CN102553651A - Alumina carrier, preparation method thereof, silver catalyst prepared from same and application of silver catalyst - Google Patents
Alumina carrier, preparation method thereof, silver catalyst prepared from same and application of silver catalyst Download PDFInfo
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- CN102553651A CN102553651A CN2010106117449A CN201010611744A CN102553651A CN 102553651 A CN102553651 A CN 102553651A CN 2010106117449 A CN2010106117449 A CN 2010106117449A CN 201010611744 A CN201010611744 A CN 201010611744A CN 102553651 A CN102553651 A CN 102553651A
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Abstract
The invention relates to a porous alpha-alumina carrier of a silver catalyst for use in production of ethylene oxide by oxidizing ethylene. The carrier comprises: (a) at least 85 percent by weight of Al2O3 and (b) a composite zirconium oxide prepared from zirconium and one or more metals selected from the IIIB family of a periodic table of elements and IVB family elements except zirconium, wherein alpha-alumina accounts for at least 85 percent by weight of the total weight of alumina; and the content of the composite zirconium oxide counted by the total weight of metal elements thereof based on the total weight of the carrier is 0.01-10 percent by weight. The silver catalyst prepared from the carrier shows high activity and high selectivity in a process for producing ethylene oxide by oxidizing ethylene, and particularly has improved selectivity. Moreover, the invention further relates to a preparation method of the carrier, a catalyst prepared from the carrier and an application thereof.
Description
Technical field
The present invention relates to a kind of carrier, its preparation method and application thereof that is used for silver-containing catalyst; More particularly the present invention relates to a kind of ethene oxidation production oxirane that is used for alumina support, its preparation method of silver catalyst and the silver catalyst that makes by this carrier, also relate to this catalyst and produce the purposes in the oxirane in the ethene oxidation.
Background technology
The ethene oxidation mainly generates oxirane under the silver catalyst effect, side reaction takes place simultaneously generate carbon dioxide and water etc., and wherein activity, selectivity and stability are the main performance index of silver catalyst.So-called activity is meant reaction temperature required when process for ethylene oxide production reaches certain reaction load.Reaction temperature is low more, and activity of such catalysts is high more.So-called selectivity is meant that conversion of ethylene in the reaction becomes the ratio of overall reaction molal quantity of molal quantity and the ethene of oxirane.So-called stability then is expressed as active and fall off rate optionally, and the fall off rate stability of small catalyst more is just good more.The silver catalyst that in the process of ethene oxidation production oxirane, uses high activity, high selectivity and have good stability can be increased economic efficiency greatly, and the silver catalyst of therefore making high activity, high selectivity and good stability is the main direction of silver catalyst research.The performance of silver catalyst has the important relationship except that composition and the preparation method with catalyst, and the performance and the preparation method of the carrier that also uses with catalyst have important relationship.
Preparation and administration to active component and the auxiliary agent that the preparation method of silver catalyst mainly comprises porous carrier (like aluminium oxide) these two processes to the said carrier.What its carrier was generally selected for use is 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, crystal structure, the surface catalysis performance is also very complicated, directly influences the performance of silver catalyst.
The primary raw material of preparation alumina support is the hydrate (being aluminium hydroxide again) of aluminium oxide, 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 impurity and moisture influence more or less in addition causes the surface physics, chemical property of aluminium oxide all very complicated.α-the Al that selects for use for silver catalyst
2O
3Though its surface has only the soda acid center of very small amount, their meetings and active component acting in conjunction, impelling conversion of ethylene is oxirane.
Carrier need provide certain area load active component, and active component is dispersed on it, and this has just proposed 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 mainly is the dewatering hole of alumina raw material crystal grain, is slit between the big or small parallel-plate face of 1-2nm basically; 2) 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; 3) 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 roasting mode etc. all can impact the pore structure and the physical property of silver catalyst carrier, and then influences the performance of catalyst.
In general; The main method of preparation silver catalyst carrier is; With adding binding agent and various additives etc. in the alumina powder raw material, even through batch mixing and kneading, extrusion molding is difform base substrate (Raschig ring, spheric granules, porous column, the shape of a saddle etc.) then; The final high temperature sintering is processed the alpha-alumina supports product of porous heat-resistant, and is of US 5063195, US 5703001 and US 5801259 etc.
