CN102553651B - The application of alumina support, its preparation method, the silver catalyst be made up of it and this silver catalyst - Google Patents
The application of alumina support, its preparation method, the silver catalyst be made up of it and this silver catalyst Download PDFInfo
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Abstract
The present invention relates to a kind of porous alpha-alumina supports of producing oxirane silver catalyst for ethylene, this carrier comprises: a) Al of at least 85 % by weight
2o
3, Alpha-alumina accounts at least 85 % by weight of aluminium oxide gross weight; B) by zirconium be selected from the compound Zirconium oxide that one or more metals in periodic table of elements IIIB race and the IVB race element except zirconium are formed, based on the gross weight of carrier, this compound Zirconium oxide with the content of the total amount of its metallic element for 0.01-10 % by weight.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, especially has the selective of improvement.In addition, the invention still further relates to the preparation method of described carrier, and the catalyst be made up of this 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, 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, also relates to the purposes of this catalyst in ethylene production oxirane.
Background technology
Under silver catalyst effect, ethylene mainly generates oxirane, 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.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.The performance of silver catalyst is except having important relationship with the composition of catalyst and preparation method, and performance and the preparation method of the carrier also used with catalyst have important relationship.
The preparation method of silver catalyst mainly 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.What its carrier was generally selected is 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, crystal structure, and surface catalysis performance is also very complicated, directly affects the performance of silver catalyst.
The primary raw material preparing alumina support is the hydrate of aluminium oxide (being aluminium hydroxide again), 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: 1) primary particle intercrystalline hole, the mainly dewatering hole of alumina raw material crystal grain, be substantially 1-2nm size parallel-plate face between gap; 2) hole between alumina raw material offspring, changing with the effusion of moisture and crystalline phase change in roasting, is hole more than tens nanometer; 3) 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 (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, as described in US5063195, US5703001 and US5801259 etc.
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 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 the manufacture method of carrier, 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 in alpha-alumina supports, the loading type silver catalyst be made up of this carrier, when the oxidation epoxy ethane for catalyzed ethylene, obtains the selective of obviously improvement.
Therefore, the object of this invention is to provide a kind of novel alpha-alumina supports, the silver catalyst be made up of it is produced in the process of oxirane at ethylene and is demonstrated good activity and selectivity, especially has the selective of improvement.
Another object of the present invention is to provide a kind of preparation method of above-mentioned carrier.
Another object of the present invention is to provide a kind of silver catalyst prepared by above-mentioned carrier.
An also object of the present invention is to provide the application of above-mentioned silver catalyst in ethylene production oxirane.
These and other objects of the present invention, feature and advantage will become more clear after reading this description.
One aspect of the present invention provides a kind of porous alpha-alumina supports of producing oxirane silver catalyst for ethylene, and this carrier comprises following component based on its gross weight:
A) Al of at least 85 % by weight
2o
3, wherein Alpha-alumina is at least 85 % by weight based on the content of aluminium oxide gross weight;
B) by zirconium be selected from the compound Zirconium oxide that one or more metals in periodic table of elements IIIB race and the IVB race element except zirconium are formed, based on the gross weight of carrier, this compound Zirconium oxide with the content of the total amount of its metallic element for 0.01-10 % by weight, preferred 0.1-7 % by weight.
In porous alpha-alumina supports of the present invention, aluminium oxide obviously should account for the overwhelming majority, and typically, based on the gross weight of porous alpha-alumina supports, alumina content is at least 85 % by weight.When raw alumina roasting being become Alpha-alumina, all Alpha-alumina can not can be transformed into by all aluminium oxide.Therefore, in porous alpha-alumina supports of the present invention, based on the gross weight of aluminium oxide, α-Al
2o
3content be generally at least 85 % by weight, preferably at least 90 % by weight.
In porous alpha-alumina supports of the present invention, as components b) compound Zirconium oxide be modified component, the existence of this component makes the loading type silver catalyst be made up of this alpha-alumina supports produce the effect improved when catalyzed ethylene epoxy ethane, this comprises the activity and selectivity of raising, especially has the selective of improvement.
