CN115364854A - Preparation method of silver catalyst for producing ethylene oxide by ethylene oxidation, silver catalyst and application - Google Patents
Preparation method of silver catalyst for producing ethylene oxide by ethylene oxidation, silver catalyst and application Download PDFInfo
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- CN115364854A CN115364854A CN202110553689.0A CN202110553689A CN115364854A CN 115364854 A CN115364854 A CN 115364854A CN 202110553689 A CN202110553689 A CN 202110553689A CN 115364854 A CN115364854 A CN 115364854A
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- silver
- silver catalyst
- catalyst
- carrier
- ammonia solution
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- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 97
- 239000004332 silver Substances 0.000 title claims abstract description 97
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000005977 Ethylene Substances 0.000 title claims abstract description 21
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 9
- 230000003647 oxidation Effects 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 24
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 24
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 23
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-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
- 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 20
- 229960001484 edetic acid Drugs 0.000 claims abstract description 19
- 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 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 13
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- -1 amine compound Chemical class 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000002791 soaking Methods 0.000 claims abstract description 4
- 238000005470 impregnation Methods 0.000 claims description 24
- 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
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 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
- 238000001035 drying Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 238000002386 leaching Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 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
- 229910052792 caesium Inorganic materials 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
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 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
- VZSXFJPZOCRDPW-UHFFFAOYSA-N carbanide;trioxorhenium Chemical compound [CH3-].O=[Re](=O)=O VZSXFJPZOCRDPW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052744 lithium Inorganic materials 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 30
- 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
- 239000007864 aqueous solution Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process 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
- 230000007423 decrease Effects 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002105 nanoparticle Substances 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
- 239000012752 auxiliary agent Substances 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
- 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-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
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000003556 assay Methods 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
- 238000000151 deposition Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000000977 initiatory effect 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
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 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
- 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
- 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
- 238000005979 thermal decomposition reaction Methods 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
- 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
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, a silver catalyst and application. The method comprises the following steps: s1, obtaining a silver-ammonia solution, wherein the silver-ammonia solution comprises a silver-containing compound, ethylene diamine tetraacetic acid, nano zirconium dioxide particles, an amine compound, water, an alkali metal assistant, an optional rhenium assistant and a co-assistant thereof; s2, mixing alpha-Al 2 O 3 And (3) soaking the 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: porous alumina carrier containing EDTA andafter the zirconium dioxide particles with nanometer sizes are soaked in the silver-ammonia solution, the silver catalyst prepared from the zirconium dioxide particles has higher selectivity, and is particularly suitable for the reaction of producing ethylene oxide by oxidizing ethylene.
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 oxidizing ethylene, the silver catalyst prepared by the method, and application of the silver catalyst in the reaction of producing ethylene oxide by oxidizing ethylene.
Background
Ethylene is oxidized under the action of a silver catalyst to mainly generate ethylene oxide, and side reactions occur to generate carbon dioxide and water, wherein the activity, selectivity and stability are main performance indexes of the silver catalyst. By activity is meant the reaction temperature required for the ethylene oxide production process 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. The stability is expressed as the rate of decrease in activity and selectivity, with the lower the rate, the better the stability of the catalyst. The silver catalyst with high activity, high selectivity and good stability is used in the process of producing ethylene oxide by oxidizing ethylene, so that the economic benefit can be greatly improved, and the preparation of the silver catalyst with high activity, high selectivity and good stability is the main direction of research on the silver catalyst. The performance of the silver catalyst is not only important in relation to the composition of the catalyst and the preparation method, but also important in relation to the performance of the carrier used in the catalyst and the preparation method.
The preparation method of the silver catalyst in the prior art comprises 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 of silver catalyst, the catalyst is prepared by reacting alpha-Al 2 O 3 Suitable specific surface area and pore structure are required for the carrier as the main component, 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 generation of carbon dioxide as a byproduct of deep oxidation is avoided. Chinese patent CN1009437B is prepared by mixing alumina trihydrate with proper proportion and has a specific surface of 0.2-2 m 2 The alumina carrier with pore volume larger than 0.5ml/g, wherein the pore radius larger than 30 μm accounts for less than 25 percent, and the selectivity of the catalyst for ethylene epoxidation reaction can reach 83 to 84 percent.
