CN1342609A - Process for preparing high-purity nm or submicron alumina particles in losse form - Google Patents
Process for preparing high-purity nm or submicron alumina particles in losse form Download PDFInfo
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- CN1342609A CN1342609A CN 00125966 CN00125966A CN1342609A CN 1342609 A CN1342609 A CN 1342609A CN 00125966 CN00125966 CN 00125966 CN 00125966 A CN00125966 A CN 00125966A CN 1342609 A CN1342609 A CN 1342609A
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- aluminium
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Abstract
A process for preparing nm-or submicron-class high-purity alumina in loose state features that the ordinary industry-class raw materials are used for low cost, and includes such steps as adding solvent and additive to aluminium alkoxide to obtain liquid-phase aluminium alkoxide, and hydrolyzing to obtain high-purity nm alumina. Its advantages are loose product and uniform granularity because of hydrolysis in liquid phase, ordinary reaction temp. and low cost.
Description
The present invention relates to a kind of method for preparing high-purity ultra-fine alumina, the method for a kind of particle diameter of preparation of saying so more specifically less than the high purity aluminium oxide of 1um.
At present, very extensive for the research of super-fine material, successful ultrafine powder oxide compound such as the SiO for preparing
2, ZrO
2Deng a lot.The present invention is high-purity ultra-fine alumina (Al
2O
3) preparation method of powder.
According to the retrieval, up to the present, the method for making of nano aluminium oxide mainly is to utilize the rafifinal metal at HgCl
2Effect under in the middle of the aqueous solution inorganic method synthetic aluminum oxide powder.As Chinese patent 95105843.6, Chinese patent ZL92104368.6 and German Patent 2604083, the shortcoming of this method is to utilize highly toxic substance HgCl
2Make the catalysis inducer, all unfavorable for environmental protection, health, and this technology very easily introduces impurity, though can obtain the thinner particle of granularity, product purity is not high, size-grade distribution is wide and inhomogeneous.
The exsiccated ammonium alum pyrolysis method is the main method of producing high purity aluminium oxide both at home and abroad at present.As English Patent 514538, Germany patent 2215594 and 2419544, the shortcoming of this method is that expense is big, the long industrially scalable that is not suitable for of treatment time.And the method for domestic common employing is: high-purity tschermigite is dewatered down at 210～250 ℃, and the volume of dehydration back alum increases, and needs just can carry out high temperature pyrolysis with after its pulverizing.The shortcoming of this method is that need to pulverize back pyrolysis and decomposition rate under this kind condition slow, reduces the throughput of stove, though purity is better relatively for the product that obtains, and a large amount of NH of discharging in the production process
3And SO
2Seriously polluted, sulfur-bearing in the product aluminum oxide, granularity are inhomogeneous.
Because developing rapidly and actual needs of science and technology, press for a kind of granularity meticulousr, good dispersity and more highly purified Al
2O
3Powder.The object of the present invention is to provide the preparation method of the good high purity aluminium oxide of a kind of more highly purified granularity fine dispersion.
Present method is that traditional organoaluminum method for hydrolysis is referred to that mainly aluminum alkyls and aluminum alkoxide hydrolysis method prepare the improvement of aluminum oxide and replenish, though purity better hydrolysis temperature height, inhomogeneous, the bad dispersibility of granularity are only carried out in the hydrolysis of traditional method under the independent effect of high purity water.Characterization step described in the Chinese patent ZL97104442.2 comprises: (1) reacts low-carbon alcohol and metallic aluminium to 1～10h down at 80～100 ℃, add isooctyl alcohol, reacted 2～6h hour, promptly obtain low-carbon alkoxy after the filtration, iso-octyl aluminium, described metallic aluminium, low-carbon alcohol, the mol ratio of isooctyl alcohol is 1: 3～4: 2～3, (2) low-carbon alkoxy that obtains in (1) step, add deionized water in the iso-octyl aluminium, at 80～110 ℃ of following hydrolysis reaction 1～20h, obtain hydrolysate, telling low-carbon alcohol that hydrolysis produces returns (1) step and recycles, (3) steam the remaining alcohol of hydrolysate, then at 100～110 ℃ of down aging 1～30h, 110～120 ℃ of oven dry, obtain α-A
2O
3H
2O, (4) are with α-A
2O
3H
2O obtains high-purity γ-A at 500～650 ℃ of following roasting 4～6h
2O
3The basic characteristics of this method are to introduce iso-octyl in low-carbon alkoxy aluminium, obtain being the low-carbon alkoxy of liquid, different octyloxy aluminium under the room temperature, and being hydrolyzed as raw material makes high purity aluminium oxide.Thereby making hydrolysis material be beneficial to conveying cuts down the consumption of energy.But its hydrolysis temperature is also higher at 80～110 ℃, filter under flocculating aids, easily to introduce impurity, and the purity of used metallic aluminium higher＞99.5%.
