CN102874854B - Preparation method of 5N high-purity nanometer alumina powder - Google Patents
Preparation method of 5N high-purity nanometer alumina powder Download PDFInfo
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- CN102874854B CN102874854B CN201210436415.4A CN201210436415A CN102874854B CN 102874854 B CN102874854 B CN 102874854B CN 201210436415 A CN201210436415 A CN 201210436415A CN 102874854 B CN102874854 B CN 102874854B
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Abstract
The invention discloses a preparation method of 5N high-purity nanometer alumina powder. The preparation method is characterized by comprising the steps as follows: agitating a precursor of 5N aluminium isopropoxide, deionized water and dispersing agent based on mol ratio of 1: 10 to 30: 0.5 to 2 at 85 to 100 DEG C, and reflowing and hydrolyzing for 3 to 5 hours to obtain a hydrolyzing mixture; steaming the hydrolyzing mixture at 80 to 100 DEG C to obtain byproduct isopropanol which is generated in the hydrolyzing reaction and an azeotrope solution of the isopropanol and the water; then centrifugally filtering the product to obtain hydrated alumina; then transferring the hydrated alumina into a roasting furnace to be dried for 8 to 15 minutes at 80 to 110 DEG C; roasting the hydrated alumina for 25 to 45 minutes at 500 to 700 DEG C to obtain 5N high-purity gamma-Al2O3 powder with granularity of 5 to 50nm and D50 of 25nm; then continuously heating to reach 1050 to 1200 DEG C, and roasting for 30 to 50 minutes to obtain the 5N high-purity alpha-Al2O3 powder with granularity of 10 to 100nm and D50 of 50nm.
Description
Technical field
The present invention relates to a kind of method of 5N high purity nanometer alumina, particularly relate to aluminium alcoholates and disperse hydrolysis and microwave drying roasting process integration to prepare the method for 5N high purity nanometer alumina powder.
Background technology
High purity nanometer alumina powder, not only purity is high, and granularity reaches nano level (1～100nm), narrow particle size distribution, good dispersity.The small-size effect that nano-powder has, surface-interface effect, quantum size effect and macro quanta tunnel effect etc., make it in fields such as catalysis, optical filtering, photoabsorption, medicine, magneticmedium and novel materials, have broad application prospects.High purity nanometer alumina has good optics, electric property and mechanical property is used widely in modern high technology field of new, as being used as crystalline ceramics raw material, fluorescent material, sapphire crystal material, catalyzer, laserable material and semiconductor substrate etc.In recent years, development along with whole world LED industry, high purity aluminium oxide is processed to sapphire, for LED substrate material, favored by LED industry, current global 80%LED enterprise adopts sapphire as substrate material, along with eliminating the enforcement of incandescent light plan both at home and abroad, its demand will constantly increase.
Produce high-purity α-Al both at home and abroad
2o
3the method of powder mainly contains exsiccated ammonium alum pyrolysis method, aluminium carbonate ammonium pyrolysis method (being called again improvement exsiccated ammonium alum pyrolysis method), alkoxide hydrolysis, choline hydrolysis method, rafifinal activated water solution etc., also has some other method newly developed also to rest on laboratory stage.Wherein aluminium alcoholates hydrolysis method is the important method that current production purity reaches high-purity alpha-alumina, is also industry research focus processing method, this method technological process environmental protection, and pollution-free, shortcoming process costs is higher, technological process is controlled comparatively strict.The aluminum oxide powder product that this legal system is standby, its purity can reach 99.999%, and fine size needs special Countermeasures but granularity reaches nano level.
