CN104973620B - The production method of bulky grain sodium stannate crystal - Google Patents
The production method of bulky grain sodium stannate crystal Download PDFInfo
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- CN104973620B CN104973620B CN201510436922.1A CN201510436922A CN104973620B CN 104973620 B CN104973620 B CN 104973620B CN 201510436922 A CN201510436922 A CN 201510436922A CN 104973620 B CN104973620 B CN 104973620B
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Abstract
The present invention discloses the production method of a kind of bulky grain sodium stannate crystal, comprises the following steps: the preparation of (1) sodium stannate solution；(2) prepared by crystal seed: the part sodium stannate solution after purifying clarification concentrates at vacuum 0.07～0.09Mpa, mixing speed 80～100r/min, 100～130 DEG C, until solution Baume degrees is 1.15～1.20Be, psychrolusia crystallisation by cooling, centrifuge dripping, sieve, obtain crystal seed；(3) crystallization: another part sodium stannate solution after clarification will be purified and be 0.02～0.06Mpa in vacuum, concentrate at mixing speed 40～80r/min, 80～100 DEG C, during until solution Baume degrees is 1.06～1.09Be, add 3～the crystal seed of 5% of end product quality, continue to concentrate until the Baume degrees of concentrated solution is to 1.20～1.23Be；(4) separate and dry.The inventive method is simple to operate, and energy consumption is low, and obtained product is uniform, stable crystal form is consistent, granule is big, specific surface area is little, be unlikely to deteriorate, water dissolution clarity is high, serviceability is good.
Description
Technical field
The invention belongs to the preparation field of sodium stannate, be related specifically to the production method of a kind of bulky grain sodium stannate crystal.
Background technology
Sodium stannate contains three water of crystallization, for colourless hexagonal or white powder.140 DEG C lose three water of crystallization.At sky
Gas easily absorbs moisture and carbon dioxide generates stannic hydroxide and sodium carbonate.Sodium stannate major part is white powder currently on the market
Shape, specific surface area is big, rotten after easily absorbing water and carbon dioxide, and then affects the water dissolution clarity of product, have impact on product
Serviceability.
The preparation method of sodium stannate has alkaline hydrolysis, fusion method etc. at present, and no matter which kind of method prepares sodium stannate, the most all needs
Want condensing crystallizing just can obtain.Crystallization is that the atom in solution, lewis' acid carry out arrangement formation crystal under certain condition
Process.Product crystallization process and growth mechanism are sufficiently complex.According to growing two step theories, the growth of crystal to be experienced successively and to turn
Move diffusion and two steps are reacted on surface.Research shows, if the degree of supersaturation of solution is higher, crystal growth mostly is diffusion and controlled
Journey；Otherwise then may be for surface reaction controlling process.
Sodium stannate crystallization is the process that sodium stannate separates out from solution with crystal state, is work main during sodium stannate produces
Skill unit, this process is considerably complicated, by solution composition, acidity, degree of supersaturation and the shadow of the factor such as mixing speed, temperature
Ringing, they affect the shape of crystal, size, color, purity, yield etc. the most directly or indirectly.
Original sodium stannate crystallization processes uses the mode of direct condensing crystallizing mostly, such as application number:
200910047619.7, denomination of invention: a kind of method utilizing stannum and ashbury metal to produce sodium stannate, it comprises the following steps: (1)
Stannum and ashbury metal are carried out at a temperature of 300 DEG C to 550 DEG C with sodium hydroxide, oxidant in reactor prepared of chemical reaction
Granular thick sodium stannate；Course of reaction be sodium hydroxide and oxidant are gradually added in the stannum of fusing and ashbury metal until
Reaction is completely；(2) with water, granular thick sodium stannate is dissolved；(3) solution is carried out refined purification；(4) carry refined
The sodium stannate solution of pure gained carries out concentrating, separates, dries prepared finished product.The problem that the method exists is as above described in us
, the crystal obtained is tiny powder, and specific surface area is big, rotten after easily absorbing water and carbon dioxide, and then have impact on product
The water dissolution clarity of product, have impact on the serviceability of product.
And application number: 201410216582.7, denomination of invention: a kind of sodium stannate prepares method for crystallising；And the public affairs such as Li Xiangyan
" common-ion effect application in sodium stannate crystallizes " opened, all by adding sodium hydroxide in sodium stannate solution, utilizes same
Ionic effect carries out the crystallization of sodium stannate.But the purpose of the method is to raise labour productivity, and reduce energy consumption, and gained
The product arrived is still tiny powder, and problem yet suffers from.
