CN104152691B - 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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- CN104152691B CN104152691B CN201410388477.1A CN201410388477A CN104152691B CN 104152691 B CN104152691 B CN 104152691B CN 201410388477 A CN201410388477 A CN 201410388477A CN 104152691 B CN104152691 B CN 104152691B
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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 biological dump leaching process of outdoor stripping copper-sulphide ores.
Background technology
Domestic early stage copper mining often adopts strip mining transformation, and such as certain Large-scale Copper adopts strip mining transformation, and existing have outdoor stripping waste containing copper 2.5 hundred million tons, and copper average grade is 0.229%, and copper metal amount is 55.4 ten thousand tons.Peeling off some oxidized ore therebetween through oxidation alteration for many years, in addition production is at that time stacked in barren rock by concentrated, and the oxidisability of Copper Ores mineral in waste rock pile waste containing copper is increased, and averaged oxygen rate is about 5%.
Traditional copper-sulphide ores treatment technology obtains copper ore concentrates by floating and enriching, then produces copper by pyrometallurgical smelting-electrolytic refining process.Because outdoor stripping waste containing copper is lower containing copper grade, degree of oxidation is high, adopts conventional processing technique to be difficult to the Appropriate application realizing this part waste containing copper resource.
Biological metallurgy technology is new industrialization technology that is efficient in nonferrous metal resource exploitation, low consumption, utilizes some can the microorganism of oxygenolysis mineral lattice, is destroyed by mineral lattice, makes wherein valuable metal Element release out, then give enrichment.Being generally used for the mineral that the traditional method such as process low grade ore, complicated mineral, outdoor stripping barren rock, mine tailing stone is difficult to utilize, is the multi-crossed disciplines technology such as biology, metallurgy, chemistry, mineral.
In the biological dump leaching technology of copper mine, Chinese patent (notification number: 1265001C) discloses and utilizes normal temperature acidophilic bacteria thiobacillus ferrooxidant, thiobacillus thiooxidans and ferric oxide leptospirillum to carry out the technique of dump leaching to copper mine.Chinese patent (notification number: 100413983C) discloses and utilizes normal temperature acidophilic bacteria leptospirillum ferriphilum and thermophilic thiobacillus to the leaching method of chalcopyrite.
In biological heap leaching process, acidophilic bacteria is to the oxidation meeting release of heat of ore, and acidophilic bacteria is to heat sensitive, 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 outdoor stripping copper sulfide ore, this kind of 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:
A biological dump leaching process for outdoor stripping copper-sulphide ores, comprises the steps:
(1) gather containing Acidithiobacillus ferrooxidans strain GF (
acidithiobacillusferrooxidans), Acidithiobacillus thiooxidans (
acidithiobacillusthiooxidans), iron protoxide hook end spirobacteria (
leptospirillumferrooxidans) acidic mine water, carry out seed selection, domestication and amplification culture, obtain normal temperature acidophilic bacteria; Gather containing leptospirillum ferriphilum (
leptospirillumferripHilum), bacillus acidophilus belong to bacterium (
acidipHiliumspp.), Sulfobacillus bacterium (
sulfobacillusspp) and thermophilic thiobacillus (
acidithiobacilluscaldus) 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 containing Acidithiobacillus ferrooxidans strain GF, Acidithiobacillus thiooxidans, iron protoxide hook end spirobacteria gathered is added nutritive ingredient: 9K basic medium and FeSO
47H
2o44.2g/L nutrient solution, regulating and controlling temperature 25 ~ 30 DEG C, pH is 1.5 ~ 2.0, cultivates; Domestication and amplification culture condition are: in the environment of 9K basic medium, add the pyrite Ore powder that granularity is less than 0.070mm, the weight of the sulfurous iron ore added 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: by gather belong to bacterium containing leptospirillum ferriphilum, bacillus acidophilus, the acidic mine water of Sulfobacillus bacterium and thermophilic thiobacillus adds nutritive ingredient: 9K basic medium, FeSO
47H
2o22g/L and yeast powder 0.1g/L, regulating and controlling temperature 45 ~ 50 DEG C, pH is 1.8 ~ 2.5, cultivates; Domestication and amplification culture condition are: in the environment of 9K basic medium, add the pyrite Ore powder that granularity is less than 0.070mm, the weight amount of the sulfurous iron ore added 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) ore that outdoor stripping copper-sulphide ores is pulverized, Sieving and casing is less than 2mm is carried out heap to build, and bury breather line, temp probe and stopple coupon underground in the heap of ore deposit; The object burying breather line underground provides oxygen to the bacterium in the heap of ore deposit, buries temp probe and stopple coupon underground so that temperature and analyze Leaching reaction changing conditions in the heap of ore deposit in the heap of Real-Time Monitoring ore deposit.
(3) ore after first building heap with tap water carries out dripping pouring, washes away the mud in ore; Again with dilution heat of sulfuric acid to heap in ore drip pouring, in and ore in basic gangue; Dilute sulphuric acid pH value is 1 ~ 2, and ore deposit heap effluent liquid acidity reaches pH value when being 1 ~ 2, drips to drench and terminates.
