CN1265001C - New technology of leaching copper sulfide ore using copper ore acidic ore pit water containing bacteria - Google Patents

New technology of leaching copper sulfide ore using copper ore acidic ore pit water containing bacteria Download PDF

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CN1265001C
CN1265001C CNB021459711A CN02145971A CN1265001C CN 1265001 C CN1265001 C CN 1265001C CN B021459711 A CNB021459711 A CN B021459711A CN 02145971 A CN02145971 A CN 02145971A CN 1265001 C CN1265001 C CN 1265001C
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ore
copper
acidic
bacterium
leaching
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CN1493704A (en
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阮仁满
陈景河
温建康
巫銮东
孙雪南
李宏煦
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Beijing General Research Institute for Non Ferrous Metals
Zijin Mining Group Co Ltd
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Beijing General Research Institute for Non Ferrous Metals
Fujian Zijin Mining Industry Co Ltd
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Abstract

The present invention relates to a new technology for leaching a copper sulfide ore by using acidic ore pit water of a copper ore containing bacteria. The technology of the present invention is characterized in that copper sulfide ores are processed in a classified mode according to different grades of the copper sulfide ores, the microorganisms which are contained in the acidic ore pit water of the copper ore are used for spraying ore heaps, and the leach liquor which contains copper is extracted and electrodeposited to form cathode copper. In the leaching process, a balancing process of acid and iron is also carried out to maintain a pH value of a system to be favorable for the activity of leaching bacteria. The technology of the present invention can fully use mineral resources, can improve the recovery level of the copper, can save cost, can improve benefit, and is favorable for improving the quality of products; meanwhile, waste acidic ore pit water of mines can changed into valuable materials, the processing cost of environmental protection is reduced, and the pressure of the environmental protection is relieved.

