CN103357441B - Silver catalyst carrier, its preparation method, the catalyst be made up of it and application - Google Patents

Silver catalyst carrier, its preparation method, the catalyst be made up of it and application Download PDF

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CN103357441B
CN103357441B CN201210087079.7A CN201210087079A CN103357441B CN 103357441 B CN103357441 B CN 103357441B CN 201210087079 A CN201210087079 A CN 201210087079A CN 103357441 B CN103357441 B CN 103357441B
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carrier
content
component
compound
silver
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CN103357441A (en
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林强
李贤丰
陈建设
李金兵
张志祥
代武军
曹淑媛
任冬梅
孙欣欣
高立新
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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
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention provides a kind of carrier of silver catalyst, this carrier comprises following component: the Al of a, 85 ~ 99.9wt% 2o 3, wherein Alpha-alumina is>=85wt% based on aluminium oxide gross weight; B, compound Zirconium oxide containing zirconium and metal M, wherein metal M is be selected from one or more elements in periodic table of elements IIA race, IIIB race and the IVB race element except zirconium, and in this compound Zirconium oxide, the total amount of metallic element accounts for total weight of carrier content is 0.01-10wt%; With alkaline-earth metal and/or its compound of c, one or more periodic table of elements IIA race; It is 0.01-5wt% that its metallic element weight accounts for total weight of carrier content.The silver catalyst be made up of this carrier is produced in the process of oxirane at ethylene and is demonstrated good activity and selectivity, and especially selective tool has clear improvement.In addition, the invention still further relates to the preparation method of described carrier, and the silver catalyst be made up of this carrier and application thereof.

Description

Silver catalyst carrier, its preparation method, the catalyst be made up of it and application
Technical field
The present invention relates to a kind of carrier for silver-containing catalyst, its preparation method and application thereof, the silver catalyst that more particularly the present invention relates to a kind of alumina support for ethylene production oxirane silver catalyst, its preparation method and obtained by this carrier.
Background technology
Under silver catalyst effect, ethylene mainly generates oxirane, side reaction occurs simultaneously and generates carbon dioxide and water etc.The main performance index of silver catalyst comprises its active, selective and stability.Wherein activity generally refers to the reaction temperature that process for ethylene oxide production reaches required when necessarily reacting load; Desired reaction temperature is lower, and the activity of catalyst is higher.Selectively refer to that in reaction, ethylene conversion becomes the ratio of the molal quantity of oxirane and the overall reaction molal quantity of ethene.Stability is then 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, therefore manufacture the Main way that such silver catalyst is silver catalyst research.The performance of silver catalyst is except having important relationship with the composition of catalyst and preparation method, and performance of the carrier also used with catalyst and preparation method thereof has important relationship.
The preparation method of silver catalyst be mainly 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.Its carrier generally selects the Alpha-alumina that specific area is less.Aluminium oxide (Al 2o 3) be a kind of catalyst carrier of having many uses, its kind is very many, and its crystal structure, surface catalysis performance are also very complicated, directly affect the performance of silver catalyst.
The primary raw material preparing alumina support is the hydrate of aluminium oxide, i.e. aluminium hydroxide, and hydrated alumina dehydration can produce Louis (L) Acid and basic sites, and these L acid sites are easy to water suction and change proton (B) Acid and basic sites into.The crystal formation kind of aluminium oxide is a lot, and impurity and moisture impact more or less in addition, causes the surface physics of aluminium oxide, chemical property all very complicated.For the α-Al that silver catalyst is selected 2o 3although its surface only has the Acid and basic sites of seldom amount, their meetings and active component acting in conjunction, impel ethylene conversion to be oxirane.
Carrier needs to provide certain area load active component, and active component is thereon dispersed, and this just proposes very high requirement to the pore structure of carrier.The hole of alumina support can be divided into three types: the first, primary particle intercrystalline hole, the mainly dewatering hole of alumina raw material crystal grain, be substantially 1-2nm size parallel-plate face between gap; The second, hole between alumina raw material offspring, changing with the effusion of moisture and crystalline phase change in roasting, is hole more than tens nanometer; The third, pore creating material and carrier shaping time produce defective hole and macropore.Therefore, the alumina raw material proportioning of variety classes and particle diameter, the consumption of pore creating material and molding mode and baking modes etc. all can impact the pore structure of silver catalyst carrier and physical property, and then affect the performance of catalyst.
In general, the main method preparing silver catalyst carrier is, binding agent and various additives etc. are added by alumina powder raw material, even through batch mixing and kneading, then extrusion molding is difform base substrate, as Raschig ring, spheric granules, porous cylindrical, the shape of a saddle etc., final high temperature sintering makes the alpha-alumina supports product of porous heat-resistant, specifically can see patent documents such as US5063195, US5703001 and US5801259.