(4) the normal temperature acidophilic bacteria of amplification and middle temperature acidophilic bacteria are joined in dilute sulphuric acid respectively, regulate pH1.5 ~ 2.0, normal temperature acidophilic bacteria acidic solution droplets is poured in the heap of ore deposit, when temperature rises to 40 ~ 45 DEG C, middle temperature acidophilic bacteria acidic solution droplets is poured in the heap of ore deposit; Preferred control is dripped and is drenched oxidation reduction potential at 530 ~ 580mv, takes drip pouring daytime, stops night dripping drenching technique.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 energy needed for 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, control to drip according to the temperature variations in the heap of ore deposit and drench speed.
(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 achieve outdoor stripping low-grade copper sulfide ores Bioleaching, 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; The leaching ore deposit bacterium-Acidithiobacillus ferrooxidans strain GF adopted, Acidithiobacillus thiooxidans, iron protoxide hook end spirobacteria, leptospirillum ferriphilum, the bacterium belonging to bacillus acidophilus's genus, the bacterium belonging to Sulfobacillus and thermophilic thiobacillus kind are widely distributed, are easy to obtain.
Accompanying drawing explanation
fig. 1for the process flow sheet of the embodiment of the present invention.
Embodiment
Embodiment one
Domestic certain Large-scale Copper early stage adopts strip mining transformation, and existing have outdoor 2.5 hundred million tons, stripping cupric abandoned mine ore, and copper average grade is 0.229%, and copper metal amount is 55.4 ten thousand tons.In waste containing copper, 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 waste containing copper, main gangue mineral has quartz, chlorite, mica group, kaolinite etc.During oxidation alteration for many years, in addition overburden operation, some oxidized ore is concentrated and is stacked in barren rock, and the oxidisability of the ore mineral of copper in waste rock pile waste containing copper is increased, and averaged oxygen rate is about 5%.
As shown in Figure 1, biological dump leaching process comprises the steps:
(1) seed selection of bacterium, domestication and amplification culture.
Gather the acid drift water of above-mentioned outdoor stripping cupric abandoned mine, in this acid drift water, belong to bacterium, Sulfobacillus bacterium and thermophilic thiobacillus containing Acidithiobacillus ferrooxidans strain GF, Acidithiobacillus thiooxidans, iron protoxide hook end spirobacteria, leptospirillum ferriphilum, bacillus acidophilus.
The seed selection condition of normal temperature acidophilic bacteria is: the acidic mine water of collection is added nutritive ingredient: 9K basic medium and FeSO
47H
2o44.2g/L, regulating and controlling temperature 28 DEG C, pH is 1.7, cultivates; Domestication and amplification culture condition are: in the environment of 9K basic medium, add the pyrite Ore powder that granularity is less than 0.070mm, the sulfurous iron ore amount added 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 nutritive ingredient 9K basic medium, FeSO
47H
2o22g/L and yeast powder 0.1g/L, regulating and controlling temperature 47 DEG C, pH is 1.8, cultivates; Domestication and amplification culture condition are: in the environment of 9K basic medium, add the pyrite Ore powder that granularity is less than 0.070mm, the sulfurous iron ore amount added 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) ore pulverizing, sieve, build heap.
Pulverize after the collection of outdoor stripping low-grade copper sulfide ores, after screening, collection cut size is less than 2mm ore, be transported to stockyard to carry out building heap, build in heap process and keep ore to form nature stacking as far as possible, ore particles is evenly distributed, prevent deflection, avoid being compacted, to keep good ventilation property; Bury breather line, temp probe and stopple coupon underground when heap is built simultaneously.
(3) pre-treatment before biological dump leaching
After ore storage has been built, the ore after first building heap with tap water carries out dripping 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 carries out dripping with dilute sulphuric acid and drenches, in and basic gangue in ore, controlling dilute sulphuric acid acidity is pH value 1 ~ 2, drips and drenches speed control at 2 ~ 10L/m
2h, when stockyard effluent liquid acidity is constant pH value 1 ~ 2 time, dilute sulphuric acid pretreatment stage regards as end.
(4) biological dump leaching.
Normal temperature through three grades of amplification culture is bitten sour bacterium to be joined in dilution heat of sulfuric acid, and dilution heat of sulfuric acid pH value is 1.9, and in leach liquor, bacterial concentration is not less than 10
7individual/ml, carry out dripping pouring to ore deposit heap by Cemented filling, when ore deposit stack temperature reaches 42 DEG C, temperature in three grades of amplification culture is bitten sour bacterium and joins in dilution heat of sulfuric acid, keep dilution heat of sulfuric acid pH value to be 1.8, in leach liquor, bacterial concentration is not less than 10
7individual/ml, carries out dripping pouring to ore deposit heap by Cemented filling.
Sour bacterium is bitten and middle temperature is bitten in the leaching process of sour bacterium, temperature, CO in the heap of Real-Time Monitoring ore deposit at inoculation normal temperature
2, O
2and composition in leach liquor, control to drip according to the temperature variations in the heap of ore deposit and drench speed at 3 ~ 15L/m
2h, a pouring 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 drip pouring daytime when dripping and drenching, and stops night dripping the technique of drenching.
(5) displacement of leach liquor.
Stockyard leach liquor delivers 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, adds iron wire in collection leach liquor to displacement slot and replace, with copper sponge preparation.The iron wire added is the waste and old iron wire after weak acid scrubbing, and add-on is 2.8g/L leach liquor.The copper sponge produced is delivered to copper smelting plant and is produced electrolytic copper, and displaced liquid returns lean solution pond preparation biochemical lixivium.
When extraction time is 180 days, copper leaching rate is more than 58%.
Claims (3)
1. a biological dump leaching process for outdoor stripping copper-sulphide ores, comprises the steps:
(1) gather the acidic mine water containing Acidithiobacillus ferrooxidans strain GF, Acidithiobacillus thiooxidans, iron protoxide hook end spirobacteria, carry out seed selection, domestication and amplification culture, obtain normal temperature acidophilic bacteria; Gather belong to bacterium containing leptospirillum ferriphilum, bacillus acidophilus, the acidic mine water of Sulfobacillus bacterium and thermophilic thiobacillus carries out seed selection, domestication and amplification culture, warm acidophilic bacteria in acquisition;
(2) heap after outdoor stripping copper-sulphide ores pulverizing, screening is built, and bury breather line, temp probe and stopple coupon underground in the heap of ore deposit;
(3) ore after first building heap with tap water carries out dripping and drenches, then drips pouring with dilution heat of sulfuric acid to ore in heap, and dilute sulphuric acid pH value is 1 ~ 2, and ore deposit heap effluent liquid acidity reaches pH value when being 1 ~ 2, drips to drench and terminates;
(4) the normal temperature acidophilic bacteria of amplification and middle temperature acidophilic bacteria are joined in dilute sulphuric acid respectively, regulate pH=1.5 ~ 2.0, normal temperature acidophilic bacteria acidic solution droplets is poured in the heap of ore deposit, when temperature rises to 40 ~ 45 DEG C, middle temperature acidophilic bacteria acidic solution droplets is poured in the heap of ore deposit;
(5), when the Cu2+ concentration of leach liquor is 2 ~ 5g/L in the heap of ore deposit, metal recovery operation is delivered to;
It is characterized in that, in described step (1):
The seed selection condition of normal temperature acidophilic bacteria is: the acidic mine water containing Acidithiobacillus ferrooxidans strain GF, Acidithiobacillus thiooxidans, iron protoxide hook end spirobacteria gathered is added nutritive ingredient: 9K basic medium and FeSO47H2O44.2g/L nutrient solution, regulating and controlling temperature 25 ~ 30 DEG C, pH is 1.5 ~ 2.0, cultivates; Domestication and amplification culture condition are: in the environment of 9K basic medium, add the pyrite Ore powder that granularity is less than 0.070mm, the weight of the sulfurous iron ore added 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, obtains the normal temperature acidophilic bacteria that bacteria concentration is 107 ~ 109/ml;
The seed selection condition of middle temperature acidophilic bacteria is: by gather belong to bacterium containing leptospirillum ferriphilum, bacillus acidophilus, the acidic mine water of Sulfobacillus bacterium and thermophilic thiobacillus adds nutritive ingredient: 9K basic medium, FeSO47H2O22g/L and yeast powder 0.1g/L, regulating and controlling temperature 45 ~ 50 DEG C, pH is 1.8 ~ 2.5, cultivates; Domestication and amplification culture condition are: in the environment of 9K basic medium, add the pyrite Ore powder that granularity is less than 0.070mm, the weight of the sulfurous iron ore added 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, obtains the middle temperature acidophilic bacteria that bacteria concentration is 107 ~ 109/ml.
2. the biological dump leaching process of a kind of outdoor stripping copper-sulphide ores as described in claim 1, is characterized in that:
The ore that the middle Sieving and casing of described step (2) is less than 2mm carries out heap and builds.
3. the biological dump leaching process of a kind of outdoor stripping copper-sulphide ores as described in claim 1, is characterized in that:
Control in step (4) to drip and drench oxidation reduction potential at 530 ~ 580mv, take drip pouring daytime, stop night dripping drenching technique.
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| CN108130424B (en) * | 2016-11-30 | 2019-08-16 | 有研工程技术研究院有限公司 | A kind of method of pyrite cinder biological desulphurization upgrading collaboration recycling valuable metal |
| CN107418913B (en) * | 2017-06-14 | 2020-12-22 | 湖南省农业生物技术研究中心 | Application of microbial agent for converting heavy metal cadmium in polluted soil |
| CN107244698B (en) * | 2017-06-17 | 2019-03-08 | 浙江正奇世荣科技有限公司 | A kind of preparation method of iron oxide red |
| CN107287444B (en) * | 2017-07-12 | 2018-11-13 | 云南省核工业二0九地质大队 | A kind of low grade copper oxide ore dump leaching drop leaching technique |
| CN110616329B (en) * | 2019-09-30 | 2021-04-30 | 长春黄金研究院有限公司 | Method for recovering tin from tin-containing waste |
| 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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