CN1177014A - Method for obtg. gold, silver and other noble metals from anode and contg. high concn. arsenic and lead - Google Patents
Method for obtg. gold, silver and other noble metals from anode and contg. high concn. arsenic and lead Download PDFInfo
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- CN1177014A CN1177014A CN96112638A CN96112638A CN1177014A CN 1177014 A CN1177014 A CN 1177014A CN 96112638 A CN96112638 A CN 96112638A CN 96112638 A CN96112638 A CN 96112638A CN 1177014 A CN1177014 A CN 1177014A
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Abstract
In the invented method we use NaOH to extract high As, Pb anode mud and use composite extracting agent to recover gold from the solution. It is characterized by that As and Pb are removed from anode mud under conditions of solid : liquid =1:8-20, and temp. 80-90 deg. C, the NaOH used is 100-300 g/L. After removal of As and Pb, prior art rechnology is used to recover gold, silver and other noble metal. The invented method possesses the advantages of high in metal rocovery, easy in operation, simple in equipment and no pollution to environment.
Description
The present invention relates to from anode mud with high As and Pb wet method and extract the method for gold and silver and valuable metal.
High-arsenic material, the particularly high arsenic anode sludge are the important source material of non-ferrous metal and precious metal, and dearsenification is a recognized techniques difficult point of handling such material always.Handle such material with prior art (oxidizing roasting, pressurization leaching, bacterium leaching, acidic oxidation leach) and carry out dearsenification, often have that environmental pollution is serious, equipment is difficult to solve, long, the high temporary transient insoluble problem of cost of cycle, therefore, how a lot of in the world countries all solve this difficult problem in research, " precious metal ", 1992,13 (2), P.30-34 reported a kind of " the high pressure dearsenification of the lead anode slurry of the low gold and silver of high arsenic " technology.This article is a raw material with the low gold and silver lead anode slurry of high arsenic, adopts pressurization to leach dearsenification; Dearsenification slag nitration mixture leaches antimony, bismuth, copper, lead; Leached mud melting, electrolysis get finished product silver; Silver anode slime is carried gold.Leach in the operation in pressurization, this article NaOH digestion (concentration 30～80g/L is good with 50g/L), 110～150 ℃ of digestion temperature (150 ℃ is good), 2～4 hours time (2 hours is good), oxygen is pressed 6kg/cm
2, stagnation pressure 6.8kg/cm
2The arsenic extrusion rate of this article is 73.4～94.14%, takes off the gold and silver alloy of output purity～99% behind the antimony bismuth copper-lead. and this technology dearsenification effect is better, but needs high-tension apparatus, operates not too safe.
CN l035321A discloses a kind of method with composite extractant (comprising that alcohol mixture adds phosphoric acid tri-n-butyl (TBP)) production High Purity Gold, but it is only applicable to extraction recovery gold from solution, can not directly apply to the high arsenic solid materials or the anode sludge.
The objective of the invention is to overcome the weak point that prior art exists, a kind of method of extracting gold and silver and valuable metal from anode mud with high As and Pb is proposed, utilize the inventive method, dearsenification relatively thoroughly, device simple, easy to operate, cost is low, non-environmental-pollution, can not bring the valuable metal loss simultaneously again.
