CN105435855B - The preparation method and application of alumina support and its silver catalyst of load - Google Patents
The preparation method and application of alumina support and its silver catalyst of load Download PDFInfo
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- CN105435855B CN105435855B CN201410394696.0A CN201410394696A CN105435855B CN 105435855 B CN105435855 B CN 105435855B CN 201410394696 A CN201410394696 A CN 201410394696A CN 105435855 B CN105435855 B CN 105435855B
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Abstract
The invention discloses a kind of methods preparing silver catalyst alumina support, include the following steps：Step I, it includes 50 mesh, 500 purpose, three water A1 to prepare2O3, not less than the one water A1 of vacation of 200 mesh2O3, fluoride-mineralization agent and nickel or nickel compound containing solid mixture；Then acid solution is added to mediate with solid mixture；Step II obtains the alumina support by the material obtained in step I through molding, drying and roasting.According to the alumina support that method provided by the invention is obtained, large specific surface area, and there is higher intensity；The silver catalyst made of the alumina support shows good activity and selectivity during ethylene produces ethylene oxide.
Description
Technical field
The present invention relates to catalyst and catalyst carrier technical fields, specifically, being related to a kind of for ethylene oxy metaplasia
At the nickeliferous alpha-alumina supports of ethylene oxide, the preparation and application of the silver catalyst of its load.
Background technology
Ethylene mainly generates ethylene oxide (EO) under silver catalyst effect, while side reaction occurs and generates titanium dioxide
Carbon and water etc., wherein activity, selectivity and stability are the main performance index of silver catalyst.So-called activity refers to ethylene oxide
Production process reaches reaction temperature required when certain reaction load, and reaction temperature is lower, and the activity of catalyst is higher.So-called choosing
Selecting property refers to that ethylene is converted to the ratio between the molal quantity of ethylene oxide and the overall reaction molal quantity of ethylene in reaction.So-called stability is then
It is expressed as the fall off rate of activity and selectivity, the stability of fall off rate more small catalyst is better.
The preparation method of silver catalyst includes preparation and the application activearm of porous carrier (such as aluminium oxide) in the prior art
Point and auxiliary agent to the carrier on the two processes.
It is catalyzed using high activity, silver that is highly selective and having good stability during ethylene produces ethylene oxide
Agent can greatly improve economic benefit, therefore manufacture high activity, highly selective and good stability silver catalyst are silver-colored catalysis
The Main way of agent research.
Invention content
For deficiency in the prior art, the present invention provides a kind of sides preparing the alumina support for silver catalyst
Method can obtain the alumina support of preferable specific surface area and intensity, and water absorption rate is higher；The alumina support is used
In preparing silver catalyst, the activity and selectivity of silver catalyst can be improved, there is wide application prospect.
According to an aspect of the invention, there is provided a kind of preparation method of alumina support for silver catalyst, packet
Include following steps：
Step I, it includes three water A1 of -500 purpose of 50 mesh to prepare2O3, not less than the one water A1 of vacation of 200 mesh2O3, fluoride mine
The solid mixture of agent and nickel or nickel compound containing；Then acid solution is added to mediate with solid mixture；
Step II obtains the alumina support by the material obtained in step I through molding, drying and roasting.
According to the method for the invention specific embodiment, the nickel compound containing is selected from nickel oxide, nickelous carbonate, nitre
Sour nickel, nickel chloride and nickel sulfate, are preferably selected from nickel oxide and nickel nitrate.Based on the gross mass of the solid mixture, the nickel
Or the amount of nickel compound containing is calculated as 0.001-5wt%, preferably 0.01-1.0wt%, such as 0.02- with the weight of nickel element
1.0wt%, such as 0.02-0.4wt%, more preferably 0.02-0.3wt%, such as 0.02-0.25wt%.