Add auxiliary agent toward contact in the preparation process of silver catalyst carrier, in order to improve the performance of carrier.Propose like US6787656 and US5145824: in alumina support, add the performance that zirconium (Zr) can improve carrier; And Chinese patent Granted publication CN 1126597C and CN 1130257C claim: in alumina support, add the performance that cerium (Ce) or zirconium colloidal sol can improve carrier.
The improvement that above-mentioned these methods are brought carrier property and activity of such catalysts and selectivity is also very limited; Therefore this area still need be improved the manufacturing approach of carrier; Be beneficial to produce the better catalyst of performance better silver catalyst, especially selectivity.
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; The result finds; When comprising a certain amount of compound Zirconium oxide in the alpha-alumina supports, the loading type silver catalyst of being processed by this carrier obtains obvious improved selectivity when being used for the oxidation epoxy ethane of catalyzed ethylene.
Therefore, the purpose of this invention is to provide a kind of novel alpha-alumina supports, in the process of ethene oxidation production oxirane, demonstrate good activity and selectivity, especially have improved selectivity by its silver catalyst of processing.
Another object of the present invention provides a kind of preparation method of above-mentioned carrier.
A purpose more of the present invention provides a kind of silver catalyst by above-mentioned preparing carriers.
An also purpose of the present invention provides above-mentioned silver catalyst and produces the application in the oxirane in the ethene oxidation.
Of the present invention these will become more clear with other purposes, characteristic and advantage after reading this specification.
One aspect of the present invention provides a kind of porous alpha-alumina supports that is used for ethene oxidation production oxirane with silver catalyst, and this carrier comprises following component based on its gross weight:
A) Al of at least 85 weight %
2O
3, wherein Alpha-alumina is at least 85 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 family and the IVB family element except that zirconium form; Gross weight based on carrier; This compound Zirconium oxide is 0.01-10 weight % in the content of the total amount of its metallic element, preferred 0.1-7 weight %.
In porous alpha-alumina supports of the present invention, aluminium oxide obviously should account for the overwhelming majority, and usually, based on the gross weight of porous alpha-alumina supports, alumina content is at least 85 weight %.When the raw alumina roasting is become Alpha-alumina, can not all can be transformed into Alpha-alumina 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 weight %, preferred at least 90 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 of being processed by this alpha-alumina supports when the catalyzed ethylene epoxy ethane, produce improved effect; Activity and selectivity that this comprises raising especially have improved selectivity.
For the compound Zirconium oxide that is comprised in the carrier of the present invention, preferred wherein said one or more metals that are selected from periodic table of elements IIIB family and the IVB family element except that zirconium are one or more IIIB family elements, especially yttrium and/or cerium.For example, said compound Zirconium oxide be zirconium dioxide and ceria, with yttria or the composite oxides that form with ceria and yttria.
In a preferred embodiment of carrier of the present invention, can be used for compound Zirconium oxide of the present invention and can use following formula (I) expression:
ZrM
xO
2+y (I)
Wherein M is one or more metals that are selected from periodic table of elements IIIB family and the IVB family element except that zirconium; X is the number of 0.01-0.3; The number of preferred 0.05-0.2 and y are the number that makes compound Zirconium oxide be electroneutral and determined by the chemical valence of the element beyond the deoxygenation in the compound Zirconium oxide and frequency.As IIIB family element, can mention cerium, yttrium, lanthanum or its combination.To the present invention advantageously, M is one or more IIIB family 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 weight % in the content of the total amount of its metallic element, is preferably 0.1-7 weight %.
In addition, in a preferred embodiment of the invention, compound Zirconium oxide exists with in the following crystalline phase one or more: four directions (quadrature), cube with monocline mutually.Particularly preferably be, in porous alpha-alumina supports of the present invention, (quadrature) crystalline phase compound Zirconium oxide in four directions accounts for more than the 10 weight % of compound Zirconium oxide gross weight.
Alpha-alumina supports of the present invention need form through high temperature sintering usually, and sintering obtains porous material.In a preferred embodiment of carrier of the present invention, the porous alpha-alumina supports has following characteristic: crushing strength＞20N/ grain, and preferred 30-150N/ grain, specific area is 0.2-2.0m
2/ g, preferred 0.5-1.8m
2/ g, water absorption rate>=30%, preferred>=40% and pore volume are 0.35-0.85ml/g, are preferably 0.40-0.8ml/g.In a further preferred embodiment of the present invention, alpha-alumina supports has following characteristic: crushing strength is the 30-150N/ grain, and specific area is 0.5-1.8m
2/ g, water absorption rate>=40% and pore volume are 0.40-0.8ml/g.