Description

The copper mine acidic mine water that application contains bacterium leaches the technology of copper from copper-sulphide ores
Technical field
The present invention relates to a kind of copper-sulphide ores extract technology, particularly a kind of utilization contains the technology of the copper mine acidic mine water leaching copper of bacterium.
Background technology
In the explored copper resource of China, major part is low-grade, unmanageable copper mine, for example certain province has a Purple Mountain copper mine to be one to have verified to belong to and contain the low-grade large-scale copper deposit of arsenic, secondly its THE RECOGNITION OF MAIN COPPER is copper glance, piece enargite and enargite based on alpha chalcocite and covellite, adopts traditional dressing and smelting process to handle, investment is big, the cost height, pollution is heavy, with profitless.Therefore, be necessary to provide a kind of novel process.
Summary of the invention
The purpose of this invention is to provide a kind of new extraction process for copper, this technology is different from traditional dressing and smelting process, does not promptly need to become concentrate and high melt, novel process flue dust and sulfur dioxide gas that exhaust emission is not big through traditional beneficiation enrichment of high energy consumption.This technology system utilizes the microorganism that the acidic mine water in mine itself contains to carry out the leaching of copper, and extraction, the electrodeposition process of the full wet method of process.This technology is improved environmental pollution greatly, but and utilization of waste material, also be provided with the acid balance system simultaneously, improve quality product, and can obtain bigger benefit.
For achieving the above object, the present invention takes following design: the copper mine acidic mine water that a kind of application contains bacterium leaches the technology of copper from copper-sulphide ores, it may further comprise the steps:
(1), gather the copper mine acidic mine water contain thiobacillus ferrooxidant, thiobacillus thiooxidans and ferric oxide leptospirillum microorganism, carry out seed selection, domestication and the amplification culture mixed bacterium that strengthened subsequently;
(2), ore is divided into pay ore, dump leaching ore and barren rock by the grade of copper, described pay ore is the ore of cut-off grade more than 0.2% of copper; The ore of telling behind the pay ore is called the dump leaching ore; At the material peeled off of mining workshop section, its copper grade 0.2% hereinafter referred to as barren rock;
(3), dump leaching ore in (2) is pulverized, build heap, spray and contain enhancing mixed bacterium acidic mine water, leach liquor extracts after entering the rich solution pond, back extraction, electrodeposition obtain cathode copper; Pay ore is pulverized, ore grinding, the granularity of ore grinding is carried out granulation afterwards less than 1mm, the granularity of granulation between 8mm-10mm, after incorporate broken good dump leaching ore into and build heap together, spray and contain enhancing mixed bacterium acidic mine water; With the barren rock fragmentation, broken granularity is stored up, is sprayed the pH value that contains enhancing mixed bacterium acidic mine water less than 350mm and is 1.8-2.5, pond in the middle of leach liquor enters, middle pond liquid is delivered to the lean solution pond, and lean solution pond liquid is delivered to and built the heap operation in the dump leaching ore technology or spray contains enhancing mixed bacterium acidic mine water operation;
(4), in leaching process, superfluous acid and iron adopt neutralisation and anionresin acid diffusive dialysis method to make Balance Treatment.
Described is to add basic medium to carry out in pit water to the seed selection that contains bacterium sour water of gathering, and adds nutritive substance and is: (NH 4) 2SO 40.5-3g/L, KCl 0.05-0.1g/L, K 2HPO 40.1-0.5g/L, MgSO 47H 2O 0.1-0.5g/L, Ca (NO 3) 20.01g/L, FeSO 47H 2O 11.11-44.43g/L, described domestication is not contain FeSO 47H 2O, MgSO 47H 2O, Ca (NO 3) 2Basic medium in add the copper mine ore powder of granularity less than 0.076mm, adding the pulp density that forms behind the ore powder is the 5-25% weight percent, pH value is between 1.7-2.5, taming bacteria concentration is 10 7-10 9G/ml, described microorganism growth temperature is 15-42 ℃.
Described acidic mine water is the acidic mine water of Purple Mountain copper mine; Described ore is a Purple Mountain ore.
