CN103357441A - Silver catalyst carrier and preparation method thereof as well as catalyst prepared by silver catalyst carrier and application thereof - Google Patents
Silver catalyst carrier and preparation method thereof as well as catalyst prepared by silver catalyst carrier and application thereof Download PDFInfo
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- CN103357441A CN103357441A CN2012100870797A CN201210087079A CN103357441A CN 103357441 A CN103357441 A CN 103357441A CN 2012100870797 A CN2012100870797 A CN 2012100870797A CN 201210087079 A CN201210087079 A CN 201210087079A CN 103357441 A CN103357441 A CN 103357441A
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Abstract
The invention provides a silver catalyst carrier. The carrier comprises the following components in percentage by weight: 85-99.9 percent of Al2O3, compound zirconium oxide containing zirconium and metal M, and one or more group IIA alkaline earth and/or compounds thereof of the periodic table of elements, wherein alpha-alumina is more than or equal to 85 percent of the total weight of the alumina; the metal M is one or more elements of group IIA, group IIIB and group IVB except zirconium in the periodic table of elements, and the total weight of metal elements in the compound zirconium oxide is 0.01-10 percent of the total weight of the carrier by weight; the weight of the metal elements of the group IIA alkaline earth and/or compounds is 0.01-5 percent of the total weight of the carrier. The silver catalyst prepared from the carrier shows excellent activity and selectivity in the process of producing ethylene oxide by ethylene oxidization, and the selectivity of the silver catalyst is remarkably improved. Furthermore, the invention also relates to a method for preparing the carrier, a silver catalyst prepared by the carrier and application thereof.
Description
Technical field
The present invention relates to a kind of carrier for silver-containing catalyst, its preparation method and application thereof, more particularly the present invention relates to a kind ofly produce oxirane with alumina support, its preparation method of silver catalyst and the silver catalyst that is made by this carrier for ethylene.
Background technology
Ethylene mainly generates oxirane under the silver catalyst effect, side reaction occurs simultaneously generate carbon dioxide and water etc.The main performance index of silver catalyst comprises its activity, selective and stable.Active reaction temperature required when referring to generally that process for ethylene oxide production reaches certain reaction load wherein; Desired reaction temperature is lower, and the activity of catalyst is higher.Conversion of ethylene becomes the ratio of the overall reaction molal quantity of the molal quantity of oxirane and ethene in selectively referring to react.Stable then be the fall off rate of activity and selectivity, the fall off rate more stability of small catalyst is just better.The silver catalyst that uses high activity, high selectivity and have good stability in the process of ethylene production oxirane can be increased economic efficiency greatly, therefore makes the main direction that such silver catalyst is silver catalyst research.The performance of silver catalyst has the important relationship except composition and the preparation method with catalyst, and performance of the carrier that also uses 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 (such as aluminium oxide) and auxiliary agent to as described in this two processes on the carrier.Its carrier is generally selected the less Alpha-alumina of specific area.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 of preparation alumina support is the hydrate of aluminium oxide, i.e. aluminium hydroxide, and the hydrated alumina dehydration can produce Louis (L) soda acid center, and these L acid sites are easy to suction and change proton (B) soda acid center into.The crystal formation kind of aluminium oxide is a lot, and in addition impurity and moisture impact more or less causes the surface physics of aluminium oxide, chemical property all very complicated.α-the Al that selects for silver catalyst
2O
3Although its surface only has the seldom soda acid center of amount, their meetings and active component acting in conjunction, impelling conversion of ethylene is oxirane.
Carrier need to provide certain area load active component, and with the active component Uniform Dispersion thereon, this has just proposed very high requirement to the pore structure of carrier.The hole of alumina support can be divided into three types: the first, and primary particle intercrystalline hole mainly is the dewatering hole of alumina raw material crystal grain, is slit between the parallel-plate face of 1-2nm size substantially; The second, hole between the alumina raw material offspring, effusion and crystalline phase variation with moisture in roasting change, and are the hole more than the tens nanometer; The third, the defective hole and the macropore that produce when pore creating material and carrier moulding.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 pore structure and the physical property of silver catalyst carrier, and then affect the performance of catalyst.
