CN104878209A - Method of leaching gold and silver targets in copper anode mud - Google Patents
Method of leaching gold and silver targets in copper anode mud Download PDFInfo
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- CN104878209A CN104878209A CN201510328717.3A CN201510328717A CN104878209A CN 104878209 A CN104878209 A CN 104878209A CN 201510328717 A CN201510328717 A CN 201510328717A CN 104878209 A CN104878209 A CN 104878209A
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to a method of leaching gold and silver targets in copper anode mud. The method comprises the three stages: oxidizing roasting-sulfuric acid leaching, oxidant-free chlorine salt leaching, and formic acid reduction-thiosulfate leaching. Chlorine salt leaching residues are reduced by the formic acid, and the thiosulfate leaching is carried out on the sulfuric leaching residues to effectively leach silver and lead, and palladium is partially dissolved out. The chlorine salt leaching residues are reduced by the formic acid, and then are subjected to the thiosulfate leaching so as to effectively leach silver and the rest of palladium. The method can be used for efficiently leaching gold, silver, palladium, copper, selenium, lead and other various valuable metals, and is low in damage on environment and low in requirement for anticorrosion of equipment.
Description
Technical field
The present invention relates to technical field of wet metallurgy, specifically a kind of method leaching gold and silver palladium from copper anode mud.
Background technology
Copper anode mud is a kind of by product in electrolytic refining course of copper, and it is rich in gold and silver, palladium, copper, selenium, lead and other elements usually.At present, domestic for copper anode mud still based on traditional pyrogenic attack.First adopt sulfurization roasting-sulfuric acid leaching technique leach copper and reclaim selenium in baking flue gas, retailoring is carried out to sulfuric acid leaching slag and obtains precious metals containing lead, then the alloy that oxidation refining can obtain containing gold and silver and palladium is carried out to precious metals containing lead.High-purity each single precious metal can be obtained again afterwards by operations such as a series of electrolysis, meltings.The technical maturity of pyrogenic attack, but its precious metal reclaims the flue dust that link produces the harmful elements such as a large amount of leaded, arsenic, serious environment pollution.China also has some large-scale smelteries to adopt the method process copper anode mud of hydrometallurgy at present.Employing sulfurization roasting-sulfuric acid leaching copper-ammonia leaching silver-nitric acid leaching lead-chlorination is more typically had to soak " the Fuchunjiang River technique " of golden flow process and adopt oxidizing roasting-sulfuric acid leaching copper-chlorination leaching gold-S-WAT to soak " the Chongqing technique " of silver-colored flow process.In these two kinds of techniques, Gold leaching all adopts the potassium cloride means of adding strong oxidizer, and palladium can be leached with gold, but it requires high to equipment anticorrosion.
From copper anode mud, reclaim the environmental pollution that exists in the process of gold and silver palladium and equipment anticorrosion requires the problems such as high for industrial at present, specially propose the present invention.
Summary of the invention
The object of the invention is to provide a kind of for copper anode mud and can effectively leach valuable metal, the novel methods few and low to equipment anticorrosion requirement to environmental hazard such as gold and silver palladium.
Technical scheme of the present invention is:
From copper anode mud, leach a method for gold and silver palladium, oxidizing roasting-sulfuric acid leaching, the leaching of anaerobic agent villaumite, formic acid reduction-thiosulfate leaching are combined; Control the reaction conditions of each link of this technique, oxidizing roasting-sulfuric acid leaching stage can effectively leach copper and selenium; Anaerobic agent villaumite leaching stage can effectively Leaching of Silver and lead, also makes the stripping of palladium part; Formic acid reduction-thiosulfate leaching the stage can effectively Leaching of Gold and residual palladium.
Specifically by copper anode mud fine grinding, then carry out low-temperature oxidation roasting make the sulfide of copper and selenium oxidized, part palladium is oxidized to palladous oxide in the process, then carries out sulfuric acid leaching process to calcining copper and selenium are leached, and precious metal stripping hardly; The villaumite leaching process that sulfuric acid leaching slag carries out anaerobic agent again makes silver and lead be leached, and part palladium is also leached simultaneously, and gold stripping hardly; Villaumite leached mud reduces through formic acid, and palladous oxide is reduced to palladium metal, and reducing slag makes gold and residual palladium be dissolved through thiosulfate leaching process again.
First copper anode mud is finely ground to-0.045mm in aforesaid method and accounts for more than 90%.
Low-temperature oxidation roasting reaction conditions is: maturing temperature 360 ~ 370 DEG C, roasting time 50 ~ 70min; Sulfuric acid leaching reaction conditions: sulfuric acid concentration 2.0 ~ 2.5M, hydrochloric acid or sodium-chlor or ammonium chloride concentration are 0.03 ~ 0.05M, temperature 80 ~ 90 DEG C, reaction times 120 ~ 180min.
