CN110354849A - Loading type silver catalyst and its preparation method and application - Google Patents
Loading type silver catalyst and its preparation method and application Download PDFInfo
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- CN110354849A CN110354849A CN201810252746.XA CN201810252746A CN110354849A CN 110354849 A CN110354849 A CN 110354849A CN 201810252746 A CN201810252746 A CN 201810252746A CN 110354849 A CN110354849 A CN 110354849A
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- Prior art keywords
- argent
- preparation
- silver catalyst
- catalyst
- loading type
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 74
- 239000004332 silver Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000011068 loading method Methods 0.000 title claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 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 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 14
- 239000005977 Ethylene Substances 0.000 claims description 13
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 10
- 229920002401 polyacrylamide Polymers 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 229910052702 rhenium Inorganic materials 0.000 claims description 7
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 239000003795 chemical substances by application 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 Substances 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 239000007788 liquid 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 compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical group CCN QUSNBJAOOMFDIB-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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 2
- -1 Putriscine Chemical compound 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [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 Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 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 compound [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 Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims 2
- 150000003839 salts Chemical class 0.000 claims 2
- 229940031098 ethanolamine Drugs 0.000 claims 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000002803 maceration Methods 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 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
- 238000004458 analytical method Methods 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
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 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
- 238000012937 correction Methods 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
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response 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
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004448 titration 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
-
- 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
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 catalyst preparation technical field, it is related to a kind of loading type silver catalyst and its preparation method and application.The loading type silver catalyst includes the Argent grain of alumina support and load thereon, the average grain diameter of the Argent grain is 100-400nm, Argent grain of the particle diameter in ± 50% range of average grain diameter accounts for 70% or more of whole Argent grains, and Argent grain of the particle diameter in ± 20% range of average grain diameter accounts for 50% or more of whole Argent grains.By introducing suitable particular polymers in preparation, the reunion between silver granuel can be reduced, control silver granuel is uniformly distributed on carrier, and the nanoparticle size of silver-colored active component is uniform adjustable in made silver catalyst, Argent grain spacing is obvious, and the performance of catalyst is higher.
Description
Technical field
The invention belongs to catalyst preparation technical fields, more particularly, to a kind of loading type silver catalyst, a kind of load
The preparation method of type silver catalyst and the application of the loading type silver catalyst.
Background technique
Ethylene oxide is large petroleum that demand is only second to polyethylene in ethene derivatives as a kind of chemical products
It is former to have become indispensable organic chemical industry in a series of related industries development in various countries in petrochemical industry for work articles
Material.Industrial ethylene epoxidizing generates in the reaction of ethylene oxide, work of the gaseous mixture containing ethylene and oxygen in silver catalyst
Ethylene oxide is produced under, under certain reaction condition.
Currently, in industrial ethylene epoxidation field, silver catalyst is still unique widely used in actual production to have
Catalyst is imitated, the catalyst is usually using aluminium oxide as carrier, using silver as active component, while including the auxiliary agent of certain other elements
With coassist agent to improve its catalytic performance, silver catalyst activity, selectivity and stability three are mainly investigated in practical applications
Main performance indicator.Activity refers to the space-time yield that catalyst is applicable in or required reaction temperature under certain space-time yield
Degree, wherein the space-time yield being applicable in it is higher or required under certain space-time yield reaction temperature it is lower, the work of silver catalyst
Property is higher.Selectivity refers to that ethylene is converted to the molal quantity of principal product ethylene oxide and the molal quantity of ethylene overall reaction in reaction
The ratio between.Stability is then expressed as the rate of decay of catalyst activity and/or selectivity under certain reaction condition, wherein being catalyzed
Agent stability is better, and the service life is longer.The performance of silver catalyst imitates economy during ethylene produces ethylene oxide
Benefit influence is very big, and the activity, selectivity and stability for improving silver catalyst are the Main ways of silver catalyst research.
Solution dipping method is main method used in industrial production silver catalyst, as passed through commonly in US9006127
Infusion process filters out carrier after carrier is immersed the silver ammino solution containing active component, heats at 200~500 DEG C and silver catalyst is made.
Equally make heat resolve containing silver components at 100~400 DEG C with after the maceration extract processing carrier of different formulations in CN87103275A
And be reduced, silver catalyst is made.
In order to improve the performance of silver catalyst, researchers attempt to improve catalyst from every side, make silver-colored catalysis
Argent grain is evenly distributed to improve its stability to be one of direction in agent.With stanniferous compound in EP0226234A1
Reduction silver, is distributed silver granuel on carrier relatively uniform.CN101898132A uses natural botanical extraction liquid in a mild condition
Silver ion is restored, in the case where not adding auxiliary agent, close to the level of industrial catalyst, which has green the performance of catalyst
The characteristics of color, and Argent grain is evenly distributed.
Although above patent document prepares ethylene epoxidizing silver catalyst using different methods, bring from every side not
Still there is improved space with the improvement of degree, but on control silver granuel fractions distribution.
Summary of the invention
Under the background of the above-mentioned prior art, the present inventor has carried out various aspects in the preparation field of silver catalyst
A large amount of experimental study, as a result, it has been found that the reunion between silver granuel can be reduced by introducing suitable particular polymers in preparation,
Control silver granuel is uniformly distributed on carrier, and the nanoparticle size of silver-colored active component is uniform adjustable in made silver catalyst,
Argent grain spacing is obvious, and the performance of catalyst is higher.
The first aspect of the present invention provides a kind of loading type silver catalyst, which includes alumina support
Average grain diameter with the Argent grain of load thereon, the Argent grain is 100-400nm, and particle diameter is in average grain diameter
Argent grain in ± 50% range accounts for 70% or more of whole Argent grains, and particle diameter is in ± 20% range of average grain diameter
Argent grain account for 50% or more of whole Argent grains；Preferably, the average grain diameter of the Argent grain is 120-300nm,
Argent grain of the grain diameter in ± 50% range of average grain diameter accounts for 80% or more of whole Argent grains, and particle diameter is average
Argent grain in ± 20% range of particle diameter accounts for 60% or more of whole Argent grains.
The silver catalyst that surface Argent grain is mutually bonded together compared with prior art, silver catalyst particle of the invention point
Divergence is fine, and rare adhesion, size distribution are also more uniform between silver granuel.
Alumina support of the present invention can be the various porous alumina carriers in ethylene epoxidizing silver catalyst field, can
It is prepared according to method known to those skilled in the art or conventional, specifically, the crushing strength of the alumina support is 30-
300N/, preferably 40-200N/；Specific surface area is 0.6-3.0m2/g, preferably 1.2-2.2m2/g；Kong Rongwei 0.3-
1.0ml/g, preferably 0.4-0.8ml/g.
The second aspect of the present invention provides a kind of preparation method of loading type silver catalyst, includes the following steps:
Step I prepares Ag-containing compound, organic amine, water, polymer, optional alkali metal promoter, optional alkaline-earth metal
The mixed liquor of auxiliary agent, optional rhenium auxiliary agent；
Alumina support is dipped in the mixed liquor by step II, carrier is filtered out after being sufficiently impregnated, then activate through dry
The loading type silver catalyst is made；
The polymer is polyvinylpyrrolidone and/or polyacrylamide.
According to the present invention, the mixed liquor of argentiferous described in step I and a variety of auxiliary agents can be according to silver catalyst preparation field
The known or conventional method of technical staff be made.Preferably, the temperature of the mixed liquor is maintained at 30 DEG C or less.
Key of the invention is that the addition of polymer, the presence of polymer can make the generation of subsequent silver nano-grain more
Add it is regular orderly, be uniformly dispersed and be not adhered, to promote the dispersion of Argent grain.So that catalyst has good activity, selection
Property and stability.
There is no particular limitation for molecular weight of the present invention to polymer used, considers from industrial application angle, it is preferable that institute
The molecular weight for stating polyvinylpyrrolidone is 8000-500000；The polyacrylamide is middle-molecular-weihydroxyethyl polyacrylamide, generally
Refer to that molecular weight is lower than 6,000,000, the polyacrylamide higher than 2,000,000, preferred molecular weight is 5,000,000 or less.
According to the present invention, the effect that can be realized with the substantially comparable polymer of various metal promoter dosages is added, it is excellent
Selection of land, on the basis of the weight of mixed liquor, the concentration of the polymer is 0.001%-1%, preferably 0.008%-0.1%.
In the present invention, the polymer can be directly added into, and can also be added in the form of a solution, if being added in the form of a solution, institute
Water or organic amine may be selected in the solvent for stating solution.
In the present invention, other components in mixed liquor, including Ag-containing compound, organic amine, alkali metal promoter, alkaline-earth metal
Auxiliary agent, the specific choice of rhenium auxiliary agent and dosage can determine that the present invention is not particularly limited this according to this field conventional scheme.
Specifically, the Ag-containing compound can be silver nitrate and/or silver oxalate, on the basis of the weight of mixed liquor, silver
The content of element can be 1-40wt%.