In the present invention, the crushing strength of carrier refers to side crush intensity, measures through intensity of pressure appearance; Specific area adopts nitrogen physisorption BET method to measure; Water absorption rate is measured through densimetry; And pore volume adopts pressure mercury method to measure.
Another aspect of the present invention provides a kind of method for preparing porous alpha-alumina supports of the present invention, comprises the steps:
I) form 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 a wherein said gibbsite and a false water aluminium oxide is 1: 1-16: 1, and total consumption of a said gibbsite and a false water aluminium oxide should make the porous alpha-alumina supports finished product of final acquisition comprise the Al of at least 85 weight %
2O
3
Iii) by zirconium be selected from compound Zirconium oxide, any presoma that can be converted into this compound Zirconium oxide or its combination that one or more metals in periodic table of elements IIIB family and the IVB family element except that zirconium form; The consumption of this compound Zirconium oxide, its precursor or its combination should make that be 0.01-10 weight % at compound Zirconium oxide described in the final porous alpha-alumina supports finished product that obtains in the content of the total amount of its metallic element, preferred 0.1-7 weight %;
Iv) based on component i) and gross weight ii) be 0.01-5.0 weight %, the mineralizer of preferred 1-2 weight %;
V) based on component i)-iii) gross weight is the binding agent of 15-60 weight %; And
Vi) an amount of water;
II) with step I) in the mixture moulding that obtains, obtain formed body; And
III) formed body that obtains drying steps II), and its roasting become the porous alpha-alumina supports.
In preparing carriers method of the present invention,, need to use gibbsite, i.e. component i) as alumina source.Component i) is the pressed powder form usually.For the purpose of the present invention, granularity component i) is generally the 50-500 order.
In preparing carriers method of the present invention, also need use a false water aluminium oxide as alumina component, promptly component is ii).Component ii) is the pressed powder form usually.For the purpose of the present invention, component granularity ii) is generally greater than 200 orders.
The weight ratio of a gibbsite and a false water aluminium oxide is generally 1: 1-16: 1, be preferably 1: 1-6: 1.Should be appreciated that total consumption of a gibbsite and a false water aluminium oxide should make the porous alpha-alumina supports finished product of final acquisition comprise the Al of at least 85 weight %
2O
3
In preparing carriers method of the present invention; The compound Zirconium oxide that iii) uses as component is preceding text to the described compound Zirconium oxide of silver catalyst, and this paper all is applicable to the compound Zirconium oxide of mentioning in the preparing carriers method about all descriptions of the compound Zirconium oxide that carrier comprises.
The compound Zirconium oxide that iii) uses as component is known; Can commercially obtain; For example be used to prepare the tetragonal phase zirconium oxide powder of zirconia ceramics material; Zirconia TZP powder (be often referred to the cubic phase ceramics powder that contains yttrium and/or cerium, TZP is an english abbreviation, means the tetragonal phase zirconium oxide powder), zirconia YSZ powder (YSZ means the stable zirconia of yttrium) etc.
As the compound Zirconium oxide that component is iii) mentioned, also can be through the methods known in the art preparation.For example can use any presoma preparation that can be converted into the compound Zirconium oxide of the present invention, like the method preparation of mentioning through patent CN1257132C, CN1528706A, CN1274637C etc.To this; As any presoma that can be converted into compound Zirconium oxide; Can mention the mixture of zirconium and IIIB family and/or the IVB group 4 transition metal except that zirconium, the oxide of zirconium and IIIB family and/or the IVB group 4 transition metal except that zirconium, sulfate, acetate, nitrate, oxalates etc. or its mixture.Precursor as component is mentioned in iii) is preferably selected from down 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 preparing carriers method of the present invention, the adding of mineralizer is the crystal formation conversion for accelerated oxidation aluminium.The present invention preferably uses the fluoride-mineralization agent; Inorganic fluoride more preferably; Comprise hydrogen fluoride, ammonium fluoride, aluminum fluoride, magnesium fluoride, ice crystal etc., be preferably and be selected from hydrogen fluoride, aluminum fluoride, ammonium fluoride, magnesium fluoride and the ice crystal one or more, be preferably ammonium fluoride especially.For the purpose of the present invention, the addition of mineralizer is generally component i) and the 0.01-5.0 weight % of gross weight ii), preferred 1-2 weight %.
