CN104862474B - A kind of biological extraction regulated and controled altogether based on pH and current potential is containing the method for heavy metal in heavy metal waste - Google Patents
A kind of biological extraction regulated and controled altogether based on pH and current potential is containing the method for heavy metal in heavy metal waste Download PDFInfo
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Abstract
A kind of biological extraction regulated and controled altogether based on pH and current potential is containing the method for heavy metal in heavy metal waste, comprise the following steps: during leaching containing heavy metal waste addicted to acid ferrum oxidizing microorganisms microbial inoculum, the pH value of Whole Process Control Leaching Systems is 1.0～4.0, in combination with oxidant and reducing agent, the oxidation-reduction potential of Leaching Systems is regulated and controled, make the oxidation reduction potential control of Leaching Systems at 420mV～650mV；And the pH value of Leaching Systems is stepped up stage by stage in leaching process, the oxidation-reduction potential of Leaching Systems is stepped up stage by stage, and leaching total time, final realization was leached containing the efficient of heavy metal in heavy metal waste addicted to acid ferrum oxidizing microorganisms microbial inoculum within 8h.The method of the present invention can accelerate Bioleaching metal in sludge, shortens extraction time, reduces acid consumption, and is greatly improved Bioleaching efficiency.
Description
Technical field
The present invention relates to the processing method containing heavy metal waste in field of Environment Protection, be specifically related to one and contain based on efficient Bioleaching
The method of heavy metal in heavy metal waste.
Background technology
Electroplating sludge is the ultimate solid waste of Surface Processing Industry, and its easily accumulation, instability, difficult degradation, amount are greatly (according to environmental protection
Portion adds up about 23,060,000 tons/year), and toxic component is complicated, especially contains the toxic heavy metals such as substantial amounts of chromium, copper, nickel, zinc,
It is listed in state key hazardous waste.But simultaneously in electroplating sludge rich in various heavy content far above mineral exploration and exploitation product
Position, its potential value is the highest, is a kind of rare cheap reproducible nonferrous metal resource.
Comprehensive utilization of waste materials, turns waste into wealth, and extracts valuable metal from plating waste residue, and this saves energy and reduce the cost, sustainable development
One important content.The first step that electric plating sludge resource recycles is extract technology.Prior art often utilizes mineral acid (as
HCl、HNO3Or H2SO4Deng), the chemical method resource such as organic acid (such as citric acid, oxalic acid etc.) or ammonia leaching reclaim plating
Heavy metal in mud, although can realize heavy metal recovery in electroplating sludge in the short time, but these processing methods economy,
There is such or such limitation in the feature of environmental protection and technical feasibility, specifically include: (1) flow process is longer, relatively costly, metal
The response rate is relatively low, and separation and Extraction is more difficult, and comprehensive utilization effect is poor；(2) energy consumption is high, pollutes big, and working environment is severe, produces
Raw secondary residue and the problem such as waste gas, waste water；(3) more being applicable to of traditional recovery method processes recovery high-grade, composition letter
Single electroplating sludge；Electroplating sludge for low-grade, complicated component can only fill place because of the reason such as technical bottleneck, economical one
Reason or discarded.
Biological extraction (or bioleaching) as the recycling new technique grown up on the basis of biological metallurgy in recent years,
Gradually receive publicity in reclamation of solid wastes processes.Bioleaching is to utilize the oxidation of microorganism, molten, the metabolite chela of acid
The effects such as conjunction make the dissolving metal in mineral, thus reach to extract the technology of metal purpose.This technology is owing to having low cost, ring
Border is friendly, and material forms the features such as the strictest restriction, is especially suitable for processing complicated, low-grade containing metal solid refuse.
This technology be applied to the earliest Cu, Co, Ni, Zn, U etc. low-grade, dispersion, intractable metal sulfide ore or its oxidation
The leaching of mineral, or hinder, in order to remove, the surface impurity (such as biological oxidation pretreatment gold mine) contacted with metal, and obtain
Scale is applied, and becomes the cutting edge technology of mineral resources processing and utilization in the world.Due to the advantage that biological extraction is unique, can make
For important supplement and the improvement of tradition electroplating sludge leaching technologies, it is alternatively the resource profit that such difficult mud provides new simultaneously
By approach, but prior art seldom has and utilizes biological extraction that the heavy metal in electroplating sludge carries out the relevant of recycling treatment
Report.
CN 102719657 A Chinese patent literature discloses the heavy metal in a kind of bioleaching resource recovery electroplating sludge
Method, but the method trivial operations, such as, add and process object electroplating sludge carried out pretreatment (such as drying, grinding, mistake
Sieve etc.) and the process such as microorganism collection, and strain composition simple (only using thiobacillus ferrooxidant or thiobacillus thiooxidans), soak
Go out process length (it is generally required to 5-6 days), thus this technical scheme exists, and processing speed is relatively low, integrated operation cost high, process effect
The most poor and process the applicable object problem such as single (cupric or nickel mud), actual commercial Application there may be certain limit
Property processed.
CN 103451437 A Chinese patent literature discloses the recovery method of the valuable metal body refuse of a kind of cupric cobalt nickel.The method
Propose to assist the copper in Ore Leaching electroplating sludge or nickel with biological adjuvant, but acid consumption is big, produces secondary pollution many, and not public
Being opened in Chemical Leaching is in main technical process, and how biological assistant processes electroplating sludge thus reclaim and obtain the metals such as copper nickel.Cause
This, the method substantially can only the integrated conduct method of heavy metal in electroplating sludge based on Chemical Leaching at last.
In sum, existing electroplating sludge biologic treating technique have that consumption acid is big, it is simple to process object, length return period, place
The problems such as reason efficiency is low, treatment effect is preferable not enough, are also difficult to industrial applications.
Summary of the invention
The technical problem to be solved is, overcomes the deficiency and defect mentioned in background above technology, it is provided that a kind of favourable
In accelerate Bioleaching metal in sludge, shorten extraction time, reduce acid consumption, be greatly improved Bioleaching efficiency based on pH
The biological extraction regulated and controled altogether with current potential contains the method for heavy metal in heavy metal waste.
For solving above-mentioned technical problem, the technical scheme that the present invention proposes is a kind of biological extraction regulated and controled altogether based on pH and current potential
Containing the method for heavy metal in heavy metal waste, the method is particularly suitable for the process of electroplating sludge, the most also can popularization and application to it
He containing heavy metal waste, specifically include following steps:
During leaching containing heavy metal waste addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable, the pH value of Whole Process Control Leaching Systems
1.0～4.0, in combination with oxidant and reducing agent, the oxidation-reduction potential of Leaching Systems is regulated and controled, make Leaching Systems
Oxidation reduction potential control at 420mV～650mV；And the pH value of Leaching Systems is stepped up stage by stage in leaching process,
The oxidation-reduction potential of Leaching Systems is stepped up stage by stage, and leaching total time, final realization aoxidized micro-life addicted to acid ferrum within 8h
Thing composite bacteria agent capable is to containing the efficient leaching of heavy metal in heavy metal waste.
