CN115364854B - Preparation method of silver catalyst for ethylene oxide production by ethylene oxidation, silver catalyst and application - Google Patents
Preparation method of silver catalyst for ethylene oxide production by ethylene oxidation, silver catalyst and application Download PDFInfo
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- CN115364854B CN115364854B CN202110553689.0A CN202110553689A CN115364854B CN 115364854 B CN115364854 B CN 115364854B CN 202110553689 A CN202110553689 A CN 202110553689A CN 115364854 B CN115364854 B CN 115364854B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 109
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 106
- 239000004332 silver Substances 0.000 title claims abstract description 106
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000005977 Ethylene Substances 0.000 title claims abstract description 20
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 230000003647 oxidation Effects 0.000 title claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title description 7
- 238000000034 method Methods 0.000 claims abstract description 34
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 29
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 25
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 21
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 21
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims abstract description 21
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 21
- 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 19
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 18
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 16
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- -1 amine compound Chemical class 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 20
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 claims description 18
- 229910052792 caesium Inorganic materials 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 claims description 2
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 2
- 229910003449 rhenium oxide Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940071536 silver acetate Drugs 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 2
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 28
- 239000007864 aqueous solution Substances 0.000 description 16
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 16
- 239000011521 glass Substances 0.000 description 16
- 239000011259 mixed solution Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229940100890 silver compound Drugs 0.000 description 2
- 150000003379 silver compounds Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Chemical group 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 229910052916 barium silicate Inorganic materials 0.000 description 1
- HMOQPOVBDRFNIU-UHFFFAOYSA-N barium(2+);dioxido(oxo)silane Chemical compound [Ba+2].[O-][Si]([O-])=O HMOQPOVBDRFNIU-UHFFFAOYSA-N 0.000 description 1
- QKYBEKAEVQPNIN-UHFFFAOYSA-N barium(2+);oxido(oxo)alumane Chemical compound [Ba+2].[O-][Al]=O.[O-][Al]=O QKYBEKAEVQPNIN-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003375 selectivity assay Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent 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
- 239000011593 sulfur Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic 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
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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 belongs to the field of silver catalysts, and relates to a preparation method of a silver catalyst for producing ethylene oxide by ethylene oxidation, the silver catalyst and application thereof. The method comprises the following steps: s1, obtaining a silver ammonia solution, wherein the silver ammonia solution comprises a silver-containing compound, ethylenediamine tetraacetic acid, nanometer zirconium dioxide particles, an amine compound, water, an alkali metal auxiliary agent, an optional rhenium auxiliary agent and a co-auxiliary agent thereof; s2, immersing the alpha-Al 2O3 carrier in the silver ammonia solution obtained in the step S1, and then carrying out solid-liquid separation and roasting to obtain the silver catalyst. Compared with the prior art, the invention has the following advantages: after the porous alumina carrier is immersed in silver ammonia solution containing ethylenediamine tetraacetic acid and nano-sized zirconium dioxide particles, the silver catalyst prepared from the porous alumina carrier has higher selectivity and is particularly suitable for the reaction of ethylene oxidation to produce ethylene oxide.
Description
Technical Field
The invention belongs to the field of silver catalysts, and particularly relates to a preparation method of a silver catalyst for producing ethylene oxide by ethylene oxidation, the silver catalyst prepared by the method and application of the silver catalyst in the reaction for producing ethylene oxide by ethylene oxidation.
Background
Ethylene is oxidized to mainly generate ethylene oxide under the action of a silver catalyst, and side reactions simultaneously occur to generate carbon dioxide and water, wherein the activity, the selectivity and the stability are main performance indexes of the silver catalyst. The activity refers to the reaction temperature required for the production process of the ethylene oxide to reach a certain reaction load. The lower the reaction temperature, the higher the activity of the catalyst. By selectivity is meant the ratio of the moles of ethylene converted to ethylene oxide in the reaction to the total moles of ethylene reacted. Stability is expressed as the rate of decrease in activity and selectivity, with lower rates indicating better catalyst stability. The use of a silver catalyst with high activity, high selectivity and good stability in the process of producing ethylene oxide by ethylene oxidation can greatly improve economic benefit, so that the production of the silver catalyst with high activity, high selectivity and good stability is the main direction of silver catalyst research. The performance of the silver catalyst has important relation with the composition of the catalyst and the preparation method, and also has important relation with the performance of a carrier used by the catalyst and the preparation method.