In general, the main method of preparation silver catalyst carrier is, binding agent and various additives etc. will be added in the alumina powder raw material, even through batch mixing and kneading, then extrusion molding is difform base substrate, such as Raschig ring, spheric granules, porous cylindrical, the shape of a saddle etc., the final high temperature sintering is made the alpha-alumina supports product of porous heat-resistant, specifically can be referring to patent documentations such as US5063195, US5703001 and US5801259.
Add auxiliary agent toward contact in the preparation process of silver catalyst carrier, in order to improve the performance of carrier.Propose such as US6787656 and US5145824: in alumina support, add the performance that zirconium (Zr) can improve carrier; And Chinese patent Granted publication CN1126597C and CN1130257C claim: add the performance that cerium (Ce) or zirconium colloidal sol can improve carrier in alumina support; Patent CN02160081 proposes to add the silver catalyst carrier that the compound of heavy alkaline-earth metal is made in the alumina powder raw material, load active component is made silver catalyst again, its activity, selectively all is improved.
Above-mentioned these methods are also very limited to the improvement that the activity and selectivity of carrier property and catalyst brings, therefore this area still needs carrier and manufacture method thereof are improved, be beneficial to produce the better silver catalyst of performance, especially selective better catalyst.
Summary of the invention
Situation in view of above-mentioned prior art, the 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 the alpha-alumina supports, the loading type silver catalyst of being made by this carrier is selectively obviously improved when being used for the oxidation epoxy ethane of catalyzed ethylene.
Therefore, the purpose of this invention is to provide a kind of alumina support, in the process of ethylene production oxirane, demonstrate good activity and selectivity by its silver catalyst of making.
The invention provides a kind of carrier of silver catalyst, this carrier comprises the Al of following component: a, 85～99.9wt%
2O
3, wherein Alpha-alumina based on the aluminium oxide gross weight is 〉=85wt%; B, contain the compound Zirconium oxide of zirconium and metal M, wherein metal M is one or more elements that are selected from periodic table of elements IIA family, IIIB family and the IVB family element except zirconium, and to account for total weight of carrier content be 0.01-10wt% to the total amount of metallic element in this compound Zirconium oxide; Alkaline-earth metal and/or its compound with c, one or more periodic table of elements IIA family; It is 0.01-5wt% that its metallic element weight accounts for total weight of carrier content.
For example, compound Zirconium oxide of the present invention is the composite oxides of zirconium dioxide and ceria, zirconium dioxide and yttria or zirconium dioxide and ceria and yttria formation.
In carrier of the present invention, aluminium oxide should account for the overwhelming majority; Usually, based on the gross weight of carrier, alumina content is 85wt% at least.In addition, with the raw alumina roasting time, be not that 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%, preferred 90wt% at least.Alpha-alumina supports of the present invention need 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 is so that the loading type silver catalyst of being made by this carrier produces improved effect when the catalyzed ethylene epoxy ethane, and this comprises the activity and selectivity that improves catalyst.
The mol ratio of zirconium and metal M is 1 in the preferred components b of the present invention: 0.01-0.3, and more preferably its mol ratio is 1: 0.05-0.2, to account for total weight of carrier content be 0.1-7wt% to the total amount of metallic element in the compound Zirconium oxide; To account for total weight of carrier content be 0.1-3wt% to metallic element weight in the amount of component b.
In one embodiment of the invention, the compound Zirconium oxide of tetragonal phase accounts for more than the 10wt% of compound Zirconium oxide gross weight in the preferred vector product.Among the present invention, compound Zirconium oxide exists with in the following crystalline phase one or more: four directions (quadrature), cube and monoclinic phase; Wherein advantageously four directions (quadrature) crystalline phase to account for the content of compound Zirconium oxide gross weight The more the better, the carrier crushing strength that so prepares is higher.
