CN102168176B - Comprehensive recycling process for valuable metal roasting-cyaniding gold-containing tailing - Google Patents
Comprehensive recycling process for valuable metal roasting-cyaniding gold-containing tailing Download PDFInfo
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- CN102168176B CN102168176B CN2011100565520A CN201110056552A CN102168176B CN 102168176 B CN102168176 B CN 102168176B CN 2011100565520 A CN2011100565520 A CN 2011100565520A CN 201110056552 A CN201110056552 A CN 201110056552A CN 102168176 B CN102168176 B CN 102168176B
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Abstract
The invention discloses a comprehensive recycling process for valuable metal roasting-cyaniding gold-containing tailing, belonging to comprehensive recycling and utilization of industrial solid waste. The process comprises the following steps: selecting hydrochloric acid, chlorine and sodium hypochlorite as a leaching agent to leach gold, silver, iron, lead and arsenic to the maximum extent; adsorbing gold and silver with activated carbon, removing and recycling arsenic and lead through a series of solid-liquid separation and conversion, evaporating and crystallizing a ferric chloride solution subjected to impurity removal, thus finally producing a ferric chloride hexahydrate product, and realizing the comprehensive recycling process for valuable metal in the tailing. For the process, the available raw material sources are wide, the processing cost is low, the step-by-step impurity removal is thorough, all the impurities are recycled, no secondary pollution is generated, and the comprehensive recycling process can be used for fully realizing clean production, is environment-friendly and convenient for industrial production and has good promotion and application values.
Description
Technical field
The invention belongs to industrial residue comprehensive reutilization method, be specifically related to roasting---cyaniding contains golden tailings comprehensive recycling process.
Background technology
It is to extract a kind of of back residue tailings at gold that roasting---cyaniding contains golden tailings.Roasting-cyanide process is one of existing main gold extraction technology of China in China's gold production, and 90% smelting enterprise all adopts this kind technology in the gold industry, and the characteristics of this technical process are that the aurin powder is carried out sulfurization roasting about 640 ℃; Leach copper with dilute sulphuric acid; Copper is reclaimed in pickling liquor, and acid leaching residue transfers to alkalescence, and sodium cyanide leaches gold; Leach liquor reclaims gold and silver through zinc dust precipitation, and the leached mud after washing is roasting---cyanidation tailings.This kind tailings (iron level is more than 35%) is existing to be used for cement industry mainly as additive; And iron level lower be disposed to the mine tailing storehouse, wherein in the tailings contained gold (content 1.8g/t), silver (content 60g/t), plumbous valuable metals such as (content 2.0%) all not by comprehensive reutilization.And national gold industry produces this kind of 5000t tailings every day approximately, is example with area, the little Qinling Mountains, the Sanmenxia Gorge, Henan, China two big pan district with area, Zhaoyuan, Shandong only, and area, the little Qinling Mountains is had an area of the 60km radius and produced this kind tailings 1500t every day approximately; Area, Zhaoyuan, Shandong produces the 2500t tailings every day approximately; Its quantity is big to have some idea of, and tailings is stacked through transporting for long-distance to the cement mill or being disposed to the mine tailing storehouse, not only contaminate environment; And its potential huge economic value abandoned, very unfortunately.
Because the occurrence form of gold and silver in this kind tailings is very complicated, it is mainly by parcels such as MOX, gangues, and traditional technology is if will further extract very difficulty of valuable metal.Though the correlative study personnel have proposed many treatment processs, the most frequently used method is that tailings is regrinded-dump leaching, and its recovery is low, and because during reused prussiate, be prone to cause second environmental pollution.Also have the correlative study personnel to study the utilization to the iron in the tailings, the iron production iron that promptly extracts wherein is product, but foreign matter content is not up to standard mostly, and impurity-eliminating effect is bad, can not reach relevant national standard, fails to be promoted widely.
Summary of the invention
The object of the invention is to provide a kind of with roasting---the valuable element comprehensive reutilization in the cyanidation tailings, and do not produce the environment-friendly type recovery technology of new pollution.
