CN103769233A - Catalyst carrier and preparation method as well as catalyst prepared by carrier and application of catalyst - Google Patents

Catalyst carrier and preparation method as well as catalyst prepared by carrier and application of catalyst Download PDF

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CN103769233A
CN103769233A CN201210413961.6A CN201210413961A CN103769233A CN 103769233 A CN103769233 A CN 103769233A CN 201210413961 A CN201210413961 A CN 201210413961A CN 103769233 A CN103769233 A CN 103769233A
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carrier
catalyst
earth metal
powder
component
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CN103769233B (en
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林强
孙欣欣
李金兵
陈建设
张志祥
林伟
李贤丰
任冬梅
曹淑媛
王辉
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention provides a catalyst carrier and a preparation method as well as a catalyst prepared by the carrier and an application of the catalyst. According to the preparation method, activated aluminum oxide with various crystalline phases and of various types is employed, including one or more mixtures of gamma-A12O3, rho-A12O3, alpha-A12O3, kappa-A12O3, theta-A12O3 and the like, preferably one, two or three mixtures of gamma-A12O3, rho-A12O3 and alpha-A12O3, to replace or partially replace hydrate (namely aluminum hydroxide) of aluminum oxide as one of raw materials for preparing the carrier to prepare the carrier of a silver catalyst. The performances of the carrier prepared with the method are improved obviously. The carrier shows good activity and selectivity in an ethylene oxidation to oxirane process after loading silver and various active components to prepare the silver catalyst, and particularly, the selectivity is improved obviously.

Description

Catalyst carrier and preparation method and catalyst and the application thereof prepared by this carrier
Technical field
The present invention relates to catalyst field, be specifically related to a kind of silver catalyst carrier and preparation method thereof, and the catalyst of being made by it and application; Relate more specifically to a kind of preparation method and the carrier of being made by the method and the silver catalyst making and application of producing the alumina support of oxirane silver catalyst for ethylene.
Background technology
Under silver catalyst effect, ethylene mainly generates oxirane, side reaction occurs simultaneously and generate carbon dioxide and water etc.The main performance index of silver catalyst comprises its activity, selective and stability.Wherein activity generally refers to reaction temperature required when process for ethylene oxide production reaches certain reaction load; Desired reaction temperature is lower, and the activity of catalyst is higher.Selectively refer to that ethene in reaction changes into the ratio of the molal quantity of oxirane and the overall reaction molal quantity of ethene.Stability is the fall off rate of activity and selectivity, and the fall off rate more stability of small catalyst is just better.The silver catalyst that uses high activity, high selectivity and have good stability in the process of ethylene production oxirane can be increased economic efficiency greatly, and therefore manufacturing such silver catalyst is the main direction of silver catalyst research.The performance of silver catalyst is except having important relationship with composition and the preparation method of catalyst, and performance of the carrier also using with catalyst and preparation method thereof has important relationship.
The preparation method of silver catalyst be mainly the preparation and administration to active component of porous carrier (as aluminium oxide) and auxiliary agent to as described in this two processes on carrier.Its carrier is generally selected the Alpha-alumina that specific area is less.Aluminium oxide (Al 2o 3) be a kind of catalyst carrier of having many uses, its kind is very many, and its crystal structure, surface catalysis performance are also very complicated, directly affect the performance of silver catalyst.
Carrier need to provide certain area load active component, and active component is thereon dispersed, 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: the first, and primary particle intercrystalline hole, is mainly the dewatering hole of alumina raw material crystal grain, is gap between the parallel-plate face of 1-2nm size substantially; The second, hole between alumina raw material offspring, effusion and crystalline phase variation with moisture in roasting change, and are hole more than tens nanometer; The third, the defective hole and the macropore that when pore creating material and carrier moulding, produce.The pore structure of carrier can impact physical property, and then affects the performance of catalyst.
The primary raw material of generally preparing alumina support is the hydrate of aluminium oxide, be aluminium hydroxide, hydrated alumina dehydration can produce Louis (L) soda acid center, and these L acid sites are easy to water suction and change proton (B) soda acid center 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.α-the Al selecting for silver catalyst 2o 3although its surface only has the soda acid center of little amount, their meetings and active component acting in conjunction, impel ethene to be converted into oxirane.