Summary of the invention
The invention aims to overcome the deficiencies in the prior art, it is provided that one prepares bulky grain stannic acid by adding crystal seed
The production method of sodium crystal, the inventive method is simple to operate, and energy consumption is low, and obtained product is uniform, stable crystal form consistent, granule
Greatly, specific surface area is little, be unlikely to deteriorate, water dissolution clarity is high, serviceability is good.
To achieve these goals, the present invention is achieved by the following technical solutions:
The production method of a kind of bulky grain sodium stannate crystal, comprises the following steps:
(1) preparation of sodium stannate solution: with scruff, sodium hydroxide and sodium nitrate as raw material, calcine under the high temperature conditions
To sodium stannate crude product, sodium stannate crude product water logging is gone out, obtains sodium stannate solution, then purify clarification；
(2) prepared by crystal seed: will purify the part sodium stannate solution after clarifying in vacuum-0.07～-0.09Mpa, stirring
Concentrate at speed 80～100r/min, 100～130 DEG C, until solution Baume degrees is 1.15～1.20 ° of Be', psychrolusia cooling knot
Crystalline substance, centrifuge dripping, sieves, obtains crystal seed；
(3) crystallization: another part sodium stannate solution after purifying clarification is-0.02～-0.06Mpa in vacuum, stirs
Mix and concentrate at speed 40～80r/min, 80～100 DEG C, during until solution Baume degrees is 1.06～1.09 ° of Be', add final producing
The 3 of quality～the crystal seed of 5%, continue to concentrate until the Baume degrees of concentrated solution is to 1.20～1.23 ° of Be'；
(4) separate and dry: by the product centrifugation after crystallization, drying, obtaining bulky grain sodium stannate product.
The temperature of the above calcining is 400～900 DEG C.
The mass ratio of the above scruff, sodium hydroxide and sodium nitrate is 80～100: 80～100: 20～25, described
Scruff is that electrolysis produces waste residue produced by stannous sulfate.
In the above sodium stannate solution, Sn4+Concentration is 60～70g/L, and free sodium hydroxide concentration is 50～80g/L.
The above time purifying clarification is 48～72h.
The temperature of the above psychrolusia controls at 5～10 DEG C, and the time of crystallisation by cooling is 10～30min.
The mesh number that the above sieves is 200～250 mesh.
In the above crystallizes, it is 10～15g/s that crystal seed adds speed.
The above temperature dried is 100～130 DEG C, and the time of described drying is 30～60min.
Compared with prior art, the invention has the beneficial effects as follows:
1. the product granularity obtained by the present invention is 180～300 μm, the product granularity that the direct condensing crystallizing of former technique obtains
It is 75～120 μm, and the product of the present invention is uniform, stable crystal form is consistent, granule is big, specific surface area is little, be unlikely to deteriorate, water dissolution
Clarity is high, serviceability is good.
2. the present invention is in the case of the concentration of certain tin ion and free sodium hydroxide, by accurately control vacuum,
Mixing speed and thickening temperature prepare ultra-fine crystal seed.Utilize ultra-fine crystal seed to induce, strictly control crystallization condition, pass through Baume degrees
Judge to crystallize terminal, thus obtained bulky grain sodium stannate crystal, filled up the blank of sodium stannate crystallization art, operation letter
Just, energy consumption is low.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to
The scope that embodiment represents.
Embodiment 1:
With scruff, sodium hydroxide and sodium nitrate example in mass ratio for 80:80:20 as raw material, forge under 400 DEG C of hot conditionss
Burning obtains sodium stannate crude product, sodium stannate crude product water logging is gone out, obtains sodium stannate solution, Sn4+Concentration is 60g/L, free hydrogen-oxygen
Change na concn is 50g/L, then purifies clarification 48h, obtains sodium stannate and purifies settled solution；At 1m3Enamel reaction still adds
Sodium stannate purifies settled solution 0.5m3, to open stirring and vacuum pump, adjust vacuum to-0.07Mpa, mixing speed controls
100r/min, steam heats and is incubated 130 DEG C, until solution Baume degrees is 1.15,5 DEG C of psychrolusia crystallisation by cooling, centrifuge dripping,
Cross 200 mesh sieve, obtain ultra-fine 27.3kg sodium stannate crystal seed.At 5m3Enamel reaction still adds sodium stannate and purifies settled solution
3.3m3, opening vacuum pump to vacuum is-0.06Mpa, and mixing speed controls at 40r/min, is steam heated to 100 DEG C, concentrates
The Baume degrees of liquid is to adding 5.0kg crystal seed during 1.09 ° of Be', it is 10g/s that crystal seed adds speed, continues to concentrate until concentrated solution
Baume degrees is to 1.20 ° of Be'.The said goods solution is put and dries to centrifuge, at 100 DEG C, dry 60min, obtain bulky grain stannic acid
Sodium product 128kg.
Embodiment 2:
With scruff, sodium hydroxide and sodium nitrate example in mass ratio for 85:95:20 as raw material, forge under 600 DEG C of hot conditionss
Burning obtains sodium stannate crude product, sodium stannate crude product water logging is gone out, obtains sodium stannate solution, Sn4+Concentration is 60g/L, free hydrogen-oxygen
Change na concn is 60g/L, then purifies clarification 55h, obtains sodium stannate and purifies settled solution；At 1m3Enamel reaction still adds
Sodium stannate purifies settled solution 0.5m3, to open stirring and vacuum pump, adjust vacuum to-0.08Mpa, mixing speed controls
90r/min, steam heats and is incubated 120 DEG C, until solution Baume degrees is 1.17 ° of Be', 8 DEG C of psychrolusia crystallisation by cooling, centrifugal drying
Dry, cross 230 mesh sieve, obtain ultra-fine 25.5kg sodium stannate crystal seed.At 5m3Enamel reaction still adds sodium stannate purification clarification molten
Liquid 3.3m3, opening vacuum pump to vacuum is-0.04Mpa, and mixing speed controls at 50r/min, is steam heated to 100 DEG C, dense
The Baume degrees of contracting liquid is to adding 7.9kg crystal seed during 1.08 ° of Be', it is 12g/s that crystal seed adds speed, continues to concentrate until concentrated solution
Baume degrees to 1.21 ° of Be'.The said goods solution is put and dries to centrifuge, at 110 DEG C, dry 50min, obtain bulky grain stannum
Acid sodium product 128kg.
Embodiment 3:
With scruff, sodium hydroxide and sodium nitrate example in mass ratio for 90:100:23 as raw material, under 800 DEG C of hot conditionss
Calcining obtains sodium stannate crude product, sodium stannate crude product water logging is gone out, obtains sodium stannate solution, Sn4+Concentration is 70g/L, free hydrogen
Sodium oxide concentration is 70g/L, then purifies clarification 65h, obtains sodium stannate and purifies settled solution；At 1m3Enamel reaction still adds
Enter sodium stannate and purify settled solution 0.5m3, to open stirring and vacuum pump, adjust vacuum to-0.09Mpa, mixing speed controls
80r/min, steam heats and is incubated 110 DEG C, until solution Baume degrees is 1.18 ° of Be', 10 DEG C of psychrolusia crystallisation by cooling, centrifugal
Dry, cross 240 mesh sieve, obtain ultra-fine 32.6kg sodium stannate crystal seed.At 5m3Enamel reaction still adds sodium stannate purified solution
3.3m3, opening vacuum pump to vacuum is-0.03Mpa, and mixing speed controls at 60r/min, is steam heated to 90 DEG C, concentrates
The Baume degrees of liquid is to adding 11.5kg crystal seed during 1.07 ° of Be', it is 13g/s that crystal seed adds speed, continues to concentrate until concentrated solution
Baume degrees is to 1.23 ° of Be'.The said goods solution is put and dries to centrifuge, at 120 DEG C, dry 40min, obtain bulky grain stannic acid
Sodium product 218kg.
Embodiment 4:
With scruff, sodium hydroxide and sodium nitrate example in mass ratio for 100:100:25 as raw material, under 900 DEG C of hot conditionss
Calcining obtains sodium stannate crude product, sodium stannate crude product water logging is gone out, obtains sodium stannate solution, Sn4+Concentration is 70g/L, free hydrogen
Sodium oxide concentration is 80g/L, then purifies clarification 72h, obtains sodium stannate and purifies settled solution；At 1m3Enamel reaction still adds
Enter sodium stannate and purify settled solution 0.5m3, to open stirring and vacuum pump, adjust vacuum to-0.08Mpa, mixing speed controls
80r/min, steam heats and is incubated 100 DEG C, until solution Baume degrees is 1.20 ° of Be', 8 DEG C of psychrolusia crystallisation by cooling, centrifugal drying
Dry, grind, cross 250 mesh sieve, obtain ultra-fine 31.8kg sodium stannate crystal seed.At 5m3Adding tin concentration in enamel reaction still is
The sodium stannate purified solution 3.3m of 70g/L3, opening vacuum pump to vacuum is-0.02Mpa, and mixing speed controls at 80r/
Min, is steam heated to 80 DEG C, adds 13.9kg crystal seed during the Baume degrees of concentrated solution to 1.06 ° Be', and crystal seed adds speed and is
15g/s, continues to concentrate until the Baume degrees of concentrated solution is to 1.21 ° of Be'.The said goods solution is put to centrifuge drying, 130
Dry 30min at DEG C, obtain bulky grain sodium stannate product 223kg.
