CN102899687A - Separation and extraction process for crude lead containing indium - Google Patents
Separation and extraction process for crude lead containing indium Download PDFInfo
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- CN102899687A CN102899687A CN2012104528883A CN201210452888A CN102899687A CN 102899687 A CN102899687 A CN 102899687A CN 2012104528883 A CN2012104528883 A CN 2012104528883A CN 201210452888 A CN201210452888 A CN 201210452888A CN 102899687 A CN102899687 A CN 102899687A
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Abstract
The invention relates to a process for extracting indium from crude lead containing indium by adopting an electrolysis-extraction method, particularly relates to a separation and extraction process for crude lead containing indium, and belongs to the technical field of non-ferrous metal smelting. The separation and extraction process comprises the following processing steps: (1) casting the crude lead containing indium into an anode plate for electrolysis in a silicofluoric acid lead medium, with the lead ion concentration of 40-80g/L, the acidity of silicofluoric acid of 80-120g/L, and the current density of 80-120A/m2; (2) when the concentration of indium in electrolyte reaches 30-60g/L, pumping out the electrolyte for extraction and reverse extraction, and separating indium from zinc through the displacement of working procedures, with extraction liquid being mixture of P204 and sulfonated kerosene, and the dosage of the extraction liquid being 25-20% of the volume of the pumped electrolyte; and (3) precipitating tin and lead on a cathode, and feeding anode slime into an anode slime treatment system for recycling valuable metals in the anode slime. The separation and extraction process abandons conventional slag formation through oxidation in a harsh operating environment, is conducive to solving the problem of waste water and waste residue discharge, is safe in production, and can significantly improve the recovery rate of the indium and reduce the processing cost.
Description
Technical field
The present invention relates to adopt electrolysis---extracting process belongs to the non-ferrous metal metallurgy technical field from the technique of extracting indium from indium-containing blister lead.
Background technology
Contain 0.001～0.1% indium in the plumbous zinc ore in some places of China, in the pyrometallurgy of zinc process, indium mainly is enriched in the zinc metallurgy by-product lead bullion, and content is generally between 0.5～5%.Indium-containing crude lead becomes the important indium raw material of carrying, and China's indium output has the considerable pyrometallurgy of zinc that comes from.The tradition indium-extracting process is the lead bullion oxidative slagging, and indium enters in the oxidation scum, and scum silica frost is through acidleach, and indium enters solution, then through extraction, extracts thick indium, and the producer of carrying indium at present from the zinc metallurgy lead bullion adopts this technique substantially.This technique weak point is, need to consume a large amount of alkali during oxidative slagging, operating environment is poor, harm large (plumbous oxide flue dust), during acidic leaching, need repeatedly to leach, put forward the indium total recovery and only can reach 92%, extract fluorine chlorion that sulfuric acid that later raffinate contains 20～60g/L adds and a large amount of heavy metal ion, it is high to process the waste water cost, and it is qualified to be difficult to processing, along with the enhancing of Environmental Protection in China consciousness, the law enforcement for environmental protection dynamics has been strengthened in many places, does not allow trade effluent to discharge, traditional indium factory of carrying has run into the environmental protection bottleneck, even is forced to stop factory.
Summary of the invention
The objective of the invention is the problems referred to above for traditional technology, the recovery technique of indium in a kind of indium-containing crude lead is provided, abandoned the abominable oxidative slagging of traditional operation environment, be conducive to solve waste water and waste sludge discharge problem, production safety can significantly improve the rate of recovery of indium, cuts down finished cost.
Realize that the technical scheme that purpose of the present invention adopts is: 1. indium-containing crude lead is cast into positive plate electrolysis in fluosilicic lead plumbate medium, plumbum ion concentration is 40～80g/L, silicofluoric acid acidity 80～120g/L, current density 80～120A/ ㎡; 2. when indium concentration reaches 30～60g/L in the electrolytic solution, extract electrolytic solution out and extract, back extraction, the displacement operation is extracted indium, and the extraction liquid organic phase is the mixed solution of P204 and sulfonated kerosene, extracts consumption for extracting 25～20% of electrolytic solution volume out at every turn; 3. tin and lead are separated out at negative electrode, and the anode sludge is sent into ANODE SLIME TREATMENT system recoveries valuable metal wherein.
Temperature during described electrolysis is 30～43 ℃, adds hydrochloric acid, ox glue and wooden calcium sulfonate in the electrolytic process, and every day 1～2 time, addition is that hydrochloric acid 1L/t is plumbous, and ox glue 0.8kg/t is plumbous, and 1.5 kg/t of wooden calcium sulfonate are plumbous.
Should be first to the bath composition analysis before extraction of indium, correspondence extracts after removing the metal ion that affects the indium extraction again, and the P204 in the extraction liquid and sulfonated kerosene volume ratio are 3:7, and raffinate returns in the electrowinning process and recycles.
The replacement cycle of negative electrode is 3～4 days, cleans the water of cathode and anode and the water of the washing anode sludge and recycles as the electrolytic solution make up water.
In above-mentioned technique of the present invention, lead metal during energising in the anode can be easy to enter solution, at negative electrode, plumbous and the tin close with plumbous current potential is separated out at pole plate, carrying out along with electrolysis, indium is constantly enrichment in containing lead electrolytic solution, and when indium concentration touched the mark, extraction electrolytic solution carried out extracting process and carries indium.Need electrolytic solution is carried out pre-treatment before extraction of indium, removing affects some metal ion that extracts in the electrolytic solution that normally carries out, and for example adds reagent, and corresponding metal is removed from solution with coprecipitation mode, and then electrolytic solution just can carry out extracting operation.Horizontal extraction process is adopted in extraction, because electrolytic solution contains indium concentration far above the solution of traditional method, so the extraction liquid volume significantly is lower than traditional method.Raffinate medium after the extraction still contains silicofluoric acid, a small amount of Cl that brings in the extraction process
-, F
-Can not exert an influence to plumbous electrolysis, raffinate can return electrolysis.Also contain the negative foreign ion of current potential in the raffinate, such as tin ion, zine ion, cadmium ion etc., tin can be separated out at negative electrode with plumbous, can enrichment in electrolytic solution, zinc, cadmium, current potential is lower, and content is lower in the lead bullion, and allowed higher concentration to be present in the electrolytic solution and can not affect electrolysis normally to carry out, can circulate the long duration.Raffinate adopts the way of electrodeposition after removing lead, remove a part of foreign ion after, raffinate can be circulated in the electrolysis again for a long time.Owing to kept higher suitable temp in the electrolytic process, electrolytic solution moisture has volatilization, clean the water of anode and cathode and the water of the washing anode sludge and can be used as the electrolytic solution make up water, thereby do not produce efflux wastewater, the washing water that produce in the technique, technique itself just can consume, and contained metal ion reclaims thereupon.85% of indium content enters into electrolytic solution in this technique lead bullion, be recycled by extraction, remaining 15% indium is stayed in the anode sludge with alloy form, the recovery of indium can be adopted full wet process (the applicant has patent to declare in addition) in the anode sludge, and valuable metal indium wherein, copper, bismuth, antimony, tin, silver, lead all are recycled.
Compare with traditional slagging process, beneficial effect of the present invention is as follows:
1. operating environment is improved, and traditional slag making has a large amount of plumbous oxide airborne dusts, and environment and operator are endangered greatly.
2. wastewater flow rate reduces more than 95%, the waste water source of traditional technology maximum is raffinate, this solution contains the heavy metal ion such as the sulfuric acid of 20～60g/L and a large amount of antimony, arsenic, iron, lead, cadmium, copper, zinc, tin, and the F that brings in the reagent that adds for the leaching yield that improves indium and the extraction process
-, Cl
-Plasma, processing raffinate needs higher expense, can produce a large amount of outer draining and waste residue.This technique, the liquor capacity during extraction only are 1/30～1/150 of traditional extraction liquid, and raffinate can all return electrolysis, do not produce waste water.Have unavoidably the evaporating, emitting, dripping or leaking of liquid or gas phenomenon in the production, because electrolytic solution value is higher, itself is small, during technological design, consider recvery facility.
3. be electrochemical dissolution owing to indium, power consumption is low, and expense is few, and traditional technology is through oxidative slagging, repeatedly acidleach, expense is higher, and processing one ton of lead bullion, to produce thick indium expense only be half of traditional technology, and lead is that the trade mark is plumbous, and tin is that content is about 20% tin lead skim, and metal values significantly promotes.
