CN102051479B - Biological stirring leaching method of ordinary-temperature acidophilic leaching-ore bacteria and high-arsenic high-grade primary copper sulfide ore - Google Patents
Biological stirring leaching method of ordinary-temperature acidophilic leaching-ore bacteria and high-arsenic high-grade primary copper sulfide ore Download PDFInfo
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Abstract
The invention provides a biological stirring leaching method of ordinary-temperature acidophilic leaching-ore bacteria and high-arsenic high-grade primary copper sulfide ore. Ordinary-temperature acidophilic leaching-ore bacteria adopt thiobacillus ferrooxidans strain DBS02 which are preserved in China Center for Type Culture Collection, and the preserving number is CCTCC No. M2010323. The method comprises that ore is ground into 80 meshes and is added to a biological agitation leach system containing acidophilic leaching-ore bacteria to perform biological agitation leach, wherein the concentration of ore slurry is 15% to 25 % (g/ml); ferrous ion of 4 to 10 g/l is added; the PH value of the ore slurry is stabilized between 1.8 to 2.4 through the adjustment of dilute sulphuric acid; and the leaching rate of copper in the ore is up to more than 84% after 8 to 10 days of leaching. By adopting the invention, copper can be leached from high-arsenic high-grade primary copper sulfide ore without extra-fine grinding; and the invention has the advantages of high efficiency, energy conservation and environmental protection.
Description
Technical field
The present invention relates to soak ore deposit bacterium and the difficult technical field of selecting the smelting copper mine, be specifically related to normal temperature and have a liking for leaching-ore bacteria and high arsenic higher-grade chalcopyrite ore biological stirring leaching method.
Background technology
Higher-grade, easy flotation copper mine reduce gradually, and low-grade, difficulty selects the smelting copper mine day by day to come into one's own.The smelting technology of tradition copper mine is through ore reduction, ore grinding, flotation, to institute's flotation to concentrate carry out again pyrometallurgy and obtain metallic copper.The technological development utilization that Treating Low-grade Copper Ores has also had comparative maturity now obtains significant economic benefit; And difficulty is selected the smelting copper mine, the primary copper mine of especially high arsenic content, and flotation process is long and complicated, has in addition the difficult problems such as production cost is high, energy consumption is large, environmental pollution is serious, adopts existing traditional smelting technology can't obtain economic benefit at all.Therefore, provide a kind of good in economic efficiency, environmentally friendly efficient novel process is imperative.
Summary of the invention
First purpose of the present invention provides a strain has the normal temperature of highly effective ore leaching ability to have a liking for leaching-ore bacteria at normal temperatures, this bacterium is soaked the ore deposit bacterium and compares with existing, the very high ore deposit ability of soaking is namely arranged at normal temperatures, need not hot operation, save a large amount of running costs, and heavy metal there is height endurability, under up to the copper ion concentration of 48g/l, still keeps high reactivity.
Normal temperature of the present invention is had a liking for the leaching-ore bacteria name and is called thiobacillus ferrooxidant DBS02 (Thiobacillus ferrooxidans strain DBS02), be preserved in Chinese Typical Representative culture collection center on November 30th, 2010, deposit number is CCTCC NO:M 2010323; The depositary institution address is Wuhan, China Wuhan University.
Another object of the present invention provides the biological stirring leaching method of high arsenic higher-grade chalcopyrite ore, and the method need not through the flotation arsenic removal, and ore does not need Ultrafine Grinding, saves a large amount of Financial cost.The method specifically comprises the steps:
(1) then mining ore out joins in the equalizing tank through comminution to 80 order, and adding water preparation pulp density is 15～25% (g/ml), and regulating the pH value with dilute sulphuric acid is 1.8～2.4;
(2) add the middle ore of ferrous ion and step (1) through the leach liquor of the physics leaching gained of 1+1 sulfuric acid in thiobacillus ferrooxidant DBS02 cultivation pool, enlarged culturing is had a liking for leaching-ore bacteria, gets bacterium liquid;
(3) ore pulp of step (1) gained and the bacterium liquid pump of step (2) gained are entered to carry out in the biological stirring leaching system biological stirring leaching.
Above-mentioned high arsenic higher-grade chalcopyrite ore biological stirring leaching method, in the step (3), the pulp density that biological stirring leaches is 15～25% (g/ml), extraction temperature will be controlled at 25～35 ℃, slurry pH is 1.8～2.4 in the leaching process, also constantly passes into air to the biological stirring leaching system in the leaching process.
Above-mentioned high arsenic higher-grade chalcopyrite ore biological stirring leaching method, the main component of described high arsenic higher-grade chalcopyrite ore is tennantite, the average quality mark of copper reaches 31.8% in the ore, and the average quality mark of arsenic reaches 4.8%, the average quality mark of iron only 1.8%.
Above-mentioned high arsenic higher-grade chalcopyrite ore biological stirring leaching method, arsonium ion content is 0.3～0.6g/l in the leach liquor after leaching through biological stirring in the step (3), only has 3～7% arsenic to be dissolved out, remaining arsenic is all in the quarrel of ore deposit.
Above-mentioned high arsenic higher-grade chalcopyrite ore biological stirring leaching method, in the step (1) mining ore out through coarse crushing, in small, broken bits and be finely ground to 80 orders.
Above-mentioned high arsenic higher-grade chalcopyrite ore biological stirring leaching method, described high arsenic higher-grade chalcopyrite ore is through after the fine grinding, and its particle diameter is less than 0.18mm.
The dissolved oxygen of ore pulp is greater than 2mg/l in the above-mentioned high arsenic higher-grade chalcopyrite ore biological stirring leaching method, step (3), and ore pulp was through biological stirring leaching system agitation leach 8～10 days, and the leaching yield of copper reaches more than 84%.
The biological stirring leaching system can comprise the multi-stage biological oxidation trough, biological oxidation channel comprises ore pulp import and outlet, be provided with heating and condenser system, oxygen replenishing equipment and whipping device in the biological oxidation channel, stable to guarantee the biological stirring leaching system, improve reactor and leach efficient.
The function yeast of the method utilization is to soak the ore deposit bacterium from the normal temperature that large Golconda tailing dam abandoned mine heap separation domestication obtains.Through 16SrDNA and PCR-DGGE technical Analysis, this soaks the ore deposit bacterium and Acidithiobacillus ferrooxidans similarity reaches 99%, therefore is accredited as thiobacillus ferrooxidant, plays a major role in leaching process.In leaching process because the iron-holder of ore is very low, must add certain ferrous ion (4～10g/l), could keep activity and the leaching effect of bacterium.
Compared with prior art, the present invention has following advantage and effect: described high arsenic higher-grade chalcopyrite ore is through after the fine grinding, and its particle diameter need not Ultrafine Grinding less than 0.18mm, saves a large amount of running cost.The ore deposit bacterium of soaking of using namely has the very high ore deposit ability of soaking under normal temperature (25～35 ℃), need not hot operation, saves a large amount of running costs, and heavy metal is had height endurability, still keeps high reactivity under up to the copper ion concentration of 48g/l.Arsonium ion content only is 0.3～0.6g/l in the leach liquor after the process biological stirring leaches, namely only has the arsenic about 3～7% to be dissolved out, and remaining arsenic all in the quarrel of ore deposit, can be made proper arrangements after treatment.Generally speaking, the biological stirring that the present invention opens up the primary copper mine of high arsenic higher-grade leaches novel method, for the difficulty that traditional fire metallurgy process can't be smelted selects the smelting copper mine that outlet is provided, improve the mineral resources comprehensive utilization level, reducing production costs, under the prerequisite of increasing economic efficiency, reduce environmental pollution.The present invention also is very effective except being specially adapted to high arsenic higher-grade copper mine for general higher-grade copper mine.
Description of drawings
Fig. 1 is shown as the transmission electron microscope picture of thiobacillus ferrooxidant DBS02.