In general, the main method of preparing silver catalyst carrier is, to in alumina powder raw material, add binding agent and various additives etc., even through batch mixing and kneading, then extrusion molding is difform base substrate, as Raschig ring, spheric granules, porous cylindrical, the shape of a saddle etc., final high temperature sintering is made the alpha-alumina supports product of porous heat-resistant, specifically can be referring to patent documentations such as US5063195, US5703001 and US5801259.
The improvement that above-mentioned these methods are brought the activity and selectivity of carrier property and catalyst is also very limited, therefore this area still needs carrier and manufacture method thereof to improve, be beneficial to produce the better silver catalyst of performance, especially selective better catalyst.
In view of the situation of above-mentioned prior art, the inventor has carried out research extensively and profoundly at silver catalyst and alumina support field thereof, found that, with the hydrate (being aluminium hydroxide) that the activated alumina of different crystalline phases and kind replaces or part replaces aluminium oxide as the raw material of preparing carrier, can adjust the pore structure of finished product carrier, the loading type silver catalyst of being made up of this carrier, in the time of the oxidation epoxy ethane for catalyzed ethylene, is selectively obviously improved.
Summary of the invention
The object of the present invention is to provide a kind of catalyst carrier and preparation method thereof, the carrier of being made up of the method is made after silver catalyst at load silver and various active constituents, in the process of ethylene production oxirane, demonstrates good activity and selectivity.The present invention also provides a kind of silver catalyst that the alumina support prepared by the method is carrier.
The invention provides a kind of catalyst carrier, comprising:
A) porous A1 2o 3, it comprises α-A1 2o 3, described α-A1 2o 3weight content be at least 85 ~ 99.9% of total weight of carrier, preferably at least 90 ~ 99.9%; With
B) one or more alkaline-earth metal and/or alkaline earth metal compound, it is 0.01-15wt% that its metallic element weight accounts for total weight of carrier content, preferably 0.1-3wt%.
Described catalyst carrier is a kind of porous A1 of modification 2o 3carrier.
Described porous A1 2o 3preferably external diameter is 7-9mm, the cellular cylindrical α-A1 in seven apertures in the human head, five holes or three holes that honeycomb aperture is 1-3mm 2o 3particle, or external diameter is the circular α-A1 of single hole that 7-9mm, internal diameter are 3-6mm 2o 3particle.
One or more in described alkaline-earth metal preferably magnesium, calcium, strontium and barium, more preferably strontium and/or barium; One or more in oxide, sulfate, acetate, nitrate, carbonate and the oxalates of described alkaline earth metal compound preferred bases earth metal, more preferably one or more in barium monoxide, barium sulfate, barium nitrate and brium carbonate.
The crushing strength of catalyst carrier of the present invention is more than 20N/ grain, and specific area is 0.2-5.0m 2/ g, water absorption rate>=30%, pore volume is 0.35-0.85ml/g; Preferred crush strength is 40-200N/ grain, and specific area is 0.5-2.0m 2/ g, water absorption rate>=45%, and pore volume is 0.40-0.8ml/g.
In carrier of the present invention, aluminium oxide should account for the overwhelming majority; Typically, based on the gross weight of carrier, alumina content is 90wt% at least.In addition, when by raw alumina roasting, be not that all aluminium oxide all can be transformed into α-A1 2o 3; Therefore, in carrier of the present invention, based on A1 2o 3gross weight, α-A1 2o 3content be generally at least 85wt%, preferably 90wt% at least.α-A1 of the present invention 2o 3carrier need to obtain porous material by high temperature sintering conventionally.In carrier of the present invention, the alkaline-earth metal of components b is modified component, and the existence of these components makes the loading type silver catalyst of being made up of this carrier produce improved effect in the time of catalyzed ethylene epoxy ethane, and this comprises the activity and selectivity that improves catalyst.
