CN104233372B - Method for recovering copper from lead matte - Google Patents
Method for recovering copper from lead matte Download PDFInfo
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- CN104233372B CN104233372B CN201410519503.XA CN201410519503A CN104233372B CN 104233372 B CN104233372 B CN 104233372B CN 201410519503 A CN201410519503 A CN 201410519503A CN 104233372 B CN104233372 B CN 104233372B
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a method for recovering copper from lead matte. The method comprises the following steps: (1) crushing and grinding lead matte blocks into lead matte powder; (2) leaching the lead matte powder by sulfuric acid solution, continuously blowing in oxygen-enriched air and after completing leaching, carrying out solid-liquid separation to obtain leaching slags and copper sulfate leachate, wherein a leaching temperature is 70 DEG C to 90 DEG C and leaching time is 2h to 3h; (3) carrying out electrodeposition on the copper sulfate leachate, continuously blowing in air at a cathode of formed copper and simultaneously, continuously reducing current density so as to obtain cathode copper. The method disclosed by the invention is low in investment, is low in energy consumption, adopts a simple process, can produce high-purity dense copper and nearly generates zero pollution to the environment.
Description
Technical field
The invention belongs to Non-ferrous Metallurgy field, is related to a kind of method that copper is reclaimed from lead copper matte, more particularly to one
Plant the method that copper is reclaimed from lead copper matte using wet process smelting technique low energy consumption ground.
Background technology
Lead copper matte is a kind of side-product produced in shaft smelting and pyrometallurgical smelting of lead operation in lead smelting process.
The main component of lead copper matte is cuprous sulfide, vulcanized lead, Iron sulfuret. etc., and the content of wherein each element is generally：Copper：15%～
30%, lead：50%～65%, ferrum：1%～5%, sulfur：5%～15%.
For the process of lead copper matte, medium-sized and small enterprises are typically sold to copper smelting plant using lead copper matte as copper raw material, in copper
Use with refined copper ore deposit dispensing in smeltery, through the last output in the form of negative electrode electrolytic copper of copper metallurgy industry.In large-scale smeltery
In, generally by pyrogenic attack lead copper matte, lead copper matte to be blown in converter, blister copper is obtained, further refine is obtained
Electrolytic copper.But there are the serious problems such as low metal recovery rate, technological process length, running cost height, environmental pollution in the method, typically
Cannot miniaturization.
With the lifting of scientific and technological level and reaching its maturity for technology, Ye You enterprises process lead ice using new technology and method
Copper.The Chinese patent literature of publication number CN101225476A discloses a kind of " technique that copper is reclaimed from lead copper matte ", the method
Lead copper matte is processed using pressure leaching wet processing.Lead copper matte block is milled to into granularity less than 40 mesh, the lead copper matte after grinding is used
Useless electric effusion or dilution heat of sulfuric acid send into autoclave after sizing mixing, and are passed through oxygen, so as to leach copper.The leachate of cupric is using electricity
The method of deposition reclaims the copper in solution, and leached mud returns pyrometallurgical smelting of lead system and reclaims the valuable metals such as lead, silver.Although the technique
The Selectively leaching of metal can be realized, the response rate of metal is high, but is because that process conditions need High Temperature High Pressure, give operation band
To be inconvenient.The Chinese patent literature of Publication No. CN102051478A discloses " a kind of wet process for treating lead copper matte ".
The technique soaks method PROCESS FOR TREATMENT lead copper matte, lead copper matte sulphuric acid and Leaching of sodium chloride using normobaric oxygen, and lead is then with lead sulfate
Stay in slag with the form of lead chloride, after carrying out solid-liquid separation, the leachate iron reduction of cupric obtains copper sponge, after reduction
Waste liquid be used for reclaiming ferrum, leached mud returns pyrometallurgical smelting of lead system and reclaims the valuable metals such as lead, silver.Although the method can be realized
Normobaric oxygen leaching wet treatment to lead copper matte, but copper products are copper sponge.The method needs to produce copper to be applied to industry, also
Product carry out the complicated PROCESS FOR TREATMENT such as tabletting, calcining, melting, and this undoubtedly increased energy consumption and cost.Therefore, in order to solve
These problems, are badly in need of finding a kind of new technique to process lead copper matte.
