CN103566980B - The preparation method of the silver catalyst of alumina support and load thereof and application - Google Patents

The preparation method of the silver catalyst of alumina support and load thereof and application Download PDF

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CN103566980B
CN103566980B CN201210257096.0A CN201210257096A CN103566980B CN 103566980 B CN103566980 B CN 103566980B CN 201210257096 A CN201210257096 A CN 201210257096A CN 103566980 B CN103566980 B CN 103566980B
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silver catalyst
silicon
water
alumina support
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CN103566980A (en
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李贤丰
李金兵
张志祥
陈建设
王辉
蒋军
曹淑媛
林强
任冬梅
薛茜
王淑娟
林伟
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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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 kind of preparation method producing the alpha-alumina supports of oxirane silver catalyst for ethylene, the method by introducing a certain amount of silicon or silicon-containing compound in the process preparing alumina support, specific area and the intensity of gained carrier improve, and the silver catalyst be made up of this modified support significantly can improve the activity of silver catalyst when preparing oxirane for ethylene.

Description

The preparation method of the silver catalyst of alumina support and load thereof and application
Technical field
The present invention relates to catalyst and catalyst carrier technical field, specifically, relate to a kind of preparations and applicatio of the silver catalyst for ethylene generation oxirane alpha-alumina supports, its load.
Background technology
Under silver catalyst effect, ethylene mainly generates oxirane (EO), and side reaction occurs simultaneously and generates carbon dioxide and water etc., wherein active, selective and stability is the main performance index of silver catalyst.So-called activity refers to the reaction temperature that process for ethylene oxide production reaches required when necessarily reacting load, and reaction temperature is lower, and the activity of catalyst is higher.What is called is selective refers to that in reaction, ethylene conversion becomes the ratio of the molal quantity of oxirane and the overall reaction molal quantity of ethene.So-called stability is then expressed as the fall off rate of activity and selectivity, and the stability of fall off rate more small catalyst is better.
Produce at ethylene in the process of oxirane and use high activity, high selectivity and the silver catalyst that has good stability greatly to increase economic efficiency, the silver catalyst therefore manufacturing high activity, high selectivity and good stability is the Main way of silver catalyst research.
In prior art the preparation method of silver catalyst comprise the preparation and administration to active component of porous carrier (as aluminium oxide) and auxiliary agent to as described in this two processes on carrier.
In recent years, some novel silver catalyst carrier technologies of preparing are there is, such as, patent US5395812, EP1354626 and EP0927575 of catalyst company of Japan mention and apply one deck sieve and silica-sesquioxide at carrier surface, after gained carrier makes silver catalyst, there is higher selective, the active and longer life-span.Carrier involved by the patent US5145824 of Ying He Shell Co. Ltd and US5929259 is made up of the former powder of a kind of Alpha-alumina, alkaline-earth metal and zirconium-containing compound, and adds silicon-containing compound in preparation process.The carrier that the patent US5100859 of Norton company of the U.S. relates to is made up of the former powder of a kind of Alpha-alumina, alkaline-earth-metal silicate and zirconium-containing compound, and the carrier specific area that it prepares is usually at 1m 2within/g.In addition, foregoing invention all improves the performance of silver catalyst mainly through the interaction of alkaline-earth metal and auxiliary agent in silicon and carrier.
The exploitation that ethylene produces oxirane silver catalyst and carrier thereof still needs further effort.
Summary of the invention
The support modification method that employing of the present invention is different from prior art, by introducing a certain amount of element silicon in the process preparing silver catalyst alumina support, improve silicone content in carrier, specific area and the intensity of gained carrier improve, and then improve the activity of silver catalyst.
The invention provides a kind of preparation method of the alumina support for silver catalyst, comprise the steps: step I, form the mixture comprising following component: component a, 50 order-500 object three water A1 2o 3; Components b, be more than or equal to the false water A1 of 200 objects 2o 3; Amount of component b, account for the heavy alkaline earth metal compound that component a ~ e gross weight is 0-2wt%; Component d, fluoride-mineralization agent; Component e, account for silicon or silicon-containing compound that component a ~ e gross weight is 0.001-5wt%, with the weighing scale of element silicon; Component f, binding agent; And component g, appropriate water; Its roasting, by shaping and dry for the mixture obtained in step I, is then described alumina support by step II.
