CN103418443A - Preparation method of alpha-alumina molding carrier for silver catalyst - Google Patents
Preparation method of alpha-alumina molding carrier for silver catalyst Download PDFInfo
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- CN103418443A CN103418443A CN2012101512900A CN201210151290A CN103418443A CN 103418443 A CN103418443 A CN 103418443A CN 2012101512900 A CN2012101512900 A CN 2012101512900A CN 201210151290 A CN201210151290 A CN 201210151290A CN 103418443 A CN103418443 A CN 103418443A
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Abstract
The invention provides a preparation method of an alpha-alumina molding carrier for a silver catalyst. The preparation method comprises the following steps: step A, aluminum hydroxide powder and a mineralizing agent are mixed uniformly to obtain a mixture, wherein the mineralizing agent is one or a plurality of substance selected from ammonium nitrate, ammonium chloride, ammonium carbonate, ammonium hydrogen carbonate and ammonium fluoride; step B, the mixture of the step A is kneaded, molded and dried; and step C, a dried bulk of the step B is roasted to obtain the alpha-alumina molding carrier. The alpha alumina molding carrier prepared by the method has the characteristics of high compressive strength and large specific surface area; and the preparation method is low in cost and simple in process. Preferably the aluminum hydroxide powder is a mixture of diaspore and gibbsite or a mixture of the boehmite and bayerite.
Description
Technical field
The present invention relates to a kind of preparation method of alumina support, specifically, the present invention relates to a kind of preparation method of the carrier of the alpha-alumina molding for silver catalyst.
Background technology
A kind of as in eight kinds of common aluminium oxide of Alpha-alumina is important inorganic material.A series of excellent specific properties such as Alpha-alumina is high with its intensity, hardness is large, high temperature resistant, corrosion-resistant, wear-resistant, be widely used in fields such as aviation, metallurgy, mechanical industry, sensor, bioceramic, catalyst carriers.Particularly, aspect catalyst carrier, alpha-alumina supports is unique effective carrier that industrial ethylene epoxidizing is produced oxirane silver catalyst used at present.At present, generally adopt the precipitation method, sol-gel process to prepare Alpha-alumina; In roasting process, sintering under presoma high temperature, be decomposed into aluminium oxide, then experience γ, θ etc. repeatedly phase transition be Alpha-alumina.From metastable phase, to the Alpha-alumina transition process, the lattice structure of aluminium oxide is further fine and close, and the system free energy reduces, but this process is not a spontaneous process, need to cross higher energy barrier, generally under the high temperature of 1200 ℃ of left and right, just can complete.Under so high sintering temperature, once forming, Alpha-alumina crystal grain will grow up fast, mutually reunite and form vermiform hard agglomeration between particle in addition, thereby obtain that crystallite dimension is large, bad dispersibility, specific area is little, sintering activity is low Alpha-alumina; These characteristics are very unfavorable to the application of Alpha-alumina.Therefore, the method that many research workers obtain Alpha-alumina to low temperature conducts in-depth research, and wherein, comprises and adds Alpha-alumina crystal seed, dispersant, mineralizer etc.
Patent US5137959 has obtained the Alpha-alumina of ideal dimensions and shape by adding the Alpha-alumina crystal seed.And the people " Critical factors in the templated grain growth of textured reaction-bonded alumina; J Am Ceram Soc; 2000; 83 (8): 2041-2048 " such as Suvaci E also find when adding tiny Alpha-alumina lath as crystal seed, this crystal seed non-axle growth, Alpha-alumina lath that has obtained having more satisfactory mechanical property of waiting under liquid phase exists in roasting process.Gu Feng etc. " impact of the dispersant degree of polymerization on nano alumina powder jointed characteristic; functional material; 20052(36): 318-320 " select the polyethylene glycol of different polymerization degree as dispersant, adopt the precipitation method to prepare alumine hydroxide colloid, colloid just is converted into Alpha-alumina fully through 1000 ℃ of high-temperature calcinations again.Its result shows that dispersant has important impact to the size distribution of aluminium oxide, utilizes that powder granule that this dispersant can prepare is thin and evenly, average grain diameter is little, without obviously reuniting and the particle phenomenon of growing up.During domestic and international industrial production alpha-alumina supports, the producer nearly all selects fluoride to promote the generation of Alpha-alumina as mineralizer in process of production, and its Alpha-alumina obtained is platy structure, is conducive to the heat transfer in catalytic reaction process.But prepare fluoride meeting decomposes in the alpha-alumina supports process in roasting, discharge hydrogen fluoride gas, be unfavorable for environmental protection, and the less (0.20 ~ 2.00m of specific surface of the Alpha-alumina that adopts the method to obtain
2/ g).
Summary of the invention
In view of the situation of above-mentioned prior art, the present inventor has carried out research extensively and profoundly in the alpha-alumina supports preparation field, and a kind of preparation method of alpha-alumina supports is provided in the present invention.Use the method can prepare the alpha-alumina molding carrier that a kind of compression strength is high, specific area is large.
The invention provides a kind of preparation method of the carrier of the alpha-alumina molding for silver catalyst, comprise the steps: steps A, aluminium-hydroxide powder and mineralizer are mixed and obtain mixture, and wherein said mineralizer is one or more in ammonium nitrate, ammonium chloride, ammonium carbonate, carbonic hydroammonium and ammonium fluoride; Step B, by the described mixture of steps A mediated, moulding and drying; Step C, the described dry body of calcination steps B, prepare the alpha-alumina molding carrier.
The mixture that preferably described in the present invention, aluminium-hydroxide powder is a diaspore and gibbsite or the mixture of a diaspore and surge aluminium stone.More preferably, the mass ratio of described gibbsite or surge aluminium stone and a diaspore is 1.0 ~ 4.0: 1.
Preferably being blended in batch mixer in steps A of the present invention carried out, and mixing time is 15 ~ 50min.In preferred steps A, mineralizer content in mixture is 2 ~ 10wt%.
Kneading in preferred step B of the present invention is carried out in kneader, and kneading time is 20 ~ 60min.Being molded in forming machine in preferred steps B carried out, and moulding rear oxidation aluminium is shaped as seven apertures in the human head, five holes or single hole column.Dry treatment temperature in preferred steps B is 20 ~ 100 ℃, and the time is 24 ~ 48h.
Preferably the roasting in step C of the present invention comprises temperature programming and constant temperature calcining process, and the heating rate of temperature programming is 2 ~ 10 ℃/min, and the constant temperature calcining temperature is 1200 ~ 1600 ℃, and the constant temperature calcining time is 4 ~ 20h.
Use the alpha-alumina molding carrier that in the present invention, the described method of any one prepares, its compression strength is 20 ~ 70N/ grain, and specific area is 1.00 ~ 7.00m
2/ g.
In the present invention, ammonium salt decomposes in roasting process as mineralizer discharges gas, the continuous release of gas makes the state of product particle in relative " motion ", can suppress to a certain extent the reunion of product particle like this, thereby obtain the alpha-alumina supports that compression strength is high, specific area is large.The alpha-alumina supports that the present invention is prepared, it can be used for the carrier that ethylene epoxidizing is produced oxirane silver catalyst used in catalytic field.
The accompanying drawing explanation
The XRD spectra that Fig. 1 is the alpha-alumina supports of preparation in the embodiment of the present invention 1.
The specific embodiment
Further illustrate technical solution of the present invention by following examples, but protection scope of the present invention is not limited to following examples.
Embodiment 1
The gibbsite that the weighing mass ratio is 3.7: 1 and a diaspore and a certain amount of solid ammonium nitrate are put in batch mixer and are mixed 20min, obtain a kind of mixture, wherein the quality percentage composition of ammonium nitrate in mixture is 4%, mixture is transferred in kneader and is mediated 30min, be cut into the column that is shaped as five holes after kneading on forming machine, dry column 15h under 50 ℃ of conditions, again by the column roasting, heating rate is 2 ℃/min, sintering temperature is 1300 ℃, roasting time is 4h, finally is cooled to room temperature.
X-ray diffraction analysis presentation of results product is Alpha-alumina, and its XRD figure as shown in Figure 1.The compression strength that pressure tester records alpha-alumina supports is the 25N/ grain.The specific area that mercury injection method records alpha-alumina supports is 5.16m
2/ g.
Embodiment 2
The gibbsite that the weighing mass ratio is 3.7: 1 and a diaspore and a certain amount of solid ammonium nitrate are put in batch mixer and are mixed 20min, obtain a kind of mixture, wherein the quality percentage composition of ammonium nitrate in mixture is 8%, mixture is transferred in kneader and is mediated 30min, be cut into the column that is shaped as five holes after kneading on forming machine, dry column 25h under 50 ℃ of conditions, again by the column roasting, heating rate is 4 ℃/min, sintering temperature is 1300 ℃, roasting time is 4h, finally is cooled to room temperature.
X-ray diffraction analysis presentation of results product is Alpha-alumina.The compression strength that pressure tester records alpha-alumina supports is the 21N/ grain.The specific area that mercury injection method records alpha-alumina supports is 5.40m
2/ g.
Embodiment 3
The surge aluminium stone that the weighing mass ratio is 2.0: 1 and a diaspore and a certain amount of solid ammonium nitrate are put in batch mixer and are mixed 30min, obtain a kind of mixture, wherein the quality percentage composition of ammonium nitrate in mixture is 4%, mixture is transferred in kneader and is mediated 40min, be cut into the column that is shaped as single hole after kneading on forming machine, dry column 20h under 80 ℃ of conditions, again by the column roasting, heating rate is 5 ℃/min, sintering temperature is 1500 ℃, roasting time is 8h, finally is cooled to room temperature.
X-ray diffraction analysis presentation of results product is Alpha-alumina.The compression strength that pressure tester records alpha-alumina supports is the 30N/ grain.The specific area that mercury injection method records alpha-alumina supports is 4.82m
2/ g.
Embodiment 4
The gibbsite that the weighing mass ratio is 1.5: 1 and a diaspore and a certain amount of solid carbonic acid ammonium are put in batch mixer and are mixed 25min, obtain a kind of mixture, wherein the quality percentage composition of ammonium carbonate in mixture is 6%, mixture is transferred in kneader and is mediated 30min, be cut into the column that is shaped as single hole after kneading on forming machine, dry column 40h under 80 ℃ of conditions, again by the column roasting, heating rate is 3 ℃/min, sintering temperature is 1600 ℃, roasting time is 10h, finally is cooled to room temperature.
X-ray diffraction analysis presentation of results product is Alpha-alumina.The compression strength that pressure tester records alpha-alumina supports is the 39N/ grain.The specific area that mercury injection method records alpha-alumina supports is 2.82m
2/ g.
Embodiment 5
The gibbsite that the weighing mass ratio is 1.2: 1 and a diaspore and a certain amount of solid ammonium bicarbonate are put in batch mixer and are mixed 35min, obtain a kind of mixture, wherein the quality percentage composition of carbonic hydroammonium in mixture is 10%, mixture is transferred in kneader and is mediated 50min, be cut into the column that is shaped as seven apertures in the human head after kneading on forming machine, dry column 36h under 20 ℃ of conditions, again by the column roasting, heating rate is 5 ℃/min, sintering temperature is 1600 ℃, roasting time is 15h, finally is cooled to room temperature.
X-ray diffraction analysis presentation of results product is Alpha-alumina.The compression strength that pressure tester records alpha-alumina supports is the 69N/ grain.The specific area that mercury injection method records alpha-alumina supports is 3.52m
2/ g.
Embodiment 6
The surge aluminium stone that the weighing mass ratio is 3.5: 1 and a diaspore and a certain amount of solid carbonic acid ammonium and carbonic hydroammonium are put in batch mixer and are mixed 25min, obtain a kind of mixture, wherein ammonium carbonate and the carbonic hydroammonium quality percentage composition in mixture is 5% altogether, mixture is transferred in kneader and is mediated 30min, be cut into the column that is shaped as seven apertures in the human head after kneading on forming machine, dry column 35h under 60 ℃ of conditions, again by the column roasting, heating rate is 4 ℃/min, sintering temperature is 1400 ℃, roasting time is 10h, finally is cooled to room temperature.
X-ray diffraction analysis presentation of results product is Alpha-alumina.The compression strength that pressure tester records alpha-alumina supports is the 37N/ grain.The specific area that mercury injection method records alpha-alumina supports is 4.78m
2/ g.
