CN102373336B - Method for separating copper and silver from dross produced by producing copper from smelting lead - Google Patents
Method for separating copper and silver from dross produced by producing copper from smelting lead Download PDFInfo
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- CN102373336B CN102373336B CN201110343390.9A CN201110343390A CN102373336B CN 102373336 B CN102373336 B CN 102373336B CN 201110343390 A CN201110343390 A CN 201110343390A CN 102373336 B CN102373336 B CN 102373336B
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- copper
- silver
- lead
- plumbous
- alloy
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- 239000010949 copper Substances 0.000 title claims abstract description 89
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 52
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 25
- 239000004332 silver Substances 0.000 title claims abstract description 24
- 238000003723 Smelting Methods 0.000 title claims abstract description 11
- 238000007670 refining Methods 0.000 claims abstract description 20
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 17
- 229910001316 Ag alloy Inorganic materials 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000002893 slag Substances 0.000 claims description 39
- 238000009413 insulation Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 239000011343 solid material Substances 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 239000010802 sludge Substances 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 22
- 239000002184 metal Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 229910045601 alloy Inorganic materials 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 abstract 2
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000007796 conventional method Methods 0.000 abstract 1
- 241000722270 Regulus Species 0.000 description 10
- 229910052745 lead Inorganic materials 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WIKSRXFQIZQFEH-UHFFFAOYSA-N [Cu].[Pb] Chemical compound [Cu].[Pb] WIKSRXFQIZQFEH-UHFFFAOYSA-N 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 241001062472 Stokellia anisodon Species 0.000 description 1
- ZIALXKMBHWELGF-UHFFFAOYSA-N [Na].[Cu] Chemical compound [Na].[Cu] ZIALXKMBHWELGF-UHFFFAOYSA-N 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for separating copper and silver from dross produced by producing the copper from smelting lead. The method comprises the following steps of: putting solid dross materials produced by producing the copper from smelting the lead under a vacuum condition, collecting volatile materials after heating and insulating the solid dross materials for many times, and condensing the volatile materials to obtain a lead-silver alloy, wherein remaining solid is a lead- and silver-removed copper alloy; taking the lead-silver alloy as a raw material to enter a conventional lead smelting process or an electrolytic refining process, wherein the silver is enriched in anode mud, so that recovered silver is obtained; and directly taking the lead- and silver-removed copper alloy as raw materials to obtain recovered metal copper by using a conventional method. The method has the advantages of high adaptability of raw materials, simplicity, environmental protection, high metal separating and recovering efficiency, short process flow, convenience for operation and obvious economic benefit, and can be used for treating various lead-, silver- and copper-containing copper-based or lead-based alloys; a vacuum distilling method is adopted; and silver content and lead content in the remaining solid are 200g/t and 0.01% respectively.
Description
Technical field
The present invention relates to a kind of plumbous copper and silver-colored method in copper dross slag, genus vacuum metallurgy technology metal field of producing of refining that separate.
Background technology
Copper dross slag (also claiming pot face slag) is the product that the refining of lead bullion is interrupted copper removal, and it is containing Cu approximately 10～50%, Pb 40～70%, Ag 100～10000g/t and other element (As, Sb, Sn, Zn etc.).Owing to dragging for the difference of slag mode and equipment, scum silica frost form is also different, and common have forms such as loose fine particulate, bulk.The pyrometallurgy equipment of copper dross slag can be used blast furnace, reverberatory furnace, rotary kiln and electric furnace; Hydrometallurgical process can be used pickling process, ammonia leaching process.Pyrogenic process is used for processing lumpy material, and wet method is for the treatment of loose fine particle.
China processes copper dross slag and adopts soda ash-iron filings method more.Soda ash-iron filings method is to utilize soda ash to make arsenic, antimony generate sodium salt to enter slag, and makes sodium copper matte regulus, adds iron filings to reduce leaded in copper matte regulus (lead matte) and slag, and the copper-lead of raising copper matte regulus is than (Cu/Pb).
Reverberatory furnace is the equipment of the most frequently used processing copper dross slag, adopts reverberatory furnace soda ash-iron filings method to process copper dross slag lead recovery high, can reach 97%.In copper matte regulus, copper-lead can reach 5～9 than (Cu/Pb).Strain smelting adopts 9.5m
2reverberatory furnace is processed the copper dross slag containing Cu 10～20%, Pb 60～70%, and output copper matte regulus is containing Cu 26～45%, Pb 3～7%.Shaoguan Smelter is processed containing the copper dross slag output copper matte regulus of Cu 10～15%, Pb 60% and is contained Cu>40%, Pb<7%.
Blast furnace is also for the treatment of copper dross slag, adopts blast furnace to process copper dross slag generally adding before blast furnace first carrying out property sintering, is conducive to like this utilize copper-lead blast furnace, need not build other equipment again.Adopting blast furnace to process copper dross slag shortcoming is that in copper matte regulus, copper-lead is lower than (Cu/Pb), and the rate of recovery of copper is low, and a large amount of copper remains in lead, causes copper, arsenic and precious metal to circulate during the course.Shuikoushan three smeltings adopt blast furnace to process the copper dross slag containing Cu 20～30%, Pb 50～70%, and output copper matte regulus is containing Cu 35～40%, Pb 5～6%.
The difference of the employing rotary kiln processing each factory of copper dross slag is larger, is mainly that output copper matte regulus contains Cu 30～40%, contains Pb 10～15% because the process system that each factory adopts is distinguished greatly, charge composition difference is also very large.USSR (Union of Soviet Socialist Republics) Lenin's Knowles Ke Qian factory has developed electric furnace and has processed copper dross slag technology, and a Jia Qian factory of USSR (Union of Soviet Socialist Republics) electricity Xin factory and Japan also adopts this method.This method exhaust gas volumn is little, and metal loss is few, but working expense is higher.Lenin's Knowles Ke Qian factory and office reason is containing the copper dross slag of Cu 20～30%, Pb 50～70%, and output copper matte regulus is containing Cu 41.5%, Pb 6.2%.
First Germany Du Yi Regensburg smeltery processes the technique of copper dross slag in industrial employing pickling process, its scum silica frost is containing Cu 30～45%, Pb 40～60%, output 1
#electrolytic copper.First adopting ammonia leaching process to process the producer of copper dross slag is Australian CRA group, and after this Japanese eight smelteries, family also adopt this method to process copper dross slag, output 1
#electrolytic copper or copper sulfate.
Above-mentioned these art breading copper dross slags, technique is all comparatively complicated, and all needs to consume a large amount of other raw materials, and the metallic lead rate of recovery is lower.Pyrogenic attack product is containing Cu amount >50%, also with other a large amount of valuable metals, as gold and silver all need further to process and reclaim.Wet processing produces a large amount of waste water, waste liquid, has increased the cost of sewage disposal.
Summary of the invention
For residue copper alloy tool silver content and lead tolerance are reduced, and can conveniently reclaim silver metal, overcome many drawbacks of traditional soda ash-iron filings method, the invention provides a kind of copper and silver-colored method in the plumbous product of refining copper dross slag that separate, by following technical proposal, realize.
Separate copper and a silver-colored method in the plumbous product of refining copper dross slag, the following each step of process:
A. get the plumbous copper dross slag solid materials that produces of refining, be placed under vacuum condition, with the temperature rise rate of 10～15 ℃/min, be warming up to 1100～1200 ℃, insulation 30～60min; After pressure is lower than 5Pa, then continue to be warming up to 1400～1600 ℃ with the temperature rise rate of 15～20 ℃/min, insulation 1～3h; Until pressure, during lower than 20Pa, stop heating; Treat that temperature is down to below 100 ℃, close vacuum; , collect volatile matter therebetween, condensation obtains pb-ag alloy, and remaining solid is to slough plumbous and silver-colored copper alloy;
B. using steps A gained pb-ag alloy as raw material, enter conventional plumbous smelting procedure or electrorefining operation, silver is enriched in the anode sludge, is recycled silver; Steps A gained is sloughed to plumbous and silver-colored copper alloy directly as raw material, with ordinary method (as copper is smelted), be recycled metallic copper.
Refining in described steps A is plumbous produces copper dross slag solid materials the plumbous refining copper dross slag that produces is reduced after processing and made; If the plumbous copper dross slag that produces of refining is for solid materials is without reducing processing.
The present invention has the following advantages:
(1) adaptability to raw material is strong, and the method can be processed copper base or the lead 2-base alloy of various leaded, silver-colored, copper;
(2) utilize vacuum distilling method, preparation method is simple, environmental friendliness;
(3) Separation and Recovery metal efficiency is high, silver content <200g/t, lead tolerance <0.01% in remaining solid (sloughing plumbous and silver-colored copper alloy);
(4) technical process is short, easy to operate, remarkable in economical benefits.
Embodiment
Below in conjunction with embodiment, further illustrate content of the present invention, but these examples do not limit the scope of the invention.
Embodiment 1
That A. gets 50g cupric approximately 20%, leaded approximately 70%, the about 3000g/t of argentiferous reduce by the plumbous copper dross slag that produces of refining the plumbous product of the refining copper dross slag solid materials making after processing, be placed under vacuum condition, with the temperature rise rate of 10 ℃/min, be warming up to 1100 ℃, insulation 30min; After pressure is 4Pa, then continue to be warming up to 1450 ℃ with the temperature rise rate of 15 ℃/min, insulation 1h; When pressure is 10Pa, stop heating; When temperature is down to 90 ℃, close vacuum; , collect volatile matter therebetween, condensation obtains pb-ag alloy, and remaining solid is to slough plumbous and silver-colored copper alloy; Wherein, in copper alloy, residual silver amount is 180g/t; Lead tolerance >99% in pb-ag alloy, silver amount is 7800g/t;
B. using steps A gained pb-ag alloy as raw material, enter conventional plumbous smelting procedure, silver is enriched in the anode sludge, is recycled silver; Steps A gained is sloughed to plumbous and silver-colored copper alloy directly as raw material, by the copper method of smelting, be recycled metallic copper.
Embodiment 2
A. the copper argentalium alloy (the plumbous copper dross slag solid materials that produces of refining) of getting 10Kg cupric approximately 30%, leaded approximately 60%, the about 4000g/t of argentiferous, is placed under vacuum condition, with the temperature rise rate of 12 ℃/min, is warming up to 1200 ℃, insulation 40min; After pressure is 3Pa, then continue to be warming up to 1600 ℃ with the temperature rise rate of 18 ℃/min, insulation 1.5h; When pressure is 18Pa, stop heating; Treat that temperature is down to below 97 ℃, close vacuum; , collect volatile matter therebetween, condensation obtains pb-ag alloy, and remaining solid is to slough plumbous and silver-colored copper alloy; Wherein in copper alloy, residual silver amount is 27.5g/t, lead tolerance >99% in pb-ag alloy, and silver amount is 8000g/t;
B. steps A gained pb-ag alloy is entered to conventional electrolysis refining procedure as raw material, silver is enriched in the anode sludge, is recycled silver; Steps A gained is sloughed to plumbous and silver-colored copper alloy directly as raw material, by ordinary method, be recycled metallic copper.
Embodiment 3
A. the copper argentalium alloy (the plumbous copper dross slag solid materials that produces of refining) of getting 20Kg cupric approximately 40%, leaded approximately 50%, the about 4500g/t of argentiferous, is placed under vacuum condition, with the temperature rise rate of 15 ℃/min, is warming up to 1150 ℃, insulation 60min; After pressure is 4Pa, then continue to be warming up to 1400 ℃ with the temperature rise rate of 20 ℃/min, insulation 3h; When pressure is 15Pa, stop heating; When temperature is down to 80 ℃, close vacuum; , collect volatile matter therebetween, condensation obtains pb-ag alloy, and remaining solid is to slough plumbous and silver-colored copper alloy; Wherein in copper alloy, residual silver amount is 5.8g/t, lead tolerance >99% in pb-ag alloy, and silver amount is 12613g/t;
B. using steps A gained pb-ag alloy as raw material, enter conventional plumbous smelting procedure, silver is enriched in the anode sludge, is recycled silver; Steps A gained is sloughed to plumbous and silver-colored copper alloy directly as raw material, by copper, smelt and be recycled metallic copper.