The prior art silver catalyst preparation method includes two processes of preparing a porous carrier (such as alumina) and applying an active component and an auxiliary agent to the carrier. In the preparation process of the silver catalyst, for the carrier taking the alpha-Al 2O3 as a main component, a proper specific surface and a pore structure are needed, so that on one hand, enough space is provided for the ethylene epoxidation reaction to diffuse out the reaction heat, and on the other hand, the timely desorption of the reaction product ethylene oxide is facilitated, and the deep oxidation is avoided to generate by-product carbon dioxide. Chinese patent CN1009437B adopts proper proportion to mix with alumina trihydrate to prepare alumina carrier with specific surface of 0.2-2 m 2/g and pore volume of more than 0.5ml/g, wherein the pores with pore radius of more than 30 μm account for less than 25%, and the selectivity of the catalyst for ethylene epoxidation reaction can reach 83-84%.
The addition of other components to alumina supports to improve the support and improve the performance of the silver catalyst is also an important research direction. In addition, the performance of the silver catalyst can also be improved by chemically treating the alumina carrier. European patent EP0150238B1 claims to improve the crushing strength and attrition resistance of the support by using small amounts of barium aluminate or barium silicate binders during the manufacture of high purity, low surface alumina supports, which produce supports having specific surfaces less than 0.3m 2/g, and which produce catalysts having relatively low activity and selectivity. The alumina supports used in US4740493A, US4829043a and EP0501317A1 contain some amount of Ca, al, K, na soluble salts and claim to reduce the rate of catalyst selectivity decline during use. US5384302a claims that reducing the Na, K, ca, al ion content in the support by pre-treating α -Al 2O3 improves the crushing strength and abrasion resistance of the support. EP0712334B1 prepares a silver catalyst by loading effective amounts of silver, auxiliary amounts of alkali metal, auxiliary amounts of magnesium and auxiliary amounts of rhenium on a carrier containing at least 85% of alumina and 0.001-2% of magnesium in the form of oxide, and improves the stability of the catalyst. US5100859A, US5145824A, EP0900126B1 and US5801259A, US5733842a add alkaline earth metal, silicon and zirconium to α -Al 2O3 to make carrier, then impregnate silver, alkali metal auxiliary agent, rhenium auxiliary agent and its auxiliary agent to make silver catalyst, and patent indicates that alkaline earth metal, preferably calcium, strontium and barium salt are used together with zirconium compound, and the influence of both addition on catalyst performance is not known. US5739075A prepares a silver catalyst from a treated carrier by depositing a promoter amount of a rare earth metal and another promoter amount of a metal salt (alkaline earth metal or group VIII transition metal) on the surface of an alumina carrier in advance, and then calcining the catalyst, and the evaluation result shows that the selectivity reduction rate of the catalyst is smaller than that of a catalyst sample which is not subjected to the pre-deposition treatment. CN1511632a found that the activity and selectivity of the silver catalyst prepared by adding a heavy alkaline earth metal compound to an alumina raw material to prepare a carrier, impregnating a solution prepared from a silver compound, an organic amine and a specific auxiliary agent, and performing heat treatment in an oxygen-containing mixed gas are improved.
Although the above patent documents respectively adopt various methods to improve the alumina carrier, which brings about different improvements to the activity, stability and selectivity of the catalyst, the requirements for the carrier performance are continuously increased along with the large-scale industrial application of the silver catalyst with high Re selectivity, and therefore, the carrier performance is required to be continuously improved.
Disclosure of Invention
In view of the above-described state of the art, the inventors of the present invention have conducted intensive studies in the field of silver catalysts, and as a result, have found that the addition of ethylenediamine tetraacetic acid and nanosized zirconium dioxide particles to a silver ammonia solution can significantly improve the selectivity of a silver catalyst made therefrom.
The first aspect of the invention provides a preparation method of a silver catalyst for producing ethylene oxide by oxidizing ethylene, which comprises the following steps:
S1, obtaining a silver ammonia solution, wherein the silver ammonia solution comprises a silver-containing compound, ethylenediamine tetraacetic acid, nanometer zirconium dioxide particles, an amine compound, water, an alkali metal auxiliary agent, an optional rhenium auxiliary agent and a co-auxiliary agent thereof;
s2, immersing the alpha-Al 2O3 carrier in the silver ammonia solution obtained in the step S1, and then carrying out solid-liquid separation and roasting to obtain the silver catalyst.
