CN115069247A - Method for preparing supported silver catalyst, supported silver catalyst and application - Google Patents
Method for preparing supported silver catalyst, supported silver catalyst and application Download PDFInfo
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- CN115069247A CN115069247A CN202110277422.3A CN202110277422A CN115069247A CN 115069247 A CN115069247 A CN 115069247A CN 202110277422 A CN202110277422 A CN 202110277422A CN 115069247 A CN115069247 A CN 115069247A
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- catalyst
- silver
- silver catalyst
- assistant
- impregnation
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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 74
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 74
- 239000004332 silver Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000005470 impregnation Methods 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 239000007789 gas Substances 0.000 claims abstract description 24
- 238000004140 cleaning Methods 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000005977 Ethylene Substances 0.000 claims abstract description 16
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 15
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 13
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 12
- 230000004913 activation Effects 0.000 claims abstract description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 9
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- -1 amine compound Chemical class 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 150000003378 silver Chemical class 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims description 18
- 238000001994 activation Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 238000002386 leaching Methods 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Chemical class 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000008188 pellet Substances 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 4
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 4
- 229940071536 silver acetate Drugs 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
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000011148 porous material 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical class [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical class 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 class [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical class [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Chemical group 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical class [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Chemical class 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 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 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical class [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Chemical class 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical class [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000002791 soaking Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000011086 high cleaning Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 18
- 230000000694 effects Effects 0.000 description 12
- 239000012535 impurity Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003845 household chemical Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910001872 inorganic gas Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- HRLYFPKUYKFYJE-UHFFFAOYSA-N tetraoxorhenate(2-) Chemical compound [O-][Re]([O-])(=O)=O HRLYFPKUYKFYJE-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
-
- 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
Landscapes
- 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 technical field of catalyst preparation, and relates to a method for preparing a supported silver catalyst, the supported silver catalyst and application. The method comprises the following steps: step I, obtaining impregnation liquid, wherein the impregnation liquid comprises a silver-containing compound, an amine compound, water, an alkali metal assistant, an alkaline earth metal assistant, an optional rhenium assistant and a co-assistant thereof; step II, fully soaking the carrier by using the soaking solution, and then carrying out solid-liquid separation and activation to obtain a silver catalyst; and III, introducing oxygen-containing gas to carry out plasma cleaning treatment on the activated silver catalyst obtained in the step II to obtain the supported silver catalyst. The method adopts the plasma cleaning technology to clean the activated catalyst, has high cleaning efficiency and high speed, and can clean the inside of the micro-hole. The silver catalyst prepared by the method shows good initial catalytic performance in the aspect of preparing ethylene oxide by ethylene epoxidation.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a method for preparing a supported silver catalyst, the supported silver catalyst prepared by the method, and application of the supported silver catalyst in production of ethylene oxide by ethylene epoxidation. More particularly, relates to a supported silver catalyst for producing ethylene oxide by ethylene epoxidation, and a preparation method and application thereof.
Background
Ethylene oxide is a second-needed bulk petrochemical of ethylene derivatives, and is mainly used for producing ethylene glycol, polyester, surfactants and other household and industrial chemical products. Commercially high quality ethylene oxide is obtained by the catalytic epoxidation of ethylene with oxygen over a silver catalyst, with the side reaction of carbon dioxide. The preparation of silver catalyst is carried out by loading active component silver on carrier with alumina as main raw material, and adding certain amount of adjuvant and co-adjuvant to improve the performance of catalyst. Three main performance indexes of the activity, the selectivity and the stability of the silver catalyst are mainly considered in the industrial actual production. Activity means the amount of starting material reactant converted per unit volume (or mass) of catalyst per unit time under certain reaction conditions, and for ethylene epoxidation the activity of the catalyst is often measured in terms of the space time yield applicable or the reaction temperature required at a space time yield, wherein the higher the space time yield applicable or the lower the reaction temperature required at a space time yield, the higher the activity of the silver catalyst. Selectivity refers to the comparison of the extent to which the same catalyst promotes different reactions in a reaction system capable of multiple reactions, in this case the ratio of the number of moles of ethylene converted to the main product ethylene oxide to the number of moles of ethylene reacted overall. The stability refers to the ability of the catalyst to maintain unchanged performances such as activity, selectivity, antitoxicity, thermal stability and the like and structure in the catalytic reaction process, and the better the stability of the catalyst is, the longer the service life of the catalyst is. The optimization of the performance of the silver catalyst is often to improve one or more of activity, selectivity and stability.
