CN104437664A - Method for preparing alpha-alumina carrier - Google Patents
Method for preparing alpha-alumina carrier Download PDFInfo
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- CN104437664A CN104437664A CN201310421811.4A CN201310421811A CN104437664A CN 104437664 A CN104437664 A CN 104437664A CN 201310421811 A CN201310421811 A CN 201310421811A CN 104437664 A CN104437664 A CN 104437664A
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- component
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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
Abstract
The invention provides a method for preparing an alpha-alumina carrier, which comprises the following steps: 1)preparing a mixture containing the following components: a)alumina powder; b)a binder, wherein the binder is aluminium sol, the aluminium sol can be completely or partially substituted by aluminium sol formed by reacting pseudo-hydrated alpha-alumina and acid, c) a fluoride mineralizer; d)citric acid or a compound containing citric acid, the content accounts for 0.01 to 20.0wt% of the total weight from ingredient <a> to ingredient <e>; e)silicon or a silicon containing compound, the content accounts for 0.0 to 5.0wt% of the total weight from ingredient <a> to ingredient <e>; and f)water; and step 2), the mixture obtained via step 1) is mixed uniformly, is subjected to extrusion molding, is dried, and is roasted so as to obtain the alpha-aluminum oxide carrier. According to the method, the alpha-aluminum oxide carrier is prepared by adding citric acid or the compound containing citric acid, and the alpha-aluminum oxide carrier with interlocking piece-shaped crystal form and significantly increased specific surface area can be obtained.
Description
Technical field
The present invention relates to a kind of preparation method of alpha-alumina supports, more particularly, the present invention relates to a kind of method of producing the alpha-alumina supports of oxirane silver catalyst for the preparation of ethylene.
Background technology
Under silver catalyst effect, ethylene mainly generates oxirane, and side reaction occurs simultaneously and generates carbon dioxide and water, wherein active, selective and stability is the main performance index of silver catalyst.Activity refers to the reaction temperature that process for ethylene oxide production reaches required when necessarily reacting load; Reaction temperature is lower, and the activity of catalyst is higher.Selectively refer to that in reaction, ethylene conversion becomes the ratio of the molal quantity of oxirane and the overall reaction molal quantity of ethene.Stability is then expressed as the fall off rate of activity and selectivity, and the stability of fall off rate more small catalyst is better.Produce at ethylene in the process of oxirane and use high activity, high selectivity and the silver catalyst that has good stability greatly to increase economic efficiency, the silver catalyst therefore manufacturing high activity, high selectivity and good stability is the Main way of silver catalyst research.The performance of silver catalyst is except having important relationship with the composition of catalyst and preparation method, and performance and the preparation thereof of the carrier also used with catalyst have important relationship.
In prior art the preparation method of silver catalyst comprise the preparation and administration to active component of porous carrier (as aluminium oxide) and auxiliary agent to as described in this two processes on carrier.In alumina support, adding other component, to improve carrier to improve the performance of silver catalyst be an important research direction, comprising adding alkaline earth oxide or other salt compounds.EP0150238(US4428863) in the manufacture process of high-purity, low surface oxidation alumina supporter, use a small amount of barium aluminate or barium silicate binding agent, claim the crushing strength and wear resistance that can improve carrier, the specific surface of prepared carrier is less than 0.3m
2/ g, the activity and selectivity of prepared catalyst is all lower.US5384302 claims by pretreatment α-Al
2o
3na, K, Ca, Al ion concentration reduced in carrier can improve crushing strength and the abrasion resistance properties of carrier.US5739075 passes through at the alumina carrier surface rare earth metal of deposition aid amount and the slaine (alkaline-earth metal or VIII transition metal) of another kind of amount of auxiliary in advance, then calcination processing is carried out, the carrier handled well the most at last makes silver catalyst, evaluation result shows, the selective fall off rate of this catalyst is less than the catalyst sample not doing pre-deposition process.
