CN110354849B - Supported silver catalyst and preparation method and application thereof - Google Patents
Supported silver catalyst and preparation method and application thereof Download PDFInfo
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- CN110354849B CN110354849B CN201810252746.XA CN201810252746A CN110354849B CN 110354849 B CN110354849 B CN 110354849B CN 201810252746 A CN201810252746 A CN 201810252746A CN 110354849 B CN110354849 B CN 110354849B
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 145
- 239000004332 silver Substances 0.000 title claims abstract description 145
- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 121
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 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 16
- 239000011259 mixed solution Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- 239000012752 auxiliary agent Substances 0.000 claims description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 14
- 239000005977 Ethylene Substances 0.000 claims description 13
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 10
- 229920002401 polyacrylamide Polymers 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 229910052702 rhenium Inorganic materials 0.000 claims description 9
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000006735 epoxidation reaction Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 6
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Chemical class 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 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
- 230000003213 activating effect Effects 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 238000001914 filtration Methods 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
- 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
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Chemical class 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical class [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Chemical class 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
- 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
- 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
- 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
- 230000000996 additive effect Effects 0.000 claims 2
- 239000008188 pellet Substances 0.000 claims 2
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 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
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000001816 cooling 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
- 238000011161 development Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 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
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Images
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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B01J35/612—
-
- 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
-
- 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
- B01J37/0209—Impregnation involving a reaction between the support and a fluid
-
- 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
- B01J37/0213—Preparation of the impregnating solution
-
- 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 technical field of catalyst preparation, and relates to a supported silver catalyst, and a preparation method and application thereof. The supported silver catalyst comprises an alumina carrier and silver particles loaded on the alumina carrier, wherein the average particle diameter of the silver particles is 100-400nm, the silver particles with the particle diameter within the range of +/-50% of the average particle diameter account for more than 70% of all the silver particles, and the silver particles with the particle diameter within the range of +/-20% of the average particle diameter account for more than 50% of all the silver particles. By introducing a proper amount of specific polymer in the preparation process, the agglomeration among silver particles can be reduced, the silver particles are controlled to be uniformly distributed on the carrier, the nano-particles of the silver active component in the prepared silver catalyst are uniform and adjustable in size, the silver particle spacing is obvious, and the catalyst has high performance.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a supported silver catalyst, a preparation method of the supported silver catalyst and application of the supported silver catalyst.
Background
Ethylene oxide is a chemical product, is a bulk petrochemical product with the demand of ethylene derivatives second to polyethylene, and has become an indispensable organic chemical raw material in a series of related industrial development in various countries in the field of petrochemical industry. In the industrial epoxidation of ethylene to ethylene oxide, ethylene oxide is produced from a gas mixture containing ethylene and oxygen under certain reaction conditions in the presence of a silver catalyst.
At present, in the field of industrial ethylene epoxidation, a silver catalyst is still the only effective catalyst widely used in practical production, the catalyst usually takes alumina as a carrier, takes silver as an active component, and simultaneously contains an auxiliary agent and a co-auxiliary agent of certain other elements to improve the catalytic performance of the catalyst, and three main performance indexes of the activity, the selectivity and the stability of the silver catalyst are mainly considered in practical application. The activity is understood as meaning the space-time yield applicable to the catalyst or the reaction temperature required at a space-time yield, 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 ratio of the moles of ethylene converted to the main product ethylene oxide in the reaction to the moles of ethylene reacted overall. Stability is expressed as the rate of decay of the activity and/or selectivity of the catalyst under certain reaction conditions, wherein the better the stability of the catalyst, the longer its lifetime. The performance of the silver catalyst in the process of producing ethylene oxide by oxidizing ethylene has great influence on economic benefit, and the improvement of the activity, selectivity and stability of the silver catalyst is the main direction of the research of the silver catalyst.
The solution impregnation method is a main method used for industrial production of silver catalysts, for example, in US9006127, a carrier is immersed into a silver ammonia solution containing active components by a common impregnation method, then the carrier is filtered out, and the silver catalyst is prepared by heating at 200-500 ℃. In CN87103275A, after the carrier is treated by impregnation liquid with different formulas, the silver-containing component is heated and decomposed at 100-400 ℃ and reduced to prepare the silver catalyst.
