CN1321200C - Method for separating copper, arsenic and zinc from copper-smelting high-arsenic flue dust sulphuric acid leach liquor - Google Patents
Method for separating copper, arsenic and zinc from copper-smelting high-arsenic flue dust sulphuric acid leach liquor Download PDFInfo
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- CN1321200C CN1321200C CNB2005100487403A CN200510048740A CN1321200C CN 1321200 C CN1321200 C CN 1321200C CN B2005100487403 A CNB2005100487403 A CN B2005100487403A CN 200510048740 A CN200510048740 A CN 200510048740A CN 1321200 C CN1321200 C CN 1321200C
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
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Abstract
The present invention relates to a method for separating copper, arsenic and zinc from copper-smelting sulfuric acid leaching liquid containing high-arsenic flue dust. The present invention is characterized in that a mixture of zinc sulfide and arsenic sulfide is added to the copper-smelting sulfuric acid leaching liquid containing high-arsenic flue dust to be used as a vulcanizing agent, so copper is precipitated, and copper scale and copper precipitating liquid can be separated. The copper precipitating liquid is concentrated to 60 to 100 g/L of arsenic concentration and is cooled to normal temperature, and zinc sulfate heptahydrate and base crystallization liquid are separated. Sulfur dioxide gas is led in the base crystallization liquid, arsenic is separated in the form of arsenic trioxide, and the arsenic trioxide and arsenic precipitating liquid are separated. The arsenic liquid is added in a sodium sulfide aqueous solution, the zinc and the arsenic are precipitated, and the mixture of zinc sulfide and arsenic sulfide is separated as the vulcanizing agent for copper precipitation. The present invention has the core technique of sulfuration and copper precipitation, wherein impurities out of a system can not be led in the copper precipitation process, so a sulfuric acid solution similar to the zinc and the arsenic is obtained, and the vulcanizing agent is prepared in the process. The method has the advantages that the copper, the arsenic and the zinc as main components in the copper-smelting sulfuric acid leaching liquid containing high-arsenic flue dust are separated, the recovery rate is high, and the arsenic pollution is treated effectively because the arsenic is recycled in the form of the arsenic trioxide.
Description
Technical field
The present invention relates to copper and smelt the method for high-arsenic dust sulphuric leachate separating copper arsenic zinc.
Background technology
The solubility arsenic compound has flowability in the toxicity of arsenic, particularly underground water, and the improvement that makes people smelt arsenic in the high-arsenic dust to copper is more and more paid attention to.In the prior art, copper is smelted the processing of high-arsenic dust sulphuric leachate, adopts " in iron powder replacement → oxidation and deironing arsenic → condensing crystal zinc sulfate " flow process mostly.This flow process can reclaim copper, output Zinc Sulphate Heptahydrate economically, but fails effectively to administer the pollution of arsenic, because there is secondary pollution in the iron arsenic calcium slag of output.The pollution of how to administer arsenic is a social difficult problem already.
Summary of the invention
The purpose of this invention is to provide and a kind ofly smelt separating copper, arsenic, zinc the high-arsenic dust sulphuric leachate, arsenic is reclaimed with the white arsenic form from copper, thus the method for effectively administering arsenic contamination.
Technical scheme of the present invention is: smelt in the high-arsenic dust sulphuric leachate at copper, add zinc sulphide, red arsenic mixture as vulcanizing agent, make the copper precipitation, separate obtaining copper ashes and heavy copper liquid; It is 60～100g/L that the copper liquid that will sink is concentrated to arsenic concentration, is cooled to normal temperature again, obtains Zinc Sulphate Heptahydrate and crystalline mother solution through separating; In crystalline mother solution, feed sulfur dioxide gas, thus arsenic separate out with the white arsenic form, obtaining white arsenic and heavy arsenic liquid through separating again; Add sodium sulfide solution in heavy arsenic liquid, depositing zinc, arsenic separate obtaining zinc sulphide, red arsenic mixture, are re-used as the vulcanizing agent that heavy copper is used.Wastewater toxicity reduces (otherwise processed) greatly.
Core technology of the present invention is " the heavy copper of sulfuration ", and the vulcanizing agent that is adopted is zinc sulphide, red arsenic mixture, and heavy copper process is not introduced the impurity beyond the system, obtain being similar to the sulphuric acid soln of zinc, arsenic, and vulcanizing agent is by this flow process output.The present invention has realized the separation that copper is smelted main component copper, arsenic, zinc in the high-arsenic dust sulphuric leachate, rate of recovery height, and arsenic reclaims with the white arsenic form, reaches the purpose of effective improvement arsenic contamination.As an environmental protection project, have great Significance for Environment and social effect.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Embodiment:
Certain copper is smelted high-arsenic dust sulphuric leachate composition (g/L): Cu6, As10, Zn18, H
2SO
45; Press following flow processing:
1) the heavy copper of sulfuration: under the above-mentioned leach liquor whipped state, steam heating is warmed up to 50～60 ℃, the mixture vulcanizing agent that adds zinc sulphide, red arsenic, the copper that sinks reaction, stop to add zinc sulphide, red arsenic mixture when being reacted to terminal point, steam heating is warmed up to more than 85 ℃ before the filter press, press filtration, to improve strainability.The determination methods of the heavy copper terminal point of sulfuration: the solution that takes a morsel filters, and filtrate does not have blueness and is terminal point.For the first time required heavy copper vulcanizing agent reacts with Zinc Sulphate Heptahydrate and sodium sulphite, the mass ratio of Zinc Sulphate Heptahydrate and sodium sulphite is 2: 1, earlier that Zinc Sulphate Heptahydrate is complete with water dissolution, it is 10% solution that the sodium sulphite water is dissolved into concentration, two kinds of solution are mixed again, stir while mixing, steam heating is warmed up to more than 85 ℃, filter press can make vulcanizing agent.
