CN103233129A - Wet-process open treatment method of arsenic in copper ashes - Google Patents
Wet-process open treatment method of arsenic in copper ashes Download PDFInfo
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- CN103233129A CN103233129A CN2013101655966A CN201310165596A CN103233129A CN 103233129 A CN103233129 A CN 103233129A CN 2013101655966 A CN2013101655966 A CN 2013101655966A CN 201310165596 A CN201310165596 A CN 201310165596A CN 103233129 A CN103233129 A CN 103233129A
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- clorox
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Abstract
The invention discloses an open treatment method of arsenic in copper ashes and relates to a method for open pre-treatment of harmful arsenic impurities in intermediate material ashes in a copper smelting process. The wet-process open treatment method is characterized in that the treatment process comprises the following steps of: adding copper ashes to a solution containing sodium hypochlorite and sodium hydroxide; carrying out arsenic leaching reaction and filtering to obtain arsenic-removed slag and arsenic-removed solution; and recycling valuable metals including copper, lead, zinc and bismuth of the arsenic-removed slag. The wet-process open treatment method disclosed by the invention can be used for carrying out open treatment on the arsenic in the copper ashes before recycling the valuable metals, so that the subsequent recycling process of valuable metals is facilitated. Meanwhile, a utilization way for residual chlorine absorption liquid waste is found, so that the secondary pollution is avoided. Besides, the wet-process open treatment method for arsenic in the copper ashes is low in process cost and high in arsenic removal rate, and has great significance of improving environment protection, resource control and economical benefits.
Description
Technical field
The open circuit treatment process of arsenic in a kind of copper cigarette ash relates to the method that the pre-treatment of a kind of copper smelting process intermediate material cigarette ash open circuit is harmful to arsenic impurities.
Background technology
Smelt in the production process at copper, arsenic often is the associated element of copper ore concentrates, because copper raw material Market competition, containing the low high-quality copper ore concentrates resources of foreign matter content such as arsenic day by day reduces, although national regulation import copper raw material contains arsenic less than 0.5%, but along with copper throughput continues to enlarge, the total amount that enters the arsenic of copper smelting system gets more and more in recent years.
According to research, in copper flash stove smelting process, 37% arsenic enters flue dust; The electricity flue dust that gathers dust contains 4～6% arsenic approximately, also contain the worth recovery of valuable metal such as copper, for improving the comprehensive utilization ratio of resource, thisly contain the direct Returning smelting that arsenic smoke dust has, the arsenic amount that enters the flash stove with the cigarette ash form accounts for more than 50% of total arsenic amount according to statistics, this makes arsenic vicious cycle and enrichment in system, and finally the harm that pyrometallurgical smelting process and follow-up relieving haperacidity and electrolytic copper are produced is all very big, also makes also more and more higher to containing the arsenic requirement in the metallurgy of copper raw material.
For reducing the arsenic evil, make impurity open circuits such as arsenic at present, some copper smelting plant adopts the pre-arsenic removing method of roasting to handle copper cigarette ash, and only about 80%, atmospheric pollution is serious for arsenic-removing rate.Some copper smelting plant is set up the comprehensive utilization factory of cigarette ash, uses the wet processing comprehensively recovering valuable metal, but arsenic presss from both sides the generation dispersion in each operation in existing wet processing, also has an open circuit difficult problem.Simultaneously, in process of production, the chlorine that the cobalt Winning cell produces need find available approach with the clorox waste liquid that alkali absorbs, and avoids its secondary pollution.
Summary of the invention
The objective of the invention is the deficiency at above-mentioned prior art existence, proposing a kind of can effectively arsenic in the copper cigarette ash open circuit before reclaiming valuable metal in advance handles, the recovery technology that is conducive to follow-up valuable metal, effectively be beneficial to clorox waste water, with low cost, the open circuit treatment process of arsenic in the high copper cigarette ash of arsenic extrusion rate.
The objective of the invention is to be achieved through the following technical solutions.
The open circuit treatment process of arsenic in a kind of copper cigarette ash, it is characterized in that its treatment process process is copper cigarette ash to be added contain in the solution of clorox and sodium hydroxide, carry out arsenic and leach reaction, filter and obtain after the dearsenification liquid behind the slag and dearsenification, slag after the dearsenification is carried out the recovery of copper-lead zinc bismuth valuable metal.
The open circuit treatment process of arsenic in a kind of copper cigarette ash of the present invention is characterized in that the weight concentration of clorox is 4%～12% in the described solution that contains clorox and sodium hydroxide, and the weight concentration of sodium hydroxide is 1.5%～10%.
The open circuit treatment process of arsenic in a kind of copper cigarette ash of the present invention is characterized in that the described dearsenification reaction process of carrying out, and copper cigarette ash is 10～20:1 with the solid weight ratio of the solution that contains clorox and sodium hydroxide.
The open circuit treatment process of arsenic in a kind of copper cigarette ash of the present invention is characterized in that the described reaction times of carrying out the dearsenification reaction process is 1～2h, and temperature of reaction is 50 ℃-80 ℃.
The open circuit treatment process of arsenic in a kind of copper cigarette ash of the present invention, the weight ratio chemical ingredients that it is characterized in that described copper cigarette ash is: plumbous 10%～60%, arsenic 2%～5%, nickel 0.01%～0.1 %, copper 2%～20 %, zinc 2%～7%, iron 0.5%～1.5%, antimony 0.1%～5%, bismuth 1%～15%, sulphur and oxygen, carbon 30%～40%.
The open circuit treatment process of arsenic in a kind of copper cigarette ash of the present invention, it is characterized in that the clorox waste liquid after chlorine that the described solution that contains clorox and sodium hydroxide produces for the cobalt Winning cell absorbs with alkali, its weight ratio chemical ingredients is: clorox 4%～6%, sodium hydroxide 8%～10%.
The open circuit treatment process of arsenic in a kind of copper cigarette ash of the present invention, it is characterized in that the described solution that contains clorox and sodium hydroxide is the clorox waste liquid that the chemical plant produces, its weight ratio chemical ingredients is: clorox 8%～12%, sodium hydroxide 1.5%～3%.
The open circuit treatment process of arsenic in a kind of copper cigarette ash of the present invention is characterized in that described filtration obtains that liquid adopts the ferrite process dearsenification to handle the back landfill after the dearsenification.
The open circuit treatment process of arsenic in a kind of copper cigarette ash of the present invention, before copper cigarette ash reclaims the valuable metal recovery, arsenic opened a way in advance separate with valuable metal in the cigarette ash, the arsenic extrusion rate is greater than 95%, and the quantity of slag reduces 10%～20%, and sulphur reduces 90%, valuable metal enrichment and be conducive to subsequent recovery in the slag, flow process is simple, the treatment of wastes with processes of wastes against one another, recycling economy, and production cost is low, metal recovery rate is high.Especially used contained clorox in the chlorine residue absorption liquid waste liquid in the Production Flow Chart, the dearsenification of directly opening a way from copper cigarette ash had both solved arsenic open circuit problem, had solved the clorox wastewater problem again.
Description of drawings
Fig. 1 is process flow sheet of the present invention
Embodiment
The open circuit treatment process of arsenic in a kind of copper cigarette ash, its treatment process process is copper cigarette ash to be added contain in the solution of clorox and sodium hydroxide, carry out arsenic and leach reaction, filter and obtain after the dearsenification liquid behind the slag and dearsenification, slag after the dearsenification is carried out the recovery of copper-lead zinc bismuth valuable metal.
In the operation, the solution that contains clorox and sodium hydroxide that uses can adopt the chlorine residue in the production process to absorb the chlorine bleach liquor in back waste liquid or chemical plant, contain clorox 4%～8%, sodium hydroxide 1.5～10%, with cigarette ash liquid-solid ratio 10～20:1,50 ℃-80 ℃ of temperature of reaction, arsenic enters leach liquor with the sodium arseniate form, the slag rate reduces 15%～20%, copper-lead zinc-nickel ferrous metal enrichment 15%～20% in slag of coexistence, slag are transferred to cigarette ash factory and are reclaimed valuable metal, contain the leach liquor of several gram liters of arsenic, use the ferrite process dearsenification, arsenic slag landfill.
Below further specify the present invention by concrete embodiment.
Embodiment 1
Copper cigarette ash chemistry weight item: lead 50%, arsenic 4.3%, nickel 0.03 %, copper 5.6 %, zinc 6.2%, iron 0.86 %, antimony 3%, bismuth 2.18 %, sulphur and oxygen, carbon 30%.