In preparing carriers method of the present invention, also need use binding agent, promptly component is v).Add bonding agent, it generates aluminium colloidal sol with vacation one water aluminium oxide in the mixture, bonds together each component, becomes plastic paste, but for example becomes the paste of extrusion molding.Used bonding agent comprises acid, like nitric acid, formic acid, acetate, propionic acid and/or hydrochloric acid etc., and preferred nitric acid, acetate or its mixture.Perhaps can use the aluminium sol-fraction or all replace an acid and a false water aluminium oxide.When using acid as bonding agent, aqueous solution of nitric acid most preferably, wherein the weight ratio of nitric acid and water is 1: 1.25-1: 10, preferred 1: 2-1: 8.
The consumption of binding agent is conventional, as long as can each component be bonded together, and forms paste and gets final product, and for example forms extrudable paste and gets final product.Usually, the consumption of binding agent is 15-60 weight %, and 15-50 weight % preferably is based on component i)-iii) gross weight.
With step I) in each component mix after, obtain paste usually.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 the moisture 10 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 cylindricality, or other shape.
In order to make carrier that enough intensity and good surface properties arranged, dried formed body is usually 1000-1600 ℃, preferred 1200-1400 ℃ of following roasting.Under sintering temperature, usually carrier was kept 2-24 hour.Make aluminium oxide basically all be converted into α-Al through roasting
2O
3, obtain the porous alpha-alumina supports thus.In this carrier, Alpha-alumina is generally at least 85 weight % based on the content of aluminium oxide gross weight, preferably at least 90 weight %.
Support according to the present invention preparation method makes a kind of porous alpha-alumina supports of modification.This porous alpha-alumina supports can be the common form in this area; For example annular, spherical, cylindricality or porous cylindricality; 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.
In a preferred embodiment of carrier of the present invention, carrier of the present invention is support according to the present invention preparation method preparation.
The silver catalyst of being processed by porous alpha-alumina supports of the present invention has higher activity and selectivity when being used for the catalyzed ethylene oxidation and preparing oxirane, especially have improved selectivity.
Therefore; One side more of the present invention provides a kind of and has produced the used silver catalyst of oxirane by the ethene oxidation, and this catalyst comprises porous alpha-alumina supports of the present invention, and the silver that is deposited on the catalytically effective amount on 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, silver be dispersed on the surface of porous infusibility alumina support with hole in.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, the silver content in silver element in the silver catalyst is 1-30 weight %, preferred 5-26 weight %.
In a preferred embodiment of silver catalyst of the present invention, based on the gross weight of silver catalyst, the alkali metal content in alkali metal in the silver catalyst is 5-2000ppm, is preferably 10-1500ppm.This alkali metal can be to be selected among Li, Na, K, Rb and the Cs one or more, and preferred caesium and/or potassium most preferably are caesium.
In a preferred embodiment of silver catalyst of the present invention, based on the gross weight of silver catalyst, the alkaline earth metal content in alkali earth metal in the silver catalyst is 5-2000ppm, is preferably 10-1200ppm.This alkaline-earth metal can be to be selected among Mg, Ca, Sr and the 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, the rhenium content in the rhenium element in the silver catalyst is 5-1500ppm, is 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, the collaborative auxiliary agent of rhenium is 5-1000ppm in the content of element in the silver catalyst, is preferably 10-500ppm.The collaborative auxiliary element of this rhenium can be one or more in chromium, molybdenum, tungsten and the boron.
Silver catalyst of the present invention adopts preparing carriers of the present invention.This silver catalyst mode routinely prepares, for example 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 independently of one another can be before silver-loaded, in the silver-loaded or be carried on the porous alpha-alumina supports of the present invention preferably load in silver-loaded after the silver-loaded.
