CN107236864A - The method for extracting rare precious metals from flyash using Microorganism Leaching - Google Patents

The method for extracting rare precious metals from flyash using Microorganism Leaching Download PDF

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CN107236864A
CN107236864A CN201710377968.XA CN201710377968A CN107236864A CN 107236864 A CN107236864 A CN 107236864A CN 201710377968 A CN201710377968 A CN 201710377968A CN 107236864 A CN107236864 A CN 107236864A
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domestication
aspergillus niger
flyash
culture
concentration
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CN107236864B (en
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苏海锋
陈华
申鸿
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Chongqing Institute of Green and Intelligent Technology of CAS
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/02—Working-up flue dust
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/20—Obtaining alkaline earth metals or magnesium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/14—Obtaining zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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Abstract

The invention provides the method for extracting rare precious metal from flyash using Microorganism Leaching, it comprises the following steps：(1) by the use of NaOH as exciting agent, it will be pre-processed in the high-temperature high-pressure reaction kettle of flyash under hydrothermal conditions；(2) production acid domestication is carried out to aspergillus niger；(3) domestication aspergillus niger obtained by step (2) is added into the culture medium containing various concentrations mortar, by low concentration to high concentration, carries out gradient domestication；(4) by (1) gains the step of domestication aspergillus niger is inoculated in containing culture medium obtained by step (3), culture leaching is carried out；The rare precious metal includes at least one of Ti, Ga, Sr, Zr, Ba.The method can significantly improve the extraction rate of this 5 kinds of metals of Ti, Ga, Sr, Zr, Ba；A large amount of present invention, avoiding organic reagent use, environment-friendly；Whole technique of the invention is without too high-temperature, it is easy to implements and manipulates.

Description

The method for extracting rare precious metals from flyash using Microorganism Leaching
Technical field
The invention belongs to solid waste resource recycling field, and in particular to be extracted using Microorganism Leaching from flyash The method of rare precious metal.
Background technology
Flyash is main to be produced by coal-fired industries such as coal fired thermal power plants, with the fast development of power industry, power plant's scale Constantly expand, cause the discharge capacity sharp increase of China's flyash.The flyash discharge capacity of China in 1985 is 3.769 hundred million tons, In every 10 years afterwards, by 5,600,000 tons every year on average of ash discharge amounts in increase, end 2010, the ash discharge amount of China is with up to 3,000,000,000 Ton.Flyash is not high in the utilization rate of China, and 2010 annual datas show only 69%, along with sharply increasing for ash discharge amount, give The soil, water, air, environment of China cause huge harm.In China, the utilization for flyash is concentrated mainly on embankment In terms of making ground.Flyash is used for construction material earliest, makes pulverized fuel ash cement, concrete etc., and embankment is used in highway construction Filling, down-hole backfill, also have for fired fly ash brick, fly ash building block.
With deepening continuously for research, existing researcher extracts recovery aluminum oxide with the method for chemistry from flyash, This respect comes into industrialized production.In addition, also researcher is manufactured fly ash absorbent, for heavy metal pollution and The improvement of water pollution.But, flyash only accounts for 20% or so in the application of these two aspects.
Data shows that power plants flyