CN1266908A - Process for separating metallurgical materials of Zn, Cu, Cd and Pb by wet method and its application - Google Patents
Process for separating metallurgical materials of Zn, Cu, Cd and Pb by wet method and its application Download PDFInfo
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- CN1266908A CN1266908A CN99115282A CN99115282A CN1266908A CN 1266908 A CN1266908 A CN 1266908A CN 99115282 A CN99115282 A CN 99115282A CN 99115282 A CN99115282 A CN 99115282A CN 1266908 A CN1266908 A CN 1266908A
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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
A process for separating metallurgical materials of Zn, Cu,Cd and Pb by wet method includes oxidizing leaching with the mixture of ammonium persulfate and ammonia water, complexing displacement, separating Cu and Cd, and segragating Zn to respectively separate out Zn, Cu, Cd and Pb from metallurgical material of non-ferrous metals. Said process can also be used for roasted mixed sulfide ore of Zn, Cu and Pb. Its advantage are high metallic recovery and less environmental pollution.
Description
The present invention relates to the method and the application of a kind of wet separation zinc, copper, cadmium, plumbous metallurgical material, belong to non-ferrous metal hydrometallurgy separating and extracting method class.
Copper and zinc are the common products of non-ferrous metal metallurgy enterprise.The smelting of copper mainly is by pyrometallurgical smelting at present, obtains blister copper and carries out electrolysis later on again.But for the copper-contained material that contains lead, zinc, cadmium simultaneously, traditional pyrometallurgical smelting makes not only that the rate of recovery of copper is on the low side, recovery cost is high, and makes other metal damage, forms the common cupric of coloured smelting industry, zinc, cadmium, plumbous material slag.Same in the wet method refining technique of zinc, in many zinc leaching residues, because the existence of silicic acid ferrous acid thing makes zinc, cadmium content in the leached mud be difficult to lower.
As seen in copper, zinc traditional industry were smelted, it was not very good extracting for the comprehensive recovery of copper zinc, lead, cadmium, also was simultaneously to produce the major cause that harmful slag class quantity increases.
Purpose of the present invention is intended to: the separation method of a kind of copper, zinc, cadmium, plumbous metallurgical material is provided, wishes that it can reduce the quantum of output of some cupric, residues containing zinc, eliminate and reduce its pollution to environment, can also effectively improve the rate of recovery of non-ferrous metal simultaneously.
Above goal of the invention is realized by following technological approaches:
The method of a kind of wet separation zinc, copper, cadmium, plumbous metallurgical material, it is characterized in that this separation method is separated by oxidation leaching, complexing displacement, copper cadmium and segregation four procedures of zinc are formed: its described oxidation leaching operation is meant and realizes the oxidation leaching with containing zinc, copper, cadmium and plumbous metallurgical material in the mixed solution of ammonium persulphate and ammoniacal liquor, forms the complexing ion solution and the lead sulfate leached mud that contain zinc, copper, cadmium; Described complexing displacement operation is meant that the complexing ion solution that contains zinc, copper and cadmium with the zinc metal pair replaces, and makes it to form copper-cadmium slag and contains the zinc ammonia solution; Described copper cadmium separation circuit is meant with dilute sulphuric acid handles copper-cadmium slag, makes it to separate formation cadmium sulfate solution and copper sponge; Described Cadmium Sulphate forms cadmium metal after electrodeposition is handled; Copper sponge then can send back to contain zinc, copper, cadmium, complexing ion solution in participate in the complexing displacement as transfer medium; The segregation operation of described zinc is meant with dilute sulphuric acid handles formation zinc hydroxide throw out and ammonium sulfate and ammonia water mixture to containing the zinc ammonia solution, zinc hydroxide drying, calcining form zinc oxide later, and ammonium sulfate and ammonia water mixture then can be sent into oxidation leaching operation and utilize.
The segregation operation that it is characterized in that described zinc also can adopt the concentrated method of ammonia of catching up with of heating to handle containing the zinc ammonia solution, makes it to form hydroxide deposits and ammonium sulfate and ammonia water mixture.