Major programme of the present invention is: will make with extra care aluminium alcoholates be dissolved in the middle of the solvent, and add an amount of additive in the hydrolysis, hydrolysis is carried out under lower temperature, the product of gained does not need fragmentation, can obtain the meticulous product of the loose granularity of mode of appearance, and used aluminum metal purity 〉=95% gets final product.
The present invention prepares the loose nano level of mode of appearance, submicron order high purity aluminium oxide method:
1. preparation process comprises:
I) metallic aluminium and alcohol are reacted 10 down in 60～130 ℃ under the effect of catalyzer
Minute～15 hours, synthetic aluminium alcoholates, the effecting reaction of described metallic aluminium, alcohol rubs
Your ratio is 1: 1～6;
II) with I) aluminium alcoholates that obtains of step is moved in the vacuum distillation apparatus, is heated to
100～200 ℃ is to make with extra care under the condition of 1mmHg～20mmHg to carry in vacuum tightness
Pure:
III) with II) in the aluminium alcoholates that obtains be dissolved in the middle of the solvent, add high purity water and suitable
The additive of amount, reaction is hydrolyzed under 20～120 ℃;
IV) with III) in the hydrolysate that obtains filter, filter cake is under 20～80 ℃
Cryodrying, filtrate can be returned III) recycle in the step;
V) with IV) in resulting product 400～1000 ℃ of following sintering 2～8 hours
Obtain high-purity γ-A
2O
3, granularity is at 10～20nm; 400～1200 ℃ of sintering 4～
Obtained high-purity α-A in 16 hours
2O
3, granularity is at 50～300nm; The advantage of this method
Be that product granularity is controlled, good dispersity need not pulverized and can obtain the mode of appearance pine
Loose, have lower loose density spheric alumina nano powder.
2. the alcohol above-mentioned steps I) refers to C
1～C
12Alkoxyl alcohol or in the alkyl alcohol one or more, when metallic aluminium has just begun with the alcohol reaction, add an amount of aluminium alcoholates and make catalyzer, reacted 10 minutes～15 hours down at 60～130 ℃, obtain aluminium alcoholates, the effecting reaction mol ratio of described metallic aluminium, alcohol, aluminium alcoholates is 1: 1～6: 0.001～2.0.
Described C
1～C
12Alkoxyl alcohol or alkyl alcohol in C
1～C
4Alkoxyl alcohol or alkyl alcohol better.
C wherein
1～C
4Alkoxyl alcohol or alkyl alcohol can be in methyl alcohol, ethanol, propyl alcohol, butanols and the isomer thereof etc. one or more, wherein Virahol is best.
Described metallic aluminium comprises aluminium bits, aluminium powder, aluminum strip etc., and its purity 〉=95% gets final product.
3. hydrolysis reaction above-mentioned steps III), to make with extra care to such an extent that product is dissolved in the middle of the solvent, add high purity water, an amount of additive, in 20～120 ℃ of reactions 2～30 hours down, the mol ratio of described refined products, solvent, high purity water, additive is 1: 1～10: 1～8: 0.0～5.0.
4. the solvent above-mentioned steps III) is aluminium alcoholates organism that can dissolve each other such as in the middle of benzene class, aldehydes, ketone, alcohols, alkanes and the derivative thereof one or more, and additive is: one or more in S-60, WA, acetic acid, ammoniacal liquor, PVA, the whiteruss.Its purpose is to disperse solute, makes the growth conditions of aluminum oxide complete, even, consequently narrow diameter distribution, good dispersity.