It is described based on the total weight of the solid mixture according to another specific embodiment of the method for the invention
Three water A12O3Content be 48-90wt%, the content of the false water aluminium oxide is 5-50wt%, the fluoride-mineralization agent
Content is 0.1-3.0wt%；The dosage of the acid solution accounts for the 2-60wt% of the total weight of the mixture；Preferably, three water
A12O3Content be 65-85wt%, the content of the false water aluminium oxide is 10-30wt%, and the fluoride-mineralization agent contains
Amount is 1.0-3.0wt%；The dosage of the acid solution accounts for the 15-20wt% of the total weight of the mixture.
The fluoride-mineralization agent is selected from hydrogen fluoride, ammonium fluoride, aluminum fluoride, magnesium fluoride and ice crystal.The fluoride mine
The addition of agent can be with the transformation of crystal of accelerated oxidation aluminium.In a specific embodiment, the three water A12O3It is powdered.
In the above-mentioned methods, the acid solution can be with the one water A1 of vacation in mixture2O3Aluminum sol is generated, each component is glued
Knot together, becomes extrudable molding paste.The acid solution such as nitric acid, formic acid, acetic acid, propionic acid and hydrochloric acid etc. it is water-soluble
Liquid.In a specific embodiment, the acid solution is aqueous solution of nitric acid, and wherein the weight ratio of nitric acid and water is 1:1.25~
10, preferably 1:2~4.
It further include weight alkaline earth gold according to another specific embodiment of the method for the invention, in the solid mixture
Belong to compound, based on the total weight of the solid chemical compound, the amount of the heavy alkaline earth metal compound is 0-2wt%, preferably
0.1-2wt%, more preferably 0.1-1.5wt%.The heavy alkaline earth metal compound be selected from the oxide of strontium and barium, sulfate,
Acetate, nitrate, carbonate and oxalates are preferably selected from barium monoxide, barium sulfate, barium nitrate and barium carbonate；
Method according to the present invention generally yields paste after mediating the mixture in step I.Have at one
In the embodiment of body, usually first by three water A1 of -500 purpose of 50 mesh2O3, not less than the one water A1 of vacation of 200 mesh2O3, weight alkaline-earth metal
Compound (if necessary), fluoride-mineralization agent and the mixture of nickel or nickel compound containing after mixing, are transferred to and pinch
In conjunction machine, the acid solution is then added and is mediated, paste is uniformly kneaded into, is especially kneaded into extrudable molding paste
Object；Formed body is obtained after paste is molded, which can be dried to aqueous 10wt% hereinafter, drying temperature is 80-120
DEG C, drying time controls according to moisture at 1-24 hours.The shape of gained formed body can be annular, spherical shape, cylindricality, more
Hole cylindricality or other arbitrary shapes.Formed body after drying is usually in 1000~1500 DEG C, preferably 1000~1400 DEG C of temperature
Lower roasting, roasting time are no less than 1 hour, usually 2-24 hours, preferably 2-8 hours.Keep aluminium oxide substantially complete by roasting
Portion is converted into α-A12O3, such as 90% or more be converted into α-A12O3, obtain α-A12O3Carrier namely silver catalyst aluminium oxide
α-A1 in carrier2O3Content, such as 90% or more.
According to another specific embodiment of the method for the invention, the acid solution and the false water A12O3It is molten with aluminium
Glue partly or entirely replaces.When all being replaced with Aluminum sol namely the method includes：By three water of -500 mesh of 50 mesh of component a)
A12O3；C) weight alkaline earth metal compound (if needing)；D) fluoride-mineralization agent；E) nickel and/or nickel compound containing；And f) aluminium
Colloidal sol；Then said components are mediated uniformly and are molded, and obtain formed body；The dry formed body, Alpha-alumina is obtained after roasting
Carrier.The dosage of the Aluminum sol can be conventional amount used in the art, such as in terms of the aluminium oxide in Aluminum sol, account for component a),
C), d), e) and f) 5-50wt%, preferably 11-32wt% of total dosage.Similarly, when partly to replace, one water A1 of vacation2O3With
Aluminum sol in terms of aluminium oxide, account for component a), b), c), d), e) and f) total dosage 5-50wt%, preferably 11-32wt%.