In order to prepare porous alpha-alumina supports of the present invention, need use three water α-A1 2o 3, i.e. component a.This three water α-A1 2o 3for graininess, require that granularity is 50-500 order.
When preparing porous alpha-alumina supports of the present invention, optionally can use heavy alkaline earth metal compound, i.e. amount of component b in step I, its object is to improve carrier property.This heavy alkaline earth metal compound is the compound of strontium and/or barium, the oxide of such as strontium and/or barium, sulfate, acetate, nitrate, carbonate and oxalates etc.Particularly preferably use barium monoxide, barium sulfate, barium nitrate, brium carbonate or its mixture.
When preparing porous alpha-alumina supports of the present invention, adding of component d fluoride-mineralization agent is transformation of crystal in order to accelerated oxidation aluminium.The fluoride that the present invention selects is preferably inorganic fluoride, comprises one or more in hydrogen fluoride, ammonium fluoride, aluminum fluoride, magnesium fluoride and ice crystal, is particularly preferably ammonium fluoride.
When preparing porous alpha-alumina supports of the present invention, also need the silicon-containing compound adding component e.One or more advantageously for being selected from sodium metasilicate, ethyl orthosilicate, nano-silicon and Ludox of this silicon-containing compound, preferred ethyl orthosilicate, nano-silicon or its mixture.
When preparing porous alpha-alumina supports of the present invention, usually add the binding agent of component f, the vacation one water A1 in it and mixture 2o 3generate Alumina gel, each component be bonded together, becoming can the paste of extrusion molding.Binding agent used comprises acid, as nitric acid, formic acid, acetic acid, propionic acid and hydrochloric acid etc.When using acid as binding agent, preferably aqueous solution of nitric acid, wherein the weight ratio of nitric acid and water is 1:1.25 ~ 10, preferred 1:2 ~ 4.
Or in the present invention, partly or entirely replace the binding agent of component f and a false water A1 with Alumina gel 2o 3.
Mixture in step I is mediated evenly, usually obtain paste.To the present invention advantageously, if usually first by words that component a ~ e(uses) mix after, proceed in kneader, then add component f and g mediates, be evenly kneaded into paste, being especially kneaded into can the paste of extrusion molding; Obtain formed body after paste is shaping, this formed body can be dried to moisture below 10wt%, and baking temperature is 80-120 DEG C, and drying time controls at 1-24 hour according to moisture.The shape of gained formed body can be annular, spherical, cylindricality, porous column shape, or other arbitrary shape.
Dried formed body is usually at the roasting temperature of 1000 ~ 1500 DEG C, preferably 1000 ~ 1400 DEG C, and roasting time is no less than 1 hour, is generally 2-24 hour, preferred 2-8 hour.Aluminium oxide is made substantially all to be converted into α-A1 by roasting 2o 3, such as more than 90% is converted into α-A1 2o 3, obtain α-A1 2o 3carrier.
In the present invention, preferably, in solid constituent a ~ e gross weight for 100%, wherein component a is 48-90wt%, and components b is 5-50wt%, and amount of component b is 0-1.5wt%, component d be 0.1-3.0wt%, component e is 0.02-0.9wt%; And component f is 2-60wt% based on solid constituent a ~ e gross weight.More preferably, in solid constituent a ~ e gross weight for 100%, wherein component a is 65-85wt%, and components b is 10-30wt%, and amount of component b is 0.1-1.5wt%, component d be 1.0-3.0wt%, component e is 0.03-0.7wt%; And component f is 15-20wt% based on solid constituent a ~ e gross weight.
Use the alumina support that in the present invention, method prepares, preferably, its crushing strength is 20 ~ 250N/ grain, is more preferably 100 ~ 220N/ grain; Specific area is 0.2 ~ 2.0m 2/ g, is more preferably 1.0 ~ 1.5m 2/ g; Water absorption rate>=30%, more preferably>=50%.
After obtained porous alpha-alumina supports of the present invention, silver catalyst can be prepared by mode well known by persons skilled in the art or usual manner, such as, by preparing with the above-mentioned alumina support of the solution impregnation of a kind of Ag-containing compound and organic amine.
The present invention also provides a kind of preparation method of silver catalyst, comprising: steps A, with silver catalyst impregnation fluid as above alumina support of the present invention; And described silver catalyst maceration extract comprises the organic amine of Ag-containing compound that weight content is 1 ~ 40wt%, the alkali metal promoter of 5 ~ 2000ppm, the base earth metal promoter of 0 ~ 10000ppm, the rhenium auxiliary agent of 10 ~ 2000ppm and 1 ~ 24wt%; Step B, Separation of Solid and Liquid removing silver catalyst maceration extract, obtains the alumina support containing active component; With step C, by the obtained described silver catalyst of the above-mentioned activation of the alumina support containing active component.
In the present invention, in the maceration extract of silver catalyst described in preferred steps A, each composition weight content is, Ag-containing compound is 5 ~ 25wt%; Alkali metal promoter is 5 ~ 1500ppm; Base earth metal promoter is 0 ~ 8000ppm; Rhenium auxiliary agent is 100 ~ 1000ppm.
According to the inventive method, described silver compound comprises silver oxide, silver nitrate and/or silver oxalate; Described alkali metal promoter be selected from the compound of lithium, sodium, potassium, rubidium or caesium one or more, comprising cesium sulfate, cesium nitrate, lithium nitrate and/or potassium hydroxide, preferred as alkali auxiliary agent is cesium sulfate; Described base earth metal promoter be selected from the compound of magnesium, calcium, strontium or barium one or more, comprising one or more in the oxide of magnesium, calcium, strontium and barium, oxalates, sulfate, acetate and nitrate; Described rhenium auxiliary agent be selected from the oxide of rhenium, perrhenic acid, perrhenic acid caesium or ammonium perrhenate one or more, preferred described rhenium auxiliary agent is ammonium perrhenate; Described organic amine is pyridine, butylamine, ethylenediamine, 1,3-propane diamine, monoethanolamine or its mixture, and preferred described organic amine is the mixture of ethylenediamine and monoethanolamine.
In a preferred embodiment according to the present invention, the maceration extract of silver catalyst described in steps A also comprises the coassist agent of rhenium auxiliary agent, to improve the activity of gained silver catalyst, selective and stability further.The coassist agent of described rhenium auxiliary agent can be the compound of arbitrary transition metal in the periodic table of elements, or the mixture of several transistion metal compound, the oxyacid of preferred group vib and VIIB race element and salt thereof, such as wolframic acid, sodium tungstate, potassium tungstate, ammonium tungstate, wolframic acid caesium, molybdic acid, ammonium molybdate, ammonium metatungstate etc., its consumption is 0 ~ 1000wt ppm, and preferably its consumption is 0 ~ 500wt ppm.
According to the inventive method, described dipping process carries out under subatmospheric pressure conditions, carries out preferably be less than the condition of 10mmHg in vacuum under, and dip time is 10 ~ 60min.
According to the inventive method, activation described in step C be in atmosphere or oxygen content be not more than and carry out in the nitrogen oxygen atmosphere of 21v%.Its activation temperature is 180 ~ 700 DEG C, and soak time is 1 ~ 120min; Preferred described activation temperature is 200 ~ 500 DEG C, and soak time is 2 ~ 60min.
The carrier that the present invention also provides a kind of described method to prepare or silver catalyst produce the application in oxirane process at ethylene.Wherein, described ethylene oxidation reactions is carried out under oxygen and silver catalyst existence condition, and described reaction temperature is 200 ~ 275 DEG C.
The specific area of the Si modification alpha-alumina supports obtained according to the inventive method is larger than the carrier specific area without Si modification, the silver catalyst be made up of this modification alpha-alumina supports, produces at ethylene in the process of oxirane and demonstrates good activity.The present invention is all easy to obtain to the raw material that alumina support carries out modification, and preparation method's step is simple.
Detailed description of the invention
Describe the present invention in detail below in conjunction with embodiment, these embodiments only play illustration, and protection scope of the present invention is not limited thereto.
The mensuration of catalyst performance: various silver catalyst laboratories of the present invention microreactor evaluating apparatus tests its activity and selectivity.Use the stainless steel reaction pipe of internal diameter 4mm in microreactor evaluating apparatus, reaction tube is placed in heating jacket.The admission space of catalyst is 1ml, and inert filler is arranged at bottom, makes beds be positioned at the flat-temperature zone of heating jacket.
