CN1318306C - Method for preparing H2SnO3 (tin dioxide) powder - Google Patents
Method for preparing H2SnO3 (tin dioxide) powder Download PDFInfo
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- CN1318306C CN1318306C CNB2004101008435A CN200410100843A CN1318306C CN 1318306 C CN1318306 C CN 1318306C CN B2004101008435 A CNB2004101008435 A CN B2004101008435A CN 200410100843 A CN200410100843 A CN 200410100843A CN 1318306 C CN1318306 C CN 1318306C
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- acid
- metastannic acid
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Abstract
The present invention provides a preparation method of metastannic acid (H2SnO3) which has environmental protection, high efficiency and low cost, and wet method tin dioxide (SnO2) powder. In the method, the metastannic acid intermediate goods are generated by the sufficient reaction between tin and nitric acid under a closed, pressurized and oxygenic condition through controlling the reaction temperature and the reaction time; a product of metastannic acid is obtained by neutralizing, washing and drying the metastannic acid intermediate goods; a product of the superfine tin dioxide with the particle diameter less than 10 mu m is obtained by calcining and crushing the metastannic acid. The residual liquid of the reaction can be circularly used. The tail gas of the reaction contains a low content of the residual scrap of nitric oxide, and can be exhausted directly, and thereby the absorbing cost of the tail gas is avoided.
Description
Technical field
The present invention relates to a kind of manufacture method of tinbase compound powder, be specifically related to a kind of wet method and make metastannic acid (molecular formula: H
2SnO
3) and tindioxide (molecular formula: SnO
2) method of powder.
Background technology
Metastannic acid and tindioxide belong to same class tin inorganic chemical product, have the wide industrial purposes.Be mainly used in industries such as pottery, building, enamel, glass, electronics, decoration, as glaze, pigment, fire retardant, catalyzer etc.The conventional wet production method is to adopt metallic tin and concentrated nitric acid direct reaction to produce metastannic acid and tindioxide product, its main technique is: be raw material with the refined tin, make the tin flower through fusing, shrend, place and add concentrated nitric acid in the reaction vessel and carry out vigorous reaction, reaction finishes after neutralization, washing, filtration, dry output metastannic acid, and metastannic acid obtains the tindioxide product after calcining, fragmentation.Principal reaction is as follows:
3Sn+4HNO
3+H
2O→3H
2SnO
3+4NO↑ (1)
(1), (2) formula is thermopositive reaction, under normal temperature and pressure conditions, liberated heat causes part nitric acid to decompose, the reaction that is taken place is as follows:
From above-mentioned reaction as can be seen, in the traditional mode of production process, reaction produces a large amount of oxynitride and can not get effective recycling on the one hand, and nitric acid dosage is big; The discharging meeting of tail gas pollutes environment on the other hand, and follow-up environmental protection treatment expense is very big.
Summary of the invention
The object of the present invention is to provide a kind of environmental protection, efficiently, wet method is made the method for metastannic acid and tin dioxide powder cheaply.
The method that a kind of wet method of the present invention is made metastannic acid and tin dioxide powder is mainly: under the condition of airtight pressurization oxygenation, make tin and nitric acid fully react after-filtration, reaction residue returns use; The centre product get metastannic acid after neutralization washing, drying, metastannic acid gets the tindioxide product after calcining, fragmentation.Its feature is mainly:
1, airtight pressurization oxygenation reaction: in encloses container, add entry, nitric acid and metallic tin raw material in proportion, liquid-solid mass ratio is 5～13: 1, and the mass ratio of nitric acid and tin is 0.6～1.5.Afterwards, feed pressurized air (or oxygen), heat and be controlled at 100～160 ℃ of temperature range internal reactions 4～8 hours, reaction pressure is 0.7～2.0MPa, oxygen atmosphere 0.7～1.2Mpa.
According to above-mentioned reaction, the metallic tin raw material that this technology adopted is mainly tin flower or glass putty.
In this process, the main reaction that takes place is (1) formula, (2) formula.Add under the oxygen condition in airtight pressurization, the nitrogen protoxide and the oxygen that generate in the reaction process react, and generate nitrogen peroxide, and nitrogen peroxide solubleness increases, and the dissolving of tin is quickened in nitric acid regeneration again.But increase the pressure and temperature accelerated reaction, shorten the reaction times.Reaction formula is as follows:
4NO+3O
2+2H
2O→4HNO
3 (5)
3NO
2+H
2O→2HNO
3+NO↑ (6)
Formula (5), formula (6) total reaction are:
3NO+3NO
2+3O
2+3H
2O→6HNO
3 (7)
Nitric acid is technical grade, contains HNO
3About 40%.
2, neutralization washing: reaction is finished after heavy sorting can be returned after, reaction residue is added tin raw material and nitric acid in proportion and is continued reaction, and middle product (for the metastannic acid crude product) add in the carbon ammonium removes residual nitric acid after be drying to obtain the metastannic acid product with washing.
3, calcining, fragmentation: metastannic acid is output tindioxide product after calcining, fragmentation.
The present invention compares with conventional production methods, has following advantage:
1, adopt airtight pressurization oxygenation wet processing to produce metastannic acid and tindioxide, the reaction times shortens, tin transformation efficiency height, and the nitric acid consumption can reduce more than 50%.HNO with concentration 40%
3Meter, 1 ton of tindioxide acid consumption of the every production of the present invention is 0.8～1.27 ton, and the acid of conventional production methods consumption is 2.0～2.5 tons.
But 2, utilize this technology output metastannic acid and tindioxide superfine powder, particle diameter is less than 10 μ m, and particle diameter is in the majority with 0.5～5 μ m's, and technology and product have prospect for promotion and application preferably.
3, oxynitride resistates content is very low in the reaction end gas, can directly discharge, and has avoided the tail gas cost absorption, and this technology belongs to efficient and environment-friendly type technology.
Embodiment
The present invention further specifies by following examples:
Embodiment one
In 50 liters of pressurized reactors, add 28 liters in water, tin flower 2.5Kg, 4.78 liters of 39.9% industrial nitric acids were heated and are controlled at 125 ± 5 ℃, pressure 0.9MPa conditioned response 6 hours.Reaction finishes the liquid-solid separation in back, obtains 28 liters of reaction residues and intermediate product metastannic acid.The reaction residue composition is HNO
356.74g/L, Sn0.000048g/L, Fe0.00048g/L, Pb0.016g/L.Reaction residue replenishes industrial nitric acid and returns pressurized reactor for 1.72 liters, control sour tin mass ratio and be 0.952 (with last anti-condition should with), other adds tin flower 2.5Kg, reacts under above-mentioned reaction conditions, reacted residual acid is mended acid again and is returned reaction, comes and goes with this.The intermediate product metastannic acid that reaction produces is pressed existing production method and is handled, and after the neutralization washing, gets metastannic acid product 3.463Kg after drying and (contains SnO
290.67%).
Embodiment two
At 2m
3Add water 1.2m in the pressurized reactor
3, glass putty 110Kg, industrial nitric acid (contains HNO
339.9%) 270 liters, heat to 140 ℃, reaction is 5 hours under pressure 0.7MPa condition.Reaction finishes the liquid-solid separation in back, obtains reaction residue 1.15m
3With the intermediate product metastannic acid, the reaction residue composition is HNO
362.17g/L, Sn0.000585g/L, Fe0.0016g/L, Pb0.009g/L.Reaction residue replenishes industrial nitric acid and returns pressurized reactor for 130 liters, and controlling sour tin mass ratio is 1.34 (same with last reaction), adds glass putty 110Kg, reacts under above-mentioned reaction conditions, and reacted residual acid is mended acid again and returned reaction, comes and goes with this.The intermediate product metastannic acid that reaction produces is pressed existing production method and is handled, and after the neutralization washing, gets tindioxide 123Kg after drying, calcining, fragmentation, the screening.Product contains SnO
298.94%, granularity＜10 μ m account for 99%.