The addition of other components to the alumina carrier to improve the carrier and improve the performance of the silver catalyst is also an important research direction. Furthermore, the performance of the silver catalyst can also be improved by chemically treating the alumina support. European patent EP0150238B1, which claims to improve the crushing strength and abrasion resistance of the support using a small amount of barium aluminate or barium silicate binder during the manufacture of a high purity, low surface alumina support, produces a support having a specific surface of less than 0.3m 2 The catalyst prepared has low activity and selectivity per gram. US4740493A, US4829043A and EP0501317A1 use alumina supports that contain certain amounts of Ca, al, K, na soluble salts that are claimed to reduce the rate of decrease of catalyst selectivity during use. US5384302A states that alpha-Al is pretreated by 2 O 3 The content of Na, K, ca and Al ions in the carrier is reduced, and the crushing strength and the wear resistance of the carrier are improved. EP0712334B1 a silver catalyst is made by supporting an effective amount of silver, a promoter amount of an alkali metal, a promoter amount of magnesium and a promoter amount of rhenium on a support comprising at least 85% alumina and 0.001-2% magnesium in the form of an oxide, which improves the stability of the catalyst. US5100859A, US5145824A, EP0900126B1, US5801259A, US5733842A for treating alkaline earth metal, silicon, zirconiumAdding alpha-Al 2 O 3 The patent teaches that alkaline earth metal, preferably calcium, strontium and barium salts, are used with zirconium compounds and the effect of adding both on catalyst performance is unknown. US5739075A shows that the selectivity of the catalyst decreases at a rate lower than that of a sample of the catalyst which is not subjected to the predeposition treatment, by preliminarily depositing a promoter amount of a rare earth metal and another promoter amount of a metal salt (an alkaline earth metal or a group VIII transition metal) on the surface of an alumina carrier, followed by calcination treatment, and finally preparing the treated carrier into a silver catalyst. CN1511632A found that a carrier made of a heavy alkaline earth metal compound added to an alumina raw material, a solution prepared by impregnating a silver compound, an organic amine and a specific auxiliary agent, and a silver catalyst prepared by heat treatment in an oxygen-containing mixed gas have improved activity and selectivity in an ethylene oxidation reaction.
Although the above patent documents respectively adopt various methods to improve the alumina carrier, which brings about various improvements in the activity, stability and selectivity of the catalyst, the requirements for the carrier performance are continuously increasing with the large-scale industrial application of Re-containing high-selectivity silver catalysts, and therefore, the carrier performance needs to be continuously improved.
Disclosure of Invention
In view of the above-mentioned state of the art, the inventors of the present invention have conducted extensive and intensive studies in the field of silver catalysts, and as a result, have found that the addition of ethylenediaminetetraacetic acid and nano-sized zirconium dioxide particles to a silver ammonia solution can significantly improve the selectivity of silver catalysts made therefrom.
The first aspect of 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, ethylene diamine tetraacetic acid, nano zirconium dioxide particles, an amine compound, water, an alkali metal assistant, an optional rhenium assistant and a co-assistant thereof;
s2, mixing alpha-Al 2 O 3 Carrier loading stepAnd (2) soaking the silver ammonia solution obtained in the step (S1), and then carrying out solid-liquid separation and roasting to obtain the silver catalyst.
A second aspect of the present invention provides a silver catalyst prepared by the above method.
A third aspect of the invention provides the use of a silver catalyst as described above in the oxidation of ethylene to produce ethylene oxide.
Compared with the prior art, the invention has the following advantages: after the porous alumina carrier is soaked in the silver-ammonia solution containing ethylenediamine tetraacetic acid and nano-sized zirconium dioxide particles, the prepared silver catalyst has higher selectivity, and is particularly suitable for the reaction of producing ethylene oxide by ethylene oxidation.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes the embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
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, ethylene diamine tetraacetic acid, nano zirconium dioxide particles, an amine compound, water, an alkali metal assistant, an optional rhenium assistant and a co-assistant thereof;
s2, mixing alpha-Al 2 O 3 And (3) soaking the 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, and 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%, and even 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 ethylenediaminetetraacetic acid is preferably 0.01 to 20.0wt%, and more preferably 0.05 to 5.0wt%, based on the total weight of the silver-ammonia solution.