According to another specific embodiment of the method for the invention, the crushing strength 20 of the alumina support~
250N/, preferably 100~220N/；Specific surface area is 0.2~2.0m2/ g, preferably 1.0~1.5m2/g；Water absorption rate >=
30%, preferably >=50%.
According to alumina support prepared by method provided by the invention, nickel element is evenly distributed in the body phase of carrier.Institute
Obtained carrier has higher crushing strength, higher water absorption rate and higher specific surface area, is conducive to the use of carrier, has
Conducive to the dispersion for the active component being carried on the carrier.
It, can be by well known by persons skilled in the art after porous alumina support is prepared by the above method
Mode or usual manner prepare silver catalyst.
According to another aspect of the present invention, a kind of preparation method of silver catalyst is improved, including：
Step A impregnates alumina support obtained by the above method with argentiferous maceration extract；The wherein described argentiferous maceration extract includes
Content be the Ag-containing compound of 1~40wt%, the alkali metal promoter of 5~2000ppm, 0~10000ppm base earth metal promoter,
The rhenium auxiliary agent of 10~2000ppm and the organic amine of 1~24wt%；
Step B is separated by solid-liquid separation and removes silver catalyst maceration extract, obtains the silver catalyst.
In the above-mentioned methods, the preferably described argentiferous maceration extract includes the Ag-containing compound that content is 5~25wt%；5~
The alkali metal promoter of 1500ppm；The base earth metal promoter of 0~8000ppm；The rhenium auxiliary agent of 100~1000ppm.
According to the method for the present invention, the silver compound is selected from silver oxide, silver nitrate and silver oxalate；The alkali metal promoter choosing
From the compound of lithium, sodium, potassium, rubidium and caesium, wherein being preferably selected from cesium sulfate, cesium nitrate, lithium nitrate and potassium hydroxide, more preferably
Cesium nitrate, cesium sulfate；The base earth metal promoter be selected from magnesium, calcium, strontium and barium compound, wherein be preferably selected from magnesium, calcium, strontium and
Oxide, oxalates, sulfate, acetate and the nitrate of barium；The rhenium auxiliary agent is selected from oxide, perrhenic acid, the high rhenium of rhenium
Sour caesium and ammonium perrhenate, the preferably described rhenium auxiliary agent are ammonium perrhenate；The organic amine is selected from pyridine, butylamine, ethylenediamine, 1,3- third
Diamines and ethanol amine, the preferably described organic amine are the mixture of ethylenediamine and ethanol amine.
In a preferred embodiment according to the present invention, silver catalyst maceration extract described in step A further includes that rhenium helps
The coassist agent of agent, to be further improved activity, selectivity and the stability of gained silver catalyst.The coassist agent of the rhenium auxiliary agent
Can be the mixture of the compound of any transition metal or several transistion metal compounds in the periodic table of elements, preferably group vib
With the oxyacid and its salt of VIIB races elements, such as wolframic acid, sodium tungstate, potassium tungstate, ammonium tungstate, wolframic acid caesium, molybdic acid, ammonium molybdate,
Ammonium metatungstate etc., dosage are 0~1000wt ppm, and preferably its dosage is 0~500wt ppm.
According to the method for the present invention, the dipping process is to carry out under subatmospheric pressure conditions, is preferably less than in vacuum degree
It is carried out under conditions of 10mmHg, dip time is 10~60min.
Further include activation step in the step B according to another specific embodiment of the method for the invention, i.e., will
The catalyst for removing and obtaining after silver catalyst maceration extract is separated by solid-liquid separation to be activated.It is described activation be in air or oxygen content not
It is carried out in nitrogen oxygen atmosphere more than 21v%.Its activation temperature is 180~700 DEG C, and soak time is 1~120min；It is preferred that
The activation temperature is 200~500 DEG C, and soak time is 2~60min.
