CN101597690A - The method of recycling multiple precious metals from anode mud - Google Patents
The method of recycling multiple precious metals from anode mud Download PDFInfo
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- CN101597690A CN101597690A CNA2009100437807A CN200910043780A CN101597690A CN 101597690 A CN101597690 A CN 101597690A CN A2009100437807 A CNA2009100437807 A CN A2009100437807A CN 200910043780 A CN200910043780 A CN 200910043780A CN 101597690 A CN101597690 A CN 101597690A
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Abstract
The invention discloses the method that a kind of anode sludge reclaims rare precious metal, at first antianode mud carries out melting roasting screening at smelting furnace; Carry out the preimpregnation decopper(ing) after material after the roasting cools off and obtain leach liquor and leached mud; Leached mud is sent into acidleach pond get back leached mud and leach liquor, and be hydrolyzed pond and neutralization precipitation of leach liquor handled, and leached mud is sent to alkali and soaks leached mud after handle in plumbous pond and carry out pyrometallurgical smelting again and handle.Leach liquor is sent into the utilization of copper abstraction pool has the organism of cabinet to strip, and obtains copper-contained material and the surplus liquid of extraction after the extraction; Copper-contained material is sent into load the processing of stripping in the cabinet, and the back material of stripping has partly been sent in the cabinet and handled, and the residue anti-stripping agent is sent into and carried out electrodeposition in the electrodeposition pond and handle and obtain cathode copper; The surplus liquid of the extraction that obtains in the copper extraction box then is sent to settling tank and carries out precipitation process, and waste liquid is delivered to Waste Water Treatment and handled.The present invention adopts wet method to leach the high and low metal of separation, advantage in conjunction with pyrogenic process and wet production, solved the arsenic contamination that pyrometallurgical smelting exists and production technique is long, adaptability to raw material is poor, the production cycle is long and the lower problem of comprehensive recovery, gold and silver, copper, antimony, bismuth, arsenic and lead all can reach 95%.
Description
Technical field
The invention belongs to and belong to field of metallurgy, be meant that specifically a kind of pyrogenic process and wet method utilized combines, from the method for lead bronze recycling multiple precious metals from anode mud.
Background technology
The anode sludge is made up of the various materials that are insoluble to electrolytic solution that copper anode and lead anode produce in the electrorefining process.During electrolysis, the base metal dissolving that current potential is lower enters solution, and formation insolubless such as precious metal, dissipated metal, anode powder become the anode sludge.In the anode sludge, include copper, lead, antimony, bismuth, arsenic, silver, gold and platinum metals, have platinum metals, gold, most of silver, a little copper and the gold that exist with metallic state in the anode sludge exist with the form of metallic compound, and the then most of forms with oxide compound of all the other metals exist.Copper-lead anode sludge bullion content is higher, be a kind of important precious metal raw materials for production, its value is also very big, also meet country and promote circular economy policy at present, as the processing and utilizing to the copper-lead anode sludge mainly is to reclaim at a large amount of precious metals that wherein contain, subsidiary remaining heavy metal and the platinum metals etc. of reclaiming in removal process.Be used in anode slime treatment process now and mainly contain three major types: the first kind is traditional thermal process; Second class is the selecting smelting combination treatment process; The 3rd class is a wet processing process.Traditional thermal process is because the pollution that environment is produced is big; basically abandon utilization; what be widely used is selecting smelting combination treatment process and wet processing process; on Chinese patent, also announced the patent documentation of multiple this two classes production technique; these technologies have all solved the anode sludge to a certain extent in processing production process, problem and defective that aspects such as the direct recovery rate of the adaptability of raw material, construction investment, working cost, precious metal, flow process length, energy consumption, production cycle, comprehensive utilization ratio and environment protection exist.
Summary of the invention
The object of the present invention is to provide the rare precious metal direct recovery rate height in the antianode mud; reclaim wide in varietyly, the adaptability of raw material is strong, energy consumption is low, with short production cycle and comprehensive utilization ratio is high and the method for the recycling multiple precious metals from anode mud that environment protection is good.
In order to achieve the above object, concrete processing method of the present invention is as follows:
The lead bronze anode sludge to metallic scraps such as cupric, lead, antimony, bismuth, arsenic, silver, gold, platinum at first screens, and screening is to handle by the anode sludge that contains electrolytic solution is carried out high melt at smelting furnace; Material after the screening, send in the low-temperature bake stove and carry out roasting with low temperature again with gas blower adding air, enter after material after the roasting cools off and carry out the preimpregnation decopper(ing) in the decopper(ing) pond, in the decopper(ing) process, add sulfuric acid, be provided with electrode control pH value in the decopper(ing) pond, leach liquor and leached mud that process decopper(ing) pond decopper(ing) pre-preg obtains leaching.
