CN100393665C - Process for preparing antimony doped stannic oxide nano powder - Google Patents
Process for preparing antimony doped stannic oxide nano powder Download PDFInfo
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- CN100393665C CN100393665C CNB2006101368340A CN200610136834A CN100393665C CN 100393665 C CN100393665 C CN 100393665C CN B2006101368340 A CNB2006101368340 A CN B2006101368340A CN 200610136834 A CN200610136834 A CN 200610136834A CN 100393665 C CN100393665 C CN 100393665C
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Abstract
The invention discloses a making method of antimony doped stannic oxide, which comprises the following steps: dissolving antimony white in the saturated sodium hydrogen tartaric acid to obtain tartaric antimony sodium solution; allocating certain density of sodium stannate solution; blending tartaric antimony sodium solution and sodium stannate solution and adding sodium hydrogen tartaric acid as mating agent according to the doped antimony quantity of ATO nanometer powder; adding hydrogen dioxide solution as oxidizer; adjusting the pH value of composite solution through sulfuric acid; placing the composite solution in the high-pressure autoclave for certain time; cooling to indoor temperature; filtering solid; washing; drying to obtain the nanometer powder of stannic oxide.
Description
Technical field
The present invention relates to the wet chemical method preparation process in the material field, particularly is the cooperation-hydrothermal oxidization method of feedstock production stibium doping nano-tin dioxide powder with sodium stannate and stibium trioxide.
Background technology
Antimony doped stannic oxide nanometer powder (antimony doped tin oxide, ATO) as a kind of multi-functional product, in many fields such as energy-conservation, antistatic coating, air-sensitives very big application potential being arranged, is a kind of more promising tin, antimony deep processed product.At present, the method for preparing antimony doped stannic oxide nano powder mainly contains two kinds, i.e. chemical coprecipitation and hydrothermal method.In chemical coprecipitation, the raw material that is adopted is the muriate of tin and antimony, promptly in the hydrochloric acid soln of high density with butter of antimony and tin tetrachloride uniform mixing, carry out neutralizing hydrolysis with ammoniacal liquor subsequently, obtain the presoma of the coprecipitate of antimony tin oxyhydroxide as the adulterated tin dioxide powder of antimony.Presoma after filtration, the washing after, carry out high-temperature calcination again, finally obtain product (the flat Wu Jie of Li Xiong reaches Han Chuanyou, the preparation of antimony-doped stannic oxide (ATO) conductive powder body and sign [J], chemistry world, 2006: 196～198).In hydrothermal method, do the raw material except adopting tin tetrachloride and butter of antimony, the glass putty of employing, antimony iodide or ANTIMONY TRIOXIDE SB 203 99.8 PCT or metallic antimony are also arranged as raw material, under the condition that has oxygenant nitric acid or hydrogen peroxide to exist, under 120～180 ℃, carry out hydro-thermal synthetic (the high Lian of Zhang Jianrong, nanocrystalline Sb doping SnO
2(ATO) synthetic and sign [J], SCI, 2003,24 (9): 1544-1547) of powder.
But there is following shortcoming in the preparation method of the adulterated tindioxide powder of these antimony:
1) because Sb
3+And Sn
4+In hydrochloric acid system, all be very easy to hydrolysis, in the solution mixing process of butter of antimony and tin tetrachloride, need to add a large amount of hydrochloric acid and suppress its hydrolysis, and need be with a large amount of alkali neutralizing acids in the neutralizing hydrolysis process.A large amount of foreign ion chlorions of introducing make the washing process of follow-up presoma become extremely difficult.
2) the remaining chlorion in throw out will cause the reunion of powder.Simultaneously, tin, antimony muriate volatilize easily, and in the presoma calcination process, remaining muriate is volatile, cause tin, antimony loss, thereby the ratio of antimony tin is difficult for accurately control in the product.
3) in alkali neutralization precipitation process, because of Sn (OH)
4, Sb (OH)
3Solubility product have bigger difference, during co-precipitation and be difficult for realizing Sn (OH)
4, Sb (OH)
3Co-precipitation.
4) adopt ammoniacal liquor as precipitation agent, transportation, storage, use are very inconvenient; Evaporable gas has very strong pungency, causes production environment abominable.
5) after the employing co-precipitation obtained presoma, final product must be calcined, and introduce impurity easily in calcination process, cause the reunion of nano-powder, and cause the segregation of doped element, thereby it is inhomogeneous to cause antimony to mix, and influences the final performance of powder
Summary of the invention
The present invention is the deficiency that overcomes in the preparation of antimony doped stannic oxide nano powder, a kind of employing achloride system is provided, to precipitate and crystallization unites two into one, and can realize evenly mixing, and the preparation method of flow process weak point and free of contamination substantially antimony doped stannic oxide nano powder.
The technical scheme that the present invention adopts in order to achieve the above object is: earlier stibium trioxide is dissolved in the sodium hydrotartrate saturated solution, obtains the antimony tartrate sodium solution, cofabrication certain density sodium stannate solution; According to the antimony doping of ATO nanometer powder, antimony tartrate sodium solution and sodium stannate solution are mixed and add sodium hydrotartrate as Synergist S-421 95, add hydrogen peroxide simultaneously as oxygenant, regulate the acidity of mixing solutions with sulfuric acid; Above-mentioned mixing solutions reacts certain hour in autoclave, be cooled to room temperature then, solid product after filtration, wash, be drying to obtain stannic oxide nano powder.
Concrete parameter is as follows:
1. the preparation of the dissolving of stibium trioxide and sodium stannate solution
Under the room temperature, be dissolved in sodium hydrotartrate in the deionized water fully, be mixed with the solution of 150～240g/L, stibium trioxide is placed the hydrogen tartrate sodium solution of preparation, under agitation being heated to closely boils makes the stibium trioxide dissolving, filtered while hot is removed possible insolubles, and making antimony concentration is the antimony tartrate sodium solution of 40～80g/L, and the cooling back is preserved standby.The reaction that takes place in the stibium trioxide dissolution process is as follows:
2NaHC
4H
4O
6+Sb
2O
3＝Na
2[Sb
2(C
4H
2O
6)
2]+3H
2O
2NaHC
4H
4O
6+Sb
2O
3＝Na
2[Sb(OH)(C
4H
2O
6)]+3H
2O
Under the room temperature, under fully stirring, sodium stannate is dissolved in deionized water, removes by filter possible insolubles, obtain the sodium stannate solution that tin concentration is 80～120g/L.
2. the preparation of mixing solutions
Under the normal temperature, according to the doping of antimony doped stannic oxide nano powder, be the antimony tartrate sodium solution of 40～80g/L and sodium stannate solution that tin concentration is 80～120g/L with volume ratio (sodium antimony tartrate liquor capacity: be 1: 3～45 to mix the sodium stannate solution volume) with antimony concentration.According to the concentration of tin in the mixed solution, press Sn in the solution: NaHC
4H
4O
6Mol ratio is 2: 1～1.5 adding sodium hydrotartrates, stirs.According to the mol ratio of tartrate anion total in the solution and hydrogen peroxide is 5.5～6 to add hydrogen peroxide in above-mentioned mixed solution, with volumetric molar concentration is pH to 0～0.5 of the sulphuric acid soln adjusting mixing solutions of 5～9mol/L, obtains preparing the precursor liquid of antimony-doped tin dioxide powder body.
