CN105080618A - Method for preparing alpha-alumina support for silver catalyst - Google Patents
Method for preparing alpha-alumina support for silver catalyst Download PDFInfo
- Publication number
- CN105080618A CN105080618A CN201410195968.4A CN201410195968A CN105080618A CN 105080618 A CN105080618 A CN 105080618A CN 201410195968 A CN201410195968 A CN 201410195968A CN 105080618 A CN105080618 A CN 105080618A
- Authority
- CN
- China
- Prior art keywords
- alpha
- solid mixture
- silver
- gross mass
- alumina
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing an alpha-alumina support for a silver catalyst. The method comprises the steps: (A) preparing a solid mixture with the following ingredients in percentage by weight: a. 50.0-99.0wt% of diaspore, b. 0-40.0wt% of pseudo-boehmite, c. 0.01-10.0wt% of tungstenic compound, d. 0-15.0wt% of heavy alkaline earth metal containing compound and e. 0.01-10.0wt% of fluorine-containing compound; and adding a bonder and water into the obtained solid mixture, so as to obtain a mixture; and (B) kneading, molding, drying and roasting the mixture obtained in the step (A), thereby preparing the tungstenic alpha-alumina support. The silver catalyst is prepared through dipping the alumina support prepared by the method disclosed by the invention with silver and shows good selectivity and reaction activity in the reaction of producing epoxy compounds through epoxidation of olefins.
Description
Technical field
The invention belongs to catalysis technical field, relate to silver catalyst and application thereof prepared by a kind of alumina support and preparation method thereof, thus carrier.More particularly, the present invention relates to the preparation method that a kind of alkene epoxidation produces the alpha-alumina supports of epoxide silver catalyst used.
Background technology
Produce in epoxide reaction at alkene epoxidation, under certain reaction condition, the reaction mixture gas containing alkene and oxygen is under the effect of catalyst, and the accessory substance such as epoxide and a small amount of carbon dioxide, water is produced in reaction.Oxirane, as the one in epoxide, under the effect of silver-containing catalyst, can obtain using ethene and oxygen as reaction gas.Oxirane can react generating glycol with water, reacts generating glycol ether with alcohol, or reacts with amine and generate monoethanolamine.
Up to now, silver-containing catalyst remains unique effective catalyst that industrial alkene epoxidation produces epoxide.Silver-containing catalyst comprises the silver components being therewith deposited on the additional elements on carrier with one or more usually.These additional elements play the effect of auxiliary agent or coassist agent, are used for improving the catalytic performance of silver catalyst, and they are deposited on carrier by one or more maceration extracts of use.Silver-containing catalyst is generally carrier through the solution impregnation of argentiferous and/or additional elements, then obtains silver-containing catalyst through activation heat treatment.Also the silver-containing catalyst of relatively high silver content can be had by the method preparation of repeatedly flooding.Active, selective and stability evaluates the main performance index of silver-containing catalyst.
Silver-containing catalyst carrier is made up of resistant to elevated temperatures Alpha-alumina usually.The material preparing the alpha-alumina supports of silver-containing catalyst generally comprises: alpha-alumina powder and/or its presoma; Binding agent, for shortening particle bond sintering time together; Thermal decomposition burnout materials, forms material for serving as duct; Lubricant, is conducive to carrier shaping; Auxiliary agent, for improving the performance of alpha-alumina supports and/or silver-containing catalyst.In general, the method preparing alpha-alumina supports is that these raw materials are carried out batch mixing, kneading, then shaping according to difform molding blank, eventually passes high temperature sintering and makes alpha-alumina supports.Weigh alpha-alumina supports performance important parameter to have: specific area, pore volume, compression strength, water absorption rate, content etc.
