CN100593516C - Method of preparing alpha aluminium oxide fine powder by low temperature - Google Patents
Method of preparing alpha aluminium oxide fine powder by low temperature Download PDFInfo
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- CN100593516C CN100593516C CN200610012112A CN200610012112A CN100593516C CN 100593516 C CN100593516 C CN 100593516C CN 200610012112 A CN200610012112 A CN 200610012112A CN 200610012112 A CN200610012112 A CN 200610012112A CN 100593516 C CN100593516 C CN 100593516C
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- alumina
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Abstract
A low-temp process for preparing fine powder of alpha-aluminum oxide includes such steps as carrying the organic compound difficult to volatilize by the surface of the precursor of aluminum oxide withlarge specific surface area, low-temp dewatering and carbonizing in inertial gas to obtain C/aluminum oxide composition, filling O2, and fast burning C to generate high temp while quickly generatingthe fine powder of alpha-aluminum oxide.
Description
Technical field
The present invention relates to the preparation method that the low temperature short period of time prepares alpha-alumina powder, belong to chemical field.
Background technology
Although aluminum oxide industry has had the history in more than 100 year, long-time roasting aluminium hydroxide of high temperature and electric smelting method are two kinds of common methods of industrial production Alpha-alumina.The alpha aluminium oxide particle that these two kinds of methods obtain is bigger, just can further be used after need further pulverizing and sieve, and is particularly difficult when the ultra-fine Alpha-alumina of preparation, and cost is higher.How can prepare ultrafine alpha-alumina powders quickly and easily is the problem that material supplier author endeavours to study.The method that much is used to prepare ultra-fine or nano material all has been applied to the preparation of ultra-fine Alpha-alumina.The Sol-Gel method can be prepared nano oxidized aluminum precursor, but in general need 1100 ℃ of roastings 20 hours in addition the longer time, could take place complete phase transformation J.Am.Ceram.Soc., 85[6] 1467-1472 (2002), Chem.Matter., 13[8] 2595-2600 (2001) }.Hydrothermal method need be under high temperature and high pressure environment, and the crystal seed of adding is generally the α-Al of little crystal grain
2O
3Or α-Fe
2O
3, handle the long time J.Am.Ceram.Soc., 68[9] 500-505 (1985), J.Am.Ceram.Soc.83[1] 82-88 (2000) }.R.N.Das etc. { J.Am.Ceram.Soc.84[10] 2421-2423 (2001) } utilize sucrose 600 ℃ of roasting a few hours in retort furnace, obtained Alpha-alumina, but L.D.Mitchell{J.Am.Ceram.Soc., 21[22] 1773-1775 (2002) } repeat identical experiment and do not obtain Alpha-alumina, and the consumption of sucrose has reached 6: 1 by the mol ratio of sucrose/aluminum nitrate in their experiment, even 250: 1, be difficult in industrial application.
Summary of the invention
According to the shortcoming and defect that aforesaid method exists, the object of the present invention is to provide the preparation method of the ultra-fine Alpha-alumina that a kind of preparation technology is simple, the organism consumption is few, maturing temperature is low, roasting time is extremely lacked.
The transformation temperature of Alpha-alumina is greatly about 1150 ℃ in general, but under this temperature, wants that complete phase transformation need be heated 20 hours even the longer time, and industrial production is generally 1300-1400 ℃ of insulation 2-3 hour.Temperature is high more, and transformation time is just short more fully.Not only energy consumption is big in high-temperature roasting for a long time, and intergranular sintering situation can be more serious.
People such as Xie Youchang, Wang Xiaoyong, Zhu Yuexiang find that organism can spontaneously be dispersed in the surface of high-ratio surface inorganic oxide such as gama-alumina, silica gel etc., form individual layer or inferior individual layer { Adv.Catal.37,1-43 (1990); Acta.Phys.-Chim.Sin.14[10] 869-73 (1998); Acta.Phys.-Chim.Sin.15[9] 830-3 (1999) }.Lin Li studies the sucrose that individual layer or inferior individual layer are dispersed in the gama-alumina surface, find by dewater carbonization can the surperficial uniform distribution last layer carbon of gama-alumina Acta.Phys.-Chim.Sin.20[10] 1179-81 (2004); Langumuir 21[11] 5040-6 (2005) }.And the standard mole combustion heat of carbon is 394kJ.mol
-1If at the carbon of the surface coverage weight content 10% of gama-alumina, suppose that the heat that burning produces all is used for heated oxide aluminium, as calculated, the aluminum oxide temperature can be raise 1700 ℃, be higher than far away that to generate Alpha-alumina temperature required.Because temperature is very high, can shorten complete transformation time greatly simultaneously, reduce intergranular sintering.
