CN101660055B - Method for recovering toxic arsenic compounds during metal indium extraction - Google Patents
Method for recovering toxic arsenic compounds during metal indium extraction Download PDFInfo
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- CN101660055B CN101660055B CN2009101173651A CN200910117365A CN101660055B CN 101660055 B CN101660055 B CN 101660055B CN 2009101173651 A CN2009101173651 A CN 2009101173651A CN 200910117365 A CN200910117365 A CN 200910117365A CN 101660055 B CN101660055 B CN 101660055B
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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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- 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 invention relates to a technique for recovering toxic arsenic compounds during metal indium extraction by utilizing waste residues generated from lead and zinc smelting. The technique takes saturated aqueous solution of sodium sulfide as precipitant and regulates the system acidity and temperature to recover or remove arsenic in solid forms, which is contained in leachate that is obtained after the waste residues generated from the lead and zinc smelting undergo acid leaching. After analyzing, the technique achieves an arsenic removal rate (recovery rate) as high as 97.3% and simultaneously little indium loss, prevents the arsenic from being reduced into arsine gas which can escape away, and simultaneously does not affect the extraction and enrichment of the indium.
Description
Technical field
The invention belongs to metallurgy, chemical technology field, relate to a kind of recovery method that utilizes waste residue behind the lead-zinc smelting to extract toxic arsenic compounds in the indium metal process.
Background technology
In lead-zinc smelting technology, produce a large amount of leaching scums, plumbous indium slag etc.Contain metals such as a large amount of Au that recovery value is arranged, Ag, In, lead bullion in these waste residues.In plumbous zinc ore simultaneously also association the compound of a large amount of arsenic is arranged.The compound of these arsenic is along with the extraction of plumbous zinc, is enriched in gradually in the waste residue that extracts behind the plumbous zinc.In the technology of utilizing the waste residue extraction indium metal after extracting plumbous zinc be, at first the waste residue behind the lead-zinc smelting is got by the low acidleach of low temperature, remove the acid soluble metal in the waste residue, leach indium by the high temperature peracid again, obtain indium metal through extraction, reextraction, reduction, refining then.Owing to will use the leaching of high temperature peracid in the indium-extracting process, in indium-extracting process, also will use reductive agents such as iron powder simultaneously.At acidic medium and when having reductive agent to exist, the compound of arsenic is reduced to arsine gas, and arsine gas is very low in aqueous phase solubleness, and is overflowed by liquid phase, and diffusion rapidly in air.
Hydrogen arsenide is the colourless gas that has garlic smell, no obvious irritation.Hydrogen arsenide does not have industrial use value, and it can not make industrial raw material, yet non-product, but the poisonous fume that production process produces.Hydrogen arsenide belongs to hypertoxic type gaseous state poisonous substance, mainly in the respiratory tract intrusive body, can be absorbed into blood rapidly, is distributed in each internal organs of whole body with blood circulation, and is wherein maximum with liver content, is kidney, the heart and brain secondly.Hydrogen arsenide combines with red corpuscle and forms arsenic-oxyphorase mixture, causes haemolysis, causes acute renal failure.Hydrogen arsenide concentration in air only is 0.3mg/m
3The time can cause acute poisoning.
Therefore, waste residue behind lead-zinc smelting is extracted again the technology of indium, significant to the recycling of arsenic compound.
Summary of the invention
The purpose of this invention is to provide a kind of recovery method that utilizes waste residue behind the lead-zinc smelting to extract toxic arsenic compounds in the indium metal process.
The present invention reclaims the method for arsenic compound, being to use the sodium sulphite saturated aqueous solution is precipitation agent, with acidity, the temperature of the leach liquor of the waste residue behind the lead-zinc smelting after acidleach by regulation system, make arsenic in the system with recovered in solid form or remove, do not make arsenic enrichment in system, avoid hydrogen arsenide to escape and cause poisoning or contaminate environment.
It is as follows that technology is reclaimed in the concrete removal of arsenic:
After acidleach, leach liquor is with the acidity of sulphuric acid soln and water regulation system at the waste residue behind the lead-zinc smelting, makes that vitriolic concentration is 2～4mol/L in the system; Under agitation add the sodium sulphite saturated aqueous solution, in room temperature reaction 20～30 minutes; Carry out solid-liquid separation by pressure filter then, liquid phase is used for extraction of indium, and solid phase is removed or enrichment with the arsenic solid chemical compound.The add-on of sodium sulphite saturated aqueous solution; The sodium sulphite amount of substance is 5～10 times of arsenic amount of substance in the system.
Except containing arsenic, also contain a spot of antimony, bismuth etc. in the system in the leach liquor after acidleach.When adding the sodium sulphite arsenic precipitation, also removed some other material.When the acidity of system was low, the deposition rate of arsenic, antimony, tin was higher, but the rate of loss of indium is also very high; When the acidity of system was higher, acid generated hydrogen sulfide with the sodium sulphite reaction, causes the waste of sodium sulphite and hydrogen sulfide to escape.Therefore, the acidity of the hierarchy of control is the key factor in this recovery technology.A large amount of experiment showed, when the acidity control of system when sulfuric acid concentration is 2～4mol/L in system, comparatively suitable.
By analysis, the clearance of arsenic of the present invention (rate of recovery) reaches 97.3%.
The present invention has following advantage compared to existing technology:
1, the clearance height of arsenic of the present invention, the indium rate of loss is little simultaneously.
2, technology of the present invention is simple, the reaction conditions gentleness; Reacting balance, be easy to control, do not produce a large amount of hydrogen sulfide.
3, the present invention is a precipitation agent with the sodium sulphite saturated aqueous solution, the selectivity height, and cost is low, the efficient height.
Embodiment
From the lead-zinc smelting waste residue, extract the example that is recovered as of toxic arsenic compounds in the process of indium metal below with Qinghai western indium industry responsibility company limited, the recovery method of arsenic compound of the present invention is described.
1, the analysis of each constituent content in the pickling liquor
The technology of the waste residue extraction indium metal behind the plumbous zinc is extracted in utilization, be at first the waste residue behind the lead-zinc smelting to be got by the low acidleach of low temperature, remove the acid soluble metal in the waste residue, leach indium by the high temperature peracid again, obtain indium metal through extraction, reextraction, reduction, refining then.
Waste residue behind the lead-zinc smelting is got by the low acidleach of low temperature, removed the acid soluble metal in the waste residue, by after the leaching of high temperature peracid, the fluorescent spectroscopy of each constituent content of pickling liquor (be rich in indium, be used for extracting the raw material of carrying indium) the results are shown in Table shown in 1 again:
The fluorescent spectroscopy of each constituent content in table 1 pickling liquor
The fluorescent spectroscopy result of table 1 shows that the high acid leaching liquor of above-mentioned high temperature (being rich in indium, the raw material that is used for extracting) contains a large amount of arsenic, and the fluorescence spectrum semi-quantitative analysis is about 1999.84mg/L; With the ultraviolet-visible spectrophotometry analytical results is arsenic content 1832.2mg/L, and wherein indium can be enriched to 344.8mg/L.
2, the recovery of arsenic in the pickling liquor
With the acidity that sulfuric acid and water are regulated pickling liquor, make that vitriolic concentration is 3mol/L in the system; Under agitation slowly add the sodium sulphite saturated aqueous solution in system, the add-on of sodium sulphite saturated aqueous solution is: the sodium sulphite amount of substance is about 10 times of arsenic amount of substance in the system; Reaction is 30 minutes under room temperature.After reaction is finished, carry out solid-liquid separation by pressure filter, liquid phase is used for extraction of indium, and solid phase is the arsenic solid chemical compound.
3, the analysis of each constituent content behind the recovery arsenic
Liquid phase after the arsenic removal under the above-mentioned condition (being rich in indium after the arsenic removal, the raw material that is used to extract) is carried out fluorescent spectroscopy, the results are shown in Table 2.