Auxiliary agent is added, in order to improve the performance of carrier toward contact in the preparation process of silver catalyst carrier.As US6787656 and US5145824 proposes: add the performance that zirconium (Zr) can improve carrier in alumina support; And Chinese patent Granted publication CN1126597C and CN1130257C claims: add the performance that cerium (Ce) or zirconium colloidal sol can improve carrier in alumina support; The silver catalyst carrier that the compound that patent CN02160081 proposes to add heavy alkaline-earth metal in alumina powder raw material is made, then load active component makes silver catalyst, it is active, selective is all improved.
The improvement that the activity and selectivity of these methods above-mentioned to carrier property and catalyst brings is also very limited, therefore this area still needs to improve carrier and manufacture method thereof, be beneficial to produce the better silver catalyst of performance, especially selective better catalyst.
Summary of the invention
In view of the situation of above-mentioned prior art, the present inventor has carried out research extensively and profoundly at silver catalyst and alumina support field thereof, found that, when comprising a certain amount of compound Zirconium oxide and alkaline-earth metal in alpha-alumina supports, the loading type silver catalyst be made up of this carrier, when the oxidation epoxy ethane for catalyzed ethylene, selectively obviously to be improved.
Therefore, the object of this invention is to provide a kind of alumina support, the silver catalyst be made up of it is produced in the process of oxirane at ethylene and is demonstrated good activity and selectivity.
The invention provides a kind of carrier of silver catalyst, this carrier comprises following component: the Al of a, 85 ~ 99.9wt% 2o 3, wherein Alpha-alumina is>=85wt% based on aluminium oxide gross weight; B, compound Zirconium oxide containing zirconium and metal M, wherein metal M is be selected from one or more elements in periodic table of elements IIA race, IIIB race and the IVB race element except zirconium, and in this compound Zirconium oxide, the total amount of metallic element accounts for total weight of carrier content is 0.01-10wt%; With alkaline-earth metal and/or its compound of c, one or more periodic table of elements IIA race; It is 0.01-5wt% that its metallic element weight accounts for total weight of carrier content.
Such as, compound Zirconium oxide of the present invention is the composite oxides that zirconium dioxide and ceria, zirconium dioxide and yttria or zirconium dioxide and ceria and yttria are formed.
In carrier of the present invention, aluminium oxide should account for the overwhelming majority; Typically, based on the gross weight of carrier, alumina content is at least 85wt%.In addition, when by raw alumina roasting, and not all aluminium oxide all can be transformed into Alpha-alumina; Therefore, in carrier of the present invention, based on the gross weight of aluminium oxide, α-Al 2o 3content be generally at least 85wt%, preferably at least 90wt%.Alpha-alumina supports of the present invention needs to obtain porous material by high temperature sintering usually.In carrier of the present invention, the compound Zirconium oxide of components b and the alkaline-earth metal of amount of component b are modified component, the existence of these components makes the loading type silver catalyst be made up of this carrier produce the effect improved when catalyzed ethylene epoxy ethane, and this comprises the activity and selectivity improving catalyst.
In preferred components b of the present invention, the mol ratio of zirconium and metal M is 1: 0.01-0.3, and more preferably its mol ratio is 1: 0.05-0.2, and in compound Zirconium oxide, the total amount of metallic element accounts for total weight of carrier content is 0.1-7wt%; In amount of component b, metallic element weight accounts for total weight of carrier content is 0.1-3wt%.
In one embodiment of the invention, in preferred vector product, tetragonal phase compound Zirconium oxide accounts for more than the 10wt% of compound Zirconium oxide gross weight.In the present invention, compound Zirconium oxide exists with one or more in following crystalline phase: four directions (orthogonal), cubic nonlinearity monoclinic phase; Wherein advantageously four directions (orthogonal) crystalline phase to account for the content of compound Zirconium oxide gross weight The more the better, the carrier crushing strength so prepared is higher.
In the present invention, the IIA race alkaline-earth metal of amount of component b act as, and it can form compound Zirconium oxide jointly as the M metal in components b and zirconium, thus is more conducive to the formation of (orthogonal) crystalline phase compound Zirconium oxide in four directions in vector product; Its effect is also that the catalytic selectivity that its corresponding catalyst is prepared in oxirane at ethylene improves.
In preferred components b of the present invention, M is one or more metals be selected from IIIB race, more preferably yttrium, cerium and lanthanum; In described amount of component b, IIA race alkaline-earth metal is strontium or barium, preferred barium.
The carrier crushing strength > 20N/ grain that preferred the present invention prepares, specific area is 0.2-2.0m 2/ g, water absorption rate>=30%, and pore volume is 0.35-0.85ml/g; More preferably crushing strength is 30-150N/ grain, and specific area is 0.5-1.8m 2/ g, water absorption rate>=40%, and pore volume is 0.40-0.8ml/g.
The present invention also provides a kind of method preparing above-mentioned carrier, comprises the steps, step I, forms the mixture comprising following component: i, 50 order-500 object three water Al 2o 3; Ii, be greater than the false water Al of 200 objects 2o 3; The weight ratio of wherein said gibbsite and a false Water oxidize aluminium is 1 ~ 16: 1, is preferably 1 ~ 6: 1; Total consumption of described gibbsite and a false Water oxidize aluminium should make the carrier finished product finally obtained comprise the Al of at least 85wt% 2o 3; Iii, described compound Zirconium oxide, the presoma that can be converted into this compound Zirconium oxide or its combination; It is 0.01-10 % by weight that its consumption should make the total amount of metallic element in described compound Zirconium oxide account for the final carrier finished product gross weight content obtained, preferred 0.1-7 % by weight; Iv, alkaline-earth metal and/or its compound; It is 0.01-5wt% that its consumption should make alkaline earth metal content account for the final carrier finished product gross weight content obtained, preferred 0.1-3wt%; V, be the mineralizer of 0.01-5.0wt%, preferred 1-4wt% based on the gross weight of component i and ii; Vi, binding agent; And vii, appropriate water; Its roasting, by shaping and dry for the mixture obtained in step I, is then carrier finished product by Step II.
Component i gibbsite in the present invention is usually in solidapowder form; Component ii is usually also in solidapowder form.
The compound Zirconium oxide used as component iii is known, can commercially obtain, such as the preparation of the tetragonal phase zirconium oxide powder of zirconia ceramics material, zirconia TZP powder (being often referred to the tetragonal phase zirconium oxide ceramic powder containing yttrium and/or cerium), zirconia YSZ powder (YSZ means the stable zirconia of yttrium) etc.
As the compound Zirconium oxide that component iii mentions, also can be prepared by methods known in the art.Such as can use any precursor power that can be converted into compound Zirconium oxide of the present invention, as the method preparation mentioned by patent CN1562887A, CN1528706A and CN1620409A etc.
In support preparation method of the present invention, the mixture of the excellent selected among zirconium of the presoma of compound Zirconium oxide and metal M described in component iii, one or more in the mixture of the oxide of zirconium and metal M, sulfate, acetate, nitrate, carbonate or oxalates; Wherein metal M is preferably yttrium or cerium; Alkaline earth metal compound described in component iv is selected from its oxide, sulfate, acetate, nitrate, carbonate and oxalates; The heavy alkaline-earth metal of preferred use and/or its compound, the more preferably compound of barium or baric, as: barium metal, barium monoxide, barium sulfate, barium nitrate, brium carbonate or its mixture etc.; Mineralizer described in component v is fluoride, is preferably inorganic fluoride, be more preferably be selected from hydrogen fluoride, ammonium fluoride, aluminum fluoride, magnesium fluoride and ice crystal one or more, be particularly preferably ammonium fluoride.
In support preparation method of the present invention, adding of mineralizer v is transformation of crystal in order to accelerated oxidation aluminium.
In support preparation method of the present invention, also need to use component vi binding agent, as added acid as bonding agent, it generates Alumina gel with the vacation one Water oxidize aluminium in mixture, each component is bonded together, becomes plastic paste, such as becoming can the paste of extrusion molding.Acid is comprised in bonding agent used, as nitric acid, formic acid, acetic acid, propionic acid and/or hydrochloric acid etc., preferred nitric acid and/or acetic acid.When described acid is aqueous solution of nitric acid, the weight ratio of nitric acid and water is 1: 1.25 ~ 10, preferably 1: 2 ~ 8.In addition, available Alumina gel partly or entirely replaces a false water Al described in acid described in component vi and component ii 2o 3.The consumption of binding agent is conventional, as long as each component can be bonded together, and forms paste.Typically, the consumption of binding agent is 15-60wt%, preferred 15-50wt%, based on the gross weight of component i-v.
After each component mixing in step I, usually obtain paste.By shaping for gained paste, preferred extrusion molding, obtains formed body, i.e. carrier blank.This formed body can be dried to moisture less than 10 % by weight, and baking temperature is 80-200 DEG C, and drying time controls at 1-24 hour according to moisture.The shape of gained formed body can be annular, spherical, cylindricality or porous column shape, or other shape.In order to make carrier have enough intensity and good surface property, dried formed body is roasting at 1000-1600 DEG C, preferably 1200-1400 DEG C usually.Under sintering temperature, usually carrier is kept 1-24 hour.Aluminium oxide is made substantially all to be converted into α-Al by roasting 2o 3, obtain porous alpha-alumina supports thus.