The content of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, there is provided a kind of little, energy consumption of investment is low, technique
Simply, high-purity densification copper and the method that copper is reclaimed from lead copper matte to the almost nil pollution of environment can be produced.
To solve above-mentioned technical problem, the technical solution used in the present invention is a kind of method that copper is reclaimed from lead copper matte,
Comprise the following steps：
(1) lead copper matte block is crushed and is ground, obtain lead copper matte powder body；
(2) lead copper matte powder body is placed in reactor and is leached with sulfuric acid solution, the solid-liquid of lead copper matte powder body and sulfuric acid solution
Than for 1kg: 9.5L～13L, constantly blasting oxygen-enriched air in leaching process, leaching pressure is normal pressure, extraction temperature is 70 DEG C～
90 DEG C, extraction time is 2h～3h, and after the completion of leaching, Jing solid-liquid separation obtains leached mud and copper sulfate leaching liquid, and lead is with sulphuric acid
In the form of lead in gained leached mud；
(3) copper sulfate leaching liquid for obtaining step (2) carries out electrodeposition in adding electrolyzer, in electrolytic deposition process, is being formed
The negative electrode of copper constantly blasts air, while constantly reducing electric current density, the tough cathode is fine and close copper.
In above-mentioned method, in the preferred step (2), the extraction temperature is 70 DEG C～80 DEG C, during the leaching
Between be 2h～2.5h.
It is in above-mentioned method, it is preferred that in the step (3), during the constantly reduction electric current density, described
During constantly reducing electric current density, initial current density is controlled in 210A/m2～250A/m2, terminate electric current density control
In 200A/m2～245A/m2, and initial current density is more than termination electric current density.The method is constantly reducing the mistake of electric current density
Cheng Zhong, when electric current density reaches 220A/m2When, electrodeposition effect is relatively more preferable.
In above-mentioned method, it is preferred that in the step (3), current efficiency is 90%～98.5%.Current efficiency is referred to
During electrolysis, on electrode the amount of the material of actual deposition or dissolving separate out with the material that calculates by theory or meltage ratio.
In above-mentioned method, it is preferred that in the step (2), in the oxygen-enriched air, the volumetric concentration of oxygen is 65%
～90%；The mode that blasts of the oxygen-enriched air is to blowing the mode of oxygen-enriched air from reactor both sides.
In above-mentioned method, it is preferred that in the step (2), the concentration of the sulfuric acid solution be 1.2mol/L～
1.5mol/L。
In above-mentioned method, it is preferred that in the step (3), the flow of the air is 150mL/min～250mL/
min。
In above-mentioned method, it is preferred that the granularity of the lead copper matte powder body is 100 mesh～125 mesh.
In above-mentioned method, it is preferred that the leached mud returns lead smelter dispensing and uses, and is gone forward side by side with reclaiming valuable metal
One step enriching Cu；The valuable metal that the leached mud is reclaimed includes lead, silver；Also contain what is do not leached completely in the leached mud
The elements such as copper, elemental sulfur, the elemental sulfur contained in the leached mud are used for antacid as fuel treatment, the sulfur dioxide of generation.
In above-mentioned method, it is preferred that the electrolyte waste liquid that the electrolytic deposition process is produced is used as the Feedstock treating for extracting ferrum.
In the present invention, normal pressure typically refers to normal atmosphere, i.e., 105Pa。
In the present invention, the solid-to-liquid ratio of extraction time and extraction temperature, mineral granularity, mineral and leachate, Steep cencentration
Deng there is certain relation, need to consider.
