CN104152691A - Biological heap leaching process for stripping copper sulfide ore in open air - Google Patents
Biological heap leaching process for stripping copper sulfide ore in open air Download PDFInfo
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- CN104152691A CN104152691A CN201410388477.1A CN201410388477A CN104152691A CN 104152691 A CN104152691 A CN 104152691A CN 201410388477 A CN201410388477 A CN 201410388477A CN 104152691 A CN104152691 A CN 104152691A
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- bacterium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P10/20—Recycling
Abstract
The invention provides a biological heap leaching process for stripping copper sulfide ore in open air, which comprises the steps of crushing the copper sulfide ore with low copper grade and high oxidation degree, screening, stacking, dripping water and dilute sulfuric acid in sequence, adjusting the pH value, and then dripping normal-temperature acidophilic bacteria and medium-temperature acidophilic bacteria in sequence according to temperature change to replace copper in leachate. The process has the advantages of simple process, short flow, little pollution, capability of treating low-grade copper sulfide ore and the like; the adopted mineral leaching bacteria are widely distributed and are easy to obtain.
Description
Technical field
The present invention relates to biological metallurgy technical field, be specifically related to the outdoor biological dump leaching process of peeling off copper-sulphide ores.
Background technology
Domestic early stage copper mining often adopts strip mining transformation, and for example certain Large-scale Copper adopts strip mining transformation, and existing have outdoor 2.5 hundred million tons of cupric barren rocks of peeling off, and copper average grade is 0.229%, and copper metal amount is 55.4 ten thousand tons.Through oxidation alteration for many years, produced at that time and peel off therebetween some oxidized ore and concentrated and be stacked in barren rock in addition, the oxidisability of Copper Ores mineral in waste rock pile cupric barren rock is increased, averaged oxygen rate is 5% left and right.
Traditional copper-sulphide ores treatment technology obtains copper ore concentrates by floating and enriching, then produces copper by pyrometallurgical smelting-electrorefining technique.To peel off cupric barren rock lower containing copper grade due to outdoor, and degree of oxidation is high, adopts conventional process technology to be difficult to realize the reasonable utilization of this part cupric barren rock resource.
Biological metallurgy technology is new industrialization technology efficient in nonferrous metal resource exploitation, low consumption, utilizes the microorganism that some can oxygenolysis mineral lattice, and mineral lattice is destroyed, and makes wherein valuable metal Element release out, then give enrichment.Be generally used for and process low grade ore, complicated mineral, the outdoor traditional method such as barren rock, mine tailing stone of peeling off is difficult to the mineral that utilize, and is the multidisciplinary interleaving techniquess such as biology, metallurgy, chemistry, mineral.
In the biological dump leaching technology of copper mine, Chinese patent (notification number: 1265001C) has been announced the technique of utilizing normal temperature acidophilic bacteria thiobacillus ferrooxidant, thiobacillus thiooxidans and ferric oxide leptospirillum copper mine to be carried out to dump leaching.Chinese patent (notification number: 100413983C) has been announced and has been utilized normal temperature acidophilic bacteria leptospirillum ferriphilum and the leaching method of thermophilic thiobacillus to chalcopyrite.
The oxidation meeting release of heat of acidophilic bacteria to ore in biological heap leaching process, and acidophilic bacteria is to heat sensitivity, the dump leaching effect that suitable temperature just can have.
Summary of the invention
The invention provides a kind of heap bioleaching process of low-grade copper sulfide ores, especially for the outdoor copper sulfide ore of peeling off, this class ore copper grade is low and oxidisability is high.This technique has that technique is simple, strains'distribution extensively and be easy to get, flow process is short, less investment, cost are low, pollute little and can process the plurality of advantages such as low-grade copper sulfide ores.
The present invention is achieved by the following scheme:
An outdoor biological dump leaching process of peeling off copper-sulphide ores, comprises the steps:
(1) gather contain have a liking for the ferrous thiobacillus of acid oxidase (
acidithiobacillus ferrooxidans), Acidithiobacillus thiooxidans (
acidithiobacillus thiooxidans), iron protoxide hook end spirobacteria (
leptospirillum ferrooxidans) acidic mine water, carry out seed selection, domestication and amplification culture, obtain normal temperature acidophilic bacteria; Collection contain leptospirillum ferriphilum (
leptospirillum ferripHilum), bacillus acidophilus belong to bacterium (
acidipHilium spp.), sulfuration Bacillaceae bacterium (
sulfobacillus spp) and thermophilic thiobacillus (
acidithiobacillus caldus) acidic mine water carry out seed selection, domestication and amplification culture, warm acidophilic bacteria in acquisition;
The seed selection condition of normal temperature acidophilic bacteria is: the acidic mine water of being had a liking for to the ferrous thiobacillus of acid oxidase, Acidithiobacillus thiooxidans, iron protoxide hook end spirobacteria containing of collection adds nutritive ingredient: 9K basic medium and FeSO
47H
2o 44.2g/L nutrient solution, 25 ~ 30 DEG C of regulating and controlling temperatures, pH is 1.5 ~ 2.0, cultivates; Domestication and amplification culture condition are: in the environment of 9K basic medium, add granularity to be less than the pyrite Ore powder of 0.070mm, the weight of the sulfurous iron ore adding is 1～10% of nutrient solution gross weight, the inoculum size of bacterium is 8～28% of nutrient solution cumulative volume, growth temperature is 25～30 DEG C, and pH value is 1.5～2.0; Amplification culture three times step by step, obtaining bacteria concentration is 10
7～10
9the normal temperature acidophilic bacteria of individual/ml.
The seed selection condition of middle temperature acidophilic bacteria is: the acidic mine water that leptospirillum ferriphilum, bacillus acidophilus belong to bacterium, sulfuration Bacillaceae bacterium and thermophilic thiobacillus that contains gathering is added to nutritive ingredient: 9K basic medium, FeSO
47H
2o 22g/L and yeast powder 0.1g/L, 45 ~ 50 DEG C of regulating and controlling temperatures, pH is 1.8 ~ 2.5, cultivates; Domestication and amplification culture condition are: in the environment of 9K basic medium, add granularity to be less than the pyrite Ore powder of 0.070mm, the weight amount of the sulfurous iron ore adding is 1～10% of nutrient solution gross weight, the inoculum size of bacterium is 8～28% of nutrient solution cumulative volume, growth temperature is 40～45 DEG C, and pH value is 1.5～2.0; Amplification culture three times step by step, obtaining bacteria concentration is 10
7～10
9the normal temperature acidophilic bacteria of individual/ml.
(2) peel off copper-sulphide ores is pulverized, screening particle diameter is less than 2mm ore and pile and build outdoor, and bury breather line, temp probe and stopple coupon underground in pile in ore deposit; The object of burying breather line underground is to provide oxygen to the bacterium in the heap of ore deposit, buries temp probe and stopple coupon underground so that Real-Time Monitoring ore deposit is piled interior temperature and analyzed Leaching reaction changing conditions in the heap of ore deposit.
(3) first with tap water, the ore of piling after building is dripped to pouring, wash away the mud in ore; Drip pouring with dilution heat of sulfuric acid to piling interior ore again, in and ore in basic gangue; Dilute sulphuric acid pH value is 1～2, and it is 1～2 o'clock that ore deposit heap effluent liquid acidity reaches pH value, drips to drench and finishes.
(4) the normal temperature acidophilic bacteria of amplification and middle temperature acidophilic bacteria are joined respectively in dilute sulphuric acid, regulate pH1.5 ~ 2.0, normal temperature acidophilic bacteria acidic solution droplets is poured in ore deposit heap, in the time of temperature rise to 40 ~ 45 DEG C, middle temperature acidophilic bacteria acidic solution droplets is poured in the heap of ore deposit; Preferred control dripped pouring liquid oxidation reduction potential at 530～580mv, takes to drip daytime pouring, stops dripping pouring technique night.Normal temperature acidophilic bacteria and middle temperature acidophilic bacteria are with CO
2for carbon source, pass through Oxidation of Fe
2+, element S and reduction-state compound obtain the required energy of vital process, in leaching process, because bacterium can produce amount of heat to the oxidation of ore, the temperature in the heap of ore deposit will progressively raise.Temperature, CO in the heap of Real-Time Monitoring ore deposit
2, O
2and composition in leach liquor, drip pouring speed according to the temperature variations control in the heap of ore deposit.