In one embodiment of the invention, the preparation method of silver catalyst of the present invention comprises the steps:
1) 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;
2) leaching maceration extract; With
3) in air or inert gas to step 2) the gained carrier carries out activation, processes said 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, the 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 (like nitrate, sulfate and hydroxide) or its mixture of lithium, sodium, potassium, rubidium or caesium; The preferred as alkali auxiliary agent is to be selected from the compound of lithium, potassium and caesium one or more, like 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; Like in oxide, oxalates, sulfate, acetate and the nitrate of said element one or more; The compound of preferred barium and/or the compound of strontium are like 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, for example 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 activity, selectivity and the stability of further improvement gained silver catalyst.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 load of silver, carrier preferably vacuumizes in advance.
After porous alpha-alumina supports dipping argentiferous maceration extract, the leaching maceration extract carries out activation through the carrier of dipping in to step 3) then in air or inert gas.For this reason, can be with through the activation in 180-700 ℃, preferred 200-500 ℃ moving air or air-flows such as inert gas such as nitrogen, argon gas of the carrier of dipping, soak time at least 2 minutes usually, for example 2-120 minute, preferred 2-60 minute.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 the ammonium oxalate or the oxalic acid aqueous solution reaction of silver nitrate, separate out the silver oxalate deposition; After the filtration, spend deionised water, until no 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 carry out activation.Also available silver oxide replaces silver nitrate, and silver oxalate also can not analysed filter, direct and organic amine complexing, impregnated carrier then.
Prepare the method for silver catalyst through the present invention, obtain a kind of silver catalyst, this catalyst can generate oxirane with the oxidation of ethylene gas solid catalysis.
At last, according to another aspect of the invention, also provide silver catalyst according to the present invention producing the application in the oxirane by the ethene oxidation.
The present invention compares following advantage with prior art: the stable performance of the silver catalyst of being processed by porous alpha-alumina supports of the present invention; And have higher activity and selectivity; Especially have improved selectivity, be specially adapted to the reaction that oxirane is produced in the ethene oxidation.
The accompanying drawing summary
Fig. 1 is the XRD diffraction scanning spectra of used compound Zirconium oxide in embodiment 1 and 4.
Fig. 2 is the XRD diffraction scanning spectra of used compound Zirconium oxide in embodiment 2 and 5.
Fig. 3 is the XRD diffraction scanning spectra of used compound Zirconium oxide among the embodiment 3.
The mensuration of catalyst performance
Various silver catalyst of the present invention is with laboratory micro reactor (hereinafter to be referred as " little anti-") evaluating apparatus its activity of test and selectivity.The reactor that the micro anti-evaluation device uses 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 activity that the present invention adopts and optionally condition determination is following:
Reacting gas is formed (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 342g EO/mlCat./h
When stable reach above-mentioned reaction condition after the METHOD FOR CONTINUOUS DETERMINATION reactor go into, exit gas forms.Measuring the result carries out calculating selectivity by following formula after volume contraction is proofreaied and correct:
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.
Embodiment
The present invention is described further below in conjunction with embodiment, but scope of the present invention is not limited to these embodiment.
Carrier Comparative Examples 1
With 50-500 purpose three water Al
2O
3373g, the vacation one water Al of 200 mesh sieves excessively
2O
3110g and ammonium fluoride 7g put into blender and mix, and change in the kneader, add 90 milliliters of 20 weight % aqueous solution of nitric acid, but are 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 the 10 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
With 50-500 purpose three water Al
2O
3373g, the vacation one water Al of 200 mesh sieves excessively
2O
3110g, ammonium fluoride 7g and ZrO
2Mix 1.0g put into blender, change in the kneader, add 90 milliliters of 20 weight % aqueous solution of nitric acid, but be 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 the 10 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 2.
Carrier Comparative Examples 3
With 50-500 purpose three water Al
2O
3373g, the vacation one water Al of 200 mesh sieves excessively
2O
3110g, ammonium fluoride 7g, CeO
210g and ZrO
210g puts into blender and mixes, and changes in the kneader, adds 90 milliliters of 20 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 the 10 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 3.
Carrier embodiment 1
With 50-500 purpose three water Al
2O
3373g, the vacation one water Al of 200 mesh sieves excessively
2O
3110g, (its structural formula is: ZrY for ammonium fluoride 7g and compound Zirconium oxide
0.03Ce
0.04O
2.125, the tetragonal phase content is higher than 95 weight %, XRD diffraction scanning spectra is seen accompanying drawing 1) and 1g puts into blender and mixes, and changes in the kneader, and add 90 milliliters of 20 weight % aqueous solution of nitric acid, but be 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 the 10 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 invention carrier 1.
