CN102247845A - Supported type silver catalyst and preparation method thereof - Google Patents
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- CN102247845A CN102247845A CN2010101828533A CN201010182853A CN102247845A CN 102247845 A CN102247845 A CN 102247845A CN 2010101828533 A CN2010101828533 A CN 2010101828533A CN 201010182853 A CN201010182853 A CN 201010182853A CN 102247845 A CN102247845 A CN 102247845A
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Abstract
The invention discloses a supported type silver catalyst for producing ethylene oxide through ethylene oxidation and a preparation method thereof. The supported type silver catalyst is prepared by activating a main active component silver precursor and an auxiliary active component precursor, which are loaded on a carrier, through ionizing radiation. The supported type silver catalyst disclosed by the invention has the advantages of excellent property, simple and convenient preparation process, low cost, suitability for large-scale production, lowered production cost and reduced environmental pollution.
Description
Technical field
The present invention relates to a kind of silver catalyst, relate in particular to a kind of loading type silver catalyst that is used for ethene oxidation production oxirane and preparation method thereof.
Background technology
The ethene oxidation generates oxirane under the silver catalyst effect, side reaction takes place simultaneously generate carbon dioxide and water, and activity, selectivity and stability are the main performance index of silver catalyst.The performance of catalyst often with carrier on the size and the distribution situation thereof of the silver particles of disperseing closely related, so in preparation silver catalyst process, control the size and the distribution situation of silver-colored particle effectively, to reducing silver-colored load capacity, improve selection of catalysts and will produce positive impact, and can lower production cost.
Silver catalyst generally adopts immersion process for preparing in the prior art, is about in the solution of carrier immersion silver salt, organic amine and various auxiliary agent composition, makes the carrier activation of negative Ag-bearing precursor then by the pyrolytic reduction.Adopt the method for preparing loading type silver catalyst, because high temperature reduction and decomposable process usually cause migration, the recrystallization of carrier surface silver particles, cause silver-colored particulate average diameter big, the decentralization of silver on catalyst carrier reduced, thereby influenced the performance of catalyst.In order to reduce these negative effects as far as possible, the catalyst research personnel of various countries have carried out effort from different aspects.Patent US5374748 and US5444034 have proposed the multistage activation method of preparation high selectivity and stable silver catalyst, be that carrier is behind the silver salt dipping, the branch level Four activates in the inert atmosphere of oxygen content in being lower than air, makes carrier combine in comparatively gentle mode with silver salt.Patent EP716884 proposes the another kind of method for preparing silver catalyst, with the maceration extract of components such as argentiferous, caesium was earlier the ultrasonic wave processing 10 minutes of 20kHz with frequency before dipping, with such solution impregnating carrier of handling, each component is more evenly distributed, thereby improves activity of such catalysts and stability.EP0172565 proposes to activate soaked carrier with Low Temperature Steam, can avoid the sintering of metal component, and the silver granuel of the ectonexine of catalyst is more evenly distributed, thereby improve the performance of catalyst.The technology that above-mentioned patent documentation is mentioned can be improved distribution of particles to a certain extent, reduce the sintering tendency, but owing in the metallic silver particles forming process, still adopt high-temperature technology, the sintering of silver particle can't fundamentally be avoided, thereby has influenced the possible best efficiency of catalyst.
Therefore, improve selection of catalysts and activity, simplify the preparation method, reducing production costs remains the present technical issues that need to address.
Summary of the invention
At present problems of the prior art, the inventor has carried out great deal of experimental, discovery utilizes the ionising radiation reducing process to prepare loading type silver catalyst, can make catalyst have excellent selectivity, and preparation process is easy, expense is cheap, can large-scale production and lower manufacturing cost and environmental pollution.
One of purpose of the present invention provides a kind of loading type silver catalyst, it comprises carrier and be carried on the main active component silver on the carrier and help active component, it is characterized in that: described main active component silver is to be carried on the main active component silver precursor on the carrier and to help the active component precursor to make by the ionising radiation activation with helping active component.
