CN114314643B - Preparation method and application of calcium stannate - Google Patents
Preparation method and application of calcium stannate Download PDFInfo
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- CN114314643B CN114314643B CN202111526910.XA CN202111526910A CN114314643B CN 114314643 B CN114314643 B CN 114314643B CN 202111526910 A CN202111526910 A CN 202111526910A CN 114314643 B CN114314643 B CN 114314643B
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- stannate
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- HNQGTZYKXIXXST-UHFFFAOYSA-N calcium;dioxido(oxo)tin Chemical compound [Ca+2].[O-][Sn]([O-])=O HNQGTZYKXIXXST-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 134
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 28
- 239000001110 calcium chloride Substances 0.000 claims abstract description 28
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 28
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 239000007800 oxidant agent Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 239000003985 ceramic capacitor Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 23
- 239000012065 filter cake Substances 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 238000001556 precipitation Methods 0.000 claims description 11
- 239000012286 potassium permanganate Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910001424 calcium ion Inorganic materials 0.000 claims description 8
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 18
- 230000015572 biosynthetic process Effects 0.000 abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 9
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 34
- 239000000047 product Substances 0.000 description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 159000000007 calcium salts Chemical class 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- -1 hydroxyl ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229940079864 sodium stannate Drugs 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Abstract
The invention discloses a preparation method and application of calcium stannate, belonging to the technical field of chemical synthesis; the calcium stannate is synthesized by taking stannous oxide, an oxidant, a potassium hydroxide aqueous solution and calcium chloride as raw materials through a one-step method; according to the technical scheme, the mass concentration of stannous oxide and potassium hydroxide aqueous solution is optimized, the added amount of oxidant, the tin concentration and the hydroxide concentration in the oxidized reaction system and the adding rate of the precipitant calcium chloride can enable the purity of the prepared calcium stannate to be more than 99%, so that the method can be directly applied to the preparation of ceramic capacitors without post-treatment; the technical scheme provided by the invention has the advantages of simple synthesis process, high synthesis efficiency, low cost, environment-friendly synthesis process, high synthesis yield and over 99.7 percent, and can be directly applied to industrial production.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a preparation method and application of calcium stannate.
Background
Calcium stannate (CaSnO) 3 ) The appearance of the product is white crystal powder. Is a capacitor for manufacturing electronic ceramics. The fluorescent lamp has a substance which absorbs the light source and stores the light source and emits fluorescence at night.A luminous sign at night can be made.
Chinese patent CN103466562a discloses a process for preparing a precursor of calcium stannate ceramic material, firstly, respectively grinding tin dioxide and calcium carbonate (or calcium oxide) to a certain particle size, then, mixing the tin dioxide and calcium carbonate according to Sn: ca molar ratio 1: (1-1.1) preparing the mixture, agglomerating the mixture, drying and putting into CO/CO 2 And (3) heating and roasting in the atmosphere, wherein the roasting temperature is 800-1000 ℃, the roasting time is 15-60 min, and the roasting product is crushed and ground after being cooled, so that the precursor of the calcium stannate ceramic material is obtained.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a simple and rapid preparation method and application of high-purity and high-yield calcium stannate.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a process for preparing calcium stannate features that stannous oxide, oxidant, aqueous solution of potassium hydroxide and calcium chloride are used as raw materials to synthesize calcium stannate in one step.
According to the technical scheme, the mass concentration of stannous oxide and potassium hydroxide aqueous solution is optimized, the added amount of oxidant, the tin concentration and the hydroxide concentration in the oxidized reaction system and the adding rate of the precipitant calcium chloride can enable the purity of the prepared calcium stannate to be more than 99%, so that the method can be directly applied to the preparation of ceramic capacitors without post-treatment; the technical scheme provided by the invention synthesizes the calcium stannate by a one-step method, has the advantages of simple synthesis process, high synthesis efficiency, low cost, environment-friendly synthesis process, high synthesis yield and more than 99.7 percent, and can be directly applied to industrial production.
As a preferred embodiment of the preparation method of the invention, the specific preparation method of the calcium stannate comprises the following steps:
(1) Adding stannous oxide into the aqueous solution of potassium hydroxide and stirring;
(2) Adding an oxidant into the reaction system of the step (1) to perform oxidation reaction;
(3) Adding calcium chloride into the reaction system of the step (2) to carry out precipitation reaction;
(4) And (3) carrying out suction filtration on the reaction system in the step (3) to obtain a filter cake, washing the filter cake and drying to obtain calcium stannate.
As a preferred embodiment of the production method of the present invention, the mass concentration of potassium hydroxide in the aqueous potassium hydroxide solution is 120 to 322g/L.
When the mass concentration of the selected potassium hydroxide is within the range, the tin can have the best dissolving effect, and the problem that the yield or purity of the final product is reduced due to insufficient subsequent reaction caused by incomplete dissolving is avoided; the reason why the aqueous potassium hydroxide solution is selected as the reaction system solution is that potassium hydroxide is the most basic of alkali metal hydroxides, and therefore, it can dissolve stannous oxide to the maximum extent, thereby facilitating the smooth progress of the subsequent reaction.
As a preferred embodiment of the preparation method of the present invention, in the step (1), the mass-volume ratio of stannous oxide to potassium hydroxide aqueous solution is 1g: (11-22) mL.
When the mass volume ratio of stannous oxide to potassium hydroxide aqueous solution is in the above range, the purity of the obtained calcium stannate product can be more than 99%; if the adding amount of stannous oxide is too small, the concentration of hydroxide radical in the subsequent precipitation reaction is too high, so that other calcium salt impurities are introduced when calcium chloride is added for precipitation, and the purity of the prepared calcium stannate product is reduced; if the added amount of stannous oxide is too large, stannous oxide cannot be completely dissolved and the concentration of tin in the subsequent precipitation reaction is too high, so that the yield and purity of the prepared calcium stannate product are reduced.
As a preferred embodiment of the preparation method of the present invention, in the step (1), the stirring time is 0.5 to 1h.
As a preferred embodiment of the preparation method of the present invention, in the step (2), the temperature of the oxidation reaction is 50-80℃and the time of the oxidation reaction is 1-2 hours.
As a preferred embodiment of the preparation method of the present invention, in the step (2), the oxidizing agent is potassium permanganate or sodium hypochlorite.
The potassium permanganate and the sodium hypochlorite have higher oxidation potential, and the oxidation effect of the potassium permanganate and the sodium hypochlorite is strong, so that the oxidation reaction can be rapidly carried out after the potassium permanganate and the sodium hypochlorite are added to generate sodium stannate; and potassium permanganate and sodium hypochlorite are suitable for oxidation under alkaline conditions.
As a preferred embodiment of the preparation method of the present invention, in the step (2), the system potential of the oxidation reaction is (-950) - (-850) mv.
When the potential of the oxidation reaction system is within the range, the content of the obtained calcium stannate is more than or equal to 99.10 percent, and the yield of the prepared calcium stannate is more than or equal to 99.71 percent; if the potential of the oxidation reaction system is not within the range provided by the invention, the bivalent tin cannot be fully converted into tetravalent tin, so that incomplete oxidation is caused; or the oxidant is left over, thereby introducing excessive impurities resulting in a reduced content of the final product.
As a preferred embodiment of the production method of the present invention, in the step (2), the mass concentration of tin in the oxidation reaction system is 40 to 80g/L and the mass concentration of free hydroxide is 25 to 75g/L.
The mass concentration of the free hydroxyl is controlled within the range of 25-75g/L, so that the tin can achieve the optimal dissolving effect, and the tin precipitation caused by too low or too high mass concentration of the hydroxyl is avoided.
As a preferred embodiment of the preparation method of the present invention, in the step (3), the temperature of the precipitation reaction is 20-85 ℃ and the time of the precipitation reaction is 0.5-1h.
As a preferred embodiment of the preparation method of the present invention, in the step (3), the calcium chloride is added at a rate of 0.4-0.8 g/(min×L).
When the addition rate of calcium chloride is within the above range, the purity of the final product can be ensured; if the addition rate is too slow, the reaction time is too long, and the reaction efficiency is reduced; if the addition rate is too high, other calcium salt impurities are doped in the generated calcium stannate, so that the purity of the calcium stannate is reduced, and the yield of the calcium stannate is affected to a certain extent.
As a preferred embodiment of the preparation method of the present invention, in the step (3), the mass ratio of the calcium ions in the calcium chloride to the tin elements in the stannous oxide in the step (1) is (0.3-0.33): 1.
as a preferred embodiment of the preparation method of the present invention, in the step (4), the electrical conductivity of the washing liquid in washing is < 150us/cm.
As a preferred embodiment of the preparation method of the present invention, in the step (4), the drying temperature used for drying is 80-120 ℃.
In addition, the invention also provides application of the calcium stannate prepared by adopting the technical scheme of the invention in manufacturing ceramic capacitors.
Compared with the prior art, the invention has the beneficial effects that:
first: according to the technical scheme, the mass concentration of stannous oxide and potassium hydroxide aqueous solution is optimized, the added amount of oxidant, the tin concentration and the hydroxide concentration in the oxidized reaction system and the adding rate of the precipitant calcium chloride can enable the purity of the prepared calcium stannate to be more than 99%, so that the method can be directly applied to the preparation of ceramic capacitors without post-treatment;
second,: the technical scheme provided by the invention synthesizes the calcium stannate by a one-step method, has the advantages of simple synthesis process, high synthesis efficiency, low cost, environment-friendly synthesis process, high synthesis yield and over 99.7 percent, and can be directly applied to industrial production.
Drawings
Fig. 1: the preparation steps of the calcium stannate are schematically shown.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
The preparation steps of the examples and comparative examples of the present invention all adopted the preparation steps shown in fig. 1; the reagents used in the examples and comparative examples of the present invention were all obtained by the conventional purchase route unless otherwise specified.
Example 1
The synthesis steps of the calcium stannate in the embodiment of the invention are as follows:
(1) Adding 300mL of water into a reactor, adding 60g of potassium hydroxide at a stirring rate of 300r/min, continuously stirring until the potassium hydroxide is completely dissolved, and finally fixing the volume to 500mL to obtain a potassium hydroxide aqueous solution with the mass concentration of the potassium hydroxide of 120 g/L;
(2) Adding 22.7g of stannous oxide into the potassium hydroxide aqueous solution in the step (1), wherein the mass volume of the stannous oxide and the potassium hydroxide aqueous solution is 1g:22mL, stirring and reacting for 0.5h; then heating to 50-80 ℃, adding potassium permanganate until the potential is-950 mv, controlling the temperature to be 50 ℃ for reaction for 1h, wherein the mass concentration of tin in the oxidized liquid after the reaction is finished is 40g/L, and the mass concentration of free hydroxide is 25g/L;
(3) Adjusting the temperature of the reaction system in the step (2) to 20 ℃, adding 16.7g of calcium chloride into the reaction system in the step (2) under the stirring state, namely, the mass ratio of calcium ions in the calcium chloride to tin elements in the added stannous oxide is 0.301:1, the adding rate is 0.4-0.8 g/(min) L), and continuously stirring for 0.5h for suction filtration after the adding is finished to obtain a filter cake;
(4) And (3) adding pure water into the filter cake obtained in the step (3) to wash until the conductivity is 149us/cm, and then drying at 80 ℃ to obtain calcium stannate.
Example 2
The synthesis steps of the calcium stannate in the embodiment of the invention are as follows:
(1) Adding 300mL of water into a reactor, adding 142g of potassium hydroxide at a stirring rate of 400r/min, continuously stirring until the potassium hydroxide is completely dissolved, and finally fixing the volume to 500mL to obtain a potassium hydroxide aqueous solution with a mass concentration of 284g/L of potassium hydroxide;
(2) Adding 22.7g of stannous oxide into the potassium hydroxide aqueous solution in the step (1), wherein the mass volume of the stannous oxide and the potassium hydroxide aqueous solution is 1g:22mL, stirring and reacting for 1h; then heating to 50-80 ℃, adding potassium permanganate until the potential is-850 mv, controlling the temperature to 85 ℃ for reaction for 2 hours, wherein the mass concentration of tin in the oxidized liquid after the reaction is finished is 40g/L, and the mass concentration of free hydroxide is 75g/L;
(3) Adjusting the temperature of the reaction system in the step (2) to 80 ℃, adding 18.3g of calcium chloride into the reaction system in the step (2) under the stirring state, namely, the mass ratio of calcium ions in the calcium chloride to tin elements in the added stannous oxide is 0.330:1, the adding rate is 0.4-0.8 g/(min) L), and continuing stirring for 1h and suction filtering after the adding is finished to obtain a filter cake;
(4) And (3) adding pure water into the filter cake obtained in the step (3) to wash until the conductivity is 50us/cm, and then placing the filter cake at 120 ℃ for drying to obtain calcium stannate.
Example 3
The synthesis steps of the calcium stannate in the embodiment of the invention are as follows:
(1) Adding 300mL of water into a reactor, adding 79g of potassium hydroxide at a stirring rate of 500r/min, continuously stirring until the potassium hydroxide is completely dissolved, and finally fixing the volume to 500mL to obtain a potassium hydroxide aqueous solution with the mass concentration of 158g/L of potassium hydroxide;
(2) Adding 45.4g of stannous oxide into the potassium hydroxide aqueous solution in the step (1), wherein the mass volume of the stannous oxide and the potassium hydroxide aqueous solution is 1g:11mL, stirring and reacting for 0.5h; then heating to 50-80 ℃, adding potassium permanganate until the potential is-880 mv, controlling the temperature to 60 ℃ for reaction for 1h, wherein the mass concentration of tin in the oxidized liquid after the reaction is completed is 80g/L, and the mass concentration of free hydroxide is 25g/L;
(3) Adjusting the temperature of the reaction system in the step (2) to 40 ℃, adding 33.4g of calcium chloride into the reaction system in the step (2) under the stirring state, namely, the mass ratio of calcium ions in the calcium chloride to tin elements in the added stannous oxide is 0.301:1, the adding speed is 0.4-0.8 g/(min) L), and continuously stirring for 0.5h for suction filtration after the adding is finished to obtain a filter cake;
(4) And (3) adding pure water into the filter cake obtained in the step (3) to wash until the conductivity is 100us/cm, and then placing the filter cake at 95 ℃ for drying to obtain calcium stannate.
Example 4
The synthesis steps of the calcium stannate in the embodiment of the invention are as follows:
(1) Adding 300mL of water into a reactor, adding 161g of potassium hydroxide under the stirring rate of 600r/min, continuously stirring until the potassium hydroxide is completely dissolved, and finally fixing the volume to 500mL to obtain a potassium hydroxide aqueous solution with the mass concentration of 322g/L of potassium hydroxide;
(2) Adding 45.4g of stannous oxide into the potassium hydroxide aqueous solution in the step (1), wherein the mass volume of the stannous oxide and the potassium hydroxide aqueous solution is 1g:11mL, stirring and reacting for 1h; then heating to 50-80 ℃, adding sodium hypochlorite to the potential of-910 mv, controlling the temperature to 70 ℃ for reaction for 2 hours, wherein the mass concentration of tin in the oxidized liquid after the reaction is completed is 80g/L, and the mass concentration of free hydroxide is 75g/L;
(3) Adjusting the temperature of the reaction system in the step (2) to 60 ℃, adding 36.6g of calcium chloride into the reaction system in the step (2) under the stirring state, namely, the mass ratio of calcium ions in the calcium chloride to tin elements in the added stannous oxide is 0.327:1, the adding rate is 0.4-0.8 g/(min) L), and continuing stirring for 1h and suction filtration after the adding is finished to obtain a filter cake;
(4) And (3) adding pure water into the filter cake obtained in the step (3) to wash until the conductivity is 75us/cm, and then placing the filter cake at 105 ℃ for drying to obtain calcium stannate.
Comparative example 1
The only difference between the comparative example of the present invention and example 1 is that 200g of potassium hydroxide was added in step (1).
Comparative example 2
The only difference between the comparative example of the present invention and example 1 is that 60g of sodium hydroxide was added in step (1).
Comparative example 3
The only difference between the comparative example and example 1 of the present invention is that potassium permanganate was added in step (2) to a potential of-960 mv.
Comparative example 4
The only difference between the comparative example and example 1 of the present invention is that hydrogen peroxide was added to a potential of-950 mv in step (2).
Comparative example 5
The only difference between the comparative example and example 1 of the present invention is that 50g of stannous oxide, i.e. 1g of stannous oxide and 1g of aqueous potassium hydroxide solution by mass volume, is added in step (2): 10mL.
Comparative example 6
The only difference between the comparative example and example 1 of the present invention is that 20.2g of calcium chloride was added in step (3), i.e., the mass ratio of calcium ions in the calcium chloride to tin elements in the added stannous oxide was 0.364:1.
Comparative example 7
The only difference between the comparative example and example 1 of the present invention is that the calcium chloride is added in step (3) at a rate of 1.0-1.2 g/(min L).
Effect example
The weight, the content (purity) of calcium stannate and the yield of the products prepared in examples 1 to 4 and comparative examples 1 to 7 are summarized, and are specifically shown in Table 1:
table 1: purity and yield data sheet for the products obtained in examples 1-4 and comparative examples 1-7
| Product weight (g) | Purity (%) | Yield (%) | |
| Example 1 | 35.03 | 99.30 | 99.89 |
| Example 2 | 35.01 | 99.40 | 99.90 |
| Example 3 | 70.10 | 99.10 | 99.71 |
| Example 4 | 70.05 | 99.20 | 99.74 |
| Comparative example 1 | 34.20 | 90.20 | 88.56 |
| Comparative example 2 | 35.00 | 98.30 | 98.77 |
| Comparative example 3 | 35.10 | 90.10 | 90.79 |
| Comparative example 4 | 34.30 | 95.02 | 93.56 |
| Comparative example 5 | 74.10 | 92.14 | 88.99 |
| Comparative example 6 | 36.40 | 95.58 | 99.88 |
| Comparative example 7 | 34.30 | 94.87 | 93.41 |
As can be seen from examples 1-4, when the parameters are within the parameters given by the invention, the yields of the prepared products are all above 99.71% and the purities are all above 99.10%; the purity data and yield data for comparative examples 1-7 are generally lower than those for examples 1-4, and it can be seen from examples 1 and comparative example 1 that the purity of the product obtained in comparative example 1 is significantly lower than that obtained in example 1, further illustrating that when the mass concentration of potassium hydroxide is too high, the mass concentration of free hydroxide in the solution is too high, resulting in precipitation of tin and reduced purity of the final product; as can be seen from example 1 and comparative example 2, when the potassium hydroxide is changed to sodium hydroxide, the purity of the product is 98.3%, the yield is 98.77%, and both are lower than 99%, and although the effect is also lower than that of potassium hydroxide; as can be seen from example 1 and comparative example 3, when the potential controlled by the addition of the oxidizing agent is low, the yield and purity of the prepared product are significantly reduced, further illustrating that the control of the potential has an effect on the formation of sodium stannate and subsequent calcium stannate when the addition of the oxidizing agent is oxidized; as can be seen from example 1 and comparative example 4, when the oxidizing agent is changed into hydrogen peroxide, although the adjusted potential is consistent, a large amount of hydrogen peroxide is required to be added to reach the same potential because the hydrogen peroxide is easy to decompose under the alkaline condition, so that the concentration of hydroxyl ions and stannate ions in the solution is changed, and therefore, the purity and the yield of the product prepared by adopting hydrogen peroxide as the oxidizing agent to react under the same potential are also greatly reduced; as can be seen from example 1 and comparative example 5, the mass-to-volume ratio of the added stannous oxide to the aqueous potassium hydroxide solution increases, resulting in a decrease in the yield of the prepared product, further illustrating that the mass-to-volume ratio of the appropriate amount of stannous oxide to the aqueous potassium hydroxide solution in the reaction system ensures good solubility of tin and increases the yield of the reaction product; as can be seen from example 1 and comparative example 6, when the added calcium chloride is increased, the purity of the product is greatly reduced, and the addition amount of the calcium chloride is proper, so that other calcium salt impurities are avoided being introduced into the calcium stannate product, and the purity of the calcium stannate product is reduced; it can be seen from example 1 and comparative example 7 that when calcium chloride is added at too high a rate, the purity of the product is significantly lowered because it is ensured that the concentration of calcium ions in the reaction system is not locally too high when calcium chloride is added in the rate range provided by the present invention, so that other calcium salt impurities are not doped in the resultant calcium stannate.
Finally, it should be noted that the above-mentioned embodiments illustrate rather than limit the scope of the invention, and that those skilled in the art will understand that changes can be made to the technical solutions of the invention or equivalents thereof without departing from the spirit and scope of the technical solutions of the invention.
Claims (3)
1. The preparation method of the calcium stannate is characterized by comprising the following steps of:
(1) Adding stannous oxide into the aqueous solution of potassium hydroxide and stirring;
(2) Adding an oxidant into the reaction system of the step (1) to perform oxidation reaction;
(3) Adding calcium chloride into the reaction system of the step (2) to carry out precipitation reaction;
(4) Filtering the reaction system in the step (3) to obtain a filter cake, washing the filter cake and drying to obtain calcium stannate;
the mass concentration of potassium hydroxide in the potassium hydroxide aqueous solution is 120-322g/L;
in the step (1), the mass volume ratio of stannous oxide to potassium hydroxide aqueous solution is 1g: (11-22) mL;
in the step (2), the system potential of the oxidation reaction is (-950) - (-850) mv;
in the step (2), the mass concentration of tin in a system of oxidation reaction is 40-80g/L, and the mass concentration of free hydroxide radical is 25-75g/L;
in the step (3), the addition rate of the calcium chloride is 0.4-0.8 g/(min×l);
in the step (3), the mass ratio of calcium ions in calcium chloride to tin elements in stannous oxide in the step (1) is (0.3-0.33): 1, a step of;
the oxidant is potassium permanganate or sodium hypochlorite.
2. The method according to claim 1, wherein in the step (3), the temperature of the precipitation reaction is 20 to 85 ℃ and the time of the precipitation reaction is 0.5 to 1h.
3. Use of calcium stannate prepared by the preparation method according to any one of claims 1-2 for manufacturing ceramic capacitors.
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| CN101973575A (en) * | 2010-10-21 | 2011-02-16 | 易鹤翔 | Join production method of metastannic acid and stannate |
| CN103408066A (en) * | 2013-08-30 | 2013-11-27 | 中南大学 | Method for preparing alkali earth metal stannate |
| CN105366711A (en) * | 2015-12-02 | 2016-03-02 | 柳州华锡铟锡材料有限公司 | Production method for sodium stannate of ultra-low water soluble turbidity |
| JP2020196913A (en) * | 2019-05-31 | 2020-12-10 | 三菱マテリアル株式会社 | Recovery method of tin |
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| CN101973575A (en) * | 2010-10-21 | 2011-02-16 | 易鹤翔 | Join production method of metastannic acid and stannate |
| CN103408066A (en) * | 2013-08-30 | 2013-11-27 | 中南大学 | Method for preparing alkali earth metal stannate |
| CN105366711A (en) * | 2015-12-02 | 2016-03-02 | 柳州华锡铟锡材料有限公司 | Production method for sodium stannate of ultra-low water soluble turbidity |
| JP2020196913A (en) * | 2019-05-31 | 2020-12-10 | 三菱マテリアル株式会社 | Recovery method of tin |
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