The performance of silver catalyst is except having important relationship with the composition of catalyst and preparation method, and performance and the preparation method of the carrier also used with silver catalyst have important relationship.Patent US2006/021903 discloses silver-containing catalyst carrier and prepares material: a) the first particle Alpha-alumina of 50 ~ 95wt%, and its mean pore sizes is 5 ~ 100 μm; B) the second particle Alpha-alumina of 5 ~ 50wt%, its mean pore sizes be less than described first particle Alpha-alumina and be 1 ~ 10 μm; C) alkaline-earth-metal silicate jointing material.The carrier of preparation has at least 1.3m
2the surface area of/g, being greater than at least 80% of total pore volume in the mean pore sizes distribution of 0.8 μm and pore-size distribution, to be included in diameter be in the hole of 0.1 ~ 10 μm.The carrier of preparation floods through silver compound, reduces to form metallic silver particles, finally obtains silver-containing catalyst.A kind of preparation method of alpha-alumina supports is disclosed in patent CN102133544A, comprise mixed industrial α-gibbsite, a false Water oxidize aluminium, can burnout carbonaceous material, alkali salt, fluoride, binding agent and water, then obtain described alpha-alumina supports through extruded, dry and roasting.Patent EP1994/002996 discloses a kind of alpha-alumina supports containing two kinds of Alpha-alumina components.The preparation method of this alpha-alumina supports is: by least one median grain diameter 3 ~ 8 μm Alpha-alumina component, the Alpha-alumina aquation parent of q.s, after-flame agent, the titanium oxide mixing that adds can be selected arbitrarily after add water, roasting again after extrusion molding.
Provide alpha-alumina supports and silver catalyst that some activity are improved in above-mentioned prior art, but this area still needs the better alumina support of catalyzing expoxidation of olefines performance silver catalyst corresponding to it.
Summary of the invention
In view of the situation of above-mentioned prior art, the present inventor has carried out extensive, deep research in alpha-alumina supports preparation field, and research and development obtain a kind ofly in carrier preparation process, adding the preparation method of the alpha-alumina supports of Tungstenic compound and the corresponding alpha-alumina supports obtaining tungstenic; Prepare corresponding silver catalyst by dipping again, this silver catalyst is produced in epoxide reaction at alkene epoxidation and is shown good selective and reactivity.
Therefore, the invention provides a kind of preparation method of the alpha-alumina supports for silver catalyst, comprise the steps: steps A, preparation has the solid mixture of following composition: a, account for the diaspore that solid mixture gross mass is 50.0 ~ 99.0wt%; B, account for the boehmite that solid mixture gross mass is 0 ~ 40.0wt%; C, account for the Tungstenic compound that solid mixture gross mass is 0.01 ~ 10.0wt%; D, account for solid mixture gross mass be 0 ~ 15.0wt% containing heavy alkaline earth metal compound; E, account for the fluorochemical that solid mixture gross mass is 0.01 ~ 10.0wt%; And in gained solid mixture, add binding agent and water obtains mixture; Step B, mixture steps A obtained carries out mediating, shaping, dry and roasting, prepares the alpha-alumina supports of tungstenic.
In the present invention, described Tungstenic compound comprise in oxide, tungsten salt, tungstates one or more, be preferably tungsten oxide and/or ammonium tungstate.
In a kind of detailed description of the invention, the diaspore in steps A is boehmite and/or diaspore; Described boehmite is SB powder.
In the present invention, preferably, it is 75 ~ 99.0wt% that one diaspore accounts for solid mixture gross mass, it is 0 ~ 20.0wt% that boehmite accounts for solid mixture gross mass, it is 0.1 ~ 2.0wt% that Tungstenic compound accounts for solid mixture gross mass, accounting for solid mixture gross mass containing heavy alkaline earth metal compound is 0.1 ~ 2wt%, and it is 0.1 ~ 5wt% that fluorochemical accounts for solid mixture gross mass.
In the present invention, the object adding fluorochemical in preparation alpha-alumina supports process is the crystal transfer in order to accelerated oxidation aluminium.Described fluorochemical comprise in hydrogen fluoride, aluminum fluoride, ammonium fluoride, magnesium fluoride, ice crystal one or more.
In the present invention, the object adding heavy alkaline earth metal compound in preparation alpha-alumina supports process is the performance in order to improve alpha-alumina supports.Described heavy alkaline earth metal compound comprise in the oxide of strontium and/or barium, sulfate, nitrate, oxalates one or more.
In the present invention, need a diaspore, boehmite, fluorochemical, alkali salt and Tungstenic compound to mix in preparation alpha-alumina supports process.Described being blended in batch mixer is carried out, and mixing time is 15 ~ 50min.
In the present invention, in preparation alpha-alumina supports process, usually add binding agent, the boehmite in it and solid, powdery thing generates Alumina gel, each component is bonded together, and becoming can the paste of extrusion molding.Described binding agent comprise in citric acid, nitric acid, formic acid, acetic acid, propionic acid and hydrochloric acid one or more, or binding agent and boehmite Alumina gel to be replaced.When using binding agent, the weight ratio of binding agent and water is 1:1.25 ~ 10.