Catalyst of the present invention, main active component silver content is the 4wt%-24wt% of carrier gross weight, be preferably the 6wt%-20wt% of carrier gross weight, helping active component is in caesium, barium, calcium, the strontium one or more, its content is the 100-1000ppm of carrier gross weight, be preferably the 200ppm-800ppm of carrier gross weight, all the other are carrier, and described carrier is α-Al
2O
3
Another object of the present invention provides a kind of method for preparing loading type silver catalyst, comprise to comprising main active component silver precursor, helping the system of active component precursor, carrier and free radical scavenger to apply ionising radiation, to activate main active component silver precursor and to help the active component precursor.This method utilizes ray and free radical scavenger (as isopropyl alcohol) under temperate condition silver ion to be activated, thereby makes the loading type silver catalyst of high degree of dispersion.
Describedly apply ionising radiation and take one of following manner to carry out with the step that activates:
1) load is had described silver components and help the carrier of active component precursor to use to contain the solution-wet of free radical scavenger after, radiation under wetting state is preferably under vacuum or inert atmosphere;
2) load there is described silver components add and contains in the solution of free radical scavenger radiation under the solution submerged state with the carrier that helps the active component precursor;
3) described carrier adding is contained free radical scavenger and described silver components and helps in the maceration extract of active component precursor radiation under submerged state.
In method 1) and 2) at first use silver components and help active component precursor impregnated carrier, add the solution that contains free radical scavenger again, it is under moisture state or the solution submerged state carries out irradiation; In method 3) in be carrier directly to be immersed in contain free radical scavenger and silver components and help in the maceration extract of active component precursor.
Ionizing radiation of the present invention is gamma-rays, X ray or electronics, and radiographic source is optional
60Co (γ source),
137Cs (γ source), x-ray source or electron accelerator (electron beam), preferred
60Co, x-ray source or electron accelerator, more preferably
60Co.
The used radiogenic absorbed dose rate of ionizing radiation of the present invention is 10～10000Gy/min, and preferred 20～100Gy/min, absorbed dose of radiation are 0.01～1 * 10
5KGy.Described ionizing radiation reduction process does not have particular determination to temperature conditions, preferably carries out under room temperature or low temperature, more preferably at room temperature carries out.
Silver components of the present invention and help the active component corresponding precursor can be selected from halide salt, nitrate, acetate, sulfate, oxide, hydroxide and metallo-organic compound.
Silver components of the present invention and help the active component precursor to load on the carrier by a step dipping or step impregnation; Described silver components and help the active component corresponding precursor to be preconfigured to solution, solvent are selected from one or more the mixing in deionized water, hydrochloric acid, nitric acid, acetate, organic amine, the alcohols.
Free radical scavenger of the present invention can be selected from least a in the alcohols of C1～C5 and derivative thereof, the organic acid.The alcohols of described C1～C5 is preferably from ethanol, ethylene glycol, isopropyl alcohol, the tert-butyl alcohol; Described organic acid is preferably from formic acid.Described free radical scavenger is isopropyl alcohol and ethylene glycol preferably.When specifically adding free radical scavenger, use its aqueous solution usually.Be used for that load is had silver components and the wetting radicals scavenging agent solution of carrier that helps active component, the volume ratio of its free radical scavenger and water is 20～80%, preferred 30～60%; Be used for that load is had silver components and the radicals scavenging agent solution that helps the carrier submergence of active component, wherein the volume ratio of free radical scavenger and water is 1～50%, preferred 5～20%.The relative load of free scavenger solution silver components and to help the consumption of the carrier of active component precursor be 5-50%, preferred 15-30%.In the described method (3), free radical scavenger and silver components are 1～50% with helping the volume ratio of active component precursor solution.In using method (3) when flooding, can determine the adding dosage of free radical scavenger according to the volume ratio of free radical scavenger-maceration extract, the concentration that makes solution is in above-mentioned scope, and promptly the volume ratio of free radical scavenger and water is 1～50%, preferred 5～20% interior getting final product.
