CN105420755A - Method for removing arsenic from zinc sulfate electrolyte - Google Patents
Method for removing arsenic from zinc sulfate electrolyte Download PDFInfo
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- CN105420755A CN105420755A CN201510995485.7A CN201510995485A CN105420755A CN 105420755 A CN105420755 A CN 105420755A CN 201510995485 A CN201510995485 A CN 201510995485A CN 105420755 A CN105420755 A CN 105420755A
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- zinc
- arsenic
- zinc sulphate
- sulphate electrolyte
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
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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
- Y02P10/20—Recycling
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
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- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a method for removing arsenic from a zinc sulfate electrolyte in a zinc smelting process. The method comprises the following steps: (1) zinc calcine is added into the zinc sulfate electrolyte, so that the pH is adjusted; (2) a sulfurizing reagent is added into the zinc sulfate electrolyte with adjusted pH, and zinc sulfide precipitation is generated after a reaction; and (3) the zinc sulfide obtained in the step (2) is added into the zinc sulfate electrolyte for a reaction, and arsenic is removed in the form of arsenic sulfide. The method mainly solves the technical problem that arsenic in a zinc sulfate solution is difficult to remove in depth; the whole technical process is simple, efficient and environment-friendly; and great use value is achieved.
Description
Technical field
The invention belongs to the crossing domain of metallurgical engineering and environmental engineering, be specifically related to a kind of method that in zinc sulphate electrolyte, arsenic removes.
Background technology
In Zinc hydrometallurgy process, because the association of arsenic in zinc ore concentrate causes in zinc sulphate electrolyte containing certain density arsenic, the existence of arsenic has not only had a strong impact on the quality of zinc ingot metal, and may produce hypertoxic gas hydrogen arsenide in electrolytic process, there is huge safety and environment hidden danger.Therefore need the concentration strictly controlling arsenic in zinc sulphate electrolyte, all need before electrolysis electrolyte purification to remove the arsenic in solution.
Current most of enterprise all utilizes molysite chemical coprecipitation technique to add the arsenic removed in zinc electrolyte, specifically has jarosite process, hematite process, goethite process.It is by regulation and control pH and adds medicament thus make the iron ion in electrolytic solution be converted into the throw outs such as siderotil, rhombohedral iron ore, pyrrhosiderite, and the arsenic in electrolytic solution adsorb by molysite, finally reach removal with the form of co-precipitation.Because molysite adsorption efficiency is effective, causes the arsenic removal rate in electrolytic solution low, be difficult to the requirement reaching purification.In addition, the technology such as potassium permanganate oxidation-lime slurry neutralization-ironic hydroxide coprecipitation method and neutralization-atmospheric oxidation-ferric hydroxide precipitate method are also used to remove the arsenic in electrolytic solution, but all Shortcomings are as large in potassium permanganate consumption, reagent cost is high and effect is unstable etc.
Therefore the degree of depth dearsenification how carrying out high efficiency, low cost to zinc sulphate electrolyte is a difficult problem for puzzlement enterprise always.
Summary of the invention
The present invention is directed in zinc sulphate electrolyte containing arsenic impurities, the at present temporary defect without efficient deep-purifying method, object is the method providing arsenic in a kind of efficient deep purifying zinc sulphate electrolyte, it is first regulated with zinc baking sand by zinc electrolyte to add vulcanizing agent after pH and produce zinc sulphide precipitation, then add zinc sulphide precipitation and to be added in electrolytic solution by regulation and control reaction parameter to reach the object of efficient removal arsenic.After process of the present invention, in zinc sulphate electrolyte, arsenic energy steady removal is to about 0.3mg/L, achieves deep purifying and the high efficiente callback of arsenic.
The method that in zinc sulphate electrolyte, arsenic removes, comprises the steps:
1) in zinc sulphate electrolyte, zinc baking sand adjust ph is added;
2) vulcanizing agent is joined reaction in the zinc sulphate electrolyte after adjust ph and produce zinc sulphide precipitation;
3) zinc sulphide obtained in step (2) is joined reaction in new zinc sulphate electrolyte and remove arsenic.