Support according to the present invention preparation method, the porous alpha-alumina supports of obtained a kind of modification.Preferred external diameter is 7-9mm, and hole diameter is the cellular cylindrical particle of seven apertures in the human head or five holes of 1-2mm, or external diameter be 7-9mm, internal diameter is the circular particle of single hole of 3-6mm.
The present invention also provides a kind of silver catalyst, and this catalyst comprises carrier prepared by above-mentioned carrier or said method, and deposition silver on this carrier, and one or more in the collaborative auxiliary agent of optional alkali metal, alkaline-earth metal, rhenium and rhenium; Wherein, described alkali metal be selected from Li, Na, K, Rb and Cs one or more; Preferred caesium and/or potassium, most preferably be caesium; Described alkaline-earth metal be selected from Mg, Ca, Sr and Ba one or more, preferred strontium and/or barium; The collaborative auxiliary agent of described rhenium be selected from chromium, molybdenum, tungsten and boron one or more.
Silver catalyst of the present invention can be prepared in the usual way, such as, by preparing with the solution impregnation of a kind of Ag-containing compound and organic amine carrier provided by the invention.In the present invention, the collaborative auxiliary agent of alkali metal, alkaline-earth metal, rhenium and rhenium independently of one another before dipping silver, be applied in porous alpha-alumina supports while load silver or after load silver, or is immersed in porous alpha-alumina supports after silver compound is reduced; Preferably load while load silver.
In silver catalyst of the present invention, on the surface that silver is dispersed in porous refractory alumina support and in hole.Because high silver content can increase the cost of catalyst, reduce economy.Therefore, in a preferred embodiment of silver catalyst of the present invention, based on the gross weight of silver catalyst, silver content is 1-30wt%, preferred 5-26wt%; Alkali metal content is 5-2000ppm, is preferably 10-1500ppm; Alkali earth metal content is 5-2000ppm, is preferably 10-1200ppm; Rhenium constituent content is 5-1500ppm, is preferably 10-1000ppm; The collaborative auxiliary element content of rhenium is 5-1000ppm, is preferably 10-500ppm.
In one embodiment of the invention, the preparation method of silver catalyst of the present invention comprises the steps: the first step, by the solution impregnation porous alpha-alumina supports of the present invention of the collaborative auxiliary agent containing the silver compound of q.s, organic amine, optional alkali metal promoter, optional base earth metal promoter and optional rhenium auxiliary agent and optional rhenium; Second step, leaching maceration extract; With the 3rd step, in air or inert gas, second step gained carrier is activated, make described silver catalyst.
In order to prepare silver catalyst of the present invention, silver compound used can for being suitable for any silver compound preparing ethylene oxide silver catalyst.The present invention preferably uses silver oxide, silver nitrate and/or silver oxalate.
In order to prepare catalyst of the present invention, organic amine compound used can for being suitable for any organic amine compound preparing ethylene oxide silver catalyst, as long as this organic amine compound can form argent-amine complex with silver compound.For the purpose of the present invention, pyridine, butylamine, ethylenediamine, 1,3-propane diamine, monoethanolamine or its mixture is preferably used, the mixture of such as ethylenediamine and monoethanolamine.
In order to prepare catalyst of the present invention, the optional alkali metal promoter used can be compound (as nitrate, sulfate and hydroxide) or its mixture of lithium, sodium, potassium, rubidium or caesium, preferred cesium nitrate, lithium nitrate and/or potassium hydroxide.
In order to prepare catalyst of the present invention, the base earth metal promoter of optional use can be one or more in the compound of magnesium, calcium, strontium and barium, as as described in one or more in the oxide of element, oxalates, sulfate, acetate and nitrate, the compound of preferred barium and/or the compound of strontium, as barium acetate and/or strontium acetate.
In order to prepare catalyst of the present invention, the optional rhenium auxiliary agent used can be oxide, perrhenic acid, the perrhenate of rhenium, or its mixture, preferred perrhenic acid and/or perrhenate, such as perrhenic acid, perrhenic acid caesium and/or ammonium perrhenate etc.In dipping solution except silver compound, organic amine, optional alkali metal promoter, optional base earth metal promoter and optional rhenium auxiliary agent, the coassist agent of rhenium auxiliary agent can also be added, to improve the activity of gained silver catalyst, selective and stability further.The coassist agent of the rhenium auxiliary agent in the present invention can be selected from chromium, molybdenum, tungsten and boron compound one or more.
In the impregnation step, for ensureing all even abundant load of silver, carrier preferably vacuumizes in advance.
After porous alpha-alumina supports dipping argentiferous maceration extract, leaching maceration extract, then in air or inert gas to step 3) in activate through the carrier of dipping.For this reason, the carrier through dipping can be activated in the moving air of 180-700 DEG C, preferably 200-500 DEG C or inert gas are as the air-flow such as nitrogen, argon gas, soak time at least 2 minutes usually, such as 2-120 minute, preferred 2-60 minute.For ensureing that catalyst has higher activity, this activation temperature should higher than 500 DEG C.