In the present invention, solid, powdery thing obtains mixture needs and mediates after adding binding agent and water, mediate and carry out in kneader, kneading time is 20 ~ 60min, pinching into can the paste of extrusion molding, paste is shaping in forming machine, become single hole or porous cylindrical thing, column is again through super-dry process, and baking temperature is 20 ~ 100 DEG C, and the time is 20 ~ 48h, control column wet weight not higher than 10%, dried column is through roasting, and sintering temperature is 1100 ~ 1500 DEG C, and the time is 2 ~ 48h.
In the present invention, in the roasting process of preparation alpha-alumina supports, aluminium-containing substance is changed into Alpha-alumina, obtains alpha-alumina supports.Described alpha-alumina supports has following characteristics: the content of Alpha-alumina in described alumina support is not less than 90wt%, and the mass content of W elements in alumina support is 0.01 ~ 6.0wt%, is preferably 0.1 ~ 2wt%; The specific area of carrier is 0.5 ~ 3.0m
2/ g, pore volume is 0.35 ~ 0.85ml/g, and compression strength is 50 ~ 300N/ grain, water absorption rate>=30%.
Preparation alpha-alumina supports of the present invention after, those skilled in the art can by known methods or any usual manner prepare silver catalyst of the present invention.As usually used the above-mentioned alpha-alumina supports of solution impregnation of the coassist agent of organic amine, silver compound, alkali metal promoter, base earth metal promoter, optional rhenium auxiliary agent and rhenium auxiliary agent containing q.s.
Therefore, the invention provides a kind of preparation method of silver catalyst, comprise first with the above-mentioned alumina support of solution impregnation of the coassist agent containing organic amine, Ag-containing compound, alkali metal promoter, base earth metal promoter, optional rhenium auxiliary agent and rhenium auxiliary agent, leaching maceration extract again, then in oxygen-containing gas, the carrier of leaching gained is activated, namely obtain described silver catalyst.
In the present invention, preparing in silver catalyst process, adding of organic amine is to form argent-amine complex with silver compound.Described organic amine comprises 1,2-propane diamine, 1, one or more in 3-propane diamine, ethylenediamine, 1,2-butanediamine, 1,3-butanediamine, pyridine, ethamine, n-propylamine, n-butylamine, isobutylamine, tert-butylamine, sec-butylamine, monoethanolamine, Propanolamine, butanolamine.
In the present invention, preparing in silver catalyst process, silver compound comprise in silver oxide, silver nitrate, silver oxalate one or more, and the quality of described silver element accounts for 10 ~ 40% of described silver catalyst quality.
In the present invention, preparing in silver catalyst process, described alkali metal promoter comprise in lithium, sodium, potassium, rubidium, the nitrate of caesium, sulfate, hydroxide one or more, and the quality of described alkali metal promoter accounts for 5 ~ 2000ppm of described silver catalyst quality.Alkali metal promoter can dipping silver before, be applied on carrier simultaneously, afterwards, also can impregnated support-activated after be immersed on carrier.
In the present invention, preparing in silver catalyst process, described base earth metal promoter comprise in magnesium, calcium, strontium, the acetate of barium, oxalates, sulfate, nitrate one or more, and the quality of described base earth metal promoter accounts for 5 ~ 20000ppm of described silver catalyst quality.
In the present invention, preparing in silver catalyst process, described rhenium auxiliary agent comprise in rheium oxide, ammonium perrhenate, perrhenic acid, perrhenic acid caesium one or more, and the quality of described rhenium auxiliary agent accounts for 50 ~ 10000ppm of described silver catalyst quality.In the present invention, preparing in silver catalyst process, the coassist agent of described rhenium auxiliary agent comprise in the oxygen anion of cerium, sulphur, molybdenum, chromium, salt or sour form one or more.
In the present invention, preparing in silver catalyst process, solution in order to the coassist agent with the organic amine containing q.s, silver compound, alkali metal promoter, base earth metal promoter, optional rhenium auxiliary agent and rhenium auxiliary agent fully floods alpha-alumina supports prepared by said method, usually flood alpha-alumina supports be less than the condition of 10mmHg in vacuum under, dip time is 5 ~ 60min.Leaching maceration extract after dipping, then activate in the nitrogen oxygen atmosphere being not more than 21% volume at air or oxygen content, activation temperature is 150 ~ 400 DEG C, and soak time is 1 ~ 120min.