The preparation method who the invention provides a kind of above-mentioned carrier, comprises the steps:
Step 1, forms the mixture that comprises following component:
I) active A 1 2o 3powder or A1 2o 3powder and 50 order-500 object three water A1 2o 3mixture;
Described active A 1 2o 3powder content, based on i) the more than 1% of gross weight of component, is preferably more than 10%, and more preferably 100%;
Preferred described A1 2o 3a1 in powder 2o 3content is higher than 99%, more preferably higher than 99.9%.
Ii) by the vacation one water A1 of 200 mesh sieves 2o 3;
Iii) one or more alkaline-earth metal and/or its compound;
Iv) gross weight based on component i and ii is 0.01-5.0wt%, preferably the mineralizer of 1-4wt%;
V) binding agent; And
Vi) water;
Step 2, by the mixture moulding obtaining in step 1 dry, then obtains described catalyst carrier by its roasting.
After each component in step 1 is mixed, conventionally obtain paste.By gained paste, through step 2 moulding, preferably extrusion molding, obtains formed body, i.e. carrier blank.
In step 2, be dry at 80-200 ℃ by this formed body in temperature.The shape of gained formed body can be annular, spherical, cylindricality or porous column shape, or other shape.Described drying time is preferably more than 15 minutes.
The roasting at 1100-1600 ℃, preferred 1200-1500 ℃ of dried formed body.Make carrier have enough intensity and good surface property.Under the highest sintering temperature, conventionally carrier is incubated more than 1 hour.Make aluminium oxide substantially all be converted into α-A1 by roasting 2o 3, obtain thus porous alumina carrier.
In above-mentioned preparation method,
In above-mentioned carrier, the component i described in step 1 and the weight ratio of component ii are 0.1 ~ 16:1, are preferably 1 ~ 6:1.
The active A 1 of component in i) described in step 1 in preparation method of the present invention 2o 3can select the active A 1 of different crystalline phases and kind 2o 3powder or various active A 1 2o 3the mixture of powder, is pressed powder form conventionally, and requires A1 in powder 2o 3content is higher than 99%, preferably higher than 99.9%.
Active A 1 described in step 1 2o 3powder is selected from γ-A1 2o 3, ρ-A1 2o 3, α-A1 2o 3, κ-A1 2o 3and θ-A1 2o 3powder, and other various A1 2o 3one or more mutually; Preferably γ-A1 2o 3, ρ-A1 2o 3, α-A1 2o 3one, two or three in powder.
Owing to adopting the activated alumina of multiple crystalline phase and kind to replace or partly replacing the hydrate (being aluminium hydroxide) of aluminium oxide as preparing one of raw material of carrier, the performance of finished product carrier is improved, the loading type silver catalyst of being made up of this carrier, in the time of the oxidation epoxy ethane for catalyzed ethylene, is selectively obviously improved.
Component ii described in step 1) be conventionally also pressed powder form.
Component iii described in step 1) described alkaline-earth metal is selected from one or more in magnesium, calcium, strontium and barium, and alkaline earth metal compound is selected from oxide, sulfate, acetate, nitrate, carbonate and the oxalates of alkaline-earth metal; Preferably use one or more in barium monoxide, barium sulfate, barium nitrate, brium carbonate.
Component iv described in step 1) described mineralizer is fluoride, is preferably inorganic fluoride, more preferably one or more in hydrogen fluoride, ammonium fluoride, aluminum fluoride, magnesium fluoride and ice crystal (hexafluoro sodium aluminate).
In carrier of the present invention, also need to use v) binding agent of component, as add acid as bonding agent, it generates aluminium colloidal sol with the vacation one water aluminium oxide in mixture, each component is bonded together, becomes plastic paste, for example become can extrusion molding paste.
Component described in step 1 v) comprises acid, one or more in the preferred nitric acid of described acid, formic acid, acetic acid, propionic acid and hydrochloric acid, more preferably nitric acid and/or acetic acid in described bonding agent.In the time that described acid is aqueous solution of nitric acid, the weight ratio of nitric acid and water is 1:1.25 ~ 10, preferably 1:2 ~ 8.In addition, available aluminium sol-fraction or all replace described in component v a false water A1 described in acid and component ii 2o 3.
Component described in the step 1 v) consumption of binding agent is conventional, as long as each component can be bonded together, and forms paste.Typically, the consumption of binding agent be based on component i), ii), iii) and gross weight 15-60wt% iv), preferably 15-50wt%.
In carrier preparation method of the present invention, the mineralizer iv described in step 1) to add be the transformation of crystal for accelerated oxidation aluminium.
The present invention also provides a kind of silver catalyst, and this catalyst comprises:
1) catalyst carrier;
2) be deposited on the silver on this carrier;
3) alkali metal and/or alkaline-earth metal or the compound based on alkali metal and/or alkaline-earth metal;
4) rhenium metal and/or the compound based on rhenium; And
5) the collaborative auxiliary element of rhenium, it is selected from one or more metals in chromium, molybdenum, tungsten and boron, and/or is selected from the compound of one or more elements based in chromium, molybdenum, tungsten and boron.
Wherein, described alkali metal is to be selected from one or more in lithium, sodium, potassium, rubidium and caesium; Preferably caesium and/or potassium, most preferably be caesium;
Described alkaline-earth metal is to be selected from one or more in magnesium, calcium, strontium and barium, preferably strontium and/or barium;
The compound of described one or more elements based in chromium, molybdenum, tungsten and boron is the collaborative auxiliary agent of rhenium.
Silver catalyst of the present invention can be prepared in the usual way, for example, prepare by the carrier provided by the invention of the solution impregnation with a kind of Ag-containing compound and organic amine.In the present invention, the collaborative auxiliary agent of alkali metal, alkaline-earth metal, rhenium and rhenium before dipping silver, be applied in porous alpha-alumina supports in load silver or after load silver, or is immersed in porous alpha-alumina supports independently of one another after silver compound is reduced; Preferably load in load silver.
In silver catalyst of the present invention, silver is dispersed on the surface of porous infusibility alumina support and in 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, the weight content of silver is 1-35%, preferably 5-30%; The weight content of alkali metal is 5-2000ppm, is preferably 10-1500ppm; The weight content of alkali earth metal is 10-40000ppm, is preferably 800-25000ppm; The weight content of rhenium element is 5-1500ppm, is preferably 10-1000ppm; The weight content of the collaborative auxiliary element of rhenium is 5-1000ppm, is preferably 10-500ppm.
In one embodiment of the invention, the preparation method of silver catalyst of the present invention comprises the steps: the first step, by the solution impregnation porous alpha-alumina supports of the present invention of the collaborative auxiliary agent containing the silver compound of q.s, organic amine, optional alkali metal promoter, optional base earth metal promoter and optional rhenium auxiliary agent and optional rhenium; Second step, leaching maceration extract; With the 3rd step, in air or inert gas, second step gained carrier is activated, make described silver catalyst.
In order to prepare silver catalyst of the present invention, silver compound used can 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, organic amine compound used 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 mixture of for example ethylenediamine and monoethanolamine.
In order to prepare catalyst of the present invention, the optional alkali metal promoter using can be compound (as nitrate, sulfate and hydroxide) or its mixture of lithium, sodium, potassium, rubidium or caesium, preferably cesium nitrate, lithium nitrate and/or potassium hydroxide.
In order to prepare catalyst of the present invention, one or more in the compound that the optional base earth metal promoter using can be magnesium, calcium, strontium and barium, as as described in one or more in oxide, oxalates, sulfate, acetate and the nitrate of element, the preferably compound of 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 using can be oxide, perrhenic acid, the perrhenate of rhenium, or its mixture, preferably 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, can also add the coassist agent of rhenium auxiliary agent, further to improve the activity of gained silver catalyst, selective and stability.The coassist agent of the rhenium auxiliary agent in the present invention can be to be selected from one or more in chromium, molybdenum, tungsten and boron compound.
In impregnation steps, for guaranteeing all even abundant loads of silver, carrier preferably vacuumizes in advance.