For the compound Zirconium oxide comprised in carrier of the present invention, preferably wherein said one or more metals be selected from periodic table of elements IIIB race and the IVB race element except zirconium are one or more IIIB race elements, especially yttrium and/or cerium.Such as, described compound Zirconium oxide be zirconium dioxide and ceria, with yttria or the composite oxides that formed with ceria and yttria.
In a preferred embodiment of carrier of the present invention, compound Zirconium oxide used in the present invention can represent with following formula (I):
ZrM
xO
2+y(I)
Wherein M is selected from one or more metals in periodic table of elements IIIB race and the IVB race element except zirconium, x is the number of 0.01-0.3, the number of preferred 0.05-0.2, and y is the number making compound Zirconium oxide be electroneutral and determined by chemical valence and the frequency of the element beyond deoxygenation in compound Zirconium oxide.As IIIB race element, cerium, yttrium, lanthanum or its combination can be mentioned.To the present invention advantageously, M is one or more IIIB race elements, is preferably yttrium, cerium or its combination.
In porous alpha-alumina supports of the present invention, based on the gross weight of this carrier, compound Zirconium oxide is generally 0.01-10 % by weight with the content of the total amount of its metallic element, is preferably 0.1-7 % by weight.
In addition, in a preferred embodiment of the invention, compound Zirconium oxide exists with one or more in following crystalline phase: four directions (orthogonal), cubic nonlinearity monoclinic phase.Particularly preferably be, in porous alpha-alumina supports of the present invention, four directions (orthogonal) crystalline phase compound Zirconium oxide accounts for more than 10 % by weight of compound Zirconium oxide gross weight.
Alpha-alumina supports of the present invention needs to be formed by high temperature sintering usually, and sintering obtains porous material.In a preferred embodiment of carrier of the present invention, porous alpha-alumina supports has following feature: crushing strength > 20N/ grain, preferred 30-150N/ grain, and specific area is 0.2-2.0m
2/ g, preferred 0.5-1.8m
2/ g, water absorption rate>=30%, preferably>=40%, and pore volume is 0.35-0.85ml/g, is preferably 0.40-0.8ml/g.In a further preferred embodiment of the present invention, alpha-alumina supports has following feature: 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.
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.
Another aspect provides a kind of method preparing porous alpha-alumina supports of the present invention, comprise the steps:
I) mixture comprising following component is formed:
I) 50 order-500 object three water Al
2o
3;
Ii) the false water Al of 200 objects is greater than
2o
3, the weight ratio of wherein said gibbsite and a false Water oxidize aluminium is 1: 1-16: 1, and total consumption of described gibbsite and a false Water oxidize aluminium should make the porous alpha-alumina supports finished product finally obtained comprise the Al of at least 85 % by weight
2o
3;
Iii) by zirconium and be selected from the compound Zirconium oxide that one or more metals in periodic table of elements IIIB race and the IVB race element except zirconium are formed, any presoma that can be converted into this compound Zirconium oxide or its combine, the consumption of this compound Zirconium oxide, its precursor or its combination should to make described in the final porous alpha-alumina supports finished product obtained compound Zirconium oxide with the content of the total amount of its metallic element for 0.01-10 % by weight, preferred 0.1-7 % by weight;
Iv) based on component i) and gross weight ii) be 0.01-5.0 % by weight, the mineralizer of preferred 1-2 % by weight;
V) based on component i)-iii) gross weight be the binding agent of 15-60 % by weight; And
Vi) appropriate water;
II) by step I) in the mixture that obtains shaping, obtain formed body; And
III) drying steps II) in the formed body that obtains, and its roasting is become porous alpha-alumina supports.
In support preparation method of the present invention, as alumina source, need to use gibbsite, i.e. component i).Component i) usually in solidapowder form.For the purpose of the present invention, component i) granularity be generally 50-500 order.
In support preparation method of the present invention, also need to use false Water oxidize aluminium, i.e. a component ii as alumina component).Component ii) usually in solidapowder form.For the purpose of the present invention, component ii) granularity be generally and be greater than 200 orders.