In the present invention, the IIA family alkaline-earth metal of amount of component b act as, and it can be used as M metal and the compound Zirconium oxide of the common formation of zirconium in the components b, thereby more is conducive to the formation of (quadrature) crystalline phase compound Zirconium oxide in four directions in the vector product; Its effect is that also its corresponding catalyst improves at the catalytic selectivity that ethylene prepares in the oxirane.
M is one or more metals that are selected from the IIIB family, more preferably yttrium, cerium and lanthanum in the preferred components b of the present invention; IIA family alkaline-earth metal is strontium or barium in the described amount of component b, preferred barium.
The carrier crushing strength that preferred the present invention prepares＞20N/ grain, 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 the 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 for preparing above-mentioned carrier, comprises the steps that step I forms the mixture that comprises following component: i, 50 orders-500 purpose, three water Al
2O
3Ii, greater than the false water Al of 200 purposes
2O
3The weight ratio of wherein said gibbsite and a false water aluminium oxide is 1～16: 1, is preferably 1～6: 1; Total consumption of described gibbsite and a false water aluminium oxide should be so that the final carrier finished product that obtains comprises at least Al of 85wt%
2O
3Iii, described compound Zirconium oxide, the presoma that can be converted into this compound Zirconium oxide or its combination; Its consumption should be so that the carrier finished product gross weight content that the total amount of metallic element accounts for final acquisition in the described compound Zirconium oxide be the 0.01-10 % by weight, preferred 0.1-7 % by weight; Iv, alkaline-earth metal and/or its compound; Its consumption should be so that alkaline earth metal content accounts for the carrier finished product gross weight content of final acquisition is 0.01-5wt%, preferred 0.1-3wt%; V, be 0.01-5.0wt% based on the gross weight of component i and ii, the mineralizer of preferred 1-4wt%; Vi, binding agent; And vii, an amount of water; Step II with mixture moulding and the drying that obtains among the step I, is the carrier finished product with its roasting then.
Component i gibbsite among the present invention is the pressed powder form usually; Component ii also is the pressed powder form usually.
The compound Zirconium oxide that uses as component iii is known, can commercially obtain, for example for 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 that contains yttrium and/or cerium), zirconia YSZ powder (YSZ means the stable zirconia of yttrium) etc.
Compound Zirconium oxide as component iii mentions also can prepare by methods known in the art.For example can use any presoma preparation that can be converted into the compound Zirconium oxide of the present invention, such as the method preparation of mentioning by patent CN1562887A, CN1528706A and CN1620409A etc.
In carrier preparation method of the present invention, the mixture of the excellent selected among zirconium of the presoma of the described compound Zirconium oxide of component iii and metal M, 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; The described alkaline earth metal compound of component iv is selected from its oxide, sulfate, acetate, nitrate, carbonate and oxalates; Preferred heavy alkaline-earth metal and/or its compound of using, the more preferably compound of barium or baric, as: barium metal, barium monoxide, barium sulfate, barium nitrate, brium carbonate or its mixture etc.; The described mineralizer of component v is fluoride, is preferably inorganic fluoride, more preferably is selected from hydrogen fluoride, ammonium fluoride, aluminum fluoride, magnesium fluoride and the ice crystal one or more, is particularly preferably ammonium fluoride.
In carrier preparation method of the present invention, the adding of mineralizer v is the transformation of crystal for accelerated oxidation aluminium.
