CN1150991C - Silver catalyst for producing epoxyethane - Google Patents
Silver catalyst for producing epoxyethaneInfo
- Publication number
- CN1150991C CN1150991C CNB011263458A CN01126345A CN1150991C CN 1150991 C CN1150991 C CN 1150991C CN B011263458 A CNB011263458 A CN B011263458A CN 01126345 A CN01126345 A CN 01126345A CN 1150991 C CN1150991 C CN 1150991C
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- Prior art keywords
- catalyst
- silver
- nickel
- gram
- silver catalyst
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 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 present invention relates to a silver catalyst for producing epoxyethane, which mainly solves the problems that the stability of the silver catalyst is low and the selectivity and the activity of the catalyst are easy to descend with the elapse of start-up time existed in the prior art. The present invention better solves the problems by adopting the technical scheme of adding metallic nickel component in the silver catalyst. The silver catalyst can be used in the industrial production of epoxyethane by utilizing ethene epoxidation.
Description
Technical field
The present invention relates to be used to produce the silver catalyst of oxirane.
Background technology
Loading type silver catalyst is widely used in the reaction that industrial ethylene epoxidizing generates oxirane.Catalyst usually with Alpha-alumina as carrier, as main active constituent, add a spot of co-catalyst with silver simultaneously.The performance of silver catalyst plays a part very important to the technology that ethylene epoxidizing generates oxirane.Stability is an important performance of silver catalyst.The high stability catalyst has prolonged the service life of catalyst, also has only the high stability catalyst just to be suitable for driving under the high load capacity to use, thereby has improved economic benefit.
Document CN1,017, introduced a kind of silver catalyst of epoxidation of ethylene among the 780B, it is that the silver-colored amine complex liquid that will contain barium, potassium, caesium, sodium, cerium is immersed on the alpha-alumina supports of handling with lanthanum chloride solution, makes through heat treatment.The gained catalyst has high selectivity and high activity.Introduced a kind of silver catalyst that contains ionic state nickel and preparation method thereof in the document WO 95/07754, the common co-catalyst of this loading type silver catalyst argentiferous, ionic state alkali metal catalyst, ionic state rhenium and rhenium, ionic state nickel.Earlier with carrier impregnation silver and co-catalyst solution, drying, dipping contains the solution of ionic state nickel again, after dry catalyst.This catalyst is compared with the silver catalyst that does not contain ionic state nickel, has the function that delays the selectivity downward trend.
Summary of the invention
Technical problem to be solved by this invention is that to overcome the silver catalyst stability that existence prepares in the conventional art high not enough, selection of catalysts and the active shortcoming that descends with the driving passage of time easily provide a kind of new silver catalyst that is used to produce oxirane.This catalyst is used for ethylene epoxidizing generation reacting ethylene oxide and has high stability, has advantage of high activity simultaneously.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of silver catalyst that is used to produce oxirane comprises following component in catalyst weight percentage:
A) 50～94% alpha-alumina supports;
B) 5～40% silver;
C) 0.01～5% metallic nickel.
In the technique scheme, be 0.04～2% in the consumption preferable range of catalyst weight percentage metallic nickel.Also to contain 0.001～1% alkali metal catalyst in the catalyst weight percentage catalyst, the consumption preferable range of alkali metal catalyst is 0.001～0.3%, and more preferably scope is 0.02～0.06%.
Co-catalyst can improve the performance of silver catalyst.Co-catalyst can be before silver, add catalyst simultaneously afterwards or with silver.
Preparation of catalysts method of the present invention comprises that a silver, co-catalyst and metallic nickel are carried on the alpha-alumina supports.
The specific surface of the alpha-alumina supports of particularly suitable is 0.01～20 meter
2/ gram, preferable range is 0.1～5 meter
2/ gram; Water absorption rate is 0.1～1.0 a milliliter/gram, and preferable range is 0.2～0.8 a milliliter/gram.
The Preparation of catalysts method concrete steps that the present invention is used to produce oxirane are as follows:
The preparation of carrier can be adopted and add binding agent, pore-foaming agent, water etc., the method for batch mixing, kneading, moulding, high-temperature roasting again in alumina powder.