3. hydrothermal oxidization
Above-mentioned precursor liquid is placed autoclave, and the compactedness of autoclave is 50～70%, carries out hydro-thermal reaction 2～4h under 180～240 ℃, is cooled to room temperature then.The reaction that takes place in the process is as follows:
[Sb
2(C
4H
2O
6)
2]
2-+12H
2O
2+12H
+＝2Sb
5++8CO
2+20H
2O
Sb(OH)C
4H
2O
6 2-+6H
2O
2+7H
+＝Sb
5++4CO
2+11H
2O
[Sn
x(C
4H
4O
6)
y]
4x-2y+5yH
2O
2+2yH
+＝4yCO
2+xSn
4++8yH
2O
[Sn
x(C
4H
2O
6)
y]
4x-4y+5yH
2O
2+4yH
+＝4yCO
2+xSn
4++8yH
2O
Sb
5++5H
2O＝Sb(OH)
5↓+5H
+
Sn
4++4H
2O＝Sn(OH)
4↓+4H
+
Sb
3++3H
2O＝Sb(OH)
3↓+3H
+
The Sb (OH) that generates
3, Sb (OH)
5And Sn (OH)
4Dehydration reaction takes place under High Temperature High Pressure:
2Sb(OH)
3＝Sb
2O
3+3H
2O
2Sb(OH)
5＝Sb
2O
5+5H
2O
Sn(OH)
4＝SnO
2+2H
2O
4. the washing of product, drying
The material that reaction generates is cooled to the room temperature after-filtration, with 5～8 washings of deionization moisture of the solid substance quantity (weight) of 5～8 times of generations, till the generation of barium chloride solution detection less than barium sulfate precipitate with 0.1mol/L.Use the ethanol branch secondary washing of 0.5～1.5 times of product volume (weight) then, the washing after filter cake in vacuum drying oven in 60～80 ℃ of dryings, the solid that obtains after the drying promptly obtains final product through grinding, the antimony content of product (weight) is 1～10%, surplus is tin and oxygen, and granularity is 20～80nm.
It is that raw material prepares antimony doped stannic oxide nano powder that the present invention is applicable to sodium stannate, sodium hydrotartrate, hydrogen peroxide, stibium trioxide, sulfuric acid, and wherein the doping of antimony is 1～10% (weight).Described sodium stannate, sodium hydrotartrate, hydrogen peroxide, sulfuric acid are technical pure or analytical reagent, and stibium trioxide is a technical pure reagent.
The present invention has compared following characteristics with other method:
(1) hydrothermal oxidization and complexes system are introduced in the preparation of stibium doping nano-tin dioxide powder simultaneously, can be controlled the release rate of tin ion and antimony ion, realize the even doping of antimony in tindioxide, flow process is short, and is simple to operate.
(2) preparation of presoma and the dehydration of presoma are carried out in same process, loss of material is few in the pilot process, and the direct yield height can reduce the contaminated chance of product.
(3) the present invention does not need the high-temperature calcination dehydration, and hydrothermal temperature is lower, avoids high-temperature calcination to cause the segregation of antimony in powder, thereby causes antimony skewness in tindioxide.
(4) the present invention adopts non-villaumite system, avoids Yin Xi, the easy hydrolysis of antimony muriate and adopts concentrated acid solution, avoids remaining in the corrosive nature of chlorion in follow-up use in the powder.
(5) adopt oxidation system, under lower temperature, antimony is existed with the pentavalent form, make that powder electroconductibility is better.
Description of drawings
Fig. 1 is a process flow diagram of the present invention;
Fig. 2 is the transmission electron microscope photo of the adulterated tin dioxide powder of antimony of preparation;
Fig. 3 is the XRD figure spectrum of the adulterated tin dioxide powder of corresponding antimony.
Embodiment
Embodiment 1: industrial stibium trioxide, its main component is: Sb
2O
399.7%, As
2O
30.05%, PbO 0.003%, Fe
2O
30.003%, other is 0.24% years old; The analytical pure sodium stannate, its main component is: Na
2SnO
33H
2O＞98%, alkali insolubles 0.1%, muriate 0.005%, vitriol 0.05%.Sodium hydrotartrate, sulfuric acid, hydrogen peroxide are analytical reagent.
The 60g stibium trioxide of mentioned component and 80g sodium hydrotartrate are dissolved in the 1L deionized water, under agitation are heated to closely and boil, and dissolve fully until stibium trioxide.Filtered while hot, filtrate is cooled to room temperature, and the concentration that obtains antimony is the antimony tartrate sodium solution of 46g/L.Under the room temperature, the 240g sodium stannate of mentioned component is dissolved in the 1L deionized water, filters, and obtains the sodium stannate solution that tin concentration is 103g/L.Get above-mentioned sodium stannate solution of 0.8L and 0.18L antimony tartrate sodium solution and mix, add sodium hydrotartrate 66g, stirring makes it to dissolve fully, adds hydrogen peroxide 0.2L, regulates pH of mixed value to 0～0.5 with the sulphuric acid soln of 9mol/L.Mixed solution is placed the autoclave of 2L, be heated to 180 ℃ of reactions 4h, cool to room temperature subsequently, filter, use the 600ml deionized water washing sediment, the barium chloride solution with 0.1mol/L in wash water detects less than the barium sulfate precipitate generation, uses twice of 100ml analytical pure absolute ethanol washing then.Filter cake is dry 8h under 70 ℃, obtains light blue powder 113.3g.Product is through chemical analysis, and the content of antimony (weight) is 8.04%, and tin is 70.52%, and surplus is an oxygen.The direct recovery rate of tin, antimony is greater than 97%, and the transmission electron microscope photo of product is seen Fig. 2, and x-ray diffraction pattern is seen Fig. 3.