Fluoride, as a kind of mineralizer, has a wide range of applications in the preparation process of alumina support.CN1034678A is by three water Alpha-aluminas of granularity, ratio appropriate mix and a false water Alpha-alumina and the mixing of carbonaceous material, flux, fluoride, binding agent and water, and kneaded and formed, alpha-alumina supports is made in drying roasting.The specific surface of this carrier is 0.2 ~ 2m
2/ g, the hole that pore radius is greater than 30 μm accounts for total pore volume less than 25%; This carrier is through dipping silver compound and co-catalyst and after dry activation, for ethylene epoxy ethane, selective up to 83 ~ 84%.CN101007287A by three water Alpha-aluminas of certain particle size, a false water Alpha-alumina, a certain amount of can after-flame carbonaceous material, flux, fluoride, optional heavy alkaline-earth metal Compound Phase mixing, binding agent and water is added after mixing, mediate evenly, extruded, drying roasting, makes alpha-alumina supports; The specific surface of described carrier is 0.2 ~ 2.0m
2/ g, pore volume is 0.35 ~ 0.85ml/g, water absorption rate>=30%, crushing strength 30 ~ 120N/ grain.The solution impregnation of this carrier argent-amine complex, alkali metal compound, alkaline earth metal compound, after dry activation, obtained silver catalyst is used for ethylene epoxidizing epoxy ethane.CN1634652A, in carrier preparation, does not use pore creating material, but is directly mixed mutually with a false Water oxidize aluminium, flux, fluoride with certain proportion by three water Alpha-aluminas, add binding agent and water after mixing, mediate evenly, extruded, drying roasting, makes alpha-alumina supports.The carrier specific surface that this invention is made is 0.2 ~ 2.0m
2/ g, pore volume is 0.35 ~ 0.85ml/g, water absorption rate>=30%, crushing strength 20 ~ 90N/ grain.The solution impregnation of this carrier argent-amine complex, alkali metal compound and alkaline earth metal compound, after dry activation, obtained silver catalyst is used for ethylene epoxidizing epoxy ethane.
Although above-mentioned patent document adopts respectively add the method such as alkaline earth metal compound or fluoride to improve alumina support in alumina raw material, improvement is in various degree brought to the activity and selectivity of catalyst, but along with the heavy industrialization of middle high selectivity silver catalyst is applied, this area is also improving constantly the requirement of alumina support performance.
Summary of the invention
In view of the situation of above-mentioned prior art, the present inventor has carried out experimental study extensively and profoundly at silver catalyst and alumina support field thereof, found that by adopting the method for adding citric acid complex in feed particles to prepare alumina support, the alpha-alumina supports that specific area increases can be prepared.
Therefore, the invention provides a kind of method preparing alpha-alumina supports, comprise the steps: step I, preparation comprises the mixture of following component, a: alumina powder; B: binding agent, described binding agent is Alumina gel, and described Alumina gel can be all or part of with a false water A1
2o
3the Alumina gel formed with acid reaction and replacing; C: fluoride-mineralization agent; D: citric acid or the compound containing citrate, its gross weight based on component a ~ e is 0.01 ~ 20.0wt%; E: silicon or silicon-containing compound, its gross weight based on component a ~ e is 0.0 ~ 5.0wt%; F: water; And step II, the mixture obtained in step I to be mediated evenly, dry and roasting obtains described alpha-alumina supports after extrusion molding.
In the present invention, described Powder Oxidation aluminium can be hydrated alumina, such as, be three water α-A1
2o
3and/or β-gibbsite, also can be non-Water oxidize aluminium, such as, be Alpha-alumina or gama-alumina; But be more preferably hydrated alumina in the present invention, concrete as three water α-A1
2o
3and/or β-gibbsite.
In the present invention, in the described mixture of step I, except this several component of above-mentioned a ~ f, the materials such as a small amount of alkali metal and/or alkaline-earth metal can also be comprised.
In the present invention, preferably, component a is 4.5 ~ 90wt% based on the gross weight of component a ~ e, components b is 5 ~ 95wt% based on the gross weight of component a ~ e, amount of component b is 0.01 ~ 3.0wt% based on the gross weight of component a ~ e, component d is 0.05 ~ 15.0wt%, component e based on the gross weight of component a ~ e based on the gross weight of component a ~ e is 0.001 ~ 2.0wt%.In the preferred embodiment, containing a certain amount of element silicon in mixture, the alpha-alumina supports so obtained also can be largely increased by support strength while its specific area increases.
More preferably, component a is 23 ~ 80wt% based on the gross weight of component a ~ e, components b is 18 ~ 75wt% based on the gross weight of component a ~ e, amount of component b is 0.1 ~ 2.5wt% based on the gross weight of component a ~ e, component d is 0.1 ~ 10.0wt%, component e based on the gross weight of component a ~ e based on the gross weight of component a ~ e is 0.01 ~ 2.0wt%.Most preferably, component a is 68 ~ 80wt% based on the gross weight of component a ~ e, components b is 18 ~ 30wt% based on the gross weight of component a ~ e, amount of component b is 1.2 ~ 2.0wt% based on the gross weight of component a ~ e, component d is 0.5 ~ 5.0wt%, component e based on the gross weight of component a ~ e based on the gross weight of component a ~ e is 0.1 ~ 1.5wt%.
In the present invention, preferably, described acid is aqueous solution of nitric acid, and wherein the volume ratio of nitric acid and water is 1:1.25 ~ 10, preferred 1:2 ~ 4.When preparing alpha-alumina supports of the present invention, adding of amount of component b fluoride is transformation of crystal in order to accelerated oxidation aluminium, and it is used as mineralizer.In one embodiment of the invention, described fluoride-mineralization agent be selected from hydrogen fluoride, aluminum fluoride, ammonium fluoride, magnesium fluoride and ice crystal one or more, preferred fluorinated ammonium.In the present invention, described silicon-containing compound is selected from silica, silicate, carborundum, diatomite, feldspar and silester, preferred silica.
In the present invention, described citric acid or the compound containing citrate are selected from citric acid, ammonium citrate, alkali metal citrates, alkali earth salt and citric acid rare earth metal salt, optimization citric acid.Citric acid or the compound containing citrate are a kind of stronger chelating agents, and have very strong coordination ability, it and metallic aluminium ion can form highly stable chelate, therefore more favourable to the specific area improving aluminium oxide.
In the present invention, in described step II, sintering temperature is 900 ~ 1600 DEG C, preferably 1200 ~ 1500 DEG C; Aluminium oxide is made substantially all to be converted into α-A1 by roasting
2o
3, such as more than 90% is converted into α-A1
2o
3, obtain α-A1
2o
3carrier.
Therefore, according to a further aspect in the invention, additionally provide a kind of alpha-alumina supports obtained as stated above, the specific surface of this carrier is 0.5 ~ 3.0m
2/ g, water absorption rate is not less than 30%, and the amount of silicon-containing compound counts the 0.0-1wt% of vehicle weight with element silicon.The crystal formation of the vector product that the present invention obtains is such as in interlocking sheet.
Finally, the present invention also provides a kind of described α-Al
2o
3carrier produces the application in oxirane silver catalyst at ethylene.
Detailed description of the invention
The present invention is described further in conjunction with following embodiment, but scope of the present invention is not limited to these embodiments.
Comparative example 1
By 498g tri-water α-A1
2o
3, the false water A1 of 102g
2o
3with 1.50g BaSO
4put into blender to mix, be then poured in kneader.Pour in kneader after being dissolved completely in the diluted nitric acid aqueous solution (nitric acid: water=1:3, volume ratio) of 0.12 liter by 10.5g ammonium fluoride, being kneaded into can the paste of extrusion molding.Finally load in banded extruder by paste, extrusion molding is the column of diameter 8.0mm, long 6.0mm, dries more than 2 hours, make its free water content be reduced to below 10% weight at 80-120 DEG C.Dried column is put into natural gas kiln, was elevated to 1360 DEG C through 36 hours from room temperature, then constant temperature 2 hours, obtains white solid product, shows that it is α-A1 to the XRD analysis of this solid
2o
3, its related physical performance data is in table 1.