At present, effective measure of control that aluminium alcoholates method is produced the employing of alumina in Nano level process mainly contain: (1) liquid reaction phase, aluminium alcoholates hydrolytic process is introduced macromolecule dispersing agent, at hydrolysate colloid surface, adsorb, cause producing infiltration repulsion potential energy and mixing repulsion energy between particle, thereby make to occur the difficulty of reuniting, with do not add dispersion agent and compare, product surface rule, granularity is thinner, good dispersity, but the introducing of macromolecule dispersing agent, can bring impurity into unavoidably, dispersion agent has bright excess residual in the roasting stage, thereby affects product purity.Therefore, selecting easily to purify, burn, excess is few, molecular weight is little, low-cost dispersion agent is researchdevelopment direction; (2) drying stage is the process that very easily produces reunion.In order to reduce reunion, in industry, there is multiple drying means at present, as supercritical drying, vacuum freeze-drying method, ultrasonic cavitation method, micro-wave drying method etc.With the comparison of traditional drying method, these all play reduce to reunite, and reaches the object of powder nanometer, but exists technology controlling and process complicated, is difficult for the problems such as industrialization, serialization production, facility investment are large.Comparatively speaking, micro-wave drying method, although disposable apparatus investment is large, but achievement in research shows that it exists that reaction is fast, productive rate is high, good product quality, convenient post-treatment, energy-conserving and environment-protective, safety, easily realize numerous advantages such as serialization production, it is industry reform prior development direction, have broad prospect of application, the research report of nano aluminium oxide is prepared in existing microwave drying both at home and abroad; (3) the aluminium oxide calcining phase inversion stage, is also very easily to produce reunion, causes the process of product chap.Conventional stove roasting normally reduces reunion by controlling temperature rise rate and maturing temperature and time, although can reach certain effect, totally there is complex technical process, energy consumption is high, the shortcomings such as easily polluted product, constant product quality be poor, have limited its application in high purity nanometer powders industry.At present, in high-temperature roasting mode, microwave calcining is as a kind of baking modes of efficient homogenizing, there is quick heating, homogeneous heating, energy-conserving and environment-protective, highly effective and safe, can effectively control powder size, be difficult for occurring the advantages such as reunion, at home and abroad ceramic industry, mineral metallurgy industry are all used widely, also having the report in powder industry successful Application such as zirconium oxide in high purity, yttrium oxide, zinc oxide, tricobalt tetroxides both at home and abroad, is the direction of the following primary study development of related application industry.
According to the retrieval, at alkoxide process, prepare in the document and patent of high purity nanometer alumina, the report of using dispersion agent is a lot, as Ning Guiling etc., (two one-step hydrolysis are produced research [J] the Chinese journal of scientific instrument .1995 of aluminium oxide nano micro mist, 16(1): 314-318), Chinese patent " a kind of nanometer, the preparation method of submicron order aluminum oxide " (CN00125966.0) etc., the dispersion agent of wherein mentioning mainly contains polyoxyethylene glycol, polyvinyl alcohol, acetic acid, paraffin, methyl aceto acetate etc., these high molecular polymers except molecular weight large, remaining residual object height burns, be difficult for purifying, easily introduce outside the shortcomings such as impurity effect product purity, price is more expensive, increase production cost.
According to the retrieval, the report that domestic and international microwave calcining technology is applied to high purity nanometer powders is more, as (Preparation of nanosized ZnO by microwave-calcining [J] inorganic chemicals industry .2004,36(5) such as Cao Jun: 31-33), Chinese patent " a kind of method of utilizing microwave calcining to prepare tricobalt tetroxide " (CN201110198914.X) etc. all adopts Microwave Sintering Techniques to prepare powder body material.But its application of producing high purity nanometer alumina powder industry in aluminium alcoholates hydrolysis method there is not yet report.
Summary of the invention
The object of the invention is to provide for the deficiencies in the prior art a kind of preparation method of 5N high purity nanometer alumina powder, be characterized under dispersion agent exists, will after the reaction of 5N aluminum isopropylate presoma back hydrolysis, make hydrolysed mix; Centrifuging obtains hydrated aluminum oxide, and dry in stoving oven, roasting obtains 5N high-purity gamma-Al
2o
3powder, then, continues intensification roasting and obtains the high-purity α-Al of 5N
2o
3powder, has advantages of simple, cost-saving, energy-conserving and environment-protective.