Claims (1)
1. a method for preparing antimony doped stannic oxide nano powder is characterized in that: stibium trioxide is dissolved in the sodium hydrotartrate saturated solution, obtains the antimony tartrate sodium solution, cofabrication certain density sodium stannate solution; According to the antimony doping of ATO nanometer powder, antimony tartrate sodium solution and sodium stannate solution are mixed and add sodium hydrotartrate as Synergist S-421 95, add hydrogen peroxide simultaneously as oxygenant, regulate the acidity of mixing solutions with sulfuric acid; Above-mentioned mixing solutions reacts certain hour in autoclave, be cooled to room temperature then, solid product after filtration, wash, be drying to obtain stannic oxide nano powder;
Concrete parameter is as follows:
(1) preparation of the dissolving of stibium trioxide and sodium stannate solution
Under the room temperature, be dissolved in sodium hydrotartrate in the deionized water fully, be mixed with the solution of 150～240g/L, stibium trioxide is placed the hydrogen tartrate sodium solution of preparation, under agitation being heated to closely boils makes the stibium trioxide dissolving, filtered while hot is removed insolubles, and making antimony concentration is the antimony tartrate sodium solution of 40～80g/L;
Under the room temperature, under fully stirring, sodium stannate is dissolved in deionized water, removes by filter insolubles, obtain the sodium stannate solution that tin concentration is 80～120g/L;
(2) preparation of mixing solutions
According to the doping of antimony doped stannic oxide nano powder, be the antimony tartrate sodium solution of 40～80g/L and sodium stannate solution that tin concentration is 80～120g/L with volume ratio with antimony concentration be 1: 3～45 to mix; Press Sn in the solution: NaHC
4H
4O
6Mol ratio is 2: 1～1.5 adding sodium hydrotartrates, stirs; By the mol ratio of winestone acid group and hydrogen peroxide is 5.5～6 to add hydrogen peroxide in mixed solution, is pH to 0～0.5 that the sulphuric acid soln of 5～9mol/L is regulated mixing solutions with volumetric molar concentration, obtains preparing the precursor liquid of antimony-doped tin dioxide powder body;
(3) hydrothermal oxidization
Above-mentioned precursor liquid is placed autoclave, and the compactedness of autoclave is 50～70%, carries out hydro-thermal reaction 2～4h under 180～240 ℃, is cooled to room temperature then;
(4) washing of product, drying
The material cooled and filtered of reaction generation is with 5～8 washings of deionization moisture of 5～8 times of the solid substance quantities that generates, till the generation of barium chloride solution detection less than barium sulfate precipitate with 0.1mol/L; Ethanol with 0.5～1.5 times of product volume divides secondary washing then, and in 60～80 ℃ of dryings, the solid that obtains after the drying promptly obtains final product through grinding to the filter cake after the washing in vacuum drying oven.
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| CN102010197B (en) * | 2010-09-29 | 2013-02-13 | 大连交通大学 | Method for preparing antimony-doped tin oxide (ATO) nano powder |
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| CN104230346B (en) * | 2014-09-18 | 2015-11-18 | 赵宝勤 | A kind of ATO/Si 3n 4composite conductive ceramic raw powder's production technology |
| KR102332043B1 (en) * | 2016-03-18 | 2021-11-29 | 바스프 에스이 | Metal-Doped Tin Oxide for Electrocatalytic Applications |
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| CN113880131A (en) * | 2021-10-20 | 2022-01-04 | 华南理工大学 | Preparation method of ATO nanocrystalline sol |
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