The condition determination of the catalyst activity and selectivity that the present invention uses is as follows:
When stable reach above-mentioned reaction condition after METHOD FOR CONTINUOUS DETERMINATION reactor enter, exit gas composition.Measurement result calculates selective S after carrying out volume contraction correction as follows:
S = ΔEO ΔEO + 0.5 × ΔCO 2 × 100 %
Wherein Δ EO is that reactor outlet gas and inlet gas ethylene oxide concentration are poor, Δ CO 2be that in reactor outlet gas and inlet gas, gas concentration lwevel is poor, get the result of the test of average as the same day of more than 10 groups test datas.
In the present invention, the specific area of carrier adopts nitrogen physisorption BET method to measure according to international test standards ISO-9277.Such as, U.S. Kang Ta company NOVA2000e type nitrogen physisorption instrument can be used to measure the specific area of carrier.The crushing strength (side pressure strength) of carrier, such as, can adopt Dalian Chemical Research &. Design Inst. to produce DL II type intelligence detector for strength of particles and measure; Random selecting 30 support samples, average after measuring radial crushing strength and obtain.In the present invention, term used " water absorption rate " refers to the volume of the carrier saturated adsorption water of unit mass, and unit is ml/g.Assay method is: (quality is m first to take a certain amount of carrier 1), boil 1h in boiling water after, carrier taking-up is erected on the moderate wet gauze of water content and removes the unnecessary moisture of carrier surface, finally weigh the quality m of the carrier after adsorbed water 2, by formula " water absorption rate=(m 2-m 1)/m 1/ ρ water" calculate the water absorption rate of carrier, wherein ρ waterrefer to the density of water under temperature when measuring water absorption rate and atmospheric pressure.
Following examples 1 ~ 9 are the preparation of catalyst carrier.
Embodiment 1(contrasts)
By 200 ~ 500 object three water α-A1 2o 3the false water A1 of 403g, 200 ~ 400 objects 2o 381g, NH 4f3g and BaSO 40.5g puts into blender mixing, then proceeds in kneader, adds dust technology (nitric acid: water=1:3, weight ratio) 90ml, and being kneaded into can the paste of extrusion molding.Extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, and dry 10h at 80 ~ 120 DEG C, makes free water content be reduced to below 10wt%, obtained shaping alpha-alumina supports green compact.Then these green compact are put into electric furnace, be elevated to 1400 DEG C through 30h from room temperature, constant temperature 2h, by obtained white α-A1 2o 3carrier called after Z-1, and measure its crushing strength, water absorption rate and specific area, the results are shown in Table 1.
Embodiment 2
Also comprise nano-silicon 0.24g in raw material, all the other are identical with embodiment 1.By obtained white α-A1 2o 3carrier called after Z-2, and measure its crushing strength, water absorption rate and specific area, the results are shown in Table 1.
Embodiment 3
Also comprise nano-silicon 0.60g in raw material, all the other are identical with embodiment 1.By obtained white α-A1 2o 3carrier called after Z-3, and measure its crushing strength, water absorption rate and specific area, the results are shown in Table 1.
Embodiment 4
Also comprise nano-silicon 0.84g in raw material, all the other are identical with embodiment 1.By obtained white α-A1 2o 3carrier called after Z-4, and measure its crushing strength, water absorption rate and specific area, the results are shown in Table 1.
Embodiment 5
Also comprise nano-silicon 1.43g in raw material, all the other are identical with embodiment 1.By obtained white α-A1 2o 3carrier called after Z-5, and measure its crushing strength, water absorption rate and specific area, the results are shown in Table 1.
Embodiment 6
Also comprise the ethyl orthosilicate 2.69g be dissolved in described dust technology in raw material, all the other are identical with embodiment 1.By obtained white α-A1 2o 3carrier called after Z-6, and measure its crushing strength, water absorption rate and specific area, the results are shown in Table 1.
Embodiment 7
Also comprise the ethyl orthosilicate 3.98g be dissolved in described dust technology in raw material, all the other are identical with embodiment 1.By obtained white α-A1 2o 3carrier called after Z-7, and measure its crushing strength, water absorption rate and specific area, the results are shown in Table 1.
Embodiment 8
Also comprise the ethyl orthosilicate 6.14g be dissolved in described dust technology in raw material, all the other are identical with embodiment 1.By obtained white α-A1 2o 3carrier called after Z-8, and measure its crushing strength, water absorption rate and specific area, the results are shown in Table 1.