Object of the present invention is realized by following technical measures, and wherein said raw material umber, except specified otherwise, is molfraction.
The preparation method of 5N high purity nanometer alumina powder comprises the following steps:
(1) by 5N aluminum isopropylate presoma: deionized water: dispersion agent is 1: 10～30: 0.5～2 mol ratio, add in the reactor with agitator, thermometer and reflux exchanger, in 85～100 ℃ of temperature, stirring, back hydrolysis reaction 3～5h, obtain hydrolysed mix;
(2) by said hydrolyzed mixture, in temperature, it is first 80～100 ℃, time 0.5～3h distill out by product Virahol that hydrolysis reaction generates and with the azeotrope solution of water, solution obtains Virahol through the separation of dewatering can be directly used in the synthetic raw material of high puring aluminium isopropoxide; Product obtains hydrated aluminum oxide by centrifuging again, and filtrate is aqueous dispersant, returns to step (1) and recycles, and the centrifuging time is 15～30min;
(3) hydrated aluminum oxide step (2) being obtained proceeds in stoving oven, and in 80～110 ℃ of temperature, dry 8～15min, at 500～700 ℃ of roasting 25～45min of temperature, obtains 5N high-purity gamma-Al
2o
3powder, granularity is at 5～50nm, and D50 is 25nm, then, continues to be warming up to 1050～1200 ℃ of roasting 30～50min, obtains the high-purity α-Al of 5N
2o
3powder, granularity is at 10～100nm, and D50 is 50nm.
Described dispersion agent is at least one in glucose, sucrose, maltose.
Described stoving oven is microwave baking furnace.
Performance test
1. crystal formation detects: X-ray diffraction instrument D/Max-3B;
2. granularity Detection: particle-size analyzer BI-XDC;
3. specific surface area detects: the full-automatic specific surface of BET (amassing) tester F-Sorb 2400;
4. purity detecting: micro-wave digestion melts sample, ICP-OES detects.
Test result is as shown in Table 1 below.
Tool of the present invention has the following advantages:
(1) in disperseing hydrolytic process, introduces aluminium alcoholates at least one in glucose, sucrose, maltose as dispersion agent, such dispersion agent purity is high, molecular weight is little, the excess amount of burning is few, low price, dispersing property is good, is conducive to reduce products production cost, improves product purity, the product granularity obtaining is thin, narrowly distributing, good dispersity, regular shape.
(2) at high purity nanometer alumina phase inversion roasting process, adopt microwave calcining technology, can effectively control product granularity, difficult reunion, makes product granularity reach nano level, and narrowly distributing, good dispersity, also has the advantage of energy-conserving and environment-protective, highly effective and safe in addition.Two kinds of techniques combine use, can not only obtain 5N purity high-alumina powder, and product granularity reaches nano level, obtain 5N high-purity gamma-Al
2o
3powder, granularity 5～50nm, D50(25nm), obtain the high-purity α-Al of 5N
2o
3powder, granularity 10～100nm, D50(50nm).
Embodiment
By the following examples the present invention is specifically described; be necessary to be pointed out that at this present embodiment is only used to further illustrate the present invention; can not be interpreted as the restriction to invention protection domain, some nonessential improvement and adjustment that the person skilled in the art in this field can make according to the content of the invention described above.