The adding of binding agent is for crushing strength and scuff resistance kneaded together alumina powder and the raising carrier, and finally obtains the high strength carrier.Binding agent can divide two kinds of addings, promptly permanent binding agent and temporary binding agent.Permanent binding agent can improve the crushing strength and the scuff resistance of carrier, generally chooses inorganic matter, as inorganic clay, magnesium silicate, calcium silicates, barium silicate, barium aluminate.Temporary bonding agent can be kneaded together alumina powder, is convenient to moulding.The temporary bonding agent that is suitable for has following these cellulose families and substituent cellulose family: for example cellulose, methyl or ethyl or carboxyethyl cellulose; Stearic acid, for example methyl stearate or ethyl ester; Wax class, polyolefin epoxide etc.If when making bonding agent, preferably add acids to make peptizing agent with a water aluminium oxide or a false water aluminium oxide.
Pore-foaming agent is meant the material of volatile at high temperature of certain particle size.The pore-foaming agent volatilization is left away in roasting process, makes final carrier have suitable pore size distribution.Suitable pore-foaming agent has carbonaceous material, as coke, carbon dust, graphite; Powdered plastic such as polyethylene, polystyrene, Merlon, rosin; Cellulose and cellulose-based material; Wood chip and other vegetable material such as Powdered stone shell such as pecan shell, walnut shell, hazel shell etc.
Sometimes, may bring impurity for fear of the adding of pore-foaming agent, thereby catalyst is caused adverse effect, also can be by control the pore size distribution of carrier with the mixed method of varigrained alumina powder.
Alumina powder, binding agent, pore-foaming agent and water after fully mediating, are made certain shape.The shape of carrier can be spherical, block, ball shape, cylindric, Raschig ring shape, porous circular cylinder shape, clover shape or the like.Through 60～200 ℃ of oven dry, high-temperature roasting promptly obtains alpha-alumina supports in air again above-mentioned article shaped.The temperature of high-temperature roasting is 1000～1700 ℃, and better scope is 1200～1600 ℃, and preferably scope is 1300～1500 ℃.Roasting time is 1～20 hour, and better scope is 1～6 hour.
The method that silver is carried on the carrier has a variety of.Can use the silver nitrate aqueous solution impregnated carrier, with hydrogen, hydrazine or formaldehyde silver ion reduction be become argent then.The ammonia spirit impregnated carrier of also available silver oxalate or silver carbonate, drying makes silver ion reduction become argent through heating.The best way be mixture with a kind of silver salt-organic solvent/reducing agent-water as silver-colored maceration extract, behind the impregnated carrier, make silver ion reduction become argent through heat treatment, this method can make argent be carried on the carrier with the fine particulate of high degree of dispersion.
Mixture as the silver salt-organic solvent/reducing agent-water of silver-colored maceration extract, silver salt wherein comprises inorganic salts and organic salt, as silver nitrate, silver carbonate, silver sulfate, silver chlorate, silver oxalate, silver acetate, actol, succinic acid silver, glycolic silver, preferred silver oxalate.Organic solvent/reducing agent both can be used as the solvent of silver salt, can under the situation of heating, be reduced into the silver of ionic state the silver of metallic state simultaneously again, can adopt organic amine, especially alkanolamine, Alkylenediamine are as the mixture of ethylenediamine, propane diamine, monoethanolamine, Propanolamine, butanolamine and their mixture or they and ammonia.Silver maceration extract compound method commonly used has two kinds, can illustrate by following two examples.An example is that the mixture of silver oxide and ethylenediamine and oxalic acid is reacted, generate a kind of mixture of silver oxalate-ethylenediamine that contains as silver-colored maceration extract, note avoiding a silver oxide directly to join ethylenediamine, because the silver of Sheng Chenging-ethylenediamine solution instability thus sets off an explosion easily.Another example is: liquor argenti nitratis ophthalmicus and ammonium oxalate solution are mixed, generation silver oxalate precipitation, the precipitation of cyclic washing gained is with flush away nitrate anion wherein, with ethylenediamine solution dissolving silver oxalate precipitation, the mixture of the silver oxalate-ethylenediamine of gained can be used as silver-colored maceration extract then.