4. metal recovery rate obviously improves, and the total yield of indium can reach more than 96%.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
Embodiment 1(carries out in the laboratory): indium-containing crude lead 395.5kg, its composition are Pb90.8%, In2.98%, Cu0.13%, Zn0.08%, Sn4.17%, Ag3366g/t, lead bullion is cast positive plate, and pure lead is that negative plate carries out electrolysis, electrolytic condition, current density 100～120A/ ㎡, 38～42 ℃ of electrolysis temperatures, plumbum ion concentration 50～70g/L, free acid 100～80g/L, add wooden calcium sulfonate every day, ox glue, hydrochloric acid, cathode deposition period 4 days is through 10 cycle electrolysis, surplus anode scrap 107.25kg, the actual lead bullion 288.25kg that drops into, product contains 195 liters of indium electrolytic solution, on average contains indium 37.66g/L, the each extraction contains indium electrolytic solution 25%, through extracting front pre-treatment, get thick indium 7.290kg after the extraction, contain indium 99.0%.Raffinate does not cause detrimentally affect as circulation of elecrolyte four times to electrolysis, and get anode sludge 13.36kg, content: Pb 8.04%, and In 19.32%, and Ag 9.66%, Sn3.54%, Cu2.08%, Bi20.0%, Sb20.0%.From the electrolysis result, lead bullion drops into the indium that indium 8.570kg enters electrolytic solution altogether 85.69%, and entering anode sludge indium has 14.53%, recovery of extraction 98.28%, total yield 98.74%.Be that 2 ﹟ electricity is plumbous behind the cathode sheets ingot casting, the ingot casting slag is stanniferous 28.36% slicker solder slag.Lead recovery 98.65%.
Embodiment 2(carries out in this technique demonstration plant at 600 ton/years of lead): actual 49.274 tons of the lead bullion that drop into, its composition: Pb 91.31%, In3.156%, Ag4316g/T, Sn 4.145%, and lead bullion is cast positive plate, and electricity lead carries out electrolysis for negative plate.Electrolytic condition: current density 90～110A/ ㎡, 35～40 ℃ of electrolysis temperatures, plumbum ion concentration 40～60g/L, free acid 90～110g/L.Add wooden calcium sulfonate, ox glue, hydrochloric acid twice every day, cathode deposition period 4 days～3 days, through 15 cycle electrolysis, processing contains indium electrolytic solution 42m3, on average contain indium 32g/L, the each extraction contains indium electrolytic solution 20%, and electrolytic solution is through extracting front pre-treatment, and thick indium contains indium 1254.185kg after the extraction, electrolytic solution and intermediate material contain indium 61.804kg, get anode sludge 2257.68kg, grade Pb 11.26%, In9.43%, Ag9.98%, Sn6.1% from the electrolysis result, drops into indium 1555.087kg altogether, enter electrolytic solution indium 86.43%, enter anode sludge indium 13.69%, recovery of extraction 97.86%, total yield 98.27%.Be that the plumbous part of 2 ﹟ electricity reaches 1 ﹟ electricity lead behind the cathode sheets ingot casting, the ingot casting slag is stanniferous 30.17% slicker solder slag.Lead recovery 98.81%.
Embodiment 3(carries out in the laboratory): indium-containing crude lead 186.27kg, its composition are Pb88.92%, In4.58%, Cu0.56%, Zn0.06%, Sn4.28%, Ag3157g/t, lead bullion is cast positive plate, and electricity lead carries out electrolysis, electrolytic condition for negative plate, current density 80～100A/ ㎡, 30～35 ℃ of electrolysis temperatures, plumbum ion concentration 60～80g/L, free acid 100～120g/L, add wooden calcium sulfonate every day, ox glue, hydrochloric acid, cathode deposition period 4 days is through 6 cycle electrolysis, surplus anode scrap 55.81kg, the actual lead bullion 130.46kg that drops into, product contains 88 liters of indium electrolytic solution, on average contains indium 57.61g/L, the each extraction contains indium electrolytic solution 25%, through extracting front pre-treatment, get thick indium 5.072kg after the extraction, contain indium 98.23%.Raffinate is as circulation of elecrolyte three times.Get anode sludge 6.784kg, content: Pb 8.92%, In 13.27%, and Ag 6.11%, Sn3.07%, Cu9.97%, Bi14.30%, Sb24.89%.From the electrolysis result, lead bullion drops into the indium that indium 5.975kg enters electrolytic solution altogether 84.85%, and entering anode sludge indium has 15.07%, recovery of extraction 98.27%, total yield 98.45%.Be that 2 ﹟ electricity is plumbous behind the cathode sheets ingot casting, the ingot casting slag is stanniferous 29.03% slicker solder slag.Lead recovery 97.84%.
Annotate: enter the indium of electrolytic solution and enter anode sludge indium sum and be not equal to 100%, be the sample examination analytical error.
Claims (4)
1.. the separation-extraction technology of an indium-containing crude lead is characterized in that: 1. indium-containing crude lead is cast into positive plate electrolysis in fluosilicic lead plumbate medium, plumbum ion concentration is 40～80g/L, silicofluoric acid acidity 80～120g/L, current density 80～120A/ ㎡; 2. when indium concentration reaches 30～60g/L in the electrolytic solution, extract electrolytic solution out and extract, back extraction, the displacement operation is extracted indium, and the extraction liquid organic phase is the mixed solution of P204 and sulfonated kerosene, extracts consumption for extracting 25～20% of electrolytic solution volume out at every turn; 3. tin and lead are separated out at negative electrode, and the anode sludge is sent into ANODE SLIME TREATMENT system recoveries valuable metal wherein.