In carrier preparation method of the present invention, also need use component vi binding agent, as add acid as bonding agent, vacation one water aluminium oxide in it and the mixture generates aluminium colloidal sol, each component is bonded together, becomes plastic paste, but for example become the paste of extrusion molding.Comprise acid in the used bonding agent, such as nitric acid, formic acid, acetic acid, propionic acid and/or hydrochloric acid etc., preferred nitric acid and/or acetic acid.When described acid was aqueous solution of nitric acid, the weight ratio of nitric acid and water was 1: 1.25～10, preferred 1: 2～8.In addition, available aluminium sol-fraction or all replace the described acid of component vi and the described false water Al of component ii
2O
3The consumption of binding agent is conventional, as long as each component can be bonded together, and the formation paste gets final product.Usually, the consumption of binding agent is 15-60wt%, and preferred 15-50wt% is based on the gross weight of component i-v.
After each component mixing among the step I, usually obtain paste.With the moulding of gained paste, preferred extrusion molding obtains formed body, i.e. the carrier blank.This formed body can be dried to below moisture 10 % by weight, and baking temperature is 80-200 ℃, and be controlled at 1-24 hour according to moisture drying time.The shape of gained formed body can be annular, sphere, cylindricality or porous column shape, or other shape.In order to make carrier that enough intensity and good surface property be arranged, dried formed body is usually 1000-1600 ℃, preferred 1200-1400 ℃ of lower roasting.Under sintering temperature, usually carrier is kept 1-24 hour.Make aluminium oxide substantially all be converted into α-Al by roasting
2O
3, obtain thus the porous alpha-alumina supports.
Support according to the present invention preparation method makes a kind of porous alpha-alumina supports 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 is that 7-9mm, internal diameter are the circular particle of single hole of 3-6mm.
The present invention also provides a kind of silver catalyst, and this catalyst comprises the carrier of above-mentioned carrier or said method preparation, and is deposited on the silver on this carrier, and in the collaborative auxiliary agent of optional alkali metal, alkaline-earth metal, rhenium and rhenium one or more; Wherein, described alkali metal is to be selected among Li, Na, K, Rb and the Cs one or more; Preferred caesium and/or potassium most preferably are caesium; Described alkaline-earth metal is to be selected among Mg, Ca, Sr and the Ba one or more, preferred strontium and/or barium; The collaborative auxiliary agent of described rhenium is to be selected from chromium, molybdenum, tungsten and the boron one or more.
Silver catalyst of the present invention can prepare in the usual way, for example 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 before dipping silver, be applied on the porous alpha-alumina supports in the load silver or after the load silver, or is immersed in after silver compound is reduced on the porous alpha-alumina supports independently of one another; Preferably load in load silver.
In silver catalyst of the present invention, silver is dispersed on the surface of porous infusibility alumina support and in the 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; The 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, with the solution impregnation porous alpha-alumina supports of the present invention of the collaborative auxiliary agent of the silver compound, organic amine that contain q.s, optional alkali metal promoter, optional base earth metal promoter and optional rhenium auxiliary agent and optional rhenium; Second step, the 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, used silver compound can be for being suitable for preparing any silver compound of 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, used organic amine compound can be for being suitable for preparing any organic amine compound of 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, preferably use pyridine, butylamine, ethylenediamine, 1,3-propane diamine, monoethanolamine or its mixture, for example mixture of ethylenediamine and monoethanolamine.
In order to prepare catalyst of the present invention, the optional alkali metal promoter that uses can be compound (such 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, in the compound that the optional base earth metal promoter that uses can be magnesium, calcium, strontium and barium one or more, one or more in the oxide of element, oxalates, sulfate, acetate and the nitrate as described, the compound of preferred barium and/or the compound of strontium are such as barium acetate and/or strontium acetate.
In order to prepare catalyst of the present invention, the optional rhenium auxiliary agent that uses 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 the dipping solution except silver compound, organic amine, optional alkali metal promoter, optional base earth metal promoter and optional rhenium auxiliary agent, the coassist agent that can also add the rhenium auxiliary agent is with the activity of further improvement gained silver catalyst, selective and stable.The coassist agent of the rhenium auxiliary agent among the present invention can be to be selected from chromium, molybdenum, tungsten and the boron compound one or more.