Embodiment 1
By 498g tri-water α-A1
2o
3, the false water A1 of 102g
2o
3, 8g citric acid puts into blender and mixes, and is then poured in kneader.Pour in kneader after being dissolved completely in the diluted nitric acid aqueous solution (nitric acid: water=1:3, volume ratio) of 0.12 liter by 10.5g ammonium fluoride, being kneaded into can the paste of extrusion molding.Finally load in banded extruder by paste, extrusion molding is the column of diameter 8.0mm, long 6.0mm, dries more than 2 hours, make its free water content be reduced to below 10% weight at 80-120 DEG C.Dried column is put into natural gas kiln, was elevated to 1360 DEG C through 36 hours from room temperature, then constant temperature 2 hours, obtains white solid product, shows that it is α-A1 to the XRD analysis of this solid
2o
3, its related physical performance data is in table 1.
Embodiment 2
By 498g tri-water α-A1
2o
3, the false water A1 of 102g
2o
3, 15g citric acid puts into blender and mixes, and is then poured in kneader.Pour in kneader after being dissolved completely in the diluted nitric acid aqueous solution (nitric acid: water=1:3, volume ratio) of 0.12 liter by 10.5g ammonium fluoride, being kneaded into can the paste of extrusion molding.Finally load in banded extruder by paste, extrusion molding is the column of diameter 8.0mm, long 6.0mm, dries more than 2 hours, make its free water content be reduced to below 10% weight at 80-120 DEG C.Dried column is put into natural gas kiln, was elevated to 1360 DEG C through 36 hours from room temperature, then constant temperature 2 hours, obtains white solid product, shows that it is α-A1 to the XRD analysis of this solid
2o
3, its related physical performance data is in table 1.
Embodiment 3
By 498g tri-water α-A1
2o
3, the false water A1 of 102g
2o
3, 15g citric acid and 1.05g silica puts into blender and mixes, and is then poured in kneader.Pour in kneader after being dissolved completely in the diluted nitric acid aqueous solution (nitric acid: water=1:3, volume ratio) of 0.12 liter by 10.5g ammonium fluoride, being kneaded into can the paste of extrusion molding.Finally load in banded extruder by paste, extrusion molding is the column of diameter 8.0mm, long 6.0mm, dries more than 2 hours, make its free water content be reduced to below 10% weight at 80-120 DEG C.Dried column is put into natural gas kiln, was elevated to 1360 DEG C through 36 hours from room temperature, then constant temperature 2 hours, obtains white solid product, shows that it is α-A1 to the XRD analysis of this solid
2o
3, its related physical performance data is in table 1.
Table 1
| Intensity (N/ grain) | Water absorption rate (%) | Specific area (m 2/g） | |
| Comparative example 1 | 83 | 47.99 | 0.810 |
| Embodiment 1 | 60 | 48.43 | 0.954 |
| Embodiment 2 | 55 | 51.25 | 1.577 |
| Embodiment 3 | 136 | 48.66 | 1.298 |
As seen from Table 1, compared with comparative example 1, adopt in each embodiment and add alumina support obtained by citric acid in the feed all there is larger specific area, and according to the sign of SEM, the crystal formation of above-mentioned alumina support is interlocking sheet.When especially adding a certain amount of element silicon in carrier preparation process, the alpha-alumina supports so obtained also can be largely increased by support strength while its specific area increases.
Claims (10)
1. prepare a method for alpha-alumina supports, comprise the steps:
Step I, preparation comprises the mixture of following component,
A: alumina powder;
B: binding agent, described binding agent is Alumina gel, and described Alumina gel can be all or part of with a false water A1
2o
3the Alumina gel formed with acid reaction and replacing;
C: fluoride-mineralization agent;
D: citric acid or the compound containing citrate, its gross weight based on component a ~ e is 0.01 ~ 20.0wt%;
E: silicon or silicon-containing compound, its gross weight based on component a ~ e is 0.0 ~ 5.0wt%;
F: water;
Step II, mediates the mixture obtained in step I evenly, dry and roasting obtains described alpha-alumina supports after extrusion molding.
2. method according to claim 1, it is characterized in that: component a is 4.5 ~ 90wt% based on the gross weight of component a ~ e, components b is 5 ~ 95wt% based on the gross weight of component a ~ e, amount of component b is 0.01 ~ 3.0wt% based on the gross weight of component a ~ e, component d is 0.05 ~ 15.0wt%, component e based on the gross weight of component a ~ e based on the gross weight of component a ~ e is 0.001 ~ 2.0wt%.