In a second aspect, the present invention provides a silver catalyst prepared by the above process.
A third aspect of the present invention provides the use of the silver catalyst described above in a reaction for the oxidation of ethylene to ethylene oxide.
Compared with the prior art, the invention has the following advantages: after the porous alumina carrier is immersed in silver ammonia solution containing ethylenediamine tetraacetic acid and nano-sized zirconium dioxide particles, the silver catalyst prepared from the porous alumina carrier has higher selectivity and is particularly suitable for the reaction of ethylene oxidation to produce ethylene oxide.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The invention provides a preparation method of a silver catalyst for producing ethylene oxide by ethylene oxidation, which comprises the following steps:
S1, obtaining a silver ammonia solution, wherein the silver ammonia solution comprises a silver-containing compound, ethylenediamine tetraacetic acid, nanometer zirconium dioxide particles, an amine compound, water, an alkali metal auxiliary agent, an optional rhenium auxiliary agent and a co-auxiliary agent thereof;
s2, immersing the alpha-Al 2O3 carrier in the silver ammonia solution obtained in the step S1, and then carrying out solid-liquid separation and roasting to obtain the silver catalyst.
According to the method of the present invention, in step S1, the diameter of the nano zirconium dioxide particles is preferably 1 to 100 nm, more preferably 10 to 80 nm; the content of the nano zirconium dioxide particles is preferably 0.001 to 1.5wt%, more preferably 0.01 to 1.0wt%, still more preferably 0.1 to 0.3wt%, based on the total weight of the silver-ammonia solution.
According to the method of the present invention, in step S1, the content of ethylenediamine tetraacetic acid is preferably 0.01 to 20.0wt%, more preferably 0.05 to 5.0wt%, based on the total weight of the silver ammonia solution.
According to the method of the present invention, in step S1, the amine compound is used as a solvent, and specifically, may be selected from one or more of ammonia, ethylamine, N-propylamine, ethylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, N-dimethylformamide, ethanolamine, and propanolamine; the content of amine compounds in the impregnating solution is 10-90 wt% based on the weight of the silver-ammonia solution.
According to the method of the present invention, in step S1, the silver-containing compound is preferably one or more of silver acetate, silver nitrate, silver oxalate; generally, the silver-containing compound is added in such an amount that the silver content in the silver catalyst is 2 to 39wt%, preferably 10 to 35wt% on an atomic basis, based on the total weight of the silver catalyst.
In the present invention, the specific choice and amounts of the alkali metal promoter, rhenium promoter and co-promoter may be any conventional choice in the art.
Specifically, in step S1, the alkali metal auxiliary may be selected from a compound of lithium, sodium, potassium, rubidium, or cesium, or a combination of any two or more thereof; the alkali metal auxiliary is added in such an amount that the content of the alkali metal in the silver catalyst is 1 to 2000ppm, preferably 5 to 1500ppm, based on the total weight of the silver catalyst.
In step S1, the rhenium promoter is selected from one or more of rhenium oxide, perrhenic acid, cesium perrhenate, rhenium (vii) methyl trioxide, and ammonium perrhenate; the rhenium promoter is added in an amount such that the content of rhenium metal in the silver catalyst is 0 to 2000ppm, preferably 100 to 1000ppm, in terms of atoms, based on the total weight of the silver catalyst. The rhenium co-promoter can be selected from one or more of manganese, chromium, sulfur, cobalt, molybdenum, nickel-containing salts or acid forms; the addition amount of the co-promoter of rhenium is such that the content of the co-promoter of rhenium in atomic terms in the silver catalyst is 0 to 2000ppm. The various promoters may be applied to the support before, simultaneously with, or after impregnation of the silver, or may be impregnated on the support after the silver compound has been reduced.
In the step S2, a porous alpha-alumina carrier commonly used in silver catalyst production can be selected, wherein the content of alpha-A1 2O3 is more than 90 percent, and the catalyst has the following characteristics: crushing strength is 20-200N/grain; the specific surface is 0.2-3.0 m 2/g; the water absorption is not lower than 30%; the pore volume is 0.30-0.85 ml/g.
According to the invention, the impregnation in the step S2 can be carried out according to a conventional method in the field, the alumina carrier is completely impregnated in the solution obtained in the step S1, the impregnation time can be 10-300 minutes, the temperature of the impregnation solution is kept below 30 ℃, and the silver-containing compound and the like are prevented from being decomposed by heating and separated out in advance; the impregnation process can be accelerated by decompressing to below 100mmHg pressure, and the surface of the carrier is suitable for full infiltration without tiny bubbles and the inner and outer surfaces.
