CN106311353A - Alpha-alumina support, corresponding silver catalyst and application - Google Patents

Alpha-alumina support, corresponding silver catalyst and application Download PDF

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CN106311353A
CN106311353A CN201510381538.6A CN201510381538A CN106311353A CN 106311353 A CN106311353 A CN 106311353A CN 201510381538 A CN201510381538 A CN 201510381538A CN 106311353 A CN106311353 A CN 106311353A
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silver
quality
silver catalyst
alpha
alumina
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CN106311353B (en
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王辉
林伟
李贤丰
李金兵
李秀聪
曹淑媛
孙欣欣
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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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    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
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    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses an alpha-alumina support, a corresponding silver catalyst, preparation methods for the alpha-alumina support and the corresponding silver catalyst and an application of the silver catalyst in production of epoxy compounds from alkenes through epoxidation. The methods comprise the steps: subjecting siliceous alumina monohydrate, which serves as a raw material, fluorides and alkaline earth metal compounds, which serve as assistants to kneading, forming, drying and roasting, thereby preparing the alpha-alumina support, wherein the mass of silicon (by SiO2) in the alumina monohydrate accounts for 0.05% to 10.0% that of the alumina monohydrate; and dipping the prepared support in a solution containing organic amine, a silver compound, a tungsten assistant, a rhenium assistant and an alkali metal assistant, and carrying out leaching and activating, thereby preparing the silver catalyst. The silver catalyst can represent very good selectivity and stability in a reaction for producing the epoxy compounds from the alkenes through epoxidation, particularly in a reaction for producing ethylene oxide from ethylene through epoxidation, and the speed of selectivity increase is high.

Description

A kind of alpha-alumina supports, corresponding silver catalyst and application
Technical field
The invention belongs to catalysis technical field, relate to a kind of alpha-alumina supports and corresponding silver catalyst, they Preparation method, and this silver catalyst produces the application in epoxide at epoxidation reaction of olefines.
Background technology
Oxirane is a kind of important basic petrochemical Organic Ingredients, and it can derive more than 100 kind of chemical industry Product and chemicals, mainly for the production of polyester, antifreezing agent, unsaturated polyester resin, lubricant, plasticizer, The industries such as nonionic surfactant and explosive, coating, ink, additionally can be used for producing special solvent, Purposes is quite varied.The main method of commercial synthesis ethylene glycol is to produce ethylene, second through petrochemical industry route at present Alkene occurs epoxidation reaction to produce oxirane under the effect of silver catalyst.Silver catalyst generally comprise carrier, The active component silver being deposited on carrier and one or more additional elements components, these additional elements play auxiliary agent Or the effect of coassist agent, is used for improving the catalytic performance of silver catalyst.Silver catalyst carrier is the most high temperature resistant Alpha-alumina.The performance of silver catalyst in addition to having important relationship with the composition of catalyst and preparation method, also with Performance and the preparation method of alpha-alumina supports have important relationship.
High-temperature roasting is one of step preparing alpha-alumina supports.In roasting process, aluminium oxide undergoes phase transition, Sintering, causes the significantly decline of carrier specific surface, the active constituent of load so can be caused to assemble, catalyst Inactivations etc., leverage the service life of catalyst and the popularization and application of technology.Oxidation of ethylene produces epoxy second Alkane is strong exothermal reaction, and the alpha-alumina supports with suitable specific surface and aperture just has bigger effective catalysis Surface, reactant and product molecule can quickly pass in and out catalyst surfaces externally and internally, reaction heat carried in time simultaneously Walk, prevent thermal accumlation, make the activity of catalyst and stability be improved.The modification of carrier can improve α- Alumina support and the performance of silver catalyst, as improve carrier surface Acidity of Aikalinity, improve carrier specific surface area and Pore structure, improve active component silver dispersibility on carrier, regulation silver surface electronics situation, modulation reactant The adsorption desorption situation planted, thus improve the catalytic performance of silver catalyst.But it is loaded down with trivial details that the method has operating process, The deficiency of preparation time length.
In industrial processes, not only the activity of silver catalyst, selectivity, stability are paid close attention to, and silver is urged It is also that people are paid close attention to that agent selectivity promotes speed.For production efficiency, quick selectivity promotes speed Degree can improve production efficiency, expands yield.For economic benefit, quick selectivity promotes speed and ties up The stability holding catalyst can substantially reduce running cost, it is thus achieved that more product, increases economic efficiency.
Summary of the invention
In order to improve the performance of silver catalyst, the present inventor has done substantial amounts of experimentation, finds only choosing With a siliceous water aluminium oxide as raw material, fluoride and alkaline earth metal compound as auxiliary agent, a wherein water oxidation In aluminum, element silicon quality is (with SiO2Meter) account for the 0.05~10.0% of a water quality of alumina, through kneading, molding, Be dried, roasting, prepare alpha-alumina supports, then with containing organic amine, silver compound, tungsten auxiliary agent, rhenium auxiliary agent, Carrier prepared by the solution impregnation of alkali metal promoter, makes silver catalyst through leaching, activation.This silver catalyst In alkene epoxidation produces epoxide reaction, particularly in ethylene epoxidizing produces reacting ethylene oxide The selectivity that can do well and stability, and selectivity lifting speed is fast.