The leached mud that obtains in the decopper(ing) pond is sent in the acidleach pond, adds sulfuric acid and sodium-chlor in the acidleach pond successively, also is provided with electrode control pH value in the acidleach pond, and get back leached mud and leach liquor are handled by acidleach in the acidleach pond.The leach liquor that is obtained by the acidleach pond is sent in the hydrolytic tank, antimony chloride in the leach liquor precipitates in hydrolytic tank separates out, precipitation is separated out the leach liquor of antimony chloride and is sent into the neutralization precipitation pond, adding yellow soda ash precipitates the bismuth in the leach liquor and separates out in the neutralization precipitation pond, also be provided with electrode control pH value in the neutralization precipitation pond, the post precipitation liquid in the neutralization precipitation pond is sent in the copper extraction tank to be handled; The leached mud that the acidleach pond obtains is sent to alkali and soaks the leached mud that adds in the plumbous pond after sodium hydroxide is handled, and the leached mud that obtains carries out pyrometallurgical smelting again to be handled.
The leach liquor that the decopper(ing) pond obtains is sent in the copper abstraction pool, and utilizing has the organism in the cabinet to strip, and is undertaken obtaining copper-contained material and the surplus liquid of extraction behind the copper extraction process by the copper abstraction pool.Copper-contained material is sent into load the processing of stripping in the cabinet, and a material part that obtains after the reextraction has been sent in the cabinet and handled, and remaining anti-stripping agent is sent into the cathode copper that arrives that carries out the electrodeposition processing in the electrodeposition pond; The surplus liquid of the extraction that obtains in the copper extraction box then is sent to settling tank to carry out precipitation process and obtains metals such as antimony, gold, and the waste liquid of settling tank is delivered to Waste Water Treatment and handled.
After adopting anode mud treatment method of the present invention, draw by correlation test and large-scale production:
Hang down sour preimpregnation decopper(ing) in the decopper(ing) pond, send under the conditions of air at normal temperature and gas blower, the leaching yield of Cu can reach more than 80%, and the leaching yield of As can arrive 30%.
Utilize organism to extract at the copper abstraction pool, separating copper, antimony, arsenic, the percentage extraction of copper reaches more than 99%, and antimony and arsenic then are not extracted.
The surplus liquid of extraction that contains antimony and arsenic adopts alkali to carry out neutralization precipitation, and the deposition rate of antimony and arsenic also all reaches more than 99%.
Adopt vitriol lixiviation to handle to the leached mud that obtains in the decopper(ing) pond, the leaching yield of Sb, Bi, As, Cu all reaches more than 98.5%, and base metal is leached fully, and the leaching yield of Pb then is lower than 4%; The leached mud that the process vitriol lixiviation is handled the then metal of main enrichment is Pb, Au, Ag, adopts the pyrometallurgical smelting treatment effect good again, the extraction yield height; The leach liquor of handling through vitriol lixiviation adopts hydrolysis-neutralization precipitation-extraction-neutral processing method, extracts antimony, bismuth and copper, rate of recovery height, metal quality height.
Adopt wet method to leach and separate base metal and precious metal, make concentration of precious metal in last tailings, adopt the processing method of pyrogenic process to carry out the melting recovery again, fully combine the advantage that pyrogenic process and wet production possess separately, fundamentally solved the arsenic contamination that pyrometallurgical smelting exists, solved other again and produced that the production technique that exists is long, adaptability to raw material is poor, the production cycle is long and the lower problem of comprehensive recovery.
Adopt sulfuric acid to substitute hydrochloric acid in the acidleach of acidleach pond, solved the hydrochloric acid volatilization and had a strong impact on operating environment, solved plumbous scattering problem again.
Adopt anode mud treatment method of the present invention, the gold and silver precious metal rate of recovery surpasses 95%, and the rate of recovery of other base metals is: copper, antimony, bismuth, arsenic and lead all can reach 95%.
Description of drawings
Accompanying drawing is the process flow sheet of the method for recycling multiple precious metals from anode mud of the present invention.
Embodiment
Below in conjunction with drawings and Examples the technology of the present invention is described further.
