CN103233129B - 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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- CN103233129B CN103233129B CN201310165596.6A CN201310165596A CN103233129B CN 103233129 B CN103233129 B CN 103233129B CN 201310165596 A CN201310165596 A CN 201310165596A CN 103233129 B CN103233129 B CN 103233129B
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- arsenic
- dearsenification
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- sodium hydroxide
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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
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
An open circuit treatment process for arsenic in Bellamya aeruginosa, relates to the method that the pre-treatment of a kind of Copper making process intermediate material cigarette ash open circuit is harmful to arsenic impurities.
Background technology
In Copper making production process, arsenic is often the associated element of copper ore concentrates, due to copper raw material Market competition, the high-quality copper ore concentrates resource low containing foreign matter contents such as arsenic day by day reduces, although national regulation import copper raw material is less than 0.5% containing arsenic, but in recent years along with copper throughput continuous enlargement, the total amount entering the arsenic of copper metallurgy industry gets more and more.
According to research, in copper Flash Smelting Furnace smelting process, 37% arsenic enters flue dust; Electricity gather dust flue dust about containing 4 ~ 6% arsenic, also be worth reclaiming containing valuable metals such as copper, for improving the comprehensive utilization ratio of resource, this direct Returning smelting had containing arsenic smoke dust, the arsenic amount entering Flash Smelting Furnace with cigarette ash form according to statistics accounts for more than 50% of total arsenic amount, this makes arsenic vicious cycle and enrichment in system, finally all very large to the harm of pyrometallurgical smelting process and follow-up relieving haperacidity and electrolytic copper production, also makes also more and more higher containing arsenic requirement in metallurgy of copper raw material.
At present for reducing arsenic evil, make the impurity open circuits such as arsenic, some copper smelting plant adopts roasting pre-arsenic removing method process Bellamya aeruginosa, and arsenic-removing rate is only about 80%, and atmospheric pollution is serious.Some copper smelting plant sets up the comprehensive utilization factory of cigarette ash, uses wet processing comprehensively recovering valuable metal, but arsenic presss from both sides generation dispersion in each operation in existing wet processing, also there is an open circuit difficult problem.Meanwhile, in process of production, the clorox waste liquid of the chlorine Alkali absorption that cobalt Winning cell produces, needs to find available approach, avoids its secondary pollution.
Summary of the invention
The object of the invention is the deficiency existed for above-mentioned prior art, propose one can effectively arsenic in Bellamya aeruginosa to be opened a way in advance process before recovery valuable metal, be conducive to the recovery process of follow-up valuable metal, effectively be beneficial to sodium hypochlorite waste water, with low cost, the open circuit treatment process of arsenic in the Bellamya aeruginosa that arsenic extrusion rate is high.
The object of the invention is to be achieved through the following technical solutions.
The open circuit treatment process of arsenic in a kind of Bellamya aeruginosa, it is characterized in that its treatment process process is added by Bellamya aeruginosa in the solution containing clorox and sodium hydroxide, carry out arsenic Leaching reaction, filter and to obtain after dearsenification liquid after slag and dearsenification, slag after dearsenification is carried out the recovery of copper-lead zinc bismuth valuable metal.
The open circuit treatment process of arsenic in a kind of Bellamya aeruginosa of the present invention, it is characterized in that described containing in the solution of clorox and sodium hydroxide, the weight concentration of clorox is 4% ~ 12%, and the weight concentration of sodium hydroxide is 1.5% ~ 10%.
The open circuit treatment process of arsenic in a kind of Bellamya aeruginosa of the present invention, it is characterized in that described carrying out dearsenification reaction process, Bellamya aeruginosa is 10 ~ 20:1 with the molten solvent and solute weight ratio containing clorox and sodium hydroxide.
The open circuit treatment process of arsenic in a kind of Bellamya aeruginosa of the present invention, it is characterized in that the described reaction times of carrying out dearsenification reaction process is 1 ~ 2h, temperature of reaction is 50 DEG C-80 DEG C.
The open circuit treatment process of arsenic in a kind of Bellamya aeruginosa of the present invention, it is characterized in that the weight ratio chemical composition of described Bellamya aeruginosa 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 Bellamya aeruginosa of the present invention, it is characterized in that the described solution containing clorox and sodium hydroxide is the clorox waste liquid after the chlorine Alkali absorption of cobalt Winning cell generation, its weight ratio chemical composition is: clorox 4% ~ 6%, sodium hydroxide 8% ~ 10%.
The open circuit treatment process of arsenic in a kind of Bellamya aeruginosa of the present invention, it is characterized in that the described solution containing clorox and sodium hydroxide is the clorox waste liquid that chemical plant produces, its weight ratio chemical composition is: clorox 8% ~ 12%, sodium hydroxide 1.5% ~ 3%.
The open circuit treatment process of arsenic in a kind of Bellamya aeruginosa of the present invention, is characterized in that described filtration obtains liquid after dearsenification and adopts landfill after ferrite process dearsenification process.