Carrier is taken out from silver-colored maceration extract, dry, after Overheating Treatment, obtain finished catalyst.During heat treatment, hot gas flows through wet carrier, removes organic solvent and water in the carrier that dries, and silver is deposited on the carrier with the metal fine shape.Heat treatment atmosphere can be air, nitrogen, oxygen, hydrogen, carbon dioxide, steam or their mixture.Heat treatment temperature can be selected 80～700 ℃ for use, preferred 150～500 ℃.Heat treatment time can be selected for use 1 minute～10 hours, was preferably 2～30 minutes.
Co-catalyst can improve the catalytic performance of silver catalyst effectively, as performances such as selectivity, activity, stability.Alkali metal is the most frequently used co-catalyst of a class, wherein is best with the caesium.The example of the alkali metal catalyst raw material that is suitable for has, alkali-metal nitrate, hydroxide, oxide, carbonate, oxalates, carboxylate, alkoxide or their mixture, instantiation has cesium carbonate, rubidium nitrate, potassium hydroxide, sodium acetate, lithium oxalate.Co-catalyst can be before silver impregnated in carrier, simultaneously or be applied on the carrier afterwards.
The method of nickel introducing catalyst can contain the solution of ionic state nickel with carrier impregnation, with reducing agent such as hydrogen, hydrazine, oxyammonia or formaldehyde ionic state nickel is reduced into metal state nickel then, and the nickel metal is carried on the carrier.Preferred reducing agent is hydrogen, hydrazine.When adopting hydrogen as reducing agent, reduction temperature is 300～1500 ℃.Being used for nickel compound of the present invention is can be by the nickel compound of proper method dissolving, the oxide that comprises nickel, the hydroxide of nickel, nickel salt such as nitrate, sulfate, carbonate, chloride, fluoride, acetate, oxalates are preferably selected nitrate, carbonate, acetate for use.Some nickel compound is slightly soluble or insoluble in water, can make it dissolving by adding acid or alkali, or by selecting for use suitable solvent to make it dissolving.Better, can in solution containing nickel, add complexing agent, as ammonia, ethylenediamine, monoethanolamine.Nickel can be before adding silver, be incorporated in the catalyst afterwards or simultaneously, preferably is incorporated in the catalyst before adding silver or simultaneously.
Catalyst of the present invention is used for ethene and oxirane is produced in the molecular oxygen reaction.The process conditions of being put down in writing in process conditions that adopted and the common document are close.The process conditions that silver catalyst of the present invention can adopt are: reaction temperature is preferably in 200～280 ℃ at 150～300 ℃; Reaction pressure is preferably in 15～30 kilograms/square centimeter at 10～40 kilograms/square centimeter; Gas compartment speed was at 1000～30000 hours
-1, better at 3000～15000 hours
-1The volume of unstripped gas is formed can be 0.5～40% ethene, 3～10% oxygen; 5～30% carbon dioxide, a spot of inhibitor, all the other are inactive gas, as nitrogen, argon gas, water vapour or rudimentary hydrocarbon, as methane, ethane.Inhibitor in the unstripped gas can be regulated the reactivity worth of catalyst within the specific limits, usually adopt halide or nitrogen-containing compound, halide can be chloride, bromide, fluoride or iodide, for example dichloroethanes, chloroethanes, dichloroethylene, vinyl chloride, monochlor-benzene, dichlorobenzene.Nitrogen-containing compound such as nitropropane.The inhibitor that contains 0.1～20 part of volume in the unstripped gas of per 1,000,000 parts of volumes.
Selectivity, activity and stability are three main performances of silver catalyst.Selectivity is meant that conversion of ethylene becomes the molar percentage of oxirane.Activity is meant that the height of reactor exit ethylene oxide concentration that is to say under the situation of fixing other condition (as temperature, pressure, air speed etc.), if it is low more to reach the needed temperature of a certain definite ethylene oxide concentration, activity of such catalysts is just high more.When silver catalyst was used in epoxidation of ethylene, along with the passing of service time, selection of catalysts can descend gradually, and reaction temperature can rise gradually.For the relatively selectivity between the different catalysts and the difference of reaction temperature, should measure at approximately identical reaction condition with under about identical service time.For this reason, used the notion of " initial reaction performance " in this article." initial reaction performance " is meant under identical reaction condition, and catalyst reaches selectivity and the reaction temperature in about 1～5 day behind the air speed of appointment and the oxirane exit concentration.
