CN100368296C - Method for preparing Nano alpht-A12O3 through catalyzing calcinations in low tempeature - Google Patents
Method for preparing Nano alpht-A12O3 through catalyzing calcinations in low tempeature Download PDFInfo
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- CN100368296C CN100368296C CNB2006100321760A CN200610032176A CN100368296C CN 100368296 C CN100368296 C CN 100368296C CN B2006100321760 A CNB2006100321760 A CN B2006100321760A CN 200610032176 A CN200610032176 A CN 200610032176A CN 100368296 C CN100368296 C CN 100368296C
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Abstract
This invention discloses a method for preparing nanoscale alpha-Al2O3 by low-temperature catalytic calcination. The method adopts soluble inorganic Al salt as the raw material, carbonate solution as the precipitating agent, and polyethylene glycol aqueous solution as the dispersant. The method comprises: (1) dropping the Al salt solution into the carbonate solution at a mol ratio of 1 : (2-8) with stirring at 30-80 deg.C and pH of 8.5-10 to obtain a precusor of basic aluminium carbonate; (2) washing the precursor, adding a composite catalyst, dehydrating, drying and calcining at 800 deg.C for 2 h to obtain spheric alpha-Al2O3 nanopowder with diameters of 70-140 nm. The method largely reduces the phase-change temperature of alpha-Al2O3, and can obtain alpha-Al2O3 nanopowder with good dispersibility and crystallinity. The method has such advantages as low cost, simple process, simple equipment and high product purity, and can be used in such fields as precision ceramics, electronics and aerospace industry.
Description
Technical field
The present invention relates to a kind of nano alumina powder jointed preparation method.Specifically a kind of low-temperature catalyzed calcining prepares nanometer α-Al
2O
3Method.
Background technology
Nano aluminium oxide shows a series of excellent properties because of its intensive volume effect, quantum size effect, surface effects and macro quanta tunnel effect in all many-sides such as light, electricity, thermodynamics and chemical reactions.Can be widely used in fields such as high technology ceramics, electronics, aerospace, laserable material.At present, prepare ultra-fine α-Al
2O
3Method comprise mechanical ball milling, gas-phase reaction method, sol-gel method, thermal decomposition method and combustion synthesis method.Mechanical ball milling needs the long time of high-energy ball milling and very easily introduces impurity, gas phase synthesis method requires special equipment and unit cost higher, sol-gel method adopts metal alkoxide as raw material, because the cost excessive cycle higher and gelation of metal alkoxide has limited the application of this method, combustion synthesis method has been applied to ultra-fine α-Al
2O
3Production process in, but the powder granule size distribution broad and the agglomeration that prepare by this method are more serious, thermal decomposition method is a kind of simple relatively and effective means.But, because aluminum oxide α phase transformation belongs to lattice reconstruct phase transformation, relate to moving of the bigger oxonium ion of ionic radius, need very high energy, so the transformation temperature height, usually about 1200 ℃.At high temperature, powder granule is very easily reunited, and forms a series of hard aggregation structures in irregular shape, causes product α-Al
2O
3Powder has lost the inherent premium properties.CN 1369434A discloses a kind of preparation method of alumina powder with high sinter activity, and it obtains α-Al
2O
3Temperature be 1200 ℃.CN 1583567A discloses a kind of nano alumina powder jointed preparation method of hard aggregation-free, and it obtains α-Al
2O
3Temperature be 1150 ℃.CN 1762816A discloses a kind of high dispersibility alpha-Al
2O
3The preparation method of nano-powder, it adopts the method for adding mineralizer to obtain α-Al
2O
3Temperature be 960 ℃, grain diameter 182nm.α-the Al that adopts above method to prepare
2O
3Because calcining temperature is higher, powder granule is reunited serious, and dispersing property is relatively poor, and finally causes powder to lose many nanometer α-Al
2O
3The inherent premium properties.At present, calcining temperature also not occurring is lower than 900 ℃ of α-Al that obtain perfect crystalline both at home and abroad
2O
3Report.
Summary of the invention
The object of the present invention is to provide and a kind ofly can reduce α-Al significantly
2O
3Transformation temperature, can obtain the α-Al of good dispersion property, perfect crystalline
2O
3Powder, cost is lower, technological process is simple, to equipment require lowly, the low-temperature catalyzed calcining that product purity is high prepares nanometer α-Al
2O
3Method.
The present invention includes following steps:
(1) be 0.2～1.0mol.L in concentration
-1Inorganic aluminum salting liquid in to add weight ratio be 1% polyoxyethylene glycol aqueous solution dispersion agent, addition is 1～3% of an aluminum salt solution volume ratio.