We find, behind difficult volatile organic compounds in the load of precursor alumina surface, obtain C/Al through the heating carbonization
2O
3Mixture, logical oxygen burning can obtain alpha-alumina fine powder rapidly.Specifically, technical scheme of the present invention is as follows:
A kind of method for preparing alpha-alumina fine powder, it is characterized in that difficult evaporable organism is loaded on the alumina precursor, under inert atmosphere, through the thermal dehydration carbonization, obtain the mixture of C/ aluminum oxide, aerating oxygen makes carbon burning in Reaktionsofen then, can prepare alpha-alumina fine powder in a short period of time.
Above-mentioned difficult volatile organic compounds can be carbohydrate, poly-hydroxy organism, many carboxyls organism, many carbonyl compound or its combination.Described carbohydrate can be sucrose, glucose, fructose, maltose, starch, dextrin; Described poly-hydroxy organism can be ethylene glycol, glycerine, polyoxyethylene glycol, polyvinyl alcohol; Described many carboxyls organism can be polyacrylic acid, citric acid.
Above-mentioned inert atmosphere is generally N
2Or Ar or its combination, the carbonization temperature of preferably dewatering is 200-700 ℃, the weight percentage of carbon is advisable with 5-50% in the C/ alumina compound.
Usually the mixture logical oxygen in vertical heater with the C/ aluminum oxide burns, at vertical heater bottom aerating oxygen, top combustion gas.The oxygen that feeds can be under the room temperature state, also can be preheating to certain temperature.The present invention according to thermogravimetric-differential thermal experiment find to begin and oxygen reaction at 350 ℃ of left and right sides carbon, so when the temperature of aerating oxygen was room temperature, furnace temperature should 〉=350 ℃.The preferred 350-800 of the temperature of preheated oxygen ℃.The aerating oxygen amount preferably makes more than 1.5 times of amount of oxygen of carbon perfect combustion.
Characteristics of the present invention are to utilize difficult volatile organic compound to load on the surface of high specific surface aluminium or aluminium hydroxide, by the low temperature dewatering carbonization, support one deck carbon at alumina surface, feed an amount of oxygen then, utilize the rapid combustion generation high temperature of carbon to generate alpha-alumina fine powder rapidly.Preparation method's technology of ultrafine alpha-alumina powders provided by the invention is simple, the organism consumption is few, maturing temperature is low, roasting time is extremely short, and it is low to consume energy, and cost is low, is adapted at industrial applying.
Description of drawings
Fig. 1 is the X-ray diffraction figure of preparation gained Alpha-alumina among the embodiment 1.
Fig. 2 is C/ gama-alumina among the embodiment 1 temperature variations during roasting in oxygen.
Fig. 3 is the sem photograph of gained Alpha-alumina among the embodiment 1.
Embodiment
Below by concrete example the present invention is described, but does not limit the present invention in any way.