In preparation method of the present invention, but ionizing radiation rear catalyst product convection drying also can use appropriate amount of deionized water to wash 1～6 time to remove foreign ion as required, and is fully dry afterwards.Drying can be carried out under normal pressure or vacuum, preferably carries out under normal pressure.Optional 50～200 ℃ of baking temperature, preferred 50～100 ℃.Optional 5～48 hours of drying time, preferred 5～24 hours.Promptly obtain silver catalyst of the present invention after the drying.
Silver components exists with the form of metallic silver corpuscle in the silver catalyst of the present invention, metallic silver corpuscle uniform particle diameter on carrier after the ionising radiation, average grain diameter is less than 10nm, and the decentralization of argent obviously improves, and catalyst performance significantly is better than using the silver catalyst of conventional method preparation.
Silver catalyst of the present invention is applicable in the reaction of ethene oxidation production oxirane.
Silver catalyst of the present invention and preparation method thereof has the following advantages:
1) silver catalyst of the present invention's preparation uses the method for ionising radiation to activate, and the argent crystalline substance degree that loads on the carrier is better, and the silver granuel footpath is little, and uniform particle diameter is controlled, and the silver catalyst that makes is active high, and selectivity is good.Compare with the silver catalyst of conventional method preparation, silver catalyst of the present invention can reduce the content of reactive metal silver.
2) because the valence state of the main active component silver of silver catalyst of the present invention is tending towards the simple substance form, can directly come into operation, not need to carry out high-temperature activation, avoid the oxidation of argent or further growing up of silver-colored particle under the high temperature;
3) the present invention uses the ionising radiation dipping to contain silver components and the carrier that helps the active component precursor, can operate under normal temperature and pressure or low temperature, has simplified preparation technology, has lowered the discharging of energy consumption and gas pollutant, energy-conserving and environment-protective.
4) method for preparing silver catalyst with the ionization radiation have expense cheap, be fit to advantage such as large-scale production.
5) use the silver catalyst of this method preparation to compare, have excellent catalyst performance with existing silver catalyst.
The specific embodiment
Following examples are to more detailed the describing for example of the present invention, but the present invention is not limited to these embodiment.
Embodiment 1
Adopt commercially available α-Al
2O
3Carrier was dried 2 hours down in 120 ℃, and cooling back weighing 100g gets the commercially available AgNO of 38.67g
3Be dissolved in the deionized water, be settled to 100ml, obtain AgNO
3Solution pipettes the AgNO that 57ml has prepared
3Solution takes by weighing the commercially available CsNO of 8.8mg
3Be dissolved in the AgNO that 57ml has prepared
3In the solution, to α-Al
2O
3The solution that carrier impregnation is prepared, leave standstill 20 minutes after, get the mixed solution of 20ml deionized water and 20ml isopropyl alcohol, pour in the carrier of negative Ag-bearing and caesium, evenly disperse hypsokinesis to go out excess solution.Product is used under vacuum
60The Co gamma emitter is irradiation 30h under the 30Gy/min close rate.Sample behind the irradiation is dry 6h under 120 ℃, obtains catalyst A, and wherein Ag content is 14.0%, and the content of Cs is 300ppm.
Embodiment 2
With the same Step By Condition of embodiment 1, different is with the commercially available CaNO of 47.2mg
3.4H
2O replaces 8.8mg CsNO
3Make catalyst B, wherein Ag content is 14.0%, and the content of Ca is 400ppm.
Embodiment 3
With the same Step By Condition of embodiment 1, different is with the commercially available SrNO of 12.5mg
3Replace 8.8mgCsNO
3Make catalyst C, wherein Ag content is 14.0%, and the content of Sr is 260ppm.