In order to improve the performance of the silver catalyst, researchers have tried to improve the catalyst from various aspects, and it is one direction to make the silver particles in the silver catalyst uniformly distributed so as to improve the stability of the silver catalyst. In EP0226234a1, silver is reduced with a tin-containing compound, so that the silver particles are distributed relatively uniformly on the carrier. CN101898132A adopts natural plant extract to reduce silver ion under mild condition, and the performance of the catalyst is close to the level of industrial catalyst without addition of auxiliary agent.
Although the above patent documents employ different methods for preparing the silver catalyst for ethylene epoxidation, which bring about various improvements in various aspects, there is still room for improvement in controlling the morphology distribution of silver particles.
Disclosure of Invention
Under the background of the prior art, the inventor of the present invention has conducted extensive experimental research in the field of preparation of silver catalysts, and as a result, has found that by introducing a proper amount of specific polymer during the preparation, the agglomeration among silver particles can be reduced, the uniform distribution of silver particles on a carrier can be controlled, the nano-particles of the silver active component in the prepared silver catalyst have uniform and adjustable size, the spacing between silver particles is obvious, and the catalyst has high performance.
The first aspect of the present invention provides a supported silver catalyst comprising an alumina support and silver particles supported thereon, the average particle diameter of the silver particles being 100-400nm, the silver particles having a particle diameter in the range of the average particle diameter ± 50% accounting for more than 70% of the total silver particles, the silver particles having a particle diameter in the range of the average particle diameter ± 20% accounting for more than 50% of the total silver particles; preferably, the silver particles have an average particle diameter of 120-300nm, the silver particles having a particle diameter within a range of. + -. 50% of the average particle diameter account for 80% or more of the total silver particles, and the silver particles having a particle diameter within a range of. + -. 20% of the average particle diameter account for 60% or more of the total silver particles.
Compared with the silver catalyst with the surfaces of silver particles bonded with each other in the prior art, the silver catalyst has the advantages of good particle dispersity, few adhesion among silver particles and more uniform particle size distribution.
The alumina carrier can be various porous alumina carriers in the field of silver catalysts for ethylene epoxidation, and can be prepared according to methods known or conventional by persons skilled in the art, and specifically, the crushing strength of the alumina carrier is 30-300N/particle, and preferably 40-200N/particle; the specific surface area is 0.6-3.0m2/g, preferably 1.2-2.2m 2/g; the pore volume is 0.3-1.0ml/g, preferably 0.4-0.8 ml/g.
The second aspect of the present invention provides a method for preparing a supported silver catalyst, comprising the steps of:
step I, preparing a mixed solution of a silver-containing compound, organic amine, water, a polymer, an optional alkali metal auxiliary agent, an optional alkaline earth metal auxiliary agent and an optional rhenium auxiliary agent;
step II, soaking an alumina carrier in the mixed solution, filtering out the carrier after full soaking, and drying and activating to obtain the supported silver catalyst;
the polymer is polyvinylpyrrolidone and/or polyacrylamide.
According to the present invention, the mixed solution containing silver and various additives in step I can be prepared according to the methods known or conventional to those skilled in the art of preparing silver catalysts. Preferably, the temperature of the mixed solution is maintained below 30 ℃.
The key point of the invention is the addition of the polymer, and the existence of the polymer can ensure that the subsequent generation of the silver nano particles is more regular and ordered, and the dispersion is uniform and is not sticky, thereby promoting the dispersion of the silver particles. So that the catalyst has good activity, selectivity and stability.
The molecular weight of the polymer used in the present invention is not particularly limited, and from the viewpoint of industrial application, it is preferable that the molecular weight of the polyvinylpyrrolidone is 8000-; the polyacrylamide is medium molecular weight polyacrylamide, generally refers to polyacrylamide with molecular weight of less than 600 ten thousand and more than 200 ten thousand, and preferably has molecular weight of less than 500 ten thousand.
Good results are achieved according to the invention by adding a polymer in an amount substantially corresponding to the amount of the various metal promoters, preferably in a concentration of from 0.001% to 1%, preferably from 0.008% to 0.1%, based on the weight of the mixed liquor.
In the present invention, the polymer may be added directly or in the form of a solution, and if the polymer is added in the form of a solution, the solvent of the solution may be selected from water or organic amine.
In the present invention, the specific selection and usage of other components in the mixed solution, including the silver-containing compound, the organic amine, the alkali metal assistant, the alkaline earth metal assistant, and the rhenium assistant, can be determined according to conventional schemes in the art, and the present invention is not particularly limited thereto.
