CN114890456A - Method for deeply reducing stannic tin in stannous sulfate solution - Google Patents
Method for deeply reducing stannic tin in stannous sulfate solution Download PDFInfo
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- CN114890456A CN114890456A CN202210420625.8A CN202210420625A CN114890456A CN 114890456 A CN114890456 A CN 114890456A CN 202210420625 A CN202210420625 A CN 202210420625A CN 114890456 A CN114890456 A CN 114890456A
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Abstract
A method for deeply reducing stannic tin in a stannous sulfate solution belongs to the technical field of stannic chemical industry. The method comprises the following steps: heating a solution; capturing and reducing; filtering and separating the three; fourthly, secondary heat preservation and reduction are conducted; and fifthly, cooling and standing. The method deeply reduces the stannic tin in the stannous sulfate solution by means of capture reduction, secondary heat preservation reduction, sedimentation and the like, so that the stannic tin in the stannous sulfate solution is reduced to be below 0.05g/l from the original 0.1-0.5 g/l, the stannous sulfate solution with the reduced stannic tin is clear and transparent, the turbidity is reduced to be below 10 ℃ from the original more than or equal to 50 ℃, the chroma is reduced to be below 35 from the original 156, the purity of the stannous sulfate product produced by the method is more than or equal to 99.70 percent, the shelf life is more than 2 years, and the stannous sulfate can be used as the special stannous sulfate for the electroplating and electrolytic coloring industries. And no three wastes are generated in the production process.
Description
Technical Field
The invention relates to the technical field of tin chemical industry. In particular to a method for deeply reducing stannic tin in stannous sulfate solution.
Background
Stannous sulfate is a white or light yellow crystalline powder, can be dissolved in water and dilute sulfuric acid, and the aqueous solution is rapidly decomposed. The method is mainly used for tin plating or chemical reagents, such as acid electroplating of alloys, tinplate, cylinder pistons, steel wires and the like, bright tin plating of electronic devices and the like. In addition, the method is also used for oxidation coloring of aluminum alloy product coatings, printing and dyeing industry as mordant, hydrogen peroxide remover in organic solution, lead-acid storage battery application field and the like.
The stannous sulfate solution is formed by dissolving tin in a dilute sulfuric acid system under the action of electricity. In the process of preparing the stannous sulfate solution, because the current voltage is too high during electrolysis, the cathode plate and the anode plate are disconnected or short-circuited to form a burning plate, the tetravalent tin content in the solution is too high due to too high temperature and the like, the stannous sulfate product is yellow, the turbidity of the product is high, the quality guarantee period is short, and in the using process of a downstream electroplating and electrolytic coloring industry, the bath solution is aged, the precipitation is increased, and the electrolytic coloring effect is reduced. The content of stannic tin in the stannous sulfate solution prepared at present is generally 0.1-0.5 g/l, and the stannous sulfate product produced by using the solution contains 0.1-0.5% of stannic tin. When the tetravalent tin reaches 0.5 percent, the product has yellow color and turbidity of more than or equal to 50 degrees, the consumption of the product is increased when the product is applied to the common reaction of customers in the electroplating industry, the bath solution is easy to age, the precipitation is increased, the electrolytic coloring effect is reduced, and the retention period is only about three months. When the tetravalent tin in the stannous sulfate solution is 0.1g/l, the product color is light yellow, the turbidity is more than or equal to 30, the shelf life is half a year, when the tetravalent tin in the stannous sulfate solution is less than or equal to 0.05g/l, the product color is pure white, the shelf life is more than or equal to 2 years, the product turbidity is less than or equal to 10, and the feedback is good after the use of the electroplating and electrolytic coloring industry.
Chinese patent CN201710554713.6 discloses a method for reducing the content of stannic tin in stannous sulfate, which comprises laying a layer of stannic particles on the bottom of an electrolytic tank of stannous sulfate, adding deoxidant such as acetone oxime, sodium hydrosulfite, sodium sulfite, hydrazine, etc. into dilute sulfuric acid, controlling the voltage of the electrolytic tank, the concentration of stannic ions in the electrolytic solution, and using isopropanol, acetone, butanone, etc. to reduce the content of stannic tin produced from stannous sulfate products. In dilute sulfuric acid, the deoxidant brings impurities such as sodium salt and the like, and hydrazine is toxic and has certain influence on the environment and operators.
The national scholars Danqing (university of Wuyi, 2000, 14, 55-59) reported that the current density was controlled to inhibit stannic tin when preparing stannous sulfate in the laboratory, but the method is obtained by intermittent electrolysis under the laboratory condition, the anode area is continuously changed in the industrial mass production process, the current density is difficult to accurately control, and the method is not suitable for large-scale continuous production.
Chinese patent CN201811115352.6 discloses a method for prolonging the shelf life of stannous sulfate, which comprises the steps of adding boric acid into a sulfuric acid solution, adding pyrogallic acid, hydroquinone and ascorbic acid into the solution after electrolysis, carrying out reduction coating on stannous sulfate crystals in the concentration process of the stannous sulfate to prevent the stannous sulfate from being oxidized, wherein the added pyrogallic acid, hydroquinone and ascorbic acid can yellow under the illumination condition and can bring in impurities such as organic matters, and the like, so that the main components of a stannous sulfate product are influenced, and if the product is exposed to the illumination, the product can also easily yellow.
Therefore, it is important to develop a method that is environment-friendly, simple to operate, harmless to human body, and free from impurities.
Disclosure of Invention
The invention aims to provide a method for deeply reducing stannic tin in a stannous sulfate solution, which effectively reduces the content of four parts of tin in the stannous sulfate solution through capture reduction, secondary heat preservation reduction and sedimentation treatment processes.
In order to achieve the purpose, the technical scheme of the invention is as follows: a method for deeply reducing stannic tin in a stannous sulfate solution comprises the following steps:
(1) heating the solution: heating the stannous sulfate solution obtained by electrolysis;
(2) catching and reducing: dissolving the trapping agent in boiling water, adding the dissolved trapping agent into the solution obtained in the step (1), then adding a certain amount of reducing agent, heating and stirring until the solution is boiled, preserving heat and cooling;
(3) filtering and separating: filtering the stannous sulfate solution treated in the step (2) by using filter cloth;
(4) and (3) secondary heat preservation reduction: adding the stannous sulfate solution treated in the step (3) into a tin-containing reducing agent for reduction, heating and preserving heat;
(5) cooling and standing: and (4) cooling and standing the stannous sulfate solution treated in the step (4), and extracting supernatant to obtain the stannous sulfate solution with low stannic tin.
The heating temperature of the stannous sulfate solution in the step (1) is 80-90 ℃.
And (3) the catching agent in the step (2) is gelatin, the using amount of the gelatin is 0.05-0.5 g/l of stannous sulfate solution, the reducing agent is activated carbon, the using amount of the activated carbon is 1-5 g/l of stannous sulfate solution, and the heat preservation time is 5-20 min.
The tin-containing reducing agent in the step (4) is water-quenched tin flower, the using amount of the tin-containing reducing agent is 100-200 g/l of stannous sulfate solution, the heating temperature is 50-100 ℃, and the heat preservation time is 30-60 min.
And (5) cooling and standing until the temperature is reduced to be less than or equal to 40 ℃, wherein the standing time is 1-2 days.
Except for other descriptions, the percentages are mass percentages, and the sum of the content percentages of all the components is 100%.
Compared with the prior art, the invention has the beneficial effects that:
1. aiming at the problems of high content of stannic tin in a stannous sulfate solution, high turbidity and short shelf life of a stannous sulfate product, the method deeply reduces the stannic tin in the solution by adopting the means of capture reduction, secondary heat preservation reduction, sedimentation and the like. The gelatin is added in the catching reduction process, the gelatin forms spherical small particles with certain viscosity in a hot stannous sulfate solution, tin sulfate (tetravalent tin) suspension particles can be caught in the stirring process, the tin sulfate (tetravalent tin) suspension particles and the gelatin are bonded into larger particles, the gelatin becomes gel and a settling agent along with the reduction of the solution temperature, the gelatin and the tin sulfate (tetravalent tin) suspension particles are rapidly settled, the tin sulfate (tetravalent tin) suspension particles in the solution are effectively removed through filtration, and the gelatin cannot remain in the solution and cannot increase impurities.
2. Active carbon is added in the catching reduction process as a reducing agent, the active carbon has strong reducibility, can reduce tetravalent tin in the solution into divalent tin, reduces the content of the tetravalent tin in the solution, and simultaneously has super strong adsorption and decoloration functions, can effectively remove the color and other impurities of the stannous sulfate solution, and enables the solution to be more transparent and clear.
3. Tin flower is added into the hot stannous sulfate solution in the secondary heat preservation reduction process, because the specific surface area of the tin flower is larger than that of the tin ingot and tin particle, and the main component is tin, according to Sn 4+ +Sn＝2Sn 2+ According to the reaction principle, the stannic tin in the solution can be deeply reduced, and the reduced product is stannous existing in the form of stannous sulfate, so that the purity of the stannous sulfate product can be improved, and the purity of the stannous sulfate product can be more than or equal to 99.70%.
4. The method is characterized in that the stannic tin is deeply reduced by adopting the measures of capture reduction, secondary heat preservation reduction, sedimentation and the like, so that the stannic tin in the stannous sulfate solution is reduced to below 0.05g/l from the original 0.1-0.5 g/l, the stannous sulfate solution with the reduced stannic tin is clear and transparent, the turbidity is reduced to below 20 ℃ from the original more than or equal to 50 ℃, and the chroma is reduced to below 35 from the original 156.
5. The process has simple operation, low cost and no 'three wastes' generation.
6. The product of stannous sulfate produced by the process has a shelf life of more than 2 years, is dissolved and fast in speed, and can be used as the special stannous sulfate for the electroplating and electrolytic coloring industries.
Drawings
FIG. 1 is a process flow diagram of the method for deeply reducing stannic tin in a stannous sulfate solution according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited to the scope of the examples.
Example 1
This embodiment is an example of the method for deeply reducing stannic tin in a stannous sulfate solution according to the present invention, and includes the following steps:
dissolving 0.05g of gelatin in 10ml of boiling water, adding the dissolved gelatin into 1000ml of stannous sulfate solution of 80 ℃, adding 1g of activated carbon, heating and stirring until boiling, stirring and preserving heat for 5 minutes, cooling to room temperature, and filtering by using a filter cloth. Adding 100g of tin flower into the filtered stannous sulfate solution, heating to 50 ℃, preserving the heat for 30min, cooling to 40 ℃, standing for 1 day, taking the supernatant, and measuring the performance index of the supernatant, wherein the performance index is shown in table 1.
Example 2
This example is another example of the method for deeply reducing stannic tin in stannous sulfate solution according to the present invention, comprising the following steps:
dissolving 0.5g of gelatin in 10ml of boiling water, adding the dissolved gelatin into 1000ml of stannous sulfate solution of 80 ℃, adding 3g of activated carbon, heating and stirring until boiling, stirring and preserving heat for 15 minutes, cooling to room temperature, and filtering by using a filter cloth. Adding 150g of tin flower into the filtered stannous sulfate solution, heating to 80 ℃, keeping the temperature for 50min, cooling to 30 ℃, standing for 1.5 days, and measuring the performance index, which is shown in table 1.
Example 3
This embodiment is a further example of the method for deeply reducing stannic tin in a stannous sulfate solution according to the present invention, and the method includes the following steps:
dissolving 0.5g of gelatin in 10ml of boiling water, adding the dissolved gelatin into 1000ml of stannous sulfate solution at 100 ℃, adding 5g of active carbon, heating and stirring until boiling, stirring and preserving heat for 20 minutes, cooling to room temperature, and filtering by using filter cloth. Adding 200g of tin flower into the filtered stannous sulfate solution, heating to 90 ℃, keeping the temperature for 60min, cooling to 20 ℃, standing for 2 days, and measuring the performance index, which is shown in table 1.
The stannous sulfate solution before treatment is compared with the stannous sulfate solution obtained after treatment in the above embodiment, and the test results are as follows:
TABLE 1 comparison of Performance before and after treatment of stannous sulfate solution
As seen from the results of table 1: the stannous sulfate solution which is not treated by the method has the stannic tin content of 0.48g/l, the turbidity of 83 degrees and the chroma of 156 degrees, the content of the clear and transparent stannic tin of the stannous sulfate solution which is treated by the method is less than 0.05g/l, the turbidity of less than or equal to 20 degrees and the chroma of less than or equal to 35 degrees, and the method has obvious index effects of four parts of tin, turbidity, chroma and the like in the stannous sulfate reducing solution.
Simultaneously carrying out vacuum concentration and crystallization on the stannous sulfate solution before treatment and the stannous sulfate solution obtained after treatment in the above embodiment, wherein the vacuum concentration and crystallization conditions are that the vacuum degree is more than or equal to-0.08 MPa, the concentration time is 30min, the temperature is 90 ℃ to obtain stannous sulfate product crystals, and carrying out a comparison test on the crystals, wherein the test result is as follows:
TABLE 2 comparison of Performance before and after treatment of stannous sulfate products
As seen from the results of table 2: the stannous sulfate product produced by the stannous sulfate solution which is not treated by the method has the stannous sulfate content of 99.20 percent, the turbidity of 52 degrees and the retention period of 5.5 months, while the stannous sulfate product produced by the stannous sulfate solution which is treated by the method has the stannous sulfate content of more than or equal to 99.70 percent, the quality guarantee period of more than 2 years, the turbidity of less than 10 degrees and high dissolution speed, and can be used as the special stannous sulfate for the electroplating and electrolytic coloring industry.
Claims (5)
1. A method for deeply reducing stannum in a stannous sulfate solution is characterized by comprising the following steps:
(1) heating the solution: heating the stannous sulfate solution obtained by electrolysis;
(2) catching and reducing: dissolving the trapping agent in boiling water, adding the dissolved trapping agent into the solution obtained in the step (1), then adding a certain amount of reducing agent, heating and stirring until the solution is boiled, stirring and preserving heat, and cooling;
(3) and (3) filtering and separating: filtering the stannous sulfate solution treated in the step (2) by using filter cloth;
(4) and (3) secondary heat preservation reduction: adding the stannous sulfate solution treated in the step (3) into a tin-containing reducing agent for reduction, heating and preserving heat;
(5) cooling and standing: and (4) cooling and standing the stannous sulfate solution treated in the step (4), and extracting supernatant to obtain the stannous sulfate solution with low stannic tin.
2. The method for deeply reducing the stannic tin in the stannous sulfate solution according to claim 1, wherein the heating temperature of the stannous sulfate solution in the step (1) is 80-90 ℃.
3. The method for deeply reducing stannic tin in a stannous sulfate solution according to claim 1, wherein the capturing agent is gelatin, the dosage of the gelatin is 0.05-0.5 g/l of the stannous sulfate solution, the reducing agent is activated carbon, the dosage of the reducing agent is 1-5 g/l of the stannous sulfate solution, and the stirring and heat preservation time is 5-20 min.
4. The method for deeply reducing stannic tin in a stannous sulfate solution according to claim 1, wherein the tin-containing reducing agent in the step (4) is water-quenched stannic flower, the using amount of the water-quenched stannic flower is 100-200 g/l of the stannous sulfate solution, the heating temperature is 50-100 ℃, and the heat preservation time is 30-60 min.
5. The method for deeply reducing the tetravalent tin in a stannous sulfate solution according to claim 1, wherein the temperature reduction and standing in the step (5) is carried out until the temperature is reduced to be less than or equal to 40 ℃, and the standing time is 1-2 days.
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Citations (8)
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|---|---|---|---|---|
| GB1061853A (en) * | 1964-08-22 | 1967-03-15 | Sherritt Gordon Mines Ltd | Tin purification process |
| CN85106332A (en) * | 1985-08-20 | 1986-12-17 | 个旧市化工一厂 | A kind of preparation method of tin protochloride |
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| CN105481005A (en) * | 2016-01-20 | 2016-04-13 | 广东光华科技股份有限公司 | Preparation method of reagent-grade stannous chloride dehydrate crystals |
| CN107385469A (en) * | 2017-07-10 | 2017-11-24 | 精细化学品集团有限公司 | The method for reducing tetravalence Theil indices in stannous sulfate |
| CN107675216A (en) * | 2017-08-28 | 2018-02-09 | 深圳市新日东升电子材料有限公司 | Sedimentation agent for the sedimentation of tin cylinder and preparation method thereof and application method |
| CN109384207A (en) * | 2018-09-21 | 2019-02-26 | 郑忆依 | A kind of processing method taking off tin waste liquid |
| CN216237274U (en) * | 2021-10-20 | 2022-04-08 | 广东天承科技股份有限公司 | Filtering circulation reaction device for reducing tetravalent tin |
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2022
- 2022-04-20 CN CN202210420625.8A patent/CN114890456A/en active Pending
Patent Citations (8)
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| CN107385469A (en) * | 2017-07-10 | 2017-11-24 | 精细化学品集团有限公司 | The method for reducing tetravalence Theil indices in stannous sulfate |
| CN107675216A (en) * | 2017-08-28 | 2018-02-09 | 深圳市新日东升电子材料有限公司 | Sedimentation agent for the sedimentation of tin cylinder and preparation method thereof and application method |
| CN109384207A (en) * | 2018-09-21 | 2019-02-26 | 郑忆依 | A kind of processing method taking off tin waste liquid |
| CN216237274U (en) * | 2021-10-20 | 2022-04-08 | 广东天承科技股份有限公司 | Filtering circulation reaction device for reducing tetravalent tin |
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Application publication date: 20220812 |