Embodiment 4
With the same Step By Condition of embodiment 1, different is with the commercially available BaNO of 20.8mg
3Replace 8.8mgCsNO
3Make catalyst D, wherein Ag content is 14.0%, and the content of Ba is 545ppm.
Embodiment 5
Adopt commercially available α-Al
2O
3Carrier was dried 2 hours down in 120 ℃, and cooling back weighing 100g gets the commercially available AgNO of 38.67g
3Be dissolved in the deionized water, be settled to 100ml, obtain AgNO
3Solution pipettes the AgNO that 57ml has prepared
3Solution takes by weighing the commercially available CsNO of 10.6mg
3The SrNO commercially available with 13.0mg
3Be dissolved in the AgNO that 57ml has prepared
3In the solution, to α-Al
2O
3The solution that carrier impregnation is prepared, leave standstill 20 minutes after, get the mixed solution of 20ml deionized water and 20ml isopropyl alcohol, pour in the carrier of negative Ag-bearing, caesium and strontium, evenly disperse hypsokinesis to go out excess solution.Product is used under vacuum
60The Co gamma emitter is irradiation 30h under the 30Gy/min close rate.Sample behind the irradiation is dry 6h under 120 ℃, obtains catalyst E, and wherein Ag content is 14.0%, and the content of Cs is 360ppm, and the content of Sr is 271ppm.
Embodiment 6
With the same Step By Condition of embodiment 5, different is with the commercially available BaNO of 9.7mg
3Replace 13.0mgSrNO
3Make catalyst F, wherein Ag content is 14.0%, and the content of Cs is 360ppm, and the content of Ba is 255ppm.
Embodiment 7
Adopt commercially available α-Al
2O
3Carrier was dried 2 hours down in 120 ℃, and cooling back weighing 100g gets the commercially available AgNO of 46.96g
3Be dissolved in the deionized water, be settled to 100ml, obtain AgNO
3Solution pipettes the AgNO that 57ml has prepared
3Solution takes by weighing the commercially available CsNO of 8.8mg
3Be dissolved in the AgNO that 57ml has prepared
3In the solution, to α-Al
2O
3The solution that carrier impregnation is prepared, leave standstill 20 minutes after, get the mixed solution of 20ml deionized water and 20ml isopropyl alcohol, pour in the carrier of negative Ag-bearing and caesium, evenly disperse hypsokinesis to go out excess solution.Product is used under vacuum
60The Co gamma emitter is irradiation 30h under the 30Gy/min close rate.Sample behind the irradiation is dry 6h under 120 ℃, obtains catalyst G, and wherein Ag content is 17.0%, and the content of Cs is 300ppm.
Embodiment 8
Adopt commercially available α-Al
2O
3Carrier was dried 2 hours down in 120 ℃, and cooling back weighing 100g gets the commercially available AgNO of 23.48g
3Be dissolved in the deionized water, be settled to 100ml, obtain AgNO
3Solution pipettes the AgNO that 57ml has prepared
3Solution takes by weighing the commercially available CsNO of 8.8mg
3Be dissolved in the AgNO that 57ml has prepared
3In the solution, to α-Al
2O
3The solution that carrier impregnation is prepared, leave standstill 20 minutes after, get the mixed solution of 20ml deionized water and 20ml isopropyl alcohol, pour in the carrier of negative Ag-bearing and caesium, evenly disperse hypsokinesis to go out excess solution.Product is used under vacuum
60The Co gamma emitter is irradiation 30h under the 30Gy/min close rate.Sample behind the irradiation is dry 6h under 120 ℃, obtains catalyst H, and wherein Ag content is 8.5%, and the content of Cs is 300ppm.