In the present invention, in order to prepare silver catalyst of the present invention, the aqueous solution of silver nitrate and ammonium oxalate or oxalic acid aqueous solution is first made to react, separate out silver oxalate precipitate, filter, spend deionized water, until exist without nitrate ion, then silver oxalate is added in the aqueous solution of organic amine, then adds the coassist agent of alkali metal promoter, base earth metal promoter, optional rhenium auxiliary agent and rhenium auxiliary agent, be made into maceration extract, by alpha-alumina supports prepared by gained impregnation fluid said method, leaching maceration extract, activation, finally makes described silver catalyst.
In order to obtain the silver catalyst compared with high silver content and/or auxiliary agent content, the method that the present invention can be flooded by one or many prepares silver-containing catalyst.
The auxiliary agents such as the coassist agent of the alkali metal added in silver catalyst preparation process of the present invention, alkaline-earth metal, rhenium auxiliary agent and rhenium can before dipping silver, also can be deposited on carrier after silver compound is by activating and reducing simultaneously or deposit to afterwards on carrier.
The present invention also provides a kind of epoxidation reaction of olefines to produce the method for epoxide, described epoxidation reaction is carried out under the silver catalyst that said method prepares exists, and described alkene be selected from styrene, propylene, ethene and 1,3-butadiene one or more.
The present invention also provides more than one to state method and produces the method that the oxirane obtained is one or more materials in raw material production ethylene glycol, glycol ether and monoethanolamine.
Detailed description of the invention
The mensuration of catalyst performance:
Various silver catalyst laboratories of the present invention microreactor evaluating apparatus tests its reactivity and selective.The reactor used 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 reactivity that the present invention adopts and optionally condition determination are as table 1:
Table 1
METHOD FOR CONTINUOUS DETERMINATION reactor inlet and exit gas composition after above-mentioned reaction condition is reached when stable.Measurement result calculates selective as follows after carrying out volume contraction correction:
Wherein Δ EO is reactor outlet gas and inlet gas ethylene oxide concentration difference, Δ CO
2be that in reactor outlet gas and inlet gas, gas concentration lwevel is poor, get the result of the test of average as the same day of more than 10 groups test datas.
The present invention is described further below in conjunction with embodiment, but scope of the present invention is not limited to these embodiments.
Comparative example 1
Prepared by alpha-alumina supports: the SB powder of the boehmite of 438.0g, 50.0g, 3.0g barium salt, 8.0g fluoride are put into blender and mixed, proceed in kneader, add dust technology (nitric acid: water=1:3, volume ratio), can the paste of extrusion molding until be kneaded into.Finally paste is put into banded extruder, extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, at 80 ~ 120 DEG C, dry more than 24h, makes free water content be reduced to less than 10%.Then five dried hole columns are put into natural gas kiln kiln roasting, sintering temperature is 1200 DEG C, and constant temperature calcining 24h, is finally cooled to room temperature, obtains alpha-alumina supports.The related physical performance data of this carrier is in table 2.
The preparation of silver catalyst: take 140.0g silver nitrate and be dissolved in 150.0ml deionized water, take 64.0g ammonium oxalate to be dissolved in 520.0ml deionized water, fully dissolve, obtain liquor argenti nitratis ophthalmicus and ammonium oxalate solution, mix two kinds of solution of gained with vigorous stirring, generate white silver oxalate precipitate.Aging 1h, filters, spends deionized water filter cake until without nitrate ion in filtrate, obtain silver oxalate paste filter cake.Filter cake containing metal silver about 60wt%, moisture about 15wt%.In the glass flask that band stirs, add 60.0g ethylenediamine, 22.0g monoethanolamine and 75.0g deionized water, Keep agitation makes silver oxalate all dissolve, and keeps mixed solution temperature at-5 ~ 10 DEG C.Then add 0.5g cesium nitrate, 0.3g barium acetate, 0.4g ammonium perrhenate successively to mixed solution, then add deionized water and make solution gross mass reach 400g, mix that to make dipping solution stand-by.Get carrier 20g prepared by comparative example 1, put it in the glass container that can vacuumize, pour the dipping solution prepared into, complete submergence carrier, is evacuated to lower than 10mmHg, keeps about 15min, and then unnecessary solution is removed in leaching.Finally impregnated support samples be placed in the air of 360 DEG C and heat 3min, cooling, namely makes silver catalyst.
Evaluating catalyst: use microreactor evaluating apparatus to measure the activity and selectivity of catalyst under previous process condition to the catalyst made, result of the test lists in table 2.