The weight ratio of gibbsite and a false Water oxidize aluminium is generally 1: 1-16: 1, is preferably 1: 1-6: 1.Should be appreciated that, total consumption of gibbsite and a false Water oxidize aluminium should make the porous alpha-alumina supports finished product finally obtained comprise the Al of at least 85 % by weight
2o
3.
In support preparation method of the present invention, as component iii) the compound Zirconium oxide that uses is above to the compound Zirconium oxide described in silver catalyst, and all of the compound Zirconium oxide comprised about carrier herein describe the compound Zirconium oxide being all applicable to mention in support preparation method.
As component iii) the compound Zirconium oxide that uses is known, can commercially obtain, such as the preparation of the tetragonal phase zirconium oxide powder of zirconia ceramics material, zirconia TZP powder (is often referred to the Tetragonal ceramic powder containing yttrium and/or cerium, TZP is english abbreviation, means tetragonal phase zirconium oxide powder), zirconia YSZ powder (YSZ means the stable zirconia of yttrium) etc.
As component iii) the compound Zirconium oxide mentioned, 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 CN1257132C, CN1528706A, CN1274637C etc.To this, as any presoma that can be converted into compound Zirconium oxide, the mixture of zirconium and IIIB race and/or the IVB group 4 transition metal except zirconium can be mentioned, the oxide, sulfate, acetate, nitrate, oxalates etc. of zirconium and IIIB race and/or the IVB group 4 transition metal except zirconium or its mixture.As component iii) in the precursor mentioned, be preferably selected from lower group: the mixture of zirconium and yttrium and/or cerium, the oxide of zirconium and yttrium and/or cerium, sulfate, acetate, nitrate, oxalates or its mixture.
In support preparation method of the present invention, adding of mineralizer is transformation of crystal in order to accelerated oxidation aluminium.The present invention preferably uses fluoride-mineralization agent, be more preferably inorganic fluoride, comprise hydrogen fluoride, ammonium fluoride, aluminum fluoride, magnesium fluoride, ice crystal etc., be preferably selected from one or more in hydrogen fluoride, aluminum fluoride, ammonium fluoride, magnesium fluoride and ice crystal, be particularly preferably ammonium fluoride.For the purpose of the present invention, the addition of mineralizer is generally component i) and the 0.01-5.0 % by weight of gross weight ii), preferred 1-2 % by weight.
In support preparation method of the present invention, also need to use binding agent, i.e. component v).Add bonding agent, the vacation one Water oxidize aluminium in it and mixture generates Alumina gel, each component is bonded together, becomes plastic paste, and such as becoming can the paste of extrusion molding.Bonding agent used comprises acid, as nitric acid, formic acid, acetic acid, propionic acid and/or hydrochloric acid etc., and preferred nitric acid, acetic acid or its mixture.Or can partly or entirely replace acid and a false Water oxidize aluminium with Alumina gel.When using acid as bonding agent, most preferably aqueous solution of nitric acid, wherein the weight ratio of nitric acid and water is 1: 1.25-1: 10, preferably 1: 2-1: 8.
The consumption of binding agent is conventional, as long as each component can be bonded together, and forms paste, such as, forms extrudable paste.Typically, the consumption of binding agent is 15-60 % by weight, preferably 15-50 % by weight, based on component i)-iii) gross weight.
By step I) in the mixing of each component after, 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 2-24 hour.Aluminium oxide is made substantially all to be converted into α-Al by roasting
2o
3, obtain porous alpha-alumina supports thus.In this carrier, Alpha-alumina is generally at least 85 % by weight based on the content of aluminium oxide gross weight, and preferably at least 90 % by weight.
Support according to the present invention preparation method, the porous alpha-alumina supports of obtained a kind of modification.This porous alpha-alumina supports can be the common form in this area, such as annular, spherical, cylindricality or porous column shape, 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.
In a preferred embodiment of carrier of the present invention, carrier of the present invention is prepared by support according to the present invention preparation method.
The silver catalyst be made up of porous alpha-alumina supports of the present invention, when being used for catalyzed ethylene oxidation and preparing oxirane, has higher activity and selectivity, especially has the selective of improvement.