In above-mentioned method, preferably: described leaching process is divided into leaching early stage, leaches two stages of later stage, is leaching early stage
The pH value of Leaching Systems controls 1.0～2.5, and 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, simultaneously the oxidation reduction potential control of Leaching Systems at 550mV～
650mV。
In above-mentioned method, preferred: described leaching early stage, the division in leaching later stage are with when having at least 50% in Leaching Systems
The target heavy metal of (preferably 50%～90%) is leached as regulation and control boundary；When this initially enters the regulation and control leaching the later stage, slow
The slow oxidant that adds quickly heightens system current potential to 550mV～650mV, and period is slowly added to alkaline matter by system pH regulator
To 2.5～3.5.It is furthermore preferred that described leaching total time is 3h～8h, and the time that leaching early stage takies takies with leaching the later stage
Time of substantially equal.
In above-mentioned method, preferred: in described leaching early stage, the pH value of Leaching Systems to be monitored (main in real time
By pH combination electrode)；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 the pH value of Leaching Systems is less than 1.0, adds 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 the pH value of Leaching Systems is less than 2.5, adds alkaline matter and adjust
Control makes pH value control 2.5～4.0.
Preferred: described acid is sulphuric acid (concentrated sulphuric acid of such as 98%), and described alkaline matter is CaCO3。
In above-mentioned method, preferred: in described leaching early stage, the oxidation-reduction potential of Leaching Systems to be monitored in real time
(main by oxidation-reduction potential combination electrode (vs.Pt, Ag/AgCl))；When the oxidation-reduction potential of Leaching Systems is less than 420
During mV, it is slowly added to oxidant and improves current potential to 420mV～450mV；When oxidation-reduction potential is higher than 450mV, add
Enter reducing agent and reduce current potential to 420mV～450mV；
In the described leaching later stage, the oxidation-reduction potential of Leaching Systems is monitored in real time；Oxidoreduction electricity when Leaching Systems
When position is less than 550mV, it is slowly added to oxidant and improves current potential to 550mV～650mV；When oxidation-reduction potential is higher than 650
During mV, addition reducing agent reduction current potential to 550mV～650mV.
Preferred: described oxidant is hydrogen peroxide or Fe2(SO4)3Solution, the concentration of volume percent of described hydrogen peroxide be 10%～
30%, described Fe2(SO4)3The concentration of solution is 10～50g/L；Described reducing agent is FeSO4Solution or Na2S solution, institute
State FeSO4Solution or Na2The concentration of S solution is 5～40g/L.
The technique scheme of the present invention is based primarily upon following principle:
1) pH and oxidation-reduction potential regulation and control combined acid/CaCO of Leaching Systems of the present invention3And multiple oxidant, reducing agent are carried out
Regulate and control stage by stage in real time；PH in Leaching Systems and oxidation-reduction potential are to Bioleaching Copper in Electroplating Sludge, zinc, chromium, nickel
Important impact is had, existence form after its dissolution together deciding on heavy metal in electroplating sludge and dissolution etc. heavy metal.Plating dirt
Containing substantial amounts of metal in mud, along with the leaching of the purpose metals such as copper, zinc, nickel and chromium, Fe3+Or Fe2+Equally by a large amount of dissolutions；
The ferrous iron of dissolution is become Fe by ferrum oxidizing microorganisms Quick Oxidation3+, and system oxidation-reduction potential mainly has Fe3+/Fe2+Ratio determines；
When leaching early stage system pH (pH > 2.5) or oxidation-reduction potential too high (oxidation-reduction potential ＞ 450mV, vs Ag/AgCl),
Easily cause Fe present in Leaching Systems3+Precipitation is (such as: 3Fe3++A++2HSO4 -+6H2O→AFe3(SO4)2(OH)6+
8H+, A=K+、Na+、NH4 +or H3O+), this precipitate (such as autunezite etc.) is attached to electroplating sludge surface and inhibits
Interaction between microorganism, electroplating sludge and leachate, causes mud leaching process to be passivated；And when Leaching Systems aoxidizes
Reduction potential too low (oxidation-reduction potential ＜ 420mV, vs Ag/AgCl), system oxidation-reduction potential is less than gold in electroplating sludge
Belong to dissolution current potential, thus be also unfavorable for the efficient Fast Stripping of metal in sludge.
2) after major part purpose metal is leached in electroplating sludge, Leaching Systems regulating strategy, quick adjustment and control system pH are changed
(2.5～4.0) and heighten system oxidation-reduction potential (550mV～650mV), now in system from electroplating sludge dissolution and
Microorganism converts the Fe formed3+Rapidly Precipitation, the many autunezite based on porous of the precipitation of formation, in electroplating sludge
Leaching of Heavy Metals there is no inhibitory action, simultaneously ferrum precipitation produce acid, further promote the purpose metals such as copper, zinc, nickel and chromium
Leaching, and greatly reduce acid consumption.Additionally, suitable pH and redox environment impact are addicted to acid ferrum oxidizing microorganisms
Efficient oxidation ferrous in growth and breeding and system, such as Acidithiobacillus ferrooxidans strain GF (Acidithiobacillus ferrooxidans)
Bacterial strain converts ferrous iron under the conditions of being more suitable for lower oxidation reduction, and addicted to cleek end pylori (Leptospirillum ferriphilum)
Bacterial strain can under the conditions of high redox potential Efficient Conversion ferrum, and addicted to acid ferrum oxidizing microorganisms ferrous iron Efficient Conversion effect in turn
Also can assist maintenance system oxidation-reduction potential, finally shorten the time, it is achieved Bioleaching high efficiency.
Therefore, the present invention is according to electroplating sludge feature of raw material and functional purpose needs, in conjunction with the current potential of Fe-Cu/Zn/Cr/Ni water system
-pH relation and microbial action, it is proposed that above-mentioned high-performance bio based on electric potential regulating leaches the side of heavy metal in electroplating sludge
Method, regulates and controls to enhance bioanalysis altogether by pH and oxidation-reduction potential and leaches the heavy metal in electroplating sludge.
