CN104233372A - Method for recovering copper from lead matte - Google Patents

Method for recovering copper from lead matte Download PDF

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Publication number
CN104233372A
CN104233372A CN201410519503.XA CN201410519503A CN104233372A CN 104233372 A CN104233372 A CN 104233372A CN 201410519503 A CN201410519503 A CN 201410519503A CN 104233372 A CN104233372 A CN 104233372A
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copper
lead
leaching
current density
oxygen
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CN104233372B (en
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张虎
王富源
姚小龙
李立清
张晓峰
曹佐英
肖克
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JIYUAN XINXIN INDUSTRIAL CO LTD
Central South University
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JIYUAN XINXIN INDUSTRIAL CO LTD
Central South University
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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

The method of copper is reclaimed from lead matte
Technical field
The invention belongs to Non-ferrous Metallurgy field, relate to a kind of method reclaiming copper from lead matte, particularly relate to a kind of reclaim copper from lead matte method with utilizing wet process smelting technique less energy-consumption.
Background technology
Lead matte is in plumbous smelting process, a kind of byproduct produced in blast furnace smelting and pyrometallurgical smelting of lead operation.The main component of lead matte is cuprous sulfide, lead sulfide, Iron sulfuret etc., and wherein the content of each element is generally: copper: 15% ~ 30%, plumbous: 50% ~ 65%, iron: 1% ~ 5%, sulphur: 5% ~ 15%.
For the process of lead matte, lead matte is generally sold to copper smelting plant as copper raw material by medium and small sized enterprises, and preparing burden with smart copper mine in copper smelting plant uses, through copper metallurgy industry finally with the form output of negative electrode electrolytic copper.In large-scale smeltery, usually by pyrogenic attack lead matte, lead matte is blown in converter, obtains blister copper, then refining obtains electrolytic copper further.But the serious problems such as metal recovery rate is low, technical process is long, running cost is high, environmental pollution that the method exists, generally cannot miniaturization.
Along with the lifting of scientific and technological level and reaching its maturity of technology, Ye You enterprise adopts new technology and method process lead matte.The Chinese patent literature of publication number CN101225476A discloses one and " from lead matte, reclaims the technique of copper ", and the method adopts pressure leaching wet processing process lead matte.Lead matte block material is milled to granularity and is less than 40 orders, the lead matte after grinding sends into autoclave after sizing mixing with useless electric effusion or dilution heat of sulfuric acid, and passes into oxygen, thus leaches copper.The method of galvanic deposit that adopts the leach liquor of cupric reclaims the copper in solution, and leached mud returns the valuable metals such as pyrometallurgical smelting of lead system recoveries is plumbous, silver-colored.Although this technique can realize the Selectively leaching of metal, the rate of recovery of metal is high, because processing condition need High Temperature High Pressure, it is very inconvenient to bring to operation.Publication number is that the Chinese patent literature of CN102051478A discloses " a kind of wet process for treating lead copper matte ".This technique adopts normobaric oxygen to soak method art breading lead matte, lead matte sulfuric acid and Leaching of sodium chloride, lead is then stayed in slag with the form of lead sulfate and lead chloride, after carrying out solid-liquid separation, the leach liquor iron reduction of cupric obtains copper sponge, waste liquid after reduction is used for reclaiming iron, and leached mud returns the valuable metals such as pyrometallurgical smelting of lead system recoveries is plumbous, silver-colored.Although the method can realize the normobaric oxygen leaching wet processing to lead matte, copper products is copper sponge.The method is to be applied to industry, and also need to carry out the complicated art breading such as compressing tablet, calcining, melting to copper products, this adds production energy consumption and cost undoubtedly.Therefore, in order to address these problems, be badly in need of finding a kind of new technique and processing lead matte.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, provide a kind of invest little, energy consumption is low, technique is simple, can the fine and close copper of production high purity and the method reclaiming copper from lead matte to the almost nil pollution of environment.
For solving the problems of the technologies described above, the technical solution used in the present invention is a kind of method reclaiming copper from lead matte, comprises the following steps:
(1) lead matte block material is broken and grind, obtain lead matte powder;
(2) lead matte powder is placed in reactor sulphuric acid soln to leach, the solid-to-liquid ratio of lead matte powder and sulphuric acid soln is 1kg: 9.5L ~ 13L, constantly oxygen-rich air is blasted in leaching process, leaching pressure is normal pressure, and extraction temperature is 70 DEG C ~ 90 DEG C, and extraction time is 2h ~ 3h, after leaching completes, through solid-liquid separation, obtain leached mud and copper sulfate leaching liquid, lead is present in gained leached mud with the form of lead sulfate;
(3) added in electrolyzer by the copper sulfate leaching liquid that step (2) obtains and carry out electrodeposition, in electrolytic deposition process, constantly blast air at the negative electrode forming copper, constantly reduce current density, this cathode copper is fine and close copper simultaneously.