The solid-liquid separation in step S2 may comprise leaching, drying, preferably to minimize the excess impregnation liquid adhering to the surface of the support, while removing excess dust from the alumina support.
The drying after leaching in step S2 may be performed in an air and/or inert gas atmosphere, and the drying temperature may be 50 to 120 ℃ and the time may be 0.5 to 12 hours. And drying sufficiently until no significant change in solid quality occurs.
In the step S2, the roasting is performed in air or nitrogen-oxygen mixture with the oxygen content not more than 21%; the temperature of the roasting is controlled between 100 and 600 ℃, preferably between 150 and 500 ℃, and the time of the roasting is between 0.5 and 120 minutes, preferably between 1 and 30 minutes.
The invention also provides a silver catalyst prepared by the method. According to a preferred embodiment, the silver catalyst contains 2 to 35wt% silver, 1 to 2000ppm alkali metal, 1 to 2000ppm rhenium and 0.001 to 1.5wt% nano zirconium dioxide, based on the total weight of the silver catalyst.
The silver catalyst of the invention can be used in the production of ethylene oxide by the epoxidation of ethylene. Specifically, in the presence of the silver catalyst, a mixed gas of ethylene and a gas such as oxygen is reacted in a fixed bed micro-tubular reactor.
The present invention will be further described with reference to examples, but the scope of the present invention is not limited to these examples.
Determination of catalyst Performance
The various silver catalysts of the present invention were tested for initial performance and stability using a laboratory reactor (hereinafter abbreviated as "micro-reverse") evaluation apparatus. The reactor used in the micro-reaction evaluation device is a stainless steel tube with an inner diameter of 4mm, and the reactor is placed in a heating sleeve. The catalyst was packed in a volume of 1ml with inert packing in the lower part to allow the catalyst bed to be located in the constant temperature zone of the heating mantle.
Determination of Primary Activity and Selectivity
The activity and selectivity assay conditions used in the present invention are as follows:
Composition of reaction gas (mol%)
After the above reaction conditions were stably reached, the gas composition at the inlet and outlet of the reactor was continuously measured. After the volume shrinkage correction is carried out on the measurement result, the selectivity is calculated according to the following formula:
Where Δeo is the difference in the concentration of ethylene oxide in the outlet gas and the inlet gas ring, and the average of more than 10 sets of test data was taken as the test result on the same day.
The activity of the catalyst is measured by the reaction temperature at which a certain EO concentration is reached.
The carrier samples used in the examples and comparative examples were prepared from the same carrier formulation, and specific details are found in CN88100400.6, CN1634652a and US5063195, which are not described in detail herein.
And (3) preparing a catalyst: examples 1 to 8 and comparative example 1
Example 1
32.1G of ethylenediamine, 10.8g of ethanolamine, 3.5g of ethylenediamine tetraacetic acid and 179.8g of deionized water are added into a glass beaker with stirring to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and keeping the temperature below 40 ℃ and continuously stirring to completely dissolve the silver oxalate; then, 2.25ml of cesium nitrate aqueous solution (concentration: 0.03995g/ml based on the weight of cesium atoms), 2.78ml of ammonium perrhenate aqueous solution (concentration: 0.0162g/ml based on the weight of rhenium atoms) and 0.5g of zirconium dioxide particles (diameter: 30 nm) were sequentially added, and uniformly mixed to prepare 300g of impregnating solution for use.
15G of carrier is taken, placed into a glass container capable of being vacuumized, and added with the impregnating solution, and the carrier is completely immersed. After evacuating to above 10mmHg and holding for about 15 minutes, the excess solution was leached off. Finally, the impregnated support sample was placed in an air stream at 350 ℃ and heated for about 2 minutes to produce silver catalyst example 1.
Example 2
32.1G of ethylenediamine, 10.8g of ethanolamine, 3.5g of ethylenediamine tetraacetic acid and 179.8g of deionized water are added into a glass beaker with stirring to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and keeping the temperature below 40 ℃ and continuously stirring to completely dissolve the silver oxalate; then, 2.25ml of cesium nitrate aqueous solution (concentration: 0.03995g/ml based on the weight of cesium atoms), 2.78ml of ammonium perrhenate aqueous solution (concentration: 0.0162g/ml based on the weight of rhenium atoms) and 0.5g of zirconium dioxide particles (diameter: 60 nm) were sequentially added, and uniformly mixed to prepare 300g of impregnating solution for use.