Therefore, an object of the present invention is to provide a kind of alpha-alumina supports, and it is as loading type silver catalyst Carrier have the feature that Alpha-alumina quality accounts for carrier quality >=98%, silicon content is with SiO2It is calculated as 0.05~9.0wt%, specific surface is 0.5~4.0m2/ g, pore volume is 0.35~0.85ml/g, water absorption rate >=30%, crushing Intensity is 30~300N/ grains.
The two of the purpose of the present invention are to provide a kind of loading type silver catalyst, help including argent, tungsten auxiliary agent, rhenium Agent, alkali metal promoter and described alpha-alumina supports.The quality of described argent accounts for described silver catalyst quality 10~40%;The quality of wolfram element accounts for the 5~20000ppm of described silver catalyst quality, preferably 50~5000ppm; The quality of rhenium element accounts for the 10~10000ppm of described silver catalyst quality, preferably 100~4000ppm;Alkali metal The quality of element accounts for the 5~5000ppm of described silver catalyst quality, preferably 100~3000ppm.
The three of the purpose of the present invention are to provide the preparation method of described alpha-alumina supports, comprise the steps: step Rapid A, obtains solids by a siliceous water aluminium oxide, fluoride and alkaline earth metal compound mix homogeneously, then adds Enter binding agent and water obtains mixture;Step B, mixture step A obtained carries out mediating, molding, dry Dry, roasting, i.e. prepares alpha-alumina supports.Wherein, element silicon matter in the water aluminium oxide described in step A Amount is (with SiO2Meter) account for the 0.05~10.0% of a water quality of alumina, preferably 0.05~5.0%.
In the preparation method of alpha-alumina supports of the present invention, a described water aluminium oxide be boehmite and/ Or diaspore.Described fluoride one in fluohydric acid gas, ammonium fluoride, Afluon (Asta) and lithium fluoride or Multiple, the effect of fluoride is the transformation of crystal of accelerated oxidation aluminum, and reduces the pore of below 0.1 μm.Institute The alkaline earth metal compound stated is selected from magnesium and/or the oxide of barium, nitrate, sulfate, carbonate, oxalates With one or more in chloride, the machinery that the addition of alkaline earth metal compound can improve alumina support is strong Degree.
In the preparation method of alpha-alumina supports of the present invention, a described water quality of alumina accounts for solids quality 50.0~99.9%.Described fluoride quality accounts for the 0.1~10.0% of solids quality.Described alkaline-earth metal Compound quality accounts for the 0.1~15.0% of solids quality.
In the preparation method of alpha-alumina supports of the present invention, described binding agent is selected from citric acid, nitric acid, salt One or more in acid, formic acid, acetic acid and propanoic acid.The effect of binding agent is and the water oxygen in solids Changing aluminum and generate Alumina gel, each component be bonded together, becoming can the paste of extrusion molding.Bonding agent and water Weight ratio be 1:1~1:10.
In the preparation method of alpha-alumina supports of the present invention, in order to manufacture macropore, alumina support is made to have conjunction Suitable pore structure and specific surface area, can add can after-flame carbonaceous material.This is because carbonaceous material is in roasting In journey, oxidation generates gas effusion, thus forms macropore in the carrier.Carbonaceous material selected from polyethylene, polypropylene, One or more in petroleum coke, carbon dust, graphite and vaseline.Carbonaceous material quality accounts for solids quality 0~30%.
In the preparation method of alpha-alumina supports of the present invention, mixture can be dried to containing after kneading, molding The water yield≤10%.Baking temperature is 60~150 DEG C, and drying time controls 1~24h according to moisture.It is dried After molded body roasting 2~48h at 1200~1600 DEG C, make aluminium oxide be substantially transitioned to alpha-alumina supports.
The silver catalyst of the present invention uses above-mentioned alpha-alumina supports to prepare.The silver catalyst of the present invention can be routinely Prepared by mode, such as by by the above-mentioned alumina support system of solution impregnation of a kind of Ag-containing compound and organic amine Standby.
The interpolation of active component of the present invention silver can use traditional infusion process to implement.First by silver nitrate aqueous solution with Ammonium oxalate or oxalic acid aqueous solution react and separate out silver oxalate precipitate with vigorous stirring, then through overaging, filtration, Deionized water wash, until without nitrate ion, obtaining silver oxalate paste, then silver oxalate is dissolved in containing In organic amine and compounding agent solution, it is configured to uniform impregnation liquid, uses under conditions of vacuum is less than 10mmHg This impregnation liquid dipping alpha-alumina supports of preparing of said method, drains, air or noble gas such as nitrogen, The air-flows such as argon keep in 200~500 DEG C of temperature ranges 2~120min, to activate.Oxygen can also be used Changing silver and replace silver nitrate, silver oxalate can not also analyse filter.In order to improve the catalytic performance of silver catalyst, the present invention Silver catalyst the most also can add alkali metal promoter, tungsten auxiliary agent and rhenium auxiliary agent simultaneously, and these auxiliary agents can be Before immersion silver, it is applied on carrier simultaneously or after, it is also possible to after silver compound is reduced to, be immersed in load On body.Described dipping includes once or repeatedly, until it reaches required silver and auxiliary agent content.
The four of the purpose of the present invention are to provide a kind of alkene epoxidation and produce the silver catalyst used by epoxide, 1. its preparation method comprises the steps: step, alpha-alumina supports prepared by the present invention with containing organic amine, Silver compound, tungsten auxiliary agent, rhenium auxiliary agent and the solution impregnation of alkali metal promoter;Step 2., will dipping after α-oxygen Change alumina supporter and carry out leaching and activation, make described silver catalyst.
In the preparation method of silver catalyst of the present invention, described organic amine selected from pyridine, ethylenediamine, 1,2-fourth two Amine, 1,3-butanediamine, ethamine, n-propylamine, n-butylamine, isobutylamine, tert-butylamine, sec-butylamine, One or more in 1,2-propane diamine, 1,3-propane diamine, ethanolamine, Propanolamine and butanolamine.
In the preparation method of silver catalyst of the present invention, described silver compound is selected from silver oxide, silver nitrate and oxalic acid One or more in silver.Described tungsten auxiliary agent one or many in the oxide of tungsten, tungsten salt and tungstates Kind.One or more in rheium oxide, ammonium perrhenate, perrhenic acid and perrhenic acid caesium of described rhenium auxiliary agent. Described alkali metal promoter is selected from lithium, sodium, potassium, rubidium, the oxide of caesium, hydroxide, nitrate, carbonic acid One or more in salt, oxalates, sulfate, phosphate and acetate.In order to improve the property of silver catalyst Can, the coassist agent of alkaline-earth metal and/or rhenium can be added in the solution, described base earth metal promoter selected from magnesium, In calcium, strontium, the oxide of barium, hydroxide, oxalates, sulfate, carbonate, nitrate and acetate One or more, the coassist agent selected from cerium of described rhenium, sulfur, molybdenum, chromium formed salt or above-mentioned element with acid One or more in the oxygen anion that form exists.
In the preparation method of silver catalyst of the present invention, urge to obtain the silver of relatively high silver content and/or auxiliary agent content Agent, can prepare silver-containing catalyst by the method that one or many impregnates.
In the preparation method of silver catalyst of the present invention, described activation is to be not more than 21% at air or oxygen content The nitrogen oxygen atmosphere of volume is carried out.
In the preparation method of silver catalyst of the present invention, the temperature of described activation is 150~400 DEG C, activation time Between be 1~120min.
Except deposited silver, tungsten auxiliary agent, rhenium auxiliary agent and alkali metal promoter in alpha-alumina supports prepared by the present invention, And outside the coassist agent of the aforementioned base earth metal promoter that may be optionally added and/or rhenium, it is also possible to by other element deposition On described carrier, one or more in phosphorus, boron, chromium and titanium of other described element.
The five of the purpose of the present invention there is provided silver catalyst prepared by the present invention and produce at epoxidation reaction of olefines Application in epoxide, described alkene one in styrene, propylene, ethylene and 1,3-butadiene Or multiple, and this silver catalyst is demonstrated by well being catalyzed activity and initial selectivity.Ring prepared by said method Oxygen compound can also be further converted to 1,2-alcohol, 1,2-glycol ethers, alkanolamine.
Detailed description of the invention
The mensuration of silver catalyst catalytic performance:
The various silver catalyst laboratory microreactor evaluating apparatus of the present invention test its selectivity.Miniature instead Answering the reactor of use in device evaluating apparatus is the stainless steel reaction pipe of internal diameter 4mm, and reaction tube is placed in heating mantle In.The admission space of catalyst is 1ml, and inert filler is arranged at bottom, makes beds be positioned at the perseverance of heating mantle Warm area.
The condition determination of the activity and selectivity that the present invention uses is as shown in table 1:
Table 1
After stably reaching above-mentioned reaction condition, METHOD FOR CONTINUOUS DETERMINATION reactor inlet and exit gas composition.To mensuration After result carries out volume contraction correction, calculate selectivity as follows:
Selectivity S = Δ E O Δ E O + 0.5 × ΔCO 2 × 100 %
Wherein Δ EO is reactor outlet gas and inlet gas ethylene oxide concentration difference, Δ CO2It it is reactor outlet Gas is poor with gas concentration lwevel in inlet gas, takes the average test as the same day of more than 10 groups test datas Result.
The present invention is described further below in conjunction with embodiment, but the scope of the present invention is not limited to these enforcement Example.
