CN104862474A - Method for biologically leaching heavy metal from heavy metal-contained waste based on pH and potential co-regulation - Google Patents
Method for biologically leaching heavy metal from heavy metal-contained waste based on pH and potential co-regulation Download PDFInfo
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Abstract
The invention discloses a method for biologically leaching heavy metal from a heavy metal-contained waste based on pH and potential co-regulation. The method comprises the following steps: in a process of leaching out the heavy metal-contained waste by an acidophilic iron oxide microbial agent, the pH value of the leaching system is controlled within 1.0-4.0 in the whole process; meanwhile, an oxidizing agent is combined with a reducing agent to regulate the redox potential of the leaching system, so that the redox potential of the leaching system is controlled within 420-650 mV; the pH value of the leaching system is gradually increased phase by phase in the leaching process; the redox potential of the leaching system is gradually increased phase by phase; the total leaching time is within 8 hours; and finally, the efficient leaching of the heavy metal from the heavy metal-contained waste by the acidophilic iron oxide microbial agent is realized. The method can accelerate biologic leaching of metal from sludge to shorten the leaching time and to reduce the acid consumption, and can greatly improve the biologic leaching efficiency.
Description
Technical field
The present invention relates to the treatment process containing heavy metal waste in field of Environment Protection, be specifically related to a kind of based on the method for efficient Bioleaching containing heavy metal in heavy metal waste.
Background technology
Electroplating sludge is the ultimate solid waste of Surface Processing Industry, it easily accumulates, instability, difficult degradation, amount large (according to Chinese Ministry of Environmental Protection's statistics about 2,306 ten thousand tons/year), and toxic component is complicated, especially containing a large amount of toxic heavy metals such as chromium, copper, nickel, zinc, state key Hazardous wastes has been listed in.But the various heavy content be rich in electroplating sludge is far above mineral exploration and exploitation grade, and its potential value is very high, is a kind of rare cheap reproducible nonferrous metal resource simultaneously.
Comprehensive utilization of waste materials, turns waste into wealth, from plating waste residue, extract valuable metal, this be save energy and reduce the cost, an important content of Sustainable development.The first step that electric plating sludge resource is recycled is extract technology.Often utilize mineral acid (as HCl, HNO in prior art
3or H
2sO
4deng), the chemical process resource utilization such as organic acid (as citric acid, oxalic acid etc.) or ammonia leaching reclaims heavy metal in electroplating sludge, although heavy metal recovery in electroplating sludge can be realized in the short period of time, but there is such or such limitation in these treatment processs in economy, the feature of environmental protection and technical feasibility, specifically comprise: (1) flow process is longer, cost is higher, metal recovery rate is lower, and separation and Extraction is more difficult, and comprehensive utilization effect is poor; (2) energy consumption is high, and pollute large, operating environment is severe, produces secondary residue and the problem such as waste gas, waste water; (3) traditional recovery method is applicable to process recovery higher-grade, the simple electroplating sludge of composition; For low-grade, complicated component electroplating sludge because of the reason such as technical bottleneck, economical one can only landfill disposal or discarded.
Biological extraction (or bioleaching), as the recycling new technology grown up on biological metallurgy basis in recent years, receives publicity gradually in reclamation of solid wastes process.Bioleaching is the dissolving metal utilizing the effects such as the oxidation of microorganism, acid-soluble, meta-bolites chelating to make in mineral, thus reaches the technology of lixiviate metal object.Cost is low, environmental friendliness owing to having for this technology, material is formed to the features such as not strict restriction, is especially applicable to process complexity, low-grade containing metal solid waste.This technology is applied to that Cu, Co, Ni, Zn, U etc. are low-grade the earliest, dispersion, unmanageable metal sulfide ore or its oxide mineral leaching; or in order to remove the surface impurity (as bio-oxidation pre-treatment gold mine) hindered with metallic contact; and obtained mass-producing application, become the cutting edge technology of mineral wealth processing and utilization in the world.Due to the advantage of biological extraction uniqueness, can be used as important supplement and the improvement of traditional electroplating sludge leaching technologies, also can be the recycling approach that such difficult mud provides new simultaneously, but seldom have in prior art and utilize biological extraction to carry out the relevant report of recycling treatment to the heavy metal in electroplating sludge.
CN 102719657 A Chinese patent literature discloses a kind of method that bioleaching resource utilization reclaims the heavy metal in electroplating sludge, but the method trivial operations, such as add and pre-treatment is carried out (as dried to handling object electroplating sludge, grinding, sieve) and the process such as microorganism collection, and bacterial classification composition simple (only using thiobacillus ferrooxidant or thiobacillus thiooxidans), leaching process long (generally needing 5-6 days), thus to there is treatment rate lower for this technical scheme, integrated operation cost is high, treatment effect is poor, and the problems such as process applicable object single (cupric or nickel mud), actual industrial application may exist certain restricted.
CN 103451437 A Chinese patent literature discloses a kind of recovery method of valuable metal body refuse of cupric cobalt nickel.The method proposes with the copper in biological auxiliary assistance Ore Leaching electroplating sludge or nickel, but acid consumption is large, generation secondary pollution is many, and to be not disclosed in Chemical Leaching be in main technological process, and how biological assistant processes electroplating sludge thus reclaim obtains the metals such as copper nickel.Therefore, the method in fact can only the integrated conduct method of heavy metal in the electroplating sludge at last based on Chemical Leaching.
In sum, there is the problems such as consumption acid is large, handling object is simple, return period is long, processing efficiency is low, treatment effect is desirable not enough in existing electroplating sludge biologic treating technique, is also difficult to realize industrial applications.
Summary of the invention
Technical problem to be solved by this invention is, overcome the deficiency and defect mentioned in above background technology, provide a kind of and be conducive to accelerating Bioleaching metal in sludge, shorten extraction time, reduce acid consumption, greatly improve the biological lixiviate regulated and controled altogether based on pH and current potential of Bioleaching efficiency containing the method for heavy metal in heavy metal waste.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of method that biological lixiviate regulated and controled altogether based on pH and current potential contains heavy metal in heavy metal waste, the method is particularly suitable for the process of electroplating sludge, certainly also can apply to other containing heavy metal waste, specifically comprise the following steps:
Leaching containing in heavy metal waste process addicted to sour Fe forms microbiobacterial agent, the pH value of Whole Process Control Leaching Systems is 1.0 ~ 4.0, combined oxidant and the redox potential of reductive agent to Leaching Systems regulate and control simultaneously, make the oxidation reduction potential control of Leaching Systems at 420mV ~ 650mV; And the pH value of Leaching Systems progressively raises stage by stage in leaching process, the redox potential of Leaching Systems progressively raises stage by stage, leaches total time within 8h, finally realizes addicted to sour Fe forms microbiobacterial agent the efficient leaching containing heavy metal in heavy metal waste.