In the method for the present invention, involved main chemical reactions are as follows：
(1) leaching process：
Cu+1/2O2=CuO (1)
CuO+H2SO4=CuSO4+H2O (2)
Pb+1/2O2=PbO (3)
PbO+H2SO4=PbSO4↓+H2O (4)
Overall reaction is：
Cu+Pb+O2+2H2SO4=CuSO4+PbSO4↓+2H2O (5)
(2) electrolytic deposition process：
Fe+CuSO4=FeSO4+Cu (6)
In the present invention, wet treatment lead copper matte is soaked using normobaric oxygen, lead copper matte is leached with sulfuric acid solution, in leaching process
Oxygen is constantly passed through, copper is first oxidized, then form copper-bath, and after lead then first can be oxidized, and then form sulfur
Lead plumbate precipitation is stayed in slag.After the completion of leaching, by the leachate of cupric by electrolyzer electrodeposition, densification can be formed in negative electrode
Copper, meanwhile, the pyrometallurgical smelting of lead system that leached mud can return to reclaims the valuable elements such as lead, silver, and further enriching Cu.
Compared with prior art, it is an advantage of the current invention that：
1. the present invention in copper leaching process, leach at 70 DEG C～90 DEG C (preferably 70 DEG C～80 DEG C) by reaction temperature control
Time is 2h～3h (preferred 2h～2.5h), and reaction temperature and extraction time can be less than prior art.Blasting oxygen-enriched sky
During gas, oxygen concentration is controlled 65%～90%.Therefore, the process can substantially reduce the energy consumption in production process, and then drop
Low production cost.
2. the present invention constantly blasts air in the negative electrode for forming copper, while constantly dropping during copper sulfate bath
Low current density, can obtain negative electrode copper products of the purity more than 98%, and the tough cathode is fine and close copper, is not only solved existing
Technology can form the problem of copper sponge (low containing copper grade, usual Jing displacements reaction is generated) in tough cathode, and can be significantly
Degree improves the purity of copper products.
3. institute's by-product that the method for the present invention is produced, such as leached mud, electrolyte waste liquid etc. can be used as producing other
The raw material of product, it is thereby achieved that the zero-emission of pollutant, hardly causes any pollution to environment.
Description of the drawings
Fig. 1 is the process chart for reclaiming copper in the embodiment of the present invention from lead copper matte.
Specific embodiment
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but not therefore and
Limit the scope of the invention.
Embodiment 1：
A kind of method that copper is reclaimed from lead copper matte of present invention, its technological process is as shown in figure 1, comprise the following steps：
(1) lead copper matte block being crushed, lead copper matte powder body being worn into ball mill, granule size is 120 mesh.
(2) lead copper matte powder body is placed in reactor and is leached with sulfuric acid solution, constantly from reactor two in leaching process
Side is entered in kettle to blowing oxygen-enriched air, Oxidation Leaching copper, and actual conditions is：Sulfuric acid solution concentration：1.2mol/L, solid-to-liquid ratio：1∶
9.5, unit is kg/L, leaches pressure：Normal pressure, extraction temperature：70 DEG C, extraction time：3h, in oxygen-enriched air, the volume of oxygen is dense
Degree：65%, copper leaching rate：98.1%；Jing solid-liquid separation, obtains copper sulfate leaching liquid, lead then in the form of lead sulfate in
In leached mud, silver is not also dissolved substantially.
(3) adding copper sulfate leaching liquid carries out electrodeposition reduction in electrolyzer, anodic-cathodic adopts carbon-point, electrolytic deposition process
In, air, air mass flow are constantly blasted in the negative electrode for forming copper：150mL/min, temperature：Room temperature, while constantly reducing electricity
Current density, electric current density is from 250A/m2(initial current density) is reduced to 200A/m2(termination electric current density), current efficiency：
93.3%, negative electrode copper products are obtained, the tough cathode is fine and close copper, copper reduction rate：99.4%, tough cathode purity：98.3%.
In the present embodiment, in the lead smelter of the leached mud return pyrometallurgical smelting of lead system that step (2) is obtained, dispensing is used,
Valuable metal further enriching Cu are reclaimed, the valuable metal of recovery includes lead, silver etc..The elemental sulfur conduct contained in leached mud
Fuel treatment, the sulfur dioxide that combustion reaction is produced are used for antacid.The electrolyte waste liquid that electrolytic deposition process in step (3) is produced is used
Make to extract the Feedstock treating of ferrum.
Embodiment 2：
A kind of method that copper is reclaimed from lead copper matte of present invention, its technological process is as shown in figure 1, comprise the following steps：
(1) lead copper matte block being crushed, lead copper matte powder body being worn into ball mill, granule size is 100 mesh.
