CN103184335B - Low-grade multi-metal sulfide mineral selective bioleaching technology - Google Patents
Low-grade multi-metal sulfide mineral selective bioleaching technology Download PDFInfo
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- CN103184335B CN103184335B CN201110459874.XA CN201110459874A CN103184335B CN 103184335 B CN103184335 B CN 103184335B CN 201110459874 A CN201110459874 A CN 201110459874A CN 103184335 B CN103184335 B CN 103184335B
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Abstract
The invention provides a low-grade multi-metal sulfide mineral selective bioleaching technology. The process is as follows: pile building is performed on the raw mineral materials, dilute acid solution is adopted for presoaking, and efficient mineral leaching bacteria are led in for leaching after the acidity of the mineral pile is basically stable; pile unloading is performed when the leaching of nickel reaches more than 80 wt%, then pile building is performed again on the leaching residue, and thermophilic bacteria are led in for leaching; and when the concentration of nickel in the leaching agent is more than 2.0 g/L, open-cycle is performed on the partial leaching agent, sodium sulfide is added into the leaching agent for fractional precipitation, so as to obtain copper sulphide, zinc sulphide and nickel and cobalt sulphide products, after precipitation is completed, lime is added into the leaching agent for neutralization, wherein concentration of iron in the neutralized leaching agent is less than 1.0 g/L, and the neutralized leaching agent can be reused at the leaching stage. According to the invention, technological process is short, equipment is simple, investment conservation and zero contamination are realized, cost is low, recovery rate of valuable metal is improved, the purpose of comprehensively utilizing low-grade multi-metal sulfide mineral resources is realized, and greater economic benefits can be achieved.
Description
Technical field
The present invention relates to a kind of low-grade multi-metal sulfide selective bioleaching process, particularly low-grade Cu, Ni and Co zinc multi-metal sulfide selective bioleaching process.
Background technology
Along with the continuous exploitation of Mineral resources, ore trends towards poor, hydridization gradually, and toxic metal ion and impure mineral content are high, and many metals association relationship is close.In explored Polymetallic Minerals resource, polymetallic ore with copper association is in the great majority, copper is mainly taking chalcopyrite ore as main, contain nickel cobalt zinc ore simultaneously, grade is lower, and (usually, copper and zinc content are below 1wt%, and nickel is below 0.5wt%, cobalt is below 0.2wt%), adopt existing selecting and smelting technology technique to develop.Adopt wet processing technology, in leach liquor, concentration of iron is high, and valuable metal ions concentration is low, separates, extractive technique cost is high, and added value of product is low.Mineral composition, chemical composition, crystalline structure, embedding cloth characteristic and the leaching performance difference of dissimilar Mineral resources are large, and in solution, different valuable metal ions character also exists certain difference.Therefore, be necessary to provide a kind of and can develop the novel process that low-grade multi-metal sulfide selectivity organism leaches, realize effectively comprehensive recovery of different valuable metals.
Summary of the invention
The object of the invention is to overcome the deficiency of above-mentioned technology, provide a kind of for low-grade multi-metal sulfide selective bioleaching process, to solve the difficult problem that recovery rate of valuable metals is low.
For achieving the above object, the present invention by the following technical solutions:
A kind of low-grade Selective Leaching of Polymetallic Ore technique, comprises the following steps:
A. selectivity organism leaches: raw mineral materials is built to heap, adopt dilute acid soln preimpregnation, after ore deposit heap acidity is basicly stable, access bacterium Leptospirillum ferrooxidans Retech-SPL-1, pile bottom ventilation and carry out acid droplet pouring and leach to ore deposit;
B. soaking slag leaches again: after nickel leaching reaches more than 80wt%, unload heap, then will soak slag is transported to permanent stockyard and again builds heap, access bacterium Sulfobacillus thermosulfidooxidans Retech-ETC-1, carry out again acid droplet and drench leaching, mainly carry out the leaching of copper and the leaching of residue nickel cobalt zinc;
C. metal selective reclaims: after the concentration of nickel in selectivity organism leach liquor in step a reaches 2.0g/L, 15～20% the leach liquor open circuit that accounts for total leach liquor volume is entered to settling tank (general nickeliferous 2.0～2.6g/L in leach liquor, zinc 4.5～6.0g/L, cobalt 0.80～1.0g/L, pH is 1.5～2.0), then add sodium sulphite to carry out fractional precipitation, obtain cupric sulfide, zinc sulphide and nickelous sulfide cobalt product, having precipitated rear pH value of solution is 3.5～4.0, add lime neutralization, be adjusted to the neutral iron in Leaching Systems of also further removing by pH, in leach liquor after neutralization, the concentration of iron is lower than 1.0g/L, the selectivity that can be back to step a leaches the stage.