The bulky grain sodium stannate product index of former handicraft product (i.e. sodium stannate direct condensing crystallizing method) and embodiment 1-4 is such as
Shown in table one:
Table one
By table one it can be seen that product chemical index of the present invention and product appearance all meet standard GB/T/T26040-
The requirement of 2010, and relative to former concentration and crystallization process, the product particle that the present invention obtains is all higher than 180 μm, stable crystal form one
Cause.
Claims (9)
1. the production method of a bulky grain sodium stannate crystal, it is characterised in that comprise the following steps:
(1) preparation of sodium stannate solution: with scruff, sodium hydroxide and sodium nitrate as raw material, calcining obtains stannum under the high temperature conditions
Acid sodium crude product, goes out sodium stannate crude product water logging, obtains sodium stannate solution, then purify clarification；
(2) prepared by crystal seed: will purify the part sodium stannate solution after clarifying in vacuum-0.07～-0.09Mpa, mixing speed
Concentrate at 80～100r/min, 100～130 DEG C, until solution Baume degrees is 1.15～1.20, psychrolusia crystallisation by cooling,
Centrifuge dripping, sieves, and obtains crystal seed；
(3) crystallization: another part sodium stannate solution after purifying clarification is-0.02～-0.06Mpa in vacuum, stirs speed
Concentrate at spending 40～80r/min, 80～100 DEG C, until solution Baume degrees is 1.06～1.09Time, add final products matter
3～the crystal seed of 5% of amount, continues to concentrate until the Baume degrees of concentrated solution is to 1.20～1.23；
(4) separate and dry: by the product centrifugation after crystallization, drying, obtaining bulky grain sodium stannate product.
The production method of bulky grain sodium stannate crystal the most according to claim 1, it is characterised in that: the temperature of described calcining
It it is 400～900 DEG C.
The production method of bulky grain sodium stannate crystal the most according to claim 1, it is characterised in that: described scruff, hydrogen-oxygen
The mass ratio changing sodium and sodium nitrate is 80～100: 80～100: 20～25, and described scruff is that electrolysis produces stannous sulfate institute
The waste residue produced.
The production method of bulky grain sodium stannate crystal the most according to claim 1, it is characterised in that: described sodium stannate solution
In, Sn4+Concentration is 60～70g/L, and free sodium hydroxide concentration is 50～80g/L.
The production method of bulky grain sodium stannate crystal the most according to claim 1, it is characterised in that: described purification clarification
Time is 48～72h.
The production method of bulky grain sodium stannate crystal the most according to claim 1, it is characterised in that: the temperature of described psychrolusia
Degree controls at 5～10 DEG C, and the time of crystallisation by cooling is 10～30min.
The production method of bulky grain sodium stannate crystal the most according to claim 1, it is characterised in that the mesh number sieved described in:
It is 200～250 mesh.
The production method of bulky grain sodium stannate crystal the most according to claim 1, it is characterised in that: in described crystallization,
It is 10～15g/s that crystal seed adds speed.
The production method of bulky grain sodium stannate crystal the most according to claim 1, it is characterised in that: the temperature of described drying
Being 100～130 DEG C, the time of described drying is 30～60min.
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| CN105366711B (en) * | 2015-12-02 | 2016-12-07 | 柳州百韧特先进材料有限公司 | A kind of production method of ultralow water solublity turbidity sodium stannate |
| CN105366713B (en) * | 2015-12-10 | 2016-12-07 | 柳州百韧特先进材料有限公司 | A kind of method utilizing stannum waste residue to produce high-purity sodium stannate |
| CN113060758B (en) * | 2021-05-07 | 2023-03-24 | 云南锡业研究院有限公司 | Method for preparing stannic oxide and stannate by using tin-copper slag |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000226214A (en) * | 1999-02-08 | 2000-08-15 | Nihon Kagaku Sangyo Co Ltd | Production of high-purity alkali stannate compound |
| CN101348276A (en) * | 2008-09-02 | 2009-01-21 | 云南锡业集团（控股）有限责任公司 | Alkali metal stannate production method |
| CN101643237A (en) * | 2009-06-22 | 2010-02-10 | 云南锡业集团（控股）有限责任公司 | Method for producing sodium stannate |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000226214A (en) * | 1999-02-08 | 2000-08-15 | Nihon Kagaku Sangyo Co Ltd | Production of high-purity alkali stannate compound |
| CN101348276A (en) * | 2008-09-02 | 2009-01-21 | 云南锡业集团（控股）有限责任公司 | Alkali metal stannate production method |
| CN101643237A (en) * | 2009-06-22 | 2010-02-10 | 云南锡业集团（控股）有限责任公司 | Method for producing sodium stannate |
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