CN1143047A - Preparing method for high purity super fine dispersing ball shape AL2O3 powder - Google Patents
Preparing method for high purity super fine dispersing ball shape AL2O3 powder Download PDFInfo
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- CN1143047A CN1143047A CN 95111112 CN95111112A CN1143047A CN 1143047 A CN1143047 A CN 1143047A CN 95111112 CN95111112 CN 95111112 CN 95111112 A CN95111112 A CN 95111112A CN 1143047 A CN1143047 A CN 1143047A
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Abstract
The present invention adopts water steam to hydrolyze the aluminium alcoholate in non-polar solvent and to prepare out superfine aluminium hdroxide powder, through calcination the high purity superfine, dispersing ball shaped gama Al2O3 and alpha Al2O3 powder are obtained. The average particle diameter is 50 and 90 nm respectively.
Description
The present invention relates to high pure and ultra-fine Al
2O
3The method for making of powder.
Because alumina-ceramic has good calorifics, optics, electricity and physical and mechanical properties, also have excellent biological compatibility, so support of the catalyst and automobile engine tail gas that it is widely used as in heat-stable material, guided missile window and high-pressure mercury lamp fluorescent tube material, computer integrate circuit substrate, high-abrasive material and bioceramic material, the petrochemical complex purify solid support material.Realize the above-mentioned character of alumina-ceramic, its raw alumina powder had following requirement: high-purity (＞99.99%), ultra-fine (d＜100nm), spherical, size distribution is narrower.For example, when alumina powder was used as abrasive material, according to the requirement of polishing velocity and rubbing down surface smoothness, the size-grade distribution of aluminum oxide powder should be narrow as far as possible, and particle diameter also should be as far as possible little.
With the precursor of aluminium alcoholates, nothing more than the reason of the following aspects as preparation aluminum oxide powder:
(1) preparation of aluminium alcoholates is less demanding to raw material aluminium, and purity＞98% gets final product, and is shaped as sheet, bits etc., and equipment can realize operate continuously, makes preparation process simplify relatively.
(2) be easy to be purified to and to be used to prepare the required purity of crystalline ceramics with distillation, recrystallization technology.This is that other method can't be by comparison.
(3) aluminium alcoholates is soluble in most organic solvents, and is easy to hydrolysis.
(4) all by products in the recyclable preparation process make product cost low, and essentially no environmental pollution.
(5) the temperature synthetic and processes such as aluminium hydroxide that hydrolysis generates of aluminium alcoholates is not high.
Numerous in the past be raw material with the aluminium alcoholates, through hydrolysis--calcining prepares in the method for aluminum oxide powder [1-7], and the median size of gained aluminum oxide powder is all more than 0.2 μ m, and efficient is very low, is unfavorable at industrial utilization and extention.
[1] T.Ogihara, et al., J.Am.Ceram., (lattice Harrar difficult to understand etc. " U.S.'s pottery magazine ") 1991,74 (9) 2263-69.
[2] A.Ayral, MRS Proc., (thunder difficult to understand " investigation of materials magazine ") 1991,121,239-301.
[3] M.Ocana, Ceram.Int., (blocking that " ceramic industry ") 1992,18,99-106.
[4] M.Visca, J.Colloid ﹠amp; Int.Sci., (Wei Sika, Ke Lei " industrial research magazine ") 1979,68 (2) 308-319.
[5] A.B.Hardy, In:Ultrastracture Processing of AdvancedCeramics, J.D.Mackenzice, D.R.Ulrich (eds.), John Wieley﹠amp; Sons, (breathing out younger brother, Ma Kenxie, black Ritchie, prestige tired inferior " superlattice of advanced ceramics are handled magazine ") 1988,417-425.
[6] W.E.Rhine, H.K.Bowen, Ceram.Int., (thunder because of, Bu Wen " ceramic industry ") 1991,17,143-52.
[7] E.Ponthiu, J.Non-Cryst.Solids, (Peng Ting " amorphous solid magazine ") 1992,147﹠amp; 148,598-605.
The reason that is difficult to make ultra-fine powder is: the hydrolysis of aluminium alcoholates, the too fast and uncontrollable powder size of condensation, size distribution and pattern.
The present invention seeks to utilize water vapour to improve the dynamic conditions of aluminium alcoholates hydrolysis, the hydrolysis rate of aluminium alcoholates is reduced relatively, in whole reaction system, realize homogeneous nucleation, thereby make dispersive aluminium hydroxide powder,, can make dispersive γ-Al through calcining
2O
3And α-Al
2O
3Spherical powder, its median size are respectively 50 and 90nm, and purity can reach 99.99%.
The present invention describes the present invention in conjunction with the accompanying drawings.
Technical process of the present invention as shown in Figure 1.
The aluminium alcoholates that rectifying is made is dissolved in non-polar solvent such as normal hexane, octane, normal heptane and the gasoline, and the concentration of aluminium alcoholates is the best 0.1-0.4mol/l of being of 0.05～0.5mol/l.Blast water vapour then in this solution, add-on is 1～4 times of theoretical amount (theoretical amount is calculated required water consumption for pressing chemical equation).Question response finishes, and again to wherein adding an amount of hydrochloric acid, what of add-on depend on hope obtains the spherical super fine aluminum oxide and decides under which type of calcining temperature.At this moment reaction system is two-layer about being divided into, and the upper strata is limpid non-polar solvent, and lower floor is the mixture of aluminum hydroxide gel, water and corresponding alcohol.The upper strata solvent is poured out the drying reusable edible with decantation.The exsiccant method can be with reference to relevant document.Lower floor can reclaim the solution of ultrafine aluminium hydroxide gel, water and corresponding alcohol respectively through vacuum-drying.This aqueous alcohol solutions is reclaimed alcohol through the pure water separating method of routine, or as pure water mixing steam hydrolysis aluminium alcoholates, reclaims also passable when the concentration of alcohol in the pure water is higher.To the aluminum hydroxide gel powder of gained, can get γ-Al through calcining
2O
3Or α-Al
2O
3Ultrafine powder.
Fig. 1 is the preparation technology of ultra-fine alumina powder
As low-carbon alcohol, carbon number is advisable with 2～4, specifically, should be ethanol, Virahol and sec-butyl alcohol, it is different with pure kind that they and aluminium bits react the temperature of synthesizing aluminium alcoholates, changes between 80～150 ℃, along with increasing of carbon number in the alcohol, the also corresponding increase of synthesis temperature.Especially ethanol and Virahol are more suitable, and purity should be analytical pure.
As normal hexane, octane, normal heptane and the gasoline of non-polar solvent, purity should be analytical pure, and wherein heptane and gasoline are the most suitable.
As water vapor or the pure water mixing steam that hydrolysis is used, its vapour pressure should be between 1.01 normal atmosphere to 1.2 normal atmosphere, especially to be advisable about 1.02 normal atmosphere.
Also can add hydrochloric acid in reaction process, hydrochloric acid also should be analytical pure, and the solution that should be made into 1: 1 adds.The hydrochloric acid content that adds depends on hope obtains the ball-aluminium oxide powder and decides under what temperature, the scope of the mol ratio of hydrochloric acid and aluminium alcoholates is 0～0.3, and 0-0.1 uses always.Mol ratio is big more, the easy more ball-aluminium oxide powder that obtains under lower calcining temperature.Otherwise, need under comparatively high temps, calcining could obtain the ball-aluminium oxide powder, but the good heat resistance of this powder.
When this method of enforcement, the recovery of solvent is necessary, and is very favourable to reducing cost, and its recovery is also simple.Because these solvents do not dissolve each other with water basically, available simple decantation can be implemented, and the drying of recovery solvent is also simple, can add an amount of lime earlier, after clarification, allow solvent through after the molecular sieve, the solvent comprises water amount is lower than 10ppm just can recycle.
As the hydrogen that discharges in the building-up process, available pipe is emptying after going up to the air, and is pollution-free to atmosphere.
The stove of calcining usefulness there is no particular requirement, and conventional electric furnace, retort furnace or tunnel furnace etc. all can.