Embodiment 1
Prepared by alpha-alumina supports: the ammonium tungstate of the SB powder of the boehmite of 438.0g, 50.0g, 1.0g, 3.0g barium salt, 8.0g fluoride are put into blender and mixed, proceed in kneader, add dust technology (nitric acid: water=1:3, volume ratio), can the paste of extrusion molding until be kneaded into.Finally paste is put into banded extruder, extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, at 80 ~ 120 DEG C, dry more than 24h, makes free water content be reduced to less than 10%.Then five dried hole columns are put into natural gas kiln kiln roasting, sintering temperature is 1200 DEG C, and constant temperature calcining 24h, is finally cooled to room temperature, obtains alpha-alumina supports.The related physical performance data of this carrier is in table 2.
Its Alpha-alumina corresponding modify is only the alpha-alumina supports of preparation in embodiment 1 by the preparation of silver catalyst: identical with the silver catalyst preparation method in comparative example 1.
Evaluating catalyst: use microreactor evaluating apparatus to measure the activity and selectivity of catalyst under previous process condition to the catalyst made, result of the test lists in table 2.
Embodiment 2
Prepared by alpha-alumina supports: the ammonium tungstate of the SB powder of the boehmite of 438.0g, 50.0g, 2.0g, 2.0g barium salt, 8.0g fluoride are put into blender and mixed, proceed in kneader, add dust technology (nitric acid: water=1:3, volume ratio), can the paste of extrusion molding until be kneaded into.Finally paste is put into banded extruder, extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, at 80 ~ 120 DEG C, dry more than 24h, makes free water content be reduced to less than 10%.Then five dried hole columns are put into natural gas kiln kiln roasting, sintering temperature is 1300 DEG C, and constant temperature calcining 24h, is finally cooled to room temperature, obtains alpha-alumina supports.The related physical performance data of this carrier is in table 2.
Its Alpha-alumina corresponding modify is only the alpha-alumina supports of preparation in embodiment 2 by the preparation of silver catalyst: identical with the silver catalyst preparation method in comparative example 1.
Evaluating catalyst: use microreactor evaluating apparatus to measure the activity and selectivity of catalyst under previous process condition to the catalyst made, result of the test lists in table 2.
Embodiment 3
Prepared by alpha-alumina supports: the tungsten oxide of the boehmite of 485.5g, 2.5g, 4.0g barium salt, 8.0g fluoride are put into blender and mixed, proceed in kneader, add dust technology (nitric acid: water=1:3, volume ratio), can the paste of extrusion molding until be kneaded into.Finally paste is put into banded extruder, extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, at 80 ~ 120 DEG C, dry more than 24h, makes free water content be reduced to less than 10%.Then five dried hole columns are put into natural gas kiln kiln roasting, sintering temperature is 1300 DEG C, and constant temperature calcining 24h, is finally cooled to room temperature, obtains alpha-alumina supports.The related physical performance data of this carrier is in table 2.
Its Alpha-alumina corresponding modify is only the alpha-alumina supports of preparation in embodiment 3 by the preparation of silver catalyst: identical with the silver catalyst preparation method in comparative example 1.
Evaluating catalyst: use microreactor evaluating apparatus to measure the activity and selectivity of catalyst under previous process condition to the catalyst made, result of the test lists in table 2.
Embodiment 4
Prepared by alpha-alumina supports: the SB powder of the boehmite of 385.0g, 100.0g, 4.0g tungsten oxide, the barium salt of 3.0g, the fluoride of 8.0g are put into blender and mixed, proceed in kneader, add dust technology (nitric acid: water=1:3, volume ratio), can the paste of extrusion molding until be kneaded into.Finally paste is put into banded extruder, extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, at 80 ~ 120 DEG C, dry more than 24h, makes free water content be reduced to less than 10%.Then five dried hole columns are put into natural gas kiln kiln roasting, sintering temperature is 1200 DEG C, and constant temperature calcining 24h, is finally cooled to room temperature, obtains alpha-alumina supports.The related physical performance data of this carrier is in table 2.
Its Alpha-alumina corresponding modify is only the alpha-alumina supports of preparation in embodiment 4 by the preparation of silver catalyst: identical with the silver catalyst preparation method in comparative example 1.
Evaluating catalyst: use microreactor evaluating apparatus to measure the activity and selectivity of catalyst under previous process condition to the catalyst made, result of the test lists in table 2.