Comparative example 1
The preparation of alpha-alumina supports: weigh 491.0g boehmite, wherein element silicon matter in boehmite Amount is (with SiO2Meter) account for the 0.01% of boehmite quality, 6.0g ammonium fluoride, 3.0g barium sulfate, put into mixed Mix homogeneously in glassware, is transferred in kneader, adds dust technology (nitric acid: water=1:3, volume ratio) straight To be kneaded into can the paste of extrusion molding, paste placed in banded extruder, be extruded into five hole columns, Dry more than 24h at 60~90 DEG C, make free water content be reduced to less than 10%, then by five dried holes Column puts into natural gas kiln kiln roasting, and sintering temperature is 1300 DEG C, and constant temperature calcining 20h is finally cooled to Room temperature, obtains alpha-alumina supports.The related physical performance data of this carrier is shown in Table 2.
The preparation of silver catalyst: weigh 140.0g silver nitrate and be dissolved in 150.0ml deionized water, weigh 64.0g Ammonium oxalate is dissolved in 520.0ml deionized water, fully dissolves, and obtains silver nitrate solution and ammonium oxalate solution, It is stirred vigorously two kinds of solution of lower mixing gained, generates white silver oxalate precipitate.Aging 1h, filter, spend from Sub-water washing filter cake is until without nitrate ion in filtrate, obtaining silver oxalate paste filter cake.Filter cake contains argent About 60wt%, aqueous about 15wt%.60.0g ethylenediamine, 22.0g ethanol is added in the glass flask of band stirring Amine and 75.0g deionized water, continuously stirred make silver oxalate all dissolve, and keeps mixed solution temperature at-5~10 DEG C. Then it is sequentially added into 0.17g ammonium metatungstate, 0.24g ammonium perrhenate, 0.53g cesium sulfate to mixed solution, then adds Entering deionized water makes solution gross mass reach 400g, and it is stand-by that mix homogeneously makes dipping solution.Take comparative example 1 to make Standby carrier 20g, puts it in the glass container of energy evacuation, pours the dipping solution prepared into, soak completely Ning carrier, be evacuated to less than 10mmHg, keep about 15min, then unnecessary solution is removed in leaching. Finally impregnated support samples is placed in the air of 320 DEG C heating 3min, cooling, i.e. makes silver catalysis Agent.
Microreactor evaluating apparatus is used to measure the selection of the catalyst sample made under the conditions of previous process Property, result of the test is listed in table 3.
Embodiment 1
The preparation of alpha-alumina supports: weigh 491.0g boehmite, wherein element silicon matter in boehmite Amount is (with SiO2Meter) account for the 0.05% of boehmite quality, 6.0g ammonium fluoride, 3.0g barium sulfate, put into mixed Mix homogeneously in glassware, is transferred in kneader, adds dust technology (nitric acid: water=1:3, volume ratio) straight To be kneaded into can the paste of extrusion molding, paste placed in banded extruder, be extruded into five hole columns, Dry more than 24h at 60~90 DEG C, make free water content be reduced to less than 10%, then by five dried holes Column puts into natural gas kiln kiln roasting, and sintering temperature is 1300 DEG C, and constant temperature calcining 20h is finally cooled to Room temperature, obtains alpha-alumina supports.The related physical performance data of this carrier is shown in Table 2.
The preparation method of silver catalyst is identical with comparative example 1.
Microreactor evaluating apparatus is used to measure the selection of the catalyst sample made under the conditions of previous process Property, result of the test is listed in table 3.
Comparative example 2
The preparation of alpha-alumina supports: weigh 491.0g boehmite, wherein element silicon matter in boehmite Amount is (with SiO2Meter) account for the 0.10% of boehmite quality, 6.0g ammonium fluoride, 3.0g barium sulfate, put into mixed Mix homogeneously in glassware, is transferred in kneader, adds dust technology (nitric acid: water=1:3, volume ratio) straight To be kneaded into can the paste of extrusion molding, paste placed in banded extruder, be extruded into five hole columns, Dry more than 24h at 60~90 DEG C, make free water content be reduced to less than 10%, then by five dried holes Column puts into natural gas kiln kiln roasting, and sintering temperature is 1250 DEG C, and constant temperature calcining 20h is finally cooled to Room temperature, obtains alpha-alumina supports.The related physical performance data of this carrier is shown in Table 2.
The preparation of silver catalyst: weigh 140.0g silver nitrate and be dissolved in 150.0ml deionized water, weigh 64.0g Ammonium oxalate is dissolved in 520.0ml deionized water, fully dissolves, and obtains silver nitrate solution and ammonium oxalate solution, It is stirred vigorously two kinds of solution of lower mixing gained, generates white silver oxalate precipitate.Aging 1h, filter, spend from Sub-water washing filter cake is until without nitrate ion in filtrate, obtaining silver oxalate paste filter cake.Filter cake contains argent About 60wt%, aqueous about 15wt%.60.0g ethylenediamine, 22.0g ethanol is added in the glass flask of band stirring Amine and 75.0g deionized water, continuously stirred make silver oxalate all dissolve, and keeps mixed solution temperature at-5~10 DEG C. Then it is sequentially added into 0.50g strontium acetate, 0.24g ammonium perrhenate, 0.53g cesium sulfate to mixed solution, adds Deionized water makes solution gross mass reach 400g, and it is stand-by that mix homogeneously makes dipping solution.Take comparative example 1 to prepare Carrier 20g, put it into can evacuation glass container in, pour the dipping solution prepared into, be totally submerged Carrier, is evacuated to less than 10mmHg, keeps about 15min, and then unnecessary solution is removed in leaching. Finally impregnated support samples is placed in the air of 320 DEG C heating 3min, cooling, i.e. makes silver catalysis Agent.