The open circuit treatment process of arsenic in a kind of Bellamya aeruginosa of the present invention, before Bellamya aeruginosa reclaims valuable metal recovery, arsenic is opened a way in advance and to be separated with valuable metal in cigarette ash, 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 slag, flow process is simple, the treatment of wastes with processes of wastes against one another, and recycling economy, production cost is low, metal recovery rate is high.Especially employ clorox contained in the chlorine residue absorption liquid waste liquid in Production Flow Chart, dearsenification of directly opening a way from Bellamya aeruginosa, both solved arsenic open circuit problem, and solved again sodium hypochlorite waste water problem.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention
Embodiment
The open circuit treatment process of arsenic in a kind of Bellamya aeruginosa, its treatment process process is added by Bellamya aeruginosa in the solution containing clorox and sodium hydroxide, carry out arsenic Leaching reaction, filter and to obtain after dearsenification liquid after slag and dearsenification, slag after dearsenification is carried out the recovery of copper-lead zinc bismuth valuable metal.
In operation, the solution containing clorox and sodium hydroxide used can adopt the chlorine residue in production process to absorb the chlorine bleach liquor in rear waste liquid or chemical plant, containing clorox 4% ~ 8%, sodium hydroxide 1.5 ~ 10%, with cigarette ash liquid-solid ratio 10 ~ 20:1, temperature of reaction 50 DEG C-80 DEG C, arsenic enters leach liquor with sodium arseniate form, slag rate reduces 15% ~ 20%, the copper-lead zinc-nickel ferrous metal enrichment 15% ~ 20% in slag coexisted, slag transfers to cigarette ash factory to reclaim valuable metal, containing the leach liquor of a few gram liter of arsenic, use ferrite process dearsenification, arsenic slag landfill.
The present invention is further illustrated below by way of concrete embodiment.
Embodiment 1
Bellamya aeruginosa 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 Bellamya aeruginosa, chlorine bleach liquor's concentration 8%, sodium hydroxide 2%, liquid-solid ratio 15:1, stirring reaction 1.5h, temperature of reaction 50 DEG C, filter and to obtain after dearsenification liquid after slag and dearsenification, walk stand-by after dearsenification under liquid.
After dearsenification, slag is sent into existing cigarette ash factory and is reclaimed the valuable metals such as copper-lead zinc bismuth.Dreg chemistry composition after 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 dearsenification, arsenic slag landfill, rear liquid discharge of wastewater.
Embodiment 2
Bellamya aeruginosa chemical composition: 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 Bellamya aeruginosa, chlorine bleach liquor's concentration 12%, sodium hydroxide 2%, liquid-solid ratio 10:1, stirring reaction 1h, temperature of reaction 80 DEG C, filter and to obtain after dearsenification liquid after slag and dearsenification, walk stand-by after dearsenification under liquid.
After dearsenification, slag is sent into existing cigarette ash factory and is reclaimed the valuable metals such as copper-lead zinc bismuth.Dreg chemistry composition after 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 dearsenification, arsenic slag landfill, rear liquid waste water discharge of wastewater.
Embodiment 3
Bellamya aeruginosa chemical composition: lead 60%, arsenic 2, nickel 0.1%, copper 2, zinc 7%, iron 0.5 %, antimony 0.1%, bismuth 1%, sulphur and oxygen carbon 36%.
In Bellamya aeruginosa, add clorox and hydrogen-oxygen sodium hydroxide solution, chlorine bleach liquor's concentration 4%, sodium hydroxide 10%, liquid-solid ratio 20:1, stirring reaction 2h, temperature of reaction 60 DEG C, filter and to obtain after dearsenification liquid after slag and dearsenification, walk stand-by after dearsenification under liquid.
After dearsenification, slag is sent into existing cigarette ash factory and is reclaimed the valuable metals such as copper-lead zinc bismuth.Dreg chemistry composition after 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 dearsenification, arsenic slag landfill, rear liquid waste water discharge of wastewater.
Claims (2)
1. the open circuit treatment process of arsenic in a Bellamya aeruginosa, it is characterized in that its treatment process process is added by Bellamya aeruginosa in the solution containing clorox and sodium hydroxide, carry out arsenic Leaching reaction, filtration to obtain after dearsenification liquid after slag and dearsenification, slag after dearsenification is carried out the recovery of copper-lead zinc bismuth valuable metal; The weight ratio chemical composition of described Bellamya aeruginosa 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 described solution containing clorox and sodium hydroxide is the clorox waste liquid after the chlorine Alkali absorption of cobalt Winning cell generation, and its weight ratio chemical composition is: clorox 4% ~ 6%, sodium hydroxide 8% ~ 10%; Bellamya aeruginosa is 10 ~ 20:1 with the solution solvent and solute weight ratio containing clorox and sodium hydroxide; The described reaction times of carrying out dearsenification reaction process is 1 ~ 2h, and temperature of reaction is 50 DEG C-80 DEG C.
2. the open circuit treatment process of arsenic in a kind of Bellamya aeruginosa according to claim 1, it is characterized in that described filtration obtain dearsenification after liquid adopt landfill after ferrite process dearsenification process.
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| 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 |
| 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 |
| 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 |
| CN106011488B (en) * | 2016-07-27 | 2018-06-05 | 中南大学 | A kind of method of high arsenic-and copper-bearing cigarette ash comprehensively recovering valuable metal |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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| JP5633129B2 (en) * | 2009-09-07 | 2014-12-03 | 住友金属鉱山株式会社 | Method for separating rhenium from solutions containing perrhenic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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