3. method according to claim 2, it is characterized in that: component a is 23 ~ 80wt% based on the gross weight of component a ~ e, components b is 18 ~ 75wt% based on the gross weight of component a ~ e, amount of component b is 0.1 ~ 2.5wt% based on the gross weight of component a ~ e, component d is 0.1 ~ 10.0wt%, component e based on the gross weight of component a ~ e based on the gross weight of component a ~ e is 0.01 ~ 2.0wt%.
4. method according to claim 3, it is characterized in that: component a is 68 ~ 80wt% based on the gross weight of component a ~ e, components b is 18 ~ 30wt% based on the gross weight of component a ~ e, amount of component b is 1.2 ~ 2.0wt% based on the gross weight of component a ~ e, component d is 0.5 ~ 5.0wt%, component e based on the gross weight of component a ~ e based on the gross weight of component a ~ e is 0.1 ~ 1.5wt%.
5. according to the method in Claims 1 to 4 described in any one, it is characterized in that: described alumina powder is three water α-A1
2o
3and/or β-gibbsite.
6. according to the method in Claims 1 to 4 described in any one, it is characterized in that: described acid is aqueous solution of nitric acid, wherein the volume ratio of nitric acid and water is 1:1.25 ~ 10, preferred 1:2 ~ 4.
7., according to the method in Claims 1 to 4 described in any one, it is characterized in that: described fluoride-mineralization agent be selected from hydrogen fluoride, aluminum fluoride, ammonium fluoride, magnesium fluoride and ice crystal one or more, preferred fluorinated ammonium; Described silicon-containing compound is selected from silica, silicate, carborundum, diatomite, feldspar and silester, preferred silica.
8. according to the method in Claims 1 to 4 described in any one, it is characterized in that: the described compound containing citrate is selected from ammonium citrate, alkali metal citrates, alkali earth salt and citric acid rare earth metal salt.
9. according to the alpha-alumina supports that method described in any one in claim 1 ~ 8 prepares, it is characterized in that: specific surface is 0.5 ~ 3.0m
2/ g, water absorption rate is not less than 30%, and the amount of silicon-containing compound counts the 0-1wt% of vehicle weight with element silicon.
10. α-the Al prepared as any one method in claim 1 ~ 8
2o
3carrier or α-Al according to claim 9
2o
3carrier produces the application in oxirane silver catalyst at ethylene.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106311354A (en) * | 2015-07-02 | 2017-01-11 | 中国石油化工股份有限公司 | Method for surface modification of alumina carrier, carrier obtained therefrom and application of carrier |
| CN113087106A (en) * | 2021-02-03 | 2021-07-09 | 南京水滴智能环保装备研究院有限公司 | Method for removing silicon from acid liquor |
| CN114425373A (en) * | 2020-09-25 | 2022-05-03 | 中国石油化工股份有限公司 | Alpha-alumina carrier, preparation method thereof, silver catalyst and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106311354A (en) * | 2015-07-02 | 2017-01-11 | 中国石油化工股份有限公司 | Method for surface modification of alumina carrier, carrier obtained therefrom and application of carrier |
| CN106311354B (en) * | 2015-07-02 | 2020-07-21 | 中国石油化工股份有限公司 | Method for modifying surface of alumina carrier, carrier obtained thereby and application thereof |
| CN114425373A (en) * | 2020-09-25 | 2022-05-03 | 中国石油化工股份有限公司 | Alpha-alumina carrier, preparation method thereof, silver catalyst and application |
| CN114425373B (en) * | 2020-09-25 | 2023-09-08 | 中国石油化工股份有限公司 | Alpha-alumina carrier, preparation method, silver catalyst and application |
| CN113087106A (en) * | 2021-02-03 | 2021-07-09 | 南京水滴智能环保装备研究院有限公司 | Method for removing silicon from acid liquor |
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|---|---|
| CN104437664B (en) | 2016-09-21 |
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