Under the situation of fixation reaction condition, along with the prolongation of the time of driving, selection of catalysts can rise gradually, and reaction temperature can descend gradually.Reactivity worth after different catalysts is driven in same reaction conditions with through the same reaction time is compared with the initial reaction performance, if a certain selection of catalysts changing value and reaction temperature changing value are more little, then the stability of this catalyst is high more.In this article, for the stability height of different catalysts relatively, allow different catalysts be issued to the air speed 8000 hours of appointment at identical reaction condition
-1Behind 1.6 moles of % of oxirane exit concentration, drive continuously again to measure selectivity and reaction temperature after half a year, compare with initial selectivity and initial reaction temperature,, think that then the stability of this catalyst is high more if a certain selection of catalysts changing value and reaction temperature changing value are more little.
Silver catalyst of the present invention is used for epoxidation of ethylene, because the nickel component that adds in the catalyst is a metal state nickel, by the metallic bond effect between nickel and the silver, silver is fixed on the metallic nickel firmly, obtained effective prevention and delayed thereby make the gathering of silver and grow up, downward trend has obtained delaying with the driving passage of time for selection of catalysts and activity, has improved the stability of catalyst.Owing to nickel-silver metal key effect, silver can evenly be disperseed, thereby make silver catalyst of the present invention have advantage of high activity simultaneously.Evidence through epoxidation of ethylene, catalyst of the present invention can react about 224 ℃, shown high activity, reactivity worth after the half a year of driving, it only is 0.3～0.4% that oxirane (EO) selectivity descends, reaction temperature has only risen 2～3 ℃, has shown good stable, has obtained effect preferably.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
Alpha-alumina powder 600 grams are placed kneading machine, add 30 gram polyvinyl alcohol, 150 gram graphite, 3 gram calcium silicates, 190 gram water are fully kneaded, and are squeezed into 8 millimeters of external diameters, 4 millimeters of internal diameters, high 6.4 millimeters Raschig ring.120 ℃ of oven dry, 1460 ℃ of roastings 4 hours obtain Raschig ring shape alpha-alumina supports.
Getting 59.1 gram silver nitrates is dissolved in 200 ml waters.Other gets ammonium oxalate 26.8 grams and is dissolved in 364 ml waters.Above-mentioned two solution carry out precipitation reaction under 40 ℃, with the silver oxalate precipitate with deionized water washing that obtains, filter.With of the ethylenediamine solution dissolving of silver oxalate filter cake with 32.8 milliliters of ethylenediamines and 32.8 ml waters, add six water nickel nitrates, 29.1 grams, add cesium carbonate 0.072 gram again, add water again, make silver-colored amine complex liquid.With above-mentioned carrier 100 grams above-mentioned silver-colored amine complex liquid of excessive dipping under vacuum, pull wet feed out and drain, put into thermal decomposer, with 260 ℃ of warm air blowoff 8 minutes, take out, under nitrogen atmosphere, handled 4 hours for 400 ℃, must catalyst A.Catalyst A contains 12.8% silver by weight, 2.0% nickel, the caesium of 200ppm.
The epoxidation of ethylene performance test of catalyst A: adopt 10 milliliters of minisize reaction evaluation systems.Catalyst breakage to 12～18 orders, get 10 milliliters of internal diameters of packing into and be in 8 millimeters the stainless steel reactor, in the minisize reaction evaluation system, carry out the epoxidation of ethylene performance test, relevant reaction condition is as follows:
The unstripped gas mole is formed: C
2H
4: 28% O
2: 6.4% CO
2: 5%
Inhibitor: micro-N
2: all the other
Pressure: 2.1MPa (gauge pressure)
Air speed: 8000 hours
-1
Outlet ethylene oxide concentration: 1.6 moles of %
The epoxidation of ethylene results of property of catalyst A sees Table 1.
[embodiment 2]
Alpha-alumina powder 600 grams are placed kneading machine, add 30 gram polyvinyl alcohol, 150 gram graphite, 3 gram calcium silicates, 190 gram water are fully kneaded, and are squeezed into 8 millimeters of external diameters, 4 millimeters of internal diameters, high 6.4 millimeters Raschig ring.120 ℃ of oven dry, 1460 ℃ of roastings 4 hours obtain Raschig ring shape alpha-alumina supports.
Get six water nickel nitrates, 0.570 gram and be dissolved in the mixed solution of 0.59 milliliter of ammoniacal liquor and 100 ml waters,, pull wet feed out, oven dry with alpha-alumina supports 100 grams above-mentioned solution of excessive dipping under vacuum.Impregnated in the mixed solution of 10 milliliters of hydrazine hydrates and 90 ml waters again, pull wet feed out, oven dry obtains nickeliferous carrier.
Getting 59.1 gram silver nitrates is dissolved in 200 ml waters.Other gets ammonium oxalate 26.8 grams and is dissolved in 364 ml waters.Above-mentioned two solution carry out precipitation reaction under 40 ℃, with the silver oxalate precipitate with deionized water washing that obtains, filter.With of the ethylenediamine solution dissolving of silver oxalate filter cake with 32.8 milliliters of ethylenediamines and 32.8 ml waters.Add cesium carbonate 0.123 gram, add water again, make silver-colored amine complex liquid.With above-mentioned nickeliferous carrier 100 grams above-mentioned silver-colored amine complex liquid of excessive dipping under vacuum, pull wet feed out and drain, put into thermal decomposer, with 260 ℃ of warm air blowoff 8 minutes, take out, must catalyst B.Catalyst B contains 13.0% silver by weight, 0.040% nickel, the caesium of 349ppm.
The epoxidation of ethylene performance test methods of catalyst B is with the reactivity worth test of catalyst A among the embodiment 1.Reactivity worth the results are shown in Table 1.
[embodiment 3]
Alpha-alumina powder 600 grams are placed kneading machine, add 30 gram polyvinyl alcohol, 150 gram graphite, 3 gram calcium silicates, 190 gram water are fully kneaded, and are squeezed into 8 millimeters of external diameters, 4 millimeters of internal diameters, high 6.4 millimeters Raschig ring.120 ℃ of oven dry, 1460 ℃ of roastings 4 hours obtain Raschig ring shape alpha-alumina supports.
Get six water nickel nitrates, 2.85 grams and be dissolved in the mixed solution of 3.0 milliliters of ammoniacal liquor and 97 ml waters, with alpha-alumina supports 100 grams above-mentioned solution of excessive dipping under vacuum, pull wet feed out, oven dry was handled 4 hours for 1000 ℃ under nitrogen atmosphere, obtained nickeliferous carrier.
Getting 59.1 gram silver nitrates is dissolved in 200 ml waters.Other gets ammonium oxalate 26.8 grams and is dissolved in 364 ml waters.Above-mentioned two solution carry out precipitation reaction under 40 ℃, with the silver oxalate precipitate with deionized water washing that obtains, filter.With of the ethylenediamine solution dissolving of silver oxalate filter cake with 32.8 milliliters of ethylenediamines and 32.8 ml waters.Add cesium carbonate 0.212 gram, add water again, make silver-colored amine complex liquid.With above-mentioned nickeliferous carrier 100 grams above-mentioned silver-colored amine complex liquid of excessive dipping under vacuum, pull wet feed out and drain, put into thermal decomposer, with 260 ℃ of warm air blowoff 8 minutes, take out, must catalyst C.Catalyst C contains 13.0% silver by weight, 0.20% nickel, the caesium of 600ppm.
The epoxidation of ethylene performance test methods of catalyst C is with the reactivity worth test of catalyst A among the embodiment 1.
Reactivity worth the results are shown in Table 1.