Embodiment 9
Adopt commercially available α-Al
2O
3Carrier was dried 2 hours down in 120 ℃, and cooling back weighing 100g gets the commercially available AgNO of 38.67g
3Be dissolved in the deionized water, be settled to 100ml, obtain AgNO
3Solution pipettes the AgNO that 57ml has prepared
3Solution takes by weighing the commercially available CsNO of 10.3mg
3The CaNO commercially available with 31.2mg
3.4H
2O is dissolved in the AgNO that 57ml has prepared
3In the solution, to α-Al
2O
3The solution that carrier impregnation is prepared, leave standstill 20 minutes after, get the mixed solution of 20ml deionized water and 20ml isopropyl alcohol, pour in the carrier of negative Ag-bearing, caesium and calcium, evenly disperse hypsokinesis to go out excess solution.Product is used under vacuum
60The Co gamma emitter is irradiation 30h under the 30Gy/min close rate.Sample behind the irradiation is dry 6h under 120 ℃, obtains catalyst I, and wherein Ag content is 14.0%, and the content of Cs is 351ppm, and the content of Ca is 264ppm.
Embodiment 10
Adopt commercially available α-Al
2O
3Carrier was dried 2 hours down in 120 ℃, and cooling back weighing 100g gets the commercially available AgNO of 38.67g
3Be dissolved in the deionized water, be settled to 100ml, obtain AgNO
3Solution pipettes the AgNO that 57ml has prepared
3Solution is to α-Al
2O
3The solution that carrier impregnation is prepared leaves standstill after 20 minutes and dries at normal temperature, and the carrier of negative Ag-bearing is placed 120 ℃ dry 6 hours of baking oven, takes by weighing the commercially available CsNO of 154mg
3Be dissolved in the deionized water, be settled to 1000ml, obtain CsNO
3Solution pipettes the CsNO that 57ml has prepared
3Solution is to the α-Al of negative Ag-bearing
2O
3The solution that carrier impregnation is prepared, leave standstill 20 minutes after, get the mixed solution of 20ml deionized water and 20ml isopropyl alcohol, pour in the carrier of negative Ag-bearing and caesium, evenly disperse hypsokinesis to go out excess solution.Product is used under vacuum
60The Co gamma emitter is irradiation 30h under the 30Gy/min close rate.Sample behind the irradiation is dry 6h under 120 ℃, obtains catalyst J, and wherein Ag content is 14.0%, and the content of Cs is 300ppm.
Comparative example
Adopt commercially available α-Al
2O
3Carrier was dried 2 hours down in 120 ℃, and cooling back weighing 100g gets the commercially available AgNO of 46.96g
3Be dissolved in the deionized water, be settled to 100ml, obtain AgNO
3Solution pipettes the AgNO that 57ml has prepared
3Solution takes by weighing the commercially available CsNO of 8.8mg
3Be dissolved in the AgNO that 57ml has prepared
3In the solution, to α-Al
2O
3The solution that carrier impregnation is prepared leaves standstill after 20 minutes and dries at normal temperature, the carrier of negative Ag-bearing and caesium is placed 120 ℃ dry 6 hours of baking oven, products obtained therefrom is in air atmosphere, progressively be warming up to 450 ℃ from room temperature, and under this temperature, kept 1 hour, reduce to room temperature.Obtain catalyst K, wherein Ag content is 17.0%, and the content of Cs is 300ppm.
Various silver catalyst of the present invention is with carrying out in the homemade micro anti-evaluation device.The reactor that the micro anti-evaluation device uses is the stainless steel tube of internal diameter 4mm, and reactor places heating jacket.The loadings of catalyst is 1ml, and there is inert filler top and the bottom, and beds is positioned at the flat-temperature zone of heating jacket.