Embodiment 9
Also comprise the ethyl orthosilicate 7.92g be dissolved in described dust technology in raw material, all the other are identical with embodiment 1.By obtained white α-A1 2o 3carrier called after Z-9, and measure its crushing strength, water absorption rate and specific area, the results are shown in Table 1.
Table 1
Embodiment 1 2 3 4 5 6 7 8 9
Support samples Z-1 Z-2 Z-3 Z-4 Z-5 Z-6 Z-7 Z-8 Z-9
Crushing strength (N/ grain) 90 104 118 128 165 176 207 178 210
Water absorption rate (%) 54.11 51.98 52.06 52.42 52.33 52.87 54.03 53.52 53.11
Specific area (m 2/g) 0.986 1.13 1.27 1.285 1.275 1.167 1.199 1.305 1.215
As seen from Table 1, use catalyst carrier Z-2 to the Z-9 that the inventive method prepares, compared with the catalyst carrier Z-1 in comparative example's (in embodiment 1, technical scheme is the prior art the most close with the present invention), its crushing strength is obviously higher, water absorption rate is lower, and specific area is obviously larger.Especially in carrier preparation process, add a certain amount of ethyl orthosilicate, its crushing strength is improved especially remarkable.
Following examples 10 ~ 18 are the preparation of silver catalyst.
Embodiment 10(contrasts)
700g silver nitrate is dissolved in obtained liquor argenti nitratis ophthalmicus in 750ml deionized water; 325g ammonium oxalate is dissolved in obtained ammonium oxalate solution in the deionized water of 250ml50 DEG C; Liquor argenti nitratis ophthalmicus and ammonium oxalate solution Homogeneous phase mixing, generate white silver oxalate precipitate with vigorous stirring; After aging for silver oxalate precipitate 1h, filter, and spend deionized water filter cake until without nitrate ion in filtrate, obtained paste silver oxalate filter cake, containing metal silver about 60wt% in the filter cake obtained, moisture about 15wt%.
By 300g ethylenediamine, 110g monoethanolamine and 375g deionized water add glass flask, stir, after mixing, in obtained mixed solution, slowly add paste silver oxalate while stirring, temperature remains between-5 ~ 10 DEG C, silver oxalate is all dissolved, then adds 2.2g cesium sulfate and 1.4g strontium acetate, then add deionized water and make solution gross mass reach 2kg, make silver catalyst maceration extract, in the silver compound maceration extract obtained, silver content is 22wt%.
Get support samples Z-1 obtained in 15g embodiment 1 and put into the container that can vacuumize.Vacuum is evacuated to lower than 10mmHg, adds silver catalyst maceration extract, submergence carrier, keeps 30min.Then unnecessary silver catalyst maceration extract is removed in leaching.Carrier after dipping is heated 5min in the air stream of 350 DEG C, cooling, by obtained silver catalyst called after CZ-1, the content (wherein content is all in metal) of the silver in obtained silver catalyst and auxiliary agent is analyzed, and use microreactor evaluating apparatus to measure its activity and selectivity, the results are shown in Table 2.
Embodiment 11
Carrier Z-1 changes and makes carrier Z-2 by embodiment 11 as different from Example 10, by obtained silver catalyst called after CZ-2, the content (wherein content is all in metal) of the silver in obtained silver catalyst and auxiliary agent is analyzed, and use microreactor evaluating apparatus to measure its activity and selectivity, the results are shown in Table 2.
Embodiment 12
Carrier Z-1 changes and makes carrier Z-3 by embodiment 12 as different from Example 10, by obtained silver catalyst called after CZ-3, the content (wherein content is all in metal) of the silver in obtained silver catalyst and auxiliary agent is analyzed, and use microreactor evaluating apparatus to measure its activity and selectivity, the results are shown in Table 2.
Embodiment 13
Carrier Z-1 changes and makes carrier Z-4 by embodiment 13 as different from Example 10, by obtained silver catalyst called after CZ-4, the content (wherein content is all in metal) of the silver in obtained silver catalyst and auxiliary agent is analyzed, and use microreactor evaluating apparatus to measure its activity and selectivity, the results are shown in Table 2.