In above-mentioned method, in preferred described step (2), described extraction temperature is 70 DEG C ~ 80 DEG C, and described extraction time is 2h ~ 2.5h.
In above-mentioned method, preferably, in described step (3), describedly constantly to reduce in the process of current density, describedly constantly to reduce in the process of current density, initial current density controls at 210A/m 2~ 250A/m 2, stop current density and control at 200A/m 2~ 245A/m 2, and initial current density is greater than termination current density.The method reduces in the process of current density, when current density reaches 220A/m continuous 2time, electrodeposition effect is relatively better.
In above-mentioned method, preferably, in described step (3), current efficiency is 90% ~ 98.5%.When current efficiency refers to electrolysis, amount of substance and the material calculated by theory of actual deposition or dissolving on electrode are separated out or the ratio of meltage.
In above-mentioned method, preferably, in described step (2), in described oxygen-rich air, the volumetric concentration of oxygen is 65% ~ 90%; The mode that blasts of described oxygen-rich air is to the mode of blowing oxygen-rich air from reactor both sides.
In above-mentioned method, preferably, in described step (2), the concentration of described sulphuric acid soln is 1.2mol/L ~ 1.5mol/L.
In above-mentioned method, preferably, in described step (3), the flow of described air is 150mL/min ~ 250mL/min.
In above-mentioned method, preferably, the granularity of described lead matte powder is 100 order ~ 125 orders.
In above-mentioned method, preferably, described leached mud returns lead smelter batching and uses, to reclaim valuable metal and further enriching Cu; The valuable metal that described leached mud reclaims comprises lead, silver; Also containing the element such as copper, elemental sulfur do not leached completely in described leached mud, the elemental sulfur contained in described leached mud is as fuel treatment, and the sulfurous gas of generation is used for relieving haperacidity.
In above-mentioned method, preferably, the electrolytic solution waste liquid that described electrolytic deposition process produces is used as the Feedstock treating extracting iron.
In the present invention, normal pressure typically refers to standard atmospheric pressure, and namely 10 5pa.
In the present invention, the solid-to-liquid ratio of extraction time and extraction temperature, mineral granularity, mineral and leach liquor, Steep cencentration etc. have certain relation, need consider.
Main chemical reactions involved in method of the present invention is as follows:
(1) leaching process:
Cu+1/2O 2=CuO (1)
CuO+H 2SO 4=CuSO 4+H 2O (2)
Pb+1/2O 2=PbO (3)
PbO+H 2SO 4=PbSO 4↓+H 2O (4)
Total reaction is:
Cu+Pb+O 2+2H 2SO 4=CuSO 4+PbSO 4↓+2H 2O (5)
(2) electrolytic deposition process:
Fe+CuSO 4=FeSO 4+Cu (6)
In the present invention, adopt normobaric oxygen leaching wet processing lead matte, lead matte sulphuric acid soln leaches, in leaching process, constantly pass into oxygen, make copper first oxidized, then form copper-bath, lead then can first oxidized after, and then form lead sulfate precipitation and stay in slag.After leaching completes, by the leach liquor of cupric by electrolyzer electrodeposition, can form fine and close copper at negative electrode, meanwhile, leached mud can return the valuable elements such as pyrometallurgical smelting of lead system recoveries is plumbous, silver-colored, and further enriching Cu.
Compared with prior art, the invention has the advantages that:
1. the present invention is in copper leaching process, and temperature of reaction controls at 70 DEG C ~ 90 DEG C (preferably 70 DEG C ~ 80 DEG C), and extraction time is 2h ~ 3h (preferred 2h ~ 2.5h), and temperature of reaction and extraction time all can lower than prior aries.When blasting oxygen-rich air, oxygen concentration controls 65% ~ 90%.Therefore, this process can reduce the energy consumption in production process greatly, and then reduces production cost.
2. the present invention is in copper sulfate bath process, constantly air is blasted at the negative electrode forming copper, constantly reduce current density simultaneously, the cathode copper product that purity is greater than 98% can be obtained, and this cathode copper is fine and close copper, not only solve the problem that prior art can form copper sponge (low containing copper grade, usually to generate through replacement(metathesis)reaction) in cathode copper, and the purity of copper products can be increased substantially.