(5) Cu of leach liquor in the heap of ore deposit
2+when concentration is 2～5g/L, deliver to metal recovery operation, utilize the Cu in leach liquor in the heap of iron displacement ore deposit
2+.
Adopt bioleaching principle to realize the outdoor low-grade copper sulfide ores Bioleaching of peeling off, have that technique is simple, flow process is short, it is little to pollute and can process the plurality of advantages such as low grade ore; What adopt soaks ore deposit bacterium-have a liking for acid oxidase ferrous thiobacillus, Acidithiobacillus thiooxidans, iron protoxide hook end spirobacteria, leptospirillum ferriphilum, belongs to bacterium that bacillus acidophilus belongs to, belongs to that vulcanize bacterium and the thermophilic thiobacillus kind of Bacillaceae widely distributed, is easy to acquisition.
Brief description of the drawings
fig. 1for the process flow sheet of the embodiment of the present invention.
Embodiment
Embodiment mono-
Domestic early stage certain Large-scale Copper adopts strip mining transformation, and existing have outdoor 2.5 hundred million tons, a cupric abandoned mine ore of peeling off, and copper average grade is 0.229%, and copper metal amount is 55.4 ten thousand tons.In cupric barren rock, major metal mineral are pyrite, secondly be chalcopyrite, have a small amount of rhombohedral iron ore, limonite, copper glance, alpha chalcocite, purple copper, zink sulphide, lead glance, covellite etc., in cupric barren rock, main gangue mineral has quartz, chlorite, mica group, kaolinite etc.Through oxidation alteration for many years, some oxidized ore is concentrated and is stacked in barren rock during overburden operation in addition, and the oxidisability of the ore mineral of copper in waste rock pile cupric barren rock is increased, averaged oxygen rate is 5% left and right.
As shown in Figure 1, biological dump leaching process comprises the steps:
(1) seed selection of bacterium, domestication and amplification culture.
Gather the above-mentioned outdoor acid drift water of peeling off cupric abandoned mine, this acid drift water contains to be had a liking for the ferrous thiobacillus of acid oxidase, Acidithiobacillus thiooxidans, iron protoxide hook end spirobacteria, leptospirillum ferriphilum, bacillus acidophilus and belongs to bacterium, sulfuration Bacillaceae bacterium and thermophilic thiobacillus.
The seed selection condition of normal temperature acidophilic bacteria is: the acidic mine water of collection is added to nutritive ingredient: 9K basic medium and FeSO
47H
2o 44.2g/L, 28 DEG C of regulating and controlling temperatures, pH is 1.7, cultivates; Domestication and amplification culture condition are: in the environment of 9K basic medium, add granularity to be less than the pyrite Ore powder of 0.070mm, the sulfurous iron ore amount adding is 5% of nutrient solution gross weight, and the inoculum size of bacterium is 8～28% of nutrient solution cumulative volume, growth temperature is 25～30 DEG C, and pH value is 1.7; Amplification culture three times step by step, obtaining bacteria concentration is 10
7～10
9the normal temperature acidophilic bacteria of individual/ml.
The seed selection condition of middle temperature acidophilic bacteria is: the acidic mine water of collection is added to nutritive ingredient 9K basic medium, FeSO
47H
2o 22g/L and yeast powder 0.1g/L, 47 DEG C of regulating and controlling temperatures, pH is 1.8, cultivates; Domestication and amplification culture condition are: in the environment of 9K basic medium, add granularity to be less than the pyrite Ore powder of 0.070mm, the sulfurous iron ore amount adding is 9% of nutrient solution gross weight, and the inoculum size of bacterium is 8～28% of nutrient solution cumulative volume, growth temperature is 40～45 DEG C, and pH value is 1.8; Amplification culture three times step by step, obtaining bacteria concentration is 10
7～10
9the normal temperature acidophilic bacteria of individual/ml.