Embodiment 14
Carrier Z-1 changes and makes carrier Z-5 by embodiment 14 as different from Example 10, by obtained silver catalyst called after CZ-5, the content (wherein content is all in metal) of the silver in obtained silver catalyst and auxiliary agent is analyzed, and use microreactor evaluating apparatus to measure its activity and selectivity, the results are shown in Table 2.
Embodiment 15
Carrier Z-1 changes and makes carrier Z-6 by embodiment 15 as different from Example 10, by obtained silver catalyst called after CZ-6, the content (wherein content is all in metal) of the silver in obtained silver catalyst and auxiliary agent is analyzed, and use microreactor evaluating apparatus to measure its activity and selectivity, the results are shown in Table 2.
Embodiment 16
Carrier Z-1 changes and makes carrier Z-7 by embodiment 16 as different from Example 10, by obtained silver catalyst called after CZ-7, the content (wherein content is all in metal) of the silver in obtained silver catalyst and auxiliary agent is analyzed, and use microreactor evaluating apparatus to measure its activity and selectivity, the results are shown in Table 2.
Embodiment 17
Carrier Z-1 changes and makes carrier Z-8 by embodiment 17 as different from Example 10, by obtained silver catalyst called after CZ-8, the content (wherein content is all in metal) of the silver in obtained silver catalyst and auxiliary agent is analyzed, and use microreactor evaluating apparatus to measure its activity and selectivity, the results are shown in Table 2.
Embodiment 18
Carrier Z-1 changes and makes carrier Z-9 by embodiment 18 as different from Example 10, by obtained silver catalyst called after CZ-9, the content (wherein content is all in metal) of the silver in obtained silver catalyst and auxiliary agent is analyzed, and use microreactor evaluating apparatus to measure its activity and selectivity, the results are shown in Table 2.
Table 2
Reaction temperature listed in table 2 and selective be the determination data of reaction when proceeding to the 7th day.As can be seen from Table 2, use catalyst CZ-2 to the CZ-9 that the inventive method prepares, compared with the catalyst CZ-1 in comparative example, its initial reaction temperature is obviously lower, illustrate that in the present invention, the activity of catalyst is higher, and the selective of catalyst of the present invention raises or reduces not obvious simultaneously to some extent.When especially adding a certain amount of nano-silicon in carrier preparation process, compared with comparative example, gained catalyst ethylene making oxirane, while activity obviously raises, catalyst choice also raises to some extent.And when adding a certain amount of ethyl orthosilicate in carrier preparation process, compared with comparative example, gained catalyst ethylene making oxirane, while activity significantly raises, catalyst choice fall is little.The present invention produces for ethylene the preparation method that oxirane silver catalyst provides a kind of excellence, makes the activity of silver catalyst and/or selective raising.
The foregoing is only the preferred embodiment of the present invention; but scope is not limited thereto; any those skilled in the art, in technical scope disclosed by the invention, can easily carry out changing or changing, and this change or change all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.

Claims (14)

1., for a preparation method for the alumina support of silver catalyst, comprise the steps:
Step I, forms the mixture comprising following component:
Component a, 50 order-500 object three water Al 2o 3;
Components b, be more than or equal to the false water Al of 200 objects 2o 3;
Amount of component b, account for the heavy alkaline earth metal compound that component a ~ e gross weight is 0-2wt%;
Component d, fluoride-mineralization agent;
Component e, account for silicon or silicon-containing compound that component a ~ e gross weight is 0.001-5wt%, with the weighing scale of element silicon;
Component f, binding agent; And
Component g, appropriate water;
Its roasting, by shaping and dry for the mixture obtained in step I, is then described alumina support by step II;
Silicon described in component e or silicon-containing compound be selected from ethyl orthosilicate, nano-silicon and silica gel one or more.
2. method according to claim 1, is characterized in that, silicon described in component e or silicon-containing compound are selected from ethyl orthosilicate, nano-silicon or its mixture.
3. method according to claim 1, is characterized in that, the heavy alkaline earth metal compound in amount of component b be selected from the oxide of strontium and barium, sulfate, acetate, nitrate, carbonate and oxalates one or more; Described mineralizer in component d be selected from hydrogen fluoride, ammonium fluoride, aluminum fluoride, magnesium fluoride and ice crystal one or more.
4. method according to claim 3, is characterized in that, the heavy alkaline earth metal compound in amount of component b is selected from barium monoxide, barium sulfate, barium nitrate, brium carbonate or its mixture.
5. method according to claim 1, is characterized in that, binding agent described in component f is acid.
6. method according to claim 5, is characterized in that, described acid is aqueous solution of nitric acid, and wherein the weight ratio of nitric acid and water is 1:1.25 ~ 10.
7. method according to claim 6, is characterized in that, the weight ratio of nitric acid and water is 1:2 ~ 4.
8. according to the method in claim 1 ~ 7 described in any one, it is characterized in that, partly or entirely replace the described false water Al in the described binding agent in component f and components b with Alumina gel 2o 3.
9. according to the method in claim 1 ~ 7 described in any one, it is characterized in that, in solid constituent a ~ e gross weight for 100%, wherein component a is 48-90wt%, and components b is 5-50wt%, and amount of component b is 0-1.5wt%, component d is 0.1-3.0wt%, component e is 0.02-0.9wt%; And component f is 2-60wt% based on solid constituent a ~ e gross weight.
10. method according to claim 9, is characterized in that, in solid constituent a ~ e gross weight for 100%, wherein component a is 65-85wt%, and components b is 10-30wt%, and amount of component b is 0.1-1.5wt%, component d is 1.0-3.0wt%, component e is 0.03-0.7wt%; And component f is 15-20wt% based on solid constituent a ~ e gross weight.
11., according to the method in claim 1 ~ 7 described in any one, is characterized in that, crushing strength 20 ~ 250N/ grain of the alumina support using the method to prepare; Specific area is 0.2 ~ 2.0m 2/ g; Water absorption rate>=30%.
12. methods according to claim 11, is characterized in that, the crushing strength of described alumina support is 100 ~ 220N/ grain; Specific area is 1.0 ~ 1.5m 2/ g; Water absorption rate>=50%.
The preparation method of 13. 1 kinds of silver catalysts, comprising:
Steps A, the alumina support prepared as method as described in any one in claim 1 ~ 12 with silver catalyst impregnation fluid; And described silver catalyst maceration extract comprises the organic amine of Ag-containing compound that weight content is 1 ~ 40wt%, the alkali metal promoter of 5 ~ 2000ppm, the base earth metal promoter of 0 ~ 10000ppm, the rhenium auxiliary agent of 10 ~ 2000ppm and 1 ~ 24wt%;
Step B, Separation of Solid and Liquid removing silver catalyst maceration extract, obtains the alumina support containing active component;
Step C, by the obtained described silver catalyst of the above-mentioned activation of the alumina support containing active component.
14. carriers that method prepares according to any one of claim 1-12 or the application of silver catalyst in ethylene production oxirane prepared according to method described in claim 13.
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CN105080617B (en) * 2014-05-08 2018-03-02 中国石油化工股份有限公司 A kind of preparation method and applications of alumina support
CN105327712B (en) * 2014-08-07 2018-06-15 中国石油化工股份有限公司 A kind of application of the preparation method of silver catalyst, silver catalyst and the silver catalyst
CN106311354B (en) * 2015-07-02 2020-07-21 中国石油化工股份有限公司 Method for modifying surface of alumina carrier, carrier obtained thereby and application thereof
CN106311353B (en) * 2015-07-02 2019-08-20 中国石油化工股份有限公司 A kind of alpha-alumina supports, corresponding silver catalyst and application
CN106311228B (en) * 2015-07-02 2019-06-28 中国石油化工股份有限公司 Silver catalyst, preparation method and application
CN106955692B (en) * 2016-01-08 2019-09-27 中国石油化工股份有限公司 A kind of alpha-alumina supports, silver catalyst prepared therefrom and its application
CN106955693B (en) * 2016-01-08 2022-08-19 中国石油化工股份有限公司 Alpha-alumina carrier of silver catalyst for ethylene epoxidation as well as preparation and application thereof
CN108499613A (en) * 2017-02-28 2018-09-07 中国石油化工股份有限公司 Alumina support and the preparation method and application thereof
CN108371949A (en) * 2018-02-07 2018-08-07 武汉凯迪工程技术研究总院有限公司 High wear resistance alumina support and preparation method thereof
CN115364834A (en) * 2021-05-20 2022-11-22 中国石油化工股份有限公司 Modified alpha-alumina carrier, preparation method thereof, silver catalyst and application

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