The fluorescent spectroscopy of each constituent content in the liquid phase behind table 2, the recovery arsenic
Solid phase after the arsenic removal under the above-mentioned condition is carried out fluorescent spectroscopy, the results are shown in Table 3.
The fluorescent spectroscopy of each constituent content in the solid phase behind table 3, the recovery arsenic
Show that from table 2,3 fluorescent spectroscopy result the high-temperature acid immersion liquid is after arsenic removal technology, arsenic in the liquid phase (0.145/0.002) is removed, and the clearance of arsenic (rate of recovery) reaches 97.3% by analysis.Arsenic in the solid phase (10.443) is by enrichment.Simultaneously, the indium in the liquid phase (0.025/0.025) loss amount is less, has avoided arsenic to be reduced to arsine gas and has overflowed, and does not influence the extraction and the enrichment of indium simultaneously.
Claims (1)
1. extract the recovery method of toxic arsenic compounds in the indium metal process, be the leach liquor of waste residue after acidleach behind the lead-zinc smelting with the acidity of sulphuric acid soln and water dilution regulation system, make that vitriolic concentration is 2～4mol/L in the system; Under agitation add the sodium sulphite saturated aqueous solution in room temperature reaction 20～30 minutes; Carry out solid-liquid separation by pressure filter then, liquid phase is used for extraction of indium, and solid phase is removed or enrichment with the arsenic solid chemical compound;
The add-on of described sodium sulphite saturated aqueous solution is: the sodium sulphite amount of substance is 5～10 times of arsenic amount of substance in the system.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009101173651A CN101660055B (en) | 2009-07-15 | 2009-07-15 | Method for recovering toxic arsenic compounds during metal indium extraction |
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| CN2009101173651A CN101660055B (en) | 2009-07-15 | 2009-07-15 | Method for recovering toxic arsenic compounds during metal indium extraction |
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| CN101660055A CN101660055A (en) | 2010-03-03 |
| CN101660055B true CN101660055B (en) | 2011-06-22 |
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| CN2009101173651A Expired - Fee Related CN101660055B (en) | 2009-07-15 | 2009-07-15 | Method for recovering toxic arsenic compounds during metal indium extraction |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102363842B (en) * | 2011-11-10 | 2013-04-17 | 山东国大黄金股份有限公司 | Process for recovering arsenic comprehensively by two-section roasting of arsenic-containing and carbon-containing gold concentrates |
| CN102560123A (en) * | 2012-02-22 | 2012-07-11 | 郴州丰越环保科技有限公司 | Method for utilization and harmless treatment of multi-metal material containing arsenic and indium |
| CN105039722B (en) * | 2015-06-29 | 2017-07-14 | 中南大学 | A kind of method that lead antimony flue dust preferentially removes arsenic |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1775972A (en) * | 2005-12-09 | 2006-05-24 | 韶关市华韦实业有限公司 | Technology for extracting Gallium metal from lead-zine tail ore slug smelting by extracting-electrolytic method |
| CN101041498A (en) * | 2007-04-29 | 2007-09-26 | 东北大学 | Method for reclaiming valuable element from acidic arsenic-containing biological oxidation gold extraction waste liquor |
| CN101148296A (en) * | 2007-09-20 | 2008-03-26 | 锡矿山闪星锑业有限责任公司 | Method for treating waste water of indium production |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1775972A (en) * | 2005-12-09 | 2006-05-24 | 韶关市华韦实业有限公司 | Technology for extracting Gallium metal from lead-zine tail ore slug smelting by extracting-electrolytic method |
| CN101041498A (en) * | 2007-04-29 | 2007-09-26 | 东北大学 | Method for reclaiming valuable element from acidic arsenic-containing biological oxidation gold extraction waste liquor |
| CN101148296A (en) * | 2007-09-20 | 2008-03-26 | 锡矿山闪星锑业有限责任公司 | Method for treating waste water of indium production |
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