It is generally unavoidable during the production of silver catalysts that some organic compounds or ammonia remain on the catalyst and if not removed, it will generally have an adverse effect on the catalyst performance or ethylene oxide product quality. For the silver catalyst for ethylene epoxidation, CN110035998A removed the relevant impurities by using a high temperature pretreatment method of oxygen-containing feed gas, while improving the catalyst performance. In CN102643156B, organic impurities in the application of the silver catalyst are reduced by improving the process, and the service life of the silver catalyst is obviously prolonged. For silver catalysts used in another field, CN105562048B employs steam heat treatment to relieve the inhibition of phosphorus on the activity of electrolytic silver. However, in the case of silver catalysts for ethylene epoxidation, the removal of harmful organic impurities from the activated catalyst by high-temperature oxidation or steam introduction is also accompanied by a loss of part of the promoters and active components due to excessively severe conditions, which adversely affects the performance of the catalyst, especially the catalyst life.
The above patent documents employ different methods for reducing the organic impurities which may cause influence, among which pretreatment of the catalyst to improve the catalyst is the most widely applicable method, but for the silver catalyst for ethylene epoxidation, if the treatment conditions are severer than the actual reaction conditions, the life of the catalyst is reduced, and therefore, there is still room for improvement in the methods used in the prior pretreatment operations.
Disclosure of Invention
Under the background of the prior art, the inventor of the present invention has conducted a great deal of experimental research on the pretreatment of silver catalyst, and found that the plasma cleaning conditions are mild, and the plasma cleaning can be used to achieve the effect which cannot be achieved by the conventional cleaning method. Plasma cleaning typically involves the following processes: the inorganic gas is excited into a plasma state; the plasma and the solid surface are adsorbed and reacted to generate product molecules, and the product molecules are dissociated to form gas phase which is separated from the surface of the object, so that the molecular level cleaning of the surface of the material is achieved. For a silver catalyst system, the plasma acts on the surface of a solid sample, so that not only are original pollutants and impurities on the surface removed, but also an etching effect is generated, the surface of the catalyst is roughened, a plurality of fine uniform appearances are formed, the specific surface of the sample is increased, the adhesive force of the solid surface is improved, and the initial activity and the selectivity of the catalyst are further improved.
A first aspect of the present invention provides a method for preparing a supported silver catalyst, comprising the steps of:
step I, obtaining impregnation liquid, wherein the impregnation liquid comprises a silver-containing compound, an amine compound, water, an alkali metal assistant, an alkaline earth metal assistant, an optional rhenium assistant and a co-assistant thereof;
step II, fully impregnating the carrier with the impregnation liquid, and then carrying out solid-liquid separation and activation to obtain a silver catalyst;
and III, introducing oxygen-containing gas to carry out plasma cleaning treatment on the activated silver catalyst obtained in the step II to obtain the supported silver catalyst.
A second aspect of the present invention provides a supported silver catalyst prepared by the above method.
A third aspect of the invention provides the use of a supported silver catalyst as described above in the epoxidation of ethylene to ethylene oxide.
The activated catalyst is cleaned by adopting a plasma cleaning technology, so that the cleaning efficiency is high, the speed is high, and the catalyst can be cleaned into micro-holes; the cleaned catalyst is also very dry, and the water which is unfavorable for the reaction is removed; because no solvent is used, the method is safe and environment-friendly, has small damage to the catalyst, and can prevent the redissolution of the auxiliary agent and the like. The silver catalyst prepared by the method shows good initial catalytic performance in the aspect of preparing ethylene oxide by ethylene epoxidation, and particularly has high initial reaction activity and high selectivity.
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 method for preparing a supported silver catalyst, which comprises the following steps:
step I, obtaining impregnation liquid, wherein the impregnation liquid comprises a silver-containing compound, an amine compound, water, an alkali metal assistant, an alkaline earth metal assistant, an optional rhenium assistant and a co-assistant thereof;
step II, fully soaking the carrier by using the soaking solution, and then carrying out solid-liquid separation and activation to obtain a silver catalyst;
and III, introducing oxygen-containing gas to carry out plasma cleaning treatment on the activated silver catalyst obtained in the step II to obtain the supported silver catalyst.
According to the present invention, the plasma cleaning process in step III may be performed using a plasma cleaning machine, and the plasma cleaning process may be performed under conditions including: the temperature is 5-30 ℃, the temperature does not need to be controlled specially, the method can be carried out under the normal temperature condition, the influence on the silver nanoparticles in the catalyst is reduced, the pressure is reduced to below 1MPa generally, and the flow of oxygen-containing gas is preferably 1-100 mL/min per gram of the catalyst -1 The treatment time may be 5 to 600 seconds.