As to the invention described above further improvements in methods, described group's composition addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable comprises
Addicted to acid irony bacterium (Ferroplasma acidiphilum) bacterial strain, cold-resistant addicted to acid iron-oxidizing bacteria (Acidithiobacillus ferrivorans)
Bacterial strain, Acidithiobacillus ferrooxidans strain GF (Acidithiobacillus ferrooxidans) bacterial strain, addicted to cleek end pylori
(Leptospirillum ferriphilum) bacterial strain and Sulfobacillus acidophilus (Sulfobacillus acidophilus) bacterial strain.Institute
During stating addicted to heavy metal in acid ferrum oxidizing microorganisms composite bacteria agent capable extraction electroplating sludge, Leaching Systems temperature has significant change,
System temperature is natural is increased to 50 DEG C ± 5 DEG C by 25 DEG C ± 5 DEG C, is down to room temperature the most again；Described bioleaching process is the most additional
Temperature control device, and the different strain in composite bacteria agent capable can play a significant role to be formed in the different temperatures stage and have complementary advantages.
Above-mentioned addicted in acid ferrum oxidizing microorganisms composite bacteria agent capable, it is preserving number it is furthermore preferred that described addicted to acid irony bacteria strain
CCTCC M 2015017 addicted to acid irony bacterium, its named addicted to acid irony bacterium CS1 (Ferroplasma acidiphilum
CS1), it is preserved in China typical culture collection center on January 5th, 2015 (address is positioned at Hubei China Wuhan
Wuhan University is in the school).This thermophilic acidophilic acid irony bacteria strain can be with ferrous and Organic substance yeast powder facultative autotrophy, growth temperature model
Enclosing is 10 DEG C～50 DEG C, is best suitable for growth temperature and is about 35 DEG C, growth pH value range 1.0～3.0, optimum pH about 2.0,
It it is the advantage Gu bacterium under room temperature leaching environment.
Above-mentioned addicted in acid ferrum oxidizing microorganisms composite bacteria agent capable, it is furthermore preferred that described cold-resistant be preserving number addicted to acid iron-oxidizing bacteria bacterial strain
CCTCC M's 2015009 is cold-resistant addicted to acid iron-oxidizing bacteria, and it is named cold-resistant addicted to acid iron-oxidizing bacteria CS12 (Acidithiobacillus
Ferrivorans CS12), it is preserved in China typical culture collection center on January 5th, 2015, and (address is positioned at China
The Wuhan University in Wuhan, Hubei is in the school).This is cold-resistant can be oxidized to energy with ferrous or reduced sulfur addicted to acid iron-oxidizing bacteria bacterial strain
Can autotrophy, growth temperature range is 10 DEG C～35 DEG C, and being best suitable for growth temperature is 15 DEG C～20 DEG C, growth pH value range 2.0～
3.5, being best suitable for growing pH value is 2.0, is the dominant bacteria under low-temp extraction environment.
It is above-mentioned addicted in acid ferrum oxidizing microorganisms composite bacteria agent capable, it is furthermore preferred that described Acidithiobacillus ferrooxidans strain GF bacterial strain is preservation
The Acidithiobacillus ferrooxidans strain GF of number CCTCC M 2015007, its named Acidithiobacillus ferrooxidans strain GF CS9
(Acidithiobacillus ferrooxidans CS9), it was preserved in China typical culture collection on January 5th, 2015
The heart (address is positioned at the Wuhan University in Hubei China Wuhan in the school).This Acidithiobacillus ferrooxidans strain GF bacterial strain can be with ferrous and reduction
State sulfur is energy chemautotrophy, and growth temperature range is 10 DEG C～50 DEG C, and being best suitable for growth temperature is 30 DEG C～35 DEG C, growth
PH value range 1.3～4.5, being best suitable for growing pH value is 2.0～2.5, is the advantage ferrum/sulfur oxidizing bacterium kind under room temperature leaching environment.
Above-mentioned addicted in acid ferrum oxidizing microorganisms composite bacteria agent capable, it is preserving number it is furthermore preferred that described addicted to cleek end pylori bacterial strain
CCTCC M 2015010 addicted to cleek end pylori, it is named addicted to cleek end pylori CS13 (Leptospirillum
Ferriphilum CS13), it is preserved in China typical culture collection center on January 5th, 2015, and (address is positioned at China
The Wuhan University in Wuhan, Hubei is in the school).Chemautotrophy should be carried out with ferrous iron for unique energy source, growth addicted to cleek end pylori bacterial strain
Temperature range is 10 DEG C～50 DEG C, and being best suitable for growth temperature is～40 DEG C to grow pH scope 1.0～2.8, is best suitable for growing pH
It is 1.2～2.2, is the advantage iron-oxidizing bacteria kind under medium high temperature leaching environment.
It is above-mentioned addicted in acid ferrum oxidizing microorganisms composite bacteria agent capable, it is furthermore preferred that described Sulfobacillus acidophilus bacterial strain is preserving number
The Sulfobacillus acidophilus of CCTCC M 2015006, its named Sulfobacillus acidophilus CS5 (Sulfobacillus
Acidophilus CS5), it is preserved in China typical culture collection center on January 5th, 2015, and (address is positioned at China lake
The Wuhan University in Wuhan, north is in the school).This Sulfobacillus acidophilus bacterial strain can ferrous oxide or reduced sulfur, growth temperature range
Being 15 DEG C～50 DEG C, optimum temperature is 45 DEG C～55 DEG C, grows pH value range 1.0～2.8, and being best suitable for growing pH value is 2.0,
It it is the advantage ferrum/sulfur oxidizing bacterium kind under high temperature leaching environment.
Above-mentioned each preferred strain is to sequentially pass through the oxidation of the ferrum energy and thermograde in the basic salt/Nutrient medium of specific iron content
Obtain after screening enrichment.Through the oxidation of the ferrum energy and thermograde screening enrichment in the basic salt/Nutrient medium of specific iron content,
It is primarily referred to as obtaining using the ferrous energy and thermograde (such as 15 DEG C, 30 DEG C and 45 DEG C) as selection pressure, screening enrichment
State multiple have the ferrous acidophilic microorganism bacterial strain of different physics and chemistry and metabolic characteristics and efficient oxidation (as addicted to acid irony bacteria strain,
Cold-resistant addicted to acid iron-oxidizing bacteria bacterial strain, Acidithiobacillus ferrooxidans strain GF bacterial strain, addicted to cleek end pylori bacterial strain and addicted to acid vulcanize spore
Bacillus strain etc.).It is furthermore preferred that comprise following in the basic salt/Nutrient medium of described specific iron content screening enrichment culture
The component of concentration: (NH4)2SO4, 2.5～3.5g/L；MgSO4·7H2O, 0.3～0.6g/L；K2HPO4, 0.3～0.7g/L；
KCl, 0.1～0.3g/L；Ca(NO3)2, 0.01～0.05g/L；FeSO4·7H2O, 20～60g/L；Yeast powder extract,
0.1～0.6g/L.