Because this kind tailings contains various ingredients oxide compound or salts substances such as iron, silicon, calcium, magnesium, sulphur, aluminium, gold and silver etc. are all by its parcel or be embedded in some impurity, so extract very difficult.For reaching the object of the invention, valuable element in the tailings is recycled to greatest extent, the present invention selects for use hydrochloric acid, Youxiaolin, chlorine to make leaching agent, valuable element leached to greatest extent, and treated, reclaim gold and silver wherein; And ferro element produced the water purification agent iron trichloride; The lead element enrichment becomes plumbous smart powder; Arsenic element is produced white arsenic; The comprehensive back remaining solid waste residue that reclaims is used for brickmaking.
Concrete technical scheme is following: at first with tailings and mixed in hydrochloric acid, the heating continuously stirring then adds Youxiaolin, chlorine continuously stirring, makes elements such as gold and silver, lead, iron, arsenic get into liquid phase, isolates and considers liquid and filter residue; The filter residue that is rich in silicon-dioxide, aluminium sesquioxide is used for brickmaking, and filtrating is reclaimed gold and silver through charcoal absorption; Filtrating after charcoal absorption is with iron powder or iron filings arsenic removal, and this moment, arsenic was converted into the arsine gas effusion, collected hydrogen arsenide, and its burning is converted into the white arsenic cold shock reclaims, or through adding the thermosetting arsenic mirror; The arsenic removal rear filtrate adds ammonium chloride, ammoniacal liquor, sodium sulphite and ammonium sulfide deleading, and control pH is acid, and continuously stirring filters to isolate and considers liquid and filter residue, and will be rich in the flotation of lead sulfide filter residue is plumbous smart powder; The deleading rear filtrate gets liquor ferri trichloridi with chlorine, the oxidation of liquid oxygen oxygenant, forms the Iron(III) chloride hexahydrate product through evaporative crystallization.
Used hydrochloric acid mass percent is 8-30%, and tailings and hydrochloric acid solid-to-liquid ratio are controlled at 1: 0.5-5.0.The preferred 40-150 of temperature ℃ of tailings and mixed in hydrochloric acid heating.The washing water and the water of condensation of solid-liquid separation recycle.
Its principal reaction principle is following:
Fe
2O
3+6HCl＝2FeCl
3+3H
2O
Au
3++4Cl
-＝AuCl
4 -
Pb
2++4Cl
-＝PbCl
4 2-
Ag
++2Cl
-＝AgCl
2 -
Pb
2++S
2-＝PbS↓
2AsH
3+3O
2＝As
2O
3+3H
2O
2FeCl
3+Fe＝3FeCl
2
2FeCl
2+Cl
2＝2FeCl
3
Its key problem in technology is:
1. use hydrochloric acid and add Youxiaolin, chlorine, iron, lead, gold and silver are leached to greatest extent.
2. iron powder or iron filings are reduced to ferrous iron with ferric iron and for next step deleading the basis are provided, and simultaneously arsenic are removed recovery.
3. add ammonium chloride, ammoniacal liquor and sodium sulphite, ammonium sulfide, the pH value of control appropriateness utilizes the principle of fractional precipitation to remove delead and most heavy metal, and reduces the loss of iron to greatest extent.
Advantage of the present invention is following:
1. nontoxic gold extracting
The leaching of this technology gold and silver adopts the chlorination system to leach, and synchronously gold and silver, iron, lead is once leached, and technical process is shorter, and the leaching yield of gold and silver, iron do not use highly toxic product such as sodium cyanide all more than 95% in the technology, can not cause secondary pollution.
2. many kinds of valuable metals have been realized comprehensive recovery
Gold and silver, iron get into solution after the chlorination system leaches, carry out solid-liquid separation, and filter residue is rich in silicon-dioxide as brickmaking behind thorough washing.Filtrating forms and carries golden carbon recovery gold and silver through behind the charcoal absorption gold and silver; Plumbous worry lead-in-dreg is more than 20%, but flotation is plumbous smart powder; Iron content filtrating reoxidizes processing, evaporative crystallization output ferric chloride (FeCl36H2O) product through fractional precipitation.