The inventive method comprises utilizes NaOH to leach anode mud with high As and Pb, and extracts the recovery gold with said composite extractant among the CN 1035321A (alcohol mixture adds phosphoric acid tri-n-butyl (TBP)) from solution; Feature of the present invention is that following concrete operation is arranged:
A, the anode sludge at solid-liquid than (being the solid/liquid ratio, unit is g/mL or kg/L)=1: 8～20, under 80～90 ℃ of conditions of temperature, with 100～300g/L NaOH agitation leach 1～6 hour, look the lead content different experiments and select NaOH concentration and solid-liquid ratio, preferential NaOH concentration of recommending is 180-200g/L, and the solid-liquid ratio is 1: 10-15;
B, alkali immersion liquid were chilled to room temperature 6～24 hours, reclaimed the arsenic concentrate crystallization;
C, dearsenification mother liquor are at 2～3 volts of voltages, current density 90～300A/cm
2The direct current electrodeposition is 6～20 hours under the condition, and the electrodeposition thing reclaims lead ore concentrate;
D, electrodeposition mother liquor add lime (or milk of lime) under 80～90 ℃ of stirrings, its amount for the anode pug heavy 10～30%, act on 1～6 hour, the filtered and recycled lime mud, filtrate is returned operation A;
Slag behind E, dearsenification, the lead is controlled at 365 ± 10 ℃ of atmospheric oxidation roastings 8～12 hours;
F, the thin back of burning sizing are at solid-liquid ratio: 4～10,2～3molH
2SO
4In in 80～90 ℃ of agitation leachs 1～6 hour, leach liquor adds the NaCl precipitated silver, makes it be AgCl, and the extraction flow process of incorporating silver into to be to reclaim silver, mother liquor reclaims copper;
G, sulfuric acid leached mud at solid-liquid than 1: 4～10, in 80～90 ℃ of agitation leachs 1～6 hour, hydrochloric acid leachate added 1～4 times of water 1～2 hour under stirring, and leaches precipitation among 3～5.5mol HCl, throw out stirred joined down in the stoichiometric liquor ammoniae dilutus 1～2 hour, must Sb
2O
3
H, hydrolysising mother liquid reclaim bismuth, antimony etc. with the iron displacement, and the displacement mother liquor neutralizes with lime, in and slag send the ironworks to reclaim iron, in and the mother liquor discharging;
I, HCl leached mud at solid-liquid than 1: 4～10,200～300g/LNa
2SO
315～40 ℃ of agitation leachs are 1～6 hour in the solution, and solution reclaims silver;
J, once soak silver-colored slag solid-liquid than 1: 4～10,0.2～0.5molH
2SO
4In add 50～100g/L salt, add 5～15 times of NaClO of gold content
3, 80～90 ℃ of agitation leachs 6～12 hours are extracted proof gold with alcohol mixture+TBP composite extractant from leaching agent;
K, chloride slag repeat to add hydrazine hydrate reduction under operation 1, the twice leaching silver solution stirring and get fine silver;
L, secondary soak silver-colored slag and send the smelter to reclaim valuable metals such as tin,
When implementing the inventive method, if arsenic content is not high in the raw material, above-mentioned process B can be cancelled; If gold content is very little in the raw material, operation J cancellation, trace gold reclaims in the smelter,
Compare with prior art, the present invention has following advantage:
1, the inventive method wide accommodation both had been fit to anode mud with high As and Pb, also was fit to low arsenic lead anode slurry;
2, equipment is simple, and is easy to operate, and maintenance of equipment is easy, easily realizes industrialization, and upkeep cost is low;
3, temperature is lower, and energy consumption is less;
4, reagent consumption is few, and production cost is low, and is good in economic efficiency;
5, atmospheric operation, relatively safety;
6, shift to an earlier date separation of lead, the quantity of slag is less, filters comparatively fast, has shortened flow process;
7, solved the arsenic contamination problem, and whole flow process atmosphere is better, helps protecting environment,
Description of drawings: figure l is the process flow sheet of the inventive method.
Embodiment 1
A kind of anode mud with high As and Pb, its main component are (weight %): Au0.0241, Ag8.2, Cu2.79, Fe0.12, As3.24, Sb31.67, Bi0.26, Pb7.38, SiO
23.99, Al
2O
3＜1.
Get this anode sludge 200 grams, in 2L200g/LNaOH (or reclaiming liquid of same concentrations), solid-liquid was than 1: 10, and agitation leach is 2 hours under 80 ℃ of conditions, obtained soaking slag 140 gram. each element extrusion rate (%): As95.9 wherein, Sb24.9, Pb95.33, Cu3.66. leach liquor crystallisation by cooling obtains the arsenic concentrate of following ingredients (weight %): Cu0.33, As13.14, Sb6.97, the Pb3.78. mother liquor is at 3V, 100A/cm
2The direct current electrodeposition obtained following ingredients lead ore concentrate (weight %) in 20 hours under the condition: CuO0.054, As0.74, Pb38.25, Sb28.42.