Claims (2)
1. separate copper and a silver-colored method in the plumbous product of refining copper dross slag, it is characterized in that through following each step:
A. get the plumbous copper dross slag solid materials that produces of refining, be placed under vacuum condition, with the temperature rise rate of 10～15 ℃/min, be warming up to 1100～1200 ℃, insulation 30～60min; After pressure is lower than 5Pa, then continue to be warming up to 1400～1600 ℃ with the temperature rise rate of 15～20 ℃/min, insulation 1～3h; Until pressure, during lower than 20Pa, stop heating; Treat that temperature is down to below 100 ℃, close vacuum; , collect volatile matter therebetween, condensation obtains pb-ag alloy, and remaining solid is to slough plumbous and silver-colored copper alloy;
B. using steps A gained pb-ag alloy as raw material, enter conventional plumbous smelting procedure or electrorefining operation, silver is enriched in the anode sludge, is recycled silver; Steps A gained is sloughed to plumbous and silver-colored copper alloy directly as raw material, with ordinary method, be recycled metallic copper.
2. method according to claim 1, is characterized in that: refining in described steps A is plumbous produces copper dross slag solid materials the plumbous refining copper dross slag that produces is reduced after processing and made; If the plumbous copper dross slag that produces of refining is for solid materials is without reducing processing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110343390.9A CN102373336B (en) | 2011-11-03 | 2011-11-03 | Method for separating copper and silver from dross produced by producing copper from smelting lead |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110343390.9A CN102373336B (en) | 2011-11-03 | 2011-11-03 | Method for separating copper and silver from dross produced by producing copper from smelting lead |
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| CN102373336A CN102373336A (en) | 2012-03-14 |
| CN102373336B true CN102373336B (en) | 2014-05-07 |
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| CN201110343390.9A Expired - Fee Related CN102373336B (en) | 2011-11-03 | 2011-11-03 | Method for separating copper and silver from dross produced by producing copper from smelting lead |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102676832A (en) * | 2012-05-10 | 2012-09-19 | 昆明理工大学 | Method for separating copper from lead through vacuum distillation of copper scum |
| CN102747231B (en) * | 2012-07-06 | 2014-10-22 | 赵志强 | Method for treating copper dross by induction electric furnace |
| CN103397200B (en) * | 2013-08-23 | 2015-06-10 | 阳谷祥光铜业有限公司 | Method for removing lead, zinc, arsenic, antimony, bismuth and tin from copper matte |
| CN105132708B (en) * | 2015-10-12 | 2017-07-07 | 湖南金旺铋业股份有限公司 | A kind of abundant process for reclaiming copper dross slag matte noble metal |
| CN112210672B (en) * | 2020-10-20 | 2021-12-07 | 昆明理工大学 | Method for purifying crude silver |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560606A (en) * | 2009-05-19 | 2009-10-21 | 昆明鼎邦科技有限公司 | Deleading method through vacuum distillation of noble lead materials |
| CN101696469A (en) * | 2009-10-29 | 2010-04-21 | 昆明理工大学 | Method for separating multi-element alloy of lead, bismuth, gold, silver and copper |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6017022A (en) * | 1983-07-08 | 1985-01-28 | Nippon Mining Co Ltd | Method for recovering se and ag from copper |
| JPH0456083A (en) * | 1990-06-21 | 1992-02-24 | Nec Corp | Coaxial connector |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560606A (en) * | 2009-05-19 | 2009-10-21 | 昆明鼎邦科技有限公司 | Deleading method through vacuum distillation of noble lead materials |
| CN101696469A (en) * | 2009-10-29 | 2010-04-21 | 昆明理工大学 | Method for separating multi-element alloy of lead, bismuth, gold, silver and copper |
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