(2) at 0.8～3mol.L
-1Add weight ratio in the carbonate solution and be 1% the polyoxyethylene glycol aqueous solution as dispersion agent, addition is 1～3% of a carbonate solution volume ratio.
(3) under 30～80 ℃ temperature and continuous agitation condition, aluminum salt solution is added drop-wise in the carbonate solution, the mol ratio of carbonate solution and aluminum salt solution is 2～8: 1, and controls the pH value between 8.5～10 with ammoniacal liquor; After interpolation finishes, continue to stir 5～30min;
(4) rapidly system is moved in the ice-water bath, and in system, add mixture of ice and water, dilution cooling precipitation system, the frozen water addition is 1～3 times of precipitation system volume, continues to stir 1～4h;
(5) stop to stir, vacuum filtration with filter cake deionized water wash 3～5 times, and is added by ammonium nitrate after washing finishes the last time: Neutral ammonium fluoride: crystal seed α-Al
2O
3=2～3: 1: 3～6 composite cooling catalyzer of forming, its addition is 0.5～3% of a presoma theoretical yield;
(6) precipitation after washing is finished and composite cooling mixture of catalysts adopt the dehydration of propyl carbinol component distillation, keep to stop distillation in 0.5 hour after temperature rises to 117 ℃;
(7) the alcohol material mixed solution vacuum filtration that component distillation is obtained is deposited in 60～90 ℃ of drying 8～10h with what filtration obtained;
(8) product that drying is obtained is at 800 ℃ of following calcining 2h, promptly obtain crystallization fully, the spherical α-Al of class of good dispersion property
2O
3Powder.
Described inorganic aluminate is Tai-Ace S 150, aluminum nitrate or aluminum chloride.
Described carbonate is bicarbonate of ammonia or volatile salt.
The mol ratio of described carbonate solution and aluminum salt solution changes with the variation of different carbonate and different aluminium salt, is 4-8 as the mol ratio of bicarbonate of ammonia and aluminium salt: 1, and the mol ratio of volatile salt and aluminium salt is 2-4: 1.
Described dispersion agent is Polyethylene Glycol-600 and cetomacrogol 1000.
Characteristics of the present invention are: (1) this employing inexpensive inorganic salt is a raw material, be prepared into the presoma of Aluminum Carbonate Basic ammonium earlier, it is active that this presoma has better calcining, produces a large amount of gas, the reunion that can alleviate powder granule to a certain extent in thermal decomposition process.(2) adopt the propyl carbinol component distillation to dehydrate, effectively prevented the reunion of powder granule in drying process, and propyl carbinol can use repeatedly, the rate of recovery is up to 97.5%.(3) after the composite cooling catalyzer is added in employing, reduced α-Al significantly
2O
3Transformation temperature, and obtain product α-Al
2O
3Powder is between class sphere, the about 70～140nm of grain diameter, and be evenly distributed, good dispersion property.(4) raw materials cost is low, technological process is simple, to equipment require low, the product purity height.
Description of drawings
Fig. 1 is alumina powder jointed XRD figure spectrum;
Fig. 2 is embodiment 1 α-Al
2O
3The SEM picture of powder;
Fig. 3 is embodiment 2 α-Al
2O
3The SEM picture of powder
Fig. 4 is embodiment 3 α-Al
2O
3The SEM picture of powder
Fig. 5 is embodiment 4 α-Al
2O
3The SEM picture of powder.
Embodiment
Embodiment 1:
(1) accurately measures 0.6mol.L
-1Aluminum nitrate solution 300mL, measure the 5mL weight ratio and be 1% Polyethylene Glycol-600 aqueous solution dispersion agent and add in the aluminum nitrate solution, stir;
(2) accurately measure 2mol.L
-1Sal volatile 180mL, measure the 5mL massfraction and be 1% cetomacrogol 1000 aqueous solution dispersion agent, add in the sal volatile, stir;
(3) under temperature is 40 ℃ and continuous agitation condition, with above-mentioned be added with dispersion agent really aluminum salt solution be added drop-wise in the carbonate solution, add the back that finishes with the pH value of the ammoniacal liquor hierarchy of control between 8.5～10, continue stirring 10min;
(4) rapidly system is moved in the ice-water bath, and in system, add mixture of ice and water, dilution and cooling precipitation system, the frozen water addition is 600mL, continues to stir 2h;
(5) stop to stir, vacuum filtration, precipitate with deionized water washing 3 times, each leaching requirement is 400mL, and 0.5g is added by ammonium nitrate in the washing back that finishes the last time: Neutral ammonium fluoride: crystal seed α-Al
2O
3=2: the composite cooling catalyzer of forming at 1: 4;
(6) precipitation after washing is finished and composite cooling mixture of catalysts adopt propyl carbinol 300mL, and the component distillation dehydration is kept after temperature rises to 117 ℃ and stopped distillation in 0.5 hour;
(7) the alcohol material mixed solution vacuum filtration that component distillation is obtained is deposited in 60～90 ℃ of drying 8～10h with what filtration obtained, reclaims propyl carbinol;
(8) product that drying is obtained is at 800 ℃ of following calcining 2h, promptly obtain crystallization fully, the spherical α-Al of class of good dispersion property
2O
3Powder.