5. hydrolysising reacting temperature above-mentioned steps III) is in 20～120 ℃ low scope, and the optimum hydrolysis temperature is 20～35 ℃.Normal temperature can carry out, and need not heat.
6. benzene class material refers to contain the solvent of phenyl ring in the above-mentioned method 4., as benzene,toluene,xylene etc.
Characteristics of the present invention:
Present method is that traditional organoaluminum method for hydrolysis is referred to that mainly aluminum alkyls and aluminum alkoxide hydrolysis method prepare the improvement of aluminum oxide and replenish, the hydrolysis of traditional method is only carried out under the independent effect of high purity water, though purity better the hydrolysis temperature height, easily cause inhomogeneous, the bad dispersibility of granularity.Method of the present invention is the difference of hydrolysis process and prescription, introduces solvent and add minor amounts of additives again in the process of hydrolysis, and hydrolysis reaction homogeneous in the middle of liquid phase is carried out.Its result is controllable granularity, good dispersity, need not pulverize can obtain mode of appearance loose, have a lower loose density spheric alumina nano powder.The characteristics of this method are that not only being beneficial to reaction after the purified product is dissolved also is beneficial to transportation, and do not need outer heating, thereby saving equipment and investment also reduce energy consumption.In addition, the by product that this hydrolysis obtains can be recycled, aluminum metal purity 〉=95% of utilization, and the product purity that obtains reaches 99.99～99.999%.
Further describe characteristics of the present invention with example below.Example 1:
With aluminium powder 60 grams, Virahol 300 grams, aluminium alcoholates 40 grams are put into 1 liter the four-hole boiling flask that has agitator and dual reflux prolong simultaneously, heating reflux reaction obtains thick aluminum isopropylate after 500 minutes, heat in the matrass with 1 liter of thick aluminum isopropylate immigration another, vacuumize vacuum tightness be under the 10mmHg with its purification, obtain colourless refining isopropanol aluminium.The purified aluminium alcoholates is added in the middle of the mixed liquid of 400 gram butanols and 100 gram acetone, reaction is 4 hours under adding 100 gram deionized water room temperatures, adds 3 gram S-60 and 10 gram acetic acid during reaction.Aging after-filtration, the hydrolysis rear filtrate returns again and utilizes, and filter cake is dry under 60～80 ℃, and products therefrom obtained γ-A in 4 hours at 400～800 ℃ of following sintering
2O
3Example 2:
With aluminum strip 60 grams, ethanol 300 grams, aluminum isopropylate 40 grams are put into 1 liter the four-hole boiling flask that has agitator and dual reflux prolong simultaneously, and below operation is with example 1.Refined products is dissolved in the middle of the mixed liquid of 600 gram benzene and 20 gram ether, add under the high purity water 150 gram room temperatures and reacted 28 hours, add 2 an amount of gram whiterusss and 5 gram ammoniacal liquor during reaction.Below operation is with 1.Example 3:
With aluminum strip 60 grams, isopropylcarbinol 300 grams, aluminum isopropylate 40 grams are put into 1 liter the there-necked flask that has agitator and reflux condensing tube simultaneously, and below operation is with example 1.Refined products is dissolved in the middle of the mixed liquid of 100 gram ketone, 500 gram butanols and 200 gram benzene, adding deionized water 300 grams reacted 5 hours down at 30～50 ℃, adding 2 gram WA, 5 gram paraffin are made additive during reaction, the hydrolysis after-filtration, filtrate returning can be utilized again, filter cake is dry down in 20 ℃ of room temperatures, and products therefrom obtained α-A in 4 hours at 400～1200 ℃ of following sintering
2O
3Example 4:
With aluminium bits 60 grams, propyl alcohol 320 grams, aluminum isopropylate 60 grams are put into 1 liter the four-hole boiling flask that has agitator and dual reflux prolong simultaneously, and below operation is with example 1.Refined products is dissolved in the middle of the mixed liquid of 80 gram aldehyde, 120 gram ethanol and 600 gram toluene, add deionized water 100 grams and reacted 15 hours down at 30～40 ℃, the hydrolysis after-filtration, filtrate returning can be utilized again, filter cake is dry down in 20 ℃ of room temperatures, and below operation is with example 1.Example 5:
