CN106834691A - A kind of copper anode mud wet-treating comprehensive recycling process - Google Patents
A kind of copper anode mud wet-treating comprehensive recycling process Download PDFInfo
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- CN106834691A CN106834691A CN201611245397.6A CN201611245397A CN106834691A CN 106834691 A CN106834691 A CN 106834691A CN 201611245397 A CN201611245397 A CN 201611245397A CN 106834691 A CN106834691 A CN 106834691A
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- silver
- copper
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- lead
- liquid
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/02—Elemental selenium or tellurium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
-
- 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
Abstract
The present invention provides a kind of copper anode mud wet-treating comprehensive recycling process, and the technological process is：Copper anode mud-high pressure leaching-point copper, copper leached solution send copper electrodeposition-point lead, lead sulfate-parting is obtained after dividing the heavy lead of lead liquid, the reduction of parting liquid send selen-tellurjum platinum palladium operation to extract selenium, tellurium, platinum palladium-point silver after obtaining thick bronze, silvering solution reduction is divided to obtain raw Ag powder-thick bronze casting gold anode, Gold electrolysis, electric gold is cast into ingot-raw Ag powder casting silver anode, silver electrolysis, electric silver is cast into silver ingot；Advantage is：Improve operating environment；Reduce the treating capacity of lower procedure；Improve each element rate of recovery and direct yield；Reduce the loss late of gold and silver.
Description
Technical field
The present invention relates to nonferrous metallurgy field, more particularly, to a kind of copper anode mud wet-treating comprehensive recycling process.
Background technology
Copper anode mud is a kind of important material rich in dilute your dissipated metal such as gold and silver, selenium, tellurium, platinum, palladium, wherein world's gold
Quite a few of silver-colored yield comes from copper anode mud.In recent ten years, rising steadily with the price of gold, from copper anode mud
It is efficient to reclaim the noble metals such as gold and silver and comprehensively utilize other valuable metals, paid attention to by various countries are increasingly extensive.Except constantly complete
Outside traditional pyrogenic attack technique that kind and transformation has been used, the new technology also to copper anode mud treatment is ground both at home and abroad
Study carefully.China's copper anode mud composition is more complicated, is characterized in that most of earth of positive pole content of beary metal is high, and the noble metal such as gold and silver contains
Amount is low, and composition is different.Processing method neither one fixed mode, the technique of use differs from one another.Current technique is back
Gold, silver therein, selenium and copper are received, the valuable metals such as a large amount of telluriums, tin are wasted, the substantial amounts of energy is so not only wasted, and it is dirty
Dye is serious.
The content of the invention
It is an object of the invention to be solution the deficiencies in the prior art, and a kind of copper anode mud wet-treating is provided and is comprehensively returned
Knock off skill.
The new technical scheme of the present invention is：A kind of copper anode mud wet-treating comprehensive recycling process, the technological process is：
Copper anode mud-high pressure leaching-point copper, copper leached solution send copper electrodeposition-point lead, and lead sulfate-parting is obtained after the heavy lead of point lead liquid, point
The reduction of golden liquid send selen-tellurjum platinum palladium operation to extract selenium, tellurium, platinum palladium-point silver after obtaining thick bronze, a point silvering solution reduction obtain raw Ag powder-
Thick bronze casting gold anode, Gold electrolysis, electric gold is cast into ingot-raw Ag powder casting silver anode, and silver electrolysis, electric silver is cast into silver
Ingot.