In the vulcanizate that employing aforesaid method obtains, zinc content is 60～70wt%, and nickel cobalt contents is 50～60wt%.
Extract technology as above, wherein said bacterium Leptospirillum ferrooxidans Retech-SPL-1, now be deposited in China national typical case culture collection center C CTCC, address is positioned at Wuhan University in the school, preservation date is on October 17th, 2008, and deposit number is CCTCCNo:M208162; To be that zinc ore is exclusive soak ore deposit bacterium to this bacterium, better to nickel leaching effect;
Described bacterium Sulfolobus metallicus Retech-ETC-1, now be deposited in China national typical case culture collection center C CTCC, address is positioned at Wuhan University in the school, preservation date: on May 11st, 2007, deposit number is CCTCC NO M207062; This bacterium is thermophile bacteria.
Extract technology as above, wherein builds heap described in step a, is that leach liquor thrust-augmenting nozzle and breather line are laid in heap bottom, ore deposit, will after ore reduction, build heap.
Extract technology as above, wherein preferably, described leach liquor draft-tube diameter 110mm, described breather line diameter 50mm, interval 2.0～3.0m between adjacent two pipelines.
Extract technology as above, wherein preferably, described fragmentation be by ore reduction to-50mm, particle diameter is below 50mm.
Extract technology as above, wherein preferably, in the time building heap, keeps ore to form as far as possible nature and stacks, and forms the heap naturally of multiple hole, the growth that is conducive to pile interior ventilation and leaching microbacteria.
Extract technology as above, wherein preferably, in step a and b, the bacterium number of the bacteria culture of access is 10
7individual/more than mL.
Extract technology as above, wherein preferably, the pH of the dilute acid soln used of the preimpregnation described in step a is 1.0～2.0.
Extract technology as above, wherein preferably, in step a, high 5～6m is piled in the ore deposit building up, ventilation intensity 0.8～1.0Nm
3/ m
2.h, dripping pouring intensity is 8～10L/m
2h, pH is 1.5～2.0, redox potential is lower than 500mV(vs.SCE), can effectively suppress the dissolving of iron.
Extract technology as above, wherein preferably, in step b, again builds the ore deposit of heap and piles high 8～10m, and dripping and drenching intensity is 10～12L/m2h, and pH is 1.5～2.0, and redox potential is 460～520mV(vs.SCE).
Beneficial effect of the present invention is:
1. nickel zinc selectivity leaches
The present invention adopts that the zink sulphide of seed selection is exclusive soaks ore deposit bacterium, has greatly promoted the high-efficiency dissolution of zinc, and zinc leaching rate is higher than 85wt%.Meanwhile, also promoted the dissolving of nickel, nickel leaching yield is greater than 80wt%, and comparatively speaking, the leaching velocity of cobalt is slower, therefore will soak after slag goes to permanent stockyard and continue to leach.
2. low-grade valuable metals comprehensively reclaims
Copper mainly exists with primary ore form, and under normal temperature, leaching rate is slower, and when after access thermophile bacteria, the leaching rate of copper is accelerated, more than the leaching yield of last copper reaches 65wt%.Continue to dissolve and do not soak nickel cobalt zinc completely in the first step leaching process, further improved leaching yield.Finally, nickel cobalt zinc leaching rate approaches 90wt%, has improved many metals comprehensive reutilization level.
3. effective inhibition of iron
In bioleaching process, it is very unfavorable that iron separates valuable metal, causes recovery rate of valuable metals to reduce, and must carry out deferrization process.At present, most widely used is neutralized ex iron technique, but this technique can cause the loss of nickel cobalt zinc valuable metal.The normal temperature bacterium adopting in technique of the present invention, not only can promote the dissolving in zinc-nickel ore deposit, can make Leaching Systems keep compared with low potential simultaneously, has suppressed the efficient leaching of iron, has reduced the meltage of iron from source.In addition, when after nickel cobalt zinc precipitated metal, in solution, pH raises, and adds a small amount of lime and can further reduce the content of iron, is conducive to leach liquor efficient circulation and leaches.
4. added value of product is high
Due under lower pH condition, iron precipitation capacity is less, and each precipitated metal pH difference, has certain selectivity, and cupric sulfide, zinc sulphide and nickelous sulfide cobalt product foreign matter content are low, and added value of product is high.
5. environmental friendliness
This technique does not need to become concentrate and high melt through traditional beneficiation enrichment of high energy consumption, the novel process toxic gas such as flue dust and sulfurous gas that exhaust emission is not large, and equipment is simple, reduced investment, cost are low, pollution-free, economy, obvious environment benefit.