3. institute's by-product of method generation of the present invention, as leached mud, electrolytic solution waste liquid etc., all can be used as the raw material producing other products, therefore, can realize the zero release of pollutent, cause any pollution hardly to environment.
Accompanying drawing explanation
Fig. 1 is the process flow sheet reclaiming copper in the embodiment of the present invention from lead matte.
Embodiment
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but protection domain not thereby limiting the invention.
Embodiment 1:
The method reclaiming copper from lead matte of the present invention, its technical process as shown in Figure 1, comprises the following steps:
(1) lead matte block material is broken, wear into lead matte powder with ball mill, globule size is 120 orders.
(2) lead matte powder is placed in reactor sulphuric acid soln to leach, constantly enter in still from reactor both sides to blowing oxygen-rich air in leaching process, Oxidation Leaching copper, actual conditions is: sulphuric acid soln concentration: 1.2mol/L, solid-to-liquid ratio: 1: 9.5, unit is kg/L, leach pressure: normal pressure, extraction temperature: 70 DEG C, extraction time: 3h, the volumetric concentration of oxygen in oxygen-rich air: 65%, copper leaching rate: 98.1%; Through solid-liquid separation, obtain copper sulfate leaching liquid, plumbous then be present in leached mud with the form of lead sulfate, silver is not also dissolved substantially.
(3) added in electrolyzer by copper sulfate leaching liquid and carry out electrodeposition reduction, anodic-cathodic all adopts carbon-point, in electrolytic deposition process, constantly air is blasted, air flow quantity: 150mL/min, temperature: room temperature at the negative electrode forming copper, constantly reduce current density, current density is from 250A/m simultaneously 2(initial current density) is reduced to 200A/m 2(termination current density), current efficiency: 93.3%, obtains cathode copper product, and this cathode copper is fine and close copper, copper reduction rate: 99.4%, cathode copper purity: 98.3%.
In the present embodiment, the leached mud that step (2) obtains is returned batching in the lead smelter of pyrometallurgical smelting of lead system and use, reclaim valuable metal and further enriching Cu, the valuable metal of recovery comprises lead, silver etc.The elemental sulfur contained in leached mud is as fuel treatment, and the sulfurous gas that combustion reactions produces is used for relieving haperacidity.The electrolytic solution waste liquid produced by electrolytic deposition process in step (3) is used as the Feedstock treating extracting iron.
Embodiment 2:
The method reclaiming copper from lead matte of the present invention, its technical process as shown in Figure 1, comprises the following steps:
(1) lead matte block material is broken, wear into lead matte powder with ball mill, globule size is 100 orders.
(2) lead matte powder is placed in reactor sulphuric acid soln to leach, constantly enter in still from reactor both sides to blowing oxygen-rich air in leaching process, Oxidation Leaching copper, actual conditions is: sulphuric acid soln concentration: 1.5mol/L, solid-to-liquid ratio: 1: 12, unit is kg/L, leach pressure: normal pressure, extraction temperature: 70 DEG C, extraction time: 2.5h, the volumetric concentration of oxygen in oxygen-rich air: 85%, copper leaching rate: 97.5%; Through solid-liquid separation, obtain copper sulfate leaching liquid, plumbous then be present in leached mud with the form of lead sulfate.
(3) added in electrolyzer by copper sulfate leaching liquid and carry out electrodeposition reduction, anodic-cathodic all adopts carbon-point, in electrolytic deposition process, constantly blasts air, air flow quantity: 200mL/min, temperature: room temperature, current density is from 240A/m at the negative electrode forming copper 2(initial current density) is reduced to 200A/m 2(termination current density), current efficiency: 97.6%, obtains cathode copper product, and this cathode copper is fine and close copper, copper reduction rate: 98.2%, cathode copper purity: 99.1%.
In the present embodiment, the leached mud that step (2) obtains is returned batching in the lead smelter of pyrometallurgical smelting of lead system and use, reclaim valuable metal and further enriching Cu, the valuable metal of recovery comprises lead, silver etc.The elemental sulfur contained in leached mud is as fuel treatment, and the sulfurous gas that burning produces is used for relieving haperacidity.The electrolytic solution waste liquid produced by electrolytic deposition process in step (3) is used as the Feedstock treating extracting iron.
Embodiment 3:
The method reclaiming copper from lead matte of the present invention, its technical process as shown in Figure 1, comprises the following steps:
(1) lead matte block material is broken, wear into lead matte powder with ball mill, globule size is 120 orders.