Dearsenification, lead skim do not carry out decopper(ing), directly carry out next step, at solid-liquid than 80 ℃ of agitation leachs in 1: 4.5,4.5molHCl 2 hours, obtain leached mud 35 grams, wherein the extrusion rate of each element is (%): Cu99.4, As97.2, Sb91.4, Pb98.6 (accumulative total).Leach liquor obtains containing the needle antimony oxygen (Sb of antimony 77.14% after the dilution hydrolysis of 3 times of water and ammonia are separated
2O
3).The HCl leached mud at solid-liquid than 1: 10,250g/LNa
2SO
425 ℃ of agitation leachs are 2 hours in the solution, and solution reclaims silver.Once soak silver-colored slag at solid-liquid than 1: 10,0.25Mol H
2SO
4In add 50g/L salt, add 4g NaClO
3, 80-90 ℃ of agitation leach 6 hours.Leach liquor is divided into trisection, (80% alcohol mixture+20%TBP) contacts respectively for four parts with the 10ml composite extractant, extraction and phase-splitting 3 minutes, collect extraction agent, contact 1 hour with the 2 gram ammonium oxalate aqueous solution, leach the reductive gold at 60-70 ℃, the latter makes proof gold after cleaning with water and dehydrated alcohol respectively, its purity is 99.9%, and the rate of recovery 96% is soaked golden slag and soaked once silver again with aforementioned the same terms.Soak silvering solution for twice and merge, handle to NaOH concentration with NaOH and reach 0.5Mol, 25 ℃ are stirred down and added the 5.5ml hydrazine hydrate reduction 1 hour, output silver powder through clean and embathe with 50ml 3Mol HCl after, product purity reaches 99.9%, the rate of recovery reaches 96%.
Because of bi content is low, do not reclaim separately in this experiment.
Embodiment 2
Get the said anode sludge 200 grams as embodiment 1, at solid-liquid than 1: 10, among the 250g/LNaOH in 85 ℃ of agitation leachs 4 hours. each element leaching yield is (%): Pb
-100, As98, Sb19.73 ,-24.75, the leach liquor crystallisation by cooling obtains containing the arsenic slag of arsenic 16.02%.Gold and the loss of silver in dearsenification filtrate and arsenic slag be respectively＜0.49%, and 0.02% and＜0.02%,＜0.0013%, dearsenification liquid is through room temperature 3V, 100A/cm
2The direct current electrodeposition is 6 hours under the condition, obtains containing the antimony lead concentrate of Sb31.3%, Pb23.02%.
Slag behind dearsenification, the lead was 375 ± 5 ℃ of atmospheric oxidation roastings 8 hours.Burn the thin back of sizing at solid-liquid than 1: 8,3mol H
2SO
4In in 80 ℃ of agitation leachs 2 hours. leach liquor adds 5 gram NaCl precipitate A gCl, and the extraction flow process of incorporating silver into is to reclaim silver; Mother liquor reclaims copper.The sulfuric acid leached mud takes off antimony with the method for embodiment 1 again, separates and reclaims gold and silver, and obtain needle antimony oxygen and proof gold, fine silver, gold and silver purity 99.9%, the rate of recovery 96% respectively.
Embodiment 3
A kind of anode mud with high As and Pb, its main component are (weight %): Au0.8 (g/t), Ag2.91, Cu3.02, As22.93, Sb29.38, Pb6.39, Sn1.19. get this anode sludge 200g at solid-liquid than 1: 20, in the 200g/LNaOH solution, 90 ℃ of following agitation leachs 6 hours.The leaching yield of each element is (%): Pb80.8, As94, Sb61.08. silver and golden enrichment are 3 times, following operation is pressed enriched substance the method for embodiment 1 and is separated and purification byproduct arsenic slag, antimony lead slag and needle antimony oxygen, output silver purity reaches 99.9%, the rate of recovery 96%, the content of gold is very little, does not reclaim separately.