15G of carrier is taken, placed into a glass container capable of being vacuumized, and added with the impregnating solution, and the carrier is completely immersed. After evacuating to above 10mmHg and holding for about 15 minutes, the excess solution was leached off. Finally, the impregnated support sample was placed in an air stream at 350 ℃ and heated for about 2 minutes to produce silver catalyst example 2.
Example 3
32.1G of ethylenediamine, 10.8g of ethanolamine, 3.5g of ethylenediamine tetraacetic acid and deionized water are added into a glass beaker with stirring to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and keeping the temperature below 40 ℃ and continuously stirring to completely dissolve the silver oxalate; then, 2.25ml of cesium nitrate aqueous solution (concentration: 0.03995g/ml based on the weight of cesium atoms), 2.78ml of ammonium perrhenate aqueous solution (concentration: 0.0162g/ml based on the weight of rhenium atoms) and 1.5g of zirconium dioxide particles (diameter: 30 nm) were sequentially added, and uniformly mixed to prepare 300g of impregnating solution for use.
15G of carrier is taken, placed into a glass container capable of being vacuumized, and added with the impregnating solution, and the carrier is completely immersed. After evacuating to above 10mmHg and holding for about 15 minutes, the excess solution was leached off. Finally, the impregnated support sample was placed in an air stream at 350 ℃ and heated for about 2 minutes to produce silver catalyst example 3.
Example 4
32.1G of ethylenediamine, 10.8g of ethanolamine, 3.5g of ethylenediamine tetraacetic acid and deionized water are added into a glass beaker with stirring to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and keeping the temperature below 40 ℃ and continuously stirring to completely dissolve the silver oxalate; then, 2.25ml of cesium nitrate aqueous solution (concentration: 0.03995g/ml based on the weight of cesium atoms), 2.78ml of ammonium perrhenate aqueous solution (concentration: 0.0162g/ml based on the weight of rhenium atoms) and 1.5g of zirconium dioxide particles (diameter: 60 nm) were sequentially added, and uniformly mixed to prepare 300g of impregnating solution for use.
15G of carrier is taken, placed into a glass container capable of being vacuumized, and added with the impregnating solution, and the carrier is completely immersed. After evacuating to above 10mmHg and holding for about 15 minutes, the excess solution was leached off. Finally, the impregnated support sample was placed in an air stream at 350 ℃ and heated for about 2 minutes to produce silver catalyst example 4.
Example 5
32.1G of ethylenediamine, 10.8g of ethanolamine, 10.5g of ethylenediamine tetraacetic acid and 179.8g of deionized water are added into a glass beaker with stirring to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and keeping the temperature below 40 ℃ and continuously stirring to completely dissolve the silver oxalate; then, 2.25ml of cesium nitrate aqueous solution (concentration: 0.03995g/ml based on the weight of cesium atoms), 2.78ml of ammonium perrhenate aqueous solution (concentration: 0.0162g/ml based on the weight of rhenium atoms) and 0.5g of zirconium dioxide particles (diameter: 30 nm) were sequentially added, and uniformly mixed to prepare 300g of impregnating solution for use.
15G of carrier is taken, placed into a glass container capable of being vacuumized, and added with the impregnating solution, and the carrier is completely immersed. After evacuating to above 10mmHg and holding for about 15 minutes, the excess solution was leached off. Finally, the impregnated support sample was placed in an air stream at 350 ℃ and heated for about 2 minutes to produce silver catalyst example 5.
Example 6
32.1G of ethylenediamine, 10.8g of ethanolamine, 10.5g of ethylenediamine tetraacetic acid and 179.8g of deionized water are added into a glass beaker with stirring to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and keeping the temperature below 40 ℃ and continuously stirring to completely dissolve the silver oxalate; then, 2.25ml of cesium nitrate aqueous solution (concentration: 0.03995g/ml based on the weight of cesium atoms), 2.78ml of ammonium perrhenate aqueous solution (concentration: 0.0162g/ml based on the weight of rhenium atoms) and 0.5g of zirconium dioxide particles (diameter: 60 nm) were sequentially added, and uniformly mixed to prepare 300g of impregnating solution for use.