In impregnation steps, for guaranteeing all even abundant loads of silver, carrier preferably vacuumizes in advance.
After porous alpha-alumina supports dipping argentiferous maceration extract, the leaching maceration extract, then in air or inert gas to step 3) in activate through the carrier of dipping.For this reason, can will in 180-700 ℃, preferred 200-500 ℃ moving air or the air-flows such as inert gas such as nitrogen, argon gas, activate soak time at least 2 minutes usually, for example 2-120 minute, preferred 2-60 minute through the carrier of dipping.For guaranteeing that catalyst has higher activity, this activation temperature should not be higher than 500 ℃.
In a preferred embodiment of preparation silver catalyst of the present invention, at first make the aqueous solution and ammonium oxalate or the oxalic acid aqueous solution reaction of silver nitrate, separate out the silver oxalate precipitation, after the filtration, wash with deionized water, until without nitrate ion, after drying, silver oxalate is dissolved in organic amine such as pyridine, butylamine, ethylenediamine, 1, in the aqueous solution of 3-propane diamine, monoethanolamine or its mixture, add each auxiliary agent, be made into dipping solution; Then with the gained dipping solution vacuum less than the condition of 10mmHg under dipping porous alpha-alumina supports of the present invention 10-60 minute, drain, in air or inert gas, in 200-500 ℃ temperature range, kept 2-120 minute, preferred 2-60 minute, to activate.Also available silver oxide replaces silver nitrate, and silver oxalate also can not analysed filter, direct and organic amine complexing, then impregnated carrier.
The present invention also provides above-mentioned carrier, the carrier of said method preparation or the above-mentioned application of silver catalyst in ethylene production oxirane.The stable performance of the silver catalyst of being made by carrier of the present invention, and have higher activity and selectivity, be specially adapted to the reaction that ethylene is produced oxirane.
Description of drawings
Fig. 1 is the XRD diffraction scanning spectra of employed compound Zirconium oxide in Comparative Examples 6 and embodiment 2, the 4 carrier preparation process;
Fig. 2 is embodiment 1,3, the XRD diffraction scanning spectra of employed compound Zirconium oxide in the carrier preparation process in 5 and 6.
The specific embodiment
The mensuration of catalyst performance:
Various silver catalyst of the present invention is tested its activity and selectivity with laboratory microreactor evaluating apparatus.The reactor that uses in the microreactor evaluating apparatus is the stainless steel reaction pipe of internal diameter 4mm, and reaction tube places heating jacket.The admission space of catalyst is 1ml, and inert filler is arranged at the 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:
When stable reach above-mentioned reaction condition after METHOD FOR CONTINUOUS DETERMINATION reactor inlet and exit gas form.Measurement result carries out calculating as follows after volume contraction is proofreaied and correct selective:
Selectively
Wherein Δ EO is that ethylene oxide concentration is poor in reactor outlet gas and the inlet gas, Δ CO
2Be that gas concentration lwevel is poor in reactor outlet gas and the inlet gas, get the result of the test of the average of 10 groups of above test datas as the same day.
The present invention is described further below in conjunction with embodiment, but scope of the present invention is not limited to these embodiment.Need to prove, the compound Zirconium oxide itself that uses in the carrier preparation of following examples just contains certain tetragonal phase structure, described as follows 5% and 95% two kind, but the compound Zirconium oxide Tetragonal content in the vector product after the Tetragonal content of compound Zirconium oxide raw material and the roasting can be not identical.Generally speaking, in the compound Zirconium oxide raw material Tetragonal content height then in the vector product Tetragonal content high; If but the compound Zirconium oxide raw material Tetragonal content that adds is low, or even its Tetragonal content be zero, also can compound Zirconium oxide Tetragonal content in through vector product after certain technique higher; For example described technique is the alkaline earth metal component of the certain content of interpolation among the present invention.