Through invention carrier 1 is carried out XRD research, there is tetragonal phase zircite characteristic peak in its spectrogram, through being carried out the XRF fluorescence analysis, calculates in invention carrier 1, and the mol ratio of Zr, Y, three kinds of elements of Ce is 100: 3: 4.
Carrier embodiment 2
With 50-500 purpose three water Al
2O
3373g, the vacation one water Al of 200 mesh sieves excessively
2O
3110g, (its structural formula is: ZrY for ammonium fluoride 7g and compound Zirconium oxide
0.03Ce
0.15O
2.345, the tetragonal phase content is 12 weight %, XRD diffraction scanning spectra is seen accompanying drawing 2) and 1g puts into blender and mixes, and changes in the kneader, and add 90 milliliters of 20 weight % aqueous solution of nitric acid, but be 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 the 10 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 invention carrier 2.
Through invention carrier 2 is carried out XRD research, there is tetragonal phase zircite characteristic peak in its spectrogram, through being carried out the XRF fluorescence analysis, calculates in invention carrier 2, and the mol ratio of Zr, Y, three kinds of elements of Ce is 100: 3: 15.
Carrier embodiment 3
With 50-500 purpose three water Al
2O
3373g, the vacation one water Al of 200 mesh sieves excessively
2O
3110g, ammonium fluoride 7g, (its structural formula is compound Zirconium oxide: ZrCe
0.05O
2.010, the tetragonal phase content is 5 weight %, monoclinic crystal phase content＞90 weight %; XRD diffraction scanning spectra is seen accompanying drawing 3) 1g puts into blender and mixes; Change in the kneader, add 90 milliliters of 20 weight % aqueous solution of nitric acid, but be 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 the 10 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 invention carrier 3.
Through invention carrier 3 is carried out XRD research, there is tetragonal phase zircite characteristic peak in its spectrogram, through being carried out the XRF fluorescence analysis, calculates in invention carrier 3, and the mol ratio of Zr, two kinds of elements of Ce is 100: 5.
Carrier embodiment 4
With 50-500 purpose three water Al
2O
3373g, the vacation one water Al of 200 mesh sieves excessively
2O
3110g, (its structural formula is: ZrY for ammonium fluoride 7g and compound Zirconium oxide
0.03Ce
0.04O
2.125, the tetragonal phase content is higher than 95 weight %, XRD diffraction scanning spectra is seen accompanying drawing 1) and 25g puts into blender and mixes, and changes in the kneader, and add 90 milliliters of 20 weight % aqueous solution of nitric acid, but be 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 the 10 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 invention carrier 4.
Through invention carrier 4 is carried out XRD research, there is tetragonal phase zircite characteristic peak in its spectrogram, through being carried out the XRF fluorescence analysis, calculates in invention carrier 4, and the mol ratio of Zr, Y, three kinds of elements of Ce is 100: 3: 4.
Carrier embodiment 5
With 50-500 purpose three water Al
2O
3373g, the vacation one water Al of 200 mesh sieves excessively
2O
3110g, (its structural formula is: ZrY for ammonium fluoride 7g and compound Zirconium oxide
0.03Ce
0.15O
2.345, the tetragonal phase content is 12 weight %, XRD diffraction scanning spectra is seen accompanying drawing 2) and 25g puts into blender and mixes, and changes in the kneader, and add 90 milliliters of 20 weight % aqueous solution of nitric acid, but be 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 the 10 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 invention carrier 5.
Through invention carrier 5 is carried out XRD research, there is tetragonal phase zircite characteristic peak in its spectrogram, through being carried out the XRF fluorescence analysis, calculates in invention carrier 5, and the mol ratio of Zr, Y, three kinds of elements of Ce is 100: 3: 15.
Above-mentioned comparison vehicle 1-3 and invention carrier 1-5 are measured its crushing strength, water absorption rate, specific surface and pore volume etc. respectively, and the result lists 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
Catalyst Comparative Examples 1-3 and catalyst embodiment 1-5
In the glass flask that band stirs, add the 300g ethylenediamine, 110g monoethanolamine and 375g 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 the maceration extract argentiferous 24 weight % that finally make.Add 3.0g cesium nitrate, 2.5g strontium acetate and 4.0g ammonium perrhenate, add deionized water again and make the solution gross mass reach 2000g, process maceration extract, for use.