[comparative example 1]
Alpha-alumina powder 600 grams are placed kneading machine, add 30 gram polyvinyl alcohol, 150 gram graphite, 3 gram calcium silicates, 190 gram water are fully kneaded, and are squeezed into 8 millimeters of external diameters, 4 millimeters of internal diameters, high 6.4 millimeters Raschig ring.120 ℃ of oven dry, 1460 ℃ of roastings 4 hours obtain Raschig ring shape alpha-alumina supports.
Getting 59.1 gram silver nitrates is dissolved in 200 ml waters.Other gets ammonium oxalate 26.8 grams and is dissolved in 364 ml waters.Above-mentioned two solution carry out precipitation reaction under 40 ℃, with the silver oxalate precipitate with deionized water washing that obtains, filter.With of the ethylenediamine solution dissolving of silver oxalate filter cake with 32.8 milliliters of ethylenediamines and 32.8 ml waters.Add cesium carbonate 0.123 gram, add water again, make silver-colored amine complex liquid.With above-mentioned alpha-alumina supports 100 grams above-mentioned silver-colored amine complex liquid of excessive dipping under vacuum, pull wet feed out and drain, put into thermal decomposer, with 260 ℃ of warm air blowoff 8 minutes, take out, must catalyst D.Catalyst D contains 13.0% silver by weight, the caesium of 349ppm.
The epoxidation of ethylene performance test methods of catalyst D is with the reactivity worth test of catalyst A among the embodiment 1.Reactivity worth the results are shown in Table 1.
The epoxidation of ethylene results of property of table 1 catalyst
| The catalyst numbering | The initial reaction performance | Driving afterreaction performance half a year | ΔS | ΔT | ||
| Selectivity S | Reaction temperature T | Selectivity S | Reaction temperature T | |||
| Catalyst A | 82.1％ | 224℃ | 81.7％ | 227℃ | 0.4％ | 3℃ |
| Catalyst B | 82.3％ | 225℃ | 81.9％ | 227℃ | 0.4％ | 2℃ |
| Catalyst C | 82.0％ | 224℃ | 81.7％ | 226℃ | 0.3％ | 2℃ |
| Catalyst D | 82.1％ | 232℃ | 80.6％ | 244℃ | 1.5％ | 12℃ |
Claims (5)
1, a kind of silver catalyst that is used to produce oxirane comprises following component in catalyst weight percentage:
A) 50～94% alpha-alumina supports;
B) 5～40% silver;
C) 0.01～5% metallic nickel.
2,, it is characterized in that the consumption in catalyst weight percentage metallic nickel is 0.04～2% according to the described silver catalyst that is used to produce oxirane of claim 1.
3,, it is characterized in that also to contain 0.001～1% alkali metal catalyst in the catalyst weight percentage catalyst according to the described silver catalyst that is used to produce oxirane of claim 1.
4,, it is characterized in that the consumption in alkali metal catalyst in the catalyst weight percentage catalyst is 0.001～0.3% according to the described silver catalyst that is used to produce oxirane of claim 3.
5,, it is characterized in that the consumption in alkali metal catalyst in the catalyst weight percentage catalyst is 0.02～0.06% according to the described silver catalyst that is used to produce oxirane of claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011263458A CN1150991C (en) | 2001-07-27 | 2001-07-27 | Silver catalyst for producing epoxyethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011263458A CN1150991C (en) | 2001-07-27 | 2001-07-27 | Silver catalyst for producing epoxyethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1400053A CN1400053A (en) | 2003-03-05 |
| CN1150991C true CN1150991C (en) | 2004-05-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011263458A Expired - Lifetime CN1150991C (en) | 2001-07-27 | 2001-07-27 | Silver catalyst for producing epoxyethane |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6846774B2 (en) * | 2003-04-23 | 2005-01-25 | Scientific Design Co., Inc. | Ethylene oxide catalyst |
| CN102527430B (en) | 2010-12-29 | 2014-04-30 | 中国石油化工股份有限公司 | Preparation method of silver catalyst carrier, carrier prepared by preparation method, silver catalyst prepared by carrier and application thereof |
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2001
- 2001-07-27 CN CNB011263458A patent/CN1150991C/en not_active Expired - Lifetime
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