CN107619940A - A kind of method that copper is reclaimed from metallurgical slag - Google Patents
A kind of method that copper is reclaimed from metallurgical slag Download PDFInfo
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- CN107619940A CN107619940A CN201710893153.7A CN201710893153A CN107619940A CN 107619940 A CN107619940 A CN 107619940A CN 201710893153 A CN201710893153 A CN 201710893153A CN 107619940 A CN107619940 A CN 107619940A
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- copper
- electrolytic cell
- smelting slag
- auxiliary agent
- mixed material
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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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- 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 relates to a kind of method that copper is reclaimed from metallurgical slag, using reduction roasting, again water logging, reoxidize acidleach, the mode of last cyclone electrolytic cell, auxiliary agent has been specifically added in roasting, make the reaction of metallurgical slag fully, good fluidity, beneficial to sedimentation separation.First water logging reoxidizes acidleach, and cyclone electrolytic cell is carried out 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 compares conventional cyclone electrolytic cell mode, and the rate of recovery of the invention is higher.
Description
Technical field
The present invention relates to metallurgical slag recycling field, is to be related to a kind of method that copper is reclaimed from metallurgical slag specifically.
Background technology
The world today, it is in the ascendant with green science and technology, development green economy.Traditional nonferrous metallurgy industry, bargh
It is high energy consumption, high pollution, maximum discharge enterprise.With minimizing, innoxious, recycling, reuse, recirculate to code of conduct,
To greatest extent using existing resource, and the valuable metal in high efficiente callback waste liquid, waste residue is circulated, these enterprises will be increasingly becomed
The needs further developed.Main valuable metal composition in comprehensive reutilization copper smelting slag, can be fully sharp for enterprise
Huge economic well-being of workers and staff is created with raw material, solves pollution on the environment in stacking and transport process again.Therefore, from copper smelting
Comprehensive valuable metal has far-reaching realistic meaning in economic benefit, social benefit, Environmental Effect Yidu in refining slag, is also produced 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, has higher recovery value.From copper smelting slag
From the point of view of recycling recycles present situation, the valuable constituent such as copper, nickel in copper smelting slag is primarily as the impurity in metallurgical process
Metal and remove, processing procedure long flow path, the purity of obtained sponge copper products is relatively low, the cobalt nickel particularly in slag, not only difficult
Remove, and processing cost is universal higher.
Using cyclone electrolytic cell technical finesse sludge from copper smelting leachate and directly obtain metal simple-substance electrolytic production, can be with
Extraction process is omitted, so as to which valuable metal recovery cost be greatly reduced.Elimination of the cyclone electrolytic cell to concentration polarization, which acts on, causes it
High metal recovery efficiency can be obtained, such as uses cyclone electrolytic cell technology from the acidic chloride solution containing palladium and containing rhodium metal
Middle Recover palladium and rhodium, organic efficiency have exceeded 99%.If the deposition potential of foreign ion and metal target gap are larger, eddy flow
Electrolysis is influenceed smaller, product purity height by foreign ion.
The content of the invention
In order to solve the rate of recovery of metallurgical slag recovery process and Cost Problems, returned the invention provides one kind from metallurgical slag
The method for receiving copper, it includes the steps such as roasting, water logging, acidleach, cyclone electrolytic cell, so that the copper recovery in copper smelting slag is up to
More than 99% and eliminate extraction etc. process.
A kind of method that copper is reclaimed from copper smelting slag, including：
(1) copper smelting slag, auxiliary agent and quick lime are mixed, obtains mixed material；
(2) mixed material is calcined, the solid mixture after being calcined；
(3) solid mixture is subjected to crushing grinding, with 80~95 DEG C of hot water pulps, volume and the solid of hot water mix
The mass ratio 1 of compound:1, after stirring 0.5~1.0 hour, then add 80~95 DEG C of hot water to liquid-solid ratio to be 3~5:1, it is stirred for 0.5
~1.0 hours, it is filtrated to get filtrate and filter residue；
(4) after filter residue being added into sulfuric acid, the logical oxygen progress Oxidation Leaching in autoclave, leaching 2~4 hours, afterwards
Separating treatment is carried out, obtains leachate and leached mud；
(5) after mixing by the filtrate and the leachate and adjust pH, negative electrode copper products are obtained using cyclone electrolytic cell.
The auxiliary agent is made up of following components in percentage by weight：Lime stone 12~15%, iron ore 10~13%, silicic acid
Aluminium powder 8~10%, carborundum 5~8%, flyash 3~5%, surplus are coke.
In the step (1), copper smelting slag, auxiliary agent and quick lime are 1 according to mass ratio：(2~2.5)：(5~6.5)
Mixed.
In the step (2), the temperature of the calcination process is 1000~1200 DEG C；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 particle diameter less than 0.056mm accounts for total amount in the powder after the crushing grinding
More than 75wt%.
In the step (5), the filtrate and the leachate mix 1~2 hour, adjust pH value afterwards to 4
~5, cyclone electrolytic cell is carried out, electrolyte circular flow is 30L/h during electrolysis, and current density is 50~80A/m2, temperature be 40~
50 DEG C, it is 200mg/L to control terminal copper ion concentration.
The present invention using reduction roasting, again water logging, reoxidize acidleach, the mode of last cyclone electrolytic cell is special in roasting
Add auxiliary agent, make metallurgical slag reaction fully, good fluidity, beneficial 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 compares conventional cyclone electrolytic cell mode, and the rate of recovery of the invention is higher.
Embodiment
With reference to embodiment and comparative example, the present invention is described in more detail.
Embodiment 1：
A kind of method that copper is reclaimed from copper smelting slag, including：(1) copper smelting slag, auxiliary agent and quick lime are mixed,
Obtain mixed material.Wherein, copper smelting slag, auxiliary agent and quick lime are 1 according to mass ratio:2:5 are mixed.The auxiliary agent by with
The component of lower percentage by weight is made：Lime stone 12%, iron ore 10%, aluminium silicate powder 8%, carborundum 5%, flyash 3%,
Surplus is coke.(2) mixed material is calcined, the solid mixture after being calcined.The temperature of the calcination process
Spend for 1000 DEG C；Before the mixed material is carried out into calcination process, forming processes are carried out to the mixed material in advance, obtained
To mixing pelletizing.(3) solid mixture is subjected to crushing grinding, particle diameter is less than in the powder after the crushing grinding
0.056mm powder accounts for more than the 75wt% 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, after stirring 0.5 hour, then add 80 DEG C of hot water to liquid-solid ratio to be 3:1, it is stirred for 0.5 hour, is filtrated to get filtrate and filter residue；
(4) after filter residue being added into sulfuric acid, oxygen progress Oxidation Leaching is led in autoclave, leaching 2 hours, carries out separating treatment afterwards,
Obtain leachate and leached mud；(5) filtrate and the leachate are mixed 1 hour, adjusts pH value afterwards to 4, enter
Row cyclone electrolytic cell, electrolyte circular flow is 30L/h, current density 50A/m during electrolysis2, temperature is 40 DEG C, controls terminal copper
Ion concentration is 200mg/L, obtains negative electrode copper products.Wherein, the rate of recovery of the copper in copper smelting slag is up to 99.02%.
Embodiment 2：
A kind of method that copper is reclaimed from copper smelting slag, including：(1) copper smelting slag, auxiliary agent and quick lime are mixed,
Obtain mixed material.Wherein, copper smelting slag, auxiliary agent and quick lime are 1 according to mass ratio:2.5:6.5 are mixed.The auxiliary agent
It is made up of following components in percentage by weight：Lime stone 15%, iron ore 13%, aluminium silicate powder 10%, carborundum 8%, fine coal
Ash 5%, surplus is coke.(2) mixed material is calcined, the solid mixture after being calcined.At the roasting
The temperature of reason is 1200 DEG C；Before the mixed material is carried out into calcination process, the mixed material is molded in advance
Processing, obtain mixing pelletizing.(3) solid mixture is subjected to crushing grinding, particle diameter in the powder after the crushing grinding
Powder less than 0.056mm accounts for more than the 75wt% of total amount, with 95 DEG C of hot water pulps, the volume of hot water and the matter of solid mixture
Measure ratio 1:1, after stirring 1.0 hours, then add 95 DEG C of hot water to liquid-solid ratio to be 5:1, be stirred for 1.0 hours, be filtrated to get filtrate and
Filter residue；(4) after filter residue being added into sulfuric acid, oxygen progress Oxidation Leaching is led in autoclave, leaching 4 hours, is separated afterwards
Processing, obtains leachate and leached mud；(5) filtrate and the leachate are mixed 2 hours, adjust afterwards pH value to
5, cyclone electrolytic cell is carried out, electrolyte circular flow is 30L/h, current density 80A/m during electrolysis2, temperature is 50 DEG C, and control is eventually
Point copper ion concentration is 200mg/L, obtains negative electrode copper products.Wherein, the rate of recovery of the copper in copper smelting slag is up to 99.25%.