Described extracting-back extraction is got-electrodeposition process recovery copper metal, and extraction agent is Lix984N, and volumetric concentration 5-15%, thinner are No. 260 kerosene, and volumetric concentration is 95-85%, and the current density of electrodeposition is 150-220A/m 2
Description of drawings
Fig. 1 is a process flow diagram of the present invention
Fig. 2 is the process flow diagram of an embodiment of the present invention
Embodiment
As shown in Figure 1 and Figure 2,1 is the ore digging, during mining, resulting copper mine stone is divided into pay ore 2 according to the roughly grade of copper, ore (dump leaching is used) 5, and barren rock 19, pulverize (seeing 3 among the figure, 6,20) subsequently respectively, wherein, after pulverizing, pay ore needs the broken and ore grinding of further fine powder, carry out pelletizing granulation 4 then, pelletizing is built heap 7, and leaches 8 through biology.Can design the pay ore separation operation in ore reduction, promptly in the enterprising pedestrian's work point choosing of rotary conveyor, the pay ore that sub-elects is included into the pay ore of sorting in mining workshop section.
Among the figure, all enter the solution of spray, its mother liquor is and contains bacterium acidic mine water 15, this contains seed selection (separation, enrichment), the domestication operation 16 of bacterium sour water through bacterium, obtains soaking ore deposit bacterium 17, and the liquid that obtains behind the above-mentioned spray is sent into rich solution pond 10, through extracting 11, strip 12, deliver to electrodeposition operation 13, finally obtain cathode copper 14.
Consider the same receipts of metal ion, the surplus liquid in extraction back need return spray leaching system, but its pH value is on the low side, therefore there is part directly to return lean solution pond 9, after some need carry out sour iron balance 18, go back to lean solution pond 9 again, add in this lean solution pond and soak ore deposit bacterium 17, heap 7 operations of building that lean solution pond liquid is delivered in the dump leaching ore technology leach operation 8 with biology.
The grade of ettle is lower, so the liquid behind the spray returns to middle pond 23, middle pond liquid is delivered to the lean solution pond, and middle pond liquid also can return to 22 circulations of biology leaching operation.
Among Fig. 1, all waste residues are delivered to procedure of waste residue 24, and waste residue is delivered to storage bay 25 again, and liquid collecting storehouse 26 is delivered in the liquid collecting in storing up, and treatment process 27 is delivered in some liquid collecting, handle back discharging 28, and rest part are delivered to middle pond 23.The liquid collecting slag is delivered to the combination treatment operation, and it adopts, and " iron powder replacement-lime or sheet alkali are regulated pH value-Na 2S sinks copper " process integration, contain Cu to effluxing 2+Acid waste water is handled, qualified discharge.
Among Fig. 2, the neutral method is adopted in sour iron balance, used in and medicament can use lime carbonate 31, with operation 29, strip and adopt the electrodeposition raffinate during lime carbonate is delivered to behind ore grinding 30, the electrodeposition raffinate is after wash rice 32 is oozed in acid, return the back extraction operation, acid is oozed the wash rice raffinate and is entered the rich solution pond.
Embodiment
The invention will be further described below in conjunction with embodiment
Embodiment 1
This novel process is applied to Purple Mountain copper mine stone, and Purple Mountain copper mine belongs to and contains the low-grade cupric sulfide of arsenic, and THE RECOGNITION OF MAIN COPPER is alpha chalcocite and covellite, secondly be copper glance, piece enargite and enargite, the copper average grade is 0.5%, the arsenic grade is 0.035%, sulphur grade 2.35%; Main gangue mineral is quartzy.
1, at first gathers the acidic mine water of Purple Mountain copper mine, and under biomicroscope, detect whether contain microorganisms such as thiobacillus ferrooxidant, thiobacillus thiooxidans and ferric oxide leptospirillum, in acidic mine water, add basic medium subsequently, carry out seed selection (separation, enrichment), domestication and amplification culture, the adding nutritive substance is: (NH 4) 2SO 40.5-3g/L, KCl 0.05-0.1g/L, K 2HPO 40.1-0.5g/L, MgSO 47H 2O 0.1-0.5g/L, Ca (NO 3) 20.01g/L, FeSO 47H 2O 11.11-44.43g/L, the pH that bacterium is cultivated is controlled at 1.7-2.5.It is not contain FeSO that domestication is cultivated 47H 2O, MgSO 47H 2O, Ca (NO 3) 2Basic medium in add Purple Mountain copper mine ore powder (granularity accounts for 95% less than 0.076mm's), pulp density 5-25% (weight percent), pH is controlled at 1.7-2.5.The final bacteria concentration that obtains domestication and amplification culture is 10 7-10 9Individual/ml, the microorganism growth temperature is 16-42 ℃.