Specifically, the silver-containing compound may be silver nitrate and/or silver oxalate, and the content of silver element may be 1-40wt% based on the weight of the mixed solution.
The organic amine may be one or more selected from ethylamine, ethylenediamine, n-propylamine, 1, 3-propylenediamine, n-butylamine, 1, 4-butylenediamine, ethanolamine and propanolamine, preferably two of the above organic amines, such as ethylenediamine and 1, 4-butylenediamine, and the ratio of the two may be 1: 0.2-0.5. The content of the organic amine can be 10-90wt% based on the weight of the mixed solution.
The alkali metal auxiliary agent can be selected from one or more soluble salts of lithium, sodium, potassium, rubidium and cesium, and the content of the alkali metal auxiliary agent can be 0-2000ppm, preferably 50-2000ppm, based on the weight of the mixed solution.
The alkaline earth metal auxiliary agent can be one or more of soluble salts of magnesium, calcium, strontium and barium, and the content of the alkaline earth metal auxiliary agent can be 0-8000ppm, preferably 50-8000ppm, based on the weight of the mixed solution.
The rhenium assistant can be one or more of potassium perrhenate, ammonium perrhenate and perrhenic acid, and the content of the rhenium assistant can be 0-2000ppm, preferably 100-1000 ppm.
According to the present invention, the conditions of each step in step II can adopt the conditions of preparing silver catalyst by the conventional impregnation method in the field.
Preferably, the conditions for sufficient impregnation in step II include: the pressure is below 100mm Hg and/or the temperature is 40-80 deg.C, and the time is 10-300 min. The accelerated impregnation process may be carried out by one or both of reducing the pressure to 100mm Hg or less and heating to 40-80 deg.C, preferably without fine bubbles on the surface of the support and with sufficient impregnation of the inner and outer surfaces.
According to the invention, preferably, the drying in step II is carried out in air or an inert gas atmosphere, the drying temperature being 40-100 ℃, the drying time being 2-20 minutes; the activation is carried out in flowing air or inert gas atmosphere, the activation temperature is 180-400 ℃, the activation time is 2-20 minutes, and the carrier is changed from black to glossy silver black after the activation.
A third aspect of the present invention provides a supported silver catalyst obtained by the above-mentioned production method.
In a fourth aspect, the present invention provides the use of the supported silver catalyst described above in the preparation of ethylene oxide by epoxidation of ethylene. Specifically, the application method comprises the following steps: 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 silver catalyst has uniform silver particle size and difficult agglomeration of silver particles, so that the silver catalyst has high catalytic performance and shows good activity, selectivity and stability in the reaction of preparing ethylene oxide by ethylene epoxidation.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
Exemplary embodiments of the present invention will be described in more detail by referring to the accompanying drawings.
Fig. 1 is a scanning microscope photograph of the catalysts synthesized in example 1, example 2, example 3, example 4 and comparative example 1.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below.
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 adopted by the invention are as follows:
gas composition at the reaction inlet (mol%): ethylene, 29.0 ± 1.0; oxygen, 7.3 +/-0.2; the carbon dioxide is used as a source of carbon dioxide,<3.0; 0.5 parts of water vapor; nitrogen, the balance; dichloroethane, 0.1-2.0 ppm. The reaction pressure is 2.1 MPa; airspeed of 6000h-1(ii) a The concentration of ethylene oxide in the reactor outlet tail gas was 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:
wherein, Delta EO is the concentration difference of ethylene oxide in outlet gas and inlet gas of the reactor, Delta CO2Is the difference in carbon dioxide concentration between the reactor outlet gas and the reactor inlet gas.
The various silver catalysts prepared in the examples and comparative examples of the present invention adopt a method for industrially producing a silver catalystThe pore alpha-alumina carrier is white seven-pore cylinder in appearance, the crushing strength is 65N/particle, and the specific surface area is 1.5m2The pore volume is 0.5 ml/g.
The silver particle size of each of the silver catalysts prepared in the examples of the present invention and the comparative examples was determined by analyzing the silver particle size in a scanning electron microscope photograph.