Microreactor evaluating apparatus is used to measure the selection of the catalyst sample made under the conditions of previous process Property, result of the test is listed in table 3.
Embodiment 2
Alpha-alumina supports preparation method is identical with comparative example 2.
The preparation of silver catalyst: weigh 140.0g silver nitrate and be dissolved in 150.0ml deionized water, weigh 64.0g Ammonium oxalate is dissolved in 520.0ml deionized water, fully dissolves, and obtains silver nitrate solution and ammonium oxalate solution, It is stirred vigorously two kinds of solution of lower mixing gained, generates white silver oxalate precipitate.Aging 1h, filter, spend from Sub-water washing filter cake is until without nitrate ion in filtrate, obtaining silver oxalate paste filter cake.Filter cake contains argent About 60wt%, aqueous about 15wt%.60.0g ethylenediamine, 22.0g ethanol is added in the glass flask of band stirring Amine and 75.0g deionized water, continuously stirred make silver oxalate all dissolve, and keeps mixed solution temperature at-5~10 DEG C. Then it is sequentially added into 0.21g ammonium metatungstate, 0.24g ammonium perrhenate, 0.53g cesium sulfate to mixed solution, then adds Entering deionized water makes solution gross mass reach 400g, and it is stand-by that mix homogeneously makes dipping solution.Take comparative example 1 to make Standby carrier 20g, puts it in the glass container of energy evacuation, pours the dipping solution prepared into, soak completely Ning carrier, be evacuated to less than 10mmHg, keep about 15min, then unnecessary solution is removed in leaching. Finally impregnated support samples is placed in the air of 320 DEG C heating 3min, cooling, i.e. makes silver catalysis Agent.
Microreactor evaluating apparatus is used to measure the selection of the catalyst sample made under the conditions of previous process Property, result of the test is listed in table 3.
Embodiment 3
Alpha-alumina supports preparation method is identical with comparative example 2.Except ammonium metatungstate in silver catalyst preparation method Addition quality is 0.25g, ammonium perrhenate addition quality is that outside 0.40g, other are same as in Example 2.
Microreactor evaluating apparatus is used to measure the selection of the catalyst sample made under the conditions of previous process Property, result of the test is listed in table 3.
Embodiment 4
The preparation of alpha-alumina supports: weigh 491.0g boehmite, wherein element silicon matter in boehmite Amount is (with SiO2Meter) account for the 0.35% of boehmite quality, 6.0g ammonium fluoride, 3.0g barium sulfate, put into mixed Mix homogeneously in glassware, is transferred in kneader, adds dust technology (nitric acid: water=1:3, volume ratio) straight To be kneaded into can the paste of extrusion molding, paste placed in banded extruder, be extruded into five hole columns, Dry more than 24h at 60~90 DEG C, make free water content be reduced to less than 10%, then by five dried holes Column puts into natural gas kiln kiln roasting, and sintering temperature is 1350 DEG C, and constant temperature calcining 20h is finally cooled to Room temperature, obtains alpha-alumina supports.The related physical performance data of this carrier is shown in Table 2.
The preparation of silver catalyst: weigh 140.0g silver nitrate and be dissolved in 150.0ml deionized water, weigh 64.0g Ammonium oxalate is dissolved in 520.0ml deionized water, fully dissolves, and obtains silver nitrate solution and ammonium oxalate solution, It is stirred vigorously two kinds of solution of lower mixing gained, generates white silver oxalate precipitate.Aging 1h, filter, spend from Sub-water washing filter cake is until without nitrate ion in filtrate, obtaining silver oxalate paste filter cake.Filter cake contains argent About 60wt%, aqueous about 15wt%.60.0g ethylenediamine, 22.0g ethanol is added in the glass flask of band stirring Amine and 75.0g deionized water, continuously stirred make silver oxalate all dissolve, and keeps mixed solution temperature at-5~10 DEG C. Then it is sequentially added into 0.20g ammonium tungstate, 0.39g ammonium perrhenate, 0.65g cesium nitrate to mixed solution, adds Deionized water makes solution gross mass reach 400g, and it is stand-by that mix homogeneously makes dipping solution.Take comparative example 1 to prepare Carrier 20g, put it into can evacuation glass container in, pour the dipping solution prepared into, be totally submerged Carrier, is evacuated to less than 10mmHg, keeps about 15min, and then unnecessary solution is removed in leaching. Finally impregnated support samples is placed in the air of 320 DEG C heating 3min, cooling, i.e. makes silver catalysis Agent.
Microreactor evaluating apparatus is used to measure the selection of the catalyst sample made under the conditions of previous process Property, result of the test is listed in table 3.