Claims (2)
1, a kind of method of extracting gold and silver and valuable metal from anode mud with high As and Pb, comprise and utilize NaOH to leach anode mud with high As and Pb, and extract from solution with composite extractant (alcohol mixture adds phosphoric acid tri-n-butyl (TBP)) and to reclaim gold, feature of the present invention is that following concrete operation is arranged:
A, the anode sludge solid-liquid than (be the solid/liquid ratio, unit is g/mL or kg/L)=1: 8～20,80～90 ℃ of conditions of temperature under, with 100～300g/LNaOH agitation leach 1～6 hour, look the lead content different experiments and select NaOH concentration and solid-liquid ratio;
B, alkali immersion liquid were chilled to room temperature 6～24 hours, reclaimed the arsenic concentrate crystallization;
C, dearsenification mother liquor are at 2～3 volts of voltages, current density 90～300A/cm
2The direct current electrodeposition is 6～20 hours under the condition, and the electrodeposition thing reclaims lead ore concentrate;
D, electrodeposition mother liquor add lime (or milk of lime) under 80～90 ℃ of stirrings, its amount for the anode pug heavy 10～30%, act on 1～6 hour, filter residue recovery lime mud, filtrate is returned operation A;
Slag behind E, dearsenification, the lead is controlled at 365 ± 10 ℃ of atmospheric oxidation roastings 8～12 hours;
F, burn the thin back of sizing at solid-liquid than 1: 4～10,2～3mol H
2SO
4In in 80～90 ℃ of agitation leachs 1～6 hour, leach liquor adds the NaCl precipitated silver, makes it be AgCl, and the extraction flow process of incorporating silver into to be to reclaim silver, mother liquor reclaims copper;
G, sulfuric acid leached mud at solid-liquid than 1: 4～10, in 80～90 ℃ of agitation leachs 1～6 hour, hydrochloric acid leachate added 1～4 times of water 1～2 hour under stirring, and leaches precipitation among 3～5.5molHCl, throw out stirred joined down in the stoichiometric liquor ammoniae dilutus 1～2 hour, must Sb
2O
3
H, hydrolysising mother liquid reclaim bismuth, antimony etc. with the iron displacement, and the displacement mother liquor neutralizes with lime, in and slag send the ironworks to reclaim iron, in and the mother liquor discharging;
I, HCl leached mud at solid-liquid than 1: 4～10,200～300g/LNa
2SO
315～40 ℃ of agitation leachs are 1～6 hour in the solution, and solution reclaims silver;
J, once soak silver-colored slag solid-liquid than 1: 4～10,0.2～0.5molH
2SO
4In add 50～100g/L salt, add 5～15 times of NaClO of gold content
3, 80～90 ℃ of agitation leachs 6～12 hours are extracted proof gold with alcohol mixture+TBP composite extractant from leach liquor;
K, chloride slag repeat operation I, add hydrazine hydrate reduction under twice leaching silver solution stirring and get fine silver;
L, secondary soak silver-colored slag and send the smelter to reclaim valuable metals such as tin.
