CN100378004C - Method for producing potassium stannate - Google Patents
Method for producing potassium stannate Download PDFInfo
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- CN100378004C CN100378004C CNB2006100109457A CN200610010945A CN100378004C CN 100378004 C CN100378004 C CN 100378004C CN B2006100109457 A CNB2006100109457 A CN B2006100109457A CN 200610010945 A CN200610010945 A CN 200610010945A CN 100378004 C CN100378004 C CN 100378004C
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- potassium stannate
- potassium
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- stannate
- stannic acid
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Abstract
The present invention relates to a novel method for producing potassium stannate, which belongs to the production process of an inorganic compound of potassium stannate, and is a novel method for producing the potassium stannate by tin tetrachloride. The method has the process steps that metallic tin and chlorine gas react to synthesize the tin tetrachloride; the tin tetrachloride and alkali are neutralized, and obtained precipitates are washed by water to obtain positive stannic acid after solid-liquid separation; the positive stannic acid and the potassium hydroxide synthesize the potassium stannate, and the potassium stannate products are obtained after evaporating concentration and drying. The method of the present invention has the advantages of easy operation, no production of toxic waste gases, easy treatment of waste washing water, low anticorrosion requirement of equipment, complete reaction of each production step of the postassium stannate, simple technological process, high product purity, high whiteness, high yield and low cost. The method of the present invention is a good method for the mass industrial production of the potassium stannate with high quality.
Description
Technical field
The invention belongs to a kind of production technique of mineral compound potassium stannate, is to adopt tin tetrachloride to produce the novel method of potassium stannate.
Background technology
Potassium stannate is a kind of stanniferous alkaline inorganic compound, and product is white crystals, and is soluble in water, and solution is alkalescence.Potassium stannate is widely used in electroplating industry, and it is zinc-plated to be mainly used in electron trade, automobile making, tinned food box, precision instrument etc.; Also be applied to industry such as fabric printing industry, glass, pottery, coinage.Potassium stannate is a kind of splendid zinc-plated inorganic tin salts of using, and compares with sodium stannate, has fast, the quality of coating advantages of higher of electroplating velocity; Compare with acid tin plating technique, have the bath stability height, electroplate advantages such as facility is simple.
Production method about potassium stannate, the Chinese patent CN1078444 of Zheng Tie cutting edge of a knife or a sword application in 1993, a kind of preparation method of alkali metal stannate is disclosed, be to be raw material with the metallic tin, mixing acid direct and concentrated nitric acid and concentrated hydrochloric acid reacts, the slow and strong aqua effect with reacted clear liquor then, and the white precipitate that reaction obtains is dissolved in the alkaline solution fully, add an amount of hydrogen peroxide, can obtain purified alkali metal stannate through concentrated, crystallization, oven dry and pulverizing.And a kind of preparation method of potassium stannate is provided among the Chinese patent CN1546383A of Gu Liugen 2003 application, and then be to adopt tin and concentrated nitric acid to generate β-stannic acid, again β-stannic acid and potassium hydroxide are heated congruent melting, cooling, be dissolved in water, filter, evaporation concentration is separated out the crystallized product potassium stannate.
According to our research to producing as a trial in the potassium stannate, it is main raw material with concentrated nitric acid all that above-mentioned two kinds of methods prepare potassium stannate, reaction can produce a large amount of oxynitrides such as nitrogen dioxide gas, and this is a kind of very deleterious pollutent, could discharge after need handling with the alkali lye absorption.Mix and the tin reaction with concentrated nitric acid, concentrated hydrochloric acid, if excessive acid then reacts completely, but the free acid height, neutralization needs many with alkali; If tin is excessive, then reaction not exclusively has a large amount of Bivalent Tin to exist, if do not remove, can have a strong impact on the quality of coating generation during plating, need to cause the potassium stannate transformation efficiency low after the reaction with the further oxidation Bivalent Tin of hydrogen peroxide, production cost increases, therefore, and the difficult control of reaction end.With the reaction of concentrated nitric acid and tin, the β of generation-stannic acid chemically reactive is poor, can not be dissolved in normal temperature under in the alkaline solution, need with concentrated base 200 ℃～300 ℃ congruent meltings, synthesis condition harshness, operational difficulty, increase energy consumption, facility investment and product cost; And the impurity that congruent melting process etching apparatus produces is difficult to remove, and causes product purity, whiteness not high, product in use, solution is muddy or have color after the water dissolution, the result of use that waits in using is electroplated in influence.
Summary of the invention
Technical problem to be solved by this invention provides a kind of new process for producing of potassium stannate, and its each step reaction is complete, easily operation, do not produce poisonous fume, washes is handled easily, and the requirement for anticorrosion of equipment also reduces, the transformation efficiency height of tin, reaction product purity height, production cost is low.
Solving the technical scheme that technical problem of the present invention adopts is:
1. metallic tin and chlorine reaction synthesize tin tetrachloride;
2. tin tetrachloride and alkali neutralization, the precipitation that obtains is through adding water washing, and solid-liquid separation obtains positive stannic acid;
3. positive stannic acid and the synthetic potassium stannate of potassium hydroxide after evaporation concentration, drying, obtain the potassium stannate product.
In technique scheme, chlorine is joined in the metallic tin, be swift in response, normal temperature can carry out; Reaction is thorough, and the tin transformation efficiency is greater than 99%; Reaction product purity height, tin tetrachloride content is greater than 99.5%, and heavy metal content is less than 0.01%; Though reaction raw materials is used gas (chlorine),, the reaction product tin tetrachloride is a liquid, reaction process does not have gas and produces, so can airtightly carry out, does not need a large amount of the absorption to handle.
Can provide OH with in tin tetrachloride (anhydrous or contain water) and the aqueous solution
-Alkali (as among ammonia, ammoniacal liquor, bicarbonate of ammonia, volatile salt, sodium bicarbonate, yellow soda ash, the sodium hydroxide one or more) mix, the endpoint pH that neutralizes is 2～10, than the figure of merit is that the pH value is 6～7,10 ℃～90 ℃ of neutralization reaction temperature, than the figure of merit is 40 ℃～60 ℃, add water washing then, remove Cl
-Deng impurity.The washes pH value 6～7 of this moment (mainly is to contain inorganic salt such as NH
4Cl20～30g/l etc.), do not need to do too many processing, just can discharge; The waste water stanniferous is less than 0.01g/l, and laundry operation tin rate of loss is less than 0.1%.Precipitation obtains positive stannic acid (solid is named alpha tin acid again) through washing after the solid-liquid separation.
The positive stannic acid of neutralization, solid-liquid separation gained is a kind of amphiprotic substance, has characteristics such as purity height, fine size, chemical reactivity height, and normal temperature just can be dissolved in the potassium hydroxide aqueous solution down.Therefore, compare with other stanniferous materials such as metastannic acid (being β-stannic acid again), tindioxide (synthetic or natural cassiterite), metallic tin, positive stannic acid is the splendid intermediate of synthetic potassium stannate.Synthesizing potassium stannate with it and potassium hydroxide, is to carry out under normal temperature, normal pressure, and speed of response is very fast, and a contact reacts is just finished; Reaction is thorough, no residue, and the tin transformation efficiency is greater than 99%; Reaction product purity height, potassium stannate content is greater than 98% (imported product is greater than 96% to the potassium stannate content requirement), heavy metal content is less than 0.01%.Positive stannic acid and potassium hydroxide are at normal temperature, normal pressure, and potassium hydroxide was metered into for potassium hydroxide and tin with positive stannic acid conversion in 2: 1 in molar ratio, stirred, and finished building-up reactions.Heating then, at first the form of water a large amount of in the product with water vapour removed, evaporation concentration is to all forming solid, again solid (potassium stannate xln) is put into the drying machine (as rake formula Vacuumdrier) that has stirring, further dehydration, simultaneously material is stirred diffusingly, be dried to salable product, domestic, foreign standard requirement that quality product meets.
