CN103184335A - 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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- CN103184335A CN103184335A CN201110459874XA CN201110459874A CN103184335A CN 103184335 A CN103184335 A CN 103184335A CN 201110459874X A CN201110459874X A CN 201110459874XA CN 201110459874 A CN201110459874 A CN 201110459874A CN 103184335 A CN103184335 A CN 103184335A
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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, toxic metal ion and impure mineral content height, and many metals association relationship is close.Produce in the resource at explored polymetallic ore, polymetallic ore with the copper association is in the great majority, copper is mainly based on chalcopyrite ore, 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 technology to develop.Adopt the wet processing technology, concentration of iron height in the leach liquor, valuable metal ions concentration is low, separation, extractive technique cost height, added value of product is low.The mineral composition of dissimilar Mineral resources, chemical ingredients, crystalline structure, embedding cloth characteristic and leaching performance difference are big, and also there is certain difference in different valuable metal ions character in the solution.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 objective of the invention is to overcome the deficiency of above-mentioned technology, provide a kind of at low-grade multi-metal sulfide selective bioleaching process, to solve the low difficult problem of recovery rate of valuable metals.
For achieving the above object, the present invention by the following technical solutions:
A kind of low-grade polymetallic ore selectivity extract technology may further comprise the steps:
A. selectivity organism leaching: raw mineral materials is built heap, adopt the dilute acid soln preimpregnation, treat the basicly stable back access of ore deposit heap acidity bacterium Leptospirillum ferrooxidans Retech-SPL-1, pile the bottom ventilation to the ore deposit and carry out acid droplet and drench leaching;
B. soaking slag leaches again: after the nickel leaching reaches more than the 80wt%, unload heap, to soak slag then is transported to permanent stockyard and builds heap again, insert bacterium Sulfobacillus thermosulfidooxidans Retech-ETC-1, carry out acid droplet again 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 the selectivity organism leach liquor among the step a reaches 2.0g/L, 15～20% the leach liquor open circuit that accounts for total leach liquor volume is entered settling tank (general nickeliferous 2.0～2.6g/L in the leach liquor, zinc 4.5～6.0g/L, cobalt 0.80～1.0g/L, pH is 1.5～2.0), add sodium sulphite then and carry out fractional precipitation, obtain cupric sulfide, zinc sulphide and nickelous sulfide cobalt product, pH value of solution was 3.5～4.0 after precipitation was finished, add the lime neutralization, be about to pH and transfer to the neutral iron of also further removing in the leaching system, the concentration of iron is lower than 1.0g/L in the leach liquor after the neutralization, and the selectivity that can be back to step a leaches the stage.
In the vulcanizate that the employing aforesaid method obtains, zinc content is 60～70wt%, and the nickel cobalt contents is 50～60wt%.
Aforesaid extract technology, wherein said bacterium Leptospirillum ferrooxidans Retech-SPL-1, now be deposited in China national typical case culture collection center C CTCC, the 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 the ore deposit bacterium to this bacterium, better to the nickel leaching effect;
Described bacterium Sulfolobus metallicus Retech-ETC-1, now be deposited in China national typical case culture collection center C CTCC, the 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.
Aforesaid extract technology is wherein built heap described in the step a, is that leach liquor thrust-augmenting nozzle and breather line are laid in heap bottom, ore deposit, will build heap after the ore reduction.
Aforesaid extract technology, wherein preferably, described leach liquor draft-tube diameter 110mm, described breather line diameter 50mm, interval 2.0～3.0m between adjacent two pipelines.
Aforesaid extract technology, wherein preferably, described fragmentation be with ore reduction to-50mm, namely particle diameter is below 50mm.
Aforesaid extract technology, wherein preferably, when building heap, the maintenance ore forms nature as far as possible and stacks, and forms the heap naturally of multiple hole, the growth of ventilation and leaching microbacteria in being conducive to pile.
Aforesaid extract technology, wherein preferably, among step a and the b, the bacterium number of the bacteria culture of access is 10
7Individual/more than the mL.
Aforesaid extract technology, wherein preferably, the pH of the dilute acid soln that the preimpregnation described in the step a is used is 1.0～2.0.
Aforesaid extract technology, wherein preferably, among the step a, high 5～6m is piled in the ore deposit that builds 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.
Aforesaid extract technology wherein preferably, among the step b, is built the ore deposit of heap again and is piled 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 to soak the ore deposit bacterium, has promoted the efficient dissolving of zinc greatly, and zinc leaching rate is higher than 85wt%.Simultaneously, also promoted the dissolving of nickel, the nickel leaching yield is greater than 80wt%, and comparatively speaking, the leaching velocity of cobalt is slower, therefore will soak and continue to leach after slag goes to permanent stockyard.
2. low-grade valuable metal comprehensively reclaims
Copper mainly exists with the primary ore form, and leaching rate is slower under the normal temperature, and after inserting thermophile bacteria, the leaching rate of copper is accelerated, and the leaching yield of last copper reaches more than the 65wt%.Nickel cobalt zinc continues dissolving and do not soak completely in the first step leaching process, has further improved leaching yield.Finally, nickel cobalt zinc leaching rate has improved many metals comprehensive reutilization level near 90wt%.
3. effective inhibition of iron
In the 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, during most widely used is and deferrization process, but this technology can cause the loss of nickel cobalt zinc valuable metal.The normal temperature bacterium of adopting in the technology of the present invention not only can promote the dissolving in zinc-nickel ore deposit, and the leaching system is kept than low potential, has suppressed the efficient leaching of iron, has reduced the meltage of iron from the source.In addition, behind nickel cobalt zinc precipitated metal, pH raises in the solution, adds the content that a spot of lime can further reduce iron, is conducive to the leach liquor efficient circulation and leaches.
4. added value of product height
Because under low pH condition, the iron precipitation capacity is less, and each precipitated metal pH difference, has certain selectivity, cupric sulfide, zinc sulphide and nickelous sulfide cobalt product foreign matter content are low, the added value of product height.
5. environmental friendliness
This technology does not need to become concentrate and high melt through traditional beneficiation enrichment of high energy consumption, toxic gases such as the novel process flue dust that exhaust emission is not big and sulfurous gas, 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 selective bioleaching process efficiently is provided, improved recovery rate of valuable metals, realize fully utilizing the purpose of low-grade multi-metal sulfide Mineral resources, can obtain bigger economic benefit.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Used bacterium Leptospirillum ferrooxidans Retech-SPL-1 among the present invention, now be deposited in China national typical case culture collection center C CTCC, the 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 now has been deposited in China national typical case culture collection center C CTCC, and the 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 technology of the present invention is: behind crushing raw ore, be transported to the stockyard through belt or automobile; Add dilute acid soln and carry out preimpregnation, pH inserts high-efficiency bacteria for leaching ore in basicly stable back; The nickel leaching yield reaches after 80%, unloads heap, will soak slag and be transported to permanent stockyard, inserts thermophile bacteria, carries out the leaching of copper; Leach liquor is partly opened a way and is entered settling tank, carries out valuable metal fractional precipitation and neutralization, obtains additional higher metallic sulfide, and the leach liquor reuse after the neutralization circulated to drip and drenches to the leaching stage.
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 with the pyrite form mostly, adopts traditional selecting and smelting technology, Financial cost height, no 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 the zink sulphide form, and copper exists with the chalcopyrite form, and cobalt nickel mainly is present in pentlandite and the 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, adopt
Pipeline presets not eyelet work of tube wall part down, and area is about 1/3 cambered surface, and all the other are beaten
Eyelet, eyelet are the plum blossom shape; 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 nature as far as possible and stack, form heap naturally of multiple hole, the growth of ventilation and leaching microbacteria in being conducive to pile.
(3) microbionation: the high-efficiency bacteria for leaching ore that filters out is adopted the continuously stirring device, carry out enlarged culturing step by step, the bacterium number keeps 10
7Individual/more than the mL, the redox potential of bacterium liquid is at 500mV(vs.SCE) more than; The leaching initial stage, adopt the dilute acid soln preimpregnation of pH1.0～2.0, after pH is basicly stable, insert bacterium.
(4) selectivity organism of nickel cobalt zinc ore leaches: ventilation intensity is 0.8～1.0Nm during leaching
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 suppressed the dissolving of iron.
(5) biology of copper mine leaches: unload and slag is transported to permanent stockyard behind the heap and builds heap again, pile high 9m, dripping and drenching intensity is 10～12L/m
2H, pH are 1.5～2.0, and 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 nickel concentration reaches 2.0g/L in the selective leaching fluid in the step (4), carry out part leach liquor open circuit, enter settling tank (general nickeliferous 2.0～2.6g/L in the leach liquor, zinc 4.5～6.0g/L, cobalt 0.80～1.0g/L, pH is 1.5～2.0), add sodium sulphite and carry out fractional precipitation, obtain cupric sulfide, zinc sulphide and nickelous sulfide cobalt product, having precipitated the back pH value of solution is 3.5～4.0, add the lime neutralization then, pH is transferred to neutrality, further remove the iron in the leaching system, the concentration of iron is lower than 1.0g/L in the leach liquor after the neutralization, and the selectivity that can be back to step (4) leaches the stage.
Adopt aforesaid method to obtain in the vulcanizate, zinc content is 60～70wtg%, nickel cobalt contents 50～60wt%.
Claims (9)
1. a low-grade multi-metal sulfide selective bioleaching process is characterized in that, may further comprise the steps:
A. selectivity organism leaching: raw mineral materials is built heap, and the stable back access of ore deposit heap acidity bacterium Leptospirillum ferrooxidans Retech-SPL-1 is treated in the preimpregnation of employing acid solution, piles the bottom ventilation to the ore deposit and carries out acid droplet and drench leaching;
B. soaking slag leaches again: after the nickel leaching reaches more than the 80wt%, unload heap, will soak slag then and build heap again, insert bacterium Sulfolobus metallicus Retech-ETC-1, carry out acid droplet again and drench leaching;
C. metal selective reclaims: after the concentration of nickel in the selective leaching fluid among the 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 and carry out fractional precipitation, obtain cupric sulfide, zinc sulphide and nickelous sulfide cobalt product, add lime after precipitation is finished pH is transferred to the neutral iron of also further removing in the leaching system, the selectivity that will be back to step a through the solution of neutralization leaches the stage.
Zinc content is 60～70wt% in the vulcanizate, nickel cobalt contents 50～60wt%, and neutralization back immersion liquid concentration of iron is lower than 1.0g/L.
2. extract technology as claimed in claim 1 is characterized in that,
Described bacterium Leptospirillum ferrooxidans Retech-SPL-1, now be deposited in China national typical case culture collection center C CTCC, the address is positioned at Wuhan University in the school, and 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 China national typical case culture collection center C CTCC, the address is positioned at Wuhan University in the school, preservation date: on May 11st, 2007, deposit number is CCTCC NO:M207062.
3. extract technology as claimed in claim 1 or 2 is characterized in that, extract technology as claimed in claim 1, it is characterized in that, build heap described in the step a, lay leach liquor thrust-augmenting nozzle and breather line in advance in heap bottom, ore deposit, will build heap after the ore reduction.
4. extract technology as claimed in claim 3 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.
5. extract technology as claimed in claim 3 is characterized in that, described fragmentation be with ore reduction to particle diameter below 50mm.
6. extract technology as claimed in claim 1 or 2 is characterized in that, among step a and the b, the bacterium number of the bacteria culture of access is 10
7Individual/more than the mL.
7. extract technology as claimed in claim 1 or 2 is characterized in that, the pH of the acid solution that the preimpregnation described in the step a is used is 1.0～2.0.
8. extract technology as claimed in claim 1 or 2 is characterized in that, among the step a, high 5～6m is piled in the ore deposit that builds 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.
9. extract technology as claimed in claim 1 or 2 is characterized in that, among the step b, builds the ore deposit of heap again and piles high 8～10m, and dripping and drenching intensity is 10～12L/m
2H, pH are 1.5～2.0, and redox potential is 460～520mV.
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| CN104130963A (en) * | 2014-07-31 | 2014-11-05 | 黑龙江八一农垦大学 | Acidophilic iron-oxidizing bacterium and application in copper ore leaching |
| CN104726706A (en) * | 2013-12-20 | 2015-06-24 | 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 |
| CN105803193A (en) * | 2014-12-30 | 2016-07-27 | 北京有色金属研究总院 | Method for biological comprehensive recovery of copper, cobalt and magnesium from copper cobalt sulfide ore containing magnesium |
| CN108998668A (en) * | 2018-08-24 | 2018-12-14 | 中南大学 | A method of regulation high-iron sphalerite dissolution |
| CN109929996A (en) * | 2017-12-19 | 2019-06-25 | 北京有色金属研究总院 | High iron low grade nickel sulfide ore selective bioleaching process |
| CN111349781A (en) * | 2020-04-14 | 2020-06-30 | 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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| CN108998668B (en) * | 2018-08-24 | 2020-01-31 | 中南大学 | method for regulating and controlling dissolution of high-iron sphalerite |
| CN111349781A (en) * | 2020-04-14 | 2020-06-30 | 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 |
| 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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