Embodiment 7
The gibbsite that the weighing mass ratio is 3.8: 1 and a diaspore and a certain amount of solid ammonium chloride are put in batch mixer and are mixed 30min, obtain a kind of mixture, wherein the quality percentage composition of ammonium chloride in mixture is 8%, mixture is transferred in kneader and is mediated 30min, be cut into the column that is shaped as single hole after kneading on forming machine, dry column 48h under 20 ℃ of conditions, again by the column roasting, heating rate is 8 ℃/min, sintering temperature is 1550 ℃, roasting time is 15h, finally is cooled to room temperature.
X-ray diffraction analysis presentation of results product is Alpha-alumina.The compression strength that pressure tester records alpha-alumina supports is the 20N/ grain.The specific area that mercury injection method records alpha-alumina supports is 1.50m
2/ g.
Claims (10)
1. the preparation method of the carrier of the alpha-alumina molding for silver catalyst, comprise the steps:
Steps A, mix aluminium-hydroxide powder and mineralizer to obtain mixture, and wherein said mineralizer is one or more in ammonium nitrate, ammonium chloride, ammonium carbonate, carbonic hydroammonium and ammonium fluoride;
Step B, by the described mixture of steps A mediated, moulding and drying;
Step C, the described dry body of calcination steps B, prepare the alpha-alumina molding carrier.
2. method according to claim 1, is characterized in that, the mixture of the mixture that described aluminium-hydroxide powder is a diaspore and gibbsite or a diaspore and surge aluminium stone.
3. method according to claim 2, is characterized in that, the mass ratio of described gibbsite or surge aluminium stone and a diaspore is 1.0 ~ 4.0: 1.
4. according to the described method of any one in claim 1 ~ 3, it is characterized in that, being blended in batch mixer in described steps A carried out, and mixing time is 15 ~ 50min.
5. according to the described method of any one in claim 1 ~ 3, it is characterized in that, in described steps A, mineralizer content in mixture is 2 ~ 10wt%.
6. according to the described method of any one in claim 1 ~ 3, it is characterized in that, the kneading in described step B is carried out in kneader, and kneading time is 20 ~ 60min.
7. according to the described method of any one in claim 1 ~ 3, it is characterized in that, being molded in forming machine in described step B carried out, and moulding rear oxidation aluminium is shaped as seven apertures in the human head, five holes or single hole column.
8. according to the described method of any one in claim 1 ~ 3, it is characterized in that, the dry treatment temperature in described step B is 20 ~ 100 ℃, and the time is 24 ~ 48h.
9. according to the described method of any one in claim 1 ~ 3, it is characterized in that, the roasting in described step C comprises temperature programming and constant temperature calcining process, and the heating rate of temperature programming is 2 ~ 10 ℃/min, the constant temperature calcining temperature is 1200 ~ 1600 ℃, and the constant temperature calcining time is 4 ~ 20h.
10. the alpha-alumina molding carrier prepared according to the described method of any one in claim 1 ~ 9, is characterized in that, its compression strength is 20 ~ 70N/ grain, and specific area is 1.00 ~ 7.00m
2/ g.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105233824A (en) * | 2015-11-05 | 2016-01-13 | 中国海洋石油总公司 | Silver catalyst for high selectivity oxidation of ethylene to prepare ethylene oxide, and use method thereof |
| CN109718862A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of silicon-containing alumina carrier and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990015777A1 (en) * | 1987-12-23 | 1990-12-27 | Aluminum Company Of America | Small sized alpha alumina particles and platelets |
| 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 |
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2012
- 2012-05-15 CN CN201210151290.0A patent/CN103418443B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990015777A1 (en) * | 1987-12-23 | 1990-12-27 | Aluminum Company Of America | Small sized alpha alumina particles and platelets |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| 张彬: "微波场中氢氧化铝煅烧工艺及氧化铝晶型转变研究", 《中国博士学文论文全文数据库工程科技I辑》, no. 1, 15 January 2012 (2012-01-15) * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105233824A (en) * | 2015-11-05 | 2016-01-13 | 中国海洋石油总公司 | Silver catalyst for high selectivity oxidation of ethylene to prepare ethylene oxide, and use method thereof |
| CN109718862A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of silicon-containing alumina carrier and preparation method thereof |
| CN109718862B (en) * | 2017-10-27 | 2021-11-09 | 中国石油化工股份有限公司 | Silicon-containing alumina carrier and preparation method thereof |
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