Add zinc baking sand in step (1) and electrolyte ph is adjusted to 5 ~ 9.
The ratio that step (2) is 1 ~ 5 according to S/Zn mol ratio adds vulcanizing agent.
Vulcanizing agent described in step (2) is one or more in sodium sulphite, hydrogen sulfide, Sodium sulfhydrate.
Step (2) temperature of reaction is 25 ~ 70 DEG C, and the reaction times is 0.5 ~ 3h.
The ratio being 1 ~ 5 according to the total mol ratio of As/Zn in step (3) adds the zinc sulphide of gained in step (2).
Described in step (3), temperature of reaction is 25 ~ 80 DEG C, and the reaction times is 0.5 ~ 3h.
Advantage of the present invention:
1) technique simple and stable, energy consumption is low, and effect of removing arsenic is good, and after process, in zinc sulphate electrolyte, the concentration of arsenic, at about 0.3mg/L, reaches the effect of degree of depth dearsenification.
2) by first producing zinc sulphide by zinc electrolyte, then be added in electrolytic solution by zinc sulphide and remove arsenic, whole technical process does not introduce impurity, simultaneously, compared with direct sulfuration method, not only operating environment is more convenient, and effectively prevent the loss of zinc in arsenic removal process.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Be intended to further illustrate the present invention below in conjunction with embodiment, and unrestricted the present invention.
Embodiment 1
Get 50ml zinc sulphate electrolyte, after adding enough zinc baking sands adjustment pH to 7, add sodium sulphite according to S/Zn than the ratio being 1.2, under room temperature, react 1h, filter and obtain zinc sulphide precipitation.Above-mentioned zinc sulphide is fed in other 500ml electrolytic solution according to the ratio that Zn/As mol ratio is 1.4, at 80 DEG C, reacts 3h, after filtration, obtain rich arsenic slag and the rear electrolytic solution of purification.In rich arsenic slag, arsenic grade reaches 51.5%, and Zn content is 0.12%, and in purifying electrolysis liquid, arsenic concentration is reduced to 0.4mg/L by 40.5mg/L before treatment.It can thus be appreciated that, after process of the present invention, not only reach the requirement to zinc electrolyte deep purifying, and arsenic finally achieves effective open circuit with high-grade arsenic slag, decreases the production cost of enterprise.
Embodiment 2
Get 50ml zinc sulphate electrolyte, after adding enough zinc baking sands adjustment pH to 8, add hydrogen sulfide according to S/Zn than the ratio being 1.1, under room temperature, react 0.3h, filter and obtain zinc sulphide precipitation.Above-mentioned zinc sulphide is fed in other 500ml electrolytic solution according to the ratio that Zn/As mol ratio is 1.5, at 70 DEG C, reacts 3h, after filtration, obtain rich arsenic slag and the rear electrolytic solution of purification.In rich arsenic slag, arsenic grade reaches 50.1%, and Zn content is 0.32%, and in purifying electrolysis liquid, arsenic concentration is reduced to 0.3mg/L by 48.5mg/L before treatment.It can thus be appreciated that, after process of the present invention, not only reach the requirement to zinc electrolyte deep purifying, and arsenic finally achieves effective open circuit with high-grade arsenic slag, decreases the production cost of enterprise.
Claims (7)
1. the method that in zinc sulphate electrolyte, arsenic removes, is characterized in that, comprises the steps:
1) in zinc sulphate electrolyte, zinc baking sand adjust ph is added;
2) vulcanizing agent is joined reaction in the zinc sulphate electrolyte after adjust ph and produce zinc sulphide precipitation;
3) zinc sulphide obtained in step (2) is joined reaction in new zinc sulphate electrolyte and remove arsenic.
2. the method that in zinc sulphate electrolyte according to claim 1, arsenic removes, is characterized in that, adds zinc baking sand electrolyte ph is adjusted to 5 ~ 9 in step (1).
3. the method that in zinc sulphate electrolyte according to claim 1, arsenic removes, is characterized in that, the ratio that step (2) is 1 ~ 5 according to S/Zn mol ratio adds vulcanizing agent.