Therefore, another aspect of the invention provides a kind of silver catalyst used by ethylene production oxirane, this catalyst comprises porous alpha-alumina supports of the present invention, and be deposited on the silver of the catalytically effective amount in this alpha-alumina supports, the alkali metal of optional catalysed promoted amount, the alkaline-earth metal of optional catalysed promoted amount, the rhenium of optional catalysed promoted amount, and the collaborative auxiliary agent of optional rhenium.
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, in silver catalyst in the silver content of silver element for 1-30 % by weight, preferred 5-26 % by weight.
In a preferred embodiment of silver catalyst of the present invention, based on the gross weight of silver catalyst, in silver catalyst in the alkali metal content of alkali metal for 5-2000ppm, be preferably 10-1500ppm.This alkali metal can be selected from Li, Na, K, Rb and Cs one or more, preferred caesium and/or potassium, most preferably be caesium.
In a preferred embodiment of silver catalyst of the present invention, based on the gross weight of silver catalyst, in silver catalyst in the alkaline earth metal content of alkali earth metal for 5-2000ppm, be preferably 10-1200ppm.This alkaline-earth metal can be selected from Mg, Ca, Sr and Ba one or more, preferred strontium and/or barium.
In a preferred embodiment of silver catalyst of the present invention, based on the gross weight of silver catalyst, in silver catalyst in the rhenium content of rhenium element for 5-1500ppm, be preferably 10-1000ppm.
In a preferred embodiment of silver catalyst of the present invention, if use rhenium and collaborative auxiliary agent thereof, based on the gross weight of silver catalyst, in silver catalyst, the collaborative auxiliary agent of rhenium is in the content of element for 5-1000ppm, is preferably 10-500ppm.The collaborative auxiliary element of this rhenium can be one or more in chromium, molybdenum, tungsten and boron.
Silver catalyst of the present invention adopts carrier of the present invention to prepare.This silver catalyst can be prepared in the usual way, such as, by preparing with the above-mentioned alumina support of the solution impregnation of a kind of Ag-containing compound and organic amine.If use, alkali metal, alkaline-earth metal, the collaborative auxiliary agent of rhenium and rhenium, can be carried in porous alpha-alumina supports of the present invention, preferably load while load silver independently of one another before load silver, while load silver or after load silver.
In one embodiment of the invention, the preparation method of silver catalyst of the present invention comprises the steps:
1) 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;
2) leaching maceration extract; With
3) in air or inert gas to step 2) gained carrier activates, and makes 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 alkali metal promoter of optional use can be compound (as nitrate, sulfate and hydroxide) or its mixture of lithium, sodium, potassium, rubidium or caesium, preferred as alkali auxiliary agent be selected from the compound of lithium, potassium and caesium one or more, as 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.
Prepared the method for silver catalyst by the present invention, obtain a kind of silver catalyst, ethene gas-solid phase catalytic oxidation can be generated oxirane by this catalyst.
Finally, according to another aspect of the invention, additionally provide silver catalyst according to the present invention and produced the application in oxirane by ethylene.
Compared to the prior art the present invention has the following advantages: the stable performance of the silver catalyst be made up of porous alpha-alumina supports of the present invention, and there is higher activity and selectivity, especially there is the selective of improvement, be specially adapted to the reaction that ethylene produces oxirane.
Accompanying drawing is sketched
Fig. 1 is the XRD Diffraction scans collection of illustrative plates of compound Zirconium oxide used in embodiment 1 and 4.
Fig. 2 is the XRD Diffraction scans collection of illustrative plates of compound Zirconium oxide used in embodiment 2 and 5.
Fig. 3 is the XRD Diffraction scans collection of illustrative plates of compound Zirconium oxide used in embodiment 3.
the mensuration of catalyst performance
Various silver catalyst laboratories of the present invention microreactor (hereinafter referred to as " micro-anti-") evaluating apparatus tests its activity and selectivity.The reactor that micro anti-evaluation device uses 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:
Reacting gas composition (mol%)
Ethene (C
2h
4) 28.0 ± 1.0
Oxygen (O
2) 7.4 ± 0.2
Carbon dioxide (CO
2) < 3.0
Cause steady gas (N
2) surplus
Inhibitor dichloroethanes 0.1-2.0ppm
Air speed 7000/h
Reactor outlet EO concentration 2.5mol%
Space-time yield 342gEO/mlCat./h
When stable reach above-mentioned reaction condition after METHOD FOR CONTINUOUS DETERMINATION reactor enter, exit gas composition.Measurement result calculates selective as follows after carrying out volume contraction correction:
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.
Embodiment
The present invention is described further below in conjunction with embodiment, but scope of the present invention is not limited to these embodiments.
carrier comparative example 1
By 50-500 object three water Al
2o
3373g, crosses the vacation one water Al of 200 mesh sieves
2o
3110g, and ammonium fluoride 7g puts into blender and mixes, and proceeds in kneader, adds 20 % by weight aqueous solution of nitric acid 90 milliliters, 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 DEG C-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
By 50-500 object three water Al
2o
3373g, crosses the vacation one water Al of 200 mesh sieves
2o
3110g, ammonium fluoride 7g and ZrO
21.0g 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 DEG C-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 2.
carrier comparative example 3
By 50-500 object three water Al
2o
3373g, crosses the vacation one water Al of 200 mesh sieves
2o
3110g, ammonium fluoride 7g, CeO
210g and ZrO
210g 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 DEG C-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 3.
carrier embodiment 1
By 50-500 object three water Al
2o
3373g, crosses the vacation one water Al of 200 mesh sieves
2o
3(its structural formula is: ZrY for 110g, ammonium fluoride 7g and compound Zirconium oxide
0.03ce
0.04o
2.125, tetragonal phase content is shown in accompanying drawing 1 higher than 95 % by weight, XRD Diffraction scans collection of illustrative plates) and 1g puts into blender and mixes, proceed in kneader, add 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 DEG C-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 invention carrier 1.
By carrying out XRD research to invention carrier 1, there is tetragonal-phase zirconia characteristic peak in its spectrogram, by carrying out XRF fluorescence analysis calculating to invention carrier 1, the mol ratio of Zr, Y, Ce tri-kinds of elements is 100: 3: 4.
carrier embodiment 2
By 50-500 object three water Al
2o
3373g, crosses the vacation one water Al of 200 mesh sieves
2o
3(its structural formula is: ZrY for 110g, ammonium fluoride 7g and compound Zirconium oxide
0.03ce
0.15o
2.345, tetragonal phase content is that accompanying drawing 2 is shown in by 12 % by weight, XRD Diffraction scans collection of illustrative plates) and 1g puts into blender and mixes, proceed in kneader, add 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 DEG C-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 invention carrier 2.
By carrying out XRD research to invention carrier 2, there is tetragonal-phase zirconia characteristic peak in its spectrogram, by carrying out XRF fluorescence analysis calculating to invention carrier 2, the mol ratio of Zr, Y, Ce tri-kinds of elements is 100: 3: 15.
carrier embodiment 3
By 50-500 object three water Al
2o
3373g, crosses the vacation one water Al of 200 mesh sieves
2o
3110g, ammonium fluoride 7g, (its structural formula is compound Zirconium oxide: ZrCe
0.05o
2.010, tetragonal phase content is 5 % by weight, monoclinic crystal phase content > 90 % by weight, accompanying drawing 3 is shown in by XRD Diffraction scans collection of illustrative plates) 1g puts into blender and mixes, proceed in kneader, add 20 % by weight aqueous solution of nitric acid 90 milliliters, 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 DEG C-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 invention carrier 3.
By carrying out XRD research to invention carrier 3, there is tetragonal-phase zirconia characteristic peak in its spectrogram, by carrying out XRF fluorescence analysis calculating to invention carrier 3, the mol ratio of Zr, Ce two kinds of elements is 100: 5.
carrier embodiment 4
By 50-500 object three water Al
2o
3373g, crosses the vacation one water Al of 200 mesh sieves
2o
3(its structural formula is: ZrY for 110g, ammonium fluoride 7g and compound Zirconium oxide
0.03ce
0.04o
2.125, tetragonal phase content is shown in accompanying drawing 1 higher than 95 % by weight, XRD Diffraction scans collection of illustrative plates) and 25g puts into blender and mixes, proceed in kneader, add 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 DEG C-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 invention carrier 4.
By carrying out XRD research to invention carrier 4, there is tetragonal-phase zirconia characteristic peak in its spectrogram, by carrying out XRF fluorescence analysis calculating to invention carrier 4, the mol ratio of Zr, Y, Ce tri-kinds of elements is 100: 3: 4.
carrier embodiment 5
By 50-500 object three water Al
2o
3373g, crosses the vacation one water Al of 200 mesh sieves
2o
3(its structural formula is: ZrY for 110g, ammonium fluoride 7g and compound Zirconium oxide
0.03ce
0.15o
2.345, tetragonal phase content is that accompanying drawing 2 is shown in by 12 % by weight, XRD Diffraction scans collection of illustrative plates) and 25g puts into blender and mixes, proceed in kneader, add 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 DEG C-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 invention carrier 5.
By carrying out XRD research to invention carrier 5, there is tetragonal-phase zirconia characteristic peak in its spectrogram, by carrying out XRF fluorescence analysis calculating to invention carrier 5, the mol ratio of Zr, Y, Ce tri-kinds of elements is 100: 3: 15.
Its crushing strength, water absorption rate, specific surface and pore volume etc. are measured respectively to above-mentioned comparison vehicle 1-3 and invention carrier 1-5, the results are shown in table 1 and table 2.
The physical data of table 1 comparison vehicle 1-3
The physical data of table 2 invention carrier 1-5
cOMPARATIVE CATALYST EXAMPLE 1-3 and CATALYST EXAMPLE 1-5
300g ethylenediamine is added, 110g monoethanolamine in the glass flask that band stirs, and 375g 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, 2.5g strontium acetate, and 4.0g ammonium perrhenate, then add deionized water and make solution gross mass reach 2000g, make maceration extract, stand-by.
Comparison vehicle 1-3 and invention carrier 1-5 is respectively asked for 100g, puts 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 silver catalyst for ethylene oxide, they are respectively comparative catalyst 1-3 and invention catalyst 1-5.
Analyze the respective silver content of the comparative catalyst 1-3 made and invention catalyst 1-5 and auxiliary agent content, wherein each content is all in metal.
Use microreactor evaluating apparatus above "
the mensuration of catalyst performance" measuring the activity and selectivity of each catalyst sample under the described process conditions of part, result of the test lists in table 3.
The result of the test of table 3 comparative catalyst 1-3 and invention catalyst 1-5
*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.
Claims (33)
1. produce a porous alpha-alumina supports for oxirane silver catalyst for ethylene, this carrier comprises following component based on its gross weight:
A) Al of at least 85 % by weight
2o
3, wherein Alpha-alumina is at least 85 % by weight based on the content of aluminium oxide gross weight;
B) by zirconium be selected from the compound Zirconium oxide that one or more metals in periodic table of elements IIIB race and the IVB race element except zirconium are formed, based on the gross weight of carrier, this compound Zirconium oxide with the content of the total amount of its metallic element for 0.01-10 % by weight;
Wherein said one or more metals be selected from periodic table of elements IIIB race and the IVB race element except zirconium are yttrium and cerium, and four directions (orthogonal) crystalline phase compound Zirconium oxide accounts for more than 10 % by weight of compound Zirconium oxide gross weight.
2. carrier as claimed in claim 1, wherein Alpha-alumina is at least 90 % by weight based on the content of aluminium oxide gross weight.
3. carrier as claimed in claim 1, wherein based on the gross weight of carrier, this compound Zirconium oxide with the content of the total amount of its metallic element for 0.1-7 % by weight.
4. carrier as claimed in claim 1, wherein said compound Zirconium oxide is following formula (I) compound Zirconium oxide:
ZrM
xO
2+y(I)
Wherein M is yttrium and cerium, and x is the number of 0.01-0.3, and y is the number making compound Zirconium oxide be electroneutral and determined by chemical valence and the frequency of the element beyond deoxygenation in compound Zirconium oxide.
5. carrier as claimed in claim 4, wherein x is the number of 0.05-0.2.
6. the carrier according to any one of claim 1-5, wherein this carrier has following feature: crushing strength > 20N/ grain, and specific area is 0.2-2.0m
2/ g, water absorption rate>=30%, and pore volume is 0.35-0.85ml/g.