Compound Zirconium oxide raw material used among the following embodiment obtains by purchase, wherein among Fig. 1 the corresponding compound Zirconium oxide of XRD spectra be the thin zirconia ceramics powder of TZP through after the Overheating Treatment so that its Tetragonal content decrease is 5% to obtain.
Carrier Comparative Examples 1
With 50-500 purpose three water Al
2O
3400g, excessively the vacation one water Al of 200 mesh sieves
2O
385g, ammonium fluoride 8g puts into blender and mixes, and changes in the kneader, adds 90 milliliters of 20 % by weight aqueous solution of nitric acid, but is kneaded into 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 drying is 2 hours under 80-120 ℃, and free water content is reduced to below 10 % by weight, obtains green compact.Then green compact are put into electric furnace, were elevated between 1200～1400 ℃ from room temperature through 30 hours, and under this high temperature constant temperature 2 hours, obtain white α-Al
2O
3Support samples is called comparison vehicle 1.
Carrier Comparative Examples 2
The preparation of comparison vehicle 2 is similar to the preparation of comparison vehicle 1, only " ammonium fluoride 8g " in the carrier Comparative Examples 1 is changed into " ammonium fluoride 8g and ZrO
21.0g ".
Carrier Comparative Examples 3
The preparation of comparison vehicle 3 is similar to the preparation of comparison vehicle 1, only " ammonium fluoride 8g " in the carrier Comparative Examples 1 is changed into " ammonium fluoride 8g, CeO
210g and ZrO
210g ".
Carrier Comparative Examples 4
The preparation of comparison vehicle 4 is similar to the preparation of comparison vehicle 1, only " ammonium fluoride 8g " in the carrier Comparative Examples 1 is changed into " ammonium fluoride 8g, BaSO
41g ".
Carrier Comparative Examples 5
The preparation of comparison vehicle 5 is similar to the preparation of comparison vehicle 1, only " ammonium fluoride 8g " in the carrier Comparative Examples 1 is changed into " ammonium fluoride 8g, ZrO
21g and BaSO
41g ".
Carrier Comparative Examples 6
The preparation of comparison vehicle 6 is similar to the preparation of comparison vehicle 1, only " ammonium fluoride 8g " in the carrier Comparative Examples 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, monoclinic crystal phase content＞90 % by weight, XRD diffraction scanning spectra is seen accompanying drawing 1) 1g ".
Carrier embodiment 1
The preparation of invention carrier 1 is similar to the preparation of comparison vehicle 1, only " ammonium fluoride 8g " in the carrier Comparative Examples 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 higher than 95 % by weight, and XRD diffraction scanning spectra is seen accompanying drawing 2) 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 the carrier Comparative Examples 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, monoclinic crystal phase content＞90 % by weight, XRD diffraction scanning spectra is seen accompanying drawing 1) 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 the carrier Comparative Examples 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 higher than 95 % by weight, and XRD diffraction scanning spectra is seen accompanying drawing 2) 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 the carrier Comparative Examples 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, monoclinic crystal phase content＞90 % by weight, XRD diffraction scanning spectra is seen accompanying drawing 1) 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 the carrier Comparative Examples 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 higher than 95 % by weight, and XRD diffraction scanning spectra is seen accompanying drawing 2) 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 the carrier Comparative Examples 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 higher than 95 % by weight, and XRD diffraction scanning spectra is seen accompanying drawing 2) 1g and Sr (AC)
21.5g ".
Above-mentioned comparison vehicle 1-6 and invention carrier 1-6 are measured respectively its crushing strength, water absorption rate, specific surface and pore volume etc., the results are shown in table 1 and table 2.In the present invention, the crushing strength of carrier refers to side crush intensity, measures 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 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 carrier | 0 | 0 | 1.5 | 0 | 0 | Trace |
| Barium is content (wt%) in 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 |
Annotate: A～E is expressed as follows respectively meaning in table 1 and the table 2, A: the content (% by weight) of aluminium oxide in carrier; 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 in the total amount of its metal; D: the compound Zirconium oxide of tetragonal phase accounts for the content (% by weight) of compound Zirconium oxide gross weight in the vector product; E: the content (% by weight) of alkaline-earth metal in carrier.