To comparison vehicle 1-3 and the invention carrier 1-5 100g that respectively asks for, put into the container that can vacuumize respectively.Be evacuated to vacuum and be lower than 10mmHg, to wherein putting into above maceration extract, the submergence carrier kept 30 minutes.Unnecessary maceration extract is removed in leaching afterwards.Soaked carrier was heated 5 minutes in 250 ℃ air stream, and silver catalyst for ethylene oxide is promptly processed in cooling, and they are respectively comparative catalyst 1-3 and invention catalyst 1-5.
Comparative catalyst 1-3 to processing analyzes with invention catalyst 1-5 silver content and auxiliary agent content separately, and wherein each content is all in metal.
Use the microreactor evaluating apparatus preceding text "
The mensuration of catalyst performance" measure the activity and the selectivity of each catalyst sample under the said process conditions of part, result of the test is listed in table 3.
The result of the test of table 3 comparative catalyst 1-3 and invention catalyst 1-5
*Annotate: reaction temperature is that accumulative total EO output reaches 400T/M
3Value during catalyst, selectivity are got accumulative total EO output and are reached 400T/M
3Mean value during catalyst.
Claims (23)
1. one kind is used for the ethene oxidation and produces the porous alpha-alumina supports of oxirane with silver catalyst, and this carrier comprises following component based on its gross weight:
A) Al of at least 85 weight %
2O
3, wherein Alpha-alumina is at least 85 weight %, preferably at least 90 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 family and the IVB family element except that zirconium form; Gross weight based on carrier; This compound Zirconium oxide is 0.01-10 weight % in the content of the total amount of its metallic element, preferred 0.1-7 weight %.
2. carrier as claimed in claim 1, wherein said compound Zirconium oxide are the compound Zirconium oxide of following formula (I):
ZrM
xO
2+y (I)
Wherein M is one or more metals that are selected from periodic table of elements IIIB family and the IVB family element except that zirconium; X is the number of 0.01-0.3; The number of preferred 0.05-0.2 and y are the number that makes compound Zirconium oxide be electroneutral and determined by the chemical valence of the element beyond the deoxygenation in the compound Zirconium oxide and frequency.
3. according to claim 1 or claim 2 carrier, wherein said one or more metals that are selected from periodic table of elements IIIB family and the IVB family element except that zirconium are one or more IIIB family elements, especially yttrium and/or cerium.
4. like each described carrier among the claim 1-3, wherein compound Zirconium oxide exists with in the following crystalline phase one or more: four directions (quadrature), cube with monocline mutually.
5. like each described carrier among the claim 1-4, wherein (quadrature) crystalline phase compound Zirconium oxide in four directions accounts for more than the 10 weight % of compound Zirconium oxide gross weight.
6. like each described carrier among the claim 1-5, wherein this carrier has following characteristic: crushing strength＞20N/ grain, specific area are 0.2-2.0m
2/ g, water absorption rate>=30% and pore volume are 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 are 0.40-0.8ml/g.
7. a method for preparing according to each desired porous alpha-alumina supports among the claim 1-6 comprises the steps:
I) form 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
3The weight ratio of a wherein said gibbsite and a false water aluminium oxide is 1: 1-16: 1; Be preferably 1: 1-6: 1, and total consumption of a said gibbsite and a false water aluminium oxide should make the porous alpha-alumina supports finished product of final acquisition comprise the Al of at least 85 weight %
2O
3
Iii) by zirconium be selected from compound Zirconium oxide, any presoma that can be converted into this compound Zirconium oxide or its combination that one or more metals in periodic table of elements IIIB family and the IVB family element except that zirconium form; The consumption of this compound Zirconium oxide, its precursor or its combination should make that be 0.01-10 weight % at compound Zirconium oxide described in the final porous alpha-alumina supports finished product that obtains in the content of the total amount of its metallic element, preferred 0.1-7 weight %;
Iv) based on component i) and gross weight ii) be 0.01-5.0 weight %, the mineralizer of preferred 1-2 weight %;
V) based on component i)-iii) gross weight is the binding agent of 15-60 weight %; And
Vi) an amount of water;
II) with step I) in the mixture moulding that obtains, obtain formed body; And
III) formed body that obtains drying steps II), and its roasting become the porous alpha-alumina supports.