Described point of copper：Earth of positive pole addition water and sulfuric acid carry out pulp, add water and are added in autoclave, temperature liter
During to 90 DEG C, start logical oxygen pressurization, pressure is maintained 1.2MPa, react 3 hours, temperature rises to 140 DEG C or so, reacted
Cheng Hou, is lowered the temperature, pressure release, and releases slurries filtration；
The copper leached solution treatment：Copper leached solution enters into copper electrodeposition operation, by copper electrodeposition therein into tough cathode, as product；
Described point of lead：Solid-to-liquid ratio takes 1:4；Plus Na2CO3 adjusts pH 8~9 or so, is reacted 4~5 hours at 50~70 DEG C or so, sinks
Filtered behind shallow lake, filter residue is washed with 2 times of clear water of solid reactant doses again, wash filtering, filtrate treatment, filter residue is added to heavy lead
In liquid, and nitric acid is mended, bubble-free is produced, heating response 30~50 minutes, after the completion of reaction, filtering, filter residue is with 2 times of solid reactions
The clear water washing of inventory, then refilters, and filtrate adds excess sulfuric acid, is filtered after reaction, and filter residue is lead sulfate；
The parting：Solid-to-liquid ratio takes 1:3, sulfuric acid concentration takes 120~150g/L, and NaCl takes 40~60g/L, is heated to 60~80 DEG C
Left and right, is initially added into NaClO3, reacts 2~3 hours, and clear water washing, suction filtration after the completion of reaction, filtrate use sub- sodium reduction, reaction
1~2 hour time, reducing slag is golden selenium slag, adds nitric acid according to 1:1, temperature：50~70 DEG C, reaction a period of time filters, and obtains
To bronze and parting liquid, parting liquid is reduced with SO2 and obtains coarse tellurium powder；Liquid zinc ingot metal displacement platinum palladium obtains Pt Pd concentrate after reduction；
Described point of silver：Solid-to-liquid ratio takes 1:10, sodium sulfite takes 200~300g/L, and liquid pH is adjusted into 8~9 left sides with NaOH
The right side, normal-temperature reaction 3~5 hours, reaction completion carries out suction filtration, and silver separating residues are washed with clear water again, obtain silver separating residues and point silvering solution, point
Silvering solution adds NaOH 20g/L, adds formaldehyde to solution to be produced without precipitation, and silver powder raw Ag powder is obtained after filtering；Raw Ag powder is put into point
1100~1300 DEG C in silver stove, in 1~2 day reaction time, silver ingot is obtained.
The beneficial effects of the invention are as follows：The generation of flue gas is reduced, operating environment is improved, sulfating roasting product is solved
Raw environmental issue；Increase point splicer's sequence, can both extract lead element, the treating capacity and auxiliary material that lower procedure can be reduced again are used
The treating capacity of amount and waste water；Can be with the gold, silver in synthetical recovery copper anode mud, copper, lead, selenium, tellurium, bismuth, platinum, palladium, tin, nickel
Deng each element rate of recovery and direct yield are high；The quantity of slag of tailings silver separating residues is few, accounts for 15% or so of the treating capacity of input copper anode mud,
Gold content in silver separating residues is less than 50g/t, and silver content is less than 5000g/t, reduces the loss late of gold and silver；Silver separating residues return Copper making
Or lead smelting system.
Brief description of the drawings
Fig. 1 is flow chart of the invention.
Specific embodiment
The present invention will be further described below in conjunction with the accompanying drawings.
A kind of copper anode mud wet-treating comprehensive recycling process, the technological process is：Copper anode mud-high pressure leaching-
Divide copper, copper leached solution to send copper electrodeposition-point lead, lead sulfate-parting is obtained after the heavy lead of point lead liquid, after the reduction of parting liquid obtains thick bronze
Selen-tellurjum platinum palladium operation is sent to extract selenium, tellurium, platinum palladium-point silver, a point silvering solution reduction obtains raw Ag powder-thick bronze casting gold anode, gold
Electrolysis, electric gold is cast into ingot-raw Ag powder casting silver anode, and silver electrolysis, electric silver is cast into silver ingot.
Described point of copper：Earth of positive pole addition water and sulfuric acid carry out pulp, add water and are added in autoclave, temperature liter
During to 90 DEG C, start logical oxygen pressurization, pressure is maintained 1.2MPa, react 3 hours, temperature rises to 140 DEG C or so, reacted
Cheng Hou, is lowered the temperature, pressure release, and releases slurries filtration；
The copper leached solution treatment：Copper leached solution enters into copper electrodeposition operation, by copper electrodeposition therein into tough cathode, as product；
Described point of lead：Solid-to-liquid ratio takes 1:4；Plus Na2CO3 adjusts pH 8~9 or so, is reacted 4~5 hours at 50~70 DEG C or so, sinks
Filtered behind shallow lake, filter residue is washed with 2 times of clear water of solid reactant doses again, wash filtering, filtrate treatment, filter residue is added to heavy lead
In liquid, and nitric acid is mended, bubble-free is produced, heating response 30~50 minutes, after the completion of reaction, filtering, filter residue is with 2 times of solid reactions
The clear water washing of inventory, then refilters, and filtrate adds excess sulfuric acid, is filtered after reaction, and filter residue is lead sulfate；
The parting：Solid-to-liquid ratio takes 1:3, sulfuric acid concentration takes 120~150g/L, and NaCl takes 40~60g/L, is heated to 60~80 DEG C
Left and right, is initially added into NaClO3, reacts 2~3 hours, and clear water washing, suction filtration after the completion of reaction, filtrate use sub- sodium reduction, reaction
1~2 hour time, reducing slag is golden selenium slag, adds nitric acid according to 1:1, temperature：50~70 DEG C, reaction a period of time filters, and obtains
To bronze and parting liquid, parting liquid is reduced with SO2 and obtains coarse tellurium powder；Liquid zinc ingot metal displacement platinum palladium obtains Pt Pd concentrate after reduction；
Described point of silver：Solid-to-liquid ratio takes 1:10, sodium sulfite takes 200~300g/L, and liquid pH is adjusted into 8~9 left sides with NaOH
The right side, normal-temperature reaction 3~5 hours, reaction completion carries out suction filtration, and silver separating residues are washed with clear water again, obtain silver separating residues and point silvering solution, point
Silvering solution adds NaOH 20g/L, adds formaldehyde to solution to be produced without precipitation, and silver powder raw Ag powder is obtained after filtering；Raw Ag powder is put into point
1100~1300 DEG C in silver stove, in 1~2 day reaction time, silver ingot is obtained.
Claims (2)
1. a kind of copper anode mud wet-treating comprehensive recycling process, it is characterised in that：The technological process is：Copper anode mud-height
Pressure leaching-point copper, copper leached solution send copper electrodeposition-point lead, and lead sulfate-parting is obtained after the heavy lead of point lead liquid, and the reduction of parting liquid is obtained
Selen-tellurjum platinum palladium operation is sent to extract selenium, tellurium, platinum palladium-point silver after thick bronze, a point silvering solution reduction obtains raw Ag powder-thick bronze casting gold
Anode, Gold electrolysis, electric gold is cast into ingot-raw Ag powder casting silver anode, and silver electrolysis, electric silver is cast into silver ingot.
2. a kind of copper anode mud wet-treating comprehensive recycling process according to claim 1, it is characterised in that：
（1）Described point of copper：Earth of positive pole addition water and sulfuric acid carry out pulp, add water and are added in autoclave, temperature liter
During to 90 DEG C, start logical oxygen pressurization, pressure is maintained 1.2MPa, react 3 hours, temperature rises to 140 DEG C or so, reacted
Cheng Hou, is lowered the temperature, pressure release, and releases slurries filtration；
（2）The copper leached solution treatment：Copper leached solution enters into copper electrodeposition operation, by copper electrodeposition therein into tough cathode, as product；
（3）Described point of lead：Solid-to-liquid ratio takes 1:4；Plus Na2CO3 adjusts pH 8~9 or so, reacts 4~5 at 50~70 DEG C or so small
When, being filtered after precipitation, filter residue is washed with 2 times of clear water of solid reactant doses again, washes filtering, and filtrate treatment, filter residue is added
To in heavy lead liquid, and nitric acid is mended, bubble-free is produced, heating response 30~50 minutes, after the completion of reaction, filtering, filter residue is solid with 2 times
The clear water washing of precursor reactant inventory, then refilters, and filtrate adds excess sulfuric acid, is filtered after reaction, and filter residue is lead sulfate；