According to the method of the 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; based on the weight of the silver-ammonia solution, the content of the amine compound in the impregnating solution is 10-90 wt%.
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 and silver oxalate; generally, the silver-containing compound is added in an amount such that the content of silver in the silver catalyst is 2 to 39% by weight, preferably 10 to 35% by weight, in terms of atoms, based on the total weight of the silver catalyst.
In the present invention, the specific selection and amount of the alkali metal promoter, rhenium promoter and co-promoter thereof can be selected conventionally in the art.
Specifically, in step S1, the alkali metal promoter may be selected from compounds of lithium, sodium, potassium, rubidium or cesium, or a combination of any two or more thereof; the alkali metal promoter is added in an amount such 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 aid is selected from one or more of rhenium oxide, perrhenic acid, cesium perrhenate, methyl rhenium trioxide (vii), and ammonium perrhenate; the rhenium promoter is added in an amount such that the rhenium metal content in the silver catalyst is from 0 to 2000ppm, preferably from 100 to 1000ppm, on an atomic basis, based on the total weight of the silver catalyst. The rhenium co-promoter can be selected from one or more of salts or acid forms containing manganese, chromium, sulfur, cobalt, molybdenum and nickel; the rhenium co-promoter is added in an amount such that the rhenium co-promoter is present in the silver catalyst in an amount of 0 to 2000ppm on an atomic basis. The various adjuvants 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 adopted in the production of silver catalysts can be selected, wherein alpha-A1 2 O 3 The content is more than 90 percent, and the characteristics are as follows: the crushing strength is 20-200N/grain; the specific surface area is 0.2 to 3.0m 2 (ii)/g; the water absorption rate 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 is fully carried out, the impregnation time can be 10-300 minutes, the temperature of the impregnation liquid is kept below 30 ℃, and the silver-containing compound and the like are prevented from being precipitated in advance by thermal decomposition; the impregnation process can be accelerated by reducing the pressure to 100mmHg or less, and it is preferable that the surface of the carrier is free from fine bubbles and the inner and outer surfaces are sufficiently wetted.
The solid-liquid separation in step S2 may include leaching and drying, wherein the leaching is performed to minimize the amount of excess impregnating solution attached to the surface of the carrier, and the leaching is performed while removing excess dust from the alumina carrier.
The drying after the leaching in the step S2 may be performed in air and/or an inert gas atmosphere, and the drying temperature may be 50 to 120 ℃, and the time may be 0.5 to 12 hours. Drying is carried out sufficiently until the solid mass does not change significantly.
In step S2, the roasting is carried out in air or nitrogen-oxygen mixed gas with oxygen content not more than 21%; the roasting temperature is controlled between 100 and 600 ℃, preferably between 150 and 500 ℃, and the roasting time is 0.5 to 120 minutes, preferably 1 to 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 microtubular reactor.
The present invention will be further described with reference to the following examples, but the scope of the present invention is not limited to these examples.
Determination of catalyst Performance
Various silver catalysts of the present invention were tested for their initial performance and stability using a laboratory reactor (hereinafter referred to simply as "micro-reactor") evaluation apparatus. The reactor used in the micro-reverse evaluation apparatus was a stainless steel tube having an inner diameter of 4mm, and the reactor was placed in a heating mantle. The filling volume of the catalyst is 1ml, and the lower part of the catalyst is provided with inert filler, so that a catalyst bed layer is positioned in a constant temperature area of the heating sleeve.
Determination of initial Activity and Selectivity
The assay conditions for activity and selectivity used in the present invention are as follows:
reaction gas composition (mol%)
When the reaction conditions are stably achieved, the gas composition at the inlet and outlet of the reactor is continuously measured. The selectivity was calculated after volume shrinkage correction of the measurement results according to the following formula:
where Δ EO is the difference in the ethylene oxide concentration of the outlet gas and the inlet gas, 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 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 can be found in CN88100400.6, CN1634652A and US5063195, which are not detailed herein.