In a preferred embodiment of preparation silver catalyst of the present invention, first the aqueous solution of silver nitrate and ammonium oxalate or oxalic acid aqueous solution is made to react, separate out silver oxalate precipitate, after filtration, spend deionized water, until without nitrate ion, after drying, silver oxalate is dissolved in organic amine as in the aqueous solution of pyridine, butylamine, ethylenediamine, 1,3-propane diamine, monoethanolamine or its mixture, add each auxiliary agent, be made into dipping solution; Then porous alpha-alumina supports 10-60 minute of the present invention is flooded to be less than the condition of 10mmHg in vacuum with gained dipping solution under, drain, in the temperature range of 200-500 DEG C, 2-120 minute is kept, preferred 2-60 minute, to activate in air or inert gas.Also can replace silver nitrate with silver oxide, silver oxalate also can not analyse filter, direct and organic amine complexing, then impregnated carrier.
The present invention also provides above-mentioned carrier, carrier prepared by said method or above-mentioned silver catalyst to produce the application in oxirane at ethylene.The stable performance of the silver catalyst be made up of carrier of the present invention, and there is higher activity and selectivity, be specially adapted to the reaction that ethylene produces oxirane.
Accompanying drawing explanation
Fig. 1 is the XRD Diffraction scans collection of illustrative plates of the compound Zirconium oxide used in comparative example 6 and embodiment 2,4 carrier preparation process;
Fig. 2 is the XRD Diffraction scans collection of illustrative plates of the compound Zirconium oxide used in carrier preparation process in embodiment 1,3,5 and 6.
Detailed description of the invention
The mensuration of catalyst performance:
Various silver catalyst laboratories of the present invention microreactor evaluating apparatus tests its activity and selectivity.The reactor used in microreactor evaluating apparatus is the stainless steel reaction pipe of internal diameter 4mm, and 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 activity and selectivity that the present invention adopts is as follows:
METHOD FOR CONTINUOUS DETERMINATION reactor inlet and exit gas composition after above-mentioned reaction condition is reached when stable.Measurement result calculates selective as follows after carrying out volume contraction correction:
Selective S = ΔEO ΔEO + 0.5 × Δ CO 2 × 100 %
Wherein Δ EO is reactor outlet gas and inlet gas ethylene oxide concentration difference, 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.
The present invention is described further below in conjunction with embodiment, but scope of the present invention is not limited to these embodiments.It should be noted that, the compound Zirconium oxide used in the carrier preparation of following examples is inherently containing certain tetragonal phase structure, described as follows 5% and 95% two kind, but the content of tetragonal phase of compound Zirconium oxide raw material can not be identical with the compound Zirconium oxide content of tetragonal phase in the vector product after roasting.Generally, in compound Zirconium oxide raw material content of tetragonal phase height then in vector product content of tetragonal phase high; If but the compound Zirconium oxide raw material content of tetragonal phase added is low, or even its content of tetragonal phase is zero, in vector product after certain technique also can compound Zirconium oxide content of tetragonal phase higher; Such as described technique is the alkaline earth metal component of the certain content of interpolation in the present invention.
Compound Zirconium oxide raw material used in following embodiment obtains by purchase, and wherein in Fig. 1, XRD spectra corresponding compound Zirconium oxide is that the thin zirconia ceramics powder of TZP makes its content of tetragonal phase drop to 5% and obtain after Overheating Treatment.
Carrier comparative example 1
By 50-500 object three water Al 2o 3400g, crosses the vacation one water Al of 200 mesh sieves 2o 385g, ammonium fluoride 8g puts into blender and mixes, and proceeds in kneader, adds 20 % by weight aqueous solution of nitric acid 90 milliliters, 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 at 80-120 DEG C, drying 2 hours, makes free water content be reduced to less than 10 % by weight, obtain green compact.Then green compact are put into electric furnace, be elevated between 1200 ~ 1400 DEG C from room temperature through 30 hours, and constant temperature 2 hours at such high temperatures, obtain white α-Al 2o 3support samples, is called comparison vehicle 1.
Carrier comparative example 2
The preparation of comparison vehicle 2 is similar to the preparation of comparison vehicle 1, only " ammonium fluoride 8g " in carrier comparative example 1 is changed into " ammonium fluoride 8g and ZrO 21.0g ".
Carrier comparative example 3
The preparation of comparison vehicle 3 is similar to the preparation of comparison vehicle 1, only " ammonium fluoride 8g " in carrier comparative example 1 is changed into " ammonium fluoride 8g, CeO 210g and ZrO 210g ".
Carrier comparative example 4
The preparation of comparison vehicle 4 is similar to the preparation of comparison vehicle 1, only " ammonium fluoride 8g " in carrier comparative example 1 is changed into " ammonium fluoride 8g, BaSO 41g ".