Catalyst Comparative Examples 1-6 and catalyst embodiment 1-6
Add the 310g ethylenediamine in the glass flask that band stirs, 110g monoethanolamine, and 365g deionized water obtain mixed liquor.Under stirring silver oxalate is slowly added in the gained mixed liquor, temperature remains on 35-40 ℃, and silver oxalate is all dissolved, and the addition of silver oxalate makes maceration extract argentiferous 24 % by weight that finally make.Add 3.0g cesium nitrate, 2.0g strontium acetate, and the 4.5g ammonium perrhenate, add again deionized water and make the solution gross mass reach 2000g, make maceration extract, stand-by.
Get separately 100g of comparison vehicle 1-6 and invention carrier 1-6, put into respectively the container that can vacuumize.Be evacuated to low vacuum in 10mmHg, to wherein putting into above maceration extract, the submergence carrier kept 30 minutes.Unnecessary maceration extract is removed in afterwards leaching.Carrier behind the dipping was heated 5 minutes in 250 ℃ air stream, and ethylene oxide silver catalyst is namely made in cooling, and they are respectively comparative catalyst 1-6 and invention catalyst 1-6.
Comparative catalyst 1-6 and invention catalyst 1-6 silver content and the auxiliary agent content separately made are analyzed, and wherein each content is all in metal.
Use the microreactor evaluating apparatus to measure the activity and selectivity of each catalyst sample under described process conditions of " mensuration of catalyst performance " part above, result of the test is listed in table 3.
Table 3
* annotate: reaction temperature is that accumulative total EO output reaches 400T/M
3Value during catalyst is selectively got accumulative total EO output and is reached 400T/M
3Mean value during catalyst.
By the data of table 1～3 as can be known, the loading type silver catalyst that carrier of the present invention is made is selectively obviously improved when being used for the oxidation epoxy ethane of catalyzed ethylene.
Claims (14)
1. the carrier of a silver catalyst, this carrier comprises following component:
The Al of a, 85～99.9wt%
2O
3, wherein Alpha-alumina based on the aluminium oxide gross weight is 〉=85wt%;
B, contain the compound Zirconium oxide of zirconium and metal M, wherein metal M is one or more elements that are selected from periodic table of elements IIA family, IIIB family and the IVB family element except zirconium, and to account for total weight of carrier content be 0.01-10wt% to the total amount of metallic element in this compound Zirconium oxide;
Alkaline-earth metal and/or its compound of c, one or more period of element Table II A family; It is 0.01-5wt% that its metallic element weight accounts for total weight of carrier content.
2. carrier according to claim 1 is characterized in that, the mol ratio of zirconium and metal M is 1 in the components b: 0.01-0.3.
3. carrier according to claim 1 is characterized in that, the mol ratio of zirconium and metal M is 1 in the components b: 0.05-0.2, and to account for total weight of carrier content be 0.1-7wt% to the total amount of metallic element in the compound Zirconium oxide; To account for total weight of carrier content be 0.1-3wt% to metallic element weight in the amount of component b.
4. carrier according to claim 1 is characterized in that, IIIB family metallic element is selected from yttrium, cerium and lanthanum in the described components b; IIA family alkaline-earth metal is selected from strontium and barium in the described amount of component b.
5. the described carrier of any one is characterized in that according to claim 1～4, and the crushing strength of carrier＞20N/ grain, specific area are 0.2-2.0m
2/ g, water absorption rate 〉=30%, and pore volume is 0.35-0.85ml/g; Preferred crush strength is the 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.