Preparing a catalyst: examples 1 to 8 and comparative example 1
Example 1
Adding 32.1g of ethylenediamine, 10.8g of ethanolamine, 3.5g of ethylenediamine tetraacetic acid and 179.8g of deionized water into a glass beaker with a stirrer to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and continuously stirring the mixture at the temperature of below 40 ℃ to completely dissolve the silver oxalate; then, 2.25ml of cesium nitrate aqueous solution (concentration of 0.03995g/ml, calculated as cesium atom weight), 2.78ml of ammonium perrhenate aqueous solution (concentration of 0.0162g/ml, calculated as rhenium atom weight), and 0.5g of zirconium dioxide particles (diameter of 30 nm) were added in sequence, and mixed uniformly to prepare 300g of impregnation solution for standby.
Taking 15g of the carrier, putting the carrier into a glass container capable of being vacuumized, adding the impregnation solution, and completely immersing the carrier. After evacuation to above 10mmHg for about 15 minutes, the excess solution is leached away. Finally, the impregnated support sample was heated in an air stream at 350 ℃ for about 2 minutes to produce silver catalyst example 1.
Example 2
Adding 32.1g of ethylenediamine, 10.8g of ethanolamine, 3.5g of ethylenediamine tetraacetic acid and 179.8g of deionized water into a glass beaker with a stirrer to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and continuously stirring the mixture at the temperature of below 40 ℃ to completely dissolve the silver oxalate; then, 2.25ml of cesium nitrate aqueous solution (concentration of 0.03995g/ml, by cesium atom weight), 2.78ml of ammonium perrhenate aqueous solution (concentration of 0.0162g/ml, by rhenium atom weight), and 0.5g of zirconium dioxide particles (diameter of 60 nm) were added in this order, and mixed uniformly to prepare 300g of an impregnation solution for use.
Taking 15g of the carrier, putting the carrier into a glass container capable of being vacuumized, and adding the impregnation solution to completely immerse the carrier. After evacuation to above 10mmHg for about 15 minutes, the excess solution is leached away. Finally, the impregnated support sample was heated in an air stream at 350 ℃ for about 2 minutes to produce silver catalyst example 2.
Example 3
Adding 32.1g of ethylenediamine, 10.8g of ethanolamine, 3.5g of ethylenediamine tetraacetic acid and deionized water into a glass beaker with a stirrer to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and continuously stirring the mixture at the temperature of below 40 ℃ to completely dissolve the silver oxalate; then, 2.25ml of an aqueous cesium nitrate solution (concentration of 0.03995g/ml, in terms of cesium atom weight), 2.78ml of an aqueous ammonium perrhenate solution (concentration of 0.0162g/ml, in terms of rhenium atom weight), and 1.5g of zirconium dioxide particles (diameter of 30 nm) were added in this order, and mixed uniformly to prepare 300g of an impregnation solution for use.
Taking 15g of the carrier, putting the carrier into a glass container capable of being vacuumized, and adding the impregnation solution to completely immerse the carrier. After evacuation to above 10mmHg for about 15 minutes, the excess solution is leached away. Finally, the impregnated support sample was heated in an air stream at 350 ℃ for about 2 minutes to produce silver catalyst example 3.
Example 4
Adding 32.1g of ethylenediamine, 10.8g of ethanolamine, 3.5g of ethylenediamine tetraacetic acid and deionized water into a glass beaker with a stirrer to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, keeping the temperature below 40 ℃, and continuously stirring to completely dissolve the silver oxalate; then, 2.25ml of cesium nitrate aqueous solution (concentration of 0.03995g/ml, calculated as cesium atom weight), 2.78ml of ammonium perrhenate aqueous solution (concentration of 0.0162g/ml, calculated as rhenium atom weight), and 1.5g of zirconium dioxide particles (diameter of 60 nm) were added in sequence, and mixed uniformly to prepare 300g of impregnation solution for standby.
Taking 15g of the carrier, putting the carrier into a glass container capable of being vacuumized, adding the impregnation solution, and completely immersing the carrier. After evacuation to above 10mmHg for about 15 minutes, the excess solution is leached away. Finally, the impregnated support sample was heated in an air stream at 350 ℃ for about 2 minutes to produce silver catalyst example 4.
Example 5
Adding 32.1g of ethylenediamine, 10.8g of ethanolamine, 10.5g of ethylenediamine tetraacetic acid and 179.8g of deionized water into a glass beaker with a stirrer to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and continuously stirring the mixture at the temperature of below 40 ℃ to completely dissolve the silver oxalate; then, 2.25ml of cesium nitrate aqueous solution (concentration of 0.03995g/ml, by cesium atom weight), 2.78ml of ammonium perrhenate aqueous solution (concentration of 0.0162g/ml, by rhenium atom weight), and 0.5g of zirconium dioxide particles (diameter of 30 nm) were added in this order, and mixed uniformly to prepare 300g of an impregnation solution for use.
Taking 15g of the carrier, putting the carrier into a glass container capable of being vacuumized, adding the impregnation solution, and completely immersing the carrier. After evacuation to above 10mmHg for about 15 minutes, the excess solution is leached away. Finally, the impregnated support sample was heated in an air stream at 350 ℃ for about 2 minutes to produce silver catalyst example 5.
Example 6
Adding 32.1g of ethylenediamine, 10.8g of ethanolamine, 10.5g of ethylenediamine tetraacetic acid and 179.8g of deionized water into a glass beaker with a stirrer to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and continuously stirring the mixture at the temperature of below 40 ℃ to completely dissolve the silver oxalate; then, 2.25ml of cesium nitrate aqueous solution (concentration of 0.03995g/ml, calculated as cesium atom weight), 2.78ml of ammonium perrhenate aqueous solution (concentration of 0.0162g/ml, calculated as rhenium atom weight), and 0.5g of zirconium dioxide particles (diameter of 60 nm) were added in sequence, and mixed uniformly to prepare 300g of impregnation solution for standby.
Taking 15g of the carrier, putting the carrier into a glass container capable of being vacuumized, adding the impregnation solution, and completely immersing the carrier. After evacuation to above 10mmHg for about 15 minutes, the excess solution is leached away. Finally, the impregnated support sample was heated in an air stream at 350 ℃ for about 2 minutes to produce silver catalyst example 6.
Example 7
Adding 32.1g of ethylenediamine, 10.8g of ethanolamine, 10.5g of ethylenediamine tetraacetic acid and 179.8g of deionized water into a glass beaker with a stirrer to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and continuously stirring the mixture at the temperature of below 40 ℃ to completely dissolve the silver oxalate; then, 2.25ml of cesium nitrate aqueous solution (concentration of 0.03995g/ml, calculated as cesium atom weight), 2.78ml of ammonium perrhenate aqueous solution (concentration of 0.0162g/ml, calculated as rhenium atom weight), and 1.5g of zirconium dioxide particles (diameter of 30 nm) were added in sequence, and mixed uniformly to prepare 300g of impregnation solution for standby.
Taking 15g of the carrier, putting the carrier into a glass container capable of being vacuumized, adding the impregnation solution, and completely immersing the carrier. After evacuation to above 10mmHg for about 15 minutes, the excess solution is leached away. Finally, the impregnated support sample was heated in an air stream at 350 ℃ for about 2 minutes to produce silver catalyst example 7.
Example 8
Adding 32.1g of ethylenediamine, 10.8g of ethanolamine, 10.5g of ethylenediamine tetraacetic acid and 179.8g of deionized water into a glass beaker with a stirrer to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and continuously stirring the mixture at the temperature of below 40 ℃ to completely dissolve the silver oxalate; then, 2.25ml of cesium nitrate aqueous solution (concentration of 0.03995g/ml, by cesium atom weight), 2.78ml of ammonium perrhenate aqueous solution (concentration of 0.0162g/ml, by rhenium atom weight), and 1.5g of zirconium dioxide particles (diameter of 60 nm) were added in this order, and mixed uniformly to prepare 300g of an impregnation solution for use.
Taking 15g of the carrier, putting the carrier into a glass container capable of being vacuumized, adding the impregnation solution, and completely immersing the carrier. After applying a vacuum above 10mmHg for about 15 minutes, the excess solution is leached away. Finally, the impregnated support sample was heated in an air stream at 350 ℃ for about 2 minutes to produce silver catalyst example 8.
Comparative example 1
Comparative example 1 the same procedure as in example 1 was repeated except that ethylenediaminetetraacetic acid and zirconia 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
Comparative example 3 was conducted in the same manner as in example 1 except that no ethylenediaminetetraacetic acid was added.