2 kilograms of concrete implementation steps of nano aluminium oxide of preparation are as follows in industrial production:
1. be in 9 5% 8 kilograms of 1.5 kilograms of metallic aluminiums, Virahols that are and 1 kilogram of adding synthetic tower of aluminum isopropylate with purity, be heated to 60～130 ℃, synthetic aluminium alcoholates;
2. the 1 product aluminium alcoholates that obtains of step is changed in the rectifying tower, being heated to 100～200 ℃ is that purification is made with extra care in decompression under the condition of 1mmHg～20mmHg in vacuum tightness;
3. the aluminium alcoholates that obtains in 2 is moved in the reactor, add 15 kilograms of toluene, 5 kilograms of ethanol, 1 kilogram in aldehyde, 2.8 kilograms of high purity waters, add a spot of 120 gram acetic acid and 29 gram whiterusss, reaction is hydrolyzed under 20 ℃ of room temperatures;
4. the hydrolysate that obtains in 3 is filtered, filter cake is 20～80 ℃ of following cryodryings, and filtrate can be returned in 3 steps and recycle;
With resulting product in 4 in tunnel furnace in 400～1000 ℃ of following sintering 2～8
Hour obtain high-purity γ-A
2O
3Obtained high-purity α-A in 4～16 hours at 400～1200 ℃ of sintering
2O
3
By above step need not pulverize get final product controllable granularity, 2.8 kilograms in the aluminum oxide of good dispersity, wherein γ-A
2O
3Particle diameter 12nm; α-A
2O
3Granularity 100nm; Purity 99.99%～99.999%.
Extremely low by the impurity that can find out the aluminum oxide that this technology makes in the above-mentioned example.And industrialization is easy, cleanliness without any pollution, and Working environment is better.The test result of products therefrom is attached, illustrates by the inventive method to make the loose high-purity Nano-class of mode of appearance, submicron-grade superfine aluminum oxide on a large scale.Subordinate list: example 5 analytical resultss
Specific surface area (m
2/ g): 600 100
Particle diameter (nm): 12 100
The thing phase: the result is as follows for γ α purity test:
| Impurity (ppm) | ||||||||
| ???Ca | ???Si | ????Fe | ????Na | ????Ti | ????Mg | ????Zr | ????Cu | ????K |
| ???2.0 | ???3.5 | ????0.8 | ????0.01 | ????1.0 | ????0.5 | ????0.1 | ????0.2 | ????0.01 |
Claims (7)
1. the nanometer that a form is loose, the preparation method of submicron order high purity aluminium oxide, its feature comprises in preparation process: 1) metallic aluminium and alcohol were reacted 10 minutes～15 hours down in 60～130 ℃ under the effect of catalyzer, synthetic aluminium alcoholates, the effecting reaction molar ratio of described metallic aluminium, alcohol is 1: 1～6; 2) with 1) aluminium alcoholates that obtains of step is moved in the vacuum distillation apparatus, and being heated to 100～200 ℃ is to make with extra care purification under the condition of 1mmHg～20mmHg in vacuum tightness; 3) with 2) in the aluminium alcoholates that obtains be dissolved in the middle of the solvent, add high purity water and an amount of additive, reaction is hydrolyzed under 20～120 ℃; 4) with 3) in the hydrolysate that obtains filter, filter cake is 20～80 ℃ of following cryodryings, filtrate can return 3) recycle in the step; 5) with 4) in resulting product obtained high-purity γ-A in 2～8 hours at 400～1000 ℃ of following sintering
2O
3, granularity is at 10～20nm; Obtained high-purity α-A in 4～16 hours at 400～1200 ℃ of sintering
2O
3, granularity is at 50～300nm; The advantage of this method is that product granularity is controlled, good dispersity, need not pulverize can obtain mode of appearance loose, have a lower loose density spheric alumina nano powder.
2. by the described method of claim 1, it is characterized in that the alcohol in the step 1) refers to C
1～C
12Alkoxyl alcohol or in the alkyl alcohol one or more, when metallic aluminium has just begun with the alcohol reaction, add an amount of aluminium alcoholates and make catalyzer, reacted 10 minutes～15 hours down at 60～130 ℃, obtain aluminium alcoholates, the effecting reaction mol ratio of described metallic aluminium, alcohol, aluminium alcoholates is 1: 1～6: 0.001～2.0.