Embodiment
As shown in Figure 1, this soaks ore deposit bacterium (thiobacillus ferrooxidant DBS02 CCTCC NO:M2010323) for shaft-like under the perspective electron microscopic observation, and the cell two ends are circular, the long flagellum of side arranged, thalline size 2～2.1 μ m * 0.5～0.6 μ m.
In the present embodiment, dig up mine first, ore is high arsenic content copper mine, through broken fine grinding operation, granularity is controlled at particle diameter＜0.18mm, water modulation pulp density is 15～25% (g/ml), regulate the pH value stabilization of ore pulp in 1.8～2.4 with 1+1 sulfuric acid again, get supernatant liquor and get leach liquor, the leach liquor that in thiobacillus ferrooxidant DBS02 cultivation pool, adds ferrous ion and gained, enlarged culturing is had a liking for leaching-ore bacteria, and bacterium liquid and the gained ore pulp of gained is pumped into the biological stirring leaching system, carries out biological stirring and leaches.The biological stirring leaching system can comprise three grades of biological stirring reactors (being also referred to as biological oxidation channel), on one side ore pulp enter from biological oxidation channel, Yi Bian from out, be provided with stirring system, heating and condenser system and aerating apparatus in the biological oxidation channel; Ore pulp all was about 2 days in the residence time of the second stage and the third stage about 5 days first step oxidation trough residence time, adopted the multi-stage biological oxidation trough can make leaching effect better; The anti-press capacity of reaction of high order groove is strong, and whole system is difficult for collapse, and is stable.
The invention will be further described below in conjunction with example.
The undeveloped high arsenic higher-grade chalcopyrite ore main component in certain mine is tennantite, and the average quality mark of copper reaches 31.8% in the ore, and the average quality mark of arsenic reaches 4.8%, and the average quality mark of iron only has about 1.8%.
(1) with ore through coarse crushing, in small, broken bits and be finely ground to 80 orders (particle diameter is less than 0.18mm), then be made into 15～25% (g/ml) pulp density with tap water, be stable at 1.8～2.4 with 1+1 sulfuric acid adjusting slurry pH.
(2) after ore leached through the physics of 1+1 sulfuric acid, the leach liquor of gained has contained had a liking for the leaching-ore bacteria needed nutritive substance of growing, and leach liquor is pumped in the bacterium cultivation pool, and add 4～10g/l ferrous ion, the amplification culture bacterium.
(3) according to the 15-25% pulp density ore pulp of pH=1.8～2.4 and bacterium liquid pump are entered the biological stirring leaching system, through agitation leach 8～10 days, the leaching yield of copper reached more than 84%.After leaching end, separate leach liquor and ore deposit quarrel.Through only containing the arsonium ion of 0.3～0.6g/l in the leach liquor after the biological stirring leaching, namely only have the arsenic about 3～7% to be dissolved out, remaining arsenic all in the quarrel of ore deposit, can be made proper arrangements after treatment.In the biological stirring leaching process, need slurry pH, temperature, dissolved oxygen content, concentration of heavy metal ion and bacteria content in each stage reactor of periodic monitor.The pH value of ore pulp will be controlled at 1.8～2.4, and the dissolved oxygen of ore pulp is greater than 2mg/l, and the temperature of ore pulp will be controlled at 25～35 ℃, and concentration of heavy metal ion will be stablized in the interior ore pulp of biological stirring leaching system, and it is too large to fluctuate.
The separation of the original ore immersion bacterial culture of the present invention: the mud sample separation and purification that gathers from the abandoned mine of the large Golconda tailing dam of Shaoguan City of Guangdong Province heap out, the substratum that uses is the 9K basic medium, and the nutritive ingredient of 9K basic medium is: contain 3.0 gram (NH in every liter of substratum
4)
2SO
4, 0.1 gram KCl, 0.5 gram K
2HPO
4, 0.5 gram MgSO
47H
2O, 0.01 gram Ca (NO
3)
2, 30.0 gram FeSO
47H
2O.This bacterium is inorganic chemoautotrophic bacteria, obtains energy with oxidation ferrous ion and reduced sulfur, take airborne carbonic acid gas as carbon source.
The domestication of high-efficiency bacteria for leaching ore: the primary Copper ore powder of high arsenic higher-grade (the ore particle diameter is less than 0.18mm) that in pure water, adds certain mine, initial pulp density is 5% (g/ml), the pH value is controlled at 2, after repeatedly taming, finally make this bacterium under the pulp density of 20% (g/ml), still keep active efficiently, can tolerate the cupric ion of 48g/l.
Claims (5)
1. high arsenic higher-grade chalcopyrite ore biological stirring leaching method is characterized in that may further comprise the steps:
(1) then mining ore out joins in the equalizing tank through comminution to 80 order, and adding water preparation pulp density is 15～25%g/ml, uses the pH value stabilization of 1+1 sulfuric acid adjusting ore pulp in 1.8～2.4, gets supernatant liquor and gets leach liquor;
(2) add the middle ore of ferrous ion and step (1) through the leach liquor of the physics leaching gained of 1+1 sulfuric acid in thiobacillus ferrooxidant DBS02 cultivation pool, enlarged culturing is had a liking for leaching-ore bacteria, gets bacterium liquid;
(3) ore pulp of step (1) gained and the bacterium liquid pump of step (2) gained are entered to carry out in the biological stirring leaching system biological stirring leaching, wherein the pulp density of biological stirring leaching is 15～25%g/ml, extraction temperature will be controlled at 25～35 ℃, slurry pH is 1.8～2.4 in the leaching process, also constantly pass into air to the biological stirring leaching system in the leaching process, the main component of described high arsenic higher-grade chalcopyrite ore is tennantite, the average quality mark of copper reaches 31.8% in the ore, the average quality mark of arsenic reaches 4.8%, the average quality mark of iron only 1.8%.
2. high arsenic higher-grade chalcopyrite ore biological stirring leaching method according to claim 1, it is characterized in that: arsonium ion content is 0.3～0.6g/l in the leach liquor after the process biological stirring leaches in the step (3), only have 3～7% arsenic to be dissolved out, remaining arsenic is all in the quarrel of ore deposit.
3. high arsenic higher-grade chalcopyrite ore biological stirring leaching method according to claim 1, it is characterized in that in the step (1) mining ore out through coarse crushing, in small, broken bits and be finely ground to 80 orders.
4. high arsenic higher-grade chalcopyrite ore biological stirring leaching method according to claim 3 is characterized in that: described high arsenic higher-grade chalcopyrite ore is through after the fine grinding, and its particle diameter is less than 0.18mm.
5. high arsenic higher-grade chalcopyrite ore biological stirring leaching method according to claim 1, the dissolved oxygen that it is characterized in that ore pulp in the step (3) is greater than 2mg/l, ore pulp was through biological stirring leaching system agitation leach 8～10 days, and the leaching yield of copper reaches more than 84%.
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| CN103114209A (en) * | 2013-02-01 | 2013-05-22 | 英德佳纳金属科技有限公司 | Method for leaching cobalt and copper in cobalt-copper alloy through cooperation of thiobacillus ferrooxidans |
| CN110029231B (en) * | 2019-06-03 | 2021-11-16 | 东北大学 | Bacterial leaching method of complex copper oxide ore containing multiple copper minerals |
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| CN1493704A (en) * | 2002-10-28 | 2004-05-05 | 北京有色金属研究总院 | New technology of leaching copper sulfide ore using copper ore acidic ore pit water containing bacteria |
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| CN1493704A (en) * | 2002-10-28 | 2004-05-05 | 北京有色金属研究总院 | New technology of leaching copper sulfide ore using copper ore acidic ore pit water containing bacteria |
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| Title |
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| 万淑娟等.一株氧化亚铁硫杆菌的筛选及生长条件研究.《环境工程学报》.2010,第4卷(第9期),第2146-2150页. * |
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