Embodiment 1
To in 4.5L deionized water, join in the reactor with stirring, thermometer and return channel, then 2.25Kg glucose is dissolved in deionized water, after stirring, be warming up to 85 ℃, add again 5N aluminum isopropylate 5.1Kg, stirring, back hydrolysis reaction 3h, be aluminum isopropylate: deionized water: the mol ratio reaction in 1: 10: 0.5 of glucose.After reaction finishes, first Distillation recovery by product Virahol and with the azeotrope of water, distillation time is 1.5h, then centrifugation obtains hydrolysate hydrated aluminum oxide and glucose solution, the centrifuging time is 20min, and glucose solution returns to hydrolyzation system and recycles; Product filters the hydrated aluminum oxide obtaining and proceeds to (2.45GHz, 0.3～2.85Kw is adjustable) in microwave baking furnace, is warming up to 90 ℃, after freeze-day with constant temperature 15min, is warming up at 600 ℃ of roasting 40min, obtains γ type Al
2o
3powder, then, continues to be warming up to 1050 ℃ of roasting 40min, obtains α type Al
2o
3powder.
Embodiment 2
To in 13.5L deionized water, join in the reactor with stirring, thermometer and return channel, then by 8.55Kg sucrose dissolved in deionized water, after stirring, be warming up to 85 ℃, add again 5N aluminum isopropylate 5.1Kg, stirring, back hydrolysis reaction 4h, be aluminum isopropylate: deionized water: the mol ratio reaction in 1: 30: 1 of sucrose.。After reaction finishes, first Distillation recovery by product Virahol and with the azeotrope of water, distillation time is 40min, then centrifugation obtains hydrolysate hydrated aluminum oxide and sucrose solution, the centrifuging time is 15min, sucrose solution returns to hydrolyzation system and recycles; Product filters the hydrated aluminum oxide obtaining and proceeds to (2.45GHz, 0.3～2.85Kw is adjustable) in microwave baking furnace, is warming up to 85 ℃, after freeze-day with constant temperature 15min, is warming up at 700 ℃ of roasting 35min, obtains γ type Al
2o
3powder, then, continues to be warming up to 1100 ℃ of roasting 40min, obtains α type Al
2o
3powder.
Embodiment 3
To in 6.75L deionized water, join in the reactor with stirring, thermometer and return channel, then 4.5Kg maltose is dissolved in deionized water, after stirring, be warming up to 85 ℃, add again 5N aluminum isopropylate 5.1Kg, stirring, back hydrolysis reaction 3.5h, be aluminum isopropylate: deionized water: the mol ratio reaction in 1: 15: 0.5 of sucrose.。After reaction finishes, first Distillation recovery by product Virahol and with the azeotrope of water, distillation time is 1h, then centrifugation obtains hydrolysate hydrated aluminum oxide and maltose solution, the centrifuging time is that 25min sucrose solution returns to hydrolyzation system and recycles; Product filters the hydrated aluminum oxide obtaining and proceeds to (2.45GHz, 0.3～2.85Kw is adjustable) in microwave baking furnace, is warming up to 95 ℃, after freeze-day with constant temperature 15min, is warming up at 600 ℃ of roasting 30min, obtains γ type Al
2o
3powder, then, continues to be warming up to 1150 ℃ of roasting 30min, obtains α type Al
2o
3powder.
Example 4
To in 11.25L deionized water, join in the reactor with stirring, thermometer and return channel, then by 4.5Kg glucose sugar and 8.55Kg sucrose dissolved in deionized water, after stirring, be warming up to 85 ℃, add again 5N aluminum isopropylate 5.1Kg, stirring, back hydrolysis reaction 3.5h, be aluminum isopropylate: deionized water: glucose: the mol ratio of sucrose 1: 25: 1: 1 reaction.。After reaction finishes, first Distillation recovery by product Virahol and with the azeotrope of water, distillation time is 1h, then centrifugation obtains hydrolysate hydrated aluminum oxide, dextrose plus saccharose solution, and the centrifuging time is that 25min sucrose solution returns to hydrolyzation system and recycles; Product filters the hydrated aluminum oxide obtaining and proceeds to (2.45GHz, 0.3～2.85Kw is adjustable) in microwave baking furnace, is warming up to 95 ℃, after freeze-day with constant temperature 15min, is warming up at 600 ℃ of roasting 30min, obtains γ type Al
2o
3powder, then, continues to be warming up to 1150 ℃ of roasting 30min, obtains α type Al
2o
3powder.