TABLE 1 evaluation results on day 6 of silver catalyst comparative example 1 and examples 1 to 8
| Catalyst numbering | Temperature (. Degree. C.) | Selectivity (%) |
| Silver catalyst comparative example 1 | 225 | 82.53 |
| Silver catalyst comparative example 2 | 229 | 84.72 |
| Silver catalyst comparative example 3 | 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 |
It can be seen from table 1 that the initial selectivity of the silver catalyst samples prepared by adding ethylenediaminetetraacetic acid and nano-sized zirconium dioxide particles to a silver-ammonia solution is significantly improved.
While embodiments of the present invention have been described above, the above description is illustrative, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (12)
1. A method for preparing a silver catalyst for producing ethylene oxide by oxidizing ethylene comprises the following steps:
s1, obtaining a silver-ammonia solution, wherein the silver-ammonia solution comprises a silver-containing compound, ethylene diamine tetraacetic acid, nano zirconium dioxide particles, an amine compound, water, an alkali metal assistant, an optional rhenium assistant and a co-assistant thereof;
s2, mixing alpha-Al 2 O 3 And (3) soaking the 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 content of ethylenediaminetetraacetic acid in step S1 is 0.01-20.0 wt%, preferably 0.05-5.0 wt%, based on the total weight of the silver-ammonia solution.
3. The process according to claim 1, wherein in step S1, the nano zirconium dioxide particles have a diameter of 1 to 100 nm, preferably 10 to 80 nm; the nano zirconium dioxide particles are added in an amount such that the content of the nano zirconium dioxide in the silver catalyst is 0.001 to 1.5wt%, preferably 0.01 to 1.0wt%, and more preferably 0.1 to 0.3wt%, based on the total weight of the silver catalyst.
4. The method according to any one of claims 1 to 3, 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.
5. The method according to any one of claims 1 to 3, wherein in step S1, the silver-containing compound is one or more of silver acetate, silver nitrate and silver oxalate; the silver-containing compound is added in an amount such that the content of silver in the silver catalyst is 2 to 39% by weight, preferably 10 to 35% by weight, in terms of atoms, based on the total weight of the silver catalyst.
6. The process of any one of claims 1-3, wherein in step S1, the alkali metal promoter is selected from compounds of lithium, sodium, potassium, rubidium, or cesium, or a combination of any two or more thereof; the alkali metal promoter is added in an amount such 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.
7. A process as claimed in any one of claims 1 to 3, in which, in step S1, the rhenium promoter is selected from one or more of rhenium oxide, perrhenic acid, caesium perrhenate, methyltrioxorhenium (vii) and ammonium perrhenate; the rhenium promoter is added in an amount such that the rhenium metal content in the silver catalyst is from 0 to 2000ppm, preferably from 100 to 1000ppm, on an atomic basis, based on the total weight of the silver catalyst.
8. The process according to any one of claims 1 to 3, wherein in step S2, the impregnation is carried out for a time ranging from 10 to 300 minutes, the impregnation preferably being carried out under a pressure of 100 mmHg;
the solid-liquid separation comprises leaching and drying, preferably, the drying process after leaching is carried out in air and/or inert gas atmosphere, and the drying temperature is 50-120 ℃ and the drying time is 0.1-12 h.
9. The method according to any one of claims 1 to 3, wherein in step S2, the calcination is carried out in air or a mixed gas of nitrogen and oxygen having an oxygen content of not more than 21%; the roasting temperature is controlled between 100 and 600 ℃, preferably between 150 and 500 ℃, and the roasting time is 0.5 to 120 minutes, preferably 1 to 30 minutes.
10. The method of any one of claims 1-3, wherein the alpha-Al is 2 O 3 The carrier is a porous alpha-alumina carrier, wherein alpha-A1 2 O 3 The content is more than 90 percent, and the characteristics are as follows: the crushing strength is 20-200N/grain; the specific surface area is 0.2 to 3.0m 2 (ii)/g; the water absorption rate is not lower than 30%; the pore volume is 0.30-0.85 ml/g.
11. A silver catalyst made by the method of any one of claims 1-10.
12. Use of the silver catalyst of claim 11 in the oxidation of ethylene to produce ethylene oxide.
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