Embodiment 5
The preparation of alpha-alumina supports: weigh 491.0g boehmite, wherein element silicon matter in boehmite Amount is (with SiO2Meter) account for the 0.50% of boehmite quality, 6.0g ammonium fluoride, 3.0g barium sulfate, put into mixed Mix homogeneously in glassware, is transferred in kneader, adds dust technology (nitric acid: water=1:3, volume ratio) straight To be kneaded into can the paste of extrusion molding, paste placed in banded extruder, be extruded into five hole columns, Dry more than 24h at 60~90 DEG C, make free water content be reduced to less than 10%, then by five dried holes Column puts into natural gas kiln kiln roasting, and sintering temperature is 1350 DEG C, and constant temperature calcining 20h is finally cooled to Room temperature, obtains alpha-alumina supports.The related physical performance data of this carrier is shown in Table 2.
The preparation of silver catalyst: weigh 140.0g silver nitrate and be dissolved in 150.0ml deionized water, weigh 64.0g Ammonium oxalate is dissolved in 520.0ml deionized water, fully dissolves, and obtains silver nitrate solution and ammonium oxalate solution, It is stirred vigorously two kinds of solution of lower mixing gained, generates white silver oxalate precipitate.Aging 1h, filter, spend from Sub-water washing filter cake is until without nitrate ion in filtrate, obtaining silver oxalate paste filter cake.Filter cake contains argent About 60wt%, aqueous about 15wt%.60.0g ethylenediamine, 22.0g ethanol is added in the glass flask of band stirring Amine and 75.0g deionized water, continuously stirred make silver oxalate all dissolve, and keeps mixed solution temperature at-5~10 DEG C. Then it is sequentially added into 0.27g ammonium tungstate, 0.25g ammonium perrhenate, 0.61g cesium sulfate to mixed solution, adds Deionized water makes solution gross mass reach 400g, and it is stand-by that mix homogeneously makes dipping solution.Take comparative example 1 to prepare Carrier 20g, put it into can evacuation glass container in, pour the dipping solution prepared into, be totally submerged Carrier, is evacuated to less than 10mmHg, keeps about 15min, and then unnecessary solution is removed in leaching. Finally impregnated support samples is placed in the air of 320 DEG C heating 3min, cooling, i.e. makes silver catalysis Agent.
Microreactor evaluating apparatus is used to measure the selection of the catalyst sample made under the conditions of previous process Property, result of the test is listed in table 3.
Embodiment 6
The preparation of alpha-alumina supports: weigh 491.0g boehmite, wherein element silicon matter in boehmite Amount is (with SiO2Meter) account for the 1.70% of boehmite quality, 6.0g ammonium fluoride, 3.0g barium sulfate, put into mixed Mix homogeneously in glassware, is transferred in kneader, adds dust technology (nitric acid: water=1:3, volume ratio) straight To be kneaded into can the paste of extrusion molding, paste placed in banded extruder, be extruded into five hole columns, Dry more than 24h at 60~90 DEG C, make free water content be reduced to less than 10%, then by five dried holes Column puts into natural gas kiln kiln roasting, and sintering temperature is 1380 DEG C, and constant temperature calcining 20h is finally cooled to Room temperature, obtains alpha-alumina supports.The related physical performance data of this carrier is shown in Table 2.
The preparation of silver catalyst: weigh 140.0g silver nitrate and be dissolved in 150.0ml deionized water, weigh 64.0g Ammonium oxalate is dissolved in 520.0ml deionized water, fully dissolves, and obtains silver nitrate solution and ammonium oxalate solution, It is stirred vigorously two kinds of solution of lower mixing gained, generates white silver oxalate precipitate.Aging 1h, filter, spend from Sub-water washing filter cake is until without nitrate ion in filtrate, obtaining silver oxalate paste filter cake.Filter cake contains argent About 60wt%, aqueous about 15wt%.60.0g ethylenediamine, 22.0g ethanol is added in the glass flask of band stirring Amine and 75.0g deionized water, continuously stirred make silver oxalate all dissolve, and keeps mixed solution temperature at-5~10 DEG C. Then it is sequentially added into 0.25g ammonium metatungstate, 0.40g ammonium perrhenate, 0.65g cesium nitrate to mixed solution, then adds Entering deionized water makes solution gross mass reach 400g, and it is stand-by that mix homogeneously makes dipping solution.Take comparative example 1 to make Standby carrier 20g, puts it in the glass container of energy evacuation, pours the dipping solution prepared into, soak completely Ning carrier, be evacuated to less than 10mmHg, keep about 15min, then unnecessary solution is removed in leaching. Finally impregnated support samples is placed in the air of 320 DEG C heating 3min, cooling, i.e. makes silver catalysis Agent.
Microreactor evaluating apparatus is used to measure the selection of the catalyst sample made under the conditions of previous process Property, result of the test is listed in table 3.