2, in the copper mine stone of the digging Purple Mountain, the copper mine stone of digging is divided into pay ore, dump leaching ore and barren rock according to the roughly grade of copper.Pay ore is to contain the higher pay ore of copper grade, the dump leaching ore be cut-off grade at copper more than 0.2% through the ore after sub-electing the higher-grade pay ore, barren rock is meant the material that the mining workshop section of copper grade below 0.2% peels off.
After the classification, with pay ore, dump leaching ore and barren rock are pulverized respectively.Wherein after the pay ore fragmentation, need further in small, broken bitsly, fine granularity＜1mm carries out the pelletizing granulation afterwards, and pelletizing granularity 8-10mm, pelletizing incorporate broken good ore (dump leaching ore) after through 48 hours maintenance into and build the heap bacterium together and leach.
When particle size after cracking＜the 350mm of barren rock, ore built heap, the heap height was 6m; Barren rock is stored up separately in a stockyard, piles high no requirement (NR), but the Bian Dui limit sprays and contains the bacterium acidic mine water.In technology, the solution that sprays is to insert in the copper mine acidic mine water of the Purple Mountain and has tamed and the good acidic solution that contains microorganisms such as thiobacillus ferrooxidant, thiobacillus thiooxidans and ferric oxide leptospirillum of amplification culture, and the pH value of spray liquid is 1.8-2.5.Above-mentioned domestication amplification culture liquid access amount is 10% of a spray liquid volume.The spray liquid consumption that ore biology leaches is 5-25L/ (m 2H), spray adopts the duty of having holidays by turns with leisure, can spray stop-spraying seven days (leisure) seven days.After copper ion concentration reached 1.5g/L in the leach liquor, leach liquor entered the recycle section of copper metal.
3, the recovery of copper metal
The extraction of this recovery process using, reextraction, electrodeposition operation, extraction agent adopts LiX984N, and its volumetric concentration is 5-10%, and ton copper consumes 3-3.5kg; Thinner is No. 260 kerosene, its volumetric concentration 95-90%, ton copper consumption≤100kg; Strip and adopt the electrodeposition raffinate to carry out, the current density of electrodeposition is 165-180A/m 2, current efficiency 〉=95%.Raffinate 1/3 after cupric ion reclaims carries out sour iron balance to be handled, and all the other return the lean solution pond and carry out the circulated sprinkling leaching.
4, sour iron balance: utilize ferrous iron and the reduced sulfur in the bacterial oxidation sulphide ores because the biological dump leaching of Purple Mountain copper mine is one, and the process that the copper in the mineral is leached with the form of copper-bath, therefore, the leaching process of copper also is a process of producing sour iron.Meanwhile, the extraction of cupric ion also is a H +And Cu 2+The process of exchange must be a process of producing acid in the extracting system.And that Purple Mountain copper mine contains the sour gangue of consumption is few, produces the acid amount greater than acid consumption.What therefore, finally have influence on bacterium soaks the ore deposit activity.In addition, electrodeposition process reclaims copper, because the chemistry and the physics of extraction process are carried secretly, bring the iron ion in the leach liquor into electrodeposition, influence electrolytic deposition process efficient and electrolytic copper quality, have 1/3 raffinate adopt the lime carbonate neutralisation to carry out sour iron balance before returning the lean solution pond according to above reason, the pH of the leaching system value after the processing remains between the 1.5-2.0, and iron concentration is below 10g/L; Adopted NSH816-4 type anionresin acid diffusion dialysis device to carry out sour iron balance before the electrodeposition raffinate returns reextraction and handled, the electric effusion after the processing contains concentration of iron all below 1.36g/L.
Effect of the present invention is: except being conducive to environmental protection, also helping and improve the quality of products, tough cathode produces The product cupric is more than 99.99%; Can enlarge copper utilization of resources scope, the Copper Ores copper grade of processing can be low to moderate 0.1%.