In the present invention, the oxygen-containing gas is preferably a gas having an oxygen content of 20 vol% or more; in particular, the oxygen-containing gas is preferably oxygen and/or air.
According to the method of the invention, the amine compound in step I is used as a solvent, and specifically, can be selected from one or more of ammonia water, ethylamine, N-propylamine, ethylenediamine, 1, 3-propanediamine, 1, 4-butanediamine, N-dimethylformamide, ethanolamine and propanolamine; based on the weight of the dipping solution, the content of the amine compound in the dipping solution is 10-90 wt%. The solvents and resulting impurities here need to be removed as far as possible during the activation process and the subsequent washing process.
According to the method of the present invention, the silver-containing compound in step I may be one or more of silver acetate, silver nitrate and silver oxalate; the content of the silver-containing compound in the impregnating solution is 10-40 wt% calculated by silver element based on the weight of the impregnating solution.
In the invention, the specific selection and dosage of the alkali metal assistant, the alkaline earth metal assistant, the rhenium assistant and the co-assistant thereof can be selected conventionally in the field.
Specifically, the alkali metal promoter in step I can be selected from one or more of soluble salts of lithium, sodium, potassium, rubidium and cesium; the content of the alkali metal additive in terms of elements in the impregnating solution can be 50-2000 ppm based on the weight of the impregnating solution.
The alkaline earth metal auxiliary agent in the step I can be selected from one or more soluble salts of magnesium, calcium, strontium and barium; the content of the alkaline earth metal additive in the impregnating solution can be 5-3000 ppm calculated by elements based on the weight of the impregnating solution.
The rhenium auxiliary agent in the step I can be one or more of potassium perrhenate, perrhenic acid and ammonium rhenate; the content of the rhenium aid in the impregnation liquid calculated by rhenium element can be 50-3000 ppm by weight of the impregnation liquid.
The rhenium co-promoter in the step I can be selected from one or more of salts or acid forms containing manganese, chromium, sulfur, cobalt, molybdenum and nickel; the content of the rhenium co-assistant in the impregnating solution can be 0-2000 ppm based on the weight of the impregnating solution.
The step II can be selected from porous alpha-ion commonly used in the production of silver catalystAccording to one embodiment of the present invention, the alumina carrier has a crushing strength of 30 to 500N/pellet, preferably 40 to 300N/pellet, and a specific surface area of 0.6 to 2.6m 2 A preferred concentration is 0.8 to 2.2m 2 The pore volume is 0.3 to 1.5ml/g, preferably 0.4 to 0.8 ml/g.
According to the invention, the impregnation in the step II can be carried out according to the conventional method in the field, the alumina carrier is completely impregnated in the solution obtained in the step I, the impregnation is carried out fully, the impregnation time can be 5-300 minutes, the temperature of the impregnation liquid is kept below 30 ℃, and the premature precipitation of silver-containing compounds and the like due to thermal decomposition is prevented; 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 II may comprise leaching and drying, wherein the leaching process is preferably carried out to minimize the excess impregnating solution attached to the surface of the carrier, and the excess dust in the alumina carrier can be removed at the same time as the leaching process.
The drying after the leaching in the step II can be carried out in the air and/or inert gas atmosphere, the drying temperature can be 50-120 ℃, and the drying time can be 0.1-12 h. Fully drying until the solid quality does not change obviously any more, and obtaining the precursor of the silver catalyst, wherein the precursor is attached with denser silver particles on an alumina carrier.
The activation in the step II can adopt the conventional conditions in the field, and preferably, the activation process is carried out in flowing air or inert gas atmosphere, and the activation temperature is 120-480 ℃.
When the silver content in the catalyst needs to be increased, impregnation liquid with higher silver concentration can be prepared, or the activated catalyst is repeatedly subjected to impregnation, solid-liquid separation and activation in the step II, so that the purpose of greatly increasing the content of the supported silver is achieved. The silver content of the product target is usually reached 1-3 times.
The invention also provides a supported silver catalyst prepared by the preparation method. The supported silver catalyst can be used for producing ethylene oxide by ethylene epoxidation. 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.
The plasma cleaning method comprises the following steps: the gas flow, pressure and treatment time are set according to experimental conditions, so that no dead volume of catalyst stacking is ensured during treatment, and the uniformity of the treatment degree of each catalyst particle in the treatment process can be improved by using a small shaking table or an oscillator.
The method for measuring the performance of the silver catalyst comprises the following steps: various silver catalysts prepared in the present invention were evaluated for initial catalytic reaction performance and stability using a microtubular reactor (hereinafter referred to as "microreaction"). The tubular reactor used in the microreaction evaluation device was a stainless steel reaction tube having an inner diameter of 4mm, and the reaction tube was placed in a heating jacket made of copper or aluminum. After crushing, 0.8g of catalyst particles with the size of 12-18 meshes are screened, and the catalyst particles are filled into a reactor and compacted, and an inert filler is arranged at the lower part of the reactor so that a catalyst bed layer is positioned in a constant temperature area of a heating sleeve.
The standard evaluation conditions for catalytic activity and selectivity employed in the present invention are as follows (see the examples for actual reaction conditions):
gas composition at the reaction inlet (mol%): ethylene, 30.0 ± 2.0; 4.0-8.0% of oxygen; the carbon dioxide is used as a source of carbon dioxide,<3.0 of the total weight of the mixture; nitrogen, the balance; 0.1 to 2.0ppm of dichloroethane. The reaction pressure is 2.1 MPa; airspeed of 6000h -1 (ii) a The reaction temperature is manually controlled; the target concentration of ethylene oxide in the reactor outlet tail gas was set at 2.5%.
The reactor was heated gradually from room temperature and, after the reaction had stabilized at operating conditions, the reactor inlet and outlet gas compositions were continuously measured. The measurement results were corrected for volume shrinkage, and the selectivity (S) was calculated according to the following formula:
where Δ EO is the difference in ethylene oxide concentration between the reactor outlet gas and the inlet gas, Δ CO 2 Is to turn overThe concentration difference of carbon dioxide in the outlet gas and the inlet gas of the reactor.
Method for analyzing colored impurities: 1g of the catalyst powder was sufficiently dissolved in 10ml of 10% dilute nitric acid, and the change in absorbance at 400nm was compared with a spectrophotometer.
Example 1
This example serves to illustrate the preparation of the supported catalyst of the present invention.
Step I: 55g of 1, 3-propanediamine, 15g N, N-dimethylformamide and 100g of deionized water are uniformly mixed, cooled to 10 ℃ in a water bath, 100g of silver acetate is slowly added into the mixture, after the silver acetate is completely dissolved, 0.2g of potassium nitrate, 0.8g of magnesium nitrate, 0.8g of potassium perrhenate and 0.06g of manganese nitrate are added into the mixture, and the mixture is uniformly mixed to be used as a steeping fluid for later use.
Step II: selecting 10g of porous alumina carrier for industrially producing silver catalyst, white seven-hole cylinder in appearance, 150N/grain of crushing strength and 1.6m of specific surface area 2 The pore volume is 0.7 ml/g. Immersing a carrier sample by using the prepared impregnation liquid, putting the carrier sample into a container capable of being vacuumized, vacuumizing to reduce the pressure to be below 10mmHg, fully infiltrating for half an hour, leaching redundant solution, drying the solution in an oven at 60 ℃ for 1 hour, taking the solution out, activating the solution in air at 300 ℃, and repeating the processes of impregnation, leaching, drying and activation once to improve the silver content to obtain a catalyst sample.
Step III: cleaning the catalyst sample by a plasma cleaning machine at normal temperature and under the pressure of 0.5MPa, treating the catalyst sample by oxygen plasma for 60s at the flow rate of 30 mL/g cat. -1 ·min -1 Thus obtaining the supported silver catalyst.
Example 2
Silver catalyst was prepared as in example 1 except that 0.06g of manganese nitrate in step I was replaced with 0.05g of nickel sulfate and the total weight of the solution was made constant by adding 0.01g of water, and oxygen plasma treatment time in step III was 12 seconds at a flow rate of 20 mL. multidot.g cat. -1 ·min -1 。
Example 3
The silver catalyst was prepared as in example 1 except that 15g N, N-dimethylformamide was replaced by 15g of propanolamine, 0.8g of magnesium nitrate was replaced by 0.6g of barium nitrate and the total weight of the solution was made up with 0.2g of water in step I.
Example 4
The silver catalyst was prepared as in example 1, except that in step III the catalyst sample was treated with an air plasma.
Comparative example 1
The silver catalyst was prepared as in example 1, except that the plasma cleaning treatment was not performed in step III.
Comparative example 2
The silver catalyst was prepared as in example 3, except that the plasma cleaning treatment was not performed in step III.
Test example
The initial reaction characteristics of the catalyst samples were measured using a microreactor evaluation device under the above-mentioned process conditions, and the lower the initial reaction temperature, the shorter the time taken to reach the set load according to the set program, indicating that the catalyst activity was stronger. And fresh catalyst samples are taken and dissolved according to the method to measure the absorbance at 400nm so as to measure the removal degree of the organic impurities. The test results are shown in Table 1.