6. the described carrier of any one is characterized in that according to claim 1～4, and the compound Zirconium oxide of tetragonal phase accounts for more than the 10wt% of compound Zirconium oxide gross weight in the vector product.
7. one kind prepares such as the method for carrier as described in each among the claim 1-6, comprises the steps:
Step I forms the mixture that comprises following component:
I, 50 orders-500 purpose, three water Al
2O
3
Ii, greater than the false water Al of 200 purposes
2O
3
The weight ratio of wherein said gibbsite and a false water aluminium oxide is 1～16: 1, is preferably 1～6: 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 its compound;
V, be 0.01-5.0wt% based on the gross weight of component i and ii, the mineralizer of preferred 1-4wt%;
Vi, binding agent; And
Vii, an amount of water;
Step II with mixture moulding and the drying that obtains among the step I, is the carrier finished product with its roasting then.
8. preparation method according to claim 7, it is characterized in that, the presoma selected among zirconium of the described compound Zirconium oxide of component iii and the mixture of metal M, one or more in the mixture of the oxide of zirconium and metal M, sulfate, acetate, nitrate, carbonate or oxalates; Alkaline earth metal compound is selected from its oxide, sulfate, acetate, nitrate, carbonate and oxalates among the component iv; The described mineralizer of component v is fluoride, is preferably to be selected from hydrogen fluoride, ammonium fluoride, aluminum fluoride, magnesium fluoride and the ice crystal one or more.
9. preparation method according to claim 7 is characterized in that, the described binding agent of component vi is acid, preferably from nitric acid and acetic acid.
10. preparation method according to claim 9 is characterized in that, with the aluminium sol-fraction or all replace the described acid of component vi and the described false water Al of component ii
2O
3
11. the described preparation method of any one is characterized in that according to claim 7～10, the sintering temperature in the Step II is 1000-1600 ℃, and preferred 1200-1400 ℃, roasting time is 1-24 hour.
12. silver catalyst, this catalyst comprises according to claim 1 the carrier of each described method preparation among each described carrier in-6 or the claim 7-11, and be deposited on silver on this carrier, and in the collaborative auxiliary agent of optional alkali metal, alkaline-earth metal, rhenium and rhenium one or more; Wherein, the collaborative auxiliary agent of described rhenium is to be selected from chromium, molybdenum, tungsten and the boron one or more.
13. silver catalyst according to claim 12 is characterized in that, 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; The rhenium constituent content is 5-1500ppm, is preferably 10-1000ppm; The collaborative auxiliary element content of rhenium is 5-1000ppm, is preferably 10-500ppm.
14. according to claim 1-6 each described carrier or according to claim 7-11 in the carrier of each method preparation or claim 12 or 13 described silver catalysts produce application in the oxirane at ethylene.
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| CN106955700A (en) * | 2016-01-08 | 2017-07-18 | 中国石油化工股份有限公司 | A kind of preparation method and applications of silver catalyst for alkene epoxidation |
| CN108607618A (en) * | 2016-12-09 | 2018-10-02 | 中国石油化工股份有限公司 | A kind of alumina support, the silver catalyst prepared by the carrier and its application |
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| CN106955700A (en) * | 2016-01-08 | 2017-07-18 | 中国石油化工股份有限公司 | A kind of preparation method and applications of silver catalyst for alkene epoxidation |
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| 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 |
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| CN115364854A (en) * | 2021-05-20 | 2022-11-22 | 中国石油化工股份有限公司 | Preparation method of silver catalyst for producing ethylene oxide by ethylene oxidation, silver catalyst and application |
| CN115364854B (en) * | 2021-05-20 | 2024-05-07 | 中国石油化工股份有限公司 | Preparation method of silver catalyst for ethylene oxide production by ethylene oxidation, silver catalyst and application |
| CN115382526A (en) * | 2021-05-24 | 2022-11-25 | 中国石油化工股份有限公司 | Alumina carrier, preparation method and application thereof |
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