Table 1: the Al making for example 4
2o
3product analysis detected result
Claims (1)
1. a preparation method for 5N high purity nanometer alumina powder, is characterized in that comprising the following steps:
(1) by 5N aluminum isopropylate presoma: deionized water: dispersion agent is 1: 10～30: 0.5～2 mol ratio, add in the reactor with agitator, thermometer and reflux exchanger, in 85～100 ℃ of temperature, stirring, back hydrolysis reaction 3～5h, obtain hydrolysed mix;
(2) by said hydrolyzed mixture, in temperature, it is first 80～100 ℃, time 0.5～3h distill out by product Virahol that hydrolysis reaction generates and with the azeotrope solution of water, solution obtains Virahol through the separation of dewatering can be directly used in the synthetic raw material of high puring aluminium isopropoxide; Product obtains hydrated aluminum oxide by centrifuging again, and filtrate is aqueous dispersant, returns to step (1) and recycles, and the centrifuging time is 15～30min;
(3) hydrated aluminum oxide step (2) being obtained proceeds in stoving oven, and in 80～110 ℃ of temperature, dry 8～15min, at 500～700 ℃ of roasting 25～45min of temperature, obtains 5N high-purity gamma-Al
2o
3powder, granularity is at 5～50nm, and D50 is 25nm, then, continues to be warming up to 1050～1200 ℃ of roasting 30～50min, obtains the high-purity α-Al of 5N
2o
3powder, granularity is at 10～100nm, and D50 is 50nm;
Wherein, dispersion agent is at least one in glucose, sucrose, maltose; Stoving oven is microwave baking furnace.
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| 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 |
| CN104261447A (en) * | 2014-09-23 | 2015-01-07 | 成都冠禹科技有限公司 | Production method of 5N high-purity alpha alumina powder |
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| CN106747358A (en) * | 2016-12-27 | 2017-05-31 | 扬州中天利新材料股份有限公司 | Purity is the preparation method of the series of oxidation aluminium superfines of 5N |
| CN112939045B (en) * | 2021-02-03 | 2022-12-20 | 浙江爱科新材料有限公司 | Preparation method of superfine high-purity gamma-alumina |
| CN113912092A (en) * | 2021-12-01 | 2022-01-11 | 扬州中天利新材料股份有限公司 | Preparation method of alumina ultrafine powder with purity of 5N |
| CN114524449A (en) * | 2022-03-15 | 2022-05-24 | 先导薄膜材料（广东）有限公司 | Preparation method of high-purity alumina powder |
| CN115784280A (en) * | 2022-12-21 | 2023-03-14 | 江苏金石研磨有限公司 | Preparation method of low-cost nano alumina powder |
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| CN1341559A (en) * | 2001-06-18 | 2002-03-27 | 乐清市超微细化工有限公司 | Preparation method of high-purity nanoaluminium oxide |
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| CN102476819A (en) * | 2010-11-27 | 2012-05-30 | 中国科学院兰州化学物理研究所 | Preparation method of nano alpha-alumina powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1341559A (en) * | 2001-06-18 | 2002-03-27 | 乐清市超微细化工有限公司 | Preparation method of high-purity nanoaluminium oxide |
| CN102476819A (en) * | 2010-11-27 | 2012-05-30 | 中国科学院兰州化学物理研究所 | Preparation method of nano alpha-alumina powder |
| CN102531009A (en) * | 2010-12-28 | 2012-07-04 | 上海华明高技术（集团）有限公司 | Nanoscale high-purity aluminum oxide preparation method |
| CN102328941A (en) * | 2011-09-08 | 2012-01-25 | 湘潭大学 | Method for preparing nano alumina |
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