Because be that the employing tin tetrachloride is the feedstock production potassium stannate, no Bivalent Tin exists, do not need to reoxidize with oxygenant, the quality product height, production cost is low.Synthetic potassium stannate operation is the critical process during potassium stannate is produced, and it has determined the quality, production cost etc. of potassium stannate product.Therefore, prepare positive stannic acid with tin tetrachloride, by the synthetic potassium stannate of positive stannic acid, process advantage is obvious again.In a word, it is the raw material production potassium stannate that the present invention adopts tin tetrachloride, each step reaction is complete, operation does not produce poisonous fume easily, and washes is handled easily, the requirement for anticorrosion of equipment also reduces, product purity, whiteness, output capacity are improved, and production cost reduces, and is the good method of the high-quality potassium stannate of a kind of commercial scale production.
Whole processing step of the present invention is shown in following reaction formula:
Sn+2Cl
2＝SnCl
4
SnCl
4+4OH
-＝Sn(OH)
4+4Cl
-
Sn(OH)
4+2KOH＝K
2Sn(OH)
6＝K
2SnO
3·3H
2O
Description of drawings
Fig. 1 produces the process flow sheet of potassium stannate with tin tetrachloride for the present invention
Embodiment
Example 1:
In confined conditions chlorine is joined in the metallic tin, chlorination reaction generates tin tetrachloride.Get bicarbonate of ammonia 120Kg, strong aqua 240Kg, water 600Kg and mix, stir, slowly add anhydrous stannic chloride 300Kg, regulate the tin tetrachloride add-on, in the control and endpoint pH be 6～7,40 ℃～60 ℃ of temperature.After neutralization operation is finished, add water washing precipitation 3 times, add water 3000Kg at every turn, stirred 10 minutes, clarify after 8 hours, the discharging of siphon supernatant.The precipitation of process washing obtains positive stannic acid after filtering with whizzer.Weigh, sample examination tin content calculates stanniferous weight in the positive stannic acid, takes by weighing potassium hydroxide at 2: 1 by potassium hydroxide and tin mol ratio, adds in the positive stannic acid, mixes.Heating, evaporation concentration gets potassium stannate product 340Kg after the drying in the drying machine that solid adding band stirs, potassium stannate content 98.56%, As 0.0003%, Pb0.002%, Fe 0.001%, and KCl 0.2%, free KOH 0.4%, KNO
30.01%, water-insoluble 0.04%, blue light whiteness value 82.Water-soluble liquid is limpid, 0.41 ton in ton product consumption tin.
Example 2:
The 600Kg anhydrous stannic chloride is slowly added in the 1200Kg water, add about 750Kg bicarbonate of ammonia again, N-process constantly stirs, and heating keeps 20 ℃～40 ℃ of temperature of reaction, regulates the bicarbonate of ammonia add-on, is 3.5～5 with endpoint pH in the control.After neutralization operation is finished, add water washing precipitation 3 times, add water 6000Kg at every turn, stirred 10 minutes, clarify after 8 hours, the discharging of siphon supernatant.Precipitation obtains positive stannic acid after centrifuging.Weigh, sample examination tin content calculates stanniferous weight in the positive stannic acid, takes by weighing potassium hydroxide at 2: 1 by potassium hydroxide and tin mol ratio and adds in the positive stannic acid, mixes.Heating, evaporation concentration, solid adds in the drying machine of band stirring, gets potassium stannate finished product 670Kg after the drying, potassium stannate content 99.28%, As 0.0005%, and Pb 0.002%, and Fe 0.002%, and KCl 0.1%, free KOH 0.2%, KNO
30.01%, water-insoluble 0.05%, blue light whiteness value 83.Water-soluble liquid is limpid, 0.42 ton in ton product consumption tin.
Example 3:
The 600Kg anhydrous stannic chloride is slowly added in the 600Kg water, and cool to room temperature stirs, toward wherein adding about 600Kg strong aqua, N-process should constantly stir, cooling, keep 60 ℃～80 ℃ of temperature of reaction, regulate the add-on of strong aqua, in the control and endpoint pH be 7～8.After neutralization operation is finished, add water washing precipitation 3 times, add water 6000Kg at every turn, stirred 10 minutes, clarify after 8 hours, the discharging of siphon supernatant.Precipitation obtains positive stannic acid after centrifuging.Weigh, sample examination tin content calculates stanniferous weight in the positive stannic acid, takes by weighing potassium hydroxide at 2: 1 by potassium hydroxide and tin mol ratio and adds in the positive stannic acid, mixes.Heating, evaporation concentration, solid adds in the drying machine of band stirring, gets potassium stannate finished product 685Kg after the drying, potassium stannate content 98.35%, As 0.0002%, and Pb 0.001%, and Fe 0.001%, and KCl 0.3%, free KOH 0.4%, KNO
30.01%, water-insoluble 0.03%, blue light whiteness value 81.Water-soluble liquid is limpid, 0.41 ton in ton product consumption tin.
