CN1130257C - Preparation method of load silver catalyst - Google Patents
Preparation method of load silver catalyst Download PDFInfo
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- CN1130257C CN1130257C CN 01126347 CN01126347A CN1130257C CN 1130257 C CN1130257 C CN 1130257C CN 01126347 CN01126347 CN 01126347 CN 01126347 A CN01126347 A CN 01126347A CN 1130257 C CN1130257 C CN 1130257C
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Abstract
The present invention relates to a preparation method of a load silver catalyst, which mainly solves the problem that silver grains in the prepared silver catalyst are easy to gather with the extension of reaction time, and thus, the silver catalyst is not stable enough or the activity of the silver catalyst is not high enough existed in the prior art. The present invention adopts the technical proposals that alpha-alumina is adopted as a carrier, a collosol of cerium or zirconium is added before, during or after the carrier is prepared, and then silver and cocatalysts are loaded; the prepared silver catalyst better solves the problem when used in an ethene epoxidation reaction. The preparation method can be used in the industrial production of the silver catalyst.
Description
Technical field
The present invention relates to the preparation method of loading type silver catalyst.
Background technology
Loading type silver catalyst is widely used in the reaction that industrial ethylene epoxidizing generates oxirane.Catalyst is carrier usually with the Alpha-alumina, is main active constituent with silver, adds a spot of co-catalyst simultaneously.Selectivity, activity and stability are three important performances of catalyst.The performance of silver catalyst plays a part very important to the technology that ethylene epoxidizing generates oxirane.
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.Document US 5,418 has been introduced a kind of silver catalyst in 202, the HfOCl of solubility
2, HfOCO
3, HfO (NO
3)
2, ZrOCl
2, ZrOCO
3, ZrO (NO
3)
2Add catalyst Deng as co-catalyst, wherein Hf or the Zr content in every gram catalyst is 0.01～10 micromole, and prepared silver catalyst has high activity and high stability.US5,100,859 have introduced a kind of preparation method of silver catalyst carrier, add the zirconium dioxide below 10% when the preparation carrier, and wherein the adding form of zirconium adopts zirconium dioxide, zirconium nitrate, zirconium silicate etc.The silver catalyst that makes of carrier has high selectivity and high stability thus.But, assemble easily by silver catalyst silver granuel in startup procedure that above-described these methods prepare, cause silver catalyst stability not high enough.Document CN1,080, introduced a kind of silver catalyst and preparation method thereof among the 211A, when the preparation carrier, mixed alpha-alumina powder with colloidal alumina and silica, be molded as definite shape, again high-temperature roasting, obtained applying with amorphous silicon oxide and alumina mixture the alpha-alumina supports of surfaces externally and internally, the silver catalyst that makes with this carrier has high selectivity and high stability.But the reactivity of the silver catalyst of this method preparation does not have clear improvement.
Summary of the invention
Technical problem to be solved by this invention is to overcome the not high enough or silver catalyst of the silver catalyst stability that makes in the document in the past to have high stability but active not high enough shortcoming, and a kind of preparation method of new loading type silver catalyst is provided.Silver catalyst obtained by this method has the characteristics of high selectivity, high activity and high stability.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of loading type silver catalyst may further comprise the steps successively:
A) with the Alpha-alumina be carrier, the consumption of carrier is 50～94% of a catalyst weight;
B) before alpha-alumina supports preparation, simultaneously or add the colloidal sol and the mixture thereof of cerium or zirconium afterwards, the colloidal sol addition of cerium or zirconium is counted 0.01～30% of catalyst weight with oxide;
C) load silver and co-catalyst on above-mentioned alpha-alumina supports after cerium or the processing of zirconium colloidal sol, obtain loading type silver catalyst through heat treatment, wherein Yin load capacity is 5～40% of a catalyst weight, and co-catalyst is 0.001～1% of a catalyst weight in the load capacity of weight metal.
In the technique scheme, the colloidal sol addition of cerium or zirconium is 0.1～20% of a catalyst weight in the oxide preferable range.The co-catalyst preferred version is an alkali metal, and more preferably scheme is a cesium element, and co-catalyst is 0.001～0.3% of a catalyst weight in the load capacity preferable range of weight metal, and more preferably scope is 0.002～0.1% of a catalyst weight.
In the technical scheme of the present invention, the decentralized photo of cerium colloidal sol or zirconium colloidal sol can be metal oxide, metal hydroxides, metallic salt, metal or alloy.
Cerium that adds in the colloidal sol mode or zirconium can stop effectively and delay the gathering of silver granuel in the catalyst and grow up, and the stability of catalyst is significantly improved.In addition, adding Ce elements or zr element can improve selection of catalysts and activity in silver catalyst, and especially activity of such catalysts has obtained significant raising, and at this moment, Ce elements or zr element may play the effect of co-catalyst in silver catalyst.
In the technical scheme of the present invention, the alumina support in the catalyst exists with the Alpha-alumina form, and its content is counted 50～94% of catalyst weight with aluminium oxide.
Silver content is counted 5～40% of catalyst weight with silver in the catalyst.
Co-catalyst can improve the performance of silver catalyst.Co-catalyst can be before silver, add catalyst simultaneously afterwards or with silver.
The preparation of carrier is 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 etc.Temporary bonding agent can be kneaded together the Alpha-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.
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.
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.
Colloidal sol added catalyst before adding silver.Can be before the preparation carrier, the preparation carrier simultaneously or carrier make after adding.Prepare the method that adds colloidal sol before the carrier if adopt, can get alumina powder elder generation impregnant sol, to dry, moulding, silver and co-catalyst thereof are soaked in roasting again, after the heat treatment silver catalyst.If add the method for colloidal sol when adopting the preparation carrier, can when batch mixing, add alumina powder to colloidal sol, through moulding, silver and co-catalyst thereof are soaked in roasting again, after the heat treatment silver catalyst.If adopt carrier to make the method that the back adds colloidal sol, can get the alumina support impregnant sol, oven dry, 300～1800 ℃ of following roastings 1～10 hour, preferably, soak silver and co-catalyst thereof afterwards again 400～1600 ℃ of following roastings 1～10 hour, after the heat treatment silver catalyst.
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, carbonate, oxalates, carboxylate, alkoxide or their mixture, and instantiation has cesium carbonate, rubidium nitrate, potassium hydroxide, sodium acetate, lithium oxalate.The alkali metal amount is to add 10～3000 parts of alkali metal in weight metal, preferred 20～1000 parts alkali metal in the catalyst of per 1,000,000 parts of weight.Co-catalyst can be before silver impregnated in carrier, simultaneously or be applied on the carrier afterwards.
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.Different catalysts through the reactivity worth after the driving of same reaction time, is compared with the initial reaction performance under same reaction conditions, 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, in order to compare the stability height of different catalysts, after allowing different catalysts be issued to the air speed and oxirane exit concentration of appointment at identical reaction condition, measured selectivity and reaction temperature after driving continuously again 1 year, compare with initial selectivity and initial reaction temperature, if the changing value of the changing value of a certain catalyst selectivity and reaction temperature is more little, think that then the stability of this catalyst is high more.
The silver catalyst that employing the present invention is prepared into is owing to add cerium or zirconium and composition thereof in catalyst, and cerium or zirconium are that form with colloidal sol adds, therefore be used for epoxidation of ethylene, the gathering of silver and grow up and obtained effective prevention and delay, downward trend has obtained delaying with the driving passage of time for selection of catalysts and activity, thereby improved the stability of catalyst, reactivity worth after drove 1 year, the EO selectivity descends and has only reduced by 0.2%, reaction temperature raises and has only risen 1 ℃, has obtained effect preferably.Silver catalyst with the present invention's preparation can improve selection of catalysts and activity simultaneously, and especially activity of such catalysts has obtained significant raising.
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.
Get cerium colloidal sol 0.6 gram that contains 20% (weight) ceria, add water, the above-mentioned alpha-alumina supports of dipping 100 grams, oven dry, 800 ℃ of roastings 4 hours.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 0.153 gram, add water again, make silver-colored amine complex liquid.Contain the above-mentioned silver-colored amine complex liquid of carrier excessive dipping under vacuum of cerium with above-mentioned 100 grams, pull wet feed out and drain, put into thermal decomposer,, take out with 260 ℃ of warm air blowoff 8 minutes, must catalyst A.
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: 5500 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]
Get zirconium colloidal sol 900 grams that contain 20% (weight) zirconium dioxide, add 1000 gram alpha-aluminas and soaked 1 hour, dried 10 hours for 120 ℃.
Above-mentioned alpha-alumina 600 grams that contain zirconium 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 containing the alpha-alumina supports of zirconium.
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 0.153 gram, add water again, make silver-colored amine complex liquid.Contain the above-mentioned silver-colored amine complex liquid of carrier excessive dipping under vacuum of zirconium with above-mentioned 100 grams, pull wet feed out and drain, put into thermal decomposer,, take out with 260 ℃ of warm air blowoff 8 minutes, must catalyst B.
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 600 grams are placed kneading machine, add 30 gram polyvinyl alcohol, 150 gram graphite, 3 gram calcium silicates, 30 grams contain the cerium colloidal sol of 20% (weight) ceria, 60 grams contain the zirconium colloidal sol of 20% (weight) zirconium dioxide, 90 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 containing the alpha-alumina supports of cerium and zirconium.
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 0.153 gram, add water again, make silver-colored amine complex liquid.Contain the above-mentioned silver-colored amine complex liquid of carrier excessive dipping under vacuum of cerium and zirconium with above-mentioned 100 grams, pull wet feed out and drain, put into thermal decomposer,, take out with 260 ℃ of warm air blowoff 8 minutes, must catalyst C.
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 0.153 gram, 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, must catalyst D.
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.[comparative example 2]
Alpha-alumina 600 grams are placed kneading machine, add 30 gram polyvinyl alcohol, 150 gram graphite, 3 gram calcium silicates, 60 grams contain the Ludox of 20% (weight) silica, 60 grams contain the aluminium colloidal sol of 20% (weight) aluminium oxide, 60 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 siliceous and alpha-alumina supports aluminium.
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 0.153 gram, add water again, make silver-colored amine complex liquid.With the above-mentioned silver-colored amine complex liquid of carrier excessive dipping under vacuum of the siliceous and aluminium of above-mentioned 100 grams, pull wet feed out and drain, put into thermal decomposer, with 260 ℃ of warm air blowoff 8 minutes, take out, must catalyst E.
The epoxidation of ethylene performance test methods of catalyst E 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 | The 1 year afterreaction performance of driving | ΔS | ΔT | ||
| Selectivity S | Reaction temperature T | Selectivity S | Reaction temperature T | |||
| Catalyst A | 82.3％ | 221℃ | 82.1％ | 222℃ | 0.2％ | 1℃ |
| Catalyst B | 82.1％ | 218℃ | 81.9％ | 219℃ | 0.2％ | 1℃ |
| Catalyst C | 82.4％ | 220℃ | 82.2％ | 221℃ | 0.2％ | 1℃ |
| Catalyst D | 81.2％ | 230℃ | 80.0％ | 237℃ | 1.2％ | 7℃ |
| Catalyst E | 81.9％ | 230℃ | 81.6％ | 231℃ | 0.3％ | 1℃ |
Claims (6)
1, a kind of preparation method of loading type silver catalyst may further comprise the steps successively:
A) with the Alpha-alumina be carrier, the consumption of carrier is 50～94% of a catalyst weight;
B) before alpha-alumina supports preparation, simultaneously or add the colloidal sol and the mixture thereof of cerium or zirconium afterwards, the colloidal sol addition of cerium or zirconium is counted 0.01～30% of catalyst weight with oxide;
C) load silver and co-catalyst on above-mentioned alpha-alumina supports after cerium or the processing of zirconium colloidal sol, obtain loading type silver catalyst through heat treatment, wherein Yin load capacity is 5～40% of a catalyst weight, and co-catalyst is 0.001～1% of a catalyst weight in the load capacity of weight metal.
2,, it is characterized in that the colloidal sol addition of cerium or zirconium is counted 0.1～20% of catalyst weight with oxide according to the preparation method of the described loading type silver catalyst of claim 1.
3,, it is characterized in that co-catalyst is an alkali metal according to the preparation method of the described loading type silver catalyst of claim 1.
4,, it is characterized in that co-catalyst is a cesium element according to the preparation method of the described loading type silver catalyst of claim 3.
5, according to the preparation method of the described loading type silver catalyst of claim 1, the load capacity that it is characterized in that co-catalyst is 0.001～0.3% of a catalyst weight.
6, according to the preparation method of the described loading type silver catalyst of claim 5, the load capacity that it is characterized in that co-catalyst is 0.002～0.1% of a catalyst weight.
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| CN 01126347 CN1130257C (en) | 2001-07-27 | 2001-07-27 | Preparation method of load silver catalyst |
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| 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 |
| CN103357441B (en) * | 2012-03-28 | 2016-03-30 | 中国石油化工股份有限公司 | Silver catalyst carrier, its preparation method, the catalyst be made up of it and application |
| CN108855238A (en) * | 2017-05-15 | 2018-11-23 | 中国石油化工股份有限公司 | Porous alumina carrier and preparation method thereof and silver catalyst and application |
| CN108855239A (en) * | 2017-05-15 | 2018-11-23 | 中国石油化工股份有限公司 | Porous alumina carrier and preparation method thereof and silver catalyst and application |
| CN108855237A (en) * | 2017-05-15 | 2018-11-23 | 中国石油化工股份有限公司 | Porous alumina carrier and preparation method thereof and silver catalyst and application |
| CN112295553B (en) * | 2019-08-02 | 2023-06-30 | 中国石油天然气股份有限公司 | Preparation method of modified alumina carrier |
| CN114100595A (en) * | 2020-08-28 | 2022-03-01 | 中国石油化工股份有限公司 | Silver catalyst carrier for ethylene epoxidation and preparation method thereof, silver catalyst and method for producing ethylene oxide by ethylene epoxidation |
| CN112206798B (en) * | 2020-10-29 | 2022-03-22 | 润和催化材料(浙江)有限公司 | Silver catalyst for preparing ethylene oxide by ethylene oxidation and preparation method and application thereof |
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