2) condensing crystal zinc sulfate: it is 60～100g/L that heavy copper liquid is concentrated to arsenic concentration, is cooled to normal temperature, and whizzer filters.
3) the heavy arsenic of reduction: crystalline mother solution normal temperature, whipped state feed sulfur dioxide gas down, reduce heavy arsenic reaction, stop logical sulfur dioxide gas during to the reduction terminal point, are cooled to normal temperature, the whizzer filtration.The determination methods of reduction terminal point: the solution that takes a morsel filters, the concentration of filtrate analysis arsenic, and arsenic concentration is that 20g/L is terminal point.
4) the heavy zinc arsenic of sulfuration: under the heavy arsenic liquid whipped state, thin up is to H
2SO
4Concentration is 40g/L, and adding concentration is 10% sodium sulfide solution, and steam heating is warmed up to 50～60 ℃, the zinc arsenic that sinks reaction stops to add sodium sulfide solution, filter press during to terminal point, steam heating is warmed up to more than 85 ℃ before the press filtration, to improve strainability.The determination methods of the heavy zinc arsenic terminal point of sulfuration: the pH value equals 2 and is terminal point.The waste water of output (filtrate) otherwise processed.
Claims (1)
1, a kind of copper is smelted the method for high-arsenic dust sulphuric leachate separating copper arsenic zinc, it is characterized in that smelting in the high-arsenic dust sulphuric leachate at copper, adds zinc sulphide, red arsenic mixture as vulcanizing agent, makes the copper precipitation, separates obtaining copper ashes and heavy copper liquid; It is 60～100g/L that the copper liquid that will sink is concentrated to arsenic concentration, is cooled to normal temperature again, obtains Zinc Sulphate Heptahydrate and crystalline mother solution through separating; In crystalline mother solution, feed sulfur dioxide gas, thus arsenic separate out with the white arsenic form, obtaining white arsenic and heavy arsenic liquid through separating again; Add sodium sulfide solution in heavy arsenic liquid, depositing zinc, arsenic separate obtaining zinc sulphide, red arsenic mixture, are re-used as the vulcanizing agent that heavy copper is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100487403A CN1321200C (en) | 2005-12-23 | 2005-12-23 | Method for separating copper, arsenic and zinc from copper-smelting high-arsenic flue dust sulphuric acid leach liquor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100487403A CN1321200C (en) | 2005-12-23 | 2005-12-23 | Method for separating copper, arsenic and zinc from copper-smelting high-arsenic flue dust sulphuric acid leach liquor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1789445A CN1789445A (en) | 2006-06-21 |
| CN1321200C true CN1321200C (en) | 2007-06-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2005100487403A Expired - Fee Related CN1321200C (en) | 2005-12-23 | 2005-12-23 | Method for separating copper, arsenic and zinc from copper-smelting high-arsenic flue dust sulphuric acid leach liquor |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102345016B (en) * | 2011-10-10 | 2013-01-02 | 大冶有色设计研究院有限公司 | Method for recovering arsenic and heavy metals from contaminated acid generated by metallurgical off-gas |
| CN103014355B (en) * | 2012-12-13 | 2014-12-24 | 马永涛 | Multi-metal comprehensive recycling process for copper smelting ash |
| CN105439355B (en) * | 2015-12-28 | 2018-05-25 | 中南大学 | Waste acid resource reclaim and deep treatment method and device |
| CN105624412B (en) * | 2016-01-18 | 2017-07-07 | 中南大学 | A kind of method that Combined Treatment is selected in Bellamya aeruginosa smelting |
| CN108249480A (en) * | 2017-12-22 | 2018-07-06 | 东营方圆有色金属有限公司 | A kind of comprehensive recovering process of Copper making arsenic sulfide slag, flue dust leachate arsenic |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5779136A (en) * | 1980-10-31 | 1982-05-18 | Dowa Mining Co Ltd | Selective separation of copper from solution containing various kinds of metallic ions |
| JPH11277075A (en) * | 1998-03-31 | 1999-10-12 | Dowa Mining Co Ltd | Method for removing/fixing arsenic existing in iron sulfate solution |
| CN1560289A (en) * | 2004-02-27 | 2005-01-05 | 云南铜业股份有限公司 | Method of dearsenic by parallel circulating continuous electric formation |
-
2005
- 2005-12-23 CN CNB2005100487403A patent/CN1321200C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5779136A (en) * | 1980-10-31 | 1982-05-18 | Dowa Mining Co Ltd | Selective separation of copper from solution containing various kinds of metallic ions |
| JPH11277075A (en) * | 1998-03-31 | 1999-10-12 | Dowa Mining Co Ltd | Method for removing/fixing arsenic existing in iron sulfate solution |
| CN1560289A (en) * | 2004-02-27 | 2005-01-05 | 云南铜业股份有限公司 | Method of dearsenic by parallel circulating continuous electric formation |
Non-Patent Citations (1)
| Title |
|---|
| 艾萨炉高砷烟尘综合利用新工艺 徐养良，黎英，丁昆，孔庆尧，中国有色冶金，第5期 2005 * |
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| CN1789445A (en) | 2006-06-21 |
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