7. carrier as claimed in claim 6, wherein this carrier has following feature: 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.
8. prepare a method for porous alpha-alumina supports required any one of claim 1-7, comprise the steps:
I) mixture comprising following component is formed:
I) 50 order-500 object three water Al
2o
3;
Ii) the false water Al of 200 objects is greater than
2o
3, the weight ratio of wherein said gibbsite and a false Water oxidize aluminium is 1: 1-16: 1, and total consumption of described gibbsite and a false Water oxidize aluminium should make the porous alpha-alumina supports finished product finally obtained comprise the Al of at least 85 % by weight
2o
3;
Iii) by zirconium and be selected from the compound Zirconium oxide that one or more metals in periodic table of elements IIIB race and the IVB race element except zirconium are formed, any presoma that can be converted into this compound Zirconium oxide or its combine, the consumption of this compound Zirconium oxide, its precursor or its combination should make described in the final porous alpha-alumina supports finished product obtained that compound Zirconium oxide is with the content of the total amount of its metallic element for 0.01-10 % by weight, and wherein said one or more metals be selected from periodic table of elements IIIB race and the IVB race element except zirconium are yttrium and cerium;
Iv) based on component i) and gross weight ii) be the mineralizer of 0.01-5.0 % by weight;
V) based on component i)-iii) gross weight be the binding agent of 15-60 % by weight; And
Vi) appropriate water;
II) by step I) in the mixture that obtains shaping, obtain formed body; And
III) drying steps II) in the formed body that obtains, and its roasting is become porous alpha-alumina supports.
9. method as claimed in claim 8, wherein the weight ratio of gibbsite and a false Water oxidize aluminium is 1: 1-6: 1.
10. method as claimed in claim 8, the consumption of wherein compound Zirconium oxide, its precursor or its combination should to make described in the final porous alpha-alumina supports finished product obtained compound Zirconium oxide with the content of the total amount of its metallic element for 0.1-7 % by weight.
11. methods as claimed in claim 8, wherein as component iv) the amount of mineralizer based on component i) and gross weight ii) be 1-2 % by weight.
12. methods as claimed in claim 8, wherein said compound Zirconium oxide is following formula (I) compound Zirconium oxide:
ZrM
xO
2+y(I)
Wherein M is yttrium and cerium, and x is the number of 0.01-0.3, and y is the number making compound Zirconium oxide be electroneutral and determined by chemical valence and the frequency of the element beyond deoxygenation in compound Zirconium oxide.
13. methods as claimed in claim 12, wherein x is the number of 0.05-0.2.
14. methods according to any one of claim 8-13, wherein component iii) described in the presoma of be converted into compound Zirconium oxide be selected from lower group: the mixture of zirconium and yttrium and cerium, the oxide of zirconium and yttrium and cerium, sulfate, acetate, nitrate, oxalates or its mixture.
15. methods according to any one of claim 8-13, wherein as component iv) mineralizer be fluoride-mineralization agent.
16. methods according to any one of claim 8-13, wherein as component iv) mineralizer be inorganic fluoride.
17. methods according to any one of claim 8-13, wherein as component iv) mineralizer be selected from hydrogen fluoride, ammonium fluoride, aluminum fluoride, magnesium fluoride and ice crystal one or more.
18. methods according to any one of claim 8-13, wherein said binding agent is acid.
19. methods according to any one of claim 8-13, wherein said binding agent is nitric acid and/or acetic acid.
20. methods as claimed in claim 18, wherein partly or entirely replace acid and a false water Al with Alumina gel
2o
3.
21. methods as claimed in claim 18, wherein said acid is aqueous solution of nitric acid, and wherein the weight ratio of nitric acid and water is 1: 1.25-1: 10.
22. methods as claimed in claim 21, wherein the weight ratio of nitric acid and water is 1: 2-1: 8.
23. methods according to any one of claim 8-13, wherein Step II I) in roasting carry out at the temperature of 1000-1600 DEG C, and/or keep 2-24 hour under sintering temperature.
24. methods according to any one of claim 8-13, wherein Step II I) in roasting carry out at the temperature of 1200-1400 DEG C.