15G of carrier is taken, placed into a glass container capable of being vacuumized, and added with the impregnating solution, and the carrier is completely immersed. After evacuating to above 10mmHg and holding for about 15 minutes, the excess solution was leached off. Finally, the impregnated support sample was placed in an air stream at 350 ℃ and heated for about 2 minutes to produce silver catalyst example 6.
Example 7
32.1G of ethylenediamine, 10.8g of ethanolamine, 10.5g of ethylenediamine tetraacetic acid and 179.8g of deionized water are added into a glass beaker with stirring to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and keeping the temperature below 40 ℃ and continuously stirring to completely dissolve the silver oxalate; then, 2.25ml of cesium nitrate aqueous solution (concentration: 0.03995g/ml based on the weight of cesium atoms), 2.78ml of ammonium perrhenate aqueous solution (concentration: 0.0162g/ml based on the weight of rhenium atoms) and 1.5g of zirconium dioxide particles (diameter: 30 nm) were sequentially added, and uniformly mixed to prepare 300g of impregnating solution for use.
15G of carrier is taken, placed into a glass container capable of being vacuumized, and added with the impregnating solution, and the carrier is completely immersed. After evacuating to above 10mmHg and holding for about 15 minutes, the excess solution was leached off. Finally, the impregnated support sample was placed in an air stream at 350 ℃ and heated for about 2 minutes to produce silver catalyst example 7.
Example 8
32.1G of ethylenediamine, 10.8g of ethanolamine, 10.5g of ethylenediamine tetraacetic acid and 179.8g of deionized water are added into a glass beaker with stirring to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and keeping the temperature below 40 ℃ and continuously stirring to completely dissolve the silver oxalate; then, 2.25ml of cesium nitrate aqueous solution (concentration: 0.03995g/ml based on the weight of cesium atoms), 2.78ml of ammonium perrhenate aqueous solution (concentration: 0.0162g/ml based on the weight of rhenium atoms) and 1.5g of zirconium dioxide particles (diameter: 60 nm) were sequentially added, and uniformly mixed to prepare 300g of impregnating solution for use.
15G of carrier is taken, placed into a glass container capable of being vacuumized, and added with the impregnating solution, and the carrier is completely immersed. After evacuating to above 10mmHg and holding for about 15 minutes, the excess solution was leached off. Finally, the impregnated support sample was placed in an air stream at 350 ℃ and heated for about 2 minutes to produce silver catalyst example 8.
Comparative example 1
Comparative example 1 the procedure was the same as in example 1 except that ethylenediamine tetraacetic acid and zirconium dioxide particles were not added.
Comparative example 2
The diameter of the zirconia particles added in comparative example 2 was 300 nm, and the rest of the procedure was the same as in example 1.
Comparative example 3
In comparative example 3, ethylenediamine tetraacetic acid was not added, and the other steps were the same as in example 1.
Table 1 silver catalyst comparative example 1 and day 6 evaluation results of examples 1 to 8
| Catalyst numbering | Temperature (. Degree. C.) | Selectivity (%) |
| Silver catalyst comparative example 1 | 225 | 82.53 |
| Comparative example 2 silver catalyst | 229 | 84.72 |
| Comparative example 3 silver catalyst | 226 | 84.67 |
| Silver catalyst example 1 | 223 | 85.03 |
| Silver catalyst example 2 | 224 | 85.21 |
| Silver catalyst example 3 | 225 | 85.98 |
| Silver catalyst example 4 | 226 | 86.31 |
| Silver catalyst example 5 | 221 | 84.92 |
| Silver catalyst example 6 | 223 | 85.25 |
| Silver catalyst example 7 | 224 | 85.91 |
| Silver catalyst example 8 | 226 | 86.22 |
As can be seen from Table 1, the initial selectivity of the silver catalyst samples prepared by the process of adding ethylenediamine tetraacetic acid and nano-sized zirconium dioxide particles to the silver ammonia solution was significantly improved.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (21)
1. A preparation method of a silver catalyst for producing ethylene oxide by ethylene oxidation comprises the following steps:
S1, obtaining a silver ammonia solution, wherein the silver ammonia solution comprises a silver-containing compound, ethylenediamine tetraacetic acid, nanometer zirconium dioxide particles, an amine compound, water, an alkali metal auxiliary agent, an optional rhenium auxiliary agent and a co-auxiliary agent thereof; the diameter of the nano zirconium dioxide particles is 1-100 nanometers;
s2, immersing the alpha-Al 2O3 carrier in the silver ammonia solution obtained in the step S1, and then carrying out solid-liquid separation and roasting to obtain the silver catalyst.