Embodiment 1
In the sucrose solution of 100ml 0.05g/ml, add the 10g pseudo-boehmite, stir and 95 ℃ of heating in water bath evaporates to dryness of son.The sample of evaporate to dryness was handled 2 hours in 250 ℃, retort furnace, and the dehydration carbonizing treatment is 4 hours under 600 ℃ then, nitrogen atmosphere, obtains carbon/gama-alumina mixture, and the analytical results of thermogravimetric-differential thermal (TG-DTA) shows that carbon content is 6.8% in the mixture.Get 1g carbon/gama-alumina, put into vertical quartzy bed bioreactor, be warmed up to 800 ℃ under protection of nitrogen gas, be incubated about 10 minutes, keep feeding under the condition of 800 ℃ of furnace temperature the oxygen 10 minutes of 300ml/min then, reaction finishes.From the X-ray diffraction characterization result of Fig. 1 as can be seen gama-alumina be converted into Alpha-alumina fully.Its specific surface area is 15m
2/ g.Fig. 2 is the temperature variations in the roasting process of sample in oxygen.As can be seen from the figure, when in the oxygen access tube, carbon burns rapidly, and temperature sharply rises.The very fast end of the burning of carbon begins to be reduced to furnace temperature to the interior temperature of pipe from aerating oxygen and has only experienced about 6 minutes time for 800 ℃.Because roasting time is extremely short, particle has little time sintering, so particle is less, specific surface area is bigger.Fig. 3 is the sem photograph of gained Alpha-alumina, and therefrom as can be seen, grain diameter is about 1 μ m.
Embodiment 2
Zulkovsky starch 5g is dissolved in the 200ml deionized water, adds the 10g pseudo-boehmite, stir and at 95 ℃ of heating in water bath evaporates to dryness.With the dehydration carbonizing treatment 4 hours under 600 ℃, nitrogen atmosphere of the sample behind the evaporate to dryness; obtain carbon/gama-alumina mixture; get 1g carbon/gama-alumina; put into vertical quartzy bed bioreactor; under protection of nitrogen gas, be warmed up to 800 ℃; be incubated about 10 minutes, keep feeding under the condition of 800 ℃ of furnace temperature the oxygen 10 minutes of 300ml/min then, reaction finishes.Gama-alumina is converted into Alpha-alumina entirely, and its specific surface area is 5m
2/ g.
Embodiment 3
In the sucrose solution of 100ml 0.05g/ml, add the 10g gama-alumina, stir and in 95 ℃ of heating in water bath evaporates to dryness.The sample of evaporate to dryness was handled 2 hours in 250 ℃, retort furnace, and the dehydration carbonizing treatment is 4 hours under 600 ℃ then, nitrogen atmosphere, obtains carbon/gama-alumina mixture.Get 1g carbon/gama-alumina, put into vertical quartzy bed bioreactor, be warmed up to 800 ℃ under protection of nitrogen gas, be incubated about 10 minutes, keep feeding under the condition of 800 ℃ of furnace temperature the oxygen 10 minutes of 300ml/min then, reaction finishes.Gama-alumina is converted into Alpha-alumina entirely, and its specific surface area is 5m
2/ g.
Embodiment 4
In the polyglycol solution of 100ml 0.1g/ml, add the 10g gama-alumina, stir and in 95 ℃ of heating in water bath evaporates to dryness.With the sample of evaporate to dryness dehydration carbonizing treatment 1 hour under 600 ℃, nitrogen atmosphere, obtain carbon/gama-alumina mixture.Get 1g carbon/gama-alumina, put into vertical quartzy bed bioreactor, be warmed up to 800 ℃ under protection of nitrogen gas, be incubated about 10 minutes, keep feeding under the condition of 800 ℃ of furnace temperature the oxygen 10 minutes of 300ml/min then, reaction finishes.Gama-alumina is converted into Alpha-alumina entirely, and its specific surface area is 6m
2/ g.
Embodiment 5
In the sucrose solution of 100ml 0.03g/ml, add the 3g polyoxyethylene glycol, add the 10g gama-alumina again, stir and in 95 ℃ of heating in water bath evaporates to dryness.With the sample of evaporate to dryness dehydration carbonizing treatment 1 hour under 600 ℃, nitrogen atmosphere, obtain carbon/gama-alumina mixture.Get 1g carbon/gama-alumina, put into vertical quartzy bed bioreactor, be warmed up to 800 ℃ under protection of nitrogen gas, be incubated about 10 minutes, keep feeding under the condition of 800 ℃ of furnace temperature the oxygen 10 minutes of 300ml/min then, reaction finishes.Gama-alumina is converted into Alpha-alumina entirely, and its specific surface area is 4m
2/ g.