（4）The parting：Solid-to-liquid ratio takes 1:3, sulfuric acid concentration takes 120~150g/L, and NaCl takes 40~60g/L, it is heated to 60~
80 DEG C or so, NaClO3 is initially added into, reacted 2~3 hours, clear water washing, suction filtration after the completion of reaction, filtrate use sub- sodium reduction,
1~2 hour reaction time, reducing slag is golden selenium slag, adds nitric acid according to 1:1, temperature：50~70 DEG C, react a period of time mistake
Filter, obtains bronze and parting liquid, and parting liquid is reduced with SO2 and obtains coarse tellurium powder；Liquid zinc ingot metal displacement platinum palladium obtains platinum palladium after reduction
Concentrate；
（5）Described point of silver：Solid-to-liquid ratio takes 1:10, sodium sulfite takes 200~300g/L, and liquid pH is adjusted into 8~9 with NaOH
Left and right, normal-temperature reaction 3~5 hours, reaction completion carries out suction filtration, and silver separating residues are washed with clear water again, obtain silver separating residues and point silvering solution,
Divide silvering solution to add NaOH 20g/L, add formaldehyde to solution to be produced without precipitation, silver powder raw Ag powder is obtained after filtering；Raw Ag powder is put into
Divide 1100~1300 DEG C in silver stove, in 1~2 day reaction time, obtain silver ingot.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611245397.6A CN106834691A (en) | 2016-12-29 | 2016-12-29 | A kind of copper anode mud wet-treating comprehensive recycling process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611245397.6A CN106834691A (en) | 2016-12-29 | 2016-12-29 | A kind of copper anode mud wet-treating comprehensive recycling process |
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| CN106834691A true CN106834691A (en) | 2017-06-13 |
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| CN201611245397.6A Pending CN106834691A (en) | 2016-12-29 | 2016-12-29 | A kind of copper anode mud wet-treating comprehensive recycling process |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107299359A (en) * | 2017-06-20 | 2017-10-27 | 中国科学院过程工程研究所 | A kind of method for reclaiming selenium in liquid after point copper |
| CN108034825A (en) * | 2017-12-22 | 2018-05-15 | 中国科学院过程工程研究所 | The method that wet method extracts gold and silver from the earth of positive pole |
| CN109971964A (en) * | 2019-04-25 | 2019-07-05 | 江西自立环保科技有限公司 | A kind of processing method of the high tin high-copper regeneration tin anode mud of high palladium |
| CN112695200A (en) * | 2020-12-22 | 2021-04-23 | 万载志成实业有限公司 | Method for recovering selenium, gold and silver from copper anode slime |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1766140A (en) * | 2005-09-20 | 2006-05-03 | 云南冶金集团总公司 | Novel copper recovery method by copper anode mud pressurization and pickling |
| CN101338368A (en) * | 2008-08-08 | 2009-01-07 | 中南大学 | Method for preprocessing anode sludge and recovering dissipated metal |
| CN101831553A (en) * | 2010-05-28 | 2010-09-15 | 北京科技大学 | Method for green recovery of waste circuit boards by cyanide-free full-wet whole set process |
-
2016
- 2016-12-29 CN CN201611245397.6A patent/CN106834691A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1766140A (en) * | 2005-09-20 | 2006-05-03 | 云南冶金集团总公司 | Novel copper recovery method by copper anode mud pressurization and pickling |
| CN101338368A (en) * | 2008-08-08 | 2009-01-07 | 中南大学 | Method for preprocessing anode sludge and recovering dissipated metal |
| CN101831553A (en) * | 2010-05-28 | 2010-09-15 | 北京科技大学 | Method for green recovery of waste circuit boards by cyanide-free full-wet whole set process |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107299359A (en) * | 2017-06-20 | 2017-10-27 | 中国科学院过程工程研究所 | A kind of method for reclaiming selenium in liquid after point copper |
| CN108034825A (en) * | 2017-12-22 | 2018-05-15 | 中国科学院过程工程研究所 | The method that wet method extracts gold and silver from the earth of positive pole |
| CN108034825B (en) * | 2017-12-22 | 2019-07-19 | 中国科学院过程工程研究所 | The method that wet process extracts gold and silver from the earth of positive pole |
| CN109971964A (en) * | 2019-04-25 | 2019-07-05 | 江西自立环保科技有限公司 | A kind of processing method of the high tin high-copper regeneration tin anode mud of high palladium |
| CN112695200A (en) * | 2020-12-22 | 2021-04-23 | 万载志成实业有限公司 | Method for recovering selenium, gold and silver from copper anode slime |
| CN112695200B (en) * | 2020-12-22 | 2022-05-20 | 万载志成实业有限公司 | Method for recovering selenium, gold and silver from copper anode slime |
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