The hydrometallurgy that described this method can be directly used in behind copper, the plumbous zinc mixing roasting of sulfide ores separates.
Described oxidation leaching agent also can adopt superoxol.
This wet separation zinc, copper, cadmium, plumbous its advantage of metallurgical material method of providing according to above technical scheme are: one, various metallurgical slag charges such as the copper that the zinc smeltery is produced, cadmium, zinc, not only can comprehensively reclaim cadmium, zinc, and the copper recovery of having avoided zinc, cadmium to cause in the pyrometallurgical smelting of copper is low, the infringement of equipment such as dead stove; Improve the mineral products comprehensive utilization ratio; Two, for comprehensive utilization zinc oxide acid leaching residue provides a feasible program, the lead, the cadmium metal that abandon with slag are originally used, and can be reduced the pollution of waste residue environment; Three, present method can be directly used in copper, lead, zinc, the cadmium mixing ore deposit after roasting, and it is refined without flotation is directly comprehensive, and environmentally safe.
Below further set forth the present invention, and provide embodiment.
Method for wet separation involved in the present invention mainly is applicable to some slag class things that produce in the non-ferrous metal metallurgy, as the zinc sulfate leached mud that the zinc smeltery produces, zinc chloride leached mud, zinc oxide acid leaching residue, zinc casting type slag, calcining.Water treatment deposition slag, zinc-plated slag etc.
Its concrete separation method is as follows:
At first, (wherein the concentration of ammonium sulfate should realize in 0.5～1M) ammonia liquid that oxidation leaches to the metallurgical material that will contain metals such as zinc, copper, cadmium, lead at ammonium persulfate solution.Its reason is because copper, cadmium, zinc and ammonia form the very capable of complexing ion.So after the very strong ammonium persulphate oxidation of oxidized property, leach through ammoniacal liquor, these above-mentioned three kinds of metallic elements that exist with simple substance or other formation can be become the ammino ion and enter solution, plumbous then be present in the slag with the form of water-fast lead sulfate.After only the sulfuric acid lead skim need being separated from complexing ion solution, this sulfuric acid lead skim can directly enter pyrometallurgical smelting of lead, and this just reclaims the plumbous influence that zinc exists of having got rid of for pyrogenic process.
Next, the ammino that will contain zinc, copper, cadmium closes solion and replaces the generation copper-cadmium slag and contain the zinc ammonia solution with the zinc metal.Its reason is because the energy force rate cadmium that zinc and ammino close is strong, so form in the solution that exists at the ammino ion, it is a lot of that the energy force rate of zinc displacement cadmium exists the ability of displacement cadmium in the solution to strengthen with single ion, and the activity of copper own is poor, therefore zinc can cement out the copper cadmium very soon by the copper sponge conduction electron in ammonia solution; This also is that the copper sponge that will obtain after being separated by copper-cadmium slag partly returns zinc, copper, cadmium complexing ion solution, utilizes the reason place of zinc conversion.
Its three, with dilute sulphuric acid copper-cadmium slag is separated.Generate copper sponge and Cadmium Sulphate.It is then easily molten that its reason is that elemental copper is insoluble to the diluted acid cadmium, thus can very fast cadmium be separated from copper-cadmium slag with diluted acid, and in slag, obtain purer copper sponge simultaneously; The then available electrodeposition method of cadmium in the solution draws.
Its four, catch up with ammonia to handle with dilute sulphuric acid or heating to containing the zinc ammonia solution, make it to generate hydroxide deposits, then this zinc hydroxide is filtered, drying, the calcining after get final product zinc oxide.Filtered liquid and ammonia can return the leaching operation and utilize.