In above-mentioned method, preferred: described leaching process is divided into and leaches early stage, two stages of later stage of leaching, and control 1.0 ~ 2.5 in the pH value leaching Leaching Systems in early stage, the oxidation reduction potential control of Leaching Systems is at 420mV ~ 450mV simultaneously; The pH value of phase Leaching Systems controls 2.5 ~ 4.0 after leaching, and the oxidation reduction potential control of Leaching Systems is at 550mV ~ 650mV simultaneously.
In above-mentioned method, preferred: describedly leaching early stage, leaching the division in later stage is using when there being the target heavy metal of at least 50% (preferably 50% ~ 90%) to be leached as regulation and control boundary in Leaching Systems; When this starts to enter the regulation and control of leaching the later stage, slowly add oxygenant and heighten system current potential fast to 550mV ~ 650mV, period slowly adds alkaline matter by system pH regulator to 2.5 ~ 3.5.Preferred, described leaching total time is 3h ~ 8h, and it is substantially equal to leach the time that time of taking in early stage and leaching later stage take.
In above-mentioned method, preferred: in described leaching in earlier stage, the pH value of Leaching Systems to be monitored (mainly through pH combined electrode) in real time; When the pH value of Leaching Systems is more than 2.5, acid adding carries out regulation and control makes pH value control 1.0 ~ 2.5; When Leaching Systems pH value lower than 1.0 time, add alkaline matter and carry out regulation and control and make pH value control 1.0 ~ 2.5;
In the described leaching later stage, the pH value of Leaching Systems is monitored in real time; When the pH value of Leaching Systems is more than 4.0, acid adding carries out regulation and control makes pH value control 2.5 ~ 4.0; When Leaching Systems pH value lower than 2.5 time, add alkaline matter and carry out regulation and control pH value is controlled 2.5 ~ 4.0.
Preferred: described acid is sulfuric acid (vitriol oil of such as 98%), and described alkaline matter is CaCO
3.
In above-mentioned method, preferred: in described leaching in earlier stage, the redox potential of Leaching Systems to be monitored (mainly through redox potential combined electrode (vs.Pt, Ag/AgCl)) in real time; When the redox potential of Leaching Systems is lower than 420mV, slowly adds oxygenant and improve current potential to 420mV ~ 450mV; When redox potential is higher than 450mV, adds reductive agent and reduce current potential to 420mV ~ 450mV;
In the described leaching later stage, the redox potential of Leaching Systems is monitored in real time; When the redox potential of Leaching Systems is lower than 550mV, slowly adds oxygenant and improve current potential to 550mV ~ 650mV; When redox potential is higher than 650mV, adds reductive agent and reduce current potential to 550mV ~ 650mV.
Preferred: described oxygenant is hydrogen peroxide or Fe
2(SO
4)
3solution, the concentration of volume percent of described hydrogen peroxide is 10% ~ 30%, described Fe
2(SO
4)
3the concentration of solution is 10 ~ 50g/L; Described reductive agent is FeSO
4solution or Na
2s solution, described FeSO
4solution or Na
2the concentration of S solution is 5 ~ 40g/L.
Technique scheme of the present invention is mainly based on following principle:
1) pH of Leaching Systems of the present invention and redox potential regulation and control combined acid/CaCO
3and multiple oxygenant, reductive agent carry out regulating and controlling stage by stage in real time; PH in Leaching Systems and redox potential have important impact to heavy metals such as Bioleaching Copper in Electroplating Sludge, zinc, chromium, nickel, and it determines existence form after the stripping of heavy metal in electroplating sludge and stripping jointly.Containing a large amount of metals in electroplating sludge, along with the leaching of the object metals such as copper, zinc, nickel and chromium, Fe
3+or Fe
2+equally by a large amount of stripping; The ferrous iron of stripping is become Fe by Fe forms microorganism Quick Oxidation
3+, and system redox potential mainly contains Fe
3+/ Fe
2+ratio determines; When leaching system pH in early stage (pH>2.5) or redox potential too high (redox potential > 450mV, vs Ag/AgCl), easily cause the Fe existed in Leaching Systems
3+precipitation (as: 3Fe
3++ A
++ 2HSO
4 -+ 6H
2o → AFe
3(SO
4)
2(OH)
6+ 8H
+, A=K
+, Na
+, NH
4 +or H
3o
+), this throw out (as jarosite etc.) is attached to the surperficial interaction that inhibit between microorganism, electroplating sludge and leach liquor of electroplating sludge, causes the passivation of mud leaching process; And as too low (the redox potential < 420mV of redox potential in Leaching Systems, vs Ag/AgCl), system redox potential, lower than metal dissolving current potential in electroplating sludge, is thus also unfavorable for the efficient Fast Stripping of metal in sludge.
2) after object metal most of in electroplating sludge is leached, change Leaching Systems regulating strategy, quick adjustment and control system pH (2.5 ~ 4.0) and heighten system redox potential (550mV ~ 650mV), the Fe that now in system, stripping and microbial transformation are formed from electroplating sludge
3+rapid Precipitation, the precipitation formed is main mainly with the jarosite of porous, does not have restraining effect to the Leaching of Heavy Metals in electroplating sludge, and iron precipitation produces acid simultaneously, further promote the leaching of the object metals such as copper, zinc, nickel and chromium, and greatly reduce acid consumption.In addition, suitable pH and redox environment impact are addicted to efficient oxidation ferrous in sour Fe forms microbial growth breeding and system, as Acidithiobacillus ferrooxidans strain GF (Acidithiobacillus ferrooxidans) bacterial strain is more suitable for transforming under lower oxidation reduction condition ferrous, and addicted to cleek end helicobacter (Leptospirillum ferriphilum) bacterial strain can under high redox potential condition Efficient Conversion iron, and also can assist maintenance system redox potential conversely addicted to the ferrous Efficient Conversion effect of sour Fe forms microorganism, the final shortening time, realize Bioleaching high-level efficiency.
Therefore, the present invention is according to electroplating sludge feature of raw material and functional purpose needs, in conjunction with pH-Electric Potential relation and the microbial process of Fe-Cu/Zn/Cr/Ni water system, propose the method that the above-mentioned high-performance bio based on electric potential regulating leaches heavy metal in electroplating sludge, regulate and control to enhance the heavy metal in biological process leaching electroplating sludge altogether by pH and redox potential.
