CN101748433B - Purification method of electrolyte in indium electrolysis process - Google Patents
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Abstract
A purification method of electrolyte in an indium electrolysis process comprises: (1) adding sulfuric acid solution with the concentration of 40 to 60 vt percent to indium electrolyte, and the indium concentration in indium electrolyte is 50 to 100 g/L, (2) dripping 0.5 to 1.5 mol/L soluble barium salt to the mixed solution, (3) filtering to obtain statically purified indium electrolyte, (4) heating the statically purified indium electrolyte to be evaporated to original volume, and (5) connecting the connecting pipes on the inlet and the outlet on the two opposite sides of a electrolytic bath, and connecting with a circulating pump and a sponge indium column on the pipe, wherein the sponge indium post is formed by arranging sponge indium in a fused silica column, the electrolyte which is statically purified, heated and evaluated is placed in the electrolytic bath and is circulated by the circulating pump during the whole electrolytic process, the electrolyte passes through the indium column through circulation for more times to purify the electrolyte, thus completing the dynamic purification of the electrolyte during the electrolysis process. The method of the invention is the method combining the static purification and the dynamic purification, purified the electrolyte, reduces the content of impurities of cadmium, tin, lead, bismuth, thallium and the like, and simplifies the work load of indium electrolysis.
Description
Technical field
The present invention relates to the purifying method of electrolytic solution in a kind of indium electrolysis process, comprise the static state purification of electrolyte just and the dynamic purification two portions in the electrolytic process.
Background technology
Material such as semi-conductor and thin film solar cell has very high requirement to indium metal purity, generally must reach more than 99.999%, even to 99.9999%.At present China produces thick indium and 99.99% smart indium, so the development of high purity indium and exploitation are urgent problems.The preparation method of high purity indium mainly contains chloride process, electrolytic refining process, vacuum distillation method, zone melting method etc., and in each purification techniques, electrolytic process is the most frequently used main method of indium purification.The factor that influences indium refining effect is a lot, and wherein the purity of indium electrolytic solution is one of major influence factors wherein.Purifying indium electrolytic solution, with trace impurity content such as the lead in the reduction electrolytic solution, tin, cadmium, thallium, bismuths, is a very crucial important step in the indium electrolysis process, and its purification effect directly influences the quality of electrolysis indium.At present, the purification of indium electrolytic solution generally concentrates on before the electrolysis, i.e. separately electrolytic solution is carried out purifying treatment before the electrolysis, and the static state that belongs to electrolytic solution purifies, and the lasting dynamic purification in the middle of electrolytic process is then from not mentioned.But in electrolytic process along with the indium anode dissolves gradually, some of them impurity also can be dissolved in the electrolytic solution thereupon, thereby pollution electrolytic solution, the refining effect variation that causes electrolysis later stage indium, thereby the effect of independent static purifying electrolysis liquid is limited, and carries out once more electrolytic words and also need again it is carried out static state purification if want to reuse this electrolytic solution in the once electrolytic back that finishes.The present invention breaks through the simple static thinking that purifies, and invents out a kind of electrolyte purification method that the static state purification is combined with dynamic purification, has not only guaranteed the purity of initial preparation electrolytic solution, and indium electrolytic solution is purified in electrolytic process at any time.Purify the method that combines with dynamic purification with static state and carry out purifying treatment, be enough to guarantee the purity of electrolytic solution, can directly reuse this electrolytic solution after once electrolytic finishes, need not carry out static state again and purify, can significantly reduce the workload of indium electrolysis process.
Static purifying method mainly contains the indium plate substitution method and the ion exchange resin method of purification etc., and wherein indium plate substitution method is for effective than the electropositive impurity of indium, and ion-exchange-resin process then is selective adsorption to foreign ion, needs the factor controlled more simultaneously.
Summary of the invention
The purpose of this invention is to provide a kind of more efficiently static method that combines with dynamic purification that purifies, come purifying electrolysis liquid at any time,, and simplify indium electrolysis workload greatly with the content of impurity such as cadmium, tin, lead, bismuth, thallium in the reduction indium electrolytic solution.