Embodiment 6
In the sucrose solution of 100ml 0.09g/ml, add the 10g gama-alumina, stir and in 95 ℃ of heating in water bath evaporates to dryness.With steam in sample dehydration carbonizing treatment 1 hour under 600 ℃, nitrogen atmosphere, obtain carbon/gama-alumina mixture, its carbon content is 21%.Get 1g carbon/gama-alumina, put into vertical quartzy bed bioreactor, be warmed up to 450 ℃ under protection of nitrogen gas, be incubated about 10 minutes, keep feeding under the condition of 450 ℃ of furnace temperature the oxygen 10 minutes of 300ml/min then, reaction finishes.80% gama-alumina obtains being converted into Alpha-alumina.Get 1g carbon/gama-alumina, put into vertical quartzy bed bioreactor, under protection of nitrogen gas, be warmed up to 700 ℃; be incubated about 10 minutes; keep feeding under the condition of 700 ℃ of furnace temperature the oxygen 10 minutes of 300ml/min then, reaction finishes, and gama-alumina is converted into Alpha-alumina entirely.
Claims (9)
1, a kind of method for preparing alpha-alumina fine powder, difficult evaporable organism is loaded on the surface of high specific surface aluminium or aluminium hydroxide, under inert atmosphere, through the thermal dehydration carbonization, obtain the mixture of C/ aluminum oxide, aerating oxygen makes carbon burning in Reaktionsofen then, can prepare alpha-alumina fine powder at short notice.
2, the method for claim 1 is characterized in that, described difficult evaporable organism be selected from following organic one or more: carbohydrate, poly-hydroxy organism, many carboxyls organism and many carbonyl compound; Wherein said carbohydrate is sucrose, glucose, fructose, maltose, starch and/or dextrin; Described poly-hydroxy organism is ethylene glycol, glycerine, polyoxyethylene glycol and/or polyvinyl alcohol; Described many carboxyls organism is polyacrylic acid and/or citric acid.
3, the method for claim 1 is characterized in that, described inert atmosphere is N
2Or Ar or its combination.
4, the method for claim 1 is characterized in that, the dehydration carbonization temperature is 200-700 ℃.
5, the method for claim 1 is characterized in that, the weight percentage of carbon is 5-50% in the described C/ alumina compound.
6, the method for claim 1 is characterized in that, described Reaktionsofen is a vertical heater, at vertical heater bottom aerating oxygen, top combustion gas.
7, method as claimed in claim 6 is characterized in that, the amount of oxygen that is fed is more than 1.5 times of amount of oxygen that make carbon perfect combustion.
8, the method for claim 1 is characterized in that, feeding temperature in Reaktionsofen is the oxygen of room temperature, furnace temperature 〉=350 ℃.
9, the method for claim 1 is characterized in that, before aerating oxygen, earlier oxygen preheat is arrived 350-800 ℃.
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| CN114392716A (en) * | 2022-01-07 | 2022-04-26 | 淮安锦晶纳米技术有限公司 | Process for preparing alpha-alumina fine powder at low temperature |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6461584B1 (en) * | 1999-08-16 | 2002-10-08 | National Science Council | Process of making α-alumina powder |
| CN1550452A (en) * | 2003-05-19 | 2004-12-01 | ס�ѻ�ѧ��ҵ��ʽ���� | Preparation of alpha alumina powder |
| CN1712355A (en) * | 2004-06-15 | 2005-12-28 | 住友化学株式会社 | Method for producing an alpha - alumina powder |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6461584B1 (en) * | 1999-08-16 | 2002-10-08 | National Science Council | Process of making α-alumina powder |
| CN1550452A (en) * | 2003-05-19 | 2004-12-01 | ס�ѻ�ѧ��ҵ��ʽ���� | Preparation of alpha alumina powder |
| CN1712355A (en) * | 2004-06-15 | 2005-12-28 | 住友化学株式会社 | Method for producing an alpha - alumina powder |
Non-Patent Citations (2)
| Title |
|---|
| Nanocrystalline α-Al2O3 Using Sucrose. Rabindra N.Das et al.J.Am.Ceram.Soc,Vol.84 No.10. 2001 |
| Nanocrystalline α-Al2O3 Using Sucrose. Rabindra N.Das et al.J.Am.Ceram.Soc,Vol.84 No.10. 2001 * |
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