CN113265544B - Process for recovering indium from high-lead and high-indium soot by using full wet method - Google Patents
Process for recovering indium from high-lead and high-indium soot by using full wet method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/02—Working-up flue dust
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B58/00—Obtaining gallium or indium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention disclosesA process for recovering indium from high-lead and high-indium soot by a full wet method comprises (1) leaching indium-containing soot by low acid; (2) Carrying out high acid leaching on the low acid leaching residue obtained in the step (1); (3) Adding hydrogen peroxide into the low acid leaching solution obtained in the step (1) to purify and remove tin; (4) Adding reduced iron powder into the primary purified liquid obtained in the step (3) to purify and remove Fe 3+ (ii) a (5) Extracting the secondary purified liquid obtained in the step (4); (6) Carrying out acid washing and impurity removal on the loaded organic phase obtained in the step (5); (7) Carrying out back extraction on the acid-washed loaded organic phase obtained in the step (6); (8) Replacing the stripping solution obtained in the step (7) to obtain sponge indium; (9) Pressing the sponge indium obtained in the step (8) into a ball, and then casting by using an electric furnace to obtain crude indium; (10) And (4) washing and impurity removal of hydrofluoric acid and a regenerant are carried out on the indium-poor phase obtained in the step (7), and a hydrofluoric acid post-liquid, a regenerated liquid and a regenerated organic phase are obtained.
Description
Technical Field
The invention relates to an indium smelting process, in particular to a process for recovering indium from high-lead and high-indium soot by a full wet method.
Background
Indium belongs to rare and dispersive metal, the content of indium in the earth crust is very small, the indium is distributed extremely dispersedly, minerals with high indium content are difficult to find, and zinc, lead, copper and the like with similar properties are mostly symbiotic with the earth crust, so the indium is generally recovered and produced from byproducts of smelting zinc, lead, copper and the like. However, difficulties in separation and enrichment arise from the low indium content and many chemical similarities to the associated metal.
Currently, for the recovery of indium in the high lead-containing indium-containing soot, the leaching process generally adopted is sulfuric acid and oxidant (sodium chlorate) leaching or sulfating roasting and low acid leaching or hydrochloric acid leaching. In the sulfuric acid and sodium chloride leaching process, a large amount of chlorine gas is generated in the leaching process, the field operation environment is poor, and great potential safety hazards exist; the sulfating roasting and low acid leaching process can generate a large amount of sulfur dioxide in the roasting process, the field environment is poor, and the pressure of the sulfuric acid-making process can be increased; in the hydrochloric acid leaching process, the leaching solution with high indium content obtained by leaching cannot be directly used in the extraction process, indium precipitation slag is obtained by neutralization, the leaching solution with high indium content obtained by leaching the indium precipitation slag with sulfuric acid is used in the extraction process, and lead in the soot can be leached in a large amount to produce a lead complex in the hydrochloric acid leaching process, so that lead and indium in the soot cannot be effectively separated and recovered.
Disclosure of Invention
The invention discloses a process for recovering indium from high-lead and high-indium ash by a full-wet method, which utilizes sulfuric acid as a leaching agent, adds a small amount of hydrochloric acid to open lead sulfate packages generated in the leaching process, leads in the ash are not leached into slag, indium is leached into liquid, the effective separation of lead and indium in the ash is realized, and high-grade crude indium can be produced from indium-containing leachate through the working procedures of purification, extraction, back extraction, replacement, fusion casting and the like.
A process for recovering indium from high-lead and high-indium soot by a full wet method comprises the following specific steps:
(1) The low acid leaching process of the indium-containing soot comprises the following steps: adding concentrated sulfuric acid and concentrated hydrochloric acid into the indium-containing soot, fully reacting, and separating to obtain low acid leaching residue and low acid leaching liquid rich in indium;
(2) And (2) carrying out high acid leaching on the low acid leaching residue obtained in the step (1), wherein the process of leaching the low acid leaching residue with high acid is as follows: adding concentrated sulfuric acid and concentrated hydrochloric acid into the low-acid leaching residue, fully reacting, separating to obtain high-acid leaching residue and high-acid leaching liquid rich in indium, returning the obtained high-acid leaching liquid to the step (1) to serve as a base solution, washing the obtained high-acid leaching residue with the raffinate obtained in the step (5), returning the washed high-acid leaching residue to a lead system to recover lead, and returning washing water to the step (1) to serve as the base solution;
(3) Adding hydrogen peroxide into the low acid leaching solution obtained in the step (1) for purification, and then separating to obtain primary purification slag and primary purification solution rich in indium;
(4) Adding reduced iron powder into the primary purification liquid obtained in the step (3) for purification, and then separating to obtain secondary purification slag and secondary purification liquid which meets the requirement of an extraction process and is rich in indium;
(5) Extracting the secondary purified liquid obtained in the step (4), and then separating to obtain raffinate and a loaded organic phase;
(6) Carrying out acid washing impurity removal on the loaded organic phase obtained in the step (5), and then separating to obtain acid washing water and an acid washed loaded organic phase;
(7) Carrying out back extraction on the acid-washed loaded organic phase obtained in the step (6), and then separating to obtain an indium-poor phase and an indium-rich back extraction solution;
(8) Replacing the stripping solution obtained in the step (7) to obtain sponge indium;
(9) Pressing the sponge indium obtained in the step (8) into a ball, and then casting by using an electric furnace to obtain crude indium;
(10) And (4) sequentially carrying out hydrofluoric acid washing and regenerant washing on the indium-poor phase obtained in the step (7) to obtain hydrofluoric acid after-liquid, regenerated liquid and a regenerated organic phase.
Further, in the step (1), the concentration of the sulfuric acid initial acid is 100g/L-200g/L, the concentration of the hydrochloric acid initial acid is 2g/L-10g/L, the liquid-solid ratio of the hydrochloric acid initial acid to the indium-containing soot is 6-10, the reaction temperature is 80-90 ℃, the reaction time is 4-8h, and the concentration of the sulfuric acid in the low-acid leachate is controlled to be 40g/L-150g/L.
Further, in the step (2), the concentration of the sulfuric acid initial acid is 300g/L-400g/L, the concentration of the hydrochloric acid initial acid is 2g/L-10g/L, the liquid-solid ratio of the sulfuric acid initial acid to the indium-containing soot is 3-1, the reaction temperature is 80-90 ℃, and the reaction time is 4-8h.
Further, in the step (3), enough hydrogen peroxide is added, the reaction temperature is 50-60 ℃, the mixture is fully stirred in the purification process, and the tin content in the primary purification solution is controlled to be less than 0.8g/L.
And (3) further, in the step (4), adding sufficient iron powder, wherein the reaction temperature is normal temperature, fully stirring in the purification process, and completely reducing ferric ions in the primary purification solution into ferrous ions.
Further, in the step (5), the secondary purified liquid obtained in the step (4) is extracted, the extraction phase ratio of an organic phase/an aqueous phase (O/A) is 1 to 3, and the extracting agent is a mixed liquid of P204 and sulfonated kerosene, wherein the volume of P204 is 20 to 40 percent of the volume of the mixed liquid.
Further, in the step (6), the supported organic phase obtained in the step (5) is subjected to acid washing and impurity removal through sulfuric acid with the concentration of 1.5-2.0 mol/L.
Further, in the step (7), the stripping agent is hydrochloric acid, the acidity of the hydrochloric acid for stripping is 5-6 mol/L, and the stripping solution can be recycled when the indium content is lower than 35g/L in the stripping process.
Further, in the step (8), the strip liquor is replaced by a zinc sheet.
And further, in the step (9), briquetting the sponge indium obtained in the step (8) by using a briquetting machine, controlling the moisture content of the indium briquette to be 5% -10%, and then casting by using an electric furnace to obtain crude indium.
Further, in the step (10), the concentration of hydrofluoric acid for washing hydrofluoric acid is 100-130g/L, the concentration of a regenerant for washing the regenerant is 1.5-2.0 mol/L of a mixed solution of sulfuric acid and 5% -10% of oxalic acid, the indium-poor phase obtained in the step (7) is washed by hydrofluoric acid and the regenerant to remove impurities so as to obtain a regenerated organic phase, and the regenerated organic phase is returned to the extraction process for recycling.
The invention has the advantages that:
1. generally, lead content of lead-containing indium-containing soot is not higher than 25%, lead content of ring collection soot produced from a continuous copper removal furnace fluctuates between 40% and 60%, the lead content of the soot is high, a large amount of lead sulfate is generated in a sulfuric acid leaching process, and the wrapping of indium compounds in the soot is easy to form, so that the indium leaching rate is low, and the indium recovery rate is not high; through the leaching of the mixed acid liquor of concentrated sulfuric acid and concentrated hydrochloric acid, the lead sulfate package generated in the leaching process can be opened, the indium leaching rate in the leaching process can be improved, and meanwhile, the low-concentration hydrochloric acid is controlled, so that lead in the soot can not be leached and continuously remained in the slag, and the effective separation of lead and indium in the soot is realized;
2. the method is suitable for treating the high-lead indium-containing soot, the indium in the soot is leached with elements such as zinc, arsenic, cadmium, tin and the like into the solution, the high-lead indium-containing soot is leached by concentrated sulfuric acid and concentrated hydrochloric acid mixed acid solution, the leaching rate of the indium is high, the leaching rate of the lead is extremely low, the lead is remained in the slag, the effective separation of the lead and the indium in the soot is realized, the recovery rate of the indium can reach more than 95% by two-stage leaching, and high-grade crude indium with the indium grade of more than 99% can be produced;
3. the method utilizes sulfuric acid as a main leaching agent, does not need to add an oxidant, produces the high-indium-content feed liquid, and can directly enter an extraction process;
4. compared with the traditional process, the method eliminates the potential safety and environmental protection hazards caused by adding sodium chlorate or sulfating roasting.
Detailed Description
Example 1
A process for recovering indium from high-lead and high-indium soot by a full wet method comprises the following specific steps:
(1) The low acid leaching process of the indium-containing soot comprises the following steps: adding concentrated sulfuric acid and concentrated hydrochloric acid into the indium-containing soot, fully reacting, and separating to obtain low acid leaching residue and low acid leaching liquid rich in indium;
(2) And (2) carrying out high-acid leaching on the low-acid leaching residue obtained in the step (1), wherein the process of leaching the low-acid leaching residue with high acid is as follows: adding concentrated sulfuric acid and concentrated hydrochloric acid into the low-acid leaching residue, fully reacting, separating to obtain high-acid leaching residue and high-acid leaching liquid rich in indium, returning the obtained high-acid leaching liquid to the step (1) to serve as a base solution, washing the obtained high-acid leaching residue with the raffinate obtained in the step (5), returning the washed high-acid leaching residue to a lead system to recover lead, and returning washing water to the step (1) to serve as the base solution;
(3) Adding hydrogen peroxide into the low acid leaching solution obtained in the step (1) for purification, and then separating to obtain primary purification slag and primary purification solution rich in indium;
(4) Adding reduced iron powder into the primary purified liquid obtained in the step (3) for purification, and then separating to obtain secondary purification slag and secondary purified liquid which meets the requirement of an extraction process and is rich in indium;
(5) Extracting the secondary purified liquid obtained in the step (4), and then separating to obtain raffinate and a loaded organic phase;
(6) Carrying out acid washing impurity removal on the loaded organic phase obtained in the step (5), and then separating to obtain acid washing water and an acid washed loaded organic phase;
(7) Carrying out back extraction on the acid-washed loaded organic phase obtained in the step (6), and then separating to obtain an indium-poor phase and a back extraction solution rich in indium;
(8) Replacing the stripping solution obtained in the step (7) to obtain sponge indium;
(9) Pressing the sponge indium obtained in the step (8) into a ball, and then casting by using an electric furnace to obtain crude indium;
(10) And (4) sequentially carrying out hydrofluoric acid washing and regenerant washing on the indium-poor phase obtained in the step (7) to obtain hydrofluoric acid after-liquid, regenerated liquid and a regenerated organic phase.
In the step (1), the concentration of sulfuric acid initial acid is 200g/L, the concentration of hydrochloric acid initial acid is 2g/L, the liquid-solid ratio of the sulfuric acid initial acid to indium-containing soot is 6.
In the step (2), the concentration of sulfuric acid initial acid is 400g/L, the concentration of hydrochloric acid initial acid is 2g/L, the liquid-solid ratio of the sulfuric acid initial acid to the indium-containing soot is 3.
And (4) in the step (3), adding enough hydrogen peroxide, wherein the reaction temperature is 50 ℃, fully stirring in the purification process, and controlling the tin content in the primary purification liquid to be less than 0.8g/L.
And (4) adding enough iron powder at normal temperature in the step (4), fully stirring in the purification process, and reducing all ferric ions in the primary purification solution into ferrous ions.
And in the step (5), extracting the secondary purified liquid obtained in the step (4), wherein the extraction phase ratio of an organic phase/water phase (O/A) is 1.
And in the step (6), carrying out acid washing impurity removal on the loaded organic phase obtained in the step (5) by using sulfuric acid with the concentration of 1.5 mol/L.
In the step (7), the stripping agent is hydrochloric acid, and the acidity of the hydrochloric acid for stripping is 6mol/L.
And (8) replacing the stripping solution by a zinc sheet.
And (9) briquetting the sponge indium obtained in the step (8) by using a briquetting machine, controlling the moisture content of the indium briquette to be 5%, and then casting by using an electric furnace to obtain crude indium.
In the step (10), the concentration of hydrofluoric acid for washing hydrofluoric acid is 100g/L, the concentration of a regenerant for washing the regenerant is a mixed solution of 1.5mol/L sulfuric acid and 5% oxalic acid, the indium-poor phase obtained in the step (7) is washed by hydrofluoric acid and the regenerant to remove impurities so as to obtain a regenerated organic phase, and the regenerated organic phase is returned to the extraction process for recycling.
Example 2
A process for recovering indium from high-lead and high-indium soot by a full wet method comprises the following specific steps:
(1) The low acid leaching process of the indium-containing soot comprises the following steps: adding concentrated sulfuric acid and concentrated hydrochloric acid into the indium-containing soot, fully reacting, and separating to obtain low acid leaching residue and low acid leaching liquid rich in indium;
(2) And (2) carrying out high-acid leaching on the low-acid leaching residue obtained in the step (1), wherein the process of leaching the low-acid leaching residue with high acid is as follows: adding concentrated sulfuric acid and concentrated hydrochloric acid into the low-acid leaching residue, fully reacting, separating to obtain high-acid leaching residue and high-acid leaching solution rich in indium, returning the obtained high-acid leaching solution to the step (1) to serve as a base solution, washing the obtained high-acid leaching residue with raffinate obtained in the step (5), returning the washed high-acid leaching residue to a lead system to recover lead, and returning washing water to the step (1) to serve as the base solution;
(3) Adding hydrogen peroxide into the low acid leaching solution obtained in the step (1) for purification, and then separating to obtain primary purification slag and primary purification solution rich in indium;
(4) Adding reduced iron powder into the primary purified liquid obtained in the step (3) for purification, and then separating to obtain secondary purification slag and secondary purified liquid which meets the requirement of an extraction process and is rich in indium;
(5) Extracting the secondary purified liquid obtained in the step (4), and then separating to obtain raffinate and a loaded organic phase;
(6) Carrying out acid washing impurity removal on the loaded organic phase obtained in the step (5), and then separating to obtain acid washing water and an acid washed loaded organic phase;
(7) Carrying out back extraction on the acid-washed loaded organic phase obtained in the step (6), and then separating to obtain an indium-poor phase and an indium-rich back extraction solution;
(8) Replacing the stripping solution obtained in the step (7) to obtain sponge indium;
(9) Pressing the sponge indium obtained in the step (8) into a ball, and casting by using an electric furnace to obtain crude indium;
(10) And (4) sequentially carrying out hydrofluoric acid washing and regenerant washing on the indium-poor phase obtained in the step (7) to obtain a hydrofluoric acid post-liquid, a regenerated liquid and a regenerated organic phase.
In the step (1), the concentration of the sulfuric acid initial acid is 150g/L, the concentration of the hydrochloric acid initial acid is 8g/L, the liquid-solid ratio of the hydrochloric acid initial acid to the indium-containing soot is 8, the reaction temperature is 85 ℃, the reaction time is 6h, and the concentration of the sulfuric acid in the low-acid leachate is controlled to be 90g/L.
In the step (2), the concentration of sulfuric acid initial acid is 320g/L, the concentration of hydrochloric acid initial acid is 8g/L, the liquid-solid ratio of the sulfuric acid initial acid to the indium-containing soot is 4.
And (3) adding enough hydrogen peroxide at the reaction temperature of 60 ℃, fully stirring in the purification process, and controlling the tin content in the primary purification liquid to be less than 0.8g/L.
And (4) adding enough iron powder at normal temperature in the step (4), fully stirring in the purification process, and reducing all ferric ions in the primary purification solution into ferrous ions.
In the step (5), the secondary purified liquid obtained in the step (4) is extracted, the extraction phase ratio organic phase/aqueous phase (O/A) is 1.
And in the step (6), carrying out acid washing impurity removal on the loaded organic phase obtained in the step (5) by using sulfuric acid with the concentration of 1.8 mol/L.
In the step (7), the stripping agent is hydrochloric acid, and the acidity of hydrochloric acid for stripping is 5.5mol/L.
And (8) replacing the strip liquor by a zinc sheet.
And (9) briquetting the sponge indium obtained in the step (8) by a briquetting machine, controlling the moisture content of the indium briquette to be 8%, and then casting by using an electric furnace to obtain crude indium.
And (3) in the step (10), the concentration of hydrofluoric acid for washing hydrofluoric acid is 120g/L, the regenerant for washing the regenerant is a mixed solution of sulfuric acid and 7% oxalic acid, the indium-poor phase obtained in the step (7) is washed by hydrofluoric acid and washed by the regenerant to remove impurities so as to obtain a regenerated organic phase, and the regenerated organic phase is returned to the extraction process for recycling.
Example 3
A process for recovering indium from high-lead and high-indium soot by a full wet method comprises the following specific steps:
(1) The low acid leaching process of the indium-containing soot comprises the following steps: adding concentrated sulfuric acid and concentrated hydrochloric acid into the indium-containing soot, fully reacting, and separating to obtain low acid leaching residue and low acid leaching liquid rich in indium;
(2) And (2) carrying out high acid leaching on the low acid leaching residue obtained in the step (1), wherein the process of leaching the low acid leaching residue with high acid is as follows: adding concentrated sulfuric acid and concentrated hydrochloric acid into the low-acid leaching residue, fully reacting, separating to obtain high-acid leaching residue and high-acid leaching solution rich in indium, returning the obtained high-acid leaching solution to the step (1) to serve as a base solution, washing the obtained high-acid leaching residue with raffinate obtained in the step (5), returning the washed high-acid leaching residue to a lead system to recover lead, and returning washing water to the step (1) to serve as the base solution;
(3) Adding hydrogen peroxide into the low acid leaching solution obtained in the step (1) for purification, and then separating to obtain primary purification slag and primary purification solution rich in indium;
(4) Adding reduced iron powder into the primary purified liquid obtained in the step (3) for purification, and then separating to obtain secondary purification slag and secondary purified liquid which meets the requirement of an extraction process and is rich in indium;
(5) Extracting the secondary purified liquid obtained in the step (4), and then separating to obtain raffinate and a loaded organic phase;
(6) Carrying out acid washing impurity removal on the loaded organic phase obtained in the step (5), and then separating to obtain acid washing water and an acid washed loaded organic phase;
(7) Carrying out back extraction on the acid-washed loaded organic phase obtained in the step (6), and then separating to obtain an indium-poor phase and a back extraction solution rich in indium;
(8) Replacing the stripping solution obtained in the step (7) to obtain sponge indium;
(9) Pressing the sponge indium obtained in the step (8) into a ball, and casting by using an electric furnace to obtain crude indium;
(10) And (4) sequentially carrying out hydrofluoric acid washing and regenerant washing on the indium-poor phase obtained in the step (7) to obtain hydrofluoric acid after-liquid, regenerated liquid and a regenerated organic phase.
In the step (1), the concentration of the sulfuric acid initial acid is 100g/L, the concentration of the hydrochloric acid initial acid is 10g/L, the liquid-solid ratio of the hydrochloric acid initial acid to the indium-containing soot is 10, the reaction temperature is 90 ℃, the reaction time is 8h, and the concentration of the sulfuric acid in the low-acid leaching solution is controlled to be 40g/L.
In the step (2), the concentration of the sulfuric acid initial acid is 300g/L, the concentration of the hydrochloric acid initial acid is 10g/L, the liquid-solid ratio of the sulfuric acid initial acid to the indium-containing soot is 5, the reaction temperature is 90 ℃, and the reaction time is 8h.
And (4) in the step (3), adding enough hydrogen peroxide, wherein the reaction temperature is 60 ℃, fully stirring in the purification process, and controlling the tin content in the primary purification liquid to be less than 0.8g/L.
And (4) adding enough iron powder at normal temperature in the reaction process, fully stirring in the purification process, and completely reducing ferric ions in the primary purification solution into ferrous ions.
In the step (5), the secondary purified liquid obtained in the step (4) is extracted, the extraction phase ratio organic phase/aqueous phase (O/A) is 1.
And in the step (6), carrying out acid washing impurity removal on the loaded organic phase obtained in the step (5) by using sulfuric acid with the concentration of 2.0 mol/L.
In the step (7), the stripping agent is hydrochloric acid, and the acidity of the hydrochloric acid for stripping is 5mol/L.
And (8) replacing the strip liquor by a zinc sheet.
And (9) briquetting the sponge indium obtained in the step (8) by using a briquetting machine, controlling the moisture content of the indium briquette to be 10%, and then casting by using an electric furnace to obtain crude indium.
And (3) in the step (10), the concentration of hydrofluoric acid for washing hydrofluoric acid is 130g/L, the regenerant for washing the regenerant is a mixed solution of sulfuric acid and 10% oxalic acid, the indium-poor phase obtained in the step (7) is washed by hydrofluoric acid and washed by the regenerant to remove impurities so as to obtain a regenerated organic phase, and the regenerated organic phase is returned to the extraction process for recycling.
Comparative example 1
The process for recovering indium from high-lead and high-indium soot by a full wet method is the same as that of the example 2 except that hydrochloric acid is not added in the steps (1) and (2).
Comparative example 2
The process for recovering indium from high-lead and high-indium soot by a total wet method is the same as that of the example 2 except that in the step (1), the concentration of sulfuric acid initial acid is 150g/L, and the concentration of hydrochloric acid initial acid is 1g/L in the step (1).
Comparative example 3
The process for recovering indium from high-lead and high-indium soot by a total wet method is the same as that of the example 2 except that in the step (1), the concentration of sulfuric acid initial acid is 150g/L, and the concentration of hydrochloric acid initial acid is 12g/L in the step (1).
Comparative example 4
The process for recovering indium from high-lead and high-indium soot by a total wet method is the same as that of example 2, wherein the concentration of sulfuric acid initial acid is 320g/L, and the concentration of hydrochloric acid initial acid is 1g/L in the step (2).
Comparative example 5
The process of recovering indium from high lead and high indium ash in the wet process includes the step (2), the initial sulfuric acid concentration of 320g/L and the initial hydrochloric acid concentration of 12g/L, and the rest is the same as that in example 2.
Detection and analysis:
in the above examples and comparative examples, the ring-collected soot produced from the continuous copper-removing furnace was used as a raw material, and the detection was performed according to "test and operation rules for rare and precious branch works samples", and the lead content was 52.3%, and the indium content was 2.1%.
And detecting the crude indium grade prepared by each example and comparative example, calculating the indium recovery rate, and detecting the integral leaching rate of indium and the integral leaching rate of lead in the low-acid leachate and the high-acid leachate of each example and comparative example.
As can be seen from the table above, the sulfuric acid is used as the leaching agent of the high-lead indium-containing soot, a small amount of hydrochloric acid is added to open the lead sulfate coating generated in the leaching process, lead and indium in the soot can be effectively separated, the produced indium-rich feed liquid can produce crude indium with indium content of more than 99% through the procedures of purification, extraction, replacement and casting, and the indium recovery rate can reach more than 95%; the use amount of the hydrochloric acid is too large, so that the integral dissolution rate of the lead is increased, and the subsequent separation is not facilitated; if the amount of hydrochloric acid is too small, the dissolution of indium is not promoted well, resulting in a low indium recovery rate.
And finally: the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A process for recovering indium from high-lead and high-indium soot by a full wet method is characterized by comprising the following steps: the process specifically comprises the following steps:
(1) The low acid leaching process of the indium-containing soot comprises the following steps: adding concentrated sulfuric acid and concentrated hydrochloric acid into the indium-containing soot, fully reacting, and separating to obtain low acid leaching residue and low acid leaching liquid rich in indium;
the concentration of the sulfuric acid initial acid is 100g/L-200g/L, the concentration of the hydrochloric acid initial acid is 2g/L-10g/L, the liquid-solid ratio of the hydrochloric acid initial acid to the indium-containing soot is 6-10, the reaction temperature is 80-90 ℃, the reaction time is 4-8h, and the concentration of the sulfuric acid in the low-acid leaching solution is controlled to be 40g/L-150g/L;
(2) And (2) carrying out high acid leaching on the low acid leaching residue obtained in the step (1), wherein the process of leaching the low acid leaching residue with high acid is as follows: adding concentrated sulfuric acid and concentrated hydrochloric acid into the low-acid leaching residue, fully reacting, separating to obtain high-acid leaching residue and high-acid leaching solution rich in indium, returning the obtained high-acid leaching solution to the step (1) to serve as a base solution, washing the obtained high-acid leaching residue with raffinate obtained in the step (5), returning the washed high-acid leaching residue to a lead system to recover lead, and returning washing water to the step (1) to serve as the base solution;
the concentration of the sulfuric acid initial acid is 300g/L-400g/L, the concentration of the hydrochloric acid initial acid is 2g/L-10g/L, the liquid-solid ratio of the sulfuric acid initial acid to the indium-containing soot is 3-5;
(3) Adding hydrogen peroxide into the low acid leaching solution obtained in the step (1) for purification, and then separating to obtain primary purification slag and primary purification solution rich in indium;
(4) Adding reduced iron powder into the primary purification liquid obtained in the step (3) for purification, and then separating to obtain secondary purification slag and secondary purification liquid which meets the requirement of an extraction process and is rich in indium;
(5) Extracting the secondary purified liquid obtained in the step (4), and then separating to obtain raffinate and a loaded organic phase;
(6) Carrying out acid washing impurity removal on the loaded organic phase obtained in the step (5), and then separating to obtain acid washing water and an acid washed loaded organic phase;
(7) Carrying out back extraction on the acid-washed loaded organic phase obtained in the step (6), and then separating to obtain an indium-poor phase and an indium-rich back extraction solution;
(8) Replacing the stripping solution obtained in the step (7) to obtain sponge indium;
(9) Pressing the sponge indium obtained in the step (8) into a ball, and casting by using an electric furnace to obtain crude indium;
(10) And (4) sequentially carrying out hydrofluoric acid washing and regenerant washing on the indium-poor phase obtained in the step (7) to obtain a hydrofluoric acid post-liquid, a regenerated liquid and a regenerated organic phase.
2. A process for recovering indium from high-lead and high-indium soot by the all-wet method according to claim 1, which comprises the following steps: and (3) adding enough hydrogen peroxide at the reaction temperature of 50-60 ℃, fully stirring in the purification process, and controlling the tin content in the primary purification solution to be less than 0.8g/L.
3. The all-wet method for recovering indium from high-lead and high-indium soot according to claim 1, wherein the all-wet method comprises the following steps: and (4) adding enough iron powder at normal temperature in the reaction process, fully stirring in the purification process, and completely reducing ferric ions in the primary purification solution into ferrous ions.
4. A process for recovering indium from high-lead and high-indium soot by the all-wet method according to claim 1, which comprises the following steps: in the step (5), the secondary purified liquid obtained in the step (4) is extracted, the extraction phase ratio of an organic phase/a water phase is 1-5, the extracting agent is a mixed liquid of P204 and sulfonated kerosene, wherein the volume of the P204 is 20-40% of the volume of the mixed liquid.
5. The all-wet method for recovering indium from high-lead and high-indium soot according to claim 1, wherein the all-wet method comprises the following steps: and in the step (6), carrying out acid washing impurity removal on the loaded organic phase obtained in the step (5) by using sulfuric acid with the concentration of 1.5-2.0 mol/L.
6. The all-wet method for recovering indium from high-lead and high-indium soot according to claim 1, wherein the all-wet method comprises the following steps: in the step (7), the stripping agent is hydrochloric acid, the acidity of the hydrochloric acid for stripping is 5-6 mol/L, and the stripping solution can be recycled when the indium content is lower than 35g/L in the stripping process.
7. The all-wet method for recovering indium from high-lead and high-indium soot according to claim 1, wherein the all-wet method comprises the following steps: and (8) replacing the stripping solution by a zinc sheet.
8. The all-wet method for recovering indium from high-lead and high-indium soot according to claim 1, wherein the all-wet method comprises the following steps: and (9) briquetting the sponge indium obtained in the step (8) by using a briquetting machine, controlling the moisture content of the indium briquette to be 5-10%, and then casting by using an electric furnace to obtain crude indium.
9. A process for recovering indium from high-lead and high-indium soot by the all-wet method according to claim 1, which comprises the following steps: in the step (10), the concentration of hydrofluoric acid for washing hydrofluoric acid is 100-130g/L, the concentration of a regenerant for washing the regenerant is a mixed solution of sulfuric acid and 5% -10% oxalic acid, the concentration of the sulfuric acid is 1.5-2.0 mol/L, the indium-poor phase obtained in the step (7) is washed by hydrofluoric acid and the regenerant to remove impurities to obtain a regenerated organic phase, and the regenerated organic phase is returned to the extraction process for recycling.
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