CN107619940B - A method of recycling copper from metallurgical slag - Google Patents
A method of recycling copper from metallurgical slag Download PDFInfo
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- CN107619940B CN107619940B CN201710893153.7A CN201710893153A CN107619940B CN 107619940 B CN107619940 B CN 107619940B CN 201710893153 A CN201710893153 A CN 201710893153A CN 107619940 B CN107619940 B CN 107619940B
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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
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Abstract
The method that the present invention relates to a kind of from metallurgical slag recycles copper, using reduction roasting, again water logging, reoxidize acidleach, the mode of last cyclone electrolytic cell has been specifically added auxiliary agent in roasting, make the reaction of metallurgical slag sufficiently, good fluidity, be conducive to sedimentation separation.First water logging reoxidizes acidleach, carries out cyclone electrolytic cell again after mixing water lixivium and oxidation acid leaching leachate, has certain help to the rate of recovery for improving metallic copper.The present invention is lower than traditional copper smelting slag recovery process production cost, and compared to conventional cyclone electrolytic cell mode, the rate of recovery of the invention is higher.
Description
Technical field
The present invention relates to metallurgical slag recycling fields, in particular to a kind of method for recycling copper from metallurgical slag.
Background technique
It is in the ascendant to develop green economy with green science and technology for the world today.Traditional nonferrous metallurgy industry, bargh
It is high energy consumption, high pollution, maximum discharge enterprise.With minimizing, innoxious, recycling, reuses, recirculates to code of conduct,
To greatest extent using existing resource, and high efficiente callback waste liquid, the valuable metal in waste residue are recycled, these enterprises will be increasingly becomed
The needs further developed.Main valuable metal ingredient in comprehensive reutilization copper smelting slag can be sufficiently sharp for enterprise
Huge economic well-being of workers and staff is created with raw material, and solves pollution on the environment in stacking and transport process.Therefore, Cong Tongye
Comprehensive valuable metal has far-reaching realistic meaning in economic benefit, social benefit, Environmental Effect Yidu in refining slag, also produces with China
Industry and the guiding of technology development are consistent.
Copper smelting slag contains the valuable metals such as copper, lead, silver, bismuth, zinc, cadmium, recovery value with higher.From copper smelting slag
From the point of view of resource utilization is using status, the valuable constituents such as copper, nickel in copper smelting slag are primarily as the impurity in metallurgical process
Metal and remove, treatment process long flow path, the purity of obtained sponge copper products is lower, the cobalt nickel especially in slag, not only difficult
Removal, and processing cost is generally higher.
Using cyclone electrolytic cell technical treatment sludge from copper smelting leachate and directly obtain metal simple-substance electrolytic production, can be with
Extraction process is omitted, so that valuable metal recovery cost be greatly reduced.Cyclone electrolytic cell is acted on the elimination of concentration polarization so that its
High metal recovery efficiency can be obtained, such as using cyclone electrolytic cell technology from containing palladium and containing the acidic chloride solution of rhodium metal
Middle Recover palladium and rhodium, recovery efficiency have been more than 99%.If the deposition potential of foreign ion and metal target gap are larger, eddy flow
Electrolysis is influenced smaller, product purity height by foreign ion.
Summary of the invention
In order to solve the rate of recovery and cost problem of metallurgical slag recovery process, the present invention provides one kind to return from metallurgical slag
The method for receiving copper comprising roasting, water logging, acidleach, cyclone electrolytic cell, so that the copper recovery in copper smelting slag be made to be up to
99% or more and eliminate extraction etc. processes.
A method of recycling copper from copper smelting slag, comprising:
(1) copper smelting slag, auxiliary agent and quick lime are mixed, obtains mixed material；
(2) mixed material is roasted, the solid mixture after being roasted；
(3) solid mixture is subjected to crushing grinding, with 80~95 DEG C of hot water pulps, the volume and solid of hot water are mixed
Close object mass ratio 1:1, stirring 0.5~1.0 hour after, then plus 80~95 DEG C of hot water to liquid-solid ratio be 3~5:1, be stirred for 0.5
~1.0 hours, filtrate and filter residue is obtained by filtration；
(4) after sulfuric acid being added in filter residue, the logical oxygen progress Oxidation Leaching in autoclave, leaching 2~4 hours, later
Separating treatment is carried out, leachate and leached mud are obtained；
(5) after mixing by the filtrate and the leachate and adjust pH, cathode copper products are obtained using cyclone electrolytic cell.
The auxiliary agent is made of following components in percentage by weight: lime stone 12~15%, iron ore 10~13%, silicic acid
Aluminium powder 8~10%, silicon carbide 5~8%, flyash 3~5%, surplus are coke.
In the step (1), copper smelting slag, auxiliary agent and quick lime are 1:(2~2.5 according to mass ratio): (5~6.5)
It is mixed.
In the step (2), the temperature of the calcination process is 1000~1200 DEG C；It is carried out by the mixed material
Before calcination process, forming processes are carried out to the mixed material in advance, obtain mixing pelletizing.
In the step (3), powder of the partial size less than 0.056mm accounts for total amount in the powder after the crushing grinding
75wt% or more.
In the step (5), the filtrate and the leachate are mixed 1~2 hour, adjust pH value later to 4
~5, cyclone electrolytic cell is carried out, electrolyte circular flow is 30L/h when electrolysis, and current density is 50~80A/m2, temperature be 40~
50 DEG C, control terminal copper ion concentration is 200mg/L.
The present invention using reduction roasting, again water logging, reoxidize acidleach, the mode of last cyclone electrolytic cell is special in roasting
Joined auxiliary agent, make metallurgical slag reaction sufficiently, good fluidity, be conducive to sedimentation separation.First water logging reoxidizes acidleach, mixes water logging
Cyclone electrolytic cell is carried out again after filtrate and oxidation acid leaching leachate, has certain help to the rate of recovery for improving metallic copper.Ratio of the present invention
Traditional copper smelting slag recovery process production cost is low, and compared to conventional cyclone electrolytic cell mode, the rate of recovery of the invention is higher.
Specific embodiment
Below with reference to embodiment and comparative example, the present invention is described in more detail.
Embodiment 1:
A method of recycling copper from copper smelting slag, comprising: (1) copper smelting slag, auxiliary agent and quick lime are mixed,
Obtain mixed material.Wherein, copper smelting slag, auxiliary agent and quick lime are that 1:2:5 is mixed according to mass ratio.The auxiliary agent by with
The component of lower weight percent is made: lime stone 12%, iron ore 10%, aluminium silicate powder 8%, silicon carbide 5%, flyash 3%,
Surplus is coke.(2) mixed material is roasted, the solid mixture after being roasted.The temperature of the calcination process
Degree is 1000 DEG C；Before the mixed material is carried out calcination process, forming processes are carried out to the mixed material in advance, are obtained
To mixing pelletizing.(3) solid mixture is subjected to crushing grinding, partial size is less than in the powder after the crushing grinding
The powder of 0.056mm accounts for the 75wt% or more of total amount, with 80 DEG C of hot water pulps, the volume of hot water and the mass ratio of solid mixture
1:1, stirring 0.5 hour after, then plus 80 DEG C of hot water to liquid-solid ratio be 3:1, be stirred for 0.5 hour, filtrate and filter residue be obtained by filtration；
(4) after filter residue being added sulfuric acid, lead to oxygen in autoclave and carry out Oxidation Leaching, leaching 2 hours, carry out separating treatment later,
Obtain leachate and leached mud；(5) filtrate and the leachate are mixed 1 hour, adjust pH value later to 4, into
Row cyclone electrolytic cell, electrolyte circular flow is 30L/h, current density 50A/m when electrolysis2, temperature is 40 DEG C, controls terminal copper
Ion concentration is 200mg/L, obtains cathode copper products.Wherein, the rate of recovery of the copper in copper smelting slag is up to 99.02%.