(2) pulverizing of ore, sieve, build heap.
Pulverize after peeling off low-grade copper sulfide ores collection outdoor, after screening, collection cut size is less than 2mm ore, be transported to stockyard and build heap, building in heap process keeps ore to form nature stacking as far as possible, ore particles is evenly distributed, prevent deflection, avoid being compacted, to keep good ventilation property; In the time that building, heap buries breather line, temp probe and stopple coupon underground simultaneously.
(3) pre-treatment before biological dump leaching
After ore storage has been built, the ore after first with tap water, heap being built drips pouring, washes away the mud in ore, drips and drenches speed control at 2～10L/m
2h, dripping the pouring time is 10 days, then drips with dilute sulphuric acid pourings, in and basic gangue in ore, controlling dilute sulphuric acid acidity is pH value 1～2, a pouring speed control is at 2～10L/m
2h, when stockyard effluent liquid acidity is constant during at pH value 1～2, dilute sulphuric acid pretreatment stage is regarded end as.
(4) biological dump leaching.
Join in dilution heat of sulfuric acid biting sour bacterium through the normal temperature of three grades of amplification culture, dilution heat of sulfuric acid pH value is 1.9, and in leach liquor, bacterial concentration is not less than 10
7individual/ml, is delivered to ore deposit heap by pipeline and drips pouring, in the time that ore deposit stack temperature reaches 42 DEG C, joins in dilution heat of sulfuric acid biting sour bacterium through the middle temperature of three grades of amplification culture, and keeping dilution heat of sulfuric acid pH value is 1.8, and in leach liquor, bacterial concentration is not less than 10
7individual/ml, is delivered to ore deposit heap by pipeline and drips pouring.
Bite sour bacterium and middle temperature is bitten in the leaching process of sour bacterium at inoculation normal temperature, temperature, CO in the heap of Real-Time Monitoring ore deposit
2, O
2and composition in leach liquor, drip and drench speed at 3～15L/m according to the temperature variations control in the heap of ore deposit
2h, a pouring liquid oxidation reduction potential, at 530～580mv, drips and drenches liquid pH value 1.5～2.0, drips bacterial concentration in pouring liquid and is not less than 10
7individual/ml takes to drip pouring in the time dripping pouring daytime, stops dripping the technique of drenching night.
(5) displacement of leach liquor.
Stockyard leach liquor is delivered to rich solution pond after intercepting basin is collected, and in leaching process, Real-Time Monitoring leach liquor copper ion concentration, works as Cu
2+when concentration is 3g/L, collects leach liquor and add iron wire to replace in displacement slot, to produce copper sponge.The iron wire adding is the waste and old iron wire after weak acid scrubbing, and add-on is 2.8g/L leach liquor.The copper sponge of producing is delivered to copper smelting plant and is produced electrolytic copper, and displaced liquid is returned to lean solution pond preparation biochemical lixivium.
In the time that extraction time is 180 days, copper leaching rate is more than 58%.
Claims (4)
1. an outdoor biological dump leaching process of peeling off copper-sulphide ores, comprises the steps:
(1) gather and contain the acidic mine water of having a liking for the ferrous thiobacillus of acid oxidase, Acidithiobacillus thiooxidans, iron protoxide hook end spirobacteria, carry out seed selection, domestication and amplification culture, obtain normal temperature acidophilic bacteria; Collection contains the acidic mine water that leptospirillum ferriphilum, bacillus acidophilus belong to bacterium, sulfuration Bacillaceae bacterium and thermophilic thiobacillus and carries out seed selection, domestication and amplification culture, warm acidophilic bacteria in acquisition;
(2) outdoor peeling off after copper-sulphide ores is pulverized, sieved piled and built, and bury breather line, temp probe and stopple coupon underground in the heap of ore deposit;
(3) first with tap water, to heap, the ore after building drips pourings, then drips pouring to piling interior ore with dilution heat of sulfuric acid, and dilute sulphuric acid pH value is 1～2, and it is 1～2 o'clock that ore deposit heap effluent liquid acidity reaches pH value, a pouring end;
(4) the normal temperature acidophilic bacteria of amplification and middle temperature acidophilic bacteria are joined respectively in dilute sulphuric acid, regulate pH=1.5 ~ 2.0, normal temperature acidophilic bacteria acidic solution droplets is poured in ore deposit heap, in the time of temperature rise to 40 ~ 45 DEG C, middle temperature acidophilic bacteria acidic solution droplets is poured in the heap of ore deposit;
(5) Cu of leach liquor in the heap of ore deposit
2+when concentration is 2～5g/L, deliver to metal recovery operation.