In sum, the present invention is directed to low-grade multi-metal sulfide, overcome a comprehensive recovery low technical difficult problem, a kind of efficient selective bioleaching process is provided, improve recovery rate of valuable metals, realize the object that fully utilizes low-grade multi-metal sulfide Mineral resources, can obtain larger economic benefit.
Brief description of the drawings
Fig. 1 is process flow sheet of the present invention.
Bacterium Leptospirillum ferrooxidans Retech-SPL-1 used in the present invention, now be deposited in China national typical case culture collection center C CTCC, address is positioned at Wuhan University in the school, and preservation date is on October 17th, 2008, and deposit number is CCTCC No:M208162;
Bacterium Sulfolobus metallicus Retech-ETC-1, has now been deposited in China national typical case culture collection center C CTCC, and address is positioned at Wuhan University in the school, preservation date: on May 11st, 2007, deposit number is CCTCC NO M207062.
Embodiment
The basic procedure of technique of the present invention is: by after crushing raw ore, through belt or Automobile Transportation to stockyard; Add dilute acid soln to carry out preimpregnation, the basicly stable rear access high-efficiency bacteria for leaching ore of pH; Nickel leaching yield reaches after 80%, unloads heap, will soak slag and be transported to permanent stockyard, and access thermophile bacteria, carries out the leaching of copper; Leach liquor part open circuit enters settling tank, carries out valuable metal fractional precipitation and neutralization, obtains additional higher metallic sulfide, and the leach liquor reuse after neutralization, to leaching stage, circulates to drip and drenches.
Embodiment 1
The domestic Bai Shan of Jilin Province nickel cobalt ore, belongs to multi-metal sulfide, contains nickel, cobalt, zinc, copper valuable metal, and iron level is higher, and exists mainly with pyrite form greatly, adopts traditional selecting and smelting technology, and Financial cost is high, without recovery value.Principal element analysis in table 1:
Table 1 ore principal element is analyzed
| Element | Ni | Co | Zn | Fe | Cu |
| Content/% | 0.24 | 0.04 | 0.45 | 11.22 | 0.18 |
| Element/% | S | Ca | Mg | SiO 2 | |
| Content | 7.24 | 5.38 | 6.45 | 56.64 |
A large amount of quartz, silicate are contained in this ore deposit, and zinc exists with zink sulphide form, and copper exists with chalcopyrite form, and cobalt nickel is mainly present in pentlandite and pyrite, and iron mainly exists with pyrite and pyrrhotite form.
(1) lay at the heap end: at least one of leach liquor thrust-augmenting nozzle, adopts
pipeline, the not eyelet work of the preset part of tube wall down, area is about 1/3 cambered surface, and all the other are beaten
eyelet, eyelet is plum blossom-shaped; At least one of breather line, adopts
pipeline, interval 3.0m between adjacent two pipelines.
(2) build heap: to-50mm, adopt mechanical type to build heap ore reduction, pile high 5.5m, keep ore to form as far as possible nature and stack, form naturally piling of multiple hole, the growth that is conducive to pile interior ventilation and leaching microbacteria.
(3) microbionation: the high-efficiency bacteria for leaching ore filtering out is adopted to continuously stirring device, carry out enlarged culturing step by step, bacterium number keeps 10
7individual/more than mL, the redox potential of bacterium liquid is at 500mV(vs.SCE) more than; At the leaching initial stage, adopt the dilute acid soln preimpregnation of pH1.0～2.0, after pH is basicly stable, and access bacterium.
(4) selectivity organism of nickel cobalt zinc ore leaches: the intensity of ventilating when leaching is 0.8～1.0Nm
3/ m
2.h, dripping pouring intensity is 8～10L/m
2h, pH is 1.5～2.0, redox potential is lower than 500mV(vs.SCE), effectively suppress the dissolving of iron.
(5) Bioleaching of copper mine: unload and slag is transported to permanent stockyard after heap and again builds heap, pile high 9m, dripping and drenching intensity is 10～12L/m
2h, pH is 1.5～2.0, redox potential is 460～520mV(vs.SCE), mainly carry out the leaching of copper and the leaching of residue nickel cobalt zinc.
(5) metal selective reclaims: after in the selective leaching fluid in step (4), nickel concentration reaches 2.0g/L, carry out part leach liquor open circuit, enter settling tank (general nickeliferous 2.0～2.6g/L in leach liquor, zinc 4.5～6.0g/L, cobalt 0.80～1.0g/L, pH is 1.5～2.0), add sodium sulphite to carry out fractional precipitation, obtain cupric sulfide, zinc sulphide and nickelous sulfide cobalt product, having precipitated rear pH value of solution is 3.5～4.0, then add lime neutralization, pH is adjusted to neutrality, further remove the iron in Leaching Systems, in leach liquor after neutralization, the concentration of iron is lower than 1.0g/L, the selectivity that can be back to step (4) leaches the stage.