Advantage of the present invention is the aluminium alcoholates of water steam hydrolysis in non-polar solvent, especially the low-carbon (LC) aluminium alcoholates in the gasoline, not only can make solvent cycle utilization, technology simple, and productive rate is higher, pollution-free, facility investment and running cost are all little, and the cost of product is also relatively low, can be accepted by the catalyzer and the petrochemical industry support of the catalyst production of high-pressure mercury lamp fluorescent tube, robot calculator substrate, indigo plant (red) jewel, biological ceramics, engine tail gas purification.This will be significant to the development of above industry.
Further describe the inventive method below by embodiment, but method of the present invention is not only limited to the content in the example.
Fig. 2 has provided the diffraction spectrogram of X ray, and 2 (a) are aluminium-hydroxide powder in the example 1.2 (b) are calcination attitude powder in the example 1, and 2 (c) are calcination attitude powder in the example 7.Fig. 3 has provided the transmission electron microscope photo of different amplification.
Example 1
Adding concentration in 1 liter beaker is the hexane solution 300ml of 0.15mol/l aluminum ethylate, and feeding air pressure is 1.01 atmospheric water vapors, and control steam rates and time, making add-on is about 2 times of theoretical amount.Add an amount of concentration again and be 1: 1 hydrochloric acid in reaction system, occur obvious layering in the beaker, lower floor is aluminium hydroxide, water and alcohol mixture.Method by decant reclaims the upper strata solvent, and the rate of recovery is 95%, reusable edible after dehydration, drying.The mixture of lower floor can get aluminium-hydroxide powder and alcohol solution through vacuum-drying.The alcohol water mixed solution can supply water with ordinary method dewatering and recovery alcohol or as the pure water mixing steam of preparation and separate usefulness.Bright by the X ray of Fig. 2 (a) stave that spreads out, gained aluminium hydroxide be boehmite (γ-AlOOH), its pattern shown in Fig. 3 (a), the cotton-shaped powder of group that it is made up of the staple fibre shape gel particles with certain length-to-diameter ratio, the mean length of single particle is about 15nm, and mean diameter is about 2nm.This powder 800 ℃ of calcinings 1 hour, can be got dispersive ball-aluminium oxide powder (shown in Fig. 3 (b)), and median size is about 50nm, and its X ray spectral line (Fig. 2 (b)) that spreads out shows that its crystal formation is γ-Al
2O
3The purity of this powder has been measured wherein impurity resultant through grating spectra, sees Table 1.Content of impurities is less than 100ppm.This powder weighing is 1.50g, and the rate of recovery is 98.0%.
The table 1 alumina powder assay (ppm) of mixing
| Element of Fe Si Na Ca Pb Mg Ti |
| Resultant |
| 20＜5＜10＜5＜5＜10＜10＜10＜10 |
Example 2
Adding concentration in 1 liter beaker is the n-heptane solution 300ml of 0.2mol/l aluminum isopropylate, and feeding air pressure is that 1.03 atmospheric water vapors are hydrolyzed, control water vapor add-on, and question response finishes, and does not add hydrochloric acid, and directly decant goes out the upper strata solvent.Lower floor's aluminum hydroxide gel is carried out vacuum-drying.The pattern of gained aluminium hydroxide is consistent with example 1 with crystal formation, and through 800 ℃ of calcinings 2 hours, the crystal formation of gained alumina powder was γ-Al
2O
3, its median size is 35nm, shown in Fig. 3 (c).Gained Al
2O
3The weight of powder is 3.0g, and the rate of recovery is 98%.
Example 3
Adding concentration in 1 liter beaker is the n-heptane solution 300ml of 0.3mol/l aluminum isopropylate, and feeding air pressure is that 1.04 atmospheric water vapors are hydrolyzed, control water vapor add-on, and question response finishes, and adds appropriate hydrochloric acid, and directly decant goes out the upper strata solvent.Lower floor's aluminum hydroxide gel is carried out vacuum-drying.The pattern of gained aluminium hydroxide is consistent with example 1 with crystal formation, and through 800 ℃ of calcinings 2 hours, the crystal formation of gained alumina powder was γ-Al
2O
3, its median size is 50nm, shown in Fig. 3 (d).Gained Al
2O
3The weight of powder is 4.25g, and the rate of recovery is 98.5%.