Active, optionally measure
The activity of silver catalyst among the present invention, optionally condition determination is as follows:
Reacting gas is formed (mol%)
Ethene (C
2H
4) 27-29
Oxygen (O
2) 7.2-7.6
Carbon dioxide (CO
2)＜8
Nitrogen (N
2) surplus
Inhibitor dichloroethanes 0.1ppm-2.0ppm
Reaction pressure 2.1MPa
Air speed 7000/h
Reactor outlet oxirane (EO) concentration 1.35%
(space-time yield 185gEO/mlCat./h)
When stable reach above-mentioned reaction condition after the METHOD FOR CONTINUOUS DETERMINATION reactor go into, exit gas forms.Measurement result carries out calculating as follows after volume contraction is proofreaied and correct selectivity:
Selectivity S=Δ EO/ (Δ EO+0.5 Δ CO
2) * 100%
Wherein Δ EO works off one's feeling vent one's spleen poorly with the inlet gas ethylene oxide concentration, gets the experimental result of the average of 10 groups of above experimental datas as the same day
Use the microreactor evaluating apparatus to measure activity of such catalysts and selectivity under aforementioned process conditions, experimental result sees Table 1.
The evaluation result of table 1. catalyst
| Embodiment | Catalyst | Silver content (%) | Caesium content (ppm) | Calcium content (ppm) | Content of strontium (ppm) | Barium content (ppm) | Reaction temperature (℃) | EO (％) | Selectivity (%) |
| Embodiment 1 | Catalyst A | 14.0 | 300 | 223 | 1.36 | 83.5 | |||
| Embodiment 2 | Catalyst B | 14.0 | 400 | 224 | 1.35 | 81.9 | |||
| Embodiment 3 | Catalyst C | 14.0 | 260 | 220 | 1.35 | 81.1 | |||
| Embodiment 4 | Catalyst D | 14.0 | 545 | 223 | 1.36 | 82.9 | |||
| Embodiment 5 | Catalyst E | 14.0 | 360 | 271 | 226 | 1.35 | 85.4 | ||
| Embodiment 6 | Catalyst F | 14.0 | 360 | 255 | 222 | 1.37 | 83.1 | ||
| Embodiment 7 | Catalyst G | 17.0 | 300 | 224 | 1.36 | 84.4 | |||
| Embodiment 8 | Catalyst H | 8.5 | 300 | 225 | 1.37 | 84.5 | |||
| Embodiment 9 | Catalyst I | 14.0 | 351 | 264 | 221 | 1.36 | 85.7 | ||
| Embodiment 10 | Catalyst J | 14.0 | 300 | 225 | 1.35 | 83.4 | |||
| Comparative Examples | Catalyst K | 17.0 | 300 | 223 | 1.35 | 79.8 |
From the experimental evaluation result of table 1 as can be seen, adopt ionization radiation method reduction preparation of silver catalyst, its selectivity obviously improves.
Claims (11)
1. loading type silver catalyst, comprise carrier and be carried on the main active component silver on the carrier and help active component, it is characterized in that: described main active component silver is to activate by ionising radiation to be carried on the main active component silver precursor on the carrier and to help the active component precursor to make with helping active component.
2. catalyst according to claim 1, it is characterized in that: the 4wt%-24wt% that described main active component silver content is the carrier gross weight, the described active component that helps is in caesium, barium, calcium, the strontium one or more, its content is the 100ppm-1000ppm of carrier gross weight, and described carrier is α-Al
2O
3
3. catalyst according to claim 2 is characterized in that: the content of main active component silver is the 6wt%-20wt% of carrier gross weight, and the content that helps active component is the 200ppm-800ppm of carrier gross weight.
4. the method for preparing one of claim 1-3 described catalyst, this method comprises to comprising main active component silver precursor, helping the system of active component precursor, carrier and free radical scavenger to apply ionising radiation, to activate main active component silver precursor and to help the active component precursor.