The invention described above addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable in, it is preferred that described addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable
In addicted to acid irony bacteria strain, cold-resistant addicted to acid iron-oxidizing bacteria bacterial strain, Acidithiobacillus ferrooxidans strain GF bacterial strain, addicted to cleek end pylori
Bacterial strain and Sulfobacillus acidophilus bacterial strain are by 2～4: 2～the dense quantitative proportion of bacterium of 4: 1.5～2.5: 1.0～3: 1.5～2.0
It is blended rear formulated.Each bacterial strain makes individually pure culture before composite bacteria agent capable, centrifugal receipts after reaching the respective logarithmic growth later stage
Collection thalline, counting method of blood cell microscope inspection counts, then according to the aforementioned dense quantitative proportion of preferred bacterium is mixed to form addicted to acid ferrum oxidation micro-
Biological compound fungi agent.
The above-mentioned preparation method addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable, specifically includes following steps:
By described addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable in addicted to acid irony bacteria strain, cold-resistant addicted to acid iron-oxidizing bacteria bacterial strain, addicted to acid oxygen
Change ferrous Thiobacillus bacterial strain, be placed in the basic salt/battalion of specific iron content addicted to cleek end pylori bacterial strain and Sulfobacillus acidophilus bacterial strain
Support and culture medium sequentially passes through the compounding cultivation of thermograde, tolerance mixture-metal gradient pressure formula domestication, temperature cycles gradient type
Domestication, microbe preservation improve and tolerance high ferro domestication step, i.e. preparation obtains addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable.
Described thermograde compounds cultivation and preferably refers to: by the invention described above screening enrichment addicted to acid irony bacterium CS1, cold-resistant addicted to acid
Iron-oxidizing bacteria CS12, Acidithiobacillus ferrooxidans strain GF CS9, addicted to cleek end pylori CS13 and Sulfobacillus acidophilus CS5
First single culture in the basic salt/Nutrient medium of specific iron content, centrifugal collection thalline after reaching the respective logarithmic growth later stage,
Counting method of blood cell microscope inspection counts, the most preferably according to the dense quantity of bacterium 2～4: 2～4: 1.5～2.5: 1.0～3: 1.5～2.0
Ratio be mixed to form composite flora；Again using ferrous iron as critical energy, will in proportion composite flora after preparation respectively at 15 DEG C～
Cultivate under 20 DEG C, 30 DEG C～35 DEG C and 45 DEG C～50 DEG C of three kinds of thermogrades, obtain respectively 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).It is furthermore preferred that the described basic salt of specific iron content/
Nutrient medium comprises the component of following concentration: (NH4)2SO4, 2.5～3.5g/L；MgSO4·7H2O, 0.3～0.6g/L；
K2HPO4, 0.3～0.7g/L；KCl, 0.1～0.3g/L；Ca(NO3)2, 0.01～0.05g/L；FeSO4·7H2O, 20～60
g/L；Yeast powder extract, 0.1～0.6g/L.
The domestication of described tolerance mixture-metal gradient pressure formula preferably refers to above-mentioned three kinds of different temperatures are cultivated three kinds obtained efficiently
Ferrum oxidation acidophilic microorganism composite flora I, II and III are respectively placed in mixture-metal (such as Cu, Zn, Cr, Ni, Fe etc.)
Concentration pressure gradient be 5～200mmol/L solution in step up domestication.It is furthermore preferred that during often wheel gradient is tamed, with much money
Belonging to concentration increasing degree is 5～30mmol/L.
The domestication of described temperature cycles gradient type preferably refers to three kinds will obtained after tolerance mixture-metal gradient pressure formula domestication
Heavy metal tolerance addicted to acid ferrum oxidizing microorganisms composite flora, after being about 1: 1: 1 mixing by the dense quantitative proportion of bacterium, then at 10 DEG C～
Temperature cycles gradient domestication is carried out in 50 DEG C of temperature ranges.It is furthermore preferred that the temperature amplification that each gradient uses is 5 DEG C, each
The circulation domestication number of times preferably 3～5 times of wheel thermograde, obtain adapting to wide temperature range addicted to acid ferrum oxidizing microorganisms compound bacteria
Agent.
Described microbe preservation improves and tolerance high ferro domestication preferably refers to: utilize continuous training method, is born by the ferrous energy
Lotus is improved and shortens hydraulic detention time, improves above-mentioned acquisition addicted to the acid microbe preservation of ferrum oxidizing microorganisms composite bacteria agent capable and resistance to
By high ferro ability.Wherein, it is furthermore preferred that FeSO4·7H2The load of O can be gradually increased to 90g/L, hydraulic retention from 30g/L
Time then can be foreshortened to 36～48h by 72～96h.
Through above-mentioned steps, final obtain general-purpose highly effective extraction electroplating sludge addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable.
Above-mentioned preferred technical scheme fully examines the practical situation of bioanalysis extraction electroplating sludge technique, becomes for ambient temperature
Change the key factor of the impact biology extraction such as pressure and sludge source complexity, it is provided that a kind of universal, heavy duty detergent available
Heavy metal addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable and preparation technology thereof in extraction electroplating sludge.The present invention provide addicted to acid ferrum
Oxidizing microorganisms composite bacteria agent capable (the five kinds of bacterial strains the most preferably gone out) comprises the different cultivation such as low temperature, room temperature and moderate high temperature
Type and the microbial strains of physiological property, the acquisition of these bacterial strains is not only our long-term experimentation and is sieved after observing contrast
Select, and any one therein is compared in the combination of these bacterial strains or both of which has irreplaceable significant technique effect.
The functionality advantage of these bacterial strains is complementary and organically combines, and not only substantially increases the present invention addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable
Versatility and adaptability, and achieve leaching and the recovery of heavy metal in electroplating sludge efficiently, economically, it is greatly shortened technique
In the cycle, reduce wet-leaching process costs.
Compared with prior art, it is an advantage of the current invention that: the method for the present invention can accelerate the heavy metal in Bioleaching mud,
Shorten extraction time, be greatly improved Bioleaching efficiency；And the method mild condition of the present invention, simple to operate, acid consumption is low, leaching
Going out rate high, its production cost significantly reduces than the pure chemistry acid-hatching of young eggs, and environmental pollution is little, is a kind of minimizing, innoxious and money
Sourceization leaches containing the new method of heavy metal in heavy metal waste.