Embodiment 5
Prepared by alpha-alumina supports: the boehmite of 478.0g, 10.0g sodium tungstate, 4.0g barium salt, 8.0g fluoride are put into blender and mixed, proceed in kneader, add dust technology (nitric acid: water=1:3, volume ratio), can the paste of extrusion molding until be kneaded into.Finally paste is put into banded extruder, extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, at 80 ~ 120 DEG C, dry more than 24h, makes free water content be reduced to less than 10%.Then five dried hole columns are put into natural gas kiln kiln roasting, sintering temperature is 1400 DEG C, and constant temperature calcining 24h, is finally cooled to room temperature, obtains alpha-alumina supports.The related physical performance data of this carrier is in table 2.
Its Alpha-alumina corresponding modify is only the alpha-alumina supports of preparation in embodiment 5 by the preparation of silver catalyst: identical with the silver catalyst preparation method in comparative example 1.
Evaluating catalyst: use microreactor evaluating apparatus to measure the activity and selectivity of catalyst under previous process condition to the catalyst made, result of the test lists in table 2.
Table 2
From the experimental data of table 2, by selecting a diaspore, optional SB powder, Tungstenic compound, preparing alpha-alumina supports containing heavy alkaline earth metal compound and fluorochemical as raw material in embodiment, this carrier through containing solution impregnation, the activation of organic amine, Ag-containing compound, alkali metal promoter, base earth metal promoter, optional rhenium auxiliary agent and coassist agent thereof, prepares silver-containing catalyst again.This silver-containing catalyst shows good reactivity and selective in epoxidation reaction of olefines.And from table 2 experimental data of comparative example 1 and embodiment, in alpha-alumina supports preparation process, add Tungstenic compound in embodiment and prepare alpha-alumina supports, the silver catalyst that thus prepared by carrier shows than the better reactivity of comparative example and selective in epoxidation reaction of olefines.
Claims (10)
1., for a preparation method for the alpha-alumina supports of silver catalyst, comprise the steps:
Steps A, preparation has the solid mixture of following composition:
A, account for the diaspore that solid mixture gross mass is 50.0 ~ 99.0wt%;
B, account for the boehmite that solid mixture gross mass is 0 ~ 40.0wt%;
C, account for the Tungstenic compound that solid mixture gross mass is 0.01 ~ 10.0wt%;
D, account for solid mixture gross mass be 0 ~ 15.0wt% containing heavy alkaline earth metal compound;
E, account for the fluorochemical that solid mixture gross mass is 0.01 ~ 10.0wt%;
And in gained solid mixture, add binding agent and water obtains mixture;
Step B, mixture steps A obtained carries out mediating, shaping, dry and roasting, prepares the alpha-alumina supports of tungstenic.
2. method according to claim 1, is characterized in that, the Tungstenic compound in described steps A comprise in tungsten oxide, tungsten salt and tungstates one or more, be preferably tungsten oxide and/or ammonium tungstate.
3. method according to claim 1 and 2, is characterized in that, the diaspore in steps A is boehmite and/or diaspore; Described boehmite is SB powder.
4. according to the method in claims 1 to 3 described in any one, it is characterized in that, it is 75 ~ 99.0wt% that one diaspore accounts for solid mixture gross mass, it is 0 ~ 20.0wt% that boehmite accounts for solid mixture gross mass, it is 0.1 ~ 2.0wt% that Tungstenic compound accounts for solid mixture gross mass, accounting for solid mixture gross mass containing heavy alkaline earth metal compound is 0.1 ~ 2wt%, and it is 0.1 ~ 5wt% that fluorochemical accounts for solid mixture gross mass.
5. according to the method in Claims 1 to 4 described in any one, it is characterized in that, fluorochemical in described steps A comprise in hydrogen fluoride, aluminum fluoride, ammonium fluoride, magnesium fluoride and ice crystal one or more, the heavy alkaline earth metal compound in described steps A comprise in the oxide of strontium and/or barium, sulfate, nitrate and oxalates one or more.
6. according to the method in Claims 1 to 4 described in any one, it is characterized in that, being blended in batch mixer in described steps A is carried out, and mixing time is 15 ~ 50min; Binding agent in steps A comprise in citric acid, nitric acid, formic acid, acetic acid, propionic acid and hydrochloric acid one or more; Kneading in step B is carried out in kneader, and kneading time is 20 ~ 60min; Being molded in forming machine in step B is carried out, and shaping rear shape is single hole or porous cylindrical thing; Dry treatment temperature in step B is 20 ~ 100 DEG C, and the time is 20 ~ 48h; Sintering temperature in step B is 1100 ~ 1500 DEG C, and the time is 2 ~ 48h.