At first screen, screening is to handle by the anode sludge that contains electrolytic solution is carried out high melt at smelting furnace, and temperature is controlled at 1000-1100 degree centigrade; Material after the screening, send in the low-temperature bake stove and carry out roasting with low temperature again with gas blower adding air, 500-600 degree centigrade of temperature control, enter after material after the roasting cools off and carry out the preimpregnation decopper(ing) in the decopper(ing) pond, in the decopper(ing) process, add sulfuric acid, be provided with electrode control pH value in the decopper(ing) pond, pH value control 1-2, leach liquor and leached mud that process decopper(ing) pond decopper(ing) pre-preg obtains leaching.
The leached mud that obtains in the decopper(ing) pond is sent in the acidleach pond, adds sulfuric acid and sodium-chlor in the acidleach pond successively, also is provided with electrode control pH value in the acidleach pond, and pH value is controlled at 4-5, and get back leached mud and leach liquor are handled by acidleach in the acidleach pond.The leach liquor that is obtained by the acidleach pond is sent in the hydrolytic tank, antimony chloride in the leach liquor precipitates in hydrolytic tank separates out, precipitation is separated out the leach liquor of antimony chloride and is sent into the neutralization precipitation pond, adding yellow soda ash precipitates the bismuth in the leach liquor and separates out in the neutralization precipitation pond, in the neutralization precipitation pond, also be provided with electrode control pH value, pH value is controlled at 9-10, and the post precipitation liquid in the neutralization precipitation pond is sent in the copper extraction tank to be handled; The leached mud that the acidleach pond obtains is sent to alkali and soaks the leached mud that adds in the plumbous pond after sodium hydroxide is handled, and the leached mud that obtains carries out pyrometallurgical smelting again to be handled.
The leach liquor that the decopper(ing) pond obtains is sent in the copper abstraction pool, and utilizing has the organism in the cabinet to strip, and is undertaken obtaining copper-contained material and the surplus liquid of extraction behind the copper extraction process by the copper abstraction pool.Copper-contained material is sent into load the processing of stripping in the cabinet, and a material part that obtains after the reextraction has been sent in the cabinet and handled, and remaining anti-stripping agent is sent into the cathode copper that arrives that carries out the electrodeposition processing in the electrodeposition pond; The surplus liquid of the extraction that obtains in the copper extraction box then is sent to settling tank to carry out precipitation process and obtains metals such as antimony, gold, and the waste liquid of settling tank is delivered to Waste Water Treatment and handled.
Claims (1)
1, a kind of lead bronze anode sludge reclaims the method for rare precious metal, it is characterized in that concrete processing method is:
1), at first screen, screening is to handle by the anode sludge that contains electrolytic solution is carried out high melt at smelting furnace; Material after the screening, send in the low-temperature bake stove and carry out roasting with low temperature again with gas blower adding air, enter after material after the roasting cools off and carry out the preimpregnation decopper(ing) in the decopper(ing) pond, in the decopper(ing) process, add sulfuric acid, be provided with electrode control pH value in the decopper(ing) pond, leach liquor and leached mud that process decopper(ing) pond decopper(ing) pre-preg obtains leaching.
2), the leached mud that obtains in the decopper(ing) pond sends in the acidleach pond, adds sulfuric acid and sodium-chlor in the acidleach pond successively, also is provided with electrode control pH value in the acidleach pond, get back leached mud and leach liquor are handled by acidleach in the acidleach pond.The leach liquor that is obtained by the acidleach pond is sent in the hydrolytic tank, antimony chloride in the leach liquor precipitates in hydrolytic tank separates out, precipitation is separated out the leach liquor of antimony chloride and is sent into the neutralization precipitation pond, adding yellow soda ash precipitates the bismuth in the leach liquor and separates out in the neutralization precipitation pond, also be provided with electrode control pH value in the neutralization precipitation pond, the post precipitation liquid in the neutralization precipitation pond is sent in the copper extraction tank to be handled; The leached mud that the acidleach pond obtains is sent to alkali and soaks the leached mud that adds in the plumbous pond after sodium hydroxide is handled, and the leached mud that obtains carries out pyrometallurgical smelting again to be handled.