The villaumite Leaching reaction condition of anaerobic agent: concentration of hydrochloric acid 1.4 ~ 1.6M, sodium-chlor or ammonium chloride concentration 3.4 ~ 3.6M; Temperature 60 ~ 80 DEG C, reaction times 50 ~ 70min.
The reaction conditions of formic acid reduction is: formic acid concn 0.6 ~ 0.8M, temperature 5 ~ 50 DEG C, reaction times 80 ~ 100min; The reaction conditions of thiosulfate leaching: Sulfothiorine or thiosulfuric acid ammonium concentration 1.0 ~ 1.4M, concentration of copper sulfate 0.02 ~ 0.04M, ammonia concn 0.6 ~ 1.2M, temperature 5 ~ 50 DEG C, reaction times 8 ~ 12h.
In each leaching process, liquid-solid ratio is 3 ~ 5, and stirring intensity is 300 ~ 500r/min.
The present invention can produce following effect:
(1) each valuable metal can effectively be leached.Oxidizing roasting-sulfuric acid leaching stage can leach copper and selenium, and villaumite leaching stage can the metal such as Leaching of Silver, lead, and the formic acid reduction-thiosulfate leaching stage can Leaching of Gold and palladium.
(2) few to environmental hazard.In the present invention, each leaching stage all adopts low toxicity or nontoxic reagent.
(3) require low to equipment anticorrosion.In the present invention, the reaction conditions of each leaching stage is all gentleer, and leach liquor corrodibility is not strong.
Embodiment
Following examples are intended to further illustrate content of the present invention, instead of limit the scope of the invention.
Material condition one: certain copper anode mud moisture 38%, its butt chemical composition is as shown in table 1.
The chemical composition (unit %) of table 1 copper anode mud 1
| Element | Au* | Ag* | Pd* | Se | Cu | Pb | S | Sb | Sn | Ni | Fe | As |
| Content | 103.2 | 2724.2 | 87.0 | 3.0 | 12.1 | 7.2 | 9.4 | 7.8 | 32.8 | 1.34 | 0.56 | 0.20 |
* unit is g/t.
Embodiment 1: first this copper anode mud is finely ground to-0.045mm and accounts for 95%.Then by the oxidizing roasting 60min at 365 DEG C of the anode sludge through fine grinding, then sulfuric acid leaching is carried out to calcining.Its leaching condition is: sulfuric acid 2.0M, hydrochloric acid 0.03M, temperature 85 DEG C, extraction time 150min, the leaching yield of copper, selenium is respectively 95.7% and 96.5% with this understanding.Sulfuric acid leaching slag carries out villaumite leaching again.Its leaching condition is: hydrochloric acid 1.4M, sodium-chlor 3.4M, temperature 70 C, reaction times 60min, and the leaching yield of lead, silver, palladium, antimony is respectively 94.4%, 95.6%, 35.4%, 9.3% with this understanding.Villaumite leached mud reduces after 90min and carries out thiosulfate leaching again in the 0.6M formic acid solution of 25 DEG C.Its leaching condition is: Sulfothiorine 1.0M, copper sulfate 0.02M, ammoniacal liquor 0.6M, pH 10, temperature 25 DEG C, reaction times 10h, and the leaching yield of gold, palladium is respectively 95.1% and 94.7% with this understanding.Most tin and most antimony are enriched in finishing slag.In the present embodiment, the liquid-solid ratio of each liquid-solid reaction is 4, and stirring intensity is 400r/min, and each reagent concentration all refers to initial reactive concentration, and each leaching yield all refers to stage leaching yield.
Embodiment 2: according to the method in embodiment 1, its reaction conditions is also identical with embodiment 1 unless otherwise noted.Sulfuric acid leaching condition is: sulfuric acid 2.3M, sodium-chlor 0.04M, the leaching yield of copper, selenium is respectively 96.1% and 97.1% with this understanding.Villaumite leaching condition is: hydrochloric acid 1.5M, ammonium chloride 3.5M, and the leaching yield of lead, silver, palladium, antimony is respectively 95.2%, 96.3%, 36.7%, 10.5% with this understanding.The condition of formic acid reduction and thiosulfate leaching is respectively: formic acid 0.7M; Ammonium thiosulfate 1.2M, copper sulfate 0.03M, ammoniacal liquor 0.9M, the leaching yield of gold, palladium is respectively 95.8% and 95.2% with this understanding.Most tin and most antimony are enriched in finishing slag.