Embodiment 7
The preparation of alpha-alumina supports: weigh 491.0g boehmite, wherein element silicon matter in boehmite Amount is (with SiO2Meter) account for the 3.80% of boehmite quality, 6.0g ammonium fluoride, 3.0g barium sulfate, put into mixed Mix homogeneously in glassware, is transferred in kneader, adds dust technology (nitric acid: water=1:3, volume ratio) straight To be kneaded into can the paste of extrusion molding, paste placed in banded extruder, be extruded into five hole columns, Dry more than 24h at 60~90 DEG C, make free water content be reduced to less than 10%, then by five dried holes Column puts into natural gas kiln kiln roasting, and sintering temperature is 1400 DEG C, and constant temperature calcining 20h is finally cooled to Room temperature, obtains alpha-alumina supports.The related physical performance data of this carrier is shown in Table 2.
The preparation method of silver catalyst is identical with comparative example 1.
Microreactor evaluating apparatus is used to measure the selection of the catalyst sample made under the conditions of previous process Property, result of the test is listed in table 3.
Embodiment 8
The preparation of alpha-alumina supports: weigh 491.0g boehmite, wherein element silicon matter in boehmite Amount is (with SiO2Meter) account for the 7.10% of boehmite quality, 6.0g ammonium fluoride, 3.0g barium sulfate, put into mixed Mix homogeneously in glassware, is transferred in kneader, adds dust technology (nitric acid: water=1:3, volume ratio) straight To be kneaded into can the paste of extrusion molding, paste placed in banded extruder, be extruded into five hole columns, Dry more than 24h at 60~90 DEG C, make free water content be reduced to less than 10%, then by five dried holes Column puts into natural gas kiln kiln roasting, and sintering temperature is 1420 DEG C, and constant temperature calcining 20h is finally cooled to Room temperature, obtains alpha-alumina supports.The related physical performance data of this carrier is shown in Table 2.
The preparation of silver catalyst: weigh 140.0g silver nitrate and be dissolved in 150.0ml deionized water, weigh 64.0g Ammonium oxalate is dissolved in 520.0ml deionized water, fully dissolves, and obtains silver nitrate solution and ammonium oxalate solution, It is stirred vigorously two kinds of solution of lower mixing gained, generates white silver oxalate precipitate.Aging 1h, filter, spend from Sub-water washing filter cake is until without nitrate ion in filtrate, obtaining silver oxalate paste filter cake.Filter cake contains argent About 60wt%, aqueous about 15wt%.60.0g ethylenediamine, 22.0g ethanol is added in the glass flask of band stirring Amine and 75.0g deionized water, continuously stirred make silver oxalate all dissolve, and keeps mixed solution temperature at-5~10 DEG C. Then it is sequentially added into 0.20g ammonium metatungstate, 0.25g ammonium perrhenate, 0.65g cesium nitrate to mixed solution, then adds Entering deionized water makes solution gross mass reach 400g, and it is stand-by that mix homogeneously makes dipping solution.Take comparative example 1 to make Standby carrier 20g, puts it in the glass container of energy evacuation, pours the dipping solution prepared into, soak completely Ning carrier, be evacuated to less than 10mmHg, keep about 15min, then unnecessary solution is removed in leaching. Finally impregnated support samples is placed in the air of 320 DEG C heating 3min, cooling, i.e. makes silver catalysis Agent.
Microreactor evaluating apparatus is used to measure the selection of the catalyst sample made under the conditions of previous process Property, result of the test is listed in table 3.
Table 2
Silicone content (wt%) Specific surface area (m2/g) Crushing strength (N/ grain)
Comparative example 1 0.01 1.41 209
Comparative example 2 0.06 1.87 196
Embodiment 1 0.08 2.59 154
Embodiment 2 0.08 2.59 154
Embodiment 3 0.08 2.59 154
Embodiment 4 0.27 2.43 231
Embodiment 5 0.39 2.71 243
Embodiment 6 1.97 2.68 246
Embodiment 7 4.61 2.66 261
Embodiment 8 7.96 2.75 272
Table 3
* selectivity (%) # selectivity (%)
Comparative example 1 83.0 83.2
Comparative example 2 83.4 84.5
Embodiment 1 84.6 84.9
Embodiment 2 85.1 85.5
Embodiment 3 85.9 85.8
Embodiment 4 86.0 86.1
Embodiment 5 84.7 85.1
Embodiment 6 86.2 85.9
Embodiment 7 85.7 85.9
Embodiment 8 85.3 85.8
* selectivity is the selectivity that silver catalyst is evaluated the 3rd day, and # selectivity is that silver catalyst evaluates the 30th day Selectivity.
By contrast table 2 data it can be seen that appropriate silicon content and at silver catalyst in a water aluminium oxide Preparation process adds suitably silver auxiliary agent and content and can improve the performance of silver catalyst.Appropriate element silicon energy Enough increase the specific surface area of alpha-alumina supports, improve silver and auxiliary agent dispersibility on carrier surface thereof, improve The catalytic performance of silver catalyst.Evaluating the 3rd day adding the silver catalyst that suitably prepared by silver auxiliary agent and content Selectivity be up to more than 84.0%, be close with evaluating the selectivity of the 30th day, this illustrates that this silver catalyst has There are higher catalytic selectivity and stability, and optionally promote speed quickly.It addition, embodiment 2 with The comparative example 2 not adding wolfram element in silver catalyst preparation process is compared, and evaluates the 3rd day and the choosing of the 30th day Selecting property is improved.