7. the alumina support prepared by method described in any one in claim 1 ~ 6, it is characterized in that, the content of Alpha-alumina in described alumina support is not less than 90wt%, the mass content of W elements in alumina support is 0.01 ~ 6.0wt%, is preferably 0.1 ~ 2wt%; The specific area of carrier is 0.5 ~ 3.0m
2/ g, pore volume is 0.35 ~ 0.85ml/g, and compression strength is 50 ~ 300N/ grain, water absorption rate>=30%.
8. the preparation method of a silver catalyst, comprise alumina support described in the alumina support or dipping claim 7 that first prepare by the method for solution impregnation according to any one of claim 1 ~ 6 of coassist agent containing organic amine, Ag-containing compound, alkali metal promoter, base earth metal promoter, optional rhenium auxiliary agent and rhenium auxiliary agent, leaching maceration extract again, then in oxygen-containing gas, the carrier of leaching gained is activated, namely obtain described silver catalyst.
9. the method for an epoxidation reaction of olefines production epoxide, it is characterized in that, silver catalyst that described epoxidation reaction method described in claim 8 prepares carries out under existing, and described alkene be selected from styrene, propylene, ethene and 1,3-butadiene one or more.
10. to produce the oxirane that obtains with method as claimed in claim 9 for raw material and produce the method for one or more materials in ethylene glycol, glycol ether and monoethanolamine for one kind.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410195968.4A CN105080618B (en) | 2014-05-09 | 2014-05-09 | A kind of preparation method of alpha-aluminium oxide carrier for silver catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410195968.4A CN105080618B (en) | 2014-05-09 | 2014-05-09 | A kind of preparation method of alpha-aluminium oxide carrier for silver catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105080618A true CN105080618A (en) | 2015-11-25 |
| CN105080618B CN105080618B (en) | 2017-12-19 |
Family
ID=54562482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410195968.4A Active CN105080618B (en) | 2014-05-09 | 2014-05-09 | A kind of preparation method of alpha-aluminium oxide carrier for silver catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105080618B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107442109A (en) * | 2016-06-01 | 2017-12-08 | 中国石油化工股份有限公司 | A kind of silver catalyst carrier, its preparation method and application |
| 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 |
| CN114100611A (en) * | 2020-08-28 | 2022-03-01 | 中国石油化工股份有限公司 | Carrier modified bimetallic catalyst and preparation method and application thereof |
| CN114433044A (en) * | 2020-11-05 | 2022-05-06 | 中国石油化工股份有限公司 | Alpha-alumina carrier and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1467028A (en) * | 2002-07-10 | 2004-01-14 | 中国石油化工股份有限公司 | Method for preparing vinyl epoxide argentum catalyst |
| US20090177016A1 (en) * | 2002-02-25 | 2009-07-09 | Sell Oil Company | Catalyst and process using the catalyst |
| CN102397795A (en) * | 2010-09-13 | 2012-04-04 | 中国石油化工股份有限公司 | Silver catalyst carrier for ethylene oxide production, preparation method, silver catalyst prepared by silver catalyst carrier, and application thereof |
| CN102441435A (en) * | 2010-09-30 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing alumina carrier for silver catalyst, carrier prepared by using method and application thereof |
| CN103372466A (en) * | 2012-04-25 | 2013-10-30 | 中国石油化工股份有限公司 | Preparation method of silver catalyst carrier for production of ethylene oxide and application thereof |
| CN103566981A (en) * | 2012-08-08 | 2014-02-12 | 中国石油化工股份有限公司 | Alpha-alumina carrier and preparation method thereof |
-
2014
- 2014-05-09 CN CN201410195968.4A patent/CN105080618B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090177016A1 (en) * | 2002-02-25 | 2009-07-09 | Sell Oil Company | Catalyst and process using the catalyst |
| CN1467028A (en) * | 2002-07-10 | 2004-01-14 | 中国石油化工股份有限公司 | Method for preparing vinyl epoxide argentum catalyst |
| CN102397795A (en) * | 2010-09-13 | 2012-04-04 | 中国石油化工股份有限公司 | Silver catalyst carrier for ethylene oxide production, preparation method, silver catalyst prepared by silver catalyst carrier, and application thereof |