After porous alpha-alumina supports dipping argentiferous maceration extract, leaching maceration extract, then in air or inert gas to step 3) in activate through the carrier of dipping.For this reason, can by the carrier through dipping 180-700 ℃, preferably the moving air of 200-500 ℃ or inert gas activate in as the air-flow such as nitrogen, argon gas, soak time at least 2 minutes conventionally, for example 2-120 minute, preferably 2-60 minute.For guaranteeing that catalyst has higher activity, this activation temperature should be higher than 500 ℃.
In a preferred embodiment of preparation silver catalyst of the present invention, first make the aqueous solution of silver nitrate react with ammonium oxalate or oxalic acid aqueous solution, separate out silver oxalate precipitation, after filtration, wash by deionized water, until without nitrate ion, after drying, silver oxalate is dissolved in to organic amine 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 be less than in vacuum with gained dipping solution under the condition of 10mmHg and flood porous alpha-alumina supports 10-60 minute of the present invention, drain, in air or inert gas, in the temperature range of 200-500 ℃, keep 1-120 minute, preferably 2-60 minute, to activate.Also can replace silver nitrate with silver oxide, silver oxalate also can not analysed filter, direct and organic amine complexing, then impregnated carrier.
The present invention also provides above-mentioned carrier, carrier prepared by said method or above-mentioned silver catalyst to produce the application in oxirane at ethylene.The stable performance of the silver catalyst of being made by carrier of the present invention, and there is higher activity and selectivity, be specially adapted to the reaction of ethylene production oxirane.
The specific embodiment
The mensuration of catalyst performance:
Various silver catalyst of the present invention is tested its activity and selectivity with laboratory microreactor evaluating apparatus.The reactor using in microreactor evaluating apparatus is the stainless steel reaction pipe of internal diameter 4mm, and reaction tube is placed in heating jacket.The admission space of catalyst is 1ml, and inert filler is arranged at bottom, makes beds be positioned at the flat-temperature zone of heating jacket.
The condition determination of the activity and selectivity that the present invention adopts is as follows:
Figure BDA00002304243800081
When stable reach above-mentioned reaction condition after METHOD FOR CONTINUOUS DETERMINATION reactor inlet and exit gas composition.Measurement result carries out calculating as follows selectively after volume contraction correction:
Figure BDA00002304243800082
Wherein, EO is that in reactor outlet gas and inlet gas, ethylene oxide concentration is poor, CO 2be that in reactor outlet gas and inlet gas, gas concentration lwevel is poor, get the average of 10 groups of above test datas as the result of the test on the same day.
The present invention is described further below in conjunction with embodiment, but scope of the present invention is not limited to these embodiment.
Comparative example 1
By 50-500 object three water A1 2o 3400g, excessively the vacation one water A1 of 200 mesh sieves 2o 3100g, ammonium fluoride 10g, BaSO 43g, puts into blender and mixes, and proceeds in kneader, adds 100 milliliters of 20 % by weight aqueous solution of nitric acid, be kneaded into can extrusion molding paste.Extrusion molding is the single hole column of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, at 80-120 ℃, is dried 2 hours, and free water content is reduced to below 10 % by weight, obtains green compact.Then green compact are put into electric furnace, are elevated to 1400 ℃ from room temperature, and under this high temperature constant temperature 2 hours, obtain white α-A1 2o 3support samples, is called comparison vehicle 1.
The preparation of carrier:
Embodiment 1
By α-A1 2o 3powder 400g, excessively the vacation one water A1 of 200 mesh sieves 2o 3100g, ammonium fluoride 10g, BaSO 43g puts into blender and mixes, and proceeds in kneader, adds 100 milliliters of 20 % by weight aqueous solution of nitric acid, be kneaded into can extrusion molding paste.Extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, at 80-120 ℃, is dried 2 hours, and free water content is reduced to below 10 % by weight, obtains green compact.Then green compact are put into electric furnace, are elevated to 1400 ℃ from room temperature, and under this high temperature constant temperature 2 hours, obtain white α-A1 2o 3support samples, is called invention carrier 1.
Embodiment 2
The preparation of invention carrier 2 is similar to the preparation of invention carrier 1, only by " α-A1 in carrier embodiment 1 2o 3powder 400g " change " γ-A1 into 2o 3powder 400g ".