The XRD figure of product and SEM figure see Fig. 1 (A) and Fig. 2 respectively, and the result shows: α-Al
2O
3Crystallization very complete, powder granule is the class sphere, the about 70～90nm of grain diameter and be evenly distributed the good dispersion property of powder.
Embodiment 2:
At 0.3mol.L
-1Alum liquor 300mL in to add the 5mL weight ratio be 1% the Polyethylene Glycol-600 aqueous solution, at 1.2mol.L
-1Ammonium bicarbonate soln 600mL, adding 5mL weight ratio is 1% the cetomacrogol 1000 aqueous solution, under temperature is 60 ℃ and continuous agitation condition, with above-mentioned be added with dispersion agent really aluminum salt solution be added drop-wise in the carbonate solution, adding the back that finishes uses the pH value of the ammoniacal liquor hierarchy of control between 8.5～10, continue to stir 10min, rapidly system is moved in the ice-water bath then, and in system, add mixture of ice and water, dilution cooling precipitation system, the frozen water addition is 1000mL, continue to stir 2h, stir and finish the final vacuum filtration, the precipitation that obtains is adopted deionized water wash 3 times, each leaching requirement is 400mL, and 0.5g is added by ammonium nitrate in the washing back that finishes the last time: Neutral ammonium fluoride: crystal seed α-Al
2O
3=2: the composite cooling catalyzer of forming at 1: 5, precipitation after the washing and the employing of composite cooling mixture of catalysts are added the dehydration of 350mL propyl carbinol component distillation, when rising to 117 ℃, temperature stops distillation, distillation finishes final vacuum and filters, reclaim propyl carbinol, be deposited in 60～90 ℃ of dry 8h with what filtration obtained, 800 ℃ down the products that obtain of calcining 2h (its XRD figure and SEM figure see Fig. 1 (B) and Fig. 3 respectively.
Embodiment 3:
At 0.5mol.L
-1Alum liquor 200mL in to add the 4mL weight ratio be 1% the Polyethylene Glycol-600 aqueous solution, at 2.0mol.L
-1Sal volatile 200mL in, adding 4mL weight ratio is 1% the cetomacrogol 1000 aqueous solution, under temperature is 60 ℃ and continuous agitation condition, with above-mentioned be added with dispersion agent really aluminum salt solution be added drop-wise in the carbonate solution, adding the back that finishes uses the pH value of the ammoniacal liquor hierarchy of control between 8.5～10, continue to stir 10min, rapidly system is moved in the ice-water bath then, and in system, add mixture of ice and water, dilution cooling precipitation system, the frozen water addition is 600mL, continue to stir 2h, stir and finish the final vacuum filtration, the precipitation that obtains is adopted deionized water wash 3 times, each leaching requirement is 400mL, and 0.6g is added by ammonium nitrate in the washing back that finishes the last time: Neutral ammonium fluoride: crystal seed α-Al
2O
3=3: 1: 6 composite cooling catalyzer, precipitation after the washing and composite cooling mixture of catalysts are added the dehydration of propyl carbinol 280mL component distillation, when rising to 117 ℃, temperature stops distillation, distillation finishes final vacuum and filters, reclaim propyl carbinol, be deposited in 60～90 ℃ of dry 8h with what filtration obtained, 800 ℃ down the products that obtain of calcining 2h (its XRD figure and SEM figure see Fig. 1 (C) and Fig. 4 respectively.Show by analysis: α-Al
2O
3Crystallization very complete, powder granule is the class sphere, the about 80～120nm of grain diameter and being evenly distributed, the dispersing property of powder is better.
