration
Dust technology carries out kneading, and kneading time is 30min, is finally molded on forming machine again, and the carrier after shaping is in room temperature
Dry in the air after 8h, then at 120 DEG C of drying 4h, the last 1500 DEG C of roasting 6h in Muffle furnace of carrier of drying, obtain final support C,
Its water absorption rate is 98.6%.
Weigh silver nitrate 17.0g, ammonium oxalate 8.6g is dissolved in 100.0g and is heated to 40~60 DEG C of deionized water and is made into oxalic acid
Ammonium salt solution, the silver nitrate that will be weighed up is slowly dissolved in ammonium oxalate solution, produces white silver oxalate precipitate.Precipitation is leached and is dissolved in second
In the mixed solution of diamines, monoethanolamine and water, deep blue-black complex solution is obtained.Weigh sodium nitrate 0.032g, zirconyl nitrate
1.5g is made into 2ml solution and pours into above-mentioned complex solution respectively, measures the liquid that Re element weight/mass percentage compositions are 0.5%
2.96ml is equally injected in above-mentioned solution.The support C 20g for weighing above-mentioned preparation carries out supersaturated dipping under vacuumized conditions
5h, then leaches the carrier after dipping, and 10h is aged in room temperature, then at 120 DEG C of drying 10h, NO is used afterwards2Gas is heated
To 60 DEG C for the treatment of 6h, 50min is calcined under 350 DEG C of air atmospheres, obtains finished catalyst C.
The composition of catalyst A is：Ag-Na-Re-Zr/Al2O3, wherein weight/mass percentage composition of each component in terms of oxide
For：Ag2O：16.3%, Na2O：0.03%, ReO2：0.041%, ZrO2：0.28% remaining be aluminum oxide.Leaned on by characterizing discovery
The Ag crystal grain of nearly outer surface is 10~15nm, is 40~100nm by paracentral Ag grain sizes.
Evaluating catalyst condition, contrast test appreciation condition and chromatography are with embodiment 1.Analysis result shows the catalysis
Agent after contrast experiment's appreciation condition successive reaction 200 days, to the selectivity of ethylene epoxy ethane without under obvious
Drop, shows good stability.The ethylene oxidation reactions results of property of catalyst C is shown in Table 1.
Embodiment 4
Carrier Al2O3Preparation.By a certain amount of gibbsite：One water aluminum oxide is 1:2 mixed powder mixes with accounting for
Powder quality fraction is that 18% graphite powder is well mixed, and adds calcium carbonate that mass concentration is 10% and mass concentration is
8% dust technology carries out kneading, and the kneading time is 30min, is finally molded on forming machine again, and the carrier after shaping is in room
Temperature is dried in the air after 8h, and then at 120 DEG C of drying 4h, the carrier of drying is last in 1700 DEG C of Muffle kiln roasting 8h, obtains final carrier
D, its water absorption rate is 108.3%.
Silver carbonate 54.2g is weighed, alleged silver carbonate is dissolved in the mixed solution of ethylenediamine, monoethanolamine and water, be obtained deep
Black-and-blue complex solution.Sodium nitrate 0.075g, cerous nitrate 2.7g is weighed to be made into 2ml solution respectively and pour into above-mentioned complex solution,
The liquid 6.72ml that Re element weight/mass percentage compositions are 0.5% is measured equally to inject in above-mentioned solution.Weigh the load of above-mentioned preparation
Body D20g carries out supersaturation dipping 10h under vacuumized conditions, then leaches the carrier after dipping, and 20h is aged in room temperature,
Then at 120 DEG C of drying 10h, afterwards using 60 DEG C for the treatment of 12h of special gas hydrogen sulfide, 100min is calcined under 350 DEG C of air atmospheres,
Obtain finished catalyst D.