Embodiment 2:
A method of recycling copper from copper smelting slag, comprising: (1) copper smelting slag, auxiliary agent and quick lime are mixed,
Obtain mixed material.Wherein, copper smelting slag, auxiliary agent and quick lime are that 1:2.5:6.5 is mixed according to mass ratio.The auxiliary agent
It is made of following components in percentage by weight: lime stone 15%, iron ore 13%, aluminium silicate powder 10%, silicon carbide 8%, fine coal
Ash 5%, surplus is coke.(2) mixed material is roasted, the solid mixture after being roasted.At the roasting
The temperature of reason is 1200 DEG C；Before the mixed material is carried out calcination process, the mixed material is formed in advance
Processing obtains mixing pelletizing.(3) solid mixture is subjected to crushing grinding, partial size in the powder after the crushing grinding
Less than the 75wt% or more that the powder of 0.056mm accounts for total amount, with 95 DEG C of hot water pulps, the volume of hot water and the matter of solid mixture
Amount is than 1:1, after stirring 1.0 hours, then plus 95 DEG C of hot water to liquid-solid ratio be 5:1, be stirred for 1.0 hours, be obtained by filtration filtrate and
Filter residue；(4) after filter residue being added sulfuric acid, lead to oxygen in autoclave and carry out Oxidation Leaching, leaching 4 hours, separated later
Processing, obtains leachate and leached mud；(5) filtrate and the leachate are mixed 2 hours, adjust later pH value to
5, cyclone electrolytic cell is carried out, electrolyte circular flow is 30L/h, current density 80A/m when electrolysis2, temperature is 50 DEG C, and control is eventually
Point copper ion concentration is 200mg/L, obtains cathode copper products.Wherein, the rate of recovery of the copper in copper smelting slag is up to 99.25%.
Embodiment 3:
A method of recycling copper from copper smelting slag, comprising: (1) copper smelting slag, auxiliary agent and quick lime are mixed,
Obtain mixed material.Wherein, copper smelting slag, auxiliary agent and quick lime are that 1:2:6 is mixed according to mass ratio.The auxiliary agent by with
The component of lower weight percent is made: lime stone 13%, iron ore 12%, aluminium silicate powder 9%, silicon carbide 7%, flyash 4%,
Surplus is coke.(2) mixed material is roasted, the solid mixture after being roasted.The temperature of the calcination process
Degree is 1100 DEG C；Before the mixed material is carried out calcination process, forming processes are carried out to the mixed material in advance, are obtained
To mixing pelletizing.(3) solid mixture is subjected to crushing grinding, partial size is less than in the powder after the crushing grinding
The powder of 0.056mm accounts for the 75wt% or more of total amount, with 90 DEG C of hot water pulps, the volume of hot water and the mass ratio of solid mixture
1:1, stirring 0.5 hour after, then plus 90 DEG C of hot water to liquid-solid ratio be 4:1, be stirred for 1.0 hours, filtrate and filter residue be obtained by filtration；
(4) after filter residue being added sulfuric acid, lead to oxygen in autoclave and carry out Oxidation Leaching, leaching 3 hours, carry out separating treatment later,
Obtain leachate and leached mud；(5) filtrate and the leachate are mixed 2 hours, adjust pH value later to 4, into
Row cyclone electrolytic cell, electrolyte circular flow is 30L/h, current density 60A/m when electrolysis2, temperature is 45 DEG C, controls terminal copper
Ion concentration is 200mg/L, obtains cathode copper products.Wherein, the rate of recovery of the copper in copper smelting slag is up to 99.32%.
Comparative example 1:
Cyclone electrolytic cell after wherein step leaching will be only carried out with copper smelting slag of the present invention without water logging or acidleach, then
For obtained cathode copper products for copper smelting slag, the rate of recovery of copper is only 86%.
Comparative example 2:
Using being different from other ways of recycling of the extraction etc. of cyclone electrolytic cell mode of the present invention, time of the copper in copper smelting slag
Yield is only 80% or so, and extract, the cost of stripping process it is higher.
Comparative example 3:
If being added without auxiliary agent of the invention to be mixed, two step leaching effects will be substantially reduced, so as to cause final
For cyclone electrolytic cell cathode copper products for copper smelting slag, the rate of recovery of copper is not above 90%.
It can be seen from embodiment 1-3 and comparative example 1-3 reduction roasting of the present invention, again water logging, reoxidize acid
Leaching, the mode of last cyclone electrolytic cell, step and technological parameter are that applicant verifies by repeated tests.It is roasting
When be specifically added auxiliary agent, make metallurgical slag reaction sufficiently, good fluidity, be conducive to sedimentation separation.First water logging reoxidizes acidleach, mixes
Cyclone electrolytic cell is carried out again after Heshui lixivium and oxidation acid leaching leachate, has certain help to the rate of recovery for improving metallic copper.This
Invention is lower than traditional copper smelting slag recovery process production cost, and compared to conventional cyclone electrolytic cell mode, the rate of recovery of the invention
It is higher.
Although an embodiment of the present invention has been shown and described, it will be understood by those skilled in the art that: not
A variety of change, modification, replacement and modification can be carried out to these embodiments in the case where being detached from the principle of the present invention and objective, this
The range of invention is defined by the claims and their equivalents.