Embodiment 3
The preparation of invention carrier 3 is similar to the preparation of invention carrier 1, only by " α-A1 in carrier embodiment 1 2o 3powder 400g " change " ρ-A1 into 2o 3powder 400g ".
Embodiment 4
The preparation of invention carrier 4 is similar to the preparation of invention carrier 1, only by " α-A1 in carrier embodiment 1 2o 3powder 400g " change " α-A1 into 2o 3powder 167g, γ-A1 2o 3powder 167g, ρ-A1 2o 3powder 167g ".
Embodiment 5
The preparation of invention carrier 5 is similar to the preparation of invention carrier 1, only by " α-A1 in carrier embodiment 1 2o 3powder 400g " change " α-A1 into 2o 3powder 100g, γ-A1 2o 3powder 100g, ρ-A1 2o 3powder 100g, 50-500 object three water A1 2o 3100g ".
Embodiment 6
The preparation of invention carrier 6 is similar to the preparation of invention carrier 1, only by " α-A1 in carrier embodiment 1 2o 3powder 400g " change " α-A1 into 2o 3powder 14g, γ-A1 2o 3powder 14g, ρ-A1 2o 3powder 14g, 50-500 object three water A1 2o 3358g ".
Embodiment 7
Prepared by the preparation of invention carrier 7 and invention carrier 4 similar, only by " BaSO in carrier embodiment 4 43g " change " Sr (AC) into 23.5g ".
Above-mentioned comparison vehicle 1 and invention carrier 1-6 are measured respectively to its crushing strength, water absorption rate, specific surface and pore volume etc., the results are shown in table 1.In the present invention, the crushing strength of carrier refers to side crush intensity, measures by intensity of pressure instrument; Specific area adopts nitrogen physisorption BET method to measure; Water absorption rate is measured by densimetry; And pore volume adopts pressure mercury method to measure.
Table 1
Figure BDA00002304243800101
The preparation of catalyst and performance test
Embodiment 8
In the glass flask stirring at band, add 350g ethylenediamine, 140g monoethanolamine, and 400g deionized water, obtain mixed liquor.Under stirring, silver oxalate is slowly added in gained mixed liquor, temperature remains on 10-25 ℃, and silver oxalate is all dissolved, and the addition of silver oxalate makes maceration extract argentiferous 24 % by weight that finally make.Add 3.0g cesium nitrate, 1.0g strontium acetate, and 4.5g ammonium perrhenate, then add deionized water and make solution gross mass reach 2000g, make maceration extract, stand-by.
Get comparison vehicle 1 and invention carrier 1-7 100g separately, put into respectively the container that can vacuumize.Be evacuated to low vacuum in 10mmHg, put into wherein above maceration extract, submergence carrier, keeps 30 minutes.Unnecessary maceration extract is removed in leaching afterwards.Carrier after dipping is heated 5 minutes in the air stream of 250 ℃, cooling, make ethylene oxide silver catalyst, they are respectively comparative catalyst 1 and invention catalyst 1-7.
The comparative catalyst 1 who makes and invention catalyst 1-7 silver content and auxiliary agent content are separately analyzed, and wherein each content is all in metal.
Use microreactor evaluating apparatus under the described process conditions of " mensuration of catalyst performance " part, to measure the activity and selectivity of each catalyst sample above, result of the test is listed in table 2.
Table 2
As can be seen from Table 2, comparative catalyst 1 reaction temperature (being active temperature) will be higher than the reaction temperature of catalyst of the present invention, and comparative catalyst 1 be selectively less than the selective of catalyst of the present invention.Although invention catalyst 7 reaction temperatures are close with comparative catalyst, it selectively will be higher than comparative catalyst 1.
Embodiment 9
With method Preparation Example 9 similar to Example 8, just substitute 3.0g cesium nitrate, the alternative 1g strontium acetate of 0.5g magnesium sulfate with 3.0g potassium nitrate, and add again 1g ammonium tungstate to add again deionized water beyond 4.5g ammonium perrhenate to make solution gross mass reach 2000g, make maceration extract adding, stand-by.