3. there are not sewage, solid waste discharging
This process water mainly is the washing water of solid-liquid separation, and it comes from the water of condensation in the evaporization process, closed cycle.The solid waste that produces in the technology mainly comes from solid-liquid separation twice: solid-liquid separation forms and is rich in 80% silicon-dioxide filter residue for the first time, is used for brickmaking; For the second time the filter residue of solid-liquid separation is rich in lead element, be used for plumbous flotation and form plumbous smart powder, thereby whole technology does not have solid waste and produces, and has realized environment-protecting clean production.
4. be easy to promote
Because it is bigger that China contains golden tailings raw material quantity, except that concentrating on area, Zhaoyuan, Shandong, area, the Sanmenxia Gorge, Henan, all there is distribution in a plurality of provinces in the whole nation, and this technical process environmental protection also is convenient to industriallization, has higher promotional value.
5. compare cost advantage with the iron trichloride traditional processing technology outstanding
This technology main products is liquor ferri trichloridi and solid ferric chloride (FeCl36H2O), compares with traditional processing technology, because raw material sources are in tailings, and has realized the comprehensive recovery of multiple valuable metal, and cost advantage is obvious.
Description of drawings
Figure is a process flow diagram of the present invention;
Embodiment
For the present invention is explained better, it is following to lift embodiment:
Tailings 500 grams of getting after roasting-cyaniding are put into there-necked flask (the tailings major ingredient is seen table 1); The hydrochloric acid soln that adds mass percent 20% with 1: 3 ratio of solid-to-liquid ratio; Be heated to 120 ℃, continuously stirring leached 8 hours, and the leaching yield that this moment, sampling detected Fe is more than 95%; Stop heating, add the 20g Youxiaolin again, feed chlorine simultaneously continuously, stirred 2 hours; Reaction finishes washing and filtering, gets filter residue appearance this moment and detects Au content below 0.1g/t, Ag content 6.7g/t, Pb content 0.06%; Fe content is 2.3%, Si content 85.3%, and filtrating is adsorbed through activated carbon column; Gold and silver are adsorbed, and the absorption back is detected filtrating: Au is 0g/t, Ag3.1g/t; Get charcoal absorption rear filtrate 500ml and add the 10g reduced iron powder, be heated to 100 ℃, stirring reaction 2 hours, the arsenic content that detects in the solution is 1.64mg/l, effect of removing arsenic is good, filters; Get arsenic removal rear filtrate 200ml, add 1g ammonium chloride, 1ml ammoniacal liquor, adding 1g sodium sulphite, control pH is acid, and airtight shaking left standstill, and places 3 hours, filters, and the lead content in the survey this moment filtrating is less than 0.5mg/l, and deleading is effective; The deleading rear filtrate to there not being ferrous ion, through the transpiration cooling crystallization, gets ferric chloride (FeCl36H2O) with liquid oxygen, chlorine oxidation, and according to the GB standard detection, several indexs meet the specification of quality of country about water purification agent.The washing water of solid-liquid separation are returned add in the raw material ore pulp, water of condensation is reclaimed to add in the filtration process recycle.
Mainly from the tailings that adopts after gold is carried by each gold smelting factory of roasting-cyanidation technology, each principal element content of present embodiment tailings raw material is seen table 1 to raw material of the present invention,
Table 1: tailings major ingredient table look-up
| Title | Gold (g/t) | Silver (g/t) | Copper (%) | Plumbous (%) | Sulphur (%) | Iron (%) | Arsenic (%) |
| Tailings | 1.8 | 47.1 | 0.35 | 1.97 | 1.66 | 33.85 | 0.08 |
Claims (2)
1. roasting---cyaniding contains valuable metal comprehensive reutilization technology in the golden tailings; It is characterized in that; Realize through following steps: be the mixed of the hydrochloric acid of 8%-30% at first with solid-to-liquid ratio 1: 0.5-5.0 with tailings and mass percent; Be heated to 40-150 ℃ of continuously stirring, then add Youxiaolin, chlorine continuously stirring, isolate filtrating and filter residue; The filter residue that is rich in silicon-dioxide, aluminium sesquioxide is used for brickmaking, and filtrating is reclaimed gold and silver through charcoal absorption; Filtrating after charcoal absorption is collected hydrogen arsenide with iron powder or iron filings arsenic removal, and its burning is converted into the white arsenic cold shock reclaims, or through adding the thermosetting arsenic mirror; The arsenic removal rear filtrate adds ammonium chloride, ammoniacal liquor, sodium sulphite and ammonium sulfide deleading, and control pH is acid, and continuously stirring filters to isolate filtrating and filter residue, and will be rich in the flotation of lead sulfide filter residue is plumbous smart powder; The deleading rear filtrate gets liquor ferri trichloridi with chlorine, the oxidation of liquid oxygen oxygenant, forms the Iron(III) chloride hexahydrate product through evaporative crystallization.
2. roasting as claimed in claim 1---cyaniding contains valuable metal comprehensive reutilization technology in the golden tailings, it is characterized in that, the washing water and the water of condensation of solid-liquid separation recycle.
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|---|---|---|---|
| CN2011100565520A CN102168176B (en) | 2011-03-10 | 2011-03-10 | Comprehensive recycling process for valuable metal roasting-cyaniding gold-containing tailing |
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| CN2011100565520A CN102168176B (en) | 2011-03-10 | 2011-03-10 | Comprehensive recycling process for valuable metal roasting-cyaniding gold-containing tailing |
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| CN102168176A CN102168176A (en) | 2011-08-31 |
| CN102168176B true CN102168176B (en) | 2012-11-14 |
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| CN103409632B (en) * | 2013-07-18 | 2016-01-13 | 山东国大黄金股份有限公司 | A kind of method of gold mud wet processing tail gas comprehensive reutilization |
| MX2016014770A (en) | 2014-05-12 | 2017-05-25 | Summit Mining Int Inc | Brine leaching process for recovering valuable metals from oxide materials. |
| CN104404261B (en) * | 2014-12-11 | 2015-10-07 | 江西一元再生资源有限公司 | The method of gold recovering, iron is synchronously reduced in the chloridizing roasting of a kind of refined gold ore cyaniding tailings |
| CN105170070A (en) * | 2015-07-08 | 2015-12-23 | 黄立维 | Denitration and desulfurization ferric chloride solid particles and preparation method thereof |
| CN105439355B (en) * | 2015-12-28 | 2018-05-25 | 中南大学 | Waste acid resource reclaim and deep treatment method and device |
| CN105714122B (en) * | 2016-03-08 | 2017-10-27 | 开封大学 | Reclaim gold, iron, the method for lead in cyanidation tailings |
| CN106011486A (en) * | 2016-06-03 | 2016-10-12 | 新疆星塔矿业有限公司 | Recovery technology for metals in gold ore cyanide residue chloridizing volatilization flue gas |
| CN106269289B (en) * | 2016-10-31 | 2019-01-01 | 长春黄金研究院有限公司 | A kind of method of cyanogen slag broken cyanide flotation pyrite |
| CN106676257A (en) * | 2016-12-23 | 2017-05-17 | 江西理工大学 | Arsenic removal method of arsenic-containing waste residues |
| CN109082537B (en) * | 2018-07-11 | 2020-09-01 | 开封大学 | Comprehensive utilization method of roasted gold concentrate |
| CN109593969A (en) * | 2018-12-14 | 2019-04-09 | 许金刚 | A kind of molten gold process of no cyanogen |
| CN110358925B (en) * | 2019-07-29 | 2020-05-12 | 中南大学 | Method for treating jarosite slag by chemical freeze thawing |
| CN110668550B (en) * | 2019-10-18 | 2022-06-21 | 广西森合高新科技股份有限公司 | Gold concentrate non-cyanide beneficiation tailing liquid recycling treatment method |
| CN111100995B (en) * | 2020-01-09 | 2020-12-01 | 紫金矿业集团股份有限公司 | Method for recovering gold from roasting-cyaniding tailings |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147559A (en) * | 1996-06-18 | 1997-04-16 | 高大明 | Water-chlorine process for gold extraction |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5031998B2 (en) * | 2005-04-28 | 2012-09-26 | 相田化学工業株式会社 | Precious metal recovery method |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147559A (en) * | 1996-06-18 | 1997-04-16 | 高大明 | Water-chlorine process for gold extraction |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2006-307283A 2006.11.09 |
| 姬冲.氰化尾渣提金及制备纳米铁红的研究.《山东科技大学硕士学位论文》.2005, * |
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