Claims (3)
1. a kind of method for recycling copper from copper smelting slag characterized by comprising
(1) it is that 1:2:5 is mixed according to mass ratio by copper smelting slag, auxiliary agent and quick lime, obtains mixed material；
(2) mixed material is roasted, the solid mixture after being roasted；
(3) solid mixture is subjected to crushing grinding, with 80 ~ 95 DEG C of hot water pulps, the volume and solid mixture of hot water
Mass ratio 1:1, stirring 0.5 ~ 1.0 hour after, then plus 80 ~ 95 DEG C of hot water to liquid-solid ratio be 3 ~ 5:1, it is small to be stirred for 0.5 ~ 1.0
When, filtrate and filter residue is obtained by filtration；
(4) after sulfuric acid being added in filter residue, lead to oxygen in autoclave and carry out Oxidation Leaching, leaching 2 ~ 4 hours, divided later
From processing, leachate and leached mud are obtained；
(5) filtrate and the leachate are mixed 1 hour, adjust pH value later to 4, carries out cyclone electrolytic cell, electrolysis
When electrolyte circular flow be 30L/h, current density 50A/m2, temperature is 40 DEG C, and control terminal copper ion concentration is
200mg/L obtains cathode copper products；
The auxiliary agent is made of following components in percentage by weight: lime stone 12 ~ 15%, iron ore 10 ~ 13%, alumina silicate 8 ~ 10%,
Silicon carbide 5 ~ 8%, flyash 3 ~ 5%, surplus are coke；
Copper recovery in the copper smelting slag of the method is up to 99.02%.
2. according to the method described in claim 1, it is characterized by: in the step (2), the temperature of the calcination process is
1000~1200℃；Before the mixed material is carried out calcination process, forming processes are carried out to the mixed material in advance,
Obtain mixing pelletizing.
3. according to the method described in claim 1, it is characterized by: powder in the step (3), after the crushing grinding
Powder of the middle partial size less than 0.056mm accounts for the 75wt% or more of total amount.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710893153.7A CN107619940B (en) | 2017-09-28 | 2017-09-28 | A method of recycling copper from metallurgical slag |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710893153.7A CN107619940B (en) | 2017-09-28 | 2017-09-28 | A method of recycling copper from metallurgical slag |
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| CN107619940A CN107619940A (en) | 2018-01-23 |
| CN107619940B true CN107619940B (en) | 2019-10-29 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103589819A (en) * | 2013-10-12 | 2014-02-19 | 酒泉钢铁(集团)有限责任公司 | A method for direct reduction of non-ferrous smelting slag by adding oxygen |
| CN104789783A (en) * | 2015-05-18 | 2015-07-22 | 郴州市金贵银业股份有限公司 | Process for selective efficient copper extraction and comprehensive recovery from lead copper matte |
| CN104831064A (en) * | 2015-05-17 | 2015-08-12 | 李家元 | Process of efficiently recovering copper from lead matte according to oxygen pressure acid leaching and vortex electrolysis techniques |
| CN105132692A (en) * | 2015-09-25 | 2015-12-09 | 广东环境保护工程职业学院 | Method for recovering valuable metal from secondary copper electrolysis anode mud |
-
2017
- 2017-09-28 CN CN201710893153.7A patent/CN107619940B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103589819A (en) * | 2013-10-12 | 2014-02-19 | 酒泉钢铁(集团)有限责任公司 | A method for direct reduction of non-ferrous smelting slag by adding oxygen |
| CN104831064A (en) * | 2015-05-17 | 2015-08-12 | 李家元 | Process of efficiently recovering copper from lead matte according to oxygen pressure acid leaching and vortex electrolysis techniques |
| CN104789783A (en) * | 2015-05-18 | 2015-07-22 | 郴州市金贵银业股份有限公司 | Process for selective efficient copper extraction and comprehensive recovery from lead copper matte |
| CN105132692A (en) * | 2015-09-25 | 2015-12-09 | 广东环境保护工程职业学院 | Method for recovering valuable metal from secondary copper electrolysis anode mud |
Non-Patent Citations (1)
| Title |
|---|
| 哈里亚瓦尔塔炼铜厂;冶金工业部南昌有色冶金设计院编;《闪速熔炼文集》;19750331;第153页第六节 * |
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