Embodiment 3：
A kind of method that copper is reclaimed from copper smelting slag, including：(1) copper smelting slag, auxiliary agent and quick lime are mixed,
Obtain mixed material.Wherein, copper smelting slag, auxiliary agent and quick lime are 1 according to mass ratio:2:6 are mixed.The auxiliary agent by with
The component of lower percentage by weight is made：Lime stone 13%, iron ore 12%, aluminium silicate powder 9%, carborundum 7%, flyash 4%,
Surplus is coke.(2) mixed material is calcined, the solid mixture after being calcined.The temperature of the calcination process
Spend for 1100 DEG C；Before the mixed material is carried out into calcination process, forming processes are carried out to the mixed material in advance, obtained
To mixing pelletizing.(3) solid mixture is subjected to crushing grinding, particle diameter is less than in the powder after the crushing grinding
0.056mm powder accounts for more than the 75wt% 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, after stirring 0.5 hour, then add 90 DEG C of hot water to liquid-solid ratio to be 4:1, it is stirred for 1.0 hours, is filtrated to get filtrate and filter residue；
(4) after filter residue being added into sulfuric acid, oxygen progress Oxidation Leaching is led in autoclave, leaching 3 hours, carries out separating treatment afterwards,
Obtain leachate and leached mud；(5) filtrate and the leachate are mixed 2 hours, adjusts pH value afterwards to 4, enter
Row cyclone electrolytic cell, electrolyte circular flow is 30L/h, current density 60A/m during electrolysis2, temperature is 45 DEG C, controls terminal copper
Ion concentration is 200mg/L, obtains negative electrode copper products.Wherein, the rate of recovery of the copper in copper smelting slag is up to 99.32%.
Comparative example 1：
Will be with copper smelting slag of the present invention without water logging or acidleach, and only carry out cyclone electrolytic cell after a wherein step leaches, then
For resulting negative electrode copper products for copper smelting slag, the rate of recovery of copper is only 86%.
Comparative example 2：
Using other ways of recycling such as the extractions different from cyclone electrolytic cell mode of the present invention, copper in its copper smelting slag returns
Yield is only 80% or so, and extract, the cost of stripping process it is higher.
Comparative example 3：
If the auxiliary agent for being added without the present invention is mixed, two step leaching effects will be reduced substantially, final so as to cause
For cyclone electrolytic cell negative electrode 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, its step and technological parameter are that applicant verifies by repeated tests.It is being calcined
When be specifically added auxiliary agent, make metallurgical slag reaction fully, good fluidity, beneficial 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 compares 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
In the case of departing from the principle and objective of the present invention a variety of change, modification, replacement and modification can be carried out to these embodiments, this
The scope of invention is limited by claim and its equivalent.
Claims (6)
- A kind of 1. method that copper is reclaimed from copper smelting slag, it is characterised in that including：(1) copper smelting slag, auxiliary agent and quick lime are mixed, obtains mixed material；(2) mixed material is calcined, the solid mixture after being calcined；(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, after stirring 0.5~1.0 hour, then add 80~95 DEG C of hot water to liquid-solid ratio to be 3~5:1, it is stirred for 0.5~ 1.0 hours, it is filtrated to get filtrate and filter residue；(4) after filter residue being added into sulfuric acid, oxygen progress Oxidation Leaching is led in autoclave, leaching 2~4 hours, is carried out afterwards Separating treatment, obtain leachate and leached mud；(5) after mixing by the filtrate and the leachate and adjust pH, negative electrode copper products are obtained using cyclone electrolytic cell.
- A kind of 2. method that copper is reclaimed from copper smelting slag according to claim 1, it is characterised in that：The auxiliary agent by with The component of lower percentage by weight is made：Lime stone 12~15%, iron ore 10~13%, alumina silicate 8~10%, carborundum 5~ 8%th, flyash 3~5%, surplus are coke.
- 3. according to the method for claim 1, it is characterised in that：In the step (1), copper smelting slag, auxiliary agent and raw stone Ash is 1 according to mass ratio：(2~2.5)：(5~6.5) are mixed.
- 4. according to the method for claim 4, it is characterised in that：In the step (2), the temperature of the calcination process is 1000~1200 DEG C；Before the mixed material is carried out into calcination process, forming processes are carried out to the mixed material in advance, Obtain mixing pelletizing.
- 5. the described method according to Claims 1-4, it is characterised in that：In the step (3), the crushing grinding Powder of the particle diameter less than 0.056mm accounts for more than the 75wt% of total amount in powder afterwards.
- 6. the method according to claim 1 to 5, it is characterised in that：In the step (5), the filtrate and the leaching Go out liquid to mix 1~2 hour, adjust pH value afterwards to 4~5, carry out cyclone electrolytic cell, electrolyte circular flow is during electrolysis 30L/h, current density are 50~80A/m2, temperature is 40~50 DEG C, and it is 200mg/L to control terminal copper ion concentration.
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| CN103589819A (en) * | 2013-10-12 | 2014-02-19 | 酒泉钢铁(集团)有限责任公司 | Method for directly reducing nonferrous smelting slag through oxygenation |
| 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 |
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| 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 |
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2017
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Patent Citations (4)
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| CN103589819A (en) * | 2013-10-12 | 2014-02-19 | 酒泉钢铁(集团)有限责任公司 | Method for directly reducing nonferrous smelting slag through oxygenation |
| 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 |
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