It addition, in currently preferred technical scheme, we additionally provide a kind of addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable, should
Preparation method addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable is simple, low cost；Its structure of community and function comparatively perfect, easily cultivate
Preparation, it is possible to the efficiently heavy metal in extraction electroplating sludge, it is achieved the innoxious and resource of electroplating sludge, ensures to leach simultaneously
Slag sludge qualified discharge, has preferable economy and environmental benefit.The present invention also has addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable
The high-adaptability of object " process " and " applying the wide in range property of temperature ", be i.e. suitable for the sub-primes such as Treatment of Copper, nickel, zinc, chromium or
Comprehensive high/low grade electroplating sludge, is suitable for the cultivation preparation at a temperature of long-term Various Seasonal and can efficiently extract in electroplating sludge
Heavy metal.
In a word, the present invention be relevant electroplating industry or Surface Treatment Industry garden provide a kind of economical and efficient, can be used for plating dirt
The new method that mud bioanalysis resource reclaims, this method efficiently leaching heavy metal can be applied to its in addition to electroplating sludge
His field Han heavy metal waste, efficient such as heavy metals such as discarded circuit board, municipal sludge containing heavy metal or solid waste
Leach, there is the strongest versatility, high efficiency and economy, solve in the actual application of bioanalysis the pollutant sources that runs into and
The difficult problem that ambient temperature etc. are unstable and biology extraction is the longest, has great importance.
Biomaterial preservation situation illustrates:
One strain thermophilic acidophilic acid irony bacteria strain, this bacterial strain be preserving number CCTCC M 2015017 addicted to acid irony bacteria strain, its
Named addicted to acid irony bacterium CS1 (Ferroplasma acidiphilum CS1), it is in being preserved on January 5th, 2015
State's Type Tissue Collection (is called for short CCTCC), and address is positioned at the Wuhan University in Hubei China Wuhan in the school.
One strain is cold-resistant addicted to acid iron-oxidizing bacteria bacterial strain, and this bacterial strain is the cold-resistant addicted to acid iron-oxidizing bacteria of preserving number CCTCC M 2015009
Bacterial strain, it is named cold-resistant addicted to acid iron-oxidizing bacteria CS12 (Acidithiobacillus ferrivorans CS12), and it was in 2015
Being preserved in China typical culture collection center (being called for short CCTCC) on January 5, address is positioned at the Wuhan in Hubei China Wuhan
In institution of higher education.
One strain Acidithiobacillus ferrooxidans strain GF bacterial strain, this bacterial strain be preserving number CCTCC M 2015007 addicted to acid oxidase ferrous iron sulfur
Bacillus strain, its named Acidithiobacillus ferrooxidans strain GF CS9 (Acidithiobacillus ferrooxidans CS9), it is in 2015
Being preserved in China typical culture collection center (being called for short CCTCC) on January 5, in, address is positioned at the force in Hubei China Wuhan
In Chinese institution of higher education.
One strain addicted to cleek end pylori bacterial strain, this bacterial strain be preserving number CCTCC M 2015010 addicted to cleek end pylori
Bacterial strain, it is named addicted to cleek end pylori CS13 (Leptospirillum ferriphilum CS13), and it was in 2015 1
Within 5th, being preserved in China typical culture collection center (being called for short CCTCC) moon, the Wuhan that address is positioned at Hubei China Wuhan is big
In school.
One strain Sulfobacillus acidophilus bacterial strain, this bacterial strain is the Sulfobacillus acidophilus of preserving number CCTCC M 2015006
Bacterial strain, its named Sulfobacillus acidophilus CS5 (Sulfobacillus acidophilus CS5), it was January 5 in 2015
Being preserved in China typical culture collection center (being called for short CCTCC) day, address is positioned at the Wuhan University school in Hubei China Wuhan
In.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or prior art
In description, the required accompanying drawing used is briefly described, it should be apparent that, the accompanying drawing in describing below is some realities of the present invention
Execute example, for those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to according to these accompanying drawings
Obtain other accompanying drawing.
Fig. 1 is that the leach extraction method in the embodiment of the present invention 1 is extracting the right of Copper in Electroplating Sludge, nickel, zinc and chromium with control methods
Than (ORP-oxidation-reduction potential).
Fig. 2 is that the leach extraction method in the embodiment of the present invention 2 is extracting the right of Copper in Electroplating Sludge, nickel, zinc and chromium with control methods
Than (ORP-oxidation-reduction potential).
Detailed description of the invention
For the ease of understanding the present invention, below in conjunction with Figure of description and preferred embodiment, the present invention is made more comprehensively, careful
Ground describes, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical term used hereinafter is generally understood that with those skilled in the art is identical.
Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to limit the protection model of the present invention
Enclose.
Unless otherwise specified, the various raw materials used in the present invention, reagent, instrument and equipment etc. all can be purchased by market
Can buy or can be prepared by existing method.
Embodiment 1:
A kind of biological extraction regulated and controled altogether based on pH and current potential contains the method for heavy metal in heavy metal waste, used by the present embodiment
Containing heavy metal waste mainly from the electroplating sludge of Hunan Electroplate Factory, its appearance presents green, wherein based on containing zinc chrome ferrum,
Copper nickel takes second place, and moisture content is about 65.41%.This electroplating sludge butt mainly comprises metallic element and content be respectively as follows: Fe 12.16%,
Zn 4.4%, Cr 4.39%, Cu 1.01% and Ni 1.16% etc. (seeing table 1 below).
Table 1: electroplating sludge butt main metal element content in embodiment 1
Use the method for heavy metal in the biological extraction electroplating sludge regulated and controled altogether based on pH and current potential of the present invention dirty to above-mentioned plating
Mud processes, and specifically includes following steps:
(1) adaptability pretreatment: will enter in the basic salt/Nutrient medium of specific iron content addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable
The row pre-extraction electroplating sludge continuous amplification culture of adaptability pretreatment；PH value during cultivation is 1.8 ± 0.3, and temperature is 30 ± 5 DEG C,
Basic salt/the Nutrient medium of specific iron content includes following components (NH4)2SO4, 3g/L；MgSO4·7H2O, 0.5g/L；K2HPO4,
0.5g/L；KCl, 0.1g/L；Ca(NO3)2, 0.01g/L；FeSO4·7H2O, 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, in i.e. every liter mixed serum cumulative volume,
Electroplating sludge contents on dry basis is 20-200g；System oxidation-reduction potential >=600mV after continuous oscillation cultivation, microbial total concentration is extremely
Reach 1 × 10 less8～1 × 109cells/mL。
(2) pretreatment operation is repeated: the adaptability pretreatment operation 2 of repeat the above steps (1)～5 times, it is thus achieved that stable is resistance to
By pretreatment electroplating sludge characteristic addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable.