(2) lead copper matte powder body is placed in reactor and is leached with sulfuric acid solution, constantly from reactor two in leaching process
Side is entered in kettle to blowing oxygen-enriched air, Oxidation Leaching copper, and actual conditions is：Sulfuric acid solution concentration：1.5mol/L, solid-to-liquid ratio：1∶
12, unit is kg/L, leaches pressure：Normal pressure, extraction temperature：70 DEG C, extraction time：2.5h, the volume of oxygen in oxygen-enriched air
Concentration：85%, copper leaching rate：97.5%；Jing solid-liquid separation, obtains copper sulfate leaching liquid, and lead is then in the form of lead sulfate
In leached mud.
(3) adding copper sulfate leaching liquid carries out electrodeposition reduction in electrolyzer, anodic-cathodic adopts carbon-point, electrolytic deposition process
In, air, air mass flow are constantly blasted in the negative electrode for forming copper：200mL/min, temperature：Room temperature, electric current density is from 240A/
m2(initial current density) is reduced to 200A/m2(termination electric current density), current efficiency：97.6%, negative electrode copper products are obtained, should
Tough cathode is fine and close copper, copper reduction rate：98.2%, tough cathode purity：99.1%.
In the present embodiment, in the lead smelter of the leached mud return pyrometallurgical smelting of lead system that step (2) is obtained, dispensing is used,
Valuable metal further enriching Cu are reclaimed, the valuable metal of recovery includes lead, silver etc..The elemental sulfur conduct contained in leached mud
Fuel treatment, the sulfur dioxide for producing that burns are used for antacid.The electrolyte waste liquid that electrolytic deposition process in step (3) is produced is used as to carry
Take the Feedstock treating of ferrum.
Embodiment 3：
A kind of method that copper is reclaimed from lead copper matte of present invention, its technological process is as shown in figure 1, comprise the following steps：
(1) lead copper matte block being crushed, lead copper matte powder body being worn into ball mill, granule size is 120 mesh.
(2) lead copper matte powder body is placed in reactor and is leached with sulfuric acid solution, constantly from reactor two in leaching process
Side is entered in kettle to blowing oxygen-enriched air, Oxidation Leaching copper, and actual conditions is：Sulfuric acid solution concentration：1.5mol/L, solid-to-liquid ratio：1∶
10, unit is kg/L, leaches pressure：Normal pressure, extraction temperature：90 DEG C, extraction time：2h, in oxygen-enriched air, the volume of oxygen is dense
Degree：90%, copper leaching rate：96.8%；Jing solid-liquid separation, obtains copper sulfate leaching liquid, lead then in the form of lead sulfate in
In leached mud.
(3) adding copper sulfate leaching liquid carries out electrodeposition reduction in electrolyzer, anodic-cathodic adopts carbon-point, electrolytic deposition process
In, air, air mass flow are constantly blasted in the negative electrode for forming copper：250mL/min, temperature：Room temperature, electric current density is from 250A/
m2(initial current density) is reduced to 210A/m2(termination electric current density), current efficiency：96.6%, negative electrode copper products are obtained, should
Tough cathode is fine and close copper, copper reduction rate：99.2%, tough cathode purity：99.4%.
In the present embodiment, in the lead smelter of the leached mud return pyrometallurgical smelting of lead system that step (2) is obtained, dispensing is used,
Valuable metal further enriching Cu are reclaimed, the valuable metal of recovery includes lead, silver etc..The elemental sulfur conduct contained in leached mud
Fuel treatment, the sulfur dioxide for producing that burns are used for antacid.The electrolyte waste liquid that electrolytic deposition process in step (3) is produced is used as to carry
Take the Feedstock treating of ferrum.
Embodiment 4：
A kind of method that copper is reclaimed from lead copper matte of present invention, its technological process is as shown in figure 1, comprise the following steps：
(1) lead copper matte block being crushed, lead copper matte powder body being worn into ball mill, granule size is 125 mesh.