According to another aspect of the present invention, a kind of carrier being prepared according to the method or silver-colored catalysis are also provided
Application of agent during ethylene produces ethylene oxide.Wherein, the ethylene oxidation reactions are in oxygen and silver catalyst
It is carried out under existence condition, the reaction temperature is 200~275 DEG C.
It is easy to obtain according to the raw material in method provided by the invention, and preparation method step is simple；The oxygen obtained
Change alumina supporter, large specific surface area, and there is higher intensity；The silver catalyst made of the alumina support, in ethylene oxy
Good activity and selectivity is shown during metaplasia production ethylene oxide.
Specific implementation mode
Below in conjunction with embodiment, invention is further described in detail, but does not constitute any limit to the present invention
System.
The measurement of catalyst performance：The various silver catalysts of the present invention test it with laboratory microreactor evaluating apparatus
Activity and selectivity.The stainless steel reaction pipe of internal diameter 4mm, reaction tube is used to be placed in heating mantle in microreactor evaluating apparatus
In.The admission space of catalyst is 1ml, and there is inert filler in lower part, catalyst bed is made to be located at the flat-temperature zone of heating mantle.
The determination condition for the catalyst activity and selectivity that the present invention uses is as follows：
METHOD FOR CONTINUOUS DETERMINATION reactor enters after stably reaching above-mentioned reaction condition, exit gas forms.Measurement result carries out body
Product calculates selectivity S as follows after shrinking correction：
Wherein Δ EO is that reactor outlet gas and inlet gas ethylene oxide concentration are poor, Δ CO2Reactor outlet gas with into
Gas concentration lwevel is poor in implication, takes test result of the average of 10 groups or more test datas as the same day.
In the present invention, the specific surface area of carrier is to use nitrogen physisorption according to international test standards ISO-9277
What BET methods measured.It is, for example, possible to use Kang Ta companies NOVA2000e type nitrogen physisorption instrument in the U.S. measures the ratio of carrier
Surface area.The crushing strength (side pressure strength) of carrier, such as Dalian Chemical Research ＆. Design Inst.'s intelligent of DLII types of production may be used
Grain intensity measuring device measures；30 support samples are randomly selected, are averaged to obtain after measuring radial crushing strength.In the present invention
Term " water absorption rate " used refers to the volume of the carrier saturation absorption water of unit mass, and unit is ml/g.Assay method is：First
Weigh a certain amount of carrier (quality m1), it boils carrier taking-up to be erected on the moderate wet gauze of water content after 1h in boiling water and takes off
Except the extra moisture of carrier surface, the quality m of the carrier after absorption water is finally weighed2, by formula " water absorption rate=(m2-m1)/m1/
ρWater" calculate carrier water absorption rate, wherein ρWaterRefer to the density of water under temperature and the atmospheric pressure when measuring water absorption rate.
The preparation of catalyst carrier
Embodiment 1 (comparison)
By 200~500 purpose, three water α-A12O3The one water A1 of vacation of 372g, 200~400 mesh2O3112g、MgF23g and Ba
(NO3)2The solid mixture of 0.5g is put into blender mixing, is then transferred in kneader, and dust technology (nitric acid is added:Water=1:3,
Weight ratio) 90ml, it is kneaded into extrudable molding paste.Extrusion molding is outer diameter 8.0mm, long 6.0mm, internal diameter 1.0mm
Five hole columns, the dry 10h at 80~120 DEG C make free water content be reduced to 10wt% hereinafter, molding Alpha-alumina is made
Support greenware.Then the green compact are put into electric furnace, 1400 DEG C, constant temperature 2h are increased to from room temperature through 30h, by obtained white
α-A12O3Carrier is named as Z-1, and measures its crushing strength, water absorption rate and specific surface area, the results are shown in Table 1.
Embodiment 2
It further includes Ni (NO to be put into the raw material of blender mixing3)2.6H2O0.62g, remaining is identical as comparative example 1.By institute
White α-A1 obtained2O3Carrier is named as Z-2, and measures its crushing strength, water absorption rate and specific surface area, the results are shown in Table 1.
Embodiment 3
It further includes Ni (NO to be put into the raw material of blender mixing3)2.6H2O1.49g, remaining is identical as comparative example 1.By institute
White α-A1 obtained2O3Carrier is named as Z-3, and measures its crushing strength, water absorption rate and specific surface area, the results are shown in Table 1.
Embodiment 4
It further includes Ni (NO to be put into the raw material of blender mixing3)2.6H2O2.98g, remaining is identical as comparative example 1.By institute
White α-A1 obtained2O3Carrier is named as Z-4, and measures its crushing strength, water absorption rate and specific surface area, the results are shown in Table 1.
Embodiment 5
It further includes Ni (NO to be put into the raw material of blender mixing3)2.6H2O4.47g, remaining is identical as comparative example 1.By institute
White α-A1 obtained2O3Carrier is named as Z-5, and measures its crushing strength, water absorption rate and specific surface area, the results are shown in Table 1.
Embodiment 6
It further includes Ni (NO to be put into the raw material of blender mixing3)2.6H2O5.96g, remaining is identical as comparative example 1.By institute
White α-A1 obtained2O3Carrier is named as Z-6, and measures its crushing strength, water absorption rate and specific surface area, the results are shown in Table 1.
Table 1
As seen from Table 1, catalyst carrier Z-2 to the Z-6 being prepared using the method for the present invention, with the catalysis in comparative example
Agent carrier Z-1 is compared, and crushing strength enhancing, water absorption rate increases, and specific surface area is increased, and the use of carrier is conducive to,
Be conducive to the dispersion of the active component of load.
The preparation of silver catalyst
It takes 700g silver nitrates to be dissolved in 750ml deionized waters, obtains solution.325g ammonium oxalate is taken to be dissolved in 50 DEG C of 250ml's
In deionized water, solution is obtained.Two kinds of solution of mixing gained with vigorous stirring generate white silver oxalate precipitate.Aging 1 is small
When, filtering is washed with deionized filter cake until without nitrate ion in filtrate, obtains silver oxalate paste filter cake.Filter cake contains
Metallic silver about 60 weight %, aqueous about 15 weight %.
Add 300g ethylenediamines, 110g ethanol amines and 375g deionized waters in the glass flask with stirring, obtains mixed liquor.
Silver oxalate paste obtained is slowly added into mixed liquor under stirring, temperature is maintained between -5 DEG C to 10 DEG C, makes silver oxalate
Then all dissolvings add 2.37g cesium nitrates and 1.25g strontium sulfates, then add deionized water that solution gross mass is made to reach 2000g, make
For use at maceration extract M, the silver content of maceration extract M is 22 weight %.
Support samples Z-1 to Z-6 made from 100g embodiments 1-6 is taken to be put into the different containers that can be vacuumized respectively.
Absolute pressure is evacuated to less than 10mmHg, is respectively put into the above maceration extract prepared, submerges carrier, is kept for 30 minutes.Then
Leaching removes extra solution.Carrier after dipping is heated 5 minutes in 350 DEG C of air stream, it is cooling, that is, silver-colored catalysis is made
Agent is respectively designated as CZ-1, CZ-2, CZ-3 to CZ-6.Wherein from CZ-1 to CZ-6 in silver and auxiliary agent (caesium and strontium) content
Essentially identical, wherein silver content is 16.1wt%.
1.49 grams of nickel nitrate is added in above-mentioned maceration extract M, obtains nickeliferous maceration extract.It takes in the embodiment 1 of 100g
Support samples Z-1 be put into the container that can be vacuumized, and the absolute pressure in container is evacuated to less than 10mmHg, is then added
The above-mentioned nickeliferous maceration extract prepared submerges carrier, is kept for 30 minutes.Then leaching removes extra solution.After dipping
Carrier heats 5 minutes in 350 DEG C of air stream, cooling, that is, silver catalyst is made, is named as CZ-7.Silver in CZ-7 and CZ-1
And the content of auxiliary agent (caesium and strontium) is essentially identical.
Manufactured catalyst CZ-1, CZ-2, CZ-3, CZ-4, CZ-5, CZ-6 and CZ-7 are respectively carried out to use minisize reaction
Device evaluating apparatus above "The measurement of catalyst performance" activity and the choosing of each catalyst are measured under the process conditions of part
Selecting property, temperature and selective data when reaction proceeds to the 8th day are listed in Table 2 below.
Table 2
Listed reaction temperature and selectivity are determination datas when reaction proceeds to the 8th day in table 2.It can from table 2
Go out, catalyst CZ-2 to the CZ-6 being prepared using the method for the present invention, it is initial compared with the catalyst CZ-1 in comparative example
Reaction temperature decreases, and illustrates that the activity of catalyst is enhanced, and while activity increases, catalyst choice
It is increased；And compared with the catalyst CZ-7 (carrier surface dipping nickel ion) in comparative example, the method for the present invention is prepared
Catalyst CZ-2 to CZ-6 activity quite or while increase, selectivity improves more apparent.When the system in alumina support
When the nickel element content of standby middle addition is suitable, as its activity and selectivity improves significantly, especially in catalyst CZ-2 to CZ-5
Be catalyst (CZ-3) activity and selectivity increase it is the most apparent.The present invention is that ethylene produces ethylene oxide silver catalysis
Agent, which provides, a kind of excellent prepares carrying alumina body method so that the activity and selectivity of silver catalyst is all improved.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (19)
1. a kind of method preparing silver catalyst alumina support, includes the following steps：
Step I, it includes three water A1 of -500 purpose of 50 mesh to prepare2O3, not less than the one water A1 of vacation of 200 mesh2O3, fluoride-mineralization agent with
And the solid mixture of nickel or nickel compound containing；Then acid solution is added to mediate with solid mixture；
Step II obtains the alumina support by the material obtained in step I through molding, drying and roasting；
Wherein, the amount of the gross mass based on the solid mixture, the nickel or nickel compound containing is calculated as with the weight of nickel element
0.02-0.4wt%.
2. according to the method described in claim 1, it is characterized in that, the nickel compound containing is selected from nickel oxide, nickelous carbonate, nitric acid
Nickel, nickel chloride and nickel sulfate.
3. according to the method described in claim 1, it is characterized in that, the nickel compound containing is selected from nickel oxide and nickel nitrate.
4. according to the method described in claim 1, it is characterized in that, the gross mass based on the solid mixture, the nickel or
The amount of nickel compound containing is calculated as 0.02-0.3wt% with the weight of nickel element.
5. according to the method described in claim 2, it is characterized in that, the gross mass based on the solid mixture, the nickel or
The amount of nickel compound containing is calculated as 0.02-0.3wt% with the weight of nickel element.
6. according to the method described in claim 3, it is characterized in that, the gross mass based on the solid mixture, the nickel or
The amount of nickel compound containing is calculated as 0.02-0.3wt% with the weight of nickel element.
7. the method according to any one of claim 1~6, which is characterized in that based on the total of the solid mixture
Weight, the three water A12O3Content be 48-90wt%, the content of the false water aluminium oxide is 5-50wt%, the fluorination
The content of object mineralizer is 0.1-3.0wt%；The dosage of the acid solution accounts for the 2-60wt% of the total weight of the mixture.
8. the method according to any one of claim 1~6, which is characterized in that the three water A12O3Content be 65-
The content of 85wt%, the false water aluminium oxide are 10-30wt%, and the content of the fluoride-mineralization agent is 1.0-3.0wt%；
The dosage of the acid solution accounts for the 15-20wt% of the total weight of the mixture.
9. according to the method described in any one of claim 1-6, which is characterized in that the acid solution is aqueous solution of nitric acid,
The weight ratio of middle nitric acid and water is 1:1.25~10.
10. according to the method described in claim 9, it is characterized in that, the weight ratio of the nitric acid and water is 1:2~4.
11. according to the method described in any one of claim 1-6, which is characterized in that further include in the solid mixture
Weight alkaline earth metal compound, based on the total weight of the solid chemical compound, the amount of the heavy alkaline earth metal compound is 0-
2wt%.
12. according to the method for claim 11, which is characterized in that the amount of the heavy alkaline earth metal compound is 0.1-
2wt%.
13. according to the method for claim 11, which is characterized in that the amount of the heavy alkaline earth metal compound is 0.1-
1.5wt%.
14. the method according to any one of claim 1~6, which is characterized in that the acid solution and a false water
A12O3It is partly or entirely replaced with Aluminum sol.
15. the method according to any one of claim 1~6, which is characterized in that the crushing of the alumina support is strong
Degree 20~250N/；Specific surface area is 0.2~2.0m2/g；Water absorption rate >=30%.
16. the method according to any one of claim 1~6, which is characterized in that the crushing of the alumina support is strong
Degree is 100~220N/；Specific surface area is 1.0~1.5m2/g；Water absorption rate >=50%.
17. a kind of preparation method of silver catalyst, including：
Step A impregnates the aluminium oxide being prepared according to any one of claim 1~16 the method with argentiferous maceration extract
Carrier；The wherein described argentiferous maceration extract include the Ag-containing compound of 1~40wt%, the alkali metal promoter of 5~2000ppm, 0~
Base earth metal promoter, the rhenium auxiliary agent of 10~2000ppm and the organic amine of 1~24wt% of 10000ppm；
Step B is separated by solid-liquid separation and removes silver catalyst maceration extract, obtains the silver catalyst.
18. according to the method for claim 17, which is characterized in that the argentiferous maceration extract includes the argentiferous of 5~25wt%
Compound；The alkali metal promoter of 5~1500ppm；The base earth metal promoter of 0~8000ppm；The rhenium auxiliary agent of 100~1000ppm.
19. the carrier that is prepared according to any one of claim 1-16 the methods or according to described in claim 17 or 18
Application of the silver catalyst that method is prepared in ethylene produces ethylene oxide.
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| CN1511633A (en) * | 2002-12-31 | 2004-07-14 | 中国石油化工股份有限公司北京燕山分 | Carrier for producing silver catalyst for epoxy ethane production, its preparing method and use |
| CN1634652A (en) * | 2003-12-31 | 2005-07-06 | 中国石油化工股份有限公司北京燕山分公司研究院 | Silver catalyst carrier for epoxyethane production, preparation method and application thereof |
| CN103372466A (en) * | 2012-04-25 | 2013-10-30 | 中国石油化工股份有限公司 | Preparation method of silver catalyst carrier for production of ethylene oxide and application thereof |
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| JP2013193040A (en) * | 2012-03-21 | 2013-09-30 | Nippon Shokubai Co Ltd | Catalyst for producing ethylene oxide and method for producing ethylene oxide by using the same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1511633A (en) * | 2002-12-31 | 2004-07-14 | 中国石油化工股份有限公司北京燕山分 | Carrier for producing silver catalyst for epoxy ethane production, its preparing method and use |
| CN1634652A (en) * | 2003-12-31 | 2005-07-06 | 中国石油化工股份有限公司北京燕山分公司研究院 | Silver catalyst carrier for epoxyethane production, preparation method and application thereof |
| CN103372466A (en) * | 2012-04-25 | 2013-10-30 | 中国石油化工股份有限公司 | Preparation method of silver catalyst carrier for production of ethylene oxide and application thereof |
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