Embodiment 4:
At 0.2mol.L
-1Liquor alumini chloridi 300mL in add the Polyethylene Glycol-600 aqueous solution of 4mL1%, at 1.0mol.L
-1Ammonium bicarbonate soln 240mL in, add 4mL1% the cetomacrogol 1000 aqueous solution, under temperature is 70 ℃ and continuous agitation condition, with above-mentioned be added with dispersion agent really aluminum salt solution be added drop-wise in the carbonate solution, adding the back that finishes uses the pH value of the ammoniacal liquor hierarchy of control between 8.5～10, continue to stir 10min, rapidly system is moved in the ice-water bath then, and in system, add mixture of ice and water, dilution cooling precipitation system, the frozen water addition is 700mL, continue to stir 2h, stir and finish the final vacuum filtration, the precipitation that obtains is adopted deionized water wash 3 times, each leaching requirement is 400mL, and 0.3g is added by ammonium nitrate in the washing back that finishes the last time: Neutral ammonium fluoride: crystal seed α-Al
2O
3=2: the composite cooling catalyzer of forming at 1: 4, precipitation after the washing and composite cooling mixture of catalysts are adopted the dehydration of propyl carbinol 250mL component distillation, when rising to 117 ℃, temperature stops distillation, distillation finishes final vacuum and filters, reclaim propyl carbinol, be deposited in 60～90 ℃ of dry 8h with what filtration obtained, 800 ℃ down the product that obtains of calcining 2h (its XRD figure and SEM figure see respectively and Fig. 1 (D) and Fig. 5 show by analysis: α-Al
2O
3Crystallization very complete, powder granule is the class sphere, the about 80～140nm of grain diameter and being evenly distributed, the dispersing property of powder is better.
Claims (6)
1. a low-temperature catalyzed calcining prepares nanometer α-Al
2O
3Method, it is characterized in that, may further comprise the steps:
(1) at 0.2～1.0mol.L
-1Inorganic aluminum salting liquid in add weight ratio be 1% the polyoxyethylene glycol aqueous solution as dispersion agent, addition is the 1-3% of aluminum salt solution volume ratio;
(2) at 0.8～3mol.L
-1Add weight ratio in the carbonate solution and be 1% the polyoxyethylene glycol aqueous solution as dispersion agent, addition is 1～3% of a carbonate solution volume ratio;
(3) under 30～80 ℃ temperature and continuous agitation condition, aluminum salt solution is added drop-wise in the carbonate solution, the mol ratio of carbonate solution and aluminum salt solution is 2～8: 1, and controls the pH value between 8.5～10 with ammoniacal liquor; After interpolation finishes, continue to stir 5～30min;
(4) rapidly system is moved in the ice-water bath, and in system, add mixture of ice and water, dilution cooling precipitation system, the frozen water addition is 1～3 times of precipitation system volume, continues to stir 1～4h;
(5) stop to stir, vacuum filtration with filter cake deionized water wash 3～5 times, and is added by ammonium nitrate after washing finishes the last time: Neutral ammonium fluoride: crystal seed α-Al
2O
3=2～3: 1: 3～6 composite cooling catalyzer of forming, its addition is 0.5～3% of a presoma theoretical yield;
(6) precipitation after washing is finished and composite cooling mixture of catalysts be with the dehydration of propyl carbinol component distillation, keeps to stop distillation in 0.5 hour after temperature rises to 117 ℃;
(7) the alcohol material mixed solution vacuum filtration that component distillation is obtained is with 60～90 ℃ of drying 8～10h that are deposited in after filtering;
(8) product that drying is obtained is calcined 2h down at 800 ℃, obtains the spherical α-Al of class
2O
3Powder.
2. method according to claim 1, it is characterized in that described inorganic aluminate be in Tai-Ace S 150, aluminum nitrate or the aluminum chloride any one.
3. method according to claim 1 is characterized in that described carbonate is bicarbonate of ammonia or volatile salt.
4. method according to claim 3, the mol ratio that it is characterized in that bicarbonate of ammonia and aluminium salt is 4～8: 1.
5. method according to claim 3, the mol ratio that it is characterized in that volatile salt and aluminium salt is 2～4: 1.
6. method according to claim 1 is characterized in that described dispersion agent is Polyethylene Glycol-600 or cetomacrogol 1000.
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| CN101746786B (en) * | 2008-12-08 | 2013-08-14 | 中国科学院福建物质结构研究所 | Method for preparing high-purity alpha-Al2O3 nano-crystalline material |
| CN102274720B (en) * | 2010-12-24 | 2013-04-17 | 河南科技大学 | Modified activated aluminum oxide and preparation method thereof |
| CN104445316B (en) * | 2014-11-07 | 2016-04-13 | 东莞市鸿德电池有限公司 | A kind of preparation method of nano alumina material, goods and application |
| CN106830031A (en) * | 2017-03-31 | 2017-06-13 | 河北铭万精细化工有限公司 | The production method of high purity nanometer alumina |
| CN107128958A (en) * | 2017-05-12 | 2017-09-05 | 华东理工大学 | One kind reduction α Al2O3The method that powder phase turns temperature |
| CN112745105B (en) * | 2020-12-24 | 2022-06-14 | 深圳技术大学 | High-sintering-activity alumina ceramic powder and preparation method thereof |
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| CN1583567A (en) * | 2004-06-02 | 2005-02-23 | 武汉大学 | Preparation of nano aluminum oxide without hard coacervation |
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