2. a kind of outdoor biological dump leaching process of peeling off copper-sulphide ores as described in claim 1, is characterized in that:
The seed selection condition of normal temperature acidophilic bacteria is: the acidic mine water of being had a liking for to the ferrous thiobacillus of acid oxidase, Acidithiobacillus thiooxidans, iron protoxide hook end spirobacteria containing of collection adds nutritive ingredient: 9K basic medium and FeSO
47H
2o 44.2g/L nutrient solution, 25 ~ 30 DEG C of regulating and controlling temperatures, pH is 1.5 ~ 2.0, cultivates; Domestication and amplification culture condition are: in the environment of 9K basic medium, add granularity to be less than the pyrite Ore powder of 0.070mm, the weight of the sulfurous iron ore adding is 1～10% of nutrient solution gross weight, the inoculum size of bacterium is 8～28% of nutrient solution cumulative volume, growth temperature is 25～30 DEG C, and pH value is 1.5～2.0; Amplification culture three times step by step, obtaining bacteria concentration is 10
7～10
9the normal temperature acidophilic bacteria of individual/ml;
The seed selection condition of middle temperature acidophilic bacteria is: the acidic mine water that leptospirillum ferriphilum, bacillus acidophilus belong to bacterium, sulfuration Bacillaceae bacterium and thermophilic thiobacillus that contains gathering is added to nutritive ingredient: 9K basic medium, FeSO
47H
2o 22g/L and yeast powder 0.1g/L, 45 ~ 50 DEG C of regulating and controlling temperatures, pH is 1.8 ~ 2.5, cultivates; Domestication and amplification culture condition are: in the environment of 9K basic medium, add granularity to be less than the pyrite Ore powder of 0.070mm, the weight of the sulfurous iron ore adding is 1～10% of nutrient solution gross weight, the inoculum size of bacterium is 8～28% of nutrient solution cumulative volume, growth temperature is 40～45 DEG C, and pH value is 1.5～2.0; Amplification culture three times step by step, obtaining bacteria concentration is 10
7～10
9the normal temperature acidophilic bacteria of individual/ml.
3. a kind of outdoor biological dump leaching process of peeling off copper-sulphide ores described in claim 1 or 2, is characterized in that: the ore that screening particle diameter is less than 2mm in described step (1) is piled and built.
4. a kind of outdoor biological dump leaching process of peeling off copper-sulphide ores described in claim 1 or 2, is characterized in that: the middle control of step (4) dripped pouring liquid oxidation reduction potential at 530～580mv, takes to drip daytime pouring, stops dripping pouring technique night.
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| CN107287444A (en) * | 2017-07-12 | 2017-10-24 | 云南省核工业二0九地质大队 | A kind of low grade copper oxide ore dump leaching drop drenches technique |
| CN107418913A (en) * | 2017-06-14 | 2017-12-01 | 湖南省农业生物技术研究中心 | A kind of application of the microorganism formulation of Efficient Conversion Heavy Metals in Contaminated Soils cadmium |
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| CN111321294A (en) * | 2020-03-05 | 2020-06-23 | 中国地质大学（武汉） | Method for improving leaching efficiency of chalcopyrite by directionally regulating and controlling indigenous microbial community |
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| CN111321294A (en) * | 2020-03-05 | 2020-06-23 | 中国地质大学（武汉） | Method for improving leaching efficiency of chalcopyrite by directionally regulating and controlling indigenous microbial community |
| CN111321294B (en) * | 2020-03-05 | 2021-07-09 | 中国地质大学（武汉） | Method for improving leaching efficiency of chalcopyrite by directionally regulating and controlling indigenous microbial community |
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