Claims (3)
1. the production method of a potassium stannate, its feature is made up of following steps successively:
1.1 metallic tin and chlorine reaction, synthetic tin tetrachloride;
1.2 tin tetrachloride and alkali neutralization, the precipitation that obtains is through adding water washing, and solid-liquid separation obtains positive stannic acid;
1.3 the synthetic potassium stannate of positive stannic acid and potassium hydroxide after evaporation concentration, drying, obtains the potassium stannate product.
2. potassium stannate production method as claimed in claim 1 is characterized in that tin tetrachloride and alkali neutral endpoint pH are 2～10,10 ℃～90 ℃ of neutralization reaction temperature; When just stannic acid and potassium hydroxide were synthetic, potassium hydroxide was metered into for potassium hydroxide and tin with positive stannic acid conversion in 2: 1 in molar ratio.
3. potassium stannate production method as claimed in claim 2, used alkali is one or more among ammoniacal liquor, bicarbonate of ammonia, volatile salt, sodium bicarbonate, yellow soda ash, the sodium hydroxide when it is characterized in that with tin tetrachloride, endpoint pH selects 6～7, and the neutralization reaction temperature is selected 40 ℃～60 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100109457A CN100378004C (en) | 2006-06-09 | 2006-06-09 | Method for producing potassium stannate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100109457A CN100378004C (en) | 2006-06-09 | 2006-06-09 | Method for producing potassium stannate |
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| Publication Number | Publication Date |
|---|---|
| CN1872699A CN1872699A (en) | 2006-12-06 |
| CN100378004C true CN100378004C (en) | 2008-04-02 |
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| CN112573565A (en) * | 2020-12-10 | 2021-03-30 | 广东臻鼎环境科技有限公司 | Method for preparing potassium stannate trihydrate by using tin stripping waste liquid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59174528A (en) * | 1983-03-25 | 1984-10-03 | Sony Corp | Manufacture of fine barium stannate particle |
| CN1078444A (en) * | 1993-06-22 | 1993-11-17 | 郑铁锋 | The preparation method of alkali metal stannate |
| RU2049064C1 (en) * | 1992-12-01 | 1995-11-27 | Всесоюзный научно-исследовательский институт химических реактивов и особо чистых химических веществ "ИРЕА" | Process for preparing alkaline-earth metal stannates |
| CN1546383A (en) * | 2003-12-02 | 2004-11-17 | 上海试四赫维化工有限公司 | Method for preparing potassium stannate |
-
2006
- 2006-06-09 CN CNB2006100109457A patent/CN100378004C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59174528A (en) * | 1983-03-25 | 1984-10-03 | Sony Corp | Manufacture of fine barium stannate particle |
| RU2049064C1 (en) * | 1992-12-01 | 1995-11-27 | Всесоюзный научно-исследовательский институт химических реактивов и особо чистых химических веществ "ИРЕА" | Process for preparing alkaline-earth metal stannates |
| CN1078444A (en) * | 1993-06-22 | 1993-11-17 | 郑铁锋 | The preparation method of alkali metal stannate |
| CN1546383A (en) * | 2003-12-02 | 2004-11-17 | 上海试四赫维化工有限公司 | Method for preparing potassium stannate |
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|---|---|
| CN1872699A (en) | 2006-12-06 |
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Effective date of registration: 20200605 Address after: No.98, Gejin Road, Gejiu City, Honghe Hani and Yi Autonomous Prefecture, Yunnan Province Patentee after: Yunnan Tin Research Institute Co.,Ltd. Research Design Institute Address before: 661000 No. 121 East Jinhu Road, Gejiu City, Yunnan Patentee before: YUNNAN TIN COMPANY Group Ltd. |
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