3), the leach liquor that obtains of decopper(ing) pond sends in the copper abstraction pool, utilizing has the organism in the cabinet to strip, and is undertaken obtaining copper-contained material and the surplus liquid of extraction behind the copper extraction process by the copper abstraction pool.Copper-contained material is sent into load the processing of stripping in the cabinet, and a material part that obtains after the reextraction has been sent in the cabinet and handled, and remaining anti-stripping agent is sent into the cathode copper that arrives that carries out the electrodeposition processing in the electrodeposition pond; The surplus liquid of the extraction that obtains in the copper extraction box then is sent to settling tank to carry out precipitation process and obtains metals such as antimony, gold, and the waste liquid of settling tank is delivered to Waste Water Treatment and handled.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2009100437807A CN101597690A (en) | 2009-06-20 | 2009-06-20 | The method of recycling multiple precious metals from anode mud |
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| CNA2009100437807A CN101597690A (en) | 2009-06-20 | 2009-06-20 | The method of recycling multiple precious metals from anode mud |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102286663A (en) * | 2011-08-19 | 2011-12-21 | 北京矿冶研究总院 | Treatment method of copper-containing gold mud |
| CN102899687A (en) * | 2012-11-13 | 2013-01-30 | 云南天浩稀贵金属股份有限公司 | Separation and extraction process for crude lead containing indium |
| CN103255435A (en) * | 2012-02-15 | 2013-08-21 | 重庆重冶铜业有限公司 | Recycling method for electrolyte solution produced during cathode copper production |
| CN103757421A (en) * | 2014-01-22 | 2014-04-30 | 中条山有色金属集团有限公司 | Method for extracting rare and precious metals from platinum-palladium mud |
| CN103849902A (en) * | 2014-03-25 | 2014-06-11 | 金隆铜业有限公司 | Recovery process of stibium and bismuth in copper electrolyte |
| 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 |
| CN106086440A (en) * | 2016-08-04 | 2016-11-09 | 西北矿冶研究院 | Method for separating and recovering valuable metals in Kaldo furnace smelting slag by wet method |
| CN106282574A (en) * | 2016-08-25 | 2017-01-04 | 安徽华铂再生资源科技有限公司 | Reviver electrolysis anode sludge low smelting heat technique |
| CN109280772A (en) * | 2018-10-15 | 2019-01-29 | 江西理工大学 | A method of leaching simultaneously step separation and concentration antimony, bismuth, arsenic from copper anode mud |
| CN114150154A (en) * | 2021-12-08 | 2022-03-08 | 武汉理工大学 | Recovery device and recovery method for electrolytic machining of titanium-aluminum alloy anode slag mud |
-
2009
- 2009-06-20 CN CNA2009100437807A patent/CN101597690A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102286663B (en) * | 2011-08-19 | 2012-12-26 | 北京矿冶研究总院 | Treatment method of copper-containing gold mud |
| CN102286663A (en) * | 2011-08-19 | 2011-12-21 | 北京矿冶研究总院 | Treatment method of copper-containing gold mud |
| CN103255435A (en) * | 2012-02-15 | 2013-08-21 | 重庆重冶铜业有限公司 | Recycling method for electrolyte solution produced during cathode copper production |
| CN102899687A (en) * | 2012-11-13 | 2013-01-30 | 云南天浩稀贵金属股份有限公司 | Separation and extraction process for crude lead containing indium |
| CN103757421B (en) * | 2014-01-22 | 2015-08-12 | 中条山有色金属集团有限公司 | The extracting method of rare precious metal in platinum palladium mud |
| CN103757421A (en) * | 2014-01-22 | 2014-04-30 | 中条山有色金属集团有限公司 | Method for extracting rare and precious metals from platinum-palladium mud |
| CN103849902A (en) * | 2014-03-25 | 2014-06-11 | 金隆铜业有限公司 | Recovery process of stibium and bismuth in copper electrolyte |
| 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 |
| CN106086440A (en) * | 2016-08-04 | 2016-11-09 | 西北矿冶研究院 | Method for separating and recovering valuable metals in Kaldo furnace smelting slag by wet method |
| CN106086440B (en) * | 2016-08-04 | 2017-12-22 | 西北矿冶研究院 | Method for separating and recovering valuable metals in Kaldo furnace smelting slag by wet method |
| CN106282574A (en) * | 2016-08-25 | 2017-01-04 | 安徽华铂再生资源科技有限公司 | Reviver electrolysis anode sludge low smelting heat technique |
| CN106282574B (en) * | 2016-08-25 | 2018-07-24 | 安徽华铂再生资源科技有限公司 | Reviver electrolysis anode sludge low smelting heat technique |
| CN109280772A (en) * | 2018-10-15 | 2019-01-29 | 江西理工大学 | A method of leaching simultaneously step separation and concentration antimony, bismuth, arsenic from copper anode mud |
| CN114150154A (en) * | 2021-12-08 | 2022-03-08 | 武汉理工大学 | Recovery device and recovery method for electrolytic machining of titanium-aluminum alloy anode slag mud |
| CN114150154B (en) * | 2021-12-08 | 2023-10-20 | 武汉理工大学 | Recovery device and recovery method for electrolytic processing of titanium-aluminum alloy anode slime |
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Open date: 20091209 |