The organic amine can be selected from ethamine, ethylenediamine, n-propylamine, 1,3- propane diamine, n-butylamine, 1,4- butanediamine, ethyl alcohol
One of amine and Propanolamine are a variety of, two kinds in preferably above-mentioned organic amine, for example, ethylenediamine and Putriscine, and two
The amount ratio of person can be 1:0.2-0.5.On the basis of the weight of mixed liquor, the content of the organic amine can be 10-90wt%.
The alkali metal promoter can be selected from one of soluble-salt of lithium, sodium, potassium, rubidium, caesium or a variety of, with mixed liquor
On the basis of weight, the content of the alkali metal promoter can be 0-2000ppm, preferably 50-2000ppm.
The base earth metal promoter can be selected from one of soluble-salt of magnesium, calcium, strontium, barium or a variety of, with mixed liquor
On the basis of weight, the content of the base earth metal promoter can be 0-8000ppm, preferably 50-8000ppm.
The rhenium auxiliary agent can be selected from one of potassium perrhenate, rehenic acid ammonium and perrhenic acid or a variety of, with the weight of mixed liquor
On the basis of, the content of the rhenium auxiliary agent can be 0-2000ppm, preferably 100-1000ppm.
According to the present invention, the infusion process that this field routine can be used in the condition of each step in step II prepares silver catalyst
Condition.
Preferably, it is 100mm Hg or less and/or temperature is that the condition being sufficiently impregnated described in step II, which includes: pressure,
40-80 DEG C, the time is 10-300 minutes.It can be by being decompressed to 100mm Hg pressure or less, being heated to one of 40-80 DEG C side
Simultaneously using dipping process is accelerated, sufficiently being infiltrated with carrier surface without tiny bubble, surfaces externally and internally is advisable for method or two methods.
In accordance with the present invention it is preferred that drying described in step II carries out in air or inert gas atmosphere, drying temperature
It is 40-100 DEG C, drying time is 2-20 minutes；The activation carries out in the air or inert gas atmosphere of flowing, activation temperature
Degree is 180-400 DEG C, and activation time is 2-20 minutes, and carrier becomes glossiness silver-colored black from black after activation.
The third aspect of the present invention provides the loading type silver catalyst as made from above-mentioned preparation method.
The fourth aspect of the present invention provides above-mentioned loading type silver catalyst and prepares answering in ethylene oxide in ethylene epoxidizing
With.Specifically, the application method include: in the presence of above-mentioned silver catalyst, in the miniature tubular reactor of fixed bed, ethylene with
The gaseous mixture of the gases such as oxygen is reacted.
Argent grain size uniformity, silver granuel be not easy to reunite in silver catalyst of the invention, so that the catalytic performance of silver catalyst
It is higher, good activity, selectivity and stability are shown in the reaction of ethylene epoxidizing epoxy ethane.
Other features and advantages of the present invention will then part of the detailed description can be specified.
Detailed description of the invention
Exemplary embodiment of the invention is described in more detail in conjunction with the accompanying drawings.
Fig. 1 is the flying-spot microscope for the catalyst that embodiment 1, embodiment 2, embodiment 3, embodiment 4 and comparative example 1 synthesize
Photo.
Specific embodiment
The preferred embodiment of the present invention is described in more detail below.
The measuring method of silver catalyst performance in the present invention:
The various silver catalysts prepared in the present invention are evaluated just using miniature tubular reactor (hereinafter referred to as " micro- anti-")
Beginning catalytic perfomance and stability.The tubular reactor that micro anti-evaluation device uses is the stainless steel reaction pipe of internal diameter 4mm, instead
Should pipe be placed in copper or aluminum heating mantle.Silver catalyst sieves the catalyst granules for taking size between 12~18 mesh after pulverizing
0.8g is packed into reactor compacting, and reactor lower part has inert filler to be located at catalyst bed in the flat-temperature zone of heating mantle.
The standard evaluation condition of catalytic activity and selectivity that the present invention uses is as follows:
The gas composition (mol%) of reaction inlet: ethylene, 29.0 ± 1.0；Oxygen, 7.3 ± 0.2；Carbon dioxide, < 3.0；
Vapor, 0.5；Nitrogen, surplus；Dichloroethanes, 0.1-2.0ppm.Reaction pressure 2.1MPa；Air speed 6000h-1；Reactor outlet
The concentration 2.5% of tail gas ethylene oxide.
Be gradually heated up reactor from room temperature, when stable reaction in the operating condition after, METHOD FOR CONTINUOUS DETERMINATION reactor inlet and go out
Gas composition.Measurement result calculates selectivity (S) after carrying out volume contraction correction as follows:
Wherein Δ EO is the concentration difference of reactor outlet gas and inlet gas ethylene oxide, Δ CO2For reactor outlet gas
With the concentration difference of carbon dioxide in inlet gas.
The various silver catalysts prepared in embodiment and comparative example in the present invention are porous using industrial production silver catalyst
Alpha-alumina supports, appearance white seven apertures in the human head cylindrical body, crushing strength 65N/, specific surface area 1.5m2/ g, Kong Rong 0.5ml/g.
The Argent grain size of the various silver catalysts prepared in the embodiment of the present invention and comparative example passes through aobvious to scanning electron
Silver granuel dimension analysis in micro mirror photo determines.
Embodiment 1
100g ethylenediamine, 30g Putriscine are added in 200g deionized water, mixes, after water-bath is maintained at room temperature,
It is slowly added to 110g silver oxalate thereto, is all dissolved to silver oxalate, adds 0.5g cesium nitrate, 0.4g calcium acetate, 0.3g high
Rehenic acid amine, is stirred well to and is completely dissolved, and obtains mixed solution.
3g polyvinylpyrrolidone (molecular weight 58000) is added in above-mentioned mixed solution, is kept stirring to being completely dissolved.
The porous alpha-alumina supports 30g of selection is put into the container that can be vacuumized, vacuumizing is down to pressure
10mmHg is totally submerged solid hereinafter, above-mentioned maceration extract to liquid level is added, and is kept for 30 minutes, leaching removes extra solution.Leaching
Carrier after stain air drying 10 minutes of 60 DEG C, after heat 3 minutes and activate in 400 DEG C of air stream, it is cooling, that is, make
At silver catalyst.Wherein, the average grain diameter of Argent grain is 122nm, and particle diameter is in ± 50% range of average grain diameter
Interior Argent grain accounts for 76% or more of whole Argent grains, and Argent grain of the particle diameter in ± 20% range of average grain diameter accounts for
57% or more of whole Argent grains.
Embodiment 2
The preparation of catalyst with embodiment 1, the difference is that, the dosage of polyvinylpyrrolidone reduces in step II
0.3g.In silver catalyst obtained, the average grain diameter of Argent grain is 105nm, particle diameter average grain diameter ±
Argent grain in 50% range accounts for 73% or more of whole Argent grains, and particle diameter is in ± 20% range of average grain diameter
Argent grain accounts for 60% or more of whole Argent grains.
Embodiment 3
The preparation of catalyst with embodiment 1, the difference is that, in step II with the 40g/L polyacrylamide of 5ml (point
Ten thousand) solution replaces polyvinylpyrrolidone solid to be added in mixed solution to son amount 500.In silver catalyst obtained, Argent grain
Average grain diameter be 206nm, Argent grain of the particle diameter in ± 50% range of average grain diameter account for whole Argent grains
74% or more, Argent grain of the particle diameter in ± 20% range of average grain diameter accounts for 52% or more of whole Argent grains.
Embodiment 4
The preparation of catalyst with embodiment 3, the difference is that, 40g/L polyacrylamide (molecular weight 500 in step II
Ten thousand) solution usage reduces to 1ml.In silver catalyst obtained, the average grain diameter of Argent grain is 141nm, and particle diameter is flat
Argent grain in equal ± 50% range of particle diameter accounts for 83% or more of whole Argent grains, particle diameter average grain diameter ±
Argent grain in 20% range accounts for 65% or more of whole Argent grains.
Comparative example 1
The preparation of catalyst with embodiment 1, the difference is that, polyvinylpyrrolidone or other is not added in step II
Polymer, catalyst prod surface silver granuel, which exists, is significantly adhered phenomenon.
Using the response characteristic for measuring catalyst sample under the conditions of microreactor evaluating apparatus such as previous process, to various kinds
Product are respectively evaluated one month after stable process conditions, and with titration measuring silver content, and test result is listed in table 1.
Table 1
From table 1, by embodiment 1, embodiment 2, embodiment 3, embodiment 4 and the comparison of comparative example 1 as can be seen that this hair
Bright catalyst shows better activity, selectivity and stability compared with traditional infusion process catalyst.
It is taken pictures using scanning electron microscope (SEM) to each sample, as a result as shown in Figure 1, it can be seen that in comparative example 1
The phenomenon that silver catalyst surface is mutually bonded together there are Argent grain, and silver catalyst of the invention is different, dispersion degree
Very well, rare adhesion between silver granuel, size distribution is also more uniform, and particle size can pass through the kind of the added polymer of change
Class, property and concentration are adjusted.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.
Claims (13)
1. a kind of loading type silver catalyst, which is characterized in that the loading type silver catalyst includes alumina support and loads thereon
Argent grain, the average grain diameter of the Argent grain is 100-400nm, and particle diameter is in ± 50% range of average grain diameter
Interior Argent grain accounts for 70% or more of whole Argent grains, and Argent grain of the particle diameter in ± 20% range of average grain diameter accounts for
50% or more of whole Argent grains；Preferably, the average grain diameter of the Argent grain is 120-300nm, and particle diameter is flat
Argent grain in equal ± 50% range of particle diameter accounts for 80% or more of whole Argent grains, particle diameter average grain diameter ±
Argent grain in 20% range accounts for 60% or more of whole Argent grains.
2. loading type silver catalyst according to claim 1, wherein the crushing strength of the alumina support is 30-
300N/, preferably 40-200N/；Specific surface area is 0.6-3.0m2/ g, preferably 1.2-2.2m2/g；Kong Rongwei 0.3-
1.0ml/g, preferably 0.4-0.8ml/g.
3. a kind of preparation method of loading type silver catalyst, includes the following steps:
Step I prepares Ag-containing compound, organic amine, water, polymer, optional alkali metal promoter, optional alkaline-earth metal and helps
Agent, optional rhenium auxiliary agent mixed liquor；
Alumina support is dipped in the mixed liquor by step II, carrier is filtered out after being sufficiently impregnated, then be made through dry activation
The loading type silver catalyst；
The polymer is polyvinylpyrrolidone and/or polyacrylamide.
4. preparation method according to claim 3, wherein the molecular weight of the polyvinylpyrrolidone is 8000-
500000；The polyacrylamide is middle-molecular-weihydroxyethyl polyacrylamide, and preferred molecular weight is 5,000,000 or less；With the weight of mixed liquor
On the basis of amount, the concentration of the polymer is 0.001%-1%, preferably 0.008%-0.1%.
5. preparation method according to claim 3, wherein the Ag-containing compound is silver nitrate and/or silver oxalate, with mixed
On the basis of the weight for closing liquid, the content of silver element is 1-40wt%.
6. preparation method according to claim 3, wherein the organic amine is selected from ethamine, ethylenediamine, n-propylamine, 1,3-
One of propane diamine, n-butylamine, Putriscine, ethanol amine and Propanolamine are a variety of, on the basis of the weight of mixed liquor, institute
The content for stating organic amine is 10-90wt%.
7. preparation method according to claim 3, wherein the alkali metal promoter be selected from lithium, sodium, potassium, rubidium, caesium it is solvable
Property one of salt or a variety of, on the basis of the weight of mixed liquor, the content of the alkali metal promoter is 0-2000ppm, preferably
For 50-2000ppm.
8. preparation method according to claim 3, wherein the base earth metal promoter be selected from magnesium, calcium, strontium, barium it is solvable
Property one of salt or a variety of, on the basis of the weight of mixed liquor, the content of the base earth metal promoter is 0-8000ppm, excellent
It is selected as 50-8000ppm.
9. preparation method according to claim 3, wherein the rhenium auxiliary agent is selected from potassium perrhenate, rehenic acid ammonium and perrhenic acid
One of or it is a variety of, on the basis of the weight of mixed liquor, the content of the rhenium auxiliary agent is 0-2000ppm, preferably 100-
1000ppm。
10. the preparation method according to any one of claim 3-9, wherein the item being sufficiently impregnated described in step II
It is 100mm Hg or less and/or temperature is 40-80 DEG C that part, which includes: pressure, and the time is 10-300 minutes.
11. the preparation method according to any one of claim 3-9, wherein dry described in step II in air or
It is carried out in inert gas atmosphere, drying temperature is 40-100 DEG C, and drying time is 2-20 minutes；Air of the activation in flowing
Or carried out in inert gas atmosphere, activation temperature is 180-400 DEG C, and activation time is 2-20 minutes.
12. loading type silver catalyst made from the preparation method as described in any one of claim 3-11.
13. loading type silver catalyst described in loading type silver catalyst of any of claims 1 or 2 and/or claim 12 exists
Ethylene epoxidizing prepares the application in ethylene oxide.
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Cited By (2)
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| CN111068714A (en) * | 2019-12-16 | 2020-04-28 | 北京化工大学 | Preparation method of supported silver-based multi-component nano catalyst |
| CN115814790A (en) * | 2021-09-17 | 2023-03-21 | 中国石油化工股份有限公司 | Preparation method of silver catalyst for producing ethylene oxide by ethylene oxidation, silver catalyst and application |
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