Carrier comparative example 5
The preparation of comparison vehicle 5 is similar to the preparation of comparison vehicle 1, only " ammonium fluoride 8g " in carrier comparative example 1 is changed into " ammonium fluoride 8g, ZrO 21g and BaSO 41g ".
Carrier comparative example 6
The preparation of comparison vehicle 6 is similar to the preparation of comparison vehicle 1, only " ammonium fluoride 8g " in carrier comparative example 1 is changed into " (its structural formula is: ZrCe for ammonium fluoride 8g and compound Zirconium oxide 0.05o 2.010, tetragonal phase content is 5 % by weight, and accompanying drawing 1 is shown in by monoclinic crystal phase content > 90 % by weight, XRD Diffraction scans collection of illustrative plates) and 1g ".
Carrier embodiment 1
The preparation of invention carrier 1 is similar to the preparation of comparison vehicle 1, only " ammonium fluoride 8g " in carrier comparative example 1 is changed into " (its structural formula is: ZrY for ammonium fluoride 8g, compound Zirconium oxide 0.03ce 0.04o 2.125, tetragonal phase content is shown in accompanying drawing 2 higher than 95 % by weight, XRD Diffraction scans collection of illustrative plates) 1g and BaSO 41g ".
Carrier embodiment 2
The preparation of invention carrier 2 is similar to the preparation of comparison vehicle 1, only " ammonium fluoride 8g " in carrier comparative example 1 is changed into " (its structural formula is: ZrCe for ammonium fluoride 8g, compound Zirconium oxide 0.05o 2.010, tetragonal phase content is 5 % by weight, and accompanying drawing 1 is shown in by monoclinic crystal phase content > 90 % by weight, XRD Diffraction scans collection of illustrative plates) 1g and BaSO 41g ".
Carrier embodiment 3
The preparation of invention carrier 3 is similar to the preparation of comparison vehicle 1, only " ammonium fluoride 8g " in carrier comparative example 1 is changed into " (its structural formula is: ZrY for ammonium fluoride 8g, compound Zirconium oxide 0.03ce 0.04o 2.125, tetragonal phase content is shown in accompanying drawing 2 higher than 95 % by weight, XRD Diffraction scans collection of illustrative plates) 20g and BaSO 410g ".
Carrier embodiment 4
The preparation of invention carrier 4 is similar to the preparation of comparison vehicle 1, only " ammonium fluoride 8g " in carrier comparative example 1 is changed into " (its structural formula is: ZrCe for ammonium fluoride 8g, compound Zirconium oxide 0.05o 2.010, tetragonal phase content is 5 % by weight, and accompanying drawing 1 is shown in by monoclinic crystal phase content > 90 % by weight, XRD Diffraction scans collection of illustrative plates) 20g and BaSO 410g ".
Carrier embodiment 5
The preparation of invention carrier 5 is similar to the preparation of comparison vehicle 1, only " ammonium fluoride 8g " in carrier comparative example 1 is changed into " (its structural formula is: ZrY for ammonium fluoride 8g, compound Zirconium oxide 0.03ce 0.04o 2.125, tetragonal phase content is shown in accompanying drawing 2 higher than 95 % by weight, XRD Diffraction scans collection of illustrative plates) 1g and Mg (NO 3) 23.5g ".
Carrier embodiment 6
The preparation of invention carrier 6 is similar to the preparation of comparison vehicle 1, only " ammonium fluoride 8g " in carrier comparative example 1 is changed into " (its structural formula is: ZrY for ammonium fluoride 8g, compound Zirconium oxide 0.03ce 0.04o 2.125, tetragonal phase content is shown in accompanying drawing 2 higher than 95 % by weight, XRD Diffraction scans collection of illustrative plates) 1g and Sr (AC) 21.5g ".
Its crushing strength, water absorption rate, specific surface and pore volume etc. are measured respectively to above-mentioned comparison vehicle 1-6 and invention carrier 1-6, the results are shown in table 1 and table 2.In the present invention, the crushing strength of carrier refers to side crush intensity, is measured by intensity of pressure instrument; Specific area adopts nitrogen physisorption BET method to measure; Water absorption rate is measured by densimetry; And pore volume adopts pressure mercury method to measure.