3. by the described method of claim 1, the hydrolysis reaction that it is characterized in that step 3), to make with extra care to such an extent that product is dissolved in the middle of the solvent, add high purity water, an amount of additive, reacted 2～30 hours down in 20～120 ℃, the mol ratio of described refined products, solvent, high purity water, additive is 1: 1～10: 1～8: 0.0～5.0.
4. by the described method of claim 1, it is characterized in that the solvent described in the step 3) is the organism that can dissolve each other with aluminium alcoholates such as in the middle of benzene class, aldehydes, ketone, alcohols, alkanes and the derivative thereof one or more, additive is: one or more in S-60, WA, acetic acid, ammoniacal liquor, PVA, the whiteruss.
5. by the described method of claim 1, it is characterized in that hydrolysising reacting temperature in the step 3) at 20～120 ℃, optimum temps is 20～35 ℃ low scope.
6. by the method described in the claim 1, it is characterized in that described metallic aluminium comprises aluminium bits, aluminium powder, aluminum strip etc., its purity 〉=95% gets final product.
7. by the C described in the claim 2
1～C
12Alkoxyl alcohol or alkyl alcohol in C
1～C
4Alkoxyl alcohol or alkyl alcohol better, wherein Virahol is best.
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|---|---|---|---|
| CN 00125966 CN1342609A (en) | 2000-09-11 | 2000-09-11 | Process for preparing high-purity nm or submicron alumina particles in losse form |
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|---|---|---|---|
| CN 00125966 CN1342609A (en) | 2000-09-11 | 2000-09-11 | Process for preparing high-purity nm or submicron alumina particles in losse form |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8343415B2 (en) | 2007-01-15 | 2013-01-01 | Saint-Gobain Ceramics & Plastics, Inc. | Ceramic particulate material and processes for forming same |
| CN102976371A (en) * | 2012-08-30 | 2013-03-20 | 朱作远 | Preparation method for high purity ultrafine alumina powder through aluminum alkoxide hydrolysis method |
| CN104085908A (en) * | 2014-07-16 | 2014-10-08 | 李春松 | Method for preparing high-purity aluminium oxide |
| CN106629794A (en) * | 2016-10-13 | 2017-05-10 | 北京工商大学 | Preparation method of high-gum-solubility pseudoboehmite |
| CN111205070A (en) * | 2020-03-11 | 2020-05-29 | 苏州贝尔德新材料科技有限公司 | Preparation method of easily-sintered high-purity alumina |
| CN112777630A (en) * | 2020-12-10 | 2021-05-11 | 中海油天津化工研究设计院有限公司 | Preparation method of high-purity gallium oxide |
-
2000
- 2000-09-11 CN CN 00125966 patent/CN1342609A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8343415B2 (en) | 2007-01-15 | 2013-01-01 | Saint-Gobain Ceramics & Plastics, Inc. | Ceramic particulate material and processes for forming same |
| CN102976371A (en) * | 2012-08-30 | 2013-03-20 | 朱作远 | Preparation method for high purity ultrafine alumina powder through aluminum alkoxide hydrolysis method |
| CN104085908A (en) * | 2014-07-16 | 2014-10-08 | 李春松 | Method for preparing high-purity aluminium oxide |
| CN104085908B (en) * | 2014-07-16 | 2016-05-11 | 宁波普莱斯帝金属制品有限公司 | A kind of preparation method of high-purity alpha-alumina |
| CN106629794A (en) * | 2016-10-13 | 2017-05-10 | 北京工商大学 | Preparation method of high-gum-solubility pseudoboehmite |
| CN106629794B (en) * | 2016-10-13 | 2018-10-16 | 北京工商大学 | A kind of preparation method of high peptization boehmite |
| CN111205070A (en) * | 2020-03-11 | 2020-05-29 | 苏州贝尔德新材料科技有限公司 | Preparation method of easily-sintered high-purity alumina |
| CN112777630A (en) * | 2020-12-10 | 2021-05-11 | 中海油天津化工研究设计院有限公司 | Preparation method of high-purity gallium oxide |
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