Embodiment 3: according to the method in embodiment 1, its reaction conditions is also identical with embodiment 1 unless otherwise noted.Sulfuric acid leaching condition is: sulfuric acid 2.5M, ammonium chloride 0.05M, the leaching yield of copper, selenium is respectively 96.9% and 97.7% with this understanding.Villaumite leaching condition is: hydrochloric acid 1.6M, sodium-chlor 3.6M, and the leaching yield of lead, silver, palladium, antimony is respectively 95.7%, 96.8%, 37.2%, 10.9% with this understanding.The condition of formic acid reduction and thiosulfate leaching is respectively: formic acid 0.8M; Sulfothiorine 1.4M, copper sulfate 0.04M, ammoniacal liquor 1.2M, the leaching yield of gold, palladium is respectively 96.3% and 95.7% with this understanding.Most tin and most antimony are enriched in finishing slag.
Material condition two: certain copper anode mud moisture 38%, its butt chemical composition is as shown in table 2.
The chemical composition (unit %) of table 1 copper anode mud 2
| Element | Au* | Ag* | Pd* | Se | Cu | Pb | S | Sb | Sn | Ni | Fe | As |
| Content | 142.3 | 3216.5 | 95.7 | 3.9 | 14.1 | 8.0 | 8.5 | 6.4 | 30.2 | 1.67 | 0.69 | 0.13 |
* unit is g/t.
Embodiment 4: according to the method in embodiment 1, its reaction conditions is also identical with embodiment 1 unless otherwise noted.Sulfuric acid leaching condition is: sulfuric acid 2.0M, hydrochloric acid 0.03M, the leaching yield of copper, selenium is respectively 95.4% and 96.1% with this understanding.Villaumite leaching condition is: hydrochloric acid 1.4M, sodium-chlor 3.4M, and the leaching yield of lead, silver, palladium, antimony is respectively 93.8%, 95.1%, 34.7%, 10.4% with this understanding.The condition of formic acid reduction and thiosulfate leaching is respectively: formic acid 0.6M; Sulfothiorine 1.0M, copper sulfate 0.02M, ammoniacal liquor 0.6M, the leaching yield of gold, palladium is respectively 94.7% and 94.3% with this understanding.Most tin and most antimony are enriched in finishing slag.
Embodiment 5: according to the method in embodiment 1, its reaction conditions is also identical with embodiment 1 unless otherwise noted.Sulfuric acid leaching condition is: sulfuric acid 2.3M, sodium-chlor 0.04M, the leaching yield of copper, selenium is respectively 95.7% and 96.7% with this understanding.Villaumite leaching condition is: hydrochloric acid 1.5M, ammonium chloride 3.5M, and the leaching yield of lead, silver, palladium, antimony is respectively 94.6%, 95.7%, 35.3%, 10.9% with this understanding.The condition of formic acid reduction and thiosulfate leaching is respectively: formic acid 0.7M; Ammonium thiosulfate 1.2M, copper sulfate 0.03M, ammoniacal liquor 0.9M, the leaching yield of gold, palladium is respectively 95.3% and 94.7% with this understanding.Most tin and most antimony are enriched in finishing slag.
Embodiment 6: according to the method in embodiment 1, its reaction conditions is also identical with embodiment 1 unless otherwise noted.Sulfuric acid leaching condition is: sulfuric acid 2.5M, ammonium chloride 0.05M, the leaching yield of copper, selenium is respectively 96.3% and 97.2% with this understanding.Villaumite leaching condition is: hydrochloric acid 1.6M, sodium-chlor 3.6M, and the leaching yield of lead, silver, palladium, antimony is respectively 95.2%, 96.3%, 36.1%, 11.5% with this understanding.The condition of formic acid reduction and thiosulfate leaching is respectively: formic acid 0.8M; Sulfothiorine 1.4M, copper sulfate 0.04M, ammoniacal liquor 1.2M, the leaching yield of gold, palladium is respectively 95.8% and 95.4% with this understanding.Most tin and most antimony are enriched in finishing slag.
Claims (7)
1. from copper anode mud, leach a method for gold and silver palladium, it is characterized in that, oxidizing roasting-sulfuric acid leaching, the leaching of anaerobic agent villaumite, formic acid reduction-thiosulfate leaching are combined; Control the reaction conditions of each link of this technique, oxidizing roasting-sulfuric acid leaching stage can effectively leach copper and selenium; Anaerobic agent villaumite leaching stage can effectively Leaching of Silver and lead, also makes the stripping of palladium part; Formic acid reduction-thiosulfate leaching the stage can effectively Leaching of Gold and residual palladium.