Claims (4)
1, the method and the application of a kind of wet separation zinc, copper, cadmium, plumbous metallurgical material, it is characterized in that this separation method is separated by oxidation leaching, complexing displacement, copper cadmium and segregation four procedures of zinc are formed: its described oxidation leaching operation is meant and realizes the oxidation leaching with containing zinc, copper, cadmium and plumbous metallurgical material in the mixed solution of ammonium persulphate and ammoniacal liquor, forms the complexing ion solution and the lead sulfate leached mud that contain zinc, copper, cadmium; Described complexing displacement operation is meant that the complexing ion solution that contains zinc, copper and cadmium with the zinc metal pair replaces, and makes it to form copper-cadmium slag and contains the zinc ammonia solution; Described copper cadmium separation circuit is meant with dilute sulphuric acid handles copper-cadmium slag, makes it to separate to form cadmium sulfate solution and copper sponge, and described Cadmium Sulphate forms cadmium metal after electrodeposition is handled; Copper sponge then can be sent back in the complexing ion solution that contains zinc, copper, cadmium and be participated in the complexing displacement as replacement media; The segregation operation of described zinc is meant with dilute sulphuric acid handles formation zinc hydroxide throw out and ammonium sulfate and ammonia water mixture to containing the zinc ammonia solution through row, zinc hydroxide drying, calcining get zinc oxide later, and ammonium sulfate and ammonia water mixture then can be sent into oxidation leaching operation and utilize.
2, the method for a kind of wet separation zinc according to claim 1, copper, cadmium, plumbous metallurgical material, the segregation operation that it is characterized in that described zinc also can adopt the concentrated method of ammonia of catching up with of heating to handle containing the zinc ammonia solution, makes it to form hydroxide deposits and ammonium sulfate and ammonia water mixture.
3,, it is characterized in that the hydrometallurgy that this method can be directly used in the copper after roasting, plumbous zinc mixing sulphide ores separates according to the method for claim 1 and 2 described a kind of wet separation zinc, copper, cadmium, plumbous metallurgical material.
4, according to the method for claim 1 and 2 described a kind of wet separation zinc, copper, cadmium, plumbous metallurgical material, it is characterized in that the oxygenant that is adopted can be a hydrogen peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99115282A CN1266908A (en) | 1999-03-14 | 1999-03-14 | Process for separating metallurgical materials of Zn, Cu, Cd and Pb by wet method and its application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99115282A CN1266908A (en) | 1999-03-14 | 1999-03-14 | Process for separating metallurgical materials of Zn, Cu, Cd and Pb by wet method and its application |
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| CN1266908A true CN1266908A (en) | 2000-09-20 |
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| CN99115282A Pending CN1266908A (en) | 1999-03-14 | 1999-03-14 | Process for separating metallurgical materials of Zn, Cu, Cd and Pb by wet method and its application |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824541A (en) * | 2010-04-08 | 2010-09-08 | 河池市津泰资源再生有限公司 | Treatment method of wet method zinc smelting by-products |
| CN101967574A (en) * | 2010-11-29 | 2011-02-09 | 常州市新盛电器有限公司 | Method for reducing cadmium content in process of producing lead brass sectional materials |
| CN102443701A (en) * | 2010-10-12 | 2012-05-09 | 中国科学院过程工程研究所 | Clean metallurgic comprehensive utilization method of iron vitriol slags |
| CN103668339A (en) * | 2013-10-29 | 2014-03-26 | 昆明理工大学 | Method for preparing copper powder from copper-containing slag |
| WO2015003538A1 (en) * | 2013-07-12 | 2015-01-15 | Zhang Chao | Hydrometallurgical method of metal sulfides |
| WO2015103845A1 (en) * | 2014-01-10 | 2015-07-16 | 张超 | Method for treating lead-containing raw material |
| CN104789771A (en) * | 2015-05-06 | 2015-07-22 | 昆明贵益金属材料有限公司 | Valuable metal separation method for complex copper, lead, zinc and silver mixed concentrates |
| CN104911350A (en) * | 2015-05-25 | 2015-09-16 | 张晋敏 | Tailing treatment method |
| CN105197988A (en) * | 2015-11-02 | 2015-12-30 | 扬州大学 | Ammonia process separation and refinement method of lead sulfate |
| CN103668339B (en) * | 2013-10-29 | 2016-11-30 | 昆明理工大学 | A kind of from containing the method producing copper powder copper ashes |
| CN106282572A (en) * | 2016-08-11 | 2017-01-04 | 李果 | A kind of method of comprehensive utilization of the complex multi-metal materials such as cupric zinc |
| CN112323097A (en) * | 2020-10-16 | 2021-02-05 | 昆明理工大学 | Method and system for removing sulfur dioxide in flue gas by zinc-ammonia complex coupling persulfate advanced oxidation technology |
| CN115612848A (en) * | 2022-10-27 | 2023-01-17 | 昆明理工大学 | Method for reducing copper content in zinc purification slag by ultrasonically activating persulfate |
| CN117606236A (en) * | 2023-11-22 | 2024-02-27 | 江西金德铅业股份有限公司 | Device and method for improving copper dross production index |
-
1999
- 1999-03-14 CN CN99115282A patent/CN1266908A/en active Pending
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824541B (en) * | 2010-04-08 | 2011-11-30 | 河池市津泰资源再生有限公司 | Treatment method of wet method zinc smelting by-products |
| CN101824541A (en) * | 2010-04-08 | 2010-09-08 | 河池市津泰资源再生有限公司 | Treatment method of wet method zinc smelting by-products |
| CN102443701A (en) * | 2010-10-12 | 2012-05-09 | 中国科学院过程工程研究所 | Clean metallurgic comprehensive utilization method of iron vitriol slags |
| CN102443701B (en) * | 2010-10-12 | 2014-11-05 | 中国科学院过程工程研究所 | Clean metallurgic comprehensive utilization method of iron vitriol slags |
| CN101967574A (en) * | 2010-11-29 | 2011-02-09 | 常州市新盛电器有限公司 | Method for reducing cadmium content in process of producing lead brass sectional materials |
| CN101967574B (en) * | 2010-11-29 | 2012-09-05 | 常州市新盛电器有限公司 | Method for reducing cadmium content in process of producing lead brass sectional materials |
| WO2015003538A1 (en) * | 2013-07-12 | 2015-01-15 | Zhang Chao | Hydrometallurgical method of metal sulfides |
| CN103668339B (en) * | 2013-10-29 | 2016-11-30 | 昆明理工大学 | A kind of from containing the method producing copper powder copper ashes |
| CN103668339A (en) * | 2013-10-29 | 2014-03-26 | 昆明理工大学 | Method for preparing copper powder from copper-containing slag |
| WO2015103845A1 (en) * | 2014-01-10 | 2015-07-16 | 张超 | Method for treating lead-containing raw material |
| CN104789771A (en) * | 2015-05-06 | 2015-07-22 | 昆明贵益金属材料有限公司 | Valuable metal separation method for complex copper, lead, zinc and silver mixed concentrates |
| CN104911350A (en) * | 2015-05-25 | 2015-09-16 | 张晋敏 | Tailing treatment method |
| CN104911350B (en) * | 2015-05-25 | 2017-09-22 | 厦门日懋城建园林建设股份有限公司 | A kind of tailings processing method |
| CN105197988A (en) * | 2015-11-02 | 2015-12-30 | 扬州大学 | Ammonia process separation and refinement method of lead sulfate |
| CN106282572A (en) * | 2016-08-11 | 2017-01-04 | 李果 | A kind of method of comprehensive utilization of the complex multi-metal materials such as cupric zinc |
| CN112323097A (en) * | 2020-10-16 | 2021-02-05 | 昆明理工大学 | Method and system for removing sulfur dioxide in flue gas by zinc-ammonia complex coupling persulfate advanced oxidation technology |
| CN112323097B (en) * | 2020-10-16 | 2024-04-30 | 昆明理工大学 | Method and system for removing sulfur dioxide in flue gas by zinc ammonia complexation coupling persulfate advanced oxidation technology |
| CN115612848A (en) * | 2022-10-27 | 2023-01-17 | 昆明理工大学 | Method for reducing copper content in zinc purification slag by ultrasonically activating persulfate |
| CN115612848B (en) * | 2022-10-27 | 2024-05-24 | 昆明理工大学 | Method for reducing copper content in zinc purification slag by ultrasonic activation of persulfate |
| CN117606236A (en) * | 2023-11-22 | 2024-02-27 | 江西金德铅业股份有限公司 | Device and method for improving copper dross production index |
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