2. The method according to claim 1, wherein the ethylenediamine tetraacetic acid is contained in an amount of 0.01 to 20.0wt% based on the total weight of the silver ammonia solution in step S1.
3. The method according to claim 2, wherein the ethylenediamine tetraacetic acid is present in an amount of 0.05 to 5.0wt%.
4. The method according to claim 1, wherein in step S1, the diameter of the nano zirconium dioxide particles is 10 to 80 nm; the addition amount of the nano zirconium dioxide particles is based on the total weight of the silver catalyst, so that the content of the nano zirconium dioxide in the silver catalyst is 0.001-1.5 wt%.
5. The method according to claim 4, wherein the nano zirconium dioxide particles are added in such an amount that the content of nano zirconium dioxide in the silver catalyst is 0.01 to 1.0wt%.
6. The method according to claim 5, wherein the nano zirconium dioxide particles are added in such an amount that the content of nano zirconium dioxide in the silver catalyst is 0.1 to 0.3wt%.
7. The method according to any one of claims 1 to 6, wherein in step S1, the amine compound is selected from one or more of ammonia, ethylamine, N-propylamine, ethylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, N-dimethylformamide, ethanolamine, and propanolamine; the content of the amine compound is 10-90 wt% based on the total weight of the silver-ammonia solution.
8. The method according to any one of claims 1 to 6, wherein in step S1, the silver-containing compound is one or more of silver acetate, silver nitrate, silver oxalate; the silver-containing compound is added in such an amount that the silver content in the silver catalyst is 2 to 39wt% in terms of atoms, based on the total weight of the silver catalyst.
9. The method according to claim 8, wherein the silver-containing compound is added in such an amount that the silver content in the silver catalyst is 10 to 35wt% on an atomic basis.
10. The method according to any one of claims 1 to 6, wherein in step S1, the alkali metal auxiliary is selected from a compound of lithium, sodium, potassium, rubidium or cesium or a combination of any two or more thereof; the addition amount of the alkali metal auxiliary agent is such that the content of the alkali metal in the silver catalyst is 1 to 2000ppm based on the total weight of the silver catalyst.
11. The method according to claim 10, wherein the alkali metal auxiliary is added in such an amount that the content of the alkali metal in the silver catalyst is 5 to 1500ppm.
12. The process according to any one of claims 1 to 6, wherein in step S1, the rhenium promoter is selected from one or more of rhenium oxide, perrhenic acid, cesium perrhenate, rhenium (vii) methyl trioxide and ammonium perrhenate; the rhenium promoter is added in an amount such that the content of rhenium metal in the silver catalyst is 0 to 2000ppm in terms of atoms, based on the total weight of the silver catalyst.
13. The method of claim 12 wherein the rhenium promoter is added in an amount to provide 100 to 1000ppm of rhenium metal on an atomic basis in the silver catalyst.
14. The method according to any one of claims 1 to 6, wherein in step S2, the time of the impregnation is 10 to 300 minutes;
The solid-liquid separation comprises leaching and drying.
15. The method of claim 14, wherein the impregnating is performed at a pressure of 100mmHg or less.
16. The process of claim 14 wherein the post-leaching drying is carried out in an atmosphere of air and/or an inert gas at a temperature of 50 to 120 ℃ for a period of 0.1 to 12 hours.
17. The method according to any one of claims 1 to 6, wherein in step S2, the calcination is performed in air or a nitrogen-oxygen mixture having an oxygen content of not more than 21%; the roasting temperature is controlled between 100 ℃ and 600 ℃, and the roasting time is 0.5 to 120 minutes.
18. The method of claim 17, wherein the firing temperature is controlled between 150-500 ℃ and the firing time is 1-30 minutes.
19. The method of any one of claims 1-6, wherein the α -Al 2O3 support is a porous α -alumina support, wherein the α -A1 2O3 content is 90% or more, and has the following characteristics: crushing strength is 20-200N/grain; the specific surface is 0.2-3.0 m 2/g; the water absorption is not lower than 30%; the pore volume is 0.30-0.85 ml/g.
20. A silver catalyst made by the process of any one of claims 1-19.
21. Use of the silver catalyst of claim 20 in a reaction for the oxidation of ethylene to ethylene oxide.
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