Add clorox and hydrogen-oxygen sodium hydroxide solution in the copper cigarette ash, chlorine bleach liquor's concentration 8%, sodium hydroxide 2%, liquid-solid ratio 15:1, stirring reaction 1.5h, 50 ℃ of temperature of reaction are filtered and are obtained after the dearsenification liquid behind the slag and dearsenification, after the dearsenification under the liquid step stand-by.
Slag is sent into existing cigarette ash factory and is reclaimed valuable metals such as copper-lead zinc bismuth after the dearsenification.Dreg chemistry composition after the dearsenification: lead 56.99%, arsenic 0.18%, nickel 0.06%, copper 6 %, zinc 6.85%, iron 0.96 %, antimony 3.40 %, bismuth 2.32 %, sulphur 0.5%, oxygen, chlorine, sodium 20%.
Liquid ferrite method arsenic precipitation after the dearsenification, arsenic slag landfill, back liquid discharge of wastewater.
Embodiment 2
Copper cigarette ash chemical ingredients: lead 10%, arsenic 5%, nickel 0.01 %, copper 20 %, zinc 2%, iron 1.5 %, antimony 5 %, bismuth 15 %, sulphur and oxygen, carbon 40%.
Add clorox and hydrogen-oxygen sodium hydroxide solution in the copper cigarette ash, chlorine bleach liquor's concentration 12%, sodium hydroxide 2%, liquid-solid ratio 10:1, stirring reaction 1h, 80 ℃ of temperature of reaction are filtered and are obtained after the dearsenification liquid behind the slag and dearsenification, after the dearsenification under the liquid step stand-by.
Slag is sent into existing cigarette ash factory and is reclaimed valuable metals such as copper-lead zinc bismuth after the dearsenification.Dreg chemistry composition after the dearsenification: lead 10.99%, arsenic 0.19%, nickel 0.02%, copper 23 %, zinc 2.15%, iron 1.7%, antimony 5.6 %, bismuth 17%, sulphur 0.9%, oxygen, chlorine, sodium 39%.
Liquid ferrite method arsenic precipitation after the dearsenification, arsenic slag landfill, back liquid waste water discharge of wastewater.
Embodiment 3
Copper cigarette ash chemical ingredients: lead 60%, arsenic 2, nickel 0.1%, copper 2, zinc 7%, iron 0.5 %, antimony 0.1%, bismuth 1%, sulphur and oxygen carbon 36%.
Add clorox and hydrogen-oxygen sodium hydroxide solution in the copper cigarette ash, chlorine bleach liquor's concentration 4%, sodium hydroxide 10%, liquid-solid ratio 20:1, stirring reaction 2h, 60 ℃ of temperature of reaction are filtered and are obtained after the dearsenification liquid behind the slag and dearsenification, after the dearsenification under the liquid step stand-by.
Slag is sent into existing cigarette ash factory and is reclaimed valuable metals such as copper-lead zinc bismuth after the dearsenification.Dreg chemistry composition after the dearsenification: lead 67%, arsenic 0.1%, nickel 0.06%, copper 2.3 %, zinc 7.85%, iron 0.6 %, antimony 1.02%, bismuth 1.12%, sulphur 0.3%, oxygen, chlorine, sodium 30%.
Liquid ferrite method arsenic precipitation after the dearsenification, arsenic slag landfill, back liquid waste water discharge of wastewater.
Claims (8)
1. the open circuit treatment process of arsenic in the copper cigarette ash, it is characterized in that its treatment process process is copper cigarette ash to be added contain in the solution of clorox and sodium hydroxide, carry out arsenic and leach reaction, filtration obtains after the dearsenification liquid behind the slag and dearsenification, slag after the dearsenification is carried out the recovery of copper-lead zinc bismuth valuable metal.
2. the open circuit treatment process of arsenic in a kind of copper cigarette ash according to claim 1 is characterized in that the weight concentration of clorox is 4%～12% in the described solution that contains clorox and sodium hydroxide, and the weight concentration of sodium hydroxide is 1.5%～10%.
3. the open circuit treatment process of arsenic in a kind of copper cigarette ash according to claim 1 is characterized in that the described dearsenification reaction process of carrying out, and copper cigarette ash is 10～20:1 with the solid weight ratio of the solution that contains clorox and sodium hydroxide.
4. the open circuit treatment process of arsenic in a kind of copper cigarette ash according to claim 1 is characterized in that the described reaction times of carrying out the dearsenification reaction process is 1～2h, and temperature of reaction is 50 ℃-80 ℃.