To achieve these goals, the present invention adopts following technical scheme:
The purifying method of electrolytic solution in a kind of indium electrolysis process, this method comprises the steps:
(1), to add concentration in indium electrolytic solution be 40～60vt% sulphuric acid soln, wherein, indium concentration is 50-100g/L in the described indium electrolytic solution, the purity of the used indium of electrolytic solution is more than the 90wt%;
(2), in above-mentioned mixed solution, be added dropwise to the soluble barium salt of 0.5-1.5mol/L, continuously stirring in the dropping process, wherein, soluble barium salt's add-on is to calculate according to the purity meter of indium concentration and used indium thereof in the indium electrolytic solution, and the add-on of sulphuric acid soln is to calculate according to 1～10 mole of % of sulfate ion mole number more than the barium ion mole number among the soluble barium salt, and the mixed solution after adding the soluble barium salt continues to stir 0.5～1h;
(3), filter then, make its solid-liquid separation, obtain the indium electrolytic solution after static the purification;
(4), static state is purified back electrolytic solution heating evaporation to initial volume;
(5), the import and export connecting tube of the relative both sides of electrolyzer is connected, on pipeline, be connected to recycle pump, sponge indium post, wherein, sponge indium post is formed by the sponge indium is housed in the quartz column, the electrolytic solution that static state is purified behind the heating evaporation is placed in the electrolyzer, the indium purity of the sponge indium in the sponge indium post is greater than used 1～2 rank of indium purity of electrolytic solution in the preparation electrolyzer, in whole electrolytic process, play circulation with recycle pump, thereby electrolytic solution passes through indium post purifying electrolysis liquid by repeatedly circulating, and finishes the dynamic purification of electrolytic solution in the electrolytic process.
In described step (2) and step (3), the sulfate ion mole number in the sulphuric acid soln that is added is more than 3～6 moles of % of the barium ion mole number among the soluble barium salt.
In described step (2), temperature is controlled to be-10 ℃～80 ℃.
In described step (2), temperature preferably is controlled to be 20 ℃～50 ℃.
In the purifying method of electrolytic solution, the sponge indium consumption in the described sponge indium post is the cumulative volume of the electrolytic solution in 20～200g/ liter * electrolyzer in indium electrolysis process of the present invention.
In the purifying method of electrolytic solution, the volume in the described quartz column is the cumulative volume of the electrolytic solution in 10～50ml/ liter * electrolyzer in indium electrolysis process of the present invention.
In the purifying method of electrolytic solution, the high ratio with the post footpath of the post of described quartz column is 5～15: 1 in indium electrolysis process of the present invention.
In the purifying method of electrolytic solution, the speed of circulation of described volume pump is the cumulative volume/0.2～2h of the electrolytic solution in the electrolyzer in indium electrolysis process of the present invention, and wherein, 0.2～2h is the time of the whole circulation primary of electrolytic solution in the electrolyzer.
The purifying method of indium electrolytic solution involved in the present invention comprises static the purification and dynamic purification two portions.Another fairly simple, practical, economic static purifying method promptly is provided, i.e. barium sulfate coprecipitation method is separated impurity such as a small amount of lead of existing in the solution of indium, tin, cadmium, thallium, bismuth.The method that dynamic purification is taked is in the middle of the electrolytic flow process of indium, the pillar that adds a high-purity sponge indium, in electrolytic process, with volume pump electrolytic solution is continued to beat to cycle through the indium post, not only belong to electropositive impurity, such as bismuth and most tin, lead etc., all can be on the sponge indium and be removed by replacement deposition, simultaneously other impurity also can be adsorbed on the sponge indium and remove, thereby have purified electrolytic solution.
The static purification is indium electrolytic solution for the new preparation of purifying treatment, is to utilize each impurity element and barium sulfate formation co-precipitation in the indium electrolytic solution, separates the metallic impurity that are difficult to remove in the indium electrolytic solution, and then will contain contamination precipitation and separate with solution of indium.Indium electrolytic solution commonly used at present has sulfuric acid system and hydrochloric acid system, carries out purifying treatment for all available this method of the indium electrolytic solution of any system.Precipitation agent is selected the soluble barium salt, as bariumchloride.The main body reaction formula is: Ba
2++ SO
4 2-=BaSO
4↓
Dynamic purification is that the purification in the electrolytic process is in order to solve the electrolyte contamination problem that the indium anode dissolution is caused in the electrolytic process, can guarantee the purity of electrolytic solution at any time, to improve the electrolytic refining effect of indium, simultaneously, electrolytic solution through dynamic purification can directly reuse after once electrolytic finishes, need not carry out static purifying treatment again, thereby reduce the workflow of indium electrolysis process.The way that dynamic purification is taked is in the middle of the electrolytic flow process of indium, add the pillar that high-purity sponge indium is housed, the used for electrolyte pump is beaten and is cycled through the indium post, can electropositive impurity will be belonged in the electrolytic solution by displacement, be deposited on the sponge indium such as bismuth and most tin, lead etc. and remove, other impurity also can be adsorbed on the sponge indium and remove, thereby reach the purpose of purifying electrolysis liquid.Indium electrolytic solution commonly used at present has sulfuric acid system and hydrochloric acid system, carries out dynamic purification for all available this method of the indium electrolytic solution of any system and handles.
Description of drawings
Fig. 1 is an indium electrolysis schematic flow sheet.
Fig. 2 is a sponge indium rod structure synoptic diagram.
Embodiment
Fig. 1 is an indium electrolysis schema.As shown in Figure 1, the sponge indium is packed in the quartz column, again electrolyzer 1, indium post 2, recycle pump 3 and the power supply electrolysis schematic flow sheet by Fig. 1 is connected after installing, start indium refining process.Wherein, indium rod structure synoptic diagram as shown in Figure 2, in Fig. 2, the indium post is formed by sponge indium 4 is housed in the quartz column, wherein, the end opening of indium post is the import 5 of electrolytic solution, and the suitable for reading of indium post is the outlet 6 of electrolytic solution, the outlet 6 of the import 5 of the electrolytic solution of indium post and electrolytic solution is switched to by pipeline inserts in the electrolysis flow process.
The purifying method of electrolytic solution has static the purification and dynamic purification two portions in the indium electrolysis process involved in the present invention, specifically implements by the following method:
One, the static purification
1, sulfation: to indium electrolytic solution (InSO
4Or InCl
2Solution, indium concentration is at 50-100g/L) in add 1: 1 (be water and vitriol oil volume ratio at 1: 1, the concentration of the vitriol oil is 98wt%) sulphuric acid soln, adding vitriolic mole number adds the mole number of precipitation agent according to needs and decides, can be more than 1～10 mole of % of precipitation agent, be preferably between 3～6 moles of %, to guarantee the enough acidity of electrolytic solution.
2, add precipitation agent: precipitation agent is selected the soluble barium salt, as BaCl
2With BaCl
2Be mixed with 0.5-1.5mol/L solution, dropwise add BaCl to electrolytic solution
2Solution continues to stir, and add-on is decided according to impurity level in the electrolytic solution.The purity of the used indium of one general configuration electrolytic solution is 90wt% or more than the 90wt%, pressing indium concentration 50-100g/L calculates, then impurity level can roughly provide in the 1L electrolytic solution, can provide the amount of required precipitation agent in view of the above, concrete numerical value can be controlled by following standard: according to foreign matter content different needs BaCl in the electrolytic solution
20.02 control between～the 0.2mol/L.
3, filter: continue to stir the 0.5-1h filtration after adding precipitation agent, make its solid-liquid separation, the indium electrolytic solution after being purified.
4, constant volume: will purify back electrolytic solution heating evaporation to initial volume, to guarantee indium concentration and test front and back electrolytic solution volume unanimity.
Except the amount of precipitation agent, the decontamination effect improving of electrolytic solution is subjected to the influence of temperature of reaction factor, can control between-10～80 ℃, preferably is controlled between 20～50 ℃.
Two, dynamic purification
1, the purity of sponge indium and consumption: the purity of sponge indium need exceed 1～2 rank of purity of the used indium of preparation electrolytic solution, the indium purity of even preparing electrolytic solution is lower than at 99.9% o'clock, the sponge indium is with 99.99% and above purity, if the indium of preparation electrolytic solution is 99.99% and above purity, then the sponge indium is with 99.999% and above purity.Its consumption is decided according to the amount of the indium electrolytic solution of required purification and the volume of used pillar, and every liter of electrolytic solution need be filled pillar more than 70% with 20～200g.This sponge indium can repeatedly reuse, but needs to guarantee to fill the pillar volume more than 70%.
2, fill out post: pillar can be used quartzy material, and its cumulative volume decide according to the volume of used electrolytic solution, and every liter of electrolytic solution need be with the pillar of 10～50ml, and post is high directly works in coordination with consideration with post, and ratio can be 5～15: between 1.The sponge indium is packed into behind the pillar, insert the electrolysis flow process.
3, the speed of circulation of volume pump: volume pump need be used acid proof pump, with time definite speed of circulation between 0.2～2h of the whole circulation primary of used electrolytic solution.
Below by specific embodiment technical scheme of the present invention is further described.The following examples are to further specify of the present invention, and do not limit the scope of the invention.
One, the static purification:
Get by purity is the InSO of 99.99% indium preparation
4Data before electrolytic solution 1L, indium concentration 100g/L wherein, foreign matter content see Table and handle in 1.Add the sulphuric acid soln 5.5mL of 50wt%, dropwise add 0.5mol/L BaCl while stirring for 50 ℃ at bath temperature
2Solution adds BaCl
2Amount be 0.05mol, add BaCl
2Continue behind the solution to stir half an hour, filter the InSO after purifying
4Solution, revaporization is settled to 1L, test.
Two, dynamic purification
With purity is that 99.999% sponge indium 150g packs in the quartz column of 60ml post height * post footpath=240 * 18, again electrolyzer, sponge indium post, recycle pump and power supply etc. is connected the indium refining process that starts by the electrolysis schematic flow sheet after installing.The electrolytic solution that dress 3L is crossed by above-mentioned static purifying treatment in the electrolyzer, the circulation pump speed is 8.5L/h, test electrolytic solution foreign matter content after refining finishes.
Table 1 indium electrolyte purification result table
| Foreign matter content (μ g/ml) | ?Pb | ?Sn | ?Cd | ?Tl | ?Bi |
| Before the processing | ?0.6 | ?1.1 | ?＜0.2 | ?0.5 | ?0.7 |
| After the static treatment (before the electrolysis) | ?＜0.1 | ?0.3 | ?＜0.1 | ?＜0.1 | ?＜0.1 |
| After the dynamichandling (after the electrolysis) | ?＜0.1 | ?＜0.1 | ?＜0.1 | ?＜0.1 | ?＜0.1 |
One, the static purification
Get InSO by thick indium (purity＜99%) preparation
4Data before electrolytic solution 1L, indium concentration 50g/L wherein, foreign matter content see Table and handle in 2.Add the sulphuric acid soln 17mL of 50wt%, dropwise add 1.5mol/L BaCl while stirring for 30 ℃ at bath temperature
2Solution adds BaCl
2Amount be 0.15mol, add BaCl
2Continue behind the solution to stir half an hour, refilter the InSO after purifying
4Solution, revaporization is settled to 1L, test.
Two, dynamic purification
With purity is that 99.99% sponge indium 300g packs in the quartz column of 135ml post height * post footpath=300 * 24, again electrolyzer, sponge indium post, recycle pump and power supply etc. is connected the indium refining process that starts by the electrolysis schematic flow sheet after installing.The electrolytic solution that dress 3L is crossed by above-mentioned static purifying treatment in the electrolyzer, the circulation pump speed is 6L/h, test electrolytic solution foreign matter content after refining finishes.
Table 2 indium electrolyte purification result table
| Foreign matter content (μ g/ml) | ?Pb | Sn | Cd | Tl | ?Bi |
| Before the processing | ?3.2 | 17.0 | 105.0 | 164.8 | ?0.1 |
| After the static treatment (before the electrolysis) | ?＜0.1 | 12.0 | 86.7 | 95.1 | ?＜0.1 |
| After the dynamichandling (after the electrolysis) | ?＜0.1 | 3.1 | 58.6 | 76.3 | ?＜0.1 |
Claims (8)
1. the purifying method of electrolytic solution in the indium electrolysis process, it is characterized in that: this method comprises the steps:
(1), to add concentration in indium electrolytic solution be 40～60vt% sulphuric acid soln, wherein, indium concentration is 50-100g/L in the described indium electrolytic solution, the purity of the used indium of electrolytic solution is more than the 90wt%;
(2), in above-mentioned mixed solution, be added dropwise to the soluble barium salt of 0.5-1.5mol/L, continuously stirring in the dropping process, wherein, soluble barium salt's add-on is to calculate according to the purity meter of indium concentration and used indium thereof in the indium electrolytic solution, and the add-on of sulphuric acid soln is to calculate according to 1～10 mole of % of sulfate ion mole number more than the barium ion mole number among the soluble barium salt, and the mixed solution after adding the soluble barium salt continues to stir 0.5～1h;
(3), filter then, make its solid-liquid separation, obtain the indium electrolytic solution after static the purification;
(4), static state is purified back electrolytic solution heating evaporation to initial volume;
(5), the import and export connecting tube of the relative both sides of electrolyzer is connected, on pipeline, be connected to recycle pump, sponge indium post, wherein, sponge indium post is formed by the sponge indium is housed in the quartz column, the electrolytic solution that static state is purified behind the heating evaporation is placed in the electrolyzer, the indium purity of the sponge indium in the sponge indium post is greater than used 1～2 order of magnitude of indium purity of electrolytic solution in the preparation electrolyzer, in whole electrolytic process, play circulation with recycle pump, thereby electrolytic solution passes through indium post purifying electrolysis liquid by repeatedly circulating, and finishes the dynamic purification of electrolytic solution in the electrolytic process.
2. the purifying method of electrolytic solution in the indium electrolysis process according to claim 1, it is characterized in that: in described step (2) and step (3), the sulfate ion mole number in the sulphuric acid soln that is added is more than 3～6 moles of % of the barium ion mole number among the soluble barium salt.
3. the purifying method of electrolytic solution in the indium electrolysis process according to claim 1 is characterized in that: in described step (2), temperature is controlled to be-10 ℃～80 ℃.
4. the purifying method of electrolytic solution in the indium electrolysis process according to claim 3 is characterized in that: in described step (2), temperature is controlled to be 20 ℃～50 ℃.
5. the purifying method of electrolytic solution in the indium electrolysis process according to claim 1, it is characterized in that: the sponge indium consumption in the described sponge indium post is decided according to the amount of the indium electrolytic solution of required purification and the volume of used quartz column, every liter of electrolytic solution need be filled more than 70% of quartz column volume with 20～200g.
6. the purifying method of electrolytic solution in the indium electrolysis process according to claim 1 is characterized in that: the cumulative volume in the described quartz column is decided according to the volume of used electrolytic solution, and every liter of electrolytic solution need be with the quartz column of 10～50ml.
7. the purifying method of electrolytic solution in the indium electrolysis process according to claim 6 is characterized in that: the high ratio with the post footpath of the post of described quartz column is 5～15: 1.
8. the purifying method of electrolytic solution in the indium electrolysis process according to claim 1, it is characterized in that: the speed of circulation of described volume pump is the cumulative volume/0.2～2h of the electrolytic solution in the electrolyzer, wherein, 0.2～2h is the time of the whole circulation primary of electrolytic solution in the electrolyzer.
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| CN104498993B (en) * | 2014-11-10 | 2017-03-22 | 来宾华锡冶炼有限公司 | Apparatus and method for reusing waste heat in indium electrolysis |
| CN111118545A (en) * | 2019-11-28 | 2020-05-08 | 广东先导稀材股份有限公司 | Preparation method of high-purity indium |
| CN113668017A (en) * | 2021-08-11 | 2021-11-19 | 广东长信精密设备有限公司 | High-purity indium apparatus for producing |
| CN114561670A (en) * | 2022-03-28 | 2022-05-31 | 云南锡业集团（控股）有限责任公司研发中心 | High-purity indium electrolysis device and electrolysis method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB938206A (en) * | 1960-07-12 | 1963-10-02 | Duisburger Kupferhuette | Process for the production of purest indium |
| CN1420184A (en) * | 2002-11-07 | 2003-05-28 | 长沙矿冶研究院 | Method for extracting refined indium from indium tin oxide waste material |
| CN101289712A (en) * | 2008-05-27 | 2008-10-22 | 株洲冶炼集团股份有限公司 | Process for recovering indium from indium-containing material |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB938206A (en) * | 1960-07-12 | 1963-10-02 | Duisburger Kupferhuette | Process for the production of purest indium |
| CN1420184A (en) * | 2002-11-07 | 2003-05-28 | 长沙矿冶研究院 | Method for extracting refined indium from indium tin oxide waste material |
| CN101289712A (en) * | 2008-05-27 | 2008-10-22 | 株洲冶炼集团股份有限公司 | Process for recovering indium from indium-containing material |
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