(2) lead copper matte powder body is placed in reactor and is leached with sulfuric acid solution, constantly from reactor two in leaching process
Side is entered in kettle to blowing oxygen-enriched air, Oxidation Leaching copper, and actual conditions is：Sulfuric acid concentration：1.2mol/L, solid-to-liquid ratio：1: 11, it is single
Position is kg/L, leaches pressure：Normal pressure, extraction temperature：85 DEG C, extraction time：3h, the volumetric concentration of oxygen in oxygen-enriched air
70%, copper leaching rate：95.5%；Jing solid-liquid separation, obtains copper sulfate leaching liquid, and lead is then in leaching in the form of lead sulfate
In slag.
(3) adding copper sulfate leaching liquid carries out electrodeposition reduction in electrolyzer, anodic-cathodic adopts carbon-point, electrolytic process
In, air, air mass flow are constantly blasted in the negative electrode for forming copper：250mL/min, temperature：Room temperature, electric current density is from 230A/
m2(initial current density) is reduced to 200A/m2(termination electric current density), current efficiency：94.1%, negative electrode copper products are obtained, should
Tough cathode is fine and close copper, copper reduction rate：97.4%, tough cathode purity：98%.
In the present embodiment, in the lead smelter of the leached mud return pyrometallurgical smelting of lead system that step (2) is obtained, dispensing is used,
Valuable metal further enriching Cu are reclaimed, the valuable metal of recovery includes lead, silver etc..The elemental sulfur conduct contained in leached mud
Fuel treatment, the sulfur dioxide for producing that burns are used for antacid.The electrolyte waste liquid that electrolytic deposition process in step (3) is produced is used as to carry
Take the Feedstock treating of ferrum.
Embodiment 5：
A kind of method that copper is reclaimed from lead copper matte of present invention, its technological process is as shown in figure 1, comprise the following steps：
(1) lead copper matte block being crushed, lead copper matte powder body being worn into ball mill, granule size is 120 mesh.
(2) lead copper matte powder body is placed in reactor and is leached with sulfuric acid solution, constantly from reactor two in leaching process
Side is entered in kettle to blowing oxygen-enriched air, Oxidation Leaching copper, and actual conditions is：Sulfuric acid concentration：1.3mol/L, solid-to-liquid ratio：1: 13, it is single
Position is kg/L, leaches pressure：Normal pressure, extraction temperature：80 DEG C, extraction time：2.5h, the volumetric concentration of oxygen in oxygen-enriched air：
75%, copper leaching rate：98.8%；Jing solid-liquid separation, obtains copper sulfate leaching liquid, and lead is then in leaching in the form of lead sulfate
In slag.
(3) adding copper sulfate leaching liquid carries out electrodeposition reduction in electrolyzer, anodic-cathodic adopts carbon-point, electrolytic process
In, air, air mass flow are constantly blasted in the negative electrode for forming copper：150mL/min, temperature：Room temperature, electric current density is from 250A/
m2(initial current density) is reduced to 220A/m2(termination electric current density), current efficiency：95.4%, negative electrode copper products are obtained, should
Tough cathode is fine and close copper, copper reduction rate：97.7%, tough cathode purity：98.7%.
In the present embodiment, in the lead smelter of the leached mud return pyrometallurgical smelting of lead system that step (2) is obtained, dispensing is used,
Valuable metal further enriching Cu are reclaimed, the valuable metal of recovery includes lead, silver etc..The elemental sulfur conduct contained in leached mud
Fuel treatment, the sulfur dioxide for producing that burns are used for antacid.The electrolyte waste liquid that electrolytic deposition process in step (3) is produced is used as to carry
Take the Feedstock treating of ferrum.