The composition of catalyst D is：Ag-Na-Re-Ce/Al2O3, wherein weight/mass percentage composition of each component in terms of oxide
For：Ag2O：28.4%, Na2O：0.072%, ReO2：0.095%, CeO2：0.47% remaining be aluminum oxide.Found by characterizing
Ag crystal grain near outer surface is 15~20nm, is 50~80nm by paracentral Ag grain sizes.
Evaluating catalyst condition, contrast test appreciation condition and chromatography are with embodiment 1.Analysis result shows the catalysis
Agent after contrast experiment's appreciation condition successive reaction 200 days, to the selectivity of ethylene epoxy ethane without under obvious
Drop, shows good stability.The ethylene oxidation reactions results of property of catalyst D is shown in Table 1.
The performance of the ethylene epoxy ethane of the different catalysts of table 1
Claims (4)
1. the high-efficiency silver catalyst for oxidizing ethylene into epoxy ethane that a kind of grain size rule is distributed, by main active component, auxiliary agent
With the part of carrier three composition, main active component is silver, it is characterised in that：Silver be uniformly distributed in the catalyst, and silver crystal grain grain
Footpath is in from inside to outside descending regularity distribution between 10~100nm scopes, in the catalyst.
2. high-efficiency silver catalyst for oxidizing ethylene into epoxy ethane according to claim 1, it is characterised in that described auxiliary agent
One or more in for Na, Cs, Ce, Re, Zr, the weight/mass percentage composition of each component is in catalyst：Silver is 1~30wt%,
The oxide content of auxiliary element is 0.001~10wt%, and remaining is carrier.
3. the high-efficiency silver catalyst for oxidizing ethylene into epoxy ethane being distributed according to a kind of grain size rule described in claim 1
Preparation method, it is characterized by：1) carrier and maceration extract are carried out into volume mixture, carries out catalyst dipping, the maceration extract
Including containing silver complex；2) by step 1) in the mixture that obtains carry out the separation of solid-liquid, gained solid phase particles are dried；
3) by step 2) in dried solid phase activated；Wherein, in 1)~arbitrary steps 3), the work of gas treatment is added
Sequence, the gas is the one kind or many in inert gas, chlorine, carbon monoxide, oxynitrides gas, monochlorethane gas
Kind；The gas treatment temperature is 20~200 DEG C.
4. according to the preparation method of catalyst described in claim 3, it is characterised in that the gas treatment condition be normal pressure or
2~3MPa of malleation, treatment temperature is 60~90 DEG C.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5502020A (en) * | 1993-04-14 | 1996-03-26 | Mitsubishi Petrochemical Co., Ltd. | Catalyst for production of ethylene oxide and process for producing the catalyst |
| CN1426835A (en) * | 2001-12-17 | 2003-07-02 | 北京燕山石油化工公司研究院 | Silver catalyst for epoxyethane production, its preparation method and application |
| CN103842074A (en) * | 2011-10-14 | 2014-06-04 | 圣戈本陶瓷及塑料股份有限公司 | A catalyst and catalyst carrier |
| CN105233824A (en) * | 2015-11-05 | 2016-01-13 | 中国海洋石油总公司 | Silver catalyst for high selectivity oxidation of ethylene to prepare ethylene oxide, and use method thereof |
-
2016
- 2016-11-14 CN CN201611024156.9A patent/CN106693966A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5502020A (en) * | 1993-04-14 | 1996-03-26 | Mitsubishi Petrochemical Co., Ltd. | Catalyst for production of ethylene oxide and process for producing the catalyst |
| CN1426835A (en) * | 2001-12-17 | 2003-07-02 | 北京燕山石油化工公司研究院 | Silver catalyst for epoxyethane production, its preparation method and application |
| CN103842074A (en) * | 2011-10-14 | 2014-06-04 | 圣戈本陶瓷及塑料股份有限公司 | A catalyst and catalyst carrier |
| CN105233824A (en) * | 2015-11-05 | 2016-01-13 | 中国海洋石油总公司 | Silver catalyst for high selectivity oxidation of ethylene to prepare ethylene oxide, and use method thereof |
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