4. the method that in the zinc sulphate electrolyte according to claim 1 or 3, arsenic removes, is characterized in that, the vulcanizing agent described in step (2) is one or more in sodium sulphite, hydrogen sulfide, Sodium sulfhydrate.
5. the method that in zinc sulphate electrolyte according to claim 1, arsenic removes, is characterized in that, step (2) temperature of reaction is 25 ~ 70 DEG C, and the reaction times is 0.5 ~ 3h.
6. the method that in zinc sulphate electrolyte according to claim 1, arsenic removes, is characterized in that, the ratio being 1 ~ 5:1 according to the total mol ratio of As/Zn in step (3) adds the zinc sulphide of gained in step (2).
7. the method that in the zinc sulphate electrolyte according to claim 1 or 6, arsenic removes, is characterized in that, described in step (3), temperature of reaction is 25 ~ 80 DEG C, and the reaction times is 0.5 ~ 3h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510995485.7A CN105420755B (en) | 2015-12-28 | 2015-12-28 | The method of arsenic removing in zinc sulphate electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510995485.7A CN105420755B (en) | 2015-12-28 | 2015-12-28 | The method of arsenic removing in zinc sulphate electrolyte |
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| Publication Number | Publication Date |
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| CN105420755A true CN105420755A (en) | 2016-03-23 |
| CN105420755B CN105420755B (en) | 2017-06-16 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201510995485.7A Active CN105420755B (en) | 2015-12-28 | 2015-12-28 | The method of arsenic removing in zinc sulphate electrolyte |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5028410A (en) * | 1986-08-07 | 1991-07-02 | Material-Concepts-Research Limited | Hydrometallurgical production of zinc oxide from roasted zinc concentrates |
| CN1532297A (en) * | 2003-03-20 | 2004-09-29 | 中南大学 | Method for wet zinc refining without iron slag |
| CN1900330A (en) * | 2006-06-30 | 2007-01-24 | 赤峰红烨锌冶炼有限责任公司 | Low pollution vanadium settling iron-removing wet zinc smelting method |
| CN101665265A (en) * | 2009-09-17 | 2010-03-10 | 常宁市沿江锌业有限责任公司 | Method for manufacturing zinc sulfate by utilizing high-grade arsenic zinc oxide and zinc ash from steel works |
| CN104775029A (en) * | 2014-01-10 | 2015-07-15 | 汉中锌业特种材料有限公司 | Method for discharging germanium, arsenic and antimony impurities in zinc smelting |
-
2015
- 2015-12-28 CN CN201510995485.7A patent/CN105420755B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5028410A (en) * | 1986-08-07 | 1991-07-02 | Material-Concepts-Research Limited | Hydrometallurgical production of zinc oxide from roasted zinc concentrates |
| CN1532297A (en) * | 2003-03-20 | 2004-09-29 | 中南大学 | Method for wet zinc refining without iron slag |
| CN1900330A (en) * | 2006-06-30 | 2007-01-24 | 赤峰红烨锌冶炼有限责任公司 | Low pollution vanadium settling iron-removing wet zinc smelting method |
| CN101665265A (en) * | 2009-09-17 | 2010-03-10 | 常宁市沿江锌业有限责任公司 | Method for manufacturing zinc sulfate by utilizing high-grade arsenic zinc oxide and zinc ash from steel works |
| CN104775029A (en) * | 2014-01-10 | 2015-07-15 | 汉中锌业特种材料有限公司 | Method for discharging germanium, arsenic and antimony impurities in zinc smelting |
Non-Patent Citations (3)
| Title |
|---|
| 王晶: ""酸性湿法炼锑工艺中杂质砷去除的研究与实践"", 《湖南有色金属》 * |
| 许秀莲等: ""湿法分离含锌物料中砷的工艺评述"", 《南方冶金学院学报》 * |
| 魏昶等: ""重有色金属冶炼中砷的脱除与回收"", 《中国有色金属学会第五届学术年会论文集》 * |
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| CN105420755B (en) | 2017-06-16 |
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