2. method according to claim 1, it is characterized in that, by copper anode mud fine grinding, then carry out low-temperature oxidation roasting make the sulfide of copper and selenium oxidized, palladium is partially oxidized is in the process palladous oxide, carrying out sulfuric acid leaching process to calcining again makes copper and selenium be leached, and precious metal not stripping; The villaumite leaching process that sulfuric acid leaching slag carries out anaerobic agent again makes silver and lead be leached, and part palladium is also leached simultaneously, and gold not stripping; Villaumite leached mud reduces through formic acid, and palladous oxide is reduced to palladium metal, and reducing slag makes gold and residual palladium be dissolved through thiosulfate leaching process again.
3. method according to claim 1 and 2, is characterized in that, copper anode mud is finely ground to-0.045mm and accounts for more than 90%.
4. method according to claim 1 and 2, is characterized in that, low-temperature oxidation roasting reaction conditions is: maturing temperature 360 ~ 370 DEG C, roasting time 50 ~ 70min; Sulfuric acid leaching reaction conditions: sulfuric acid concentration 2.0 ~ 2.5M, hydrochloric acid or sodium-chlor or ammonium chloride concentration are 0.03 ~ 0.05M, temperature 80 ~ 90 DEG C, reaction times 120 ~ 180min.
5. method according to claim 1 and 2, is characterized in that, the villaumite Leaching reaction condition of anaerobic agent: concentration of hydrochloric acid 1.4 ~ 1.6M, sodium-chlor or ammonium chloride concentration 3.4 ~ 3.6M; Temperature 60 ~ 80 DEG C, reaction times 50 ~ 70min.
6. method according to claim 1 and 2, is characterized in that, the reaction conditions of formic acid reduction is: formic acid concn 0.6 ~ 0.8M, temperature 5 ~ 50 DEG C, reaction times 80 ~ 100min; The reaction conditions of thiosulfate leaching: Sulfothiorine or thiosulfuric acid ammonium concentration 1.0 ~ 1.4M, concentration of copper sulfate 0.02 ~ 0.04M, ammonia concn 0.6 ~ 1.2M, temperature 5 ~ 50 DEG C, reaction times 8 ~ 12h.
7. method according to claim 1 and 2, is characterized in that, in each leaching process, liquid-solid ratio is 3 ~ 5, and stirring intensity is 300 ~ 500r/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105441677A (en) * | 2016-01-13 | 2016-03-30 | 南京信息工程大学 | Method utilizing by-product ammonium thiosulfate for leaching precious metal from flotation concentrate |
| CN111041212A (en) * | 2019-12-17 | 2020-04-21 | 江西理工大学 | Gold leaching method for copper anode mud |
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| EP0263910A1 (en) * | 1986-10-13 | 1988-04-20 | Austria Metall Aktiengesellschaft | Hydrometallurgical process for separating and concentrating gold, platinum and palladium, as well as recovering selenium from electrolytic copper refinery slimes and similar non-metallic materials |
| CN102732735A (en) * | 2012-07-20 | 2012-10-17 | 阳谷祥光铜业有限公司 | Method for recovering valued metals from melting slag of copper anode slime Kaldo furnace |
| CN102936659A (en) * | 2012-10-31 | 2013-02-20 | 崖巨钊 | Closed-circuit process technique for recovering multiple metals from copper and lead electrolysis anode mud |
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2015
- 2015-06-15 CN CN201510328717.3A patent/CN104878209A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0263910A1 (en) * | 1986-10-13 | 1988-04-20 | Austria Metall Aktiengesellschaft | Hydrometallurgical process for separating and concentrating gold, platinum and palladium, as well as recovering selenium from electrolytic copper refinery slimes and similar non-metallic materials |
| CN102732735A (en) * | 2012-07-20 | 2012-10-17 | 阳谷祥光铜业有限公司 | Method for recovering valued metals from melting slag of copper anode slime Kaldo furnace |
| CN102936659A (en) * | 2012-10-31 | 2013-02-20 | 崖巨钊 | Closed-circuit process technique for recovering multiple metals from copper and lead electrolysis anode mud |
Non-Patent Citations (3)
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| 元英进: "《制药工艺学》", 30 June 2007, 化学工业出版社 * |
| 李月娥: ""用硫代硫酸盐浸出贵金属的热力学分析"", 《贵金属》 * |
| 黄礼煌: "《金银提取技术 第3版》", 31 May 2012, 冶金工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105441677A (en) * | 2016-01-13 | 2016-03-30 | 南京信息工程大学 | Method utilizing by-product ammonium thiosulfate for leaching precious metal from flotation concentrate |
| CN111041212A (en) * | 2019-12-17 | 2020-04-21 | 江西理工大学 | Gold leaching method for copper anode mud |
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Application publication date: 20150902 |