Table 1
Comparison vehicle 1 Comparison vehicle 2 Comparison vehicle 3 Comparison vehicle 4 Comparison vehicle 5 Comparison vehicle 6
Crushing strength (N/ grain) 76 71 43 86 74 55
Water absorption rate (%) 51 59 60 52 53 53
Specific area (rice 2/ gram) 0.99 1.26 1.13 1.02 1.16 1.02
Pore volume (ml/g) 0.51 0.51 0.55 0.52 0.54 0.50
A 99 98 97 99 98 98
B 90.7 91.1 90.6 90.9 90.8 90.7
Zirconium is content (wt%) in the carrier 0 0.1 1 0 0.1 0.1
C 0 0 0 0 0 0.1
D 0 0 0 0 0 8
Cerium is content (wt%) in the carrier 0 0 1.5 0 0 Trace
Barium is content (wt%) in the carrier 0 0 0 0.1 0.1 0
Table 2
Invention carrier 1 Invention carrier 2 Invention carrier 3 Invention carrier 4 Invention carrier 5 Invention carrier 6
Crushing strength (N/ grain) 87 71 113 65 96 91
Water absorption rate (%) 53 53 54 55 52 55
Specific area (rice 2/ gram) 1.27 1.34 1.02 1.42 1.00 1.02
Pore volume (ml/g) 0.53 0.54 0.51 0.55 0.52 0.52
A 98 98 91 90 98 98
B 90.9 91.2 91.7 91.3 91.5 91.4
C 0.1 0.1 5 5 0.1 0.1
D 95 12 95 12 95 95
E Ba 0.1 Ba 0.1 Ba 2.5 Ba 2.5 Mg 0.1 Sr 0.1
Note: in table 1 and table 2, A ~ E is expressed as follows meaning, A respectively: aluminium oxide content in the carrier (% by weight); B: Alpha-alumina accounts for the content (% by weight) of aluminium oxide total amount; C: compound Zirconium oxide accounts for the content (% by weight) of carrier with the total amount of its metal; D: in vector product, tetragonal phase compound Zirconium oxide accounts for the content (% by weight) of compound Zirconium oxide gross weight; E: alkaline-earth metal content in the carrier (% by weight).
COMPARATIVE CATALYST EXAMPLE 1-6 and CATALYST EXAMPLE 1-6
310g ethylenediamine is added, 110g monoethanolamine in the glass flask that band stirs, and 365g deionized water, obtain mixed liquor.Slowly added in gained mixed liquor by silver oxalate under stirring, temperature remains on 35-40 DEG C, and silver oxalate is all dissolved, and the addition of silver oxalate makes final obtained maceration extract argentiferous 24 % by weight.Add 3.0g cesium nitrate, 2.0g strontium acetate, and 4.5g ammonium perrhenate, then add deionized water and make solution gross mass reach 2000g, make maceration extract, stand-by.
Get comparison vehicle 1-6 and invention carrier 1-6 100g separately, put into the container that can vacuumize respectively.Be evacuated to low vacuum in 10mmHg, put into above maceration extract wherein, submergence carrier, keep 30 minutes.Leaching afterwards removes unnecessary maceration extract.Heated 5 minutes in the air stream of 250 DEG C by carrier after dipping, cooling, namely make ethylene oxide silver catalyst, they are respectively comparative catalyst 1-6 and invention catalyst 1-6.
Analyze the respective silver content of the comparative catalyst 1-6 made and invention catalyst 1-6 and auxiliary agent content, wherein each content is all in metal.
Use microreactor evaluating apparatus to measure the activity and selectivity of each catalyst sample under the described process conditions of " mensuration of catalyst performance " part above, result of the test lists in table 3.
Table 3
* note: reaction temperature is that accumulative EO output reaches 400T/M 3value during catalyst, selectively gets accumulative EO output and reaches 400T/M 3mean value during catalyst.
From the data of table 1 ~ 3, the loading type silver catalyst that carrier of the present invention is made, when the oxidation epoxy ethane for catalyzed ethylene, selectively obviously to be improved.

Claims (20)

1. a carrier for silver catalyst, this carrier comprises following component:
The A1 of a, 85 ~ 99.9wt% 2o 3, wherein Alpha-alumina is>=85wt% based on aluminium oxide gross weight;
B, compound Zirconium oxide containing zirconium and metal M, wherein metal M is be selected from one or more elements in the periodic table of elements II A race, III B race and IV B race element except zirconium, and in this compound Zirconium oxide, the total amount of metallic element accounts for total weight of carrier content is 0.01-10wt%;
The alkaline-earth metal of c, one or more periodic table of elements II A race and/or alkaline earth metal compound; It is 0.01-5wt% that its metallic element weight accounts for total weight of carrier content,
Wherein, in vector product, tetragonal phase compound Zirconium oxide accounts for more than the 10wt% of compound Zirconium oxide gross weight.
2. carrier according to claim 1, is characterized in that, in components b, the mol ratio of zirconium and metal M is 1:0.01-0.3.
3. carrier according to claim 1, is characterized in that, in components b, the mol ratio of zirconium and metal M is 1:0.05-0.2, and in compound Zirconium oxide, the total amount of metallic element accounts for total weight of carrier content is 0.1-7wt%; In amount of component b, metallic element weight accounts for total weight of carrier content is 0.1-3wt%.