Example 1
100g of ethylenediamine and 30g of 1, 4-butanediamine are added into 200g of deionized water, the mixture is uniformly mixed, after a water bath is kept at room temperature, 110g of silver oxalate is slowly added into the mixture, 0.5g of cesium nitrate, 0.4g of calcium acetate and 0.3g of perrhenic acid amine are added after the silver oxalate is completely dissolved, and the mixture is fully stirred until the mixture is completely dissolved to obtain a mixed solution.
To the mixed solution was added 3g of polyvinylpyrrolidone (molecular weight: 58000), and the mixture was stirred until completely dissolved.
Putting 30g of the selected porous alpha-alumina carrier into a container capable of being vacuumized, vacuumizing to reduce the pressure to be below 10mmHg, adding the impregnation liquid until the liquid surface completely immerses the solid, keeping for 30 minutes, and leaching to remove the redundant solution. Drying the impregnated carrier in air at 60 ℃ for 10 minutes, then heating in air flow at 400 ℃ for 3 minutes for activation, and cooling to obtain the silver catalyst. Wherein the silver particles have an average particle diameter of 122nm, the silver particles having a particle diameter within a range of. + -. 50% of the average particle diameter account for 76% or more of the total silver particles, and the silver particles having a particle diameter within a range of. + -. 20% of the average particle diameter account for 57% or more of the total silver particles.
Example 2
The catalyst was prepared as in example 1 except that the amount of polyvinylpyrrolidone used in step II was reduced to 0.3 g. In the prepared silver catalyst, the average particle diameter of the silver particles is 105nm, the silver particles having a particle diameter within a range of ± 50% of the average particle diameter account for 73% or more of the total silver particles, and the silver particles having a particle diameter within a range of ± 20% of the average particle diameter account for 60% or more of the total silver particles.
Example 3
The catalyst was prepared as in example 1 except that 5ml of a 40g/L polyacrylamide (molecular weight 500 ten thousand) solution was added to the mixed solution in place of the polyvinylpyrrolidone solid in step II. In the prepared silver catalyst, the average particle diameter of the silver particles is 206nm, the silver particles with the particle diameter within the range of +/-50% of the average particle diameter account for more than 74% of all the silver particles, and the silver particles with the particle diameter within the range of +/-20% of the average particle diameter account for more than 52% of all the silver particles.
Example 4
The catalyst was prepared as in example 3, except that the amount of the 40g/L polyacrylamide (500-million molecular weight) solution used in step II was reduced to 1 ml. In the prepared silver catalyst, the average particle diameter of the silver particles is 141nm, the silver particles having a particle diameter within a range of ± 50% of the average particle diameter account for 83% or more of the total silver particles, and the silver particles having a particle diameter within a range of ± 20% of the average particle diameter account for 65% or more of the total silver particles.
Comparative example 1
The catalyst was prepared as in example 1 except that no polyvinylpyrrolidone or other polymer was added in step II and there was a significant sticking of silver particles on the surface of the catalyst product.
The reaction characteristics of the catalyst samples were measured using a microreactor evaluation apparatus under the aforementioned process conditions, each sample was evaluated for one month after the process conditions were stabilized, and the silver content was determined by titration, and the test results are shown in table 1.
TABLE 1
From table 1, it can be seen that the catalysts of the present invention show better activity, selectivity and stability compared to the conventional impregnation catalyst, as compared to example 1, example 2, example 3, example 4 and comparative example 1.
When each sample was photographed using a Scanning Electron Microscope (SEM), as shown in fig. 1, it can be seen that the silver particles adhered to each other on the surface of the silver catalyst in comparative example 1, unlike the silver catalyst of the present invention, which has a good dispersion degree, less adhesion between silver particles, a more uniform particle size distribution, and particle size adjustable by changing the kind, properties, and concentration of the added polymer.
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.
Claims (20)
1. A supported silver catalyst is characterized by comprising an alumina carrier and silver particles loaded on the alumina carrier, wherein the average particle diameter of the silver particles is 100-400nm, the silver particles with the particle diameter within the range of +/-50% of the average particle diameter account for more than 70% of all the silver particles, and the silver particles with the particle diameter within the range of +/-20% of the average particle diameter account for more than 50% of all the silver particles;
the preparation method of the supported silver catalyst comprises the following steps:
step I, preparing a mixed solution of a silver-containing compound, organic amine, water, a polymer, an optional alkali metal auxiliary agent, an optional alkaline earth metal auxiliary agent and an optional rhenium auxiliary agent;
step II, soaking an alumina carrier in the mixed solution, filtering out the carrier after full soaking, and drying and activating to obtain the supported silver catalyst;
the polymer is polyvinylpyrrolidone and/or polyacrylamide;
the molecular weight of the polyacrylamide is 2000000-6000000;
the silver-containing compound is silver nitrate and/or silver oxalate, and the content of silver element is 1-40wt% based on the weight of the mixed solution;
based on the weight of the mixed solution, the concentration of the polymer is 0.008% -0.1%.
2. The supported silver catalyst as claimed in claim 1, wherein the silver particles have an average particle diameter of 120-300nm, and the silver particles having a particle diameter within a range of. + -. 50% of the average particle diameter account for 80% or more of the total silver particles, and the silver particles having a particle diameter within a range of. + -. 20% of the average particle diameter account for 60% or more of the total silver particles.
3. The supported silver catalyst of claim 1, wherein the polyacrylamide has a molecular weight of 500 million or less.
4. The supported silver catalyst of claim 1 wherein the alumina support has a crush strength of 30-300N/pellet; the specific surface area is 0.6-3.0m2(ii)/g; the pore volume is 0.3-1.0 ml/g.
5. The supported silver catalyst of claim 4 wherein the alumina support has a crush strength of 40-200N/pellet.
6. The supported silver catalyst of claim 4, wherein the specific surface area is 1.2-2.2m2/g。
7. The supported silver catalyst of claim 4, wherein the pore volume is from 0.4 to 0.8 ml/g.
8. A method of preparing a supported silver catalyst according to any one of claims 1 to 7, comprising the steps of:
step I, preparing a mixed solution of a silver-containing compound, organic amine, water, a polymer, an optional alkali metal auxiliary agent, an optional alkaline earth metal auxiliary agent and an optional rhenium auxiliary agent;
step II, soaking an alumina carrier in the mixed solution, filtering out the carrier after full soaking, and drying and activating to obtain the supported silver catalyst;
the polymer is polyvinylpyrrolidone and/or polyacrylamide.
9. The preparation method according to claim 8, wherein the molecular weight of the polyvinylpyrrolidone is 8000-500000.
10. The method according to claim 8, wherein the organic amine is selected from one or more of ethylamine, ethylenediamine, n-propylamine, 1, 3-propanediamine, n-butylamine, 1, 4-butanediamine, ethanolamine, and propanolamine, and the content of the organic amine is 10 to 90wt% based on the weight of the mixed solution.
11. The preparation method according to claim 8, wherein the alkali metal assistant is selected from one or more soluble salts of lithium, sodium, potassium, rubidium and cesium, and the content of the alkali metal assistant is 0 to 2000ppm based on the weight of the mixed solution.
12. The production method according to claim 11, wherein the content of the alkali metal builder is 50 to 2000 ppm.
13. The method according to claim 8, wherein the alkaline earth metal additive is one or more selected from soluble salts of magnesium, calcium, strontium and barium, and the content of the alkaline earth metal additive is 0 to 8000ppm based on the weight of the mixed solution.
14. The production method according to claim 13, wherein the content of the alkaline earth metal assistant is 50 to 8000 ppm.
15. The preparation method of claim 8, wherein the rhenium aid is one or more selected from potassium perrhenate, ammonium perrhenate and perrhenic acid, and the content of the rhenium aid is 0-2000ppm based on the weight of the mixed solution.
16. The preparation method as claimed in claim 15, wherein the rhenium promoter is contained in an amount of 100-1000 ppm.
17. The production method according to any one of claims 8 to 16, wherein the conditions for sufficient impregnation in step II include: the pressure is below 100mm Hg and/or the temperature is 40-80 deg.C, and the time is 10-300 min.
18. The production method according to any one of claims 8 to 16, wherein the drying in step II is performed in an air or inert gas atmosphere, the drying temperature is 40 to 100 ℃, and the drying time is 2 to 20 minutes; the activation is carried out in flowing air or inert gas atmosphere, the activation temperature is 180-400 ℃, and the activation time is 2-20 minutes.
19. A supported silver catalyst produced by the production method according to any one of claims 8 to 16.
20. Use of the supported silver catalyst of any one of claims 1 to 7 or the supported silver catalyst of claim 19 in the epoxidation of ethylene to ethylene oxide.
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