2, according to the method for claim 1, it is characterized in that said leaching agent NaOH concentration is 180-200g/L, solid-liquid is than being l: 10-15.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96112638A CN1045794C (en) | 1996-09-16 | 1996-09-16 | Method for obtg. gold, silver and other noble metals from anode and contg. high concn. arsenic and lead |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96112638A CN1045794C (en) | 1996-09-16 | 1996-09-16 | Method for obtg. gold, silver and other noble metals from anode and contg. high concn. arsenic and lead |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1177014A true CN1177014A (en) | 1998-03-25 |
| CN1045794C CN1045794C (en) | 1999-10-20 |
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ID=5121534
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96112638A Expired - Fee Related CN1045794C (en) | 1996-09-16 | 1996-09-16 | Method for obtg. gold, silver and other noble metals from anode and contg. high concn. arsenic and lead |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586604A (en) * | 2011-01-18 | 2012-07-18 | 郴州市金贵银业股份有限公司 | Technology for wet-processing anode mud containing arsenic and lead |
| CN102634666A (en) * | 2012-04-24 | 2012-08-15 | 葫芦岛锌业股份有限公司 | Method for dearsenicating fresh high-arsenium lead anode slime under oxygen pressure |
| CN103334018A (en) * | 2013-06-19 | 2013-10-02 | 山东恒邦冶炼股份有限公司 | Method for extracting antimony and bismuth from lead anode mud |
| CN103526042A (en) * | 2013-10-25 | 2014-01-22 | 北京矿冶研究总院 | Method for extracting gold and silver from gold concentrate |
| CN104611567A (en) * | 2015-02-12 | 2015-05-13 | 池州冠华黄金冶炼有限公司 | Method for treating copper-lead anode mud with alkaline process |
| CN105907980A (en) * | 2016-04-21 | 2016-08-31 | 西北矿冶研究院 | Method for recovering noble metal from antimony-containing soot |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85106670B (en) * | 1985-08-31 | 1988-06-15 | 中国有色金属工业总公司昆明贵金属研究所 | Process for extraction of noble metal from anode mud by method of controlling potential |
| CN1011420B (en) * | 1988-06-15 | 1991-01-30 | 中国有色金属工业总公司昆明贵金属研究所 | Method using composite extractant to produce high-pure gold |
| CN1020755C (en) * | 1989-06-03 | 1993-05-19 | 中国有色金属工业总公司昆明贵金属研究所 | Wet method for treating lead anode slurry |
| CN1027977C (en) * | 1992-06-02 | 1995-03-22 | 中国有色金属工业总公司昆明贵金属研究所 | Treatment method of high arsonium lead anode mud wet process |
| CN1119678A (en) * | 1994-05-10 | 1996-04-03 | 陕西深华金属材料研究所 | Method for recovering silver, gold, antimony, copper and lead from lead anode mud |
| CN1114361A (en) * | 1994-06-28 | 1996-01-03 | 陕西深华金属材料研究所 | Method for recovering Ag, Au, Sb, Cu and Pb from Pb anode slime |
-
1996
- 1996-09-16 CN CN96112638A patent/CN1045794C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586604A (en) * | 2011-01-18 | 2012-07-18 | 郴州市金贵银业股份有限公司 | Technology for wet-processing anode mud containing arsenic and lead |
| CN102586604B (en) * | 2011-01-18 | 2013-05-08 | 郴州市金贵银业股份有限公司 | Technology for wet-processing anode mud containing arsenic and lead |
| CN102634666A (en) * | 2012-04-24 | 2012-08-15 | 葫芦岛锌业股份有限公司 | Method for dearsenicating fresh high-arsenium lead anode slime under oxygen pressure |
| CN103334018A (en) * | 2013-06-19 | 2013-10-02 | 山东恒邦冶炼股份有限公司 | Method for extracting antimony and bismuth from lead anode mud |
| CN103526042A (en) * | 2013-10-25 | 2014-01-22 | 北京矿冶研究总院 | Method for extracting gold and silver from gold concentrate |
| CN103526042B (en) * | 2013-10-25 | 2015-10-28 | 北京矿冶研究总院 | Method for extracting gold and silver from gold concentrate |
| CN104611567A (en) * | 2015-02-12 | 2015-05-13 | 池州冠华黄金冶炼有限公司 | Method for treating copper-lead anode mud with alkaline process |
| CN105907980A (en) * | 2016-04-21 | 2016-08-31 | 西北矿冶研究院 | Method for recovering noble metal from antimony-containing soot |
| CN105907980B (en) * | 2016-04-21 | 2018-09-28 | 西北矿冶研究院 | Method for recovering noble metal from antimony-containing soot |
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| Publication number | Publication date |
|---|---|
| CN1045794C (en) | 1999-10-20 |
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