| CN102441435A (en) * | 2010-09-30 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing alumina carrier for silver catalyst, carrier prepared by using method and application thereof |
| CN103372466A (en) * | 2012-04-25 | 2013-10-30 | 中国石油化工股份有限公司 | Preparation method of silver catalyst carrier for production of ethylene oxide and application thereof |
| CN103566981A (en) * | 2012-08-08 | 2014-02-12 | 中国石油化工股份有限公司 | Alpha-alumina carrier and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107442109A (en) * | 2016-06-01 | 2017-12-08 | 中国石油化工股份有限公司 | A kind of silver catalyst carrier, its preparation method and application |
| CN107442109B (en) * | 2016-06-01 | 2020-05-12 | 中国石油化工股份有限公司 | Silver catalyst carrier, preparation method and application thereof |
| 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 |
| CN109908882A (en) * | 2017-12-12 | 2019-06-21 | 高化学技术株式会社 | Prepare α-Al2O3The method of carrier and thus obtained carrier and application thereof |
| CN114100611A (en) * | 2020-08-28 | 2022-03-01 | 中国石油化工股份有限公司 | Carrier modified bimetallic catalyst and preparation method and application thereof |
| CN114100611B (en) * | 2020-08-28 | 2023-08-15 | 中国石油化工股份有限公司 | Carrier modified bimetallic catalyst and preparation method and application thereof |
| CN114433044A (en) * | 2020-11-05 | 2022-05-06 | 中国石油化工股份有限公司 | Alpha-alumina carrier and preparation method thereof |
| CN114433044B (en) * | 2020-11-05 | 2023-07-21 | 中国石油化工股份有限公司 | Alpha-alumina carrier and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105080618B (en) | 2017-12-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102441435B (en) | Method for preparing alumina carrier for silver catalyst, carrier prepared by using method and application thereof | |
| CN106311353B (en) | A kind of alpha-alumina supports, corresponding silver catalyst and application | |
| CN104549543B (en) | Alumina support, the silver catalyst being made from it and its application | |
| CN103372466B (en) | Preparation method of silver catalyst carrier for production of ethylene oxide and application thereof | |
| CN103566980B (en) | The preparation method of the silver catalyst of alumina support and load thereof and application | |
| CN101007287A (en) | Carrier of ethylene oxide silver catalyst, and its preparation method and application | |
| CN102145285A (en) | Carrier of silver catalyst for producing epoxy ethane, preparation method and application of carrier of silver catalyst | |
| CN108855237A (en) | Porous alumina carrier and preparation method thereof and silver catalyst and application | |
| CN109499558A (en) | A kind of alpha-alumina supports, silver catalyst and olefin epoxidation process | |
| CN103418380B (en) | A kind of preparation method of silver catalyst and producing in oxirane at ethylene applies | |
| CN104707592A (en) | Preparation method of alpha-alumina carrier for silver catalyst | |
| CN110038543A (en) | Alpha-alumina supports, the method for silver catalyst and ethylene epoxidizing production ethylene oxide of ethylene epoxidizing silver catalyst | |
| CN105080618A (en) | Method for preparing alpha-alumina support for silver catalyst | |
| CN104707664A (en) | Preparation method of alpha-alumina carrier for silver catalyst | |
| CN105233824B (en) | A kind of high-selective ethylene oxidation epoxy ethane silver catalyst and its application method | |
| CN105618047B (en) | A kind of method and its application preparing epoxidation silver catalyst | |
| CN104549544B (en) | Silver catalyst carrier preparation method, thus obtained silver catalyst carrier, silver catalyst and its application | |
| CN104275212A (en) | Alpha-aluminium oxide carrier for silver catalyst and preparation method thereof | |
| CN108855238A (en) | Porous alumina carrier and preparation method thereof and silver catalyst and application | |
| CN108855239A (en) | Porous alumina carrier and preparation method thereof and silver catalyst and application | |
| CN106311230A (en) | Preparation method of silver catalyst used for alkene epoxidation, catalyst and application thereof | |
| CN104275211B (en) | The preparation method and applications of silver catalyst | |
| CN104069893B (en) | Produce silver catalyst carrier, preparation method and application thereof for oxirane | |
| CN103357439A (en) | Carrier of silver catalyst for olefin epoxidation, preparation method and application | |
| CN106607028B (en) | A kind of silver catalyst and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |