CN104630467B - Biological contact oxidation pond and method for oxidizing Fe2+ in dump leaching process - Google Patents
Biological contact oxidation pond and method for oxidizing Fe2+ in dump leaching process Download PDFInfo
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- CN104630467B CN104630467B CN201310565584.2A CN201310565584A CN104630467B CN 104630467 B CN104630467 B CN 104630467B CN 201310565584 A CN201310565584 A CN 201310565584A CN 104630467 B CN104630467 B CN 104630467B
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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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Abstract
The invention discloses a biological contact oxidation pond and a method for oxidizing Fe<2+> in a dump leaching process. The biological contact oxidation pond comprises a ferrous oxidation tank, wherein a support is arranged in the ferrous oxidation tank, a microbial carrier is arranged on the support, and an aeration pipeline is arranged at the bottom of the ferrous oxidation pond. According to the biological contact oxidation pond and the method for oxidizing the Fe<2+> in the dump leaching process, in the ferrous oxidation tank, microbes adsorbed by the microbial carrier are taken as a main body, the microbes are promoted to efficiently oxidizing Fe<2+> to generate Fe<3+> in the biological contact oxidation tank by aerating and controlling appropriate temperature, pH and nutritional conditions, high microbial activity in a dump leaching system and high oxidation reduction potential in solution are realized, and oxidation efficiency of sulphide ore is improved.
Description
Technical field
The present invention relates to biological metallurgy field, in particular it relates to a kind of for Fe in heap leaching process2+The life of oxidation
Thing contact-oxidation pool and method.
Background technology
In biological heap leaching process, the upgrowth situation of acidophilic microorganism directly influences Fe in heap leaching system2+It is oxidized to Fe3+
Ability.But due to bad environments in heap leaching system, nutrition and oxygen deficiency, the micro organism quantity and activity in ore deposit heap has
Limit, to Fe2+Dysoxidation, have impact on oxidant Fe3+Regeneration, and then to practical application effect produce extreme influence.Early stage
Research have shown that the oxidation rate of sulphide ore is mainly subject to dissolved oxygen, oxidation-reduction potential and microbial activity in ore deposit heap
Affect.In the case of without enough microbial activities, ferro element is mainly with Fe in system2+In the form of, at this moment electronics is from sulphur
Compound is transferred to Fe3+And it is translated into Fe2+If microbial activity is sufficient, the Fe in the presence of iron-oxidizing bacterium2+Can weight
Newly it is converted into Fe3+, enable leaching process to continue, conversely, Fe3+Consumption will cause Fe in solution2+Occupy an leading position, from
And interrupt leaching.The dissolving of pyrite needs higher oxidation-reduction potential, if Fe2+Dysoxidation, in redox
Current potential is less than 800mV（Vs SHE, similarly hereinafter）When, oxidation rate is slower.
Microbial activity depends on the content of pH, temperature, dissolved oxygen and nutriment in heap leaching system.Current production
Practice mainly attempts in ore deposit heap the activity of raising acidophilus iron sulfur oxidizing bacterium to improve the leaching efficiency of sulphide ore, such as patent
Attempt improving the activity of microorganism by modes such as bottom ventilations in ore deposit heap in CN1509341.But according to ore deposit heap feature and
The growth characteristics of acidophilus iron-oxidizing bacterium, are relatively difficult to the growing environment of regulating and controlling microbial optimization in ore deposit heap（Dissolved oxygen, nutrition
Material etc.）, and the condition needed for growth of microorganism is with ore deposit heap optimum leaching condition and differs, it is difficult to realize the big of microorganism
Amount flourish and Fe2+Efficient oxidation, it is difficult to realize oxidation-reduction potential high in system, and if from the external solution of heap
Microbial activity problem is more feasible.The items that biological contact oxidation pond can be very good to control needed for growth of microorganism are optimum
Environmental condition, realizes that microorganism is rapid and raised growth is bred, such as in sewage disposal, using heterotrophism in biological contact oxidation pond
The raised growth of microorganism, degradation of organic substances matter, realizes Water warfare（Such as patent CN101481173, CN101643272）.For
Environmental condition in biological heap leaching process required for autotrophic microbe growth, designs suitable biological contact oxidation pond, in ore deposit heap
It is outer to realize the optimized growth conditions of acidophilus iron-oxidizing bacterium, so as to realize heap leaching system in microorganism activity improve and Fe2+
Successional efficient oxidation, is of great significance for biological oxidation efficiency tool in dump leaching is improved.
The content of the invention
It is an object of the invention to provide a kind of for Fe in heap leaching process2+The biological contact oxidation pond and method of oxidation, leads to
The concentration and activity that microorganism in heap leaching system is improved in out-pile biological contact oxidation pond is crossed, promotes Fe2+Oxidation, improve spray
The oxidation-reduction potential of liquid is drenched, oxidation-reduction potential higher in heap leaching system and microbial biomass is realized, dump leaching mineral are realized
Efficient oxidation, saves production cost.
For achieving the above object, present invention employs following technical scheme：
One kind is for Fe in heap leaching process2+The biological contact oxidation pond of oxidation, the biological contact oxidation pond includes ferrous iron
Oxidation pond 4, arranges support 7 in ferrous oxidation pond 4, and microbe carrier 6 is arranged on support 7, and bottom of pond arranges aerating pipelines 5.
The volume in the ferrous oxidation pond 4 be 1000-50000 cubic meters, depth 1-10 rice.
The microbe carrier 6 is hung on support 7 loaded in nylon net bag, is positioned over water level three in ferrous oxidation pond 4
Less than/mono-.So ensure can extract the solution of 2/3 volume in pond every time, while ensure carrier be not exposed to solution it
Outward.
The volume of the microbe carrier 6 accounts for the 2%-20% of ferrous oxidation pond body product.
The microbe carrier 6 is one or more in activated carbon, porous ceramic grain, rejected ore, zeolite, it is also possible to root
Suitable biological adsorption material is selected according to local actual environment and material cost.
In the present invention, in ferrous oxidation pond, bottom of pond laying aerating pipelines 5, carry out aeration, arrange on the aerating pipelines 5 and expose
Gas head 9.
Present invention also offers a kind of based on above-mentioned for Fe in heap leaching process2+The dump leaching of the biological contact oxidation pond of oxidation
Method, the method comprising the steps of：
1）Acidophilus iron-oxidizing bacterium from local sulfide ore stack leachate or acid wastewater in mine is in ferrous oxidation pond
Middle Amplification Culture, 24-72 hours are contacted with microbe carrier, and the absorption of acidophilus iron-oxidizing bacterium is fixed on microbe carrier；
2）Exposed into air by aerating pipelines in ferrous oxidation bottom of pond, make dissolved oxygen concentration in ferrous oxidation pond reach 4-
7mg/L, for the growth of acidophilus iron-oxidizing bacterium oxygen is provided；
3）Ore deposit heap leaching liquid or acid wastewater in mine are passed through in ferrous oxidation pond, and aoxidize 24- in ferrous oxidation pond
72 hours, after the oxidation-reduction potential of solution in pond is more than or equal to 850mV, the solution extracted in pond was sprayed as ore deposit heap
Liquid；
4）Supplement the solution lost in ferrous oxidation pond with ore deposit heap leaching liquid or acid wastewater in mine again, continue to aoxidize
Fe2+, ore deposit heap spray liquid is used further to, move in circles to the oxidation of ore deposit heap and complete.
The acidophilus iron oxidizing microorganisms that the present invention is inoculated on microbe carrier are generally Thiobacillus ferrooxidans, oxidation Asia
The Mixed Microbes such as cleek end spirillum.Initial period, mixed bacteria is from enrichment training in dump leaching leachate, local acid wastewater in mine
Support, the Amplification Culture in biological contact oxidation pond.In typically choosing the dump leaching leachate or acid waste water for enriched microorganism
Concentration of iron be 1~10g/L, pH value 1.5~2.5, containing acidophilus iron oxidizing microorganisms.The enriched medium of bacterial classification is 9K culture mediums
（(NH4)2SO43g/L, K2HPO40.5g/L, KCl0.1g/L, MgSO40.5g/L, Ca (NO3)20.01g/L）, add 10g/L
FeSO4, pH1.0-2.5.
In the present invention, the nutrition needed for growth of microorganism is added in biological contact oxidation pond, in whole process, make pond
In (NH4)2SO4Concentration reaches 1-3g/L, K2HPO4Concentration reaches 0.2-0.5g/L, and KCl concentration reaches 0.02-0.1g/L, MgSO4
Concentration reaches 0.2-0.5g/L, Ca (NO3)2Concentration reaches 0.005-0.01g/L, and microorganism concn is finally reached 10 in bacterium solution7-
108Individual/mL.
In the present invention, biological contact oxidation pond temperature control notices that biology connects at 30 DEG C~40 DEG C when winter temperature is low
The insulation of tactile oxidation pond, summer notes radiating.
In the present invention, when ore deposit heap leaching liquid pH value is less than 1.5, or Fe3+When concentration is more than 25g/L, with lime neutralization it is made
PH value is to 1.5~2.0, Fe3+Concentration is less than 20g/L, subsequently into biological contact oxidation pond.
The present invention in order to solve sulphide ore heap leaching process in microorganism Fe in heap2+The low problem of oxidation efficiency, takes life
The mode of thing contact-oxidation pool.By arranging microbe carrier in ferrous oxidation pond, bottom of pond carries out aeration, and control is suitable micro-
Biological growth conditions（Including temperature, pH and nutriment etc.）, realize in heap leaching process Fe in biological contact oxidation pond2+It is fast
Speed oxidation, is particularly well-suited to promote the dump leaching pre-oxidation of pyrite, such as the biological pre-oxidation of auriferous pyrite and using useless
Barrow heap produces acid for dump leaching spray liquid etc..
Beneficial effects of the present invention are as follows：
1）The Fe of regulating and controlling microbial is generally difficult in ore deposit heap2+Oxidation, but can more simply have in out-pile by this method
The regulation microorganism optimized growth condition of effect, realizes Fe2+Efficient oxidation, promote oxidant Fe3+Regeneration；
2）In heap leaching system, high potential can be realized using the present invention（>850mV）Spray liquid, improve whole system
In oxidation-reduction potential, be conducive to the dissolving of sulphide ore；
3）Substantial amounts of microorganism, nutriment, dissolved oxygen can enter into ore deposit heap by spray in biological contact oxidation pond
In, while also improving microbial activity and mineral oxide speed in ore deposit heap；
4）The substantial amounts of microorganism that microbe carrier is adsorbed in biological contact oxidation pond, can persistently ensure to newly entering molten
The efficient oxidability of liquid；
5）Present invention process is simple, and cost-effective, procedure parameter is easily controlled.Big tune need not be carried out to heap leaching system
It is whole, complete by slightly being transformed using the existing solution pool of heap leaching system.
Description of the drawings
Fig. 1 is using the dump leaching process schematic flow sheet of biological contact oxidation pond of the present invention；
Fig. 2 is the structural representation that microbe carrier is arranged on support of the present invention；
Fig. 3 is the structural representation of aerating pipelines of the present invention；
Fig. 4 is the concrete technology flow process figure of the embodiment of the present invention 1；
Fig. 5 is the concrete technology flow process figure of comparative example of the present invention 1；
Fig. 6 is the concrete technology flow process figure of the embodiment of the present invention 2；
Reference：1st, ore deposit heap；2nd, liquid pool is leached；3rd, pump；4th, ferrous oxidation pond；5th, aerating pipelines；6th, microbe carrier；
7th, support；8th, qualified liquid pool；9th, aeration head.
Specific embodiment
Below with the drawings and specific embodiments, the present invention is further detailed explanation.
As shown in figure 1, by the present invention biological contact oxidation pond be used in heap leaching system, the system can include ore deposit heap 1,
Leach liquid pool 2, pump 3, ferrous oxidation pond 4, aerating pipelines 5, microbe carrier 6, support 7, qualified liquid pool 8.Its Concrete workflow
Journey can be leachate pond 2 in ore deposit heap leaching solution be drawn in ferrous oxidation pond 4 by pump 3, by biological contact oxidation pond in it is thermophilic
Sour iron-oxidizing bacterium Oxidation of Fe2+, when solution oxide reduction potential in biological contact oxidation pond（Eh）During more than 850mV, pond is extracted
The 2/3 of middle solution is entered in qualified liquid pool 8, then as the spray liquid of ore deposit heap 1.
Embodiment 1
Have in difficult-treating gold mine very big one be pyrite parcel gold, but due to the Biooxidation Rate of pyrite it is inadequate
Hurry up, this part gold is difficult to effectively be exposed, and causes Heap leaching effectiveness not high, long the production cycle, so improving the oxygen of pyrite
Change efficiency for improve production efficiency, reduce production cost significant.
In the biological dump leaching pre-oxidation commerical test of certain low-grade intractable gold mine（Technological process such as Fig. 4）, ore sulfur-bearing
5.3%th, arsenic 0.2%, gold grade 2.3g/t.Ore reduction to granularity is less than into 20mm, auriferous pyrite leaching heap, ore deposit stack height is constructed
10 meters.The dump leaching initial stage, from enrichment culture acidophilus iron-oxidizing bacterium group in local acid waste water（Medium component：9K, 10g/L
FeSO4, pH1.8）, mainly include ferrous oxide hook end spirillum and Thiobacillus ferrooxidans etc..Flora is in bio-contact oxidation
Amplification Culture in pond（The volume in pond is 50000 cubic metres, and depth is 1 meter）, nutrient solution is with local acid waste water addition in pond
Growth of microorganism desired nutritional element（(NH4)2SO42g/L, K2HPO40.3g/L, KCl0.05g/L, MgSO40.3g/L, Ca
(NO3)20.01g/L）Configure and form；Load activated carbon in nylon net bag as microbe carrier, be installed on PVC and build support
On, and below 1/3rd, absorbent charcoal carrier accounts for the 2% of pond body product to be positioned over water level in pond；Aeration is carried out in pond, it is molten in solution
Solution oxygen concentration is 4.2-6.5mg/L.After 72h, when solution oxide reduction potential is more than or equal to 850mV in pond, in extracting pond
The 2/3 of solution enters spray liquid pool as the spray liquid of ore deposit heap, starts spray.In production process, the pH of typical leachate exists
1.2-1.6, total concentration of iron 12-18g/L, Fe2+Concentration 1.5-3.6g/L, Eh650-680mV.Solution ph is little in liquid pool is leached
When 1.5, neutralized using lime stone in neutralization pond, the pH value for making leachate is controlled 1.5~1.9, and by Fe3+Concentration is controlled
Less than 15g/L；Leachate after neutralization is delivered in biological contact oxidation pond, solution temperature is controlled at 30-40 DEG C in pond, led to
Aeration control Dissolved Oxygen concentration Control is crossed in 5.0-7.1mg/L, nutrient concentrations in solution are detected weekly, be added suitable
Suitable concentration range.The mean residence time of solution is 48h in biological contact oxidation pond, and the oxidation of acidophilus iron is thin in carrier and solution
Bacterium is by Fe2+It is oxidized to Fe3+, more than after 850mV, ore deposit is used in 2/3 return spray operation of solution to the oxidation-reduction potential of leachate
Heap leaching liquid supplements biological contact oxidation pond solution.Circulated sprinkling, dump leaching through 300 days is pre-oxidized, and oxidation of pyrite rate is
73.5%, scrubbed operation, alkali process neutralization step, Cyanide Leaching operation afterwards, final gold leaching rate is 84.3%.
Comparative example 1
In order to make comparisons with embodiment 1, size of the biological contact oxidation pond to Heap leaching effectiveness facilitation is inquired into, be provided with
Experimental Comparison example 1（Technological process such as Fig. 5）.Test adopts traditional dump leaching mode, using the same ore of embodiment 1.By ore deposit
Stone is crushed to granularity and is less than after 20mm, constructs auriferous pyrite leaching heap, 10 meters of ore deposit stack height.Every bar that embodiment 1 is adopted
Part is consistent.Compared with Example 1, the ore deposit heap leaching liquid in liquid pool is leached without biological contact oxidation pond, be directly entered spray
Liquid pool is leached as spray liquid, circulated sprinkling.Pre-oxidize through the dump leaching of 300 days, oxidation of pyrite rate is only 30.3%.Jing is washed
Operation, alkali process neutralization step, Cyanide Leaching operation are washed, final ore gold leaching rate is only 56.2%.
Embodiment 2
In the biological dump leaching commerical test of certain low-grade secondary copper mine（Technological process such as Fig. 6）, composition of ores is
Cu0.37%, Fe3.59%, S5.28%.Main copper mineral is vitreous copper, covellite and enargite, wherein vitreous copper in ore
More than 90% is accounted for, pyrite content 10%, main gangue mineral is feldspar, quartz, sericite.Secondary copper mine is crushed to granularity and is less than
Copper mine leaching heap is constructed after 40mm.The test production phase is continuously sprayed using local acid waste water to copper mine leaching heap, acid waste water
PH2.1, total iron content 3g/L, Eh is 690mV.But because in production process, the consumption acid of ore deposit heap is larger, and the acidity of spray liquid is not
Enough, production efficiency is relatively low.Increase in test and use biological contact oxidation pond（Volume is 1000 cubic metres, 10 meters of depth）, utilize
Copper mine hillock（Copper mine leaching rate more than 85%, containing 10% or so pyrite）Acid is produced, for the spray liquid of copper mine heap.Leachate
Jing after extraction process, raffinate enters biological contact oxidation pond to leachate in pond.Then cultivate in biological contact oxidation pond from
The acidophilus iron-oxidizing bacterium group being enriched with local sulfide ore stack leachate（Enrichment culture based component：9K culture mediums, 10g/L
FeSO4, pH1.5）, mainly include ferrous oxide hook end spirillum and Thiobacillus ferrooxidans etc..Add in biological contact oxidation pond
Plus growth of microorganism desired nutritional element（(NH4)2SO41g/L, K2HPO40.2g/L, KCl0.03g/L, MgSO40.3g/L, Ca
(NO3)20.01g/L）；Load porous ceramic grain in nylon net bag as microbe carrier, be positioned in support constructed by PVC and put
Below 1/3rd, wherein porous ceramic grain volume accounts for the 20% of pond body product to be placed in water level in pond；Aeration is carried out in pond, it is molten in solution
Solution oxygen concentration is maintained at 5.0-6.6mg/L, and solution temperature is controlled at 30-40 DEG C in pond.Fe in ferrous oxidation pond2+By microorganism oxygen
Turn to Fe3+, low sour low iron is entered after the oxidation-reduction potential of leachate is more than 850mV and sprays liquid pool, as copper mine hillock
（Cu leaching rates are more than 80%）Spray liquid.Hillock leachate is directly entered peracid high ferro spray liquid pool as the leaching of copper mine heap
Go out liquid.Then by copper mine leachate Jing extraction process, the pH of raffinate in 1.4-1.6, total concentration of iron 10-14g/L, Fe2+Concentration
1.2-3.3g/L, Eh663-690mV.The oxidized Eh850mV Posterior circles that reach of raffinate Jing biological contact oxidation ponds are used as copper mine
The spray liquid of hillock, continues the Oxidation Leaching of pyrite in copper mine hillock.The pH of leachate is reduced to 1.0 or so, acidity
Reach 18-23g/L, Fe3+Concentration reaches 20-25g/L.In experimentation, the temperature in biological contact oxidation pond is maintained at 30-40
DEG C, dissolved oxygen concentration is maintained at 5.0-6.6mg/L, and nutrient also ensures within the scope of suitably.After 24-48h, biology connects
More than after 850mV, 2/3 is used for spray liquid to Eh, is then supplemented with raffinate, moves in circles in tactile oxidation pond.The Jing heaps of 120 days
Leaching, the leaching rate of copper reaches 85%.Acid is produced in test using the pyrite in copper mine hillock realize secondary copper mine heap leaching process
In the supply of sour iron, without the need for the extra addition sulfuric acid in copper mine spray liquid again, production cost is reduced, while higher in spray liquid
Sour concentration of iron, also substantially increase the leaching rate of copper, shorten period of heap leaching.
Claims (9)
1. a kind of for Fe in heap leaching process2+The biological contact oxidation pond of oxidation, it is characterised in that the biological contact oxidation pond
Including ferrous oxidation pond (4), support (7) is set in ferrous oxidation pond (4), microbe carrier (6) is set on support (7), it is sub-
Iron oxidation pond bottom arranges aerating pipelines (5)；
The volume of the ferrous oxidation pond (4) be 1000-50000 cubic meters, depth 1-10 rice.
2. according to claim 1 for Fe in heap leaching process2+The biological contact oxidation pond of oxidation, it is characterised in that institute
During microbe carrier (6) is stated loaded on nylon net bag, hang on support (7), be positioned over water level three in ferrous oxidation pond (4)/
Less than one.
3. according to claim 1 for Fe in heap leaching process2+The biological contact oxidation pond of oxidation, it is characterised in that institute
The volume for stating microbe carrier (6) accounts for the 2%-20% of ferrous oxidation pond (4) volume.
4. according to claim 1 for Fe in heap leaching process2+The biological contact oxidation pond of oxidation, it is characterised in that institute
State microbe carrier (6) be activated carbon, one or more in porous ceramic grain, rejected ore, zeolite.
5. it is based on described in claim 1 for Fe in heap leaching process2+The heap leaching method of the biological contact oxidation pond of oxidation, the side
Method is comprised the following steps：
1) the acidophilus iron-oxidizing bacterium from local sulfide ore stack leachate or acid wastewater in mine expands in ferrous oxidation pond
Big culture, 24-72 hours are contacted with microbe carrier, and the absorption of acidophilus iron-oxidizing bacterium is fixed on microbe carrier；
2) exposed into air by aerating pipelines in ferrous oxidation pond bottom of pond, make dissolved oxygen concentration in ferrous oxidation pond reach 4-7mg/
L, for the growth of acidophilus iron-oxidizing bacterium oxygen is provided；
3) ore deposit heap leaching liquid or acid wastewater in mine are passed through in ferrous oxidation pond, and 24-72 hours, Dang Chizhong are aoxidized in pond
When the oxidation-reduction potential of solution is more than or equal to 850mV, the solution extracted in ferrous oxidation pond is used as ore deposit heap spray liquid；
4) Oxidation of Fe is continued with the solution taken away in ore deposit heap leaching liquid or acid wastewater in mine supplement ferrous oxidation pond again2+,
Ore deposit heap spray liquid is used further to, is moved in circles to the oxidation of ore deposit heap and is completed.
6. heap leaching method according to claim 5, it is characterised in that the acidophilus iron-oxidizing bacterium mainly includes that oxidation is sub-
Cleek end spirillum and Thiobacillus ferrooxidans.
7. heap leaching method according to claim 5, it is characterised in that the temperature control in the ferrous oxidation pond is in 30-40
℃。
8. heap leaching method according to claim 5, it is characterised in that add in ferrous oxidation pond and be adapted to the oxidation of acidophilus iron
The nutriment of bacterium, makes (NH4)2SO4Concentration reaches 1-3g/L, K2HPO4Concentration reaches 0.2-0.5g/L, and KCl concentration reaches
0.02-0.1g/L, MgSO4Concentration reaches 0.2-0.5g/L, Ca (NO3)2Concentration reaches 0.005-0.01g/L, is the oxidation of acidophilus iron
The growth of bacterium provides nutrition.
9. heap leaching method according to claim 5, it is characterised in that when ore deposit heap leaching liquid pH value is less than 1.5, or Fe3+It is dense
When degree is more than 25g/L, its pH value is made to 1.5~2.0, Fe with lime neutralization3+Concentration is less than 20g/L, subsequently into ferrous oxidation
Chi Zhong.
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| CN105200232B (en) * | 2015-08-27 | 2017-12-12 | 中国科学院过程工程研究所 | A kind of method that copper sulfide mineral biological dump leaching Water spray starts |
| CN105603187B (en) * | 2016-01-13 | 2017-07-11 | 南华大学 | Quick Oxidation Fe2+Moving-bed bioreactor and Quick Oxidation Fe2+Method |
| CN107673486B (en) * | 2017-11-08 | 2020-05-22 | 东华理工大学 | Composite packed column mechanism, bacterium immobilization method and leachate treatment method |
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| CN1031860A (en) * | 1987-07-10 | 1989-03-22 | 巨人湾生物科技有限公司 | The chemical/biological process of oxidize multimetallic sulphide ores |
| CN1387580A (en) * | 1999-09-01 | 2002-12-25 | 比利顿股份有限公司 | Base metal recovery from tailings drum by bacterial oxidation |
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| CN1031860A (en) * | 1987-07-10 | 1989-03-22 | 巨人湾生物科技有限公司 | The chemical/biological process of oxidize multimetallic sulphide ores |
| CN1387580A (en) * | 1999-09-01 | 2002-12-25 | 比利顿股份有限公司 | Base metal recovery from tailings drum by bacterial oxidation |
| CN102031390A (en) * | 2010-12-23 | 2011-04-27 | 紫金矿业集团股份有限公司 | Process for extracting gold from low-grade difficultly-treatable gold ore containing arsenic and carbon |
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