Example 4
Adding concentration in 1 liter beaker is the octane solution 300ml of 0.2mol/l aluminium secondary butylate, and feeding air pressure is that 1.03 atmospheric water vapors are hydrolyzed, control water vapor add-on, and question response finishes, and adds appropriate hydrochloric acid, and directly decant goes out the upper strata solvent.Lower floor's aluminum hydroxide gel is carried out vacuum-drying.The pattern of gained aluminium hydroxide is consistent with example 1 with crystal formation, and through 800 ℃ of calcinings 2 hours, the crystal formation of gained alumina powder was γ-Al
2O
3, its median size is 50nm, gained Al
2O
3The weight of powder is 2.95g, and the rate of recovery is 96.4%.
Example 5
Adding concentration in 1 liter beaker is the octane solution 300ml of 0.3mol/l aluminium secondary butylate, and feeding air pressure is that 1.04 atmospheric water vapors are hydrolyzed, control water vapor add-on, and question response finishes, and adds appropriate hydrochloric acid, and directly decant goes out the upper strata solvent.Lower floor's aluminum hydroxide gel is carried out vacuum-drying.The pattern of gained aluminium hydroxide is consistent with example 1 with crystal formation, and through 600 ℃ of calcinings 2 hours, the crystal formation of gained alumina powder was γ-Al
2O
3, its median size is 50nm, gained Al
2O
3The weight of powder is 4.5g, and the rate of recovery is 98%.
Example 6
In 1 liter beaker, add the secondary gasoline that concentration is the 0.2mol/l aluminum isopropylate (after recovery, drying) solution 300ml, feeding air pressure is that 1.02 atmospheric water vapors are hydrolyzed, control water vapor add-on, and question response finishes, add appropriate hydrochloric acid, directly decant goes out the upper strata solvent.Lower floor's aluminum hydroxide gel is carried out vacuum-drying.The pattern of gained aluminium hydroxide is consistent with example 1 with crystal formation, and through 1100 ℃ of calcinings 2 hours, the median size of gained alumina powder was 70nm, gained Al
2O
3The weight of powder is 2.95g, and the rate of recovery is 96.4%.
Example 7
Adding concentration in 1 liter beaker is the gasoline solution 300ml of 0.4mol/l aluminum ethylate, and feeding air pressure is that 1.15 atmospheric water vapors are hydrolyzed, control water vapor add-on, and question response finishes, and does not add hydrochloric acid, and directly decant goes out the upper strata solvent.Lower floor's aluminum hydroxide gel is carried out vacuum-drying.The pattern of gained aluminium hydroxide is consistent with example 1 with crystal formation, and through 1200 ℃ of calcinings 1 hour, the crystal formation of gained alumina powder was α-Al
2O
3(seeing Fig. 2 (c) X ray diffracting spectrum), its median size is 90nm, gained Al
2O
3The weight of powder is 6.00g, and the rate of recovery is 98.0%.
Claims (10)
1. one kind dissolves aluminium alcoholates with hydrolysis, prepares technology ultra-fine, the dispersing ball alumina powder, reclaims non-polar solvent, drying reusable edible through decant; To aluminum hydroxide gel liquid, through the recyclable alcoholic solution of vacuum-drying, again with ordinary method to its dehydration, drying, alcohol can also recycle; Dried aluminium-hydroxide powder can directly be calcined at a certain temperature, obtain ultra-fine, high-purity, dispersive ball-aluminium oxide powder, it is characterized in that the hydrolysis of water steam is dissolved in the aluminium alcoholates in the non-polar solvent, hydrolysising reacting temperature is lower than 90 ℃, and the pressure that adds water vapor is the 1.0-1.2 normal atmosphere.
2. technology according to claim 1 is characterized in that carbonatoms is C2～C4 in the used low-carbon (LC) aluminium alcoholates of hydrolysis reaction, is good with aluminum ethylate and aluminum isopropylate.
3. technology according to claim 1 is characterized in that hydrolysising reacting temperature should be lower than 90 ℃, being good between 50～75 ℃.
4. technology according to claim 1 is characterized in that the air pressure of the water vapor that hydrolysis reaction adds should be 1.01 to 1.03 normal atmosphere.
5. technology according to claim 1 is characterized in that the water vapor that hydrolysis reaction adds, and its add-on should be 1～4 times of theoretical amount, is good with 1.0～2 times.
6. technology according to claim 1 is characterized in that the aluminium alcoholates in the hydrolysis non-polar solvent, and its concentration should be 0.05～0.5mol/l, is good with 0.2～0.4mol/l.
7. technology according to claim 1 is characterized in that the non-polar solvent that hydrolysis is used, and comprises normal hexane, normal heptane, octane and gasoline, is good with heptane and gasoline especially.
8. technology according to claim 1 is characterized in that after the hydrolysis, and the hydrochloric acid of adding and the mol ratio of aluminium alcoholates should be between 0～0.1, and concrete amount should obtain ball-aluminium oxide with the need and decide under what calcining temperature.
9. technology according to claim 1 is to also reusable edible of the non-polar solvent of secondary recovery.
10. technology according to claim 1, to the aluminium-hydroxide powder calcining, the temperature range that can obtain the ball-aluminium oxide powder is at 500～1200 ℃.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085620C (en) * | 1997-04-09 | 2002-05-29 | 大连铁道学院精细陶瓷工程研究中心 | Technology for preparing ultra-high purity superfine aluminium oxide powder |
| CN102807243A (en) * | 2012-08-10 | 2012-12-05 | 山东大学 | Preparation method of aluminum hydroxide gel and microlite alpha-Al2O3 aggregate |
| CN102992367A (en) * | 2011-09-17 | 2013-03-27 | 阎成华 | Technology for producing high-purity ultrafine powder alumina with spherical or fibrous crystal form |
| CN103172096A (en) * | 2013-03-22 | 2013-06-26 | 哈尔滨工程大学 | Method for preparing nanometer aluminium oxide sheet |
| CN104190391A (en) * | 2014-07-02 | 2014-12-10 | 上海应用技术学院 | Catalyst and application of catalyst to method for preparing thymol |
| CN108821973A (en) * | 2018-08-14 | 2018-11-16 | 徐州工业职业技术学院 | A kind of method of clean manufacturing Fenofibrate |
-
1995
- 1995-07-14 CN CN 95111112 patent/CN1143047A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085620C (en) * | 1997-04-09 | 2002-05-29 | 大连铁道学院精细陶瓷工程研究中心 | Technology for preparing ultra-high purity superfine aluminium oxide powder |
| CN102992367A (en) * | 2011-09-17 | 2013-03-27 | 阎成华 | Technology for producing high-purity ultrafine powder alumina with spherical or fibrous crystal form |
| CN102992367B (en) * | 2011-09-17 | 2015-05-13 | 阎成华 | Technology for producing high-purity ultrafine powder alumina with spherical or fibrous crystal form |
| CN102807243A (en) * | 2012-08-10 | 2012-12-05 | 山东大学 | Preparation method of aluminum hydroxide gel and microlite alpha-Al2O3 aggregate |
| CN103172096A (en) * | 2013-03-22 | 2013-06-26 | 哈尔滨工程大学 | Method for preparing nanometer aluminium oxide sheet |
| CN103172096B (en) * | 2013-03-22 | 2015-02-25 | 哈尔滨工程大学 | Method for preparing nanometer aluminium oxide sheet |
| CN104190391A (en) * | 2014-07-02 | 2014-12-10 | 上海应用技术学院 | Catalyst and application of catalyst to method for preparing thymol |
| CN104190391B (en) * | 2014-07-02 | 2016-08-17 | 上海应用技术学院 | A kind of catalyst and the purposes in preparing thymol method thereof |
| CN108821973A (en) * | 2018-08-14 | 2018-11-16 | 徐州工业职业技术学院 | A kind of method of clean manufacturing Fenofibrate |
| CN108821973B (en) * | 2018-08-14 | 2021-04-06 | 徐州工业职业技术学院 | Clean production method of prolipofen |
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