Oxirane silver catalyst is produced for 25. 1 kinds by ethylene, this catalyst comprises porous alpha-alumina supports prepared by porous alpha-alumina supports as claimed in one of claims 1-7 or the method according to Claim 8 any one of-24, and be deposited on the silver of the catalytically effective amount in this porous alpha-alumina supports, the alkali metal of optional catalysed promoted amount, the alkaline-earth metal of optional catalysed promoted amount, the rhenium of optional catalysed promoted amount, and the collaborative auxiliary agent of optional rhenium.
26. silver catalysts according to claim 25, wherein based on the gross weight of silver catalyst, in silver catalyst with silver element note silver content for 1-30 % by weight.
27. silver catalysts according to claim 25, wherein based on the gross weight of silver catalyst, in silver catalyst with silver element note silver content for 5-26 % by weight.
28. silver catalysts according to claim 25, wherein based on the gross weight of silver catalyst, in silver catalyst in the alkali metal content of alkali metal for 5-2000ppm, and/or in the alkaline earth metal content of alkali earth metal for 5-2000ppm, in the rhenium content of rhenium element for 5-1500ppm, and/or the collaborative auxiliary agent of rhenium in the content of this collaborative auxiliary element for 5-1000ppm.
29. silver catalysts according to claim 25, wherein based on the gross weight of silver catalyst, in silver catalyst in the alkali metal content of alkali metal for 10-1500ppm, and/or in the alkaline earth metal content of alkali earth metal for 10-1200ppm, in the rhenium content of rhenium element for 10-1000ppm, and/or the collaborative auxiliary agent of rhenium in the content of this collaborative auxiliary element for 10-500ppm.
30. according to the silver catalyst of any one of claim 25-29, wherein said alkali metal be selected from Li, Na, K, Rb and Cs one or more; And/or described alkaline-earth metal be selected from Mg, Ca, Sr and Ba one or more; And/or the collaborative auxiliary element of described rhenium be selected from chromium, molybdenum, tungsten and boron one or more.
31. according to the silver catalyst of any one of claim 25-29, wherein the collaborative auxiliary agent of alkali metal, alkaline-earth metal, rhenium and rhenium is 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 after silver compound is reduced in porous alpha-alumina supports.
The application in oxirane produced by 32. silver catalysts according to any one of claim 25-31 by ethylene.
33. carriers according to any one of claim 1-7, wherein this carrier is prepared by method according to any one of claim 8-24.
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| 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 |
| CN108855237A (en) * | 2017-05-15 | 2018-11-23 | 中国石油化工股份有限公司 | Porous alumina carrier and preparation method thereof and silver catalyst and application |
| 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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| CN1217233A (en) * | 1997-11-12 | 1999-05-26 | 中国石油化工集团公司北京燕山石油化工公司研究院 | Mfg. for producing alumina carrier and use thereof |
| CN1511632A (en) * | 2002-12-31 | 2004-07-14 | 中国石油化工股份有限公司北京燕山分 | Carrier for producing silver catalyst for epoxy ethane production, its preparing method and use |
| US6787656B2 (en) * | 2001-11-06 | 2004-09-07 | Nippon Shokubai Co., Ltd. | Catalyst for production of ethylene oxide, method for production thereof, and method for production of ethylene oxide by the use of the catalyst |
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| CN1126597C (en) * | 2001-04-04 | 2003-11-05 | 中国石油化工股份有限公司 | Silver catalyst for ethylene epoxidizing reaction |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1217233A (en) * | 1997-11-12 | 1999-05-26 | 中国石油化工集团公司北京燕山石油化工公司研究院 | Mfg. for producing alumina carrier and use thereof |
| US6787656B2 (en) * | 2001-11-06 | 2004-09-07 | Nippon Shokubai Co., Ltd. | Catalyst for production of ethylene oxide, method for production thereof, and method for production of ethylene oxide by the use of the catalyst |
| CN1511632A (en) * | 2002-12-31 | 2004-07-14 | 中国石油化工股份有限公司北京燕山分 | Carrier for producing silver catalyst for epoxy ethane production, its preparing method and use |
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