As to the invention described above further improvements in methods, the described group addicted to sour Fe forms complex microbial inoculum composition comprise addicted to sour irony bacterium (Ferroplasma acidiphilum) bacterial strain, cold-resistant addicted to sour iron-oxidizing bacteria (Acidithiobacillus ferrivorans) bacterial strain, Acidithiobacillus ferrooxidans strain GF (Acidithiobacillus ferrooxidans) bacterial strain, addicted to cleek end helicobacter (Leptospirillum ferriphilum) bacterial strain with addicted to sour sulfuration genus bacillus (Sulfobacillus acidophilus) bacterial strain.In the described process addicted to heavy metal in sour Fe forms complex microbial inoculum lixiviate electroplating sludge, Leaching Systems temperature has considerable change, and system temperature nature is increased to 50 DEG C ± 5 DEG C by 25 DEG C ± 5 DEG C, and then is down to room temperature; The not additional temperature control device of described bioleaching process, and different strain in composite fungus agent can play a significant role to be formed in the differing temps stage and has complementary advantages.
Above-mentioned addicted in sour Fe forms complex microbial inoculum, preferred, described addicted to sour irony bacteria strain be preserving number CCTCC NO:M 2015017 addicted to sour irony bacterium, its called after is addicted to sour irony bacterium CS1 (Ferroplasma acidiphilum CS1), and it is preserved in China typical culture collection center (address is positioned at the Wuhan University in Hubei China Wuhan in the school) on January 5th, 2015.This thermophilic acidophilic acid irony bacteria strain can with ferrous and organism yeast powder facultative autotrophy, growth temperature range is 10 DEG C ~ 50 DEG C, and the most applicable growth temperature is about 35 DEG C, growth pH value range 1.0 ~ 3.0, optimum pH about 2.0 is the ancient bacterium of advantage under normal temperature leaching environment.
Above-mentioned addicted in sour Fe forms complex microbial inoculum, preferred, described cold-resistant be the cold-resistant addicted to sour iron-oxidizing bacteria of preserving number CCTCC NO:M 2015009 addicted to sour iron-oxidizing bacteria bacterial strain, its called after is cold-resistant addicted to sour iron-oxidizing bacteria CS12 (Acidithiobacillus ferrivorans CS12), and it is preserved in China typical culture collection center (address is positioned at the Wuhan University in Hubei China Wuhan in the school) on January 5th, 2015.This is cold-resistant can be oxidized to energy chemoautotrophy with ferrous or reduced sulfur addicted to sour iron-oxidizing bacteria bacterial strain, growth temperature range is 10 DEG C ~ 35 DEG C, the most applicable growth temperature is 15 DEG C ~ 20 DEG C, growth pH value range 2.0 ~ 3.5, the most applicable growth pH value is 2.0, is the dominant bacteria under low-temp extraction environment.
Above-mentioned addicted in sour Fe forms complex microbial inoculum, preferred, described Acidithiobacillus ferrooxidans strain GF bacterial strain is the Acidithiobacillus ferrooxidans strain GF of preserving number CCTCC NO:M 2015007, its called after Acidithiobacillus ferrooxidans strain GF CS9 (Acidithiobacillus ferrooxidans CS9), it is preserved in China typical culture collection center (address is positioned at the Wuhan University in Hubei China Wuhan in the school) on January 5th, 2015.This Acidithiobacillus ferrooxidans strain GF bacterial strain can with ferrous and reduced sulfur for energy chemoautotrophy, growth temperature range is 10 DEG C ~ 50 DEG C, the most applicable growth temperature is 30 DEG C ~ 35 DEG C, growth pH value range 1.3 ~ 4.5, the most applicable growth pH value is 2.0 ~ 2.5, is the advantage iron/sulfur oxidizing bacterium kind under normal temperature leaching environment.
Above-mentioned addicted in sour Fe forms complex microbial inoculum, preferred, described addicted to cleek end helicobacter bacterial strain be preserving number CCTCC NO:M 2015010 addicted to cleek end helicobacter, its called after is addicted to cleek end helicobacter CS13 (Leptospirillum ferriphilum CS13), and it is preserved in China typical culture collection center (address is positioned at the Wuhan University in Hubei China Wuhan in the school) on January 5th, 2015.Should be that unique energy source carries out chemoautotrophy with ferrous iron addicted to cleek end helicobacter bacterial strain, growth temperature range is 10 DEG C ~ 50 DEG C, and the most applicable growth temperature is ~ 40 DEG C, growth pH scope 1.0 ~ 2.8, the most applicable growth pH is 1.2 ~ 2.2, is the advantage Fe forms bacterial classification under medium high temperature leaching environment.
Above-mentioned addicted in sour Fe forms complex microbial inoculum, preferred, described addicted to sour sulfuration Bacillus strain be preserving number CCTCC NO:M 2015006 addicted to sour sulfuration genus bacillus, its called after is addicted to sour sulfuration genus bacillus CS5 (Sulfobacillus acidophilus CS5), and it is preserved in China typical culture collection center (address is positioned at the Wuhan University in Hubei China Wuhan in the school) on January 5th, 2015.Should can iron protoxide or reduced sulfur addicted to sour sulfuration Bacillus strain, growth temperature range is 15 DEG C ~ 50 DEG C, and optimum temperuture is 45 DEG C ~ 55 DEG C, growth pH value range 1.0 ~ 2.8, the most applicable growth pH value is 2.0, is the advantage iron/sulfur oxidizing bacterium kind under middle high temperature leaching environment.
Above-mentioned each preferred strain obtains successively in the basic salt/nutritional medium of specific iron content after the oxidation of the iron energy and thermograde screening enrichment.Through the oxidation of the iron energy and thermograde screening enrichment in the basic salt/nutritional medium of specific iron content, mainly refer to using the ferrous energy and thermograde (such as 15 DEG C, 30 DEG C and 45 DEG C) as selective pressure, screening enrichment obtain above-mentioned multiple there is different physics and chemistry and metabolic characteristics and the acidophilic microorganism bacterial strain of efficient oxidation ferrous iron (as addicted to sour irony bacteria strain, cold-resistant addicted to sour iron-oxidizing bacteria bacterial strain, Acidithiobacillus ferrooxidans strain GF bacterial strain, addicted to cleek end helicobacter bacterial strain with addicted to sour sulfuration Bacillus strain etc.).Preferred, comprise the component of following concentration in the basic salt/nutritional medium of the described specific iron content for screening enrichment culture: (NH
4)
2sO
4, 2.5 ~ 3.5g/L; MgSO
47H
2o, 0.3 ~ 0.6g/L; K
2hPO
4, 0.3 ~ 0.7g/L; KCl, 0.1 ~ 0.3g/L; Ca (NO
3)
2, 0.01 ~ 0.05g/L; FeSO
47H
2o, 20 ~ 60g/L; Yeast powder extract, 0.1 ~ 0.6g/L.
The invention described above addicted in sour Fe forms complex microbial inoculum, preferably, described addicted in sour Fe forms complex microbial inoculum addicted to sour irony bacteria strain, cold-resistant addicted to sour iron-oxidizing bacteria bacterial strain, Acidithiobacillus ferrooxidans strain GF bacterial strain, be blended rear formulated by the dense quantitative proportion of bacterium of 2 ~ 4: 2 ~ 4: 1.5 ~ 2.5: 1.0 ~ 3: 1.5 ~ 2.0 addicted to cleek end helicobacter bacterial strain with addicted to sour sulfuration Bacillus strain.Each bacterial strain makes individually pure culture before composite fungus agent, and reach collected by centrifugation thalline after the respective logarithmic growth later stage, counting method of blood cell microscope inspection counts, and is then mixed to form addicted to sour Fe forms complex microbial inoculum according to the dense quantitative proportion of aforementioned preferred bacterium.
The above-mentioned preparation method addicted to sour Fe forms complex microbial inoculum, specifically comprises the following steps:
By described addicted in sour Fe forms complex microbial inoculum addicted to sour irony bacteria strain, cold-resistant addicted to sour iron-oxidizing bacteria bacterial strain, Acidithiobacillus ferrooxidans strain GF bacterial strain, addicted to cleek end helicobacter bacterial strain be placed in the basic salt/nutritional medium of specific iron content addicted to sour sulfuration Bacillus strain and improve and tolerance high ferro domestication step through the composite cultivation of thermograde, the domestication of tolerance mixture-metal gradient pressure formula, the domestication of temperature cycle gradient type, microbe preservation successively, namely preparation obtains addicted to sour Fe forms complex microbial inoculum.
The composite cultivation of described thermograde preferably refers to: the invention described above is screened enrichment addicted to sour irony bacterium CS1, cold-resistant addicted to sour iron-oxidizing bacteria CS12, Acidithiobacillus ferrooxidans strain GF CS9, addicted to cleek end helicobacter CS13 and addicted to sour sulfuration genus bacillus CS5 first respectively at single culture in the basic salt/nutritional medium of specific iron content, reach collected by centrifugation thalline after the respective logarithmic growth later stage, counting method of blood cell microscope inspection counts, and then the preferred ratio according to the dense quantity 2 ~ 4: 2 ~ 4: 1.5 ~ 2.5: 1.0 ~ 3: 1.5 ~ 2.0 of bacterium is mixed to form composite flora; Again using ferrous iron as critical energy, composite flora after preparing in proportion is cultivated respectively under 15 DEG C ~ 20 DEG C, 30 DEG C ~ 35 DEG C and 45 DEG C ~ 50 DEG C three kinds of thermogrades, obtains composite flora I (15 DEG C ~ 20 DEG C), composite flora II (30 DEG C ~ 45 DEG C) and composite flora III (45 DEG C ~ 50 DEG C) respectively.Preferred, comprise the component of following concentration in the basic salt/nutritional medium of described specific iron content: (NH
4)
2sO
4, 2.5 ~ 3.5g/L; MgSO
47H
2o, 0.3 ~ 0.6g/L; K
2hPO
4, 0.3 ~ 0.7g/L; KCl, 0.1 ~ 0.3g/L; Ca (NO
3)
2, 0.01 ~ 0.05g/L; FeSO
47H
2o, 20 ~ 60g/L; Yeast powder extract, 0.1 ~ 0.6g/L.
The domestication of described tolerance mixture-metal gradient pressure formula preferably refers to cultivate three kinds of efficient Fe forms acidophilic microorganism composite flora I, II and III obtaining to be placed in mixture-metal (such as Cu, Zn, Cr, Ni, Fe etc.) concentration pressure gradient is respectively that the solution of 5 ~ 200mmol/L progressively improves domestication by above-mentioned three kinds of differing tempss.Preferred, often take turns in gradient domestication, heavy metal concentration increasing degree is 5 ~ 30mmol/L.
The domestication of described temperature cycle gradient type preferably refer to by three kinds of heavy metal tolerance obtaining after the domestication of tolerance mixture-metal gradient pressure formula addicted to sour Fe forms microbial composite bacteria group, after being about 1: 1: 1 mixing by the dense quantitative proportion of bacterium, then carry out the domestication of temperature cycle gradient in 10 DEG C ~ 50 DEG C temperature ranges.Preferred, the temperature amplification that each gradient adopts is 5 DEG C, and each takes turns circulation domestication number of times preferably 3 ~ 5 times of thermograde, obtain adapting to wide temperature range addicted to sour Fe forms complex microbial inoculum.
Described microbe preservation improves and the domestication of tolerance high ferro preferably refers to: utilize cultured continuously mode, improved by ferrous Energy Load and shorten hydraulic detention time, improving above-mentioned acquisition addicted to the microbe preservation of sour Fe forms complex microbial inoculum and tolerance high ferro ability.Wherein, preferred, FeSO
47H
2the load of O can be increased to 90g/L gradually from 30g/L, and hydraulic detention time then can foreshorten to 36 ~ 48h by 72 ~ 96h.
Through above-mentioned steps, final obtain general-purpose highly effective lixiviate electroplating sludge addicted to sour Fe forms complex microbial inoculum.
Above-mentioned preferred technical scheme fully examines the practical situation of biological process lixiviate electroplating sludge technique, for the key factor of the biological lixiviate of the impact such as variation of ambient temperature pressure and sludge source complicacy, provide a kind of universal, heavy duty detergent can be used for heavy metal in lixiviate electroplating sludge addicted to sour Fe forms complex microbial inoculum and preparation technology thereof.Microorganism strains addicted to comprising the different Cultural types such as low temperature, normal temperature and moderate high temperature and physiological property in sour Fe forms complex microbial inoculum (the five kinds of bacterial strains particularly optimized) provided by the invention, the acquisition of these bacterial strains is not only our long-term experimental study and is filtered out after observing contrast, and any one is wherein compared in the combination of these bacterial strains or two kinds all there is irreplaceable significant technique effect.The functionality advantage of these bacterial strains is complementary and organically combine, not only substantially increase the present invention addicted to the versatility of sour Fe forms complex microbial inoculum and adaptability, and achieve leaching and the recovery of heavy metal in electroplating sludge efficiently, economically, greatly shorten process cycle, reduce wet-leaching process costs.
Compared with prior art, the invention has the advantages that: method of the present invention can accelerate the heavy metal in Bioleaching mud, shorten extraction time, greatly improve Bioleaching efficiency; And method mild condition of the present invention, simple to operate, acid consumption is low, and leaching yield is high, and its production cost significantly reduces than pure chemistry pickling process, and environmental pollution is little, is a kind of minimizing, innoxious and resource utilization leaches novel method containing heavy metal in heavy metal waste.
In addition, in the preferred technical scheme of the present invention, we additionally provide a kind of addicted to sour Fe forms complex microbial inoculum, should be simple addicted to the preparation method of sour Fe forms complex microbial inoculum, and cost is low; Its structure of community and function comparatively perfect, easily cultivate preparation, can heavy metal efficiently in lixiviate electroplating sludge, realizes the innoxious of electroplating sludge and resource utilization, ensure leached mud mud qualified discharge simultaneously, have good economy and environment benefit.Of the present invention also have " high-adaptability of handling object " and " the wide in range property of application of temperature " addicted to sour Fe forms complex microbial inoculum, namely be applicable to sub-prime or the comprehensive high/low grade electroplating sludge such as Treatment of Copper, nickel, zinc, chromium, be applicable to cultivation preparation at long-term Various Seasonal temperature and can heavy metal efficiently in lixiviate electroplating sludge.
In a word, the present invention is that relevant electroplating industry or Surface Treatment Industry garden provide a kind of economical and efficient, can be used for the novel method that electroplating sludge biological process resource utilization reclaims, this method efficiently leaching heavy metal can be applied to except electroplating sludge except other contain heavy metal waste field, as discarded circuit board, containing the efficient leaching of the heavy metal such as municipal sludge or solid waste of heavy metal, there is very strong versatility, high efficiency and economy, solve a difficult problem for the unstable and biological lixiviate length consuming time such as the pollutant sources that runs in biological process practical application and envrionment temperature, have great importance.
Biomaterial preservation situation illustrates:
One strain thermophilic acidophilic acid irony bacteria strain, this bacterial strain be preserving number CCTCC NO:M 2015017 addicted to sour irony bacteria strain, its called after is addicted to sour irony bacterium CS1 (Ferroplasma acidiphilum CS1), it is preserved in China typical culture collection center (being called for short CCTCC) on January 5th, 2015, and address is positioned at the Wuhan University in Hubei China Wuhan in the school.
One strain is cold-resistant addicted to sour iron-oxidizing bacteria bacterial strain, this bacterial strain is the cold-resistant addicted to sour iron-oxidizing bacteria bacterial strain of preserving number CCTCC NO:M 2015009, its called after is cold-resistant addicted to sour iron-oxidizing bacteria CS12 (Acidithiobacillus ferrivorans CS12), it is preserved in China typical culture collection center (being called for short CCTCC) on January 5th, 2015, and address is positioned at the Wuhan University in Hubei China Wuhan in the school.
One strain Acidithiobacillus ferrooxidans strain GF bacterial strain, this bacterial strain is the Acidithiobacillus ferrooxidans strain GF bacterial strain of preserving number CCTCC NO:M 2015007, its called after Acidithiobacillus ferrooxidans strain GF CS9 (Acidithiobacillus ferrooxidans CS9), it is preserved in China typical culture collection center (being called for short CCTCC) on January 5th, 2015, and address is positioned at the Wuhan University in Hubei China Wuhan in the school.
One strain is addicted to cleek end helicobacter bacterial strain, this bacterial strain be preserving number CCTCC NO:M 2015010 addicted to cleek end helicobacter bacterial strain, its called after is addicted to cleek end helicobacter CS13 (Leptospirillum ferriphilum CS13), it is preserved in China typical culture collection center (being called for short CCTCC) on January 5th, 2015, and address is positioned at the Wuhan University in Hubei China Wuhan in the school.
One strain is addicted to sour sulfuration Bacillus strain, this bacterial strain be preserving number CCTCC NO:M 2015006 addicted to sour sulfuration Bacillus strain, its called after is addicted to sour sulfuration genus bacillus CS5 (Sulfobacillus acidophilus CS5), it is preserved in China typical culture collection center (being called for short CCTCC) on January 5th, 2015, and address is positioned at the Wuhan University in Hubei China Wuhan in the school.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is leach extraction method in the embodiment of the present invention 1 and the control methods contrast (ORP-redox potential) at lixiviate Copper in Electroplating Sludge, nickel, zinc and chromium.
Fig. 2 is leach extraction method in the embodiment of the present invention 2 and the control methods contrast (ORP-redox potential) at lixiviate Copper in Electroplating Sludge, nickel, zinc and chromium.
Embodiment
For the ease of understanding the present invention, hereafter will do to describe more comprehensively, meticulously to the present invention in conjunction with Figure of description and preferred embodiment, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, hereinafter used all technical terms are identical with the implication that those skilled in the art understand usually.The object of technical term used herein just in order to describe specific embodiment is not be intended to limit the scope of the invention.
Unless otherwise specified, the various starting material, reagent, instrument and equipment etc. used in the present invention are all bought by market and are obtained or prepare by existing method.
Embodiment 1:
A kind of biological lixiviate regulated and controled altogether based on pH and current potential contains the method for heavy metal in heavy metal waste, what the present embodiment was used contains heavy metal waste mainly from the electroplating sludge of Hunan Electroplate Factory, its appearance presents green, wherein to contain zinc chrome iron, copper nickel takes second place, and water ratio is about 65.41%.This electroplating sludge butt mainly forms metallic element and content is respectively: Fe 12.16%, Zn 4.4%, Cr 4.39%, Cu 1.01% and Ni 1.16% etc. (seeing table 1).
Table 1: electroplating sludge butt main metal element content in embodiment 1
Adopt the method for heavy metal in the biological lixiviate electroplating sludge regulated and controled altogether based on pH and current potential of the present invention to process above-mentioned electroplating sludge, specifically comprise the following steps:
(1) adaptability pre-treatment: the continuous enlarged culturing of pre-lixiviate electroplating sludge adaptability pre-treatment will be carried out addicted to sour Fe forms complex microbial inoculum in the basic salt/nutritional medium of specific iron content; PH value during cultivation is 1.8 ± 0.3, and temperature is 30 ± 5 DEG C, and the basic salt/nutritional medium of specific iron content comprises following component (NH
4)
2sO
4, 3g/L; MgSO
47H
2o, 0.5g/L; K
2hPO
4, 0.5g/L; KCl, 0.1g/L; Ca (NO
3)
2, 0.01g/L; FeSO
47H
2o, 44.7g/L; Yeast powder extract, 0.2g/L; In this mixed system electroplating sludge dry weight (contents on dry basis) be 2% ~ 20% (w/v, namely in often liter of mixed serum cumulative volume, electroplating sludge contents on dry basis is 20-200g; Rear system redox potential>=600mV is cultivated in continuous oscillation, and microbial total concentration at least reaches 1 × 10
8~ 1 × 10
9cells/mL.
(2) repeat pretreatment operation: the adaptability pretreatment operation 2 ~ 5 times repeating above-mentioned steps (1), obtain stable tolerance pre-treatment electroplating sludge characteristic addicted to sour Fe forms complex microbial inoculum.
(3) lixiviate electroplating sludge
Above-mentioned steps (2) is obtained afterwards addicted to sour Fe forms complex microbial inoculum and electroplating sludge, pH be 2 ± 0.2 sour water (regulating tap water pH most 2 ± 0.2 with the vitriol oil) or raffinate (raffinate is the residual solution after Leaching Systems extracting metals, water cycle in industry) be mixed to get mixed slurry, then start to carry out agitation leach, adopt air compressor at bottom ventilation in leaching process, continuously stirring leaches; 20% (v/v) is counted addicted to the inoculum size of sour Fe forms complex microbial inoculum with volume fraction in mixed slurry, mud contents on dry basis (dry weight) is 20% (w/v), leaching containing in heavy metal waste process addicted to sour Fe forms microbiobacterial agent, the pH value of Whole Process Control Leaching Systems is 1.0 ~ 3.5, combined oxidant and the redox potential of reductive agent to Leaching Systems regulate and control simultaneously, make the oxidation reduction potential control of Leaching Systems at 420mV ~ 650mV; Biological leaching process carries out under room temperature, and it is 120 ~ 300rpm that the mixing speed that continuously stirring leaches controls;
The leaching process of the present embodiment is divided into and leaches early stage, two stages of later stage of leaching; Control 1.0 ~ 2.5 in the pH value leaching (time within 4h) Leaching Systems in early stage, the oxidation reduction potential control of Leaching Systems is at 420mV ~ 450mV simultaneously; Early stage the pH value of Leaching Systems is monitored in real time in leaching; When the pH value of Leaching Systems is more than 2.5, adds sulfuric acid and carry out regulation and control and make pH value control 1.0 ~ 2.5; The redox potential of Leaching Systems is monitored in real time early stage in leaching simultaneously; When the redox potential of Leaching Systems is lower than 420mV, slowly add oxygenant volume percent be 30% hydrogen peroxide or concentration be the Fe of 30g/L
2(SO
4)
3solution improves current potential to 420mV ~ 450mV; When redox potential is higher than 450mV, then add the reductive agent FeSO that concentration is 30g/L
4solution or Na
2s solution reduces current potential to 420mV ~ 450mV;
When in Leaching Systems 50% ~ 90% target heavy metal leached after (leaching process later more than 4h), the technology controlling and process strategy that early stage is leached in adjustment is leach the technology controlling and process strategy in later stage; The pH value of phase Leaching Systems controls 2.5 ~ 3.5 after leaching, and the oxidation reduction potential control of Leaching Systems is at 550mV ~ 650mV simultaneously; When entering the leaching later stage, first add above-mentioned oxygenant and heighten Leaching Systems current potential fast to 550mV ~ 650mV, add CaCO simultaneously
3the pH value of regulation and control Leaching Systems is in 2.5 ~ 3.5; The pH value to Leaching Systems is monitored in real time phase after leaching, and when the pH value of Leaching Systems is more than 3.5, acid adding carries out regulation and control makes pH value control 2.5 ~ 3.5; When Leaching Systems pH value lower than 2.5 time, add alkaline matter CaCO
3carrying out regulation and control makes pH value control 2.5 ~ 4.0; Monitor in real time in the described leaching redox potential of later stage to Leaching Systems; When the redox potential of Leaching Systems is lower than 550mV, slowly adds above-mentioned oxygenant and improve current potential to 550mV ~ 650mV; When redox potential is higher than 650mV, adds reductive agent and reduce current potential to 550mV ~ 650mV; Extraction time finally controls at more than 8h, realizes addicted to sour Fe forms microbiobacterial agent the efficient leaching containing heavy metal in heavy metal waste.
Regulate and control altogether through above-mentioned pH and redox potential, finally realize copper, nickel, zinc, chromium leaching yield all reach more than 99% (see Fig. 1).(pH value and electric potential regulating is not applied compared with contrast Bioleaching, extraction time is about at least 10h), within bioleaching process time shorten to 8h, the leaching yields such as copper, nickel, zinc, chromium improve 5% ~ 15%, and acid consumption reduces 5% ~ 20%, react gentleer, visible, the Technology of disclosure invention significantly improves target leaching rate of heavy metals, shortens extraction time, reduce process costs, decrease secondary environmental pollution.
Embodiment 2:
A kind of biological lixiviate regulated and controled altogether based on pH and current potential contains the method for heavy metal in heavy metal waste, what the present embodiment was used contains heavy metal waste mainly from the electroplating sludge of Guangdong Treatment of Industrial Park of Plating, its appearance presents green, wherein based on heavy metals such as cupric nickel chromium triangles, water ratio is about 73.2%.In this electroplating sludge butt, main composition metallic element composition comprises: Cu 9.02%, Ni 5.72%, Cr 10.22%, Zn 1.12% and Fe 5.35% etc. (seeing table 2).
Table 2: electroplating sludge butt main metal element content in embodiment 2
Adopt the method for heavy metal in the biological lixiviate electroplating sludge regulated and controled altogether based on pH and current potential of the present invention to process above-mentioned electroplating sludge, specifically comprise the following steps:
(1) adaptability pre-treatment: the continuous enlarged culturing of pre-lixiviate electroplating sludge adaptability pre-treatment will be carried out addicted to sour Fe forms complex microbial inoculum in the basic salt/nutritional medium of specific iron content; PH value during cultivation is 1.8 ± 0.3, and temperature is 30 ± 5 DEG C, and the basic salt/nutritional medium of specific iron content comprises following component (NH
4)
2sO
4, 3g/L; MgSO
47H
2o, 0.5g/L; K
2hPO
4, 0.5g/L; KCl, 0.1g/L; Ca (NO
3)
2, 0.01g/L; FeSO
47H
2o, 44.7g/L; Yeast powder extract, 0.2g/L; In this mixed system, electroplating sludge contents on dry basis (dry weight) is 2% ~ 20% (w/v); Rear system redox potential>=600mV is cultivated in continuous oscillation, and microbial total concentration at least reaches 1 × 10
8~ 1 × 10
9cells/mL.
(2) repeat pretreatment operation: the adaptability pretreatment operation 2 ~ 5 times repeating above-mentioned steps (1), obtain stable tolerance pre-treatment electroplating sludge characteristic addicted to sour Fe forms complex microbial inoculum.
(3) lixiviate electroplating sludge
Above-mentioned steps (2) is obtained afterwards addicted to sour Fe forms complex microbial inoculum and electroplating sludge pH be 2 ± 0.2 sour water (regulating tap water pH most 2 ± 0.2 with the vitriol oil) or raffinate (raffinate is the residual solution after Leaching Systems extracting metals, water cycle in industry) be mixed to get mixed slurry, then start to carry out agitation leach, adopt air compressor at bottom ventilation in leaching process, continuously stirring leaches; 20% (v/v) is counted addicted to the inoculum size of sour Fe forms complex microbial inoculum with volume fraction in mixed slurry, mud contents on dry basis (dry weight) is 20% (w/v), leaching containing in heavy metal waste process addicted to sour Fe forms microbiobacterial agent, the pH value of Whole Process Control Leaching Systems is 1.0 ~ 3.5, combined oxidant and the redox potential of reductive agent to Leaching Systems regulate and control simultaneously, make the oxidation reduction potential control of Leaching Systems at 420mV ~ 650mV; Biological leaching process carries out under room temperature, and it is 120 ~ 300rpm that the mixing speed that continuously stirring leaches controls;
The leaching process of the present embodiment is divided into and leaches early stage, two stages of later stage of leaching; Control 1.0 ~ 2.5 in the pH value leaching (time within 4h) Leaching Systems in early stage, the oxidation reduction potential control of Leaching Systems is at 420mV ~ 450mV simultaneously; Early stage the pH value of Leaching Systems is monitored in real time in leaching; When the pH value of Leaching Systems is more than 2.5, adds sulfuric acid and carry out regulation and control and make pH value control 1.0 ~ 2.5; The redox potential of Leaching Systems is monitored in real time early stage in leaching simultaneously; When the redox potential of Leaching Systems is lower than 420mV, slowly add oxygenant volume percent be 30% hydrogen peroxide or concentration be the Fe of 30g/L
2(SO
4)
3solution improves current potential to 420mV ~ 450mV; When redox potential is higher than 450mV, then add the reductive agent FeSO that concentration is 30g/L
4solution or Na
2s solution reduces current potential to 420mV ~ 450mV;
When in Leaching Systems 50% ~ 90% target heavy metal leached after (leaching process later more than 4h), the technology controlling and process strategy that early stage is leached in adjustment is leach the technology controlling and process strategy in later stage; The pH value of phase Leaching Systems controls 2.5 ~ 3.5 after leaching, and the oxidation reduction potential control of Leaching Systems is at 550mV ~ 650mV simultaneously; When entering the leaching later stage, first add above-mentioned oxygenant and heighten Leaching Systems current potential fast to 550mV ~ 650mV, add CaCO simultaneously
3the pH value of regulation and control Leaching Systems is in 2.5 ~ 3.5; The pH value to Leaching Systems is monitored in real time phase after leaching, and when the pH value of Leaching Systems is more than 3.5, acid adding carries out regulation and control makes pH value control 2.5 ~ 3.5; When Leaching Systems pH value lower than 2.5 time, add alkaline matter CaCO
3carrying out regulation and control makes pH value control 2.5 ~ 4.0; Monitor in real time in the described leaching redox potential of later stage to Leaching Systems; When the redox potential of Leaching Systems is lower than 550mV, slowly adds above-mentioned oxygenant and improve current potential to 550mV ~ 650mV; When redox potential is higher than 650mV, adds reductive agent and reduce current potential to 550mV ~ 650mV; Extraction time finally controls at more than 8h, realizes addicted to sour Fe forms microbiobacterial agent the efficient leaching containing heavy metal in heavy metal waste.
Regulate and control altogether through above-mentioned pH and redox potential, finally realize copper, nickel, zinc, chromium leaching yield all reach more than 99% (see Fig. 2).With do not apply pH value and compare with the Bioleaching of electric potential regulating, within bioleaching process time shorten to 8h, the leaching yields such as copper, nickel, zinc, chromium improve 5% ~ 15%, acid consumption reduces 5% ~ 20%, reacts gentleer, visible, the Technology of disclosure invention significantly improves target leaching rate of heavy metals, shorten extraction time, reduce process costs, decrease secondary environmental pollution.
Use in each embodiment above the group addicted to sour Fe forms complex microbial inoculum composition comprise addicted to sour irony bacteria strain, cold-resistant addicted to sour iron-oxidizing bacteria bacterial strain, Acidithiobacillus ferrooxidans strain GF bacterial strain, addicted to cleek end helicobacter bacterial strain with addicted to sour sulfuration Bacillus strain.Specifically select addicted to sour irony bacteria strain be preserving number CCTCC NO:M 2015017 thermophilic acidophilic acid irony bacterium CS1 (Ferroplasma acidiphilum CS1), it is preserved in China typical culture collection center on January 5th, 2015; Select cold-resistant be the cold-resistant addicted to sour iron-oxidizing bacteria CS12 (Acidithiobacillus ferrivorans CS12) of preserving number preserving number CCTCC NO:M 2015009 addicted to sour iron-oxidizing bacteria, it is preserved in China typical culture collection center on January 5th, 2015; The Acidithiobacillus ferrooxidans strain GF selected is the Acidithiobacillus ferrooxidans strain GF CS9 (Acidithiobacillus ferrooxidans CS9) of preserving number CCTCC NO:M 2015007, and it is preserved in China typical culture collection center on January 5th, 2015; Select addicted to cleek end helicobacter be CCTCC NO:M 2015010 addicted to cleek end helicobacter CS13 (Leptospirillumferriphilum CS13), it is preserved in China typical culture collection center on January 5th, 2015; Select addicted to sour sulfuration genus bacillus be preserving number CCTCC NO:M 2015006 addicted to sour sulfuration genus bacillus CS5 (Sulfobacillus acidophilus CS5), it is preserved in China typical culture collection center on January 5th, 2015.
Above-mentioned the present embodiment addicted in sour Fe forms complex microbial inoculum, addicted to sour irony bacteria strain, cold-resistant addicted to sour iron-oxidizing bacteria bacterial strain, Acidithiobacillus ferrooxidans strain GF bacterial strain, be blended rear formulated by the dense quantitative proportion of bacterium of 2 ~ 4: 2 ~ 4: 1.5 ~ 2.5: 1.0 ~ 3: 1.5 ~ 2.0 addicted to cleek end helicobacter bacterial strain with addicted to sour sulfuration Bacillus strain.
The present embodiment above-mentioned addicted to sour irony bacterium CS1, cold-resistant addicted to sour iron-oxidizing bacteria CS12, Acidithiobacillus ferrooxidans strain GF CS9, addicted to cleek end helicobacter CS13 and addicted to sour sulfuration genus bacillus CS5 respectively from varying environment by ferrous oxidation and thermograde screening obtain, before composite, first distinguish pure culture to the respective logarithmic growth later stage, then collect thalline; Wherein, in the basic salt culture medium of iron content, add 0.02% (wt%) yeast powder, 20g/L FeSO addicted to sour irony bacterium CS1 simultaneously
47H
2o, pH are 1.0, temperature is cultivate under 45 DEG C of conditions; Cold-resistantly in the basic salt/nutritional medium of iron content, add 30g/L FeSO addicted to sour iron-oxidizing bacteria CS12
47H
2o, pH are 2.0, temperature is cultivate under 20 DEG C of conditions; Acidithiobacillus ferrooxidans strain GF CS9 adds 44.7g/L FeSO in the basic salt/nutritional medium of iron content
47H
2o, pH are 1.8, temperature is cultivate under 30 DEG C of conditions; In the basic salt/nutritional medium of iron content, 30g/L FeSO is added addicted to cleek end helicobacter CS13
47H
2o, pH are 1.8, temperature is cultivate under 40 DEG C of conditions; In the basic salt/nutritional medium of iron content, 0.02% (wt%) yeast powder, 30g/L FeSO is added addicted to sour sulfuration genus bacillus CS5
47H
2o, pH are 1.8, temperature is cultivate under 45 DEG C of conditions.Each bacterial strain after cultivation according to the mixing of certain bacterium dense quantitative proportion, then improves through the composite cultivation of thermograde, the domestication of tolerance mixture-metal gradient pressure formula, the domestication of temperature cycle gradient type, microbe preservation successively and obtains final addicted to sour Fe forms complex microbial inoculum after the step such as tolerance high ferro domestication in the basic salt/nutritional medium of iron content.