TABLE 1
As can be seen from table 1, the examples after the plasma cleaning treatment have significantly reduced colored impurities, significantly improved initial activity, and improved selectivity compared to the comparative examples without the plasma cleaning treatment.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not 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 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 numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
Claims (16)
1. A method of preparing a supported silver catalyst comprising the steps of:
step I, obtaining impregnation liquid, wherein the impregnation liquid comprises a silver-containing compound, an amine compound, water, an alkali metal assistant, an alkaline earth metal assistant, an optional rhenium assistant and a co-assistant thereof;
step II, fully impregnating the carrier with the impregnation liquid, and then carrying out solid-liquid separation and activation to obtain a silver catalyst;
and III, introducing oxygen-containing gas to carry out plasma cleaning treatment on the activated silver catalyst obtained in the step II to obtain the supported silver catalyst.
2. The method of claim 1, wherein the conditions of the plasma cleaning process in step III comprise: the temperature is 5-30 ℃, the pressure is below 1MPa, and the flow of oxygen-containing gas is 1-100 mL/min per gram of catalyst -1 The treatment time is 5-600 s.
3. The method according to claim 1, wherein the oxygen-containing gas is a gas having an oxygen content of 20 vol% or more; the oxygen-containing gas is preferably oxygen and/or air.
4. The method according to any one of claims 1 to 3, wherein the amine compound in step I is selected from one or more of ammonia, ethylamine, N-propylamine, ethylenediamine, 1, 3-propanediamine, 1, 4-butanediamine, N-dimethylformamide, ethanolamine and propanolamine; based on the weight of the dipping solution, the content of the amine compound in the dipping solution is 20-90 wt%.
5. The method according to any one of claims 1-3, wherein the silver-containing compound in step I is one or more of silver acetate, silver nitrate and silver oxalate; based on the weight of the impregnation liquid, the content of the silver-containing compound in the impregnation liquid is 10-40 wt% calculated by silver element.
6. The process of any one of claims 1-3, wherein the alkali metal promoter in step I is selected from one or more of soluble salts of lithium, sodium, potassium, rubidium, cesium; the content of the alkali metal additive in the impregnating solution is 50-2000 ppm calculated by elements based on the weight of the impregnating solution.
7. The method according to any one of claims 1-3, wherein the alkaline earth metal promoter in step I is selected from one or more of soluble salts of magnesium, calcium, strontium, barium; and the content of the alkaline earth metal auxiliary agent in the impregnating solution is 5-3000 ppm calculated by elements based on the weight of the impregnating solution.
8. A process as claimed in any one of claims 1 to 3, wherein the rhenium promoter in step I is selected from one or more of potassium perrhenate, perrhenic acid and ammonium perrhenate; based on the weight of the impregnation liquid, the content of the rhenium auxiliary agent in the impregnation liquid calculated by rhenium element is 50-3000 ppm.
9. The process according to any one of claims 1 to 3, wherein the rhenium co-promoter in step I is selected from one or more of manganese, chromium, sulfur, cobalt, molybdenum, nickel containing salts or acid forms; based on the weight of the dipping solution, the content of the rhenium co-additive in the dipping solution is 0-2000 ppm.
10. A process according to any one of claims 1 to 3, wherein the support in step II is a porous α -alumina support having a crush strength of 30 to 500N/pellet, preferably 40 to 300N/pellet, and a specific surface area of 0.6 to 2.6m 2 A preferred concentration is 0.8 to 2.2m 2 The pore volume is 0.3 to 1.5ml/g, preferably 0.4 to 0.8 ml/g.
11. The process according to any one of claims 1 to 3, wherein the impregnation in step II is carried out for a time of 5 to 300 minutes, the impregnation preferably being carried out under a pressure of 100 mmHg.
12. The method of any one of claims 1-3, wherein the solid-liquid separation in step II comprises leaching and drying, preferably, the drying process after leaching is carried out in air or inert gas atmosphere, and the drying temperature is 50-120 ℃ and the drying time is 0.1-12 h.
13. The method according to any one of claims 1 to 3, wherein the activation process in step II is carried out in a flowing air or inert gas atmosphere, and the activation temperature is 120 to 480 ℃.
14. A method according to any one of claims 1-3, wherein the method comprises: and (4) repeatedly carrying out impregnation, solid-liquid separation and activation in the step (II) on the activated catalyst.
15. A supported silver catalyst prepared by the process of any one of claims 1-14.
16. Use of the supported silver catalyst of claim 15 in the epoxidation of ethylene to ethylene oxide.
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