4. carrier according to claim 1, is characterized in that, in described components b, III B race metallic element is selected from yttrium, cerium and lanthanum; In described amount of component b, II A race alkaline-earth metal is selected from strontium and barium.
5. carrier according to claim 1, is characterized in that, the crushing strength >20N/ grain of carrier, and specific area is 0.2-2.0m 2/ g, water absorption rate>=30%, and pore volume is 0.35-0.85mlg.
6. carrier according to claim 5, is characterized in that, crushing strength is 30-150N/ grain, and specific area is 0.5-1.8m 2/ g, water absorption rate>=40%, and pore volume is 0.40-0.8ml/g.
7. prepare a method for carrier as claimed in claim 1, comprise the steps:
Step I, forms the mixture comprising following component:
I, 50 order-500 object three water A1 2o 3;
Ii, be greater than the false water A1 of 200 objects 2o 3; Wherein said three water A1 2o 3with a false water A1 2o 3weight ratio be 1 ~ 16:1;
Iii, described compound Zirconium oxide, the presoma that can be converted into this compound Zirconium oxide or its combination;
Iv, alkaline-earth metal and/or alkaline earth metal compound;
V, be the mineralizer of 0.01-5.0wt% based on the gross weight of component i and ii;
Vi, binding agent; And
Vii, appropriate water;
Its roasting, by shaping and dry for the mixture obtained in step I, is then carrier finished product by step II.
8. method according to claim 7, is characterized in that, three water A1 described in component ii in step I 2o 3with a false water A1 2o 3weight ratio be 1 ~ 6:1.
9. method according to claim 7, is characterized in that, in step I, component v is be the mineralizer of 1-4wt% based on the gross weight of component i and ii.
10. according to the method in claim 7-9 described in any one, it is characterized in that, one or more in the mixture of the presoma selected among zirconium of the described compound Zirconium oxide in component iii and the oxide of metal M, sulfate, acetate, nitrate, carbonate or oxalates; Alkaline earth metal compound in component iv is selected from its oxide, sulfate, acetate, nitrate, carbonate and oxalates; Described mineralizer in component v is fluoride.
11. methods according to claim 10, is characterized in that, the described mineralizer in component v be selected from hydrogen fluoride, ammonium fluoride, aluminum fluoride, magnesium fluoride and ice crystal one or more.
12., according to the method in claim 7-9 described in any one, is characterized in that, the described binding agent in component vi is acid.
13. methods according to claim 12, is characterized in that, the described binding agent in component vi is selected from nitric acid and acetic acid.
14. methods according to claim 12, is characterized in that, partly or entirely replace the described false water A1 in the described acid in component vi and component ii with Alumina gel 2o 3.
15. preparation methods according to claim 7, is characterized in that, the sintering temperature in step II is 1000-1600 DEG C, and roasting time is 1-24 hour.
16. methods according to claim 15, is characterized in that, the sintering temperature in step II is 1200-1400 DEG C.
17. 1 kinds of silver catalysts, this catalyst comprises the carrier that according to any one of carrier according to any one of claim 1-6 or claim 7-9 prepared by method, and deposition silver on this carrier, and one or more in the collaborative auxiliary agent of optional alkali metal, alkaline-earth metal, rhenium and rhenium; Wherein, the collaborative auxiliary agent of described rhenium be selected from chromium, molybdenum, tungsten and boron one or more.
18. silver catalysts according to claim 17, is characterized in that, based on the gross weight of silver catalyst, silver content is 1-30wt%; Alkali metal content is 5-2000ppm; Alkali earth metal content is 5-2000ppm; Rhenium constituent content is 5-1500ppm; The collaborative auxiliary element content of rhenium is 5-1000ppm.
19. silver catalysts according to claim 18, is characterized in that, based on the gross weight of silver catalyst, silver content is 5-26wt%; Alkali metal content is 10-1500ppm; Alkali earth metal content is 10-1200ppm; Rhenium constituent content is 10-1000ppm; The collaborative auxiliary element content of rhenium is 10-500ppm.
20. carriers according to any one of claim 1-6 or carrier that any one of claim 7-9 prepared by method or silver catalyst according to claim 17 produce the application in oxirane at ethylene.
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CN106955700B (en) * 2016-01-08 2019-08-20 中国石油化工股份有限公司 A kind of preparation method and applications of the silver catalyst for alkene epoxidation
CN108607618B (en) * 2016-12-09 2020-12-18 中国石油化工股份有限公司 Alumina carrier, silver catalyst prepared from carrier and application of silver catalyst
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
CN110354841A (en) * 2018-03-26 2019-10-22 中国石油化工股份有限公司 Silver catalyst alpha-alumina supports and preparation method thereof and ethylene epoxidizing silver catalyst and application
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