(2) lead matte powder is placed in reactor sulphuric acid soln to leach, constantly enter in still from reactor both sides to blowing oxygen-rich air in leaching process, Oxidation Leaching copper, actual conditions is: sulphuric acid soln concentration: 1.5mol/L, solid-to-liquid ratio: 1: 10, unit is kg/L, leach pressure: normal pressure, extraction temperature: 90 DEG C, extraction time: 2h, the volumetric concentration of oxygen in oxygen-rich air: 90%, copper leaching rate: 96.8%; Through solid-liquid separation, obtain copper sulfate leaching liquid, plumbous then be present in leached mud with the form of lead sulfate.
(3) added in electrolyzer by copper sulfate leaching liquid and carry out electrodeposition reduction, anodic-cathodic all adopts carbon-point, in electrolytic deposition process, constantly blasts air, air flow quantity: 250mL/min, temperature: room temperature, current density is from 250A/m at the negative electrode forming copper 2(initial current density) is reduced to 210A/m 2(termination current density), current efficiency: 96.6%, obtains cathode copper product, and this cathode copper is fine and close copper, copper reduction rate: 99.2%, cathode copper purity: 99.4%.
In the present embodiment, the leached mud that step (2) obtains is returned batching in the lead smelter of pyrometallurgical smelting of lead system and use, reclaim valuable metal and further enriching Cu, the valuable metal of recovery comprises lead, silver etc.The elemental sulfur contained in leached mud is as fuel treatment, and the sulfurous gas that burning produces is used for relieving haperacidity.The electrolytic solution waste liquid produced by electrolytic deposition process in step (3) is used as the Feedstock treating extracting iron.
Embodiment 4:
The method reclaiming copper from lead matte of the present invention, its technical process as shown in Figure 1, comprises the following steps:
(1) lead matte block material is broken, wear into lead matte powder with ball mill, globule size is 125 orders.
(2) lead matte powder is placed in reactor sulphuric acid soln to leach, constantly enter in still from reactor both sides to blowing oxygen-rich air in leaching process, Oxidation Leaching copper, actual conditions is: sulfuric acid concentration: 1.2mol/L, solid-to-liquid ratio: 1: 11, unit is kg/L, leach pressure: normal pressure, extraction temperature: 85 DEG C, extraction time: 3h, the volumetric concentration 70% of oxygen in oxygen-rich air, copper leaching rate: 95.5%; Through solid-liquid separation, obtain copper sulfate leaching liquid, plumbous then be present in leached mud with the form of lead sulfate.
(3) added in electrolyzer by copper sulfate leaching liquid and carry out electrodeposition reduction, anodic-cathodic all adopts carbon-point, in electrolytic process, constantly blasts air, air flow quantity: 250mL/min, temperature: room temperature, current density is from 230A/m at the negative electrode forming copper 2(initial current density) is reduced to 200A/m 2(termination current density), current efficiency: 94.1%, obtains cathode copper product, and this cathode copper is fine and close copper, copper reduction rate: 97.4%, cathode copper purity: 98%.
In the present embodiment, the leached mud that step (2) obtains is returned batching in the lead smelter of pyrometallurgical smelting of lead system and use, reclaim valuable metal and further enriching Cu, the valuable metal of recovery comprises lead, silver etc.The elemental sulfur contained in leached mud is as fuel treatment, and the sulfurous gas that burning produces is used for relieving haperacidity.The electrolytic solution waste liquid produced by electrolytic deposition process in step (3) is used as the Feedstock treating extracting iron.
Embodiment 5:
The method reclaiming copper from lead matte of the present invention, its technical process as shown in Figure 1, comprises the following steps:
(1) lead matte block material is broken, wear into lead matte powder with ball mill, globule size is 120 orders.
(2) lead matte powder is placed in reactor sulphuric acid soln to leach, constantly enter in still from reactor both sides to blowing oxygen-rich air in leaching process, Oxidation Leaching copper, actual conditions is: sulfuric acid concentration: 1.3mol/L, solid-to-liquid ratio: 1: 13, unit is kg/L, leach pressure: normal pressure, extraction temperature: 80 DEG C, extraction time: 2.5h, the volumetric concentration of oxygen in oxygen-rich air: 75%, copper leaching rate: 98.8%; Through solid-liquid separation, obtain copper sulfate leaching liquid, plumbous then be present in leached mud with the form of lead sulfate.