Get comparison vehicle 1 and invention carrier 1-7 100g separately, put into respectively the container that can vacuumize.Be evacuated to low vacuum in 10mmHg, put into wherein above maceration extract, submergence carrier, keeps 30 minutes.Unnecessary maceration extract is removed in leaching afterwards.Carrier after dipping is heated 5 minutes in the air stream of 250 ℃, cooling, make ethylene oxide silver catalyst, they are respectively comparative catalyst 2 and invention catalyst 8-14.
The comparative catalyst 2 who makes and invention catalyst 8-14 silver content and auxiliary agent content are separately analyzed, and wherein each content is all in metal.
Use microreactor evaluating apparatus under the described process conditions of " mensuration of catalyst performance " part, to measure the activity and selectivity of each catalyst sample above, result of the test is listed in table 3.
Table 3
Figure BDA00002304243800121
As can be seen from Table 3, comparative catalyst 2 reaction temperature (being active temperature) will be higher than catalyst of the present invention, and comparative catalyst 2 be selectively less than the selective of catalyst of the present invention.Although invention catalyst 9 reaction temperatures are close with comparative catalyst, it selectively will be higher than comparative catalyst 2.

Claims (10)

1. a catalyst carrier, comprising:
A) porous A1 2o 3, it comprises α-A1 2o 3, described α-A1 2o 3weight content be at least 85 ~ 99.9% of total weight of carrier, preferably 90 ~ 99.9%; With
B) one or more alkaline-earth metal and/or alkaline earth metal compound, it is 0.01-15wt% that its metallic element weight accounts for total weight of carrier content, preferably 0.1-3wt%;
Described porous A1 2o 3preferably external diameter is the cellular cylindrical α-A1 in 7-9mm and honeycomb aperture be 1-3mm seven apertures in the human head, five holes or three holes 2o 3particle, or external diameter is the circular α-A1 of single hole that 7-9mm and internal diameter are 3-6mm 2o 3particle;
One or more in described alkaline-earth metal preferably magnesium, calcium, strontium and barium, more preferably strontium and/or barium; One or more in oxide, sulfate, acetate, nitrate, carbonate and the oxalates of described alkaline earth metal compound preferred bases earth metal, more preferably one or more in barium monoxide, barium sulfate, barium nitrate and brium carbonate.
2. catalyst carrier according to claim 1, is characterized in that, the crushing strength of described catalyst carrier is more than 20N/ grain, is preferably 40-200N/ grain; Specific area is 0.2-5.0m 2/ g, is preferably 0.5-2.0m 2/ g; Water absorption rate is>=30%, be preferably>=45%; Pore volume is 0.35-0.85ml/g, is preferably 0.40-0.8ml/g.
3. according to a preparation method for the catalyst carrier described in right 1 or 2, comprise the following steps:
Step 1, forms the mixture that comprises following component:
I) active A 1 2o 3powder or active A 1 2o 3powder and 50 order-500 object three water A1 2o 3mixture;
Described active A 1 2o 3powder content, based on i) the more than 1% of gross weight of component, is preferably more than 10%, and more preferably 100%;
Preferred described A1 2o 3a1 in powder 2o 3content is higher than 99%, more preferably higher than 99.9%;
Ii) by the vacation one water A1 of 200 mesh sieves 2o 3;
Iii) one or more alkaline-earth metal and/or alkaline earth metal compound;
Iv) gross weight based on component i and ii is 0.01-5.0wt%, preferably the mineralizer of 1-4wt%;
V) binding agent; And
Vi) water;
Step 2, obtains formed body dry by the mixture moulding obtaining in step 1, then its roasting is obtained to described catalyst carrier.
4. method according to claim 3, is characterized in that, it is 80-200 ℃ that the formed body described in step 2 is dried in temperature; The roasting at 1100-1600 ℃, preferred 1200-1500 ℃ of dried formed body.
5. according to the method described in claim 3 or 4, it is characterized in that, the component described in step 1 i) with component ii) weight ratio be 0.1 ~ 16:1, be preferably 1 ~ 6:1.
6. according to the method described in claim 3 or 4, it is characterized in that the active A 1 of component in i) described in step 1 2o 3powder is selected from γ-A1 2o 3, ρ-A1 2o 3, α-A1 2o 3, κ-A1 2o 3and θ-A1 2o 3one or more in powder; Preferably γ-A1 2o 3, ρ-A1 2o 3or α-A1 2o 3one, two or three in powder.
7. according to the method described in claim 3 or 4, it is characterized in that, component iv described in step 1) described mineralizer is fluoride, preferably from inorganic fluoride, more preferably one or more in hydrogen fluoride, ammonium fluoride, aluminum fluoride, magnesium fluoride and ice crystal.
8. according to the method described in claim 3 or 4, it is characterized in that, the component described in step 1 v) comprises acid in bonding agent, one or more in the preferred nitric acid of described acid, formic acid, acetic acid, propionic acid and hydrochloric acid, more preferably nitric acid and/or acetic acid.
9. method according to claim 8, is characterized in that, the consumption of described binding agent be based on component i), ii), iii) and gross weight 15-60% iv), preferably 15-50%.
10. a silver catalyst that utilizes carrier according to claim 1 and 2 to prepare, this catalyst comprises:
1) catalyst carrier;
2) be deposited on the silver on this carrier;
3) alkali metal and/or alkaline-earth metal or the compound based on alkali metal and/or alkaline-earth metal;
4) rhenium metal and/or the compound based on rhenium; And
5) the collaborative auxiliary element of rhenium, it is selected from one or more metals in chromium, molybdenum, tungsten and boron, and/or is selected from the compound of one or more elements based in chromium, molybdenum, tungsten and boron.
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CN103977836A (en) * 2014-05-29 2014-08-13 湖南尔康制药股份有限公司 Narrowly distributed catalyst for fatty acid ethoxylation and preparation method of narrowly distributed catalyst
CN105435820A (en) * 2014-08-12 2016-03-30 中国石油化工股份有限公司 Alumina carrier preparation method and silver catalyst and application of silver catalyst
CN106955693A (en) * 2016-01-08 2017-07-18 中国石油化工股份有限公司 The alpha-alumina supports of ethylene epoxidizing silver catalyst and its preparation and application
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
CN105856076B (en) * 2016-06-06 2019-03-12 江西应陶康顺实业有限公司 A kind of catalyst carrier bore wall polishing process
CN109499558A (en) * 2017-09-15 2019-03-22 中国石油化工股份有限公司 A kind of alpha-alumina supports, silver catalyst and olefin epoxidation process
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CN103977836A (en) * 2014-05-29 2014-08-13 湖南尔康制药股份有限公司 Narrowly distributed catalyst for fatty acid ethoxylation and preparation method of narrowly distributed catalyst
CN105435820A (en) * 2014-08-12 2016-03-30 中国石油化工股份有限公司 Alumina carrier preparation method and silver catalyst and application of silver catalyst
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CN106955693B (en) * 2016-01-08 2022-08-19 中国石油化工股份有限公司 Alpha-alumina carrier of silver catalyst for ethylene epoxidation as well as preparation and application thereof
CN105856076B (en) * 2016-06-06 2019-03-12 江西应陶康顺实业有限公司 A kind of catalyst carrier bore wall polishing process
CN108607618A (en) * 2016-12-09 2018-10-02 中国石油化工股份有限公司 A kind of alumina support, the silver catalyst prepared by the carrier and its application
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CN109499558A (en) * 2017-09-15 2019-03-22 中国石油化工股份有限公司 A kind of alpha-alumina supports, silver catalyst and olefin epoxidation process
CN109499558B (en) * 2017-09-15 2021-09-21 中国石油化工股份有限公司 Alpha-alumina carrier, silver catalyst and olefin epoxidation method
WO2019114577A1 (en) * 2017-12-12 2019-06-20 高化学技术株式会社 METHOD FOR PREPARING α-AL2O3 CARRIER, CARRIER OBTAINED THEREBY, AND USE THEREOF

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