Adopt aforesaid method to obtain in vulcanizate, zinc content is 60～70wtg%, nickel cobalt contents 50～60wt%.
Claims (8)
1. a low-grade multi-metal sulfide selective bioleaching process, is characterized in that, comprises the following steps:
A. selectivity organism leaches: raw mineral materials is built to heap, and the preimpregnation of employing acid solution accesses bacterium Leptospirillum ferrooxidans Retech-SPL-1 after ore deposit heap acidity is stable, piles bottom ventilation and carries out acid droplet drench leaching to ore deposit;
B. soaking slag leaches again: after nickel leaching reaches more than 80wt%, unload heap, then will soak slag and again build heap, and access bacterium Sulfolobus metallicus Retech-ETC-1, then carry out acid droplet pouring and leach;
C. metal selective reclaims: after the concentration of nickel in selective leaching fluid in step a reaches 2.0g/L, 15～20% the leach liquor open circuit of total leach liquor volume will be accounted for, enter settling tank, add sodium sulphite to carry out fractional precipitation, obtain cupric sulfide, zinc sulphide and nickelous sulfide cobalt product, after having precipitated, add lime that pH is adjusted to neutral and further removes the iron in Leaching Systems, the selectivity that is back to step a through the solution of neutralization is leached to the stage;
In the zinc sulphide product that fractional precipitation obtains, zinc content is 60～70wt%, and in nickelous sulfide cobalt product, nickel cobalt contents is 50～60wt%, and in the rear immersion liquid of neutralization, concentration of iron is lower than 1.0g/L;
Wherein, described bacterium Leptospirillum ferrooxidans Retech-SPL-1, has now been deposited in Chinese Typical Representative culture collection center C CTCC, and address is positioned at Wuhan University in the school, preservation date is on October 17th, 2008, and deposit number is CCTCC No:M208162;
Described bacterium Sulfobacillus thermosulfidooxidans Retech-ETC-1, now be deposited in Chinese Typical Representative culture collection center C CTCC, address is positioned at Wuhan University in the school, and preservation date is on May 11st, 2007, and deposit number is CCTCC NO:M207062.
2. extract technology as claimed in claim 1, is characterized in that, described in step a, builds heap, lays in advance leach liquor thrust-augmenting nozzle and breather line in heap bottom, ore deposit, will after ore reduction, build heap.
3. extract technology as claimed in claim 2, is characterized in that, described leach liquor draft-tube diameter 110mm, described breather line diameter 50mm, interval 2.0～3.0m between adjacent two pipelines.
4. extract technology as claimed in claim 2, is characterized in that, described fragmentation be by ore reduction to particle diameter below 50mm.
5. extract technology as claimed in claim 1, is characterized in that, in step a and b, the bacterium number of the bacteria culture of access is 10
7individual/more than mL.
6. extract technology as claimed in claim 1, is characterized in that, the pH of the acid solution used of the preimpregnation described in step a is 1.0～2.0.
7. extract technology as claimed in claim 1, is characterized in that, in step a, high 5～6m is piled in the ore deposit building up, ventilation intensity 0.8～1.0Nm
3/ m
2.h, dripping pouring intensity is 8～10L/m
2h, pH is 1.5～2.0, redox potential is lower than 500mV.
8. extract technology as claimed in claim 1, is characterized in that, in step b, again builds the ore deposit of heap and piles high 8～10m, and dripping and drenching intensity is 10～12L/m
2h, pH is 1.5～2.0, redox potential is 460～520mV.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104726706B (en) * | 2013-12-20 | 2017-02-08 | 北京有色金属研究总院 | Low acid consumption and heap leaching new technology of high-magnesium low grade nickel sulfide ores |
| CN104130963B (en) * | 2014-07-31 | 2016-09-07 | 黑龙江八一农垦大学 | One strain is addicted to acid iron-oxidizing bacteria and the purposes in copper mine leaches thereof |
| CN105803193B (en) * | 2014-12-30 | 2018-02-06 | 北京有色金属研究总院 | A kind of method of the copper cobalt sulphide ore biological synthesis recovery copper cobalt magnesium containing magnesium |
| CN109929996B (en) * | 2017-12-19 | 2020-12-08 | 有研工程技术研究院有限公司 | Selective bioleaching process for high-iron low-grade nickel sulfide ore |
| CN108998668B (en) * | 2018-08-24 | 2020-01-31 | 中南大学 | method for regulating and controlling dissolution of high-iron sphalerite |
| CN111349781B (en) * | 2020-04-14 | 2021-12-21 | 长沙有色冶金设计研究院有限公司 | Method for reducing acid in copper sulfide concentrate by oxygen pressure leaching |
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