Claims (3)

1, a kind of application copper mine acidic mine water of containing bacterium leaches the technology of copper from copper-sulphide ores, and it is characterized in that: it may further comprise the steps:
(1), gather the copper mine acidic mine water contain thiobacillus ferrooxidant, thiobacillus thiooxidans and ferric oxide leptospirillum microorganism, carry out seed selection, domestication and the amplification culture mixed bacterium that strengthened subsequently;
(2), ore is divided into pay ore, dump leaching ore and barren rock by the grade of copper, described pay ore is the ore of cut-off grade more than 0.2% of copper; The ore of telling behind the pay ore is called the dump leaching ore; At the material peeled off of mining workshop section, its copper grade 0.2% hereinafter referred to as barren rock;
(3), dump leaching ore in (2) is pulverized, build heap, spray and contain enhancing mixed bacterium acidic mine water, leach liquor extracts after entering the rich solution pond, back extraction, electrodeposition obtain cathode copper; Pay ore is pulverized, ore grinding, the granularity of ore grinding is carried out granulation afterwards less than 1mm, the granularity of granulation between 8mm-10mm, after incorporate broken good dump leaching ore into and build heap together, spray and contain enhancing mixed bacterium acidic mine water; With the barren rock fragmentation, broken granularity is stored up, is sprayed the pH value that contains enhancing mixed bacterium acidic mine water less than 350mm and is 1.8-2.5, pond in the middle of leach liquor enters, middle pond liquid is delivered to the lean solution pond, and lean solution pond liquid is delivered to and built the heap operation in the dump leaching ore technology or spray contains enhancing mixed bacterium acidic mine water operation;
(4), in leaching process, superfluous acid and iron adopt neutralisation and anionresin acid diffusive dialysis method to make Balance Treatment.
2, the application according to claim 1 copper mine acidic mine water that contains bacterium leaches the technology of copper from copper-sulphide ores, it is characterized in that: described is to add basic medium to carry out in pit water to the seed selection that contains bacterium sour water of gathering, and adds nutritive substance and is: (NH 4) 2SO 40.5-3g/L, KCl 0.05-0.1g/L, K 2HPO 40.1-0.5g/L, MgSO 47H 2O 0.1-0.5g/L, Ca (NO 3) 20.01g/L, FeSO 47H 2O11.11-44.43g/L, described domestication is not contain FeSO 47H 2O, MgSO 47H 2O, Ca (NO 3) 2Basic medium in add the copper mine ore powder of granularity less than 0.076mm, adding the pulp density that forms behind the ore powder is the 5-25% weight percent, pH value is between 1.7-2.5, taming bacteria concentration is 10 7-10 9G/ml, described microorganism growth temperature is 15-42 ℃.
3, the application according to claim 1 and 2 copper mine acidic mine water that contains bacterium leaches the technology of copper from copper-sulphide ores, and it is characterized in that: described acidic mine water is the acidic mine water of Purple Mountain copper mine; Described ore is a Purple Mountain ore.
CNB021459711A 2002-10-28 2002-10-28 New technology of leaching copper sulfide ore using copper ore acidic ore pit water containing bacteria Expired - Lifetime CN1265001C (en)

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Cited By (1)

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CN109971944A (en) * 2019-04-19 2019-07-05 紫金矿业集团股份有限公司 From the method for low-grade secondary copper sulfide mineral high efficiente callback copper

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CN100404705C (en) * 2006-04-24 2008-07-23 南京大学 Method for extracting metal copper using microbe and its use
CN100402677C (en) * 2007-04-16 2008-07-16 中南大学 Bacteria underground heap leaching process for copper ore
CN101434918B (en) * 2007-11-13 2011-03-30 北京有色金属研究总院 Leaching-ore bacteria and high temperature heap bioleaching process for chalcopyrite ore by using the same
CN101736155B (en) * 2008-11-27 2011-06-08 北京有色金属研究总院 Method for control oxidation of pyrite in bioleaching process
CN102051479B (en) * 2010-12-14 2013-04-24 华南理工大学 Biological stirring leaching method of ordinary-temperature acidophilic leaching-ore bacteria and high-arsenic high-grade primary copper sulfide ore
CN104674002B (en) * 2014-12-12 2016-09-21 厦门紫金矿冶技术有限公司 A kind of Low Grade Copper Ore bioleaching process
CN109423453B (en) * 2017-08-25 2022-11-15 有研资源环境技术研究院(北京)有限公司 Method for culturing mineral leaching microorganisms by using acid mine wastewater
CN110090847B (en) * 2019-04-02 2022-08-16 昆明理工大学 Rapid weathering and soil formation method for sulfide mineral-containing waste rock
CN111471853A (en) * 2020-01-20 2020-07-31 中国科学院过程工程研究所 Copper ore granulating-heap leaching method
CN112522511B (en) * 2020-11-09 2021-12-10 紫金矿业集团股份有限公司 Waste rock recycling method for refuse dump

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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