The above is only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-mentioned enforcement
Example.All technical schemes belonged under thinking of the present invention belong to protection scope of the present invention.It is noted that for the art
Those of ordinary skill for, improvements and modifications under the premise without departing from the principles of the invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (7)
1. a kind of method that copper is reclaimed from lead copper matte, comprises the following steps：
（1）Lead copper matte block is crushed and ground, lead copper matte powder body is obtained；
（2）Lead copper matte powder body is placed in reactor and is leached with sulfuric acid solution, lead copper matte powder body with the solid-to-liquid ratio of sulfuric acid solution is
1kg: 9.5L～13L, constantly blasts oxygen-enriched air in leaching process, leaching pressure is normal pressure, and extraction temperature is 70 DEG C～90 DEG C,
Extraction time is 2h～3h, and after the completion of leaching, Jing solid-liquid separation obtains leached mud and copper sulfate leaching liquid, and lead is with lead sulfate
Form is present in gained leached mud；
（3）By step（2）The copper sulfate leaching liquid for obtaining carries out electrodeposition in adding electrolyzer, in electrolytic deposition process, is forming copper
Negative electrode constantly blasts air, while constantly reducing electric current density, obtains tough cathode, and the tough cathode is fine and close copper；
The step（3）In, during the constantly reduction electric current density, initial current density is controlled in 210A/m2~
250A/m2, terminate electric current density and control in 200A/m2～245A/m2, and initial current density is more than termination electric current density；
The step（3）In, current efficiency is 90%～98.5%；
The step（2）In, in the oxygen-enriched air, the volumetric concentration of oxygen is 65%～90%；The side of blasting of the oxygen-enriched air
Formula is to blowing the mode of oxygen-enriched air from reactor both sides.
2. method according to claim 1, it is characterised in that the step（2）In, the extraction temperature is 70 DEG C～80
DEG C, the extraction time is 2h～2.5h.
3. method according to claim 1 and 2, it is characterised in that the step（2）In, the concentration of the sulfuric acid solution
For 1.2mol/L～1.5mol/L.
4. method according to claim 1 and 2, it is characterised in that the step（3）In, the flow of the air is
150mL/min～250mL/min.
5. method according to claim 1 and 2, it is characterised in that the granularity of the lead copper matte powder body is 100 mesh～125
Mesh.
6. method according to claim 1 and 2, it is characterised in that the leached mud returns lead smelter dispensing and uses, with
Reclaim valuable metal further enriching Cu；The valuable metal that the leached mud is reclaimed includes lead, silver；Contain in the leached mud
Elemental sulfur as fuel treatment, the sulfur dioxide of generation is used for antacid.
7. method according to claim 1 and 2, it is characterised in that the electrolyte waste liquid that the electrolytic deposition process is produced is used as
Extract the Feedstock treating of ferrum.
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| CN104947145B (en) * | 2015-06-10 | 2018-01-12 | 云南驰宏锌锗股份有限公司 | A kind of method of high lead copper matte oxygen leaching electrodeposition process balance acid |
| CN106521553A (en) * | 2016-11-04 | 2017-03-22 | 金少平 | Process for extracting elemental copper by utilizing waste copper slag |
| CN107267761B (en) * | 2017-06-29 | 2019-08-20 | 郴州市金贵银业股份有限公司 | A kind for the treatment of process of lead copper matte oxygen pressure acid leaching residue |
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| CN102242268A (en) * | 2011-06-15 | 2011-11-16 | 金川集团有限公司 | Process for treating black copper slag through electrolytic method |
| CN102345143A (en) * | 2011-10-09 | 2012-02-08 | 中南大学 | Method for separating copper, arsenic and nickel and purifying copper electrolyte |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101225476B (en) * | 2008-02-22 | 2010-10-13 | 昆明理工大学 | Process for reclaiming copper from lead copper matte |
| CN104017991A (en) * | 2014-06-06 | 2014-09-03 | 郴州市金贵银业股份有限公司 | Process for efficiently and selectively separating copper in lead copper matte |
| CN104004907A (en) * | 2014-06-06 | 2014-08-27 | 郴州市金贵银业股份有限公司 | Method for separating copper from lead matte and comprehensively utilizing lead matte |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102242268A (en) * | 2011-06-15 | 2011-11-16 | 金川集团有限公司 | Process for treating black copper slag through electrolytic method |
| CN102345143A (en) * | 2011-10-09 | 2012-02-08 | 中南大学 | Method for separating copper, arsenic and nickel and purifying copper electrolyte |
Non-Patent Citations (1)
| Title |
|---|
| 铅冰铜氧压酸浸-电积提铜工艺及理论研究;金炳界;《中国博士学位论文全文数据库工程科技Ⅰ辑》;20120115(第1期);第36、38、43-44、51-52、59-60、66、68-69、83、85-87和93-94页 * |
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