8. method as claimed in claim 7, wherein said compound Zirconium oxide are the compound Zirconium oxide of following formula (I):
ZrM
xO
2+y (I)
Wherein M is one or more metals that are selected from periodic table of elements IIIB family and the IVB family element except that zirconium; X is the number of 0.01-0.3; The number of preferred 0.05-0.2 and y are the number that makes compound Zirconium oxide be electroneutral and determined by the chemical valence of the element beyond the deoxygenation in the compound Zirconium oxide and frequency.
9. like claim 7 or 8 described carriers, wherein said one or more metals that are selected from periodic table of elements IIIB family and the IVB family element except that zirconium are one or more IIIB family elements, especially yttrium and/or cerium.
10. like each described method among the claim 7-9, wherein said compound Zirconium oxide exists with in the following crystalline phase one or more: four directions (quadrature), cube with monocline mutually.
11. like each described method among the claim 7-10; Wherein the presoma that be converted into compound Zirconium oxide of component described in iii) is selected from down group: the mixture of zirconium and IIIB family and/or the IVB group 4 transition metal except that zirconium, oxide, sulfate, acetate, nitrate, oxalates or its mixture of zirconium and IIIB family and/or the IVB group 4 transition metal except that zirconium; Be preferably selected from down 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.
12. like each described method among the claim 7-11; Be the fluoride-mineralization agent wherein as component mineralizer iv); Be preferably inorganic fluoride, more preferably be selected from hydrogen fluoride, ammonium fluoride, aluminum fluoride, magnesium fluoride and the ice crystal one or more, be preferably ammonium fluoride especially.
13. like each described method among the claim 7-12, wherein said binding agent is acid, preferred nitric acid and/or acetate.
14. method as claimed in claim 13 is wherein with aluminium sol-fraction or a whole acid and false water Al of replacing
2O
3
15. method as claimed in claim 13, wherein said acid are aqueous solution of nitric acid, wherein the weight ratio of nitric acid and water is 1: 1.25-1: 10, preferred 1: 2-1: 8.
16. like each described method, wherein Step II I among the claim 7-15) in roasting at 1000-1600 ℃, carry out under preferred 1200-1400 ℃ the temperature, and/or maintenance 2-24 hour under sintering temperature.
17. produce oxirane by the ethene oxidation and use silver catalyst for one kind; This catalyst comprises according to each porous alpha-alumina supports or the porous alpha-alumina supports for preparing according to each method among the claim 7-16 among the claim 1-6; And the silver that is deposited on the catalytically effective amount on 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.
18. according to the silver catalyst of claim 17, wherein based on the gross weight of silver catalyst, the silver content with the silver element note in the silver catalyst is 1-30 weight %, preferred 5-26 weight %.
19. silver catalyst according to claim 17 or 18; Wherein based on the gross weight of silver catalyst, the alkali metal content in alkali metal in the silver catalyst is 5-2000ppm, is preferably 10-1500ppm; And/or be 5-2000ppm in the alkaline earth metal content of alkali earth metal; Being preferably 10-1200ppm, is 5-1500ppm in the rhenium content of rhenium element, is preferably 10-1000ppm; And/or the collaborative auxiliary agent of rhenium is 5-1000ppm in the content of this collaborative auxiliary element, is preferably 10-500ppm.
20. according to each silver catalyst of claim 15-17, wherein said alkali metal is to be selected among Li, Na, K, Rb and the Cs one or more; And/or said alkaline-earth metal is to be selected among Mg, Ca, Sr and the Ba one or more; And/or the collaborative auxiliary element of said rhenium is to be selected from chromium, molybdenum, tungsten and the boron one or more.
21. according to each silver catalyst of claim 17-20; Wherein 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 silver-loaded or after the silver-loaded, or is immersed in after silver compound is reduced on the porous alpha-alumina supports independently of one another.
22. producing the application in the oxirane by the ethene oxidation according to each described silver catalyst among the claim 17-21.
23. like each described carrier among the claim 1-5, wherein this carrier is through each said method preparation among the claim 7-16.
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| 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 |
| 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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| CN102553651B (en) | 2016-03-09 |
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