It should be noted that, embodiment described above is only used for explaining the present invention, it is not intended that the present invention's Any restriction.By referring to exemplary embodiments, invention has been described, it should be appreciated that used by wherein Word is descriptive and explanatory vocabulary rather than limited vocabulary.Can be by regulation in the claims in the present invention In the range of the present invention is modified, and in without departing substantially from scope and spirit of the present invention, the present invention is carried out Revision.Although the present invention described in it relates to specific method, material and embodiment, it is not intended that The present invention is limited to wherein disclosed particular case, and on the contrary, the present invention can be extended to other and all has identical function Methods and applications.

Claims (10)

1. an alpha-alumina supports, its preparation method comprises the steps:
Step A, obtains solids by a siliceous water aluminium oxide, fluoride and alkaline earth metal compound mix homogeneously, Add binding agent and water obtains mixture;
Step B, mixture step A obtained carries out mediating, molding, be dried and roasting, obtain described α- Alumina support;
Wherein, with SiO2Meter, in a described water aluminium oxide, element silicon quality accounts for a water quality of alumina 0.05~10.0%, preferably 0.05~5.0%.
Carrier the most according to claim 1, it is characterised in that the water aluminium oxide described in step A is Boehmite and/or diaspore;Described fluoride is selected from fluohydric acid gas, ammonium fluoride, Afluon (Asta) and fluorination One or more in lithium;Described alkaline earth metal compound is selected from magnesium and/or the oxide of barium, nitrate, sulfur One or more in hydrochlorate, carbonate, oxalates and chloride;And/or
One or more in citric acid, nitric acid, hydrochloric acid, formic acid, acetic acid and propanoic acid of described binding agent, Preferably bonding agent is 1:1~1:10 with the weight ratio of water.
Carrier the most according to claim 1 and 2, it is characterised in that in step A, a described water Quality of alumina accounts for the 50.0~99.9% of solids quality;Described fluoride quality accounts for solids quality 0.1~10.0%;Described alkaline earth metal compound quality accounts for the 0.1~15.0% of solids quality.
Carrier the most according to any one of claim 1 to 3, it is characterised in that α in described carrier- Quality of alumina accounts for carrier quality >=98%, and silicon content is with SiO2Being calculated as 0.05~9.0wt%, specific surface is 0.5~4.0m2/ g, pore volume is 0.35~0.85ml/g, water absorption rate >=30%, and crushing strength is 30~300N/ grains.
5. a silver catalyst, its preparation method comprises the steps:
1. alpha-alumina supports described in any one of Claims 1-4, is closed by step with containing organic amine, patina Thing, tungsten auxiliary agent, rhenium auxiliary agent and the solution impregnation of alkali metal promoter;
2. alpha-alumina supports after dipping, is carried out leaching and activation, obtains described silver catalyst by step.
Silver catalyst the most according to claim 5, it is characterised in that described organic amine is selected from pyridine, second Diamidogen, 1,2-butanediamine, 1,3-butanediamine, ethamine, n-propylamine, n-butylamine, isobutylamine, tert-butylamine, One or more in sec-butylamine, 1,2-propane diamine, 1,3-propane diamine, ethanolamine, Propanolamine and butanolamine.
7. according to the silver catalyst described in claim 5 or 6, it is characterised in that described silver compound is selected from oxygen Change one or more in silver, silver nitrate and silver oxalate;Described tungsten auxiliary agent selected from the oxide of tungsten, tungsten salt and One or more in tungstates;Described rhenium auxiliary agent is selected from rheium oxide, ammonium perrhenate, perrhenic acid and perrhenic acid One or more in caesium;Described alkali metal promoter is selected from lithium, sodium, potassium, rubidium, the oxide of caesium, hydrogen-oxygen One or more in compound, nitrate, carbonate, oxalates, sulfate, phosphate and acetate.
8. according to the silver catalyst described in any one of claim 5 to 7, it is characterised in that described activation exists Air or oxygen content no more than 21% volume nitrogen oxygen atmosphere in carry out, preferably activation temperature is 150~400 DEG C, Time is 1~120min.
9. according to the silver catalyst described in any one of claim 5 to 8, it is characterised in that the quality of silver accounts for institute State the 10~40% of silver catalyst quality;The quality of wolfram element accounts for the 5~20000ppm of described silver catalyst quality, It is preferably 50~5000ppm;The quality of rhenium element accounts for the 10~10000ppm of described silver catalyst quality, preferably It is 100~4000ppm;The quality of alkali metal accounts for the 5~5000ppm of described silver catalyst quality, is preferably 100~3000ppm.
10. the silver catalyst described in any one of claim 5 to 9 produces epoxy compound at epoxidation reaction of olefines Application in thing, the most described alkene one or many in styrene, propylene, ethylene and 1,3-butadiene Kind.
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CN117427666B (en) * 2023-12-22 2024-02-27 橙雨化学(大连)有限公司 Te modified alumina carrier and preparation method thereof

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