(3) extraction electroplating sludge
Above-mentioned steps (2) being obtained afterwards is the acidity of 2 ± 0.2 addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable and electroplating sludge, pH
Water (with concentrated sulphuric acid regulate tap water pH most 2 ± 0.2) or raffinate (raffinate is the raffinate after Leaching Systems extracting metals,
Water circulation in industry) it is mixed to get mixed slurry, then proceed by leaching, leaching process uses air compressor exist
Bottom ventilation, continuous stirring leaches；In mixed slurry, the inoculum concentration addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable is calculated as with volume fraction
20% (v/v), mud contents on dry basis (dry weight) is 20% (w/v), is leaching containing weight addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable
During metal waste, the pH value of Whole Process Control Leaching Systems is 1.0～3.5, in combination with oxidant and reducing agent to leaching
The oxidation-reduction potential going out system regulates and controls, and makes the oxidation reduction potential control of Leaching Systems at 420mV～650mV；Raw
Thing leaching process is carried out at room temperature, and it is 120～300rpm that the speed of agitator that continuous stirring leaches controls；
The leaching process of the present embodiment is divided into leaching early stage, leaches two stages of later stage；Leach leaching early stage (time within 4h)
The pH value of system controls 1.0～2.5, and the oxidation reduction potential control of Leaching Systems is at 420mV～450mV simultaneously；In leaching
Go out early stage the pH value of Leaching Systems is monitored in real time；When the pH value of Leaching Systems is more than 2.5, adds sulphuric acid and regulate and control
PH value is made to control 1.0～2.5；The oxidation-reduction potential of Leaching Systems is monitored in real time leaching early stage simultaneously；Work as leaching
When the oxidation-reduction potential of system is less than 420mV, it is slowly added to hydrogen peroxide that oxidant percent by volume is 30% or concentration is
The Fe of 30g/L2(SO4)3Solution improves current potential to 420mV～450mV；When oxidation-reduction potential is higher than 450mV, then
Add the reducing agent FeSO that concentration is 30g/L4Solution or Na2S solution reduces current potential to 420mV～450mV；
After the target heavy metal of 50%～90% is leached in Leaching Systems (leaching process later more than 4h), adjusts and leach
The technology controlling and process strategy of early stage is the technology controlling and process strategy leaching the later stage；After leaching the pH value of phase Leaching Systems control 2.5～
3.5, the oxidation reduction potential control of Leaching Systems is at 550mV～650mV simultaneously；When entering the leaching later stage, it is initially charged above-mentioned
Oxidant quickly heightens Leaching Systems current potential to 550mV～650mV, is simultaneously introduced CaCO3The pH value of regulation and control Leaching Systems
In 2.5～3.5；The pH value of Leaching Systems is monitored by the phase in real time after leaching, 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 the pH value of Leaching Systems is less than 2.5, add alkaline matter CaCO3
Carrying out regulation and control makes pH value control 2.5～4.0；In the described leaching later stage, the oxidation-reduction potential of Leaching Systems is monitored in real time；
When the oxidation-reduction potential of Leaching Systems is less than 550mV, it is slowly added to above-mentioned oxidant and improves current potential to 550mV～650
mV；When oxidation-reduction potential is higher than 650mV, addition reducing agent reduction current potential to 550mV～650mV；Extraction time
Finally control at more than 8h, it is achieved addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable to containing the efficient leaching of heavy metal in heavy metal waste.
Regulate and control altogether through above-mentioned pH and oxidation-reduction potential, finally realize copper, nickel, zinc, chromium leaching rate all reach more than 99%
(seeing Fig. 1).(pH value and electric potential regulating is not applied, extraction time is about at least 10h) compared with contrast Bioleaching, raw
Within the thing extract technology time foreshortens to 8h, the leaching rate such as copper, nickel, zinc, chromium improves 5%～15%, acid consumption reduce 5%～
20%, react gentleer, it is seen then that the Technology of the disclosed invention significantly improves target leaching rate of heavy metals, shortens
Extraction time, reduces process costs, decreases secondary environmental pollution.
Embodiment 2:
A kind of biological extraction regulated and controled altogether based on pH and current potential contains the method for heavy metal in heavy metal waste, used by the present embodiment
Containing heavy metal waste mainly from the electroplating sludge of Guangdong Treatment of Industrial Park of Plating, its appearance presents green, wherein with cupric nickel chromium triangle
Being main etc. heavy metal, moisture content is about 73.2%.This electroplating sludge butt mainly comprises metallic element composition include: Cu 9.02%,
Ni 5.72%, Cr 10.22%, Zn 1.12% and Fe 5.35% etc. (seeing table 2 below).
Table 2: electroplating sludge butt main metal element content in embodiment 2
Use the method for heavy metal in the biological extraction electroplating sludge regulated and controled altogether based on pH and current potential of the present invention dirty to above-mentioned plating
Mud processes, and specifically includes following steps:
(1) adaptability pretreatment: will enter in the basic salt/Nutrient medium of specific iron content addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable
The row pre-extraction electroplating sludge continuous amplification culture of adaptability pretreatment；PH value during cultivation is 1.8 ± 0.3, and temperature is 30 ± 5 DEG C,
Basic salt/the Nutrient medium of specific iron content includes following components (NH4)2SO4, 3g/L；MgSO4·7H2O, 0.5g/L；K2HPO4,
0.5g/L；KCl, 0.1g/L；Ca(NO3)2, 0.01g/L；FeSO4·7H2O, 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)；After continuous oscillation is cultivated, system oxidation is gone back
Former current potential >=600mV, microbial total concentration is at least up to 1 × 108～1 × 109cells/mL。
(2) pretreatment operation is repeated: the adaptability pretreatment operation 2 of repeat the above steps (1)～5 times, it is thus achieved that stable is resistance to
By pretreatment electroplating sludge characteristic addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable.
(3) extraction electroplating sludge
Above-mentioned steps (2) being obtained afterwards is the acid water of 2 ± 0.2 addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable and electroplating sludge pH
(regulating tap water pH most 2 ± 0.2 with concentrated sulphuric acid) or raffinate (raffinate is the raffinate after Leaching Systems extracting metals,
Water circulation in industry) it is mixed to get mixed slurry, then proceed by leaching, leaching process uses air compressor exist
Bottom ventilation, continuous stirring leaches；In mixed slurry, the inoculum concentration addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable is calculated as with volume fraction
20% (v/v), mud contents on dry basis (dry weight) is 20% (w/v), is leaching containing weight addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable
During metal waste, the pH value of Whole Process Control Leaching Systems is 1.0～3.5, in combination with oxidant and reducing agent to leaching
The oxidation-reduction potential going out system regulates and controls, and makes the oxidation reduction potential control of Leaching Systems at 420mV～650mV；Raw
Thing leaching process is carried out at room temperature, and it is 120～300rpm that the speed of agitator that continuous stirring leaches controls；
The leaching process of the present embodiment is divided into leaching early stage, leaches two stages of later stage；Leach leaching early stage (time within 4h)
The pH value of system controls 1.0～2.5, and the oxidation reduction potential control of Leaching Systems is at 420mV～450mV simultaneously；In leaching
Go out early stage the pH value of Leaching Systems is monitored in real time；When the pH value of Leaching Systems is more than 2.5, adds sulphuric acid and regulate and control
PH value is made to control 1.0～2.5；The oxidation-reduction potential of Leaching Systems is monitored in real time leaching early stage simultaneously；Work as leaching
When the oxidation-reduction potential of system is less than 420mV, it is slowly added to hydrogen peroxide that oxidant percent by volume is 30% or concentration is
The Fe of 30g/L2(SO4)3Solution improves current potential to 420mV～450mV；When oxidation-reduction potential is higher than 450mV, then
Add the reducing agent FeSO that concentration is 30g/L4Solution or Na2S solution reduces current potential to 420mV～450mV；
After the target heavy metal of 50%～90% is leached in Leaching Systems (leaching process later more than 4h), adjusts and leach
The technology controlling and process strategy of early stage is the technology controlling and process strategy leaching the later stage；After leaching the pH value of phase Leaching Systems control 2.5～
3.5, the oxidation reduction potential control of Leaching Systems is at 550mV～650mV simultaneously；When entering the leaching later stage, it is initially charged above-mentioned
Oxidant quickly heightens Leaching Systems current potential to 550mV～650mV, is simultaneously introduced CaCO3The pH value of regulation and control Leaching Systems
In 2.5～3.5；The pH value of Leaching Systems is monitored by the phase in real time after leaching, 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 the pH value of Leaching Systems is less than 2.5, add alkaline matter CaCO3
Carrying out regulation and control makes pH value control 2.5～4.0；In the described leaching later stage, the oxidation-reduction potential of Leaching Systems is monitored in real time；
When the oxidation-reduction potential of Leaching Systems is less than 550mV, it is slowly added to above-mentioned oxidant and improves current potential to 550mV～650
mV；When oxidation-reduction potential is higher than 650mV, addition reducing agent reduction current potential to 550mV～650mV；Extraction time
Finally control at more than 8h, it is achieved addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable to containing the efficient leaching of heavy metal in heavy metal waste.
Regulate and control altogether through above-mentioned pH and oxidation-reduction potential, finally realize copper, nickel, zinc, chromium leaching rate all reach more than 99%
(seeing Fig. 2).Compared with the Bioleaching not applying pH value and electric potential regulating, the bioleaching process time foreshorten to 8h with
In, the leaching rate such as copper, nickel, zinc, chromium improves 5%～15%, and acid consumption reduces 5%～20%, reacts gentleer, it is seen then that
The Technology of the disclosed invention significantly improves target leaching rate of heavy metals, shortens extraction time, reduces process costs,
Decrease secondary environmental pollution.
Various embodiments above is used addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable group composition comprise addicted to acid irony bacteria strain,
Cold-resistant addicted to acid iron-oxidizing bacteria bacterial strain, Acidithiobacillus ferrooxidans strain GF bacterial strain, addicted to cleek end pylori bacterial strain and addicted to acid vulcanize spore
Bacillus strain.Concrete select addicted to the thermophilic acidophilic acid irony bacterium CS1 that acid irony bacteria strain is preserving number CCTCC M 2015017
(Ferroplasma acidiphilum CS1), it is preserved in China typical culture collection center on January 5th, 2015；
The cold-resistant of selection is the cold-resistant addicted to acid iron-oxidizing bacteria CS12 of preserving number preserving number CCTCC M 2015009 addicted to acid iron-oxidizing bacteria
(Acidithiobacillus ferrivorans CS12), it was preserved in China typical culture collection on January 5th, 2015
The heart；The Acidithiobacillus ferrooxidans strain GF CS9 that Acidithiobacillus ferrooxidans strain GF is preserving number CCTCC M 2015007 selected
(Acidithiobacillus ferrooxidans CS9), it was preserved in China typical culture collection on January 5th, 2015
The heart；Select addicted to cleek end pylori be CCTCC M 2015010 addicted to cleek end pylori CS13 (Leptospirillum
Ferriphilum CS13), it is preserved in China typical culture collection center on January 5th, 2015；Select addicted to acid sulfur
Change Sulfobacillus acidophilus CS5 (the Sulfobacillus acidophilus that bacillus cereus is preserving number CCTCC M 2015006
CS5), it is preserved in China typical culture collection center on January 5th, 2015.
Above-mentioned the present embodiment addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable in, addicted to acid irony bacteria strain, cold-resistant addicted to acid iron-oxidizing bacteria bacterium
Strain, Acidithiobacillus ferrooxidans strain GF bacterial strain, it is by 2～4 addicted to cleek end pylori bacterial strain and Sulfobacillus acidophilus bacterial strain:
The dense quantitative proportion of bacterium of 2～4: 1.5～2.5: 1.0～3: 1.5～2.0 is formulated after being blended.
The present embodiment above-mentioned addicted to acid irony bacterium CS1, cold-resistant addicted to acid iron-oxidizing bacteria CS12, Acidithiobacillus ferrooxidans strain GF CS9,
From varying environment, ferrous oxidation and temperature ladder is passed through respectively addicted to cleek end pylori CS13 and Sulfobacillus acidophilus CS5
Degree screening obtains, and before compounding, first pure culture, to the respective logarithmic growth later stage, then collects thalline respectively；Wherein, addicted to acid irony
Bacterium CS1 is simultaneously introduced 0.02% (wt%) yeast powder, 20g/L FeSO in the basic salt culture medium of iron content4·7H2O, pH be 1.0,
Temperature is cultivated under the conditions of being 45 DEG C；Cold-resistant addicted to acid iron-oxidizing bacteria CS12 in the basic salt/Nutrient medium of iron content, add 30g/L
FeSO4·7H2O, pH are 2.0, temperature is cultivated under the conditions of being 20 DEG C；Acidithiobacillus ferrooxidans strain GF CS9 is containing iron-based
This salt/Nutrient medium adds 44.7g/L FeSO4·7H2O, pH are 1.8, temperature is cultivated under the conditions of being 30 DEG C；Addicted to ferrum
Hook end pylori CS13 adds 30g/L FeSO in the basic salt/Nutrient medium of iron content4·7H2O, pH are 1.8, temperature is
Cultivate under the conditions of 40 DEG C；Sulfobacillus acidophilus CS5 adds 0.02% (wt%) in the basic salt/Nutrient medium of iron content
Yeast powder, 30g/L FeSO4·7H2O, pH are 1.8, temperature is cultivated under the conditions of being 45 DEG C.Each bacterial strain after cultivation according to
Necessarily bacterium dense quantitative proportion mixing, then in the basic salt/Nutrient medium of iron content, sequentially pass through the compounding cultivation of thermograde, tolerate and mix
Close the steps such as the domestication of heavy metal gradient pressure formula, the domestication of temperature cycles gradient type, microbe preservation raising and tolerance high ferro domestication
Rear acquisition final addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable.
Claims (9)
1. the biological extraction regulated and controled altogether based on pH and current potential contains a method for heavy metal in heavy metal waste, comprises the following steps:
During leaching containing heavy metal waste addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable, the pH value of Whole Process Control Leaching Systems
1.0～4.0, in combination with oxidant and reducing agent, the oxidation-reduction potential of Leaching Systems is regulated and controled, make Leaching Systems
Oxidation reduction potential control at 420mV～650mV；And the pH value of Leaching Systems is stepped up stage by stage in leaching process,
The oxidation-reduction potential of Leaching Systems is stepped up stage by stage, and leaching total time, final realization aoxidized micro-life addicted to acid ferrum within 8h
Thing composite bacteria agent capable is to containing the efficient leaching of heavy metal in heavy metal waste；
Described leaching process is divided into leaching early stage, leaches two stages of later stage, controls at the pH value leaching early stage Leaching Systems
1.0～2.5, the oxidation reduction potential control of Leaching Systems is at 420mV～450mV simultaneously；The pH of phase Leaching Systems after leaching
Value controls 2.5～4.0, and the oxidation reduction potential control of Leaching Systems is at 550mV～650mV simultaneously.
Method the most according to claim 1, it is characterised in that: described leaching total time is 3h～8h, and leaching early stage accounts for
Time with to leach time of taking in later stage of substantially equal.
Method the most according to claim 1, it is characterised in that: in described leaching early stage, the pH value of Leaching Systems is entered
Row monitoring 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；Work as leaching
When going out the pH value of system less than 1.0, 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 the pH value of Leaching Systems is less than 2.5, adds alkaline matter and adjust
Control makes pH value control 2.5～4.0.
Method the most according to claim 3, it is characterised in that: described acid is sulphuric acid, and described alkaline matter is CaCO3。
Method the most according to claim 1, it is characterised in that: in described leaching early stage, the oxidoreduction to Leaching Systems
Current potential monitors in real time；When the oxidation-reduction potential of Leaching Systems is less than 420mV, it is slowly added to oxidant and improves current potential
To 420mV～450mV；When oxidation-reduction potential is higher than 450mV, addition reducing agent reduction current potential to 420mV～450
mV；
In the described leaching later stage, the oxidation-reduction potential of Leaching Systems is monitored in real time；Oxidoreduction electricity when Leaching Systems
When position is less than 550mV, it is slowly added to oxidant and improves current potential to 550mV～650mV；When oxidation-reduction potential is higher than 650
During mV, addition reducing agent reduction current potential to 550mV～650mV.
Method the most according to claim 5, it is characterised in that: described oxidant is hydrogen peroxide or Fe2(SO4)3Solution, institute
The concentration of volume percent stating hydrogen peroxide is 10%～30%, described Fe2(SO4)3The concentration of solution is 10～50g/L；Described also
Former dose is FeSO4Solution or Na2S solution, described FeSO4Solution or Na2The concentration of S solution is 5～40g/L.
7. according to the method according to any one of claim 1～6, it is characterised in that: described compound addicted to acid ferrum oxidizing microorganisms
Microbial inoculum group composition comprise addicted to acid irony bacterium (Ferroplasma acidiphilum) bacterial strain, cold-resistant addicted to acid iron-oxidizing bacteria
(Acidithiobacillus ferrivorans) bacterial strain, Acidithiobacillus ferrooxidans strain GF (Acidithiobacillus ferrooxidans)
Bacterial strain, addicted to cleek end pylori (Leptospirillum ferriphilum) bacterial strain and Sulfobacillus acidophilus (Sulfobacillus
Acidophilus) bacterial strain.
Method the most according to claim 7, it is characterised in that: described is preserving number CCTCC M addicted to acid irony bacteria strain
2015017 addicted to acid irony bacterium, its named addicted to acid irony bacterium CS1, it is preserved in Chinese Typical Representative on January 5th, 2015
Culture collection center；
Described cold-resistant addicted to acid iron-oxidizing bacteria bacterial strain be preserving number CCTCC M 2015009 cold-resistant addicted to acid iron-oxidizing bacteria, its name
For cold-resistant addicted to acid iron-oxidizing bacteria CS12, 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
Named Acidithiobacillus ferrooxidans strain GF CS9, it is preserved in China typical culture collection center on January 5th, 2015；
Described addicted to cleek end pylori bacterial strain be preserving number CCTCC M 2015010 addicted to cleek end pylori, its name
For addicted to cleek end pylori CS13, it is preserved in China typical culture collection center on January 5th, 2015；
Described Sulfobacillus acidophilus bacterial strain is the Sulfobacillus acidophilus of preserving number CCTCC M 2015006, its name
For Sulfobacillus acidophilus CS5, it is preserved in China typical culture collection center on January 5th, 2015.
Method the most according to claim 8, it is characterised in that: described addicted to acid ferrum oxidizing microorganisms composite bacteria agent capable in addicted to acid ferrum
Matter bacteria strain, cold-resistant addicted to acid iron-oxidizing bacteria bacterial strain, Acidithiobacillus ferrooxidans strain GF bacterial strain, addicted to cleek end pylori bacterial strain and addicted to
Acid sulfuration Bacillus strain be by 2～4: 2～4: 1.5～2.5: 1.0～3: 1.5～2.0 the dense quantitative proportion of bacterium be blended after join
System forms.
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| CN108239703B (en) * | 2016-12-23 | 2019-09-03 | 有研工程技术研究院有限公司 | A kind of electrochemical method and equipment controlling bioleaching process |
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