2. press the separation-extraction technology of indium-containing crude lead claimed in claim 1, it is characterized in that: the temperature during electrolysis is 35～43 ℃, add hydrochloric acid, ox glue and wooden calcium sulfonate in the electrolytic process, every day 1～2 time, addition is: hydrochloric acid 1L/t is plumbous, ox glue 0.8kg/t is plumbous, and 1.5 kg/t of wooden calcium sulfonate are plumbous.
3. press the separation-extraction technology of indium-containing crude lead claimed in claim 2, it is characterized in that: before the extraction of indium first to the bath composition analysis, correspondence extracts after removing the metal ion that affects the indium extraction again, P204 in the extraction liquid and sulfonated kerosene volume ratio are 3:6～8, and raffinate returns in the electrowinning process and recycles.
4. by the separation-extraction technology of indium-containing crude lead claimed in claim 2, it is characterized in that: the replacement cycle of negative electrode is 3～4 days, cleans the water of cathode and anode and the water of the washing anode sludge and recycles as the electrolytic solution make up water.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103266226A (en) * | 2013-04-27 | 2013-08-28 | 中南大学 | Method for extracting silver from silver-containing zinc concentrate and improving quality of zinc concentrate |
| CN104562085A (en) * | 2014-12-22 | 2015-04-29 | 芜湖金龙模具锻造有限责任公司 | Crude lead electrolytic refining method |
| CN104562084A (en) * | 2014-12-22 | 2015-04-29 | 芜湖金龙模具锻造有限责任公司 | Method for preparing electrolytic solution for refining lead bullion |
| CN109055744A (en) * | 2018-09-25 | 2018-12-21 | 中南大学 | A method of the extraction of indium from the methane sulfonic acid lead solution containing indium |
| CN109371256A (en) * | 2018-11-29 | 2019-02-22 | 大余明发矿业有限公司 | A kind of lead reclaimer and its lead recovery process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157991A (en) * | 2007-11-19 | 2008-04-09 | 仁化县银海有色金属综合回收有限公司 | Production method for extracting indium from indium-containing blister lead |
| CN101333605A (en) * | 2007-06-28 | 2008-12-31 | 深圳市中金岭南有色金属股份有限公司韶关冶炼厂 | Technology for extracting indium from indium-rich bottom lead |
| CN101597690A (en) * | 2009-06-20 | 2009-12-09 | 永兴县元泰应用材料有限公司 | The method of recycling multiple precious metals from anode mud |
| US20100167077A1 (en) * | 2007-05-23 | 2010-07-01 | Votorantim Metais Zinco S.A. | Process for producing pure metallic indium from zinc oxide and/or solution containing the metal |
-
2012
- 2012-11-13 CN CN2012104528883A patent/CN102899687A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100167077A1 (en) * | 2007-05-23 | 2010-07-01 | Votorantim Metais Zinco S.A. | Process for producing pure metallic indium from zinc oxide and/or solution containing the metal |
| CN101333605A (en) * | 2007-06-28 | 2008-12-31 | 深圳市中金岭南有色金属股份有限公司韶关冶炼厂 | Technology for extracting indium from indium-rich bottom lead |
| CN101157991A (en) * | 2007-11-19 | 2008-04-09 | 仁化县银海有色金属综合回收有限公司 | Production method for extracting indium from indium-containing blister lead |
| CN101597690A (en) * | 2009-06-20 | 2009-12-09 | 永兴县元泰应用材料有限公司 | The method of recycling multiple precious metals from anode mud |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103266226A (en) * | 2013-04-27 | 2013-08-28 | 中南大学 | Method for extracting silver from silver-containing zinc concentrate and improving quality of zinc concentrate |
| CN104562085A (en) * | 2014-12-22 | 2015-04-29 | 芜湖金龙模具锻造有限责任公司 | Crude lead electrolytic refining method |
| CN104562084A (en) * | 2014-12-22 | 2015-04-29 | 芜湖金龙模具锻造有限责任公司 | Method for preparing electrolytic solution for refining lead bullion |
| CN109055744A (en) * | 2018-09-25 | 2018-12-21 | 中南大学 | A method of the extraction of indium from the methane sulfonic acid lead solution containing indium |
| CN109371256A (en) * | 2018-11-29 | 2019-02-22 | 大余明发矿业有限公司 | A kind of lead reclaimer and its lead recovery process |
| CN109371256B (en) * | 2018-11-29 | 2023-09-22 | 大余明发矿业有限公司 | Lead recovery equipment and lead recovery process thereof |
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Application publication date: 20130130 |