5. the open circuit treatment process of arsenic in a kind of copper cigarette ash according to claim 1, the weight ratio chemical ingredients that it is characterized in that described copper cigarette ash is: plumbous 10%～60%, arsenic 2%～5%, nickel 0.01%～0.1 %, copper 2%～20 %, zinc 2%～7%, iron 0.5%～1.5%, antimony 0.1%～5%, bismuth 1%～15%, sulphur and oxygen, carbon 30%～40%.
6. the open circuit treatment process of arsenic in a kind of copper cigarette ash according to claim 1, it is characterized in that the clorox waste liquid after chlorine that the described solution that contains clorox and sodium hydroxide produces for the cobalt Winning cell absorbs with alkali, its weight ratio chemical ingredients is: clorox 4%～6%, sodium hydroxide 8%～10%.
7. the open circuit treatment process of arsenic in a kind of copper cigarette ash according to claim 1, it is characterized in that the described solution that contains clorox and sodium hydroxide is the clorox waste liquid that the chemical plant produces, its weight ratio chemical ingredients is: clorox 8%～12%, sodium hydroxide 1.5%～3%.
8. the open circuit treatment process of arsenic in a kind of copper cigarette ash according to claim 1, it is characterized in that described filtration obtain dearsenification after liquid adopt the ferrite process dearsenification to handle the back landfill.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105567983A (en) * | 2015-12-29 | 2016-05-11 | 阳谷祥光铜业有限公司 | Soot treatment process in copper smelting process |
| CN105648226A (en) * | 2014-11-15 | 2016-06-08 | 中国科学院过程工程研究所 | Method for separating antimony from arsenic in antimony-arsenic soot |
| CN105648227A (en) * | 2014-11-15 | 2016-06-08 | 中国科学院过程工程研究所 | Method for separating antimony and arsenic from antimony and arsenic-containing ash through oxidation and alkaline leaching |
| CN106011488A (en) * | 2016-07-27 | 2016-10-12 | 中南大学 | Method for comprehensively recycling valuable metal from high-arsenic copper refinery ash |
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| JP2011058016A (en) * | 2009-09-07 | 2011-03-24 | Sumitomo Metal Mining Co Ltd | Method for separating rhenium from solution containing perrhenic acid |
| CN102392136A (en) * | 2011-11-21 | 2012-03-28 | 郴州雄风稀贵金属材料股份有限公司 | Process for comprehensively recovering high arsenic polymetallic material |
| CN102389697A (en) * | 2011-09-21 | 2012-03-28 | 昆明理工大学 | Method for removing arsenic hydride in tail gas of iron making blast furnace by wet process |
| CN102433439A (en) * | 2011-12-16 | 2012-05-02 | 湖南有色金属研究院 | Method for recovering rhenium from arsenic filter cake |
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2013
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Patent Citations (4)
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| JP2011058016A (en) * | 2009-09-07 | 2011-03-24 | Sumitomo Metal Mining Co Ltd | Method for separating rhenium from solution containing perrhenic acid |
| CN102389697A (en) * | 2011-09-21 | 2012-03-28 | 昆明理工大学 | Method for removing arsenic hydride in tail gas of iron making blast furnace by wet process |
| CN102392136A (en) * | 2011-11-21 | 2012-03-28 | 郴州雄风稀贵金属材料股份有限公司 | Process for comprehensively recovering high arsenic polymetallic material |
| CN102433439A (en) * | 2011-12-16 | 2012-05-02 | 湖南有色金属研究院 | Method for recovering rhenium from arsenic filter cake |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105648226A (en) * | 2014-11-15 | 2016-06-08 | 中国科学院过程工程研究所 | Method for separating antimony from arsenic in antimony-arsenic soot |
| CN105648227A (en) * | 2014-11-15 | 2016-06-08 | 中国科学院过程工程研究所 | Method for separating antimony and arsenic from antimony and arsenic-containing ash through oxidation and alkaline leaching |
| CN105567983A (en) * | 2015-12-29 | 2016-05-11 | 阳谷祥光铜业有限公司 | Soot treatment process in copper smelting process |
| CN105567983B (en) * | 2015-12-29 | 2018-10-16 | 阳谷祥光铜业有限公司 | A kind of cigarette ash treatment process during Copper making |
| CN106011488A (en) * | 2016-07-27 | 2016-10-12 | 中南大学 | Method for comprehensively recycling valuable metal from high-arsenic copper refinery ash |
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