5. method according to claim 4 wherein saidly applies ionising radiation and takes one of following manner to carry out with the step that activates:
1) load is had described silver components and help the carrier of active component precursor to use to contain the solution-wet of free radical scavenger after, radiation under wetting state is preferably under vacuum or inert atmosphere;
2) load there is described silver components and helps the carrier of active component precursor to join in the solution that contains free radical scavenger radiation under the solution submerged state;
3) described carrier is joined contain free radical scavenger and described silver components precursor and help in the maceration extract of active component precursor radiation under submerged state.
6. method according to claim 4 is characterized in that used ionising radiation is gamma-rays, X ray or electron beam.
7. method according to claim 4, the absorption dose rate that it is characterized in that used ionising radiation is 10-10000Gy/min.
8. method according to claim 4 is characterized in that: described main active component silver precursor and help the active component precursor can be selected from corresponding with it halide salt, nitrate, oxalates, sulfate, oxide, hydroxide and metallo-organic compound.
9. method according to claim 4 is characterized in that: described main active component silver precursor and help the active component precursor to load on the carrier by a step or step impregnation; Described silver components precursor and help the active component precursor to be preconfigured to solution, solvent can be selected from one or more in deionized water, hydrochloric acid, nitric acid, organic acid, organic amine, the alcohols.
10. method according to claim 4 is characterized in that: described free radical scavenger is selected from one or more in alcohols or the formic acid, preferably is selected from a kind of in methyl alcohol, ethanol, ethylene glycol, isopropyl alcohol and the formic acid.
11. being applied to the ethene oxidation, produces in the reaction of oxirane by the described catalyst of one of claim 1-3.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102962062A (en) * | 2012-12-11 | 2013-03-13 | 西南化工研究设计院有限公司 | Catalyst for synthesis of methyl methacrylate by formaldehyde and methyl propionate and preparation method of catalyst |
| CN106311234A (en) * | 2015-07-02 | 2017-01-11 | 中国石油化工股份有限公司 | Preparation method for composite silver catalyst, and composite silver catalyst and application thereof |
| CN107398303A (en) * | 2016-05-19 | 2017-11-28 | 兰州金润宏成石油化工科技有限公司 | Catalyst carrier for producing ethylene oxide and preparation method and application thereof |
| CN111905731A (en) * | 2019-05-09 | 2020-11-10 | 中国石油化工股份有限公司 | Method for activating silver catalyst |
| CN115463656A (en) * | 2022-08-10 | 2022-12-13 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | Flue gas removing O 3 High-sulfur-resistance water-resistant catalyst, and preparation method and application thereof |
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| CN102962062A (en) * | 2012-12-11 | 2013-03-13 | 西南化工研究设计院有限公司 | Catalyst for synthesis of methyl methacrylate by formaldehyde and methyl propionate and preparation method of catalyst |
| CN102962062B (en) * | 2012-12-11 | 2014-09-17 | 西南化工研究设计院有限公司 | Catalyst for synthesis of methyl methacrylate by formaldehyde and methyl propionate and preparation method of catalyst |
| CN106311234A (en) * | 2015-07-02 | 2017-01-11 | 中国石油化工股份有限公司 | Preparation method for composite silver catalyst, and composite silver catalyst and application thereof |
| CN106311234B (en) * | 2015-07-02 | 2018-11-30 | 中国石油化工股份有限公司 | The preparation method of compound silver catalyst, the catalyst and its application |
| CN107398303A (en) * | 2016-05-19 | 2017-11-28 | 兰州金润宏成石油化工科技有限公司 | Catalyst carrier for producing ethylene oxide and preparation method and application thereof |
| CN111905731A (en) * | 2019-05-09 | 2020-11-10 | 中国石油化工股份有限公司 | Method for activating silver catalyst |
| CN111905731B (en) * | 2019-05-09 | 2022-11-18 | 中国石油化工股份有限公司 | Method for activating silver catalyst |
| CN115463656A (en) * | 2022-08-10 | 2022-12-13 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | Flue gas removing O 3 High-sulfur-resistance water-resistant catalyst, and preparation method and application thereof |
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