(3) added in electrolyzer by copper sulfate leaching liquid and carry out electrodeposition reduction, anodic-cathodic all adopts carbon-point, in electrolytic process, constantly blasts air, air flow quantity: 150mL/min, temperature: room temperature, current density is from 250A/m at the negative electrode forming copper 2(initial current density) is reduced to 220A/m 2(termination current density), current efficiency: 95.4%, obtains cathode copper product, and this cathode copper is fine and close copper, copper reduction rate: 97.7%, cathode copper purity: 98.7%.
In the present embodiment, the leached mud that step (2) obtains is returned batching in the lead smelter of pyrometallurgical smelting of lead system and use, reclaim valuable metal and further enriching Cu, the valuable metal of recovery comprises lead, silver etc.The elemental sulfur contained in leached mud is as fuel treatment, and the sulfurous gas that burning produces is used for relieving haperacidity.The electrolytic solution waste liquid produced by electrolytic deposition process in step (3) is used as the Feedstock treating extracting iron.
The above is only the preferred embodiment of the present invention, and protection scope of the present invention is also not only confined to above-described embodiment.All technical schemes belonged under thinking of the present invention all belong to protection scope of the present invention.It is noted that for those skilled in the art, improvements and modifications under the premise without departing from the principles of the invention, these improvements and modifications also should be considered as protection scope of the present invention.

Claims (10)

1. from lead matte, reclaim a method for copper, comprise the following steps:
(1) lead matte block material is broken and grind, obtain lead matte powder;
(2) lead matte powder is placed in reactor sulphuric acid soln to leach, the solid-to-liquid ratio of lead matte powder and sulphuric acid soln is 1kg: 9.5L ~ 13L, constantly oxygen-rich air is blasted in leaching process, leaching pressure is normal pressure, and extraction temperature is 70 DEG C ~ 90 DEG C, and extraction time is 2h ~ 3h, after leaching completes, through solid-liquid separation, obtain leached mud and copper sulfate leaching liquid, lead is present in gained leached mud with the form of lead sulfate;
(3) copper sulfate leaching liquid that step (2) obtains is added in electrolyzer carry out electrodeposition, in electrolytic deposition process, constantly blast air at the negative electrode forming copper, constantly reduce current density simultaneously, obtain cathode copper.
2. method according to claim 1, is characterized in that, in described step (2), described extraction temperature is 70 DEG C ~ 80 DEG C, and described extraction time is 2h ~ 2.5h.
3. method according to claim 1, is characterized in that, in described step (3), describedly constantly to reduce in the process of current density, initial current density controls at 210A/m 2~ 250A/m 2, stop current density and control at 200A/m 2~ 245A/m 2, and initial current density is greater than termination current density.
4. method according to claim 1, is characterized in that, in described step (3), current efficiency is 90% ~ 98.5%.
5. the method according to any one of Claims 1 to 4, is characterized in that, in described step (2), in described oxygen-rich air, the volumetric concentration of oxygen is 65% ~ 90%; The mode that blasts of described oxygen-rich air is to the mode of blowing oxygen-rich air from reactor both sides.
6. the method according to any one of Claims 1 to 4, is characterized in that, in described step (2), the concentration of described sulphuric acid soln is 1.2mol/L ~ 1.5mol/L.
7. the method according to any one of Claims 1 to 4, is characterized in that, in described step (3), the flow of described air is 150mL/min ~ 250mL/min.
8. the method according to any one of Claims 1 to 4, is characterized in that, the granularity of described lead matte powder is 100 order ~ 125 orders.
9. the method according to any one of Claims 1 to 4, is characterized in that, described leached mud returns lead smelter batching and uses, to reclaim valuable metal and further enriching Cu; The valuable metal that described leached mud reclaims comprises lead, silver; The elemental sulfur contained in described leached mud is as fuel treatment, and the sulfurous gas of generation is used for relieving haperacidity.
10. the method according to any one of Claims 1 to 4, is characterized in that, the electrolytic solution waste liquid that described electrolytic deposition process produces is used as the Feedstock treating extracting iron.
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Publication number Priority date Publication date Assignee Title
CN104947145A (en) * 2015-06-10 2015-09-30 云南驰宏锌锗股份有限公司 Method of balancing acid in high-lead copper sulphate oxygen pressure leaching-electrodepositing process
CN106521553A (en) * 2016-11-04 2017-03-22 金少平 Process for extracting elemental copper by utilizing waste copper slag
CN107267761A (en) * 2017-06-29 2017-10-20 郴州市金贵银业股份有限公司 A kind of lead copper matte oxygen presses the handling process of acid leaching residue
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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