Claims (3)
1, a kind of wet method is made the method for metastannic acid powder, it is characterized in that under the condition of airtight pressurization oxygenation, heating is fully reacted tin and nitric acid, reaction finish after heavy sorting from, reaction residue returns use, in the middle of the metastannic acid product add in the carbon ammonium remove residual nitric acid with washing after drying get the product metastannic acid; Wherein, the pressure of confined reaction is 0.7～2.0MPa, and oxygen partial pressure is 0.7～1.2MPa, and reaction control temperature is 100～160 ℃, and the reaction times is 4～8 hours.
2, manufacture method according to claim 1 is characterized in that adopting glass putty or tin flower and nitric acid reaction, and the liquid-solid ratio of salpeter solution and tin is 5～13: 1 during reaction, and the mass ratio of nitric acid and tin is 0.6～1.5.
3, use the method that further prepares tin dioxide powder according to the metastannic acid of the described method preparation of claim 1, it is characterized in that metastannic acid gets tin dioxide powder after calcining, fragmentation, the particle diameter of tin dioxide powder is less than 10 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004101008435A CN1318306C (en) | 2004-12-08 | 2004-12-08 | Method for preparing H2SnO3 (tin dioxide) powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004101008435A CN1318306C (en) | 2004-12-08 | 2004-12-08 | Method for preparing H2SnO3 (tin dioxide) powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1657417A CN1657417A (en) | 2005-08-24 |
| CN1318306C true CN1318306C (en) | 2007-05-30 |
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ID=35007151
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004101008435A Active CN1318306C (en) | 2004-12-08 | 2004-12-08 | Method for preparing H2SnO3 (tin dioxide) powder |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696029B (en) * | 2009-10-14 | 2011-05-11 | 大连交通大学 | Method for directly synthesizing liquid phase of tin oxide nano powder |
| CN101973575B (en) * | 2010-10-21 | 2013-05-29 | 易鹤翔 | Join production method of metastannic acid and stannate |
| CN108285170B (en) * | 2018-02-09 | 2020-07-14 | 云南锡业研究院有限公司 | Method for producing metastannic acid and stannic oxide by sulfuric acid method |
| CN108190943A (en) * | 2018-04-02 | 2018-06-22 | 郑州大学 | A kind of method that metallic tin oxidation prepares nano-stannic oxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11130432A (en) * | 1997-10-24 | 1999-05-18 | Mitsubishi Materials Corp | Production of tin oxide powder |
| CN1530325A (en) * | 2003-03-10 | 2004-09-22 | 中南大学 | Method for preparing stannic anhydride nanometer crystal with solid phase reaction |
| CN1544334A (en) * | 2003-11-14 | 2004-11-10 | 中国科学院上海硅酸盐研究所 | Stannic oxide powder preparation method |
-
2004
- 2004-12-08 CN CNB2004101008435A patent/CN1318306C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11130432A (en) * | 1997-10-24 | 1999-05-18 | Mitsubishi Materials Corp | Production of tin oxide powder |
| CN1530325A (en) * | 2003-03-10 | 2004-09-22 | 中南大学 | Method for preparing stannic anhydride nanometer crystal with solid phase reaction |
| CN1544334A (en) * | 2003-11-14 | 2004-11-10 | 中国科学院上海硅酸盐研究所 | Stannic oxide powder preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 偏锡酸及湿法二氧化锡开发与生产实践 郭应辉，云南冶金，第30卷第6期 2001 * |
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|---|---|
| CN1657417A (en) | 2005-08-24 |
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| C06 | Publication | ||
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| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Yunnan Tin Chemical Company Assignor: Research & Design Institute of Yunnan Tin Industry Group Inc. Contract fulfillment period: 2009.9.27 to 2019.8.22 contract change Contract record no.: 2009530000028 Denomination of invention: Method for preparing H2SnO3 (tin dioxide) powder Granted publication date: 20070530 License type: Exclusive license Record date: 2009.10.9 |
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| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.9.27 TO 2019.8.22; CHANGE OF CONTRACT Name of requester: YUNNAN TIN CHEMICAL CO., LTD. Effective date: 20091009 |