Claims (10)
1. the biological lixiviate regulated and controled altogether based on pH and current potential contains a method for heavy metal in heavy metal waste, comprises the following steps:
Leaching containing in heavy metal waste process addicted to sour Fe forms microbiobacterial agent, the pH value of Whole Process Control Leaching Systems is 1.0 ~ 4.0, combined oxidant and the redox potential of reductive agent to Leaching Systems regulate and control simultaneously, make the oxidation reduction potential control of Leaching Systems at 420mV ~ 650mV; And the pH value of Leaching Systems progressively raises stage by stage in leaching process, the redox potential of Leaching Systems progressively raises stage by stage, leaches total time within 8h, finally realizes addicted to sour Fe forms microbiobacterial agent the efficient leaching containing heavy metal in heavy metal waste.
2. method according to claim 1, it is characterized in that: described leaching process be divided into leach early stage, leach two stages of later stage, control 1.0 ~ 2.5 in the pH value leaching Leaching Systems in early stage, the oxidation reduction potential control of Leaching Systems is at 420mV ~ 450mV simultaneously; The pH value of phase Leaching Systems controls 2.5 ~ 4.0 after leaching, and the oxidation reduction potential control of Leaching Systems is at 550mV ~ 650mV simultaneously.
3. method according to claim 2, is characterized in that: described leaching total time is 3h ~ 8h, and it is substantially equal to leach the time that time of taking in early stage and leaching later stage take.
4. method according to claim 2, is characterized in that: in described leaching in earlier stage, monitor in real time the pH value of Leaching Systems; When the pH value of Leaching Systems is more than 2.5, acid adding carries out regulation and control makes pH value control 1.0 ~ 2.5; When Leaching Systems pH value lower than 1.0 time, add alkaline matter and carry out regulation and control and make pH value control 1.0 ~ 2.5;
In the described leaching later stage, the pH value of Leaching Systems is monitored in real time; When the pH value of Leaching Systems is more than 4.0, acid adding carries out regulation and control makes pH value control 2.5 ~ 4.0; When Leaching Systems pH value lower than 2.5 time, add alkaline matter and carry out regulation and control pH value is controlled 2.5 ~ 4.0.
5. method according to claim 4, is characterized in that: described acid is sulfuric acid, and described alkaline matter is CaCO
3.
6. method according to claim 2, is characterized in that: in described leaching in earlier stage, monitor in real time the redox potential of Leaching Systems; When the redox potential of Leaching Systems is lower than 420mV, slowly adds oxygenant and improve current potential to 420mV ~ 450mV; When redox potential is higher than 450mV, adds reductive agent and reduce current potential to 420mV ~ 450mV;
In the described leaching later stage, the redox potential of Leaching Systems is monitored in real time; When the redox potential of Leaching Systems is lower than 550mV, slowly adds oxygenant and improve current potential to 550mV ~ 650mV; When redox potential is higher than 650mV, adds reductive agent and reduce current potential to 550mV ~ 650mV.
7. method according to claim 6, is characterized in that: described oxygenant is hydrogen peroxide or Fe
2(SO
4)
3solution, the concentration of volume percent of described hydrogen peroxide is 10% ~ 30%, described Fe
2(SO
4)
3the concentration of solution is 10 ~ 50g/L; Described reductive agent is FeSO
4solution or Na
2s solution, described FeSO
4solution or Na
2the concentration of S solution is 5 ~ 40g/L.
8. the method according to any one of claim 1 ~ 7, it is characterized in that: the described group addicted to sour Fe forms complex microbial inoculum composition comprises addicted to sour irony bacterium (Ferroplasma acidiphilum) bacterial strain, cold-resistant addicted to sour iron-oxidizing bacteria (Acidithiobacillus ferrivorans) bacterial strain, Acidithiobacillus ferrooxidans strain GF (Acidithiobacillus ferrooxidans) bacterial strain, addicted to cleek end helicobacter (Leptospirillum ferriphilum) bacterial strain with addicted to sour sulfuration genus bacillus (Sulfobacillusacidophilus) bacterial strain.
9. method according to claim 8, it is characterized in that: described addicted to sour irony bacteria strain be preserving number CCTCC M2015017 addicted to sour irony bacterium, its called after is addicted to sour irony bacterium CS1, and it is preserved in China typical culture collection center on January 5th, 2015;
Described cold-resistant be the cold-resistant addicted to sour iron-oxidizing bacteria of preserving number CCTCC M 2015009 addicted to sour iron-oxidizing bacteria bacterial strain, its called after is cold-resistant addicted to sour iron-oxidizing bacteria CS12, and it is preserved in China typical culture collection center on January 5th, 2015;
Described Acidithiobacillus ferrooxidans strain GF bacterial strain is the Acidithiobacillus ferrooxidans strain GF of preserving number CCTCC M 2015007, its called after Acidithiobacillus ferrooxidans strain GF CS9, and it is preserved in China typical culture collection center on January 5th, 2015;
Described addicted to cleek end helicobacter bacterial strain be preserving number CCTCC M 2015010 addicted to cleek end helicobacter, its called after is addicted to cleek end helicobacter CS13, and it is preserved in China typical culture collection center on January 5th, 2015;
Described addicted to sour sulfuration Bacillus strain be preserving number CCTCC M 2015006 addicted to sour sulfuration genus bacillus, its called after is addicted to sour sulfuration genus bacillus CS5, and it is preserved in China typical culture collection center on January 5th, 2015.
10. method according to claim 9, is characterized in that: described addicted in sour Fe forms complex microbial inoculum addicted to sour irony bacteria strain, cold-resistant addicted to sour iron-oxidizing bacteria bacterial strain, Acidithiobacillus ferrooxidans strain GF bacterial strain, be blended rear formulated by the dense quantitative proportion of bacterium of 2 ~ 4: 2 ~ 4: 1.5 ~ 2.5: 1.0 ~ 3: 1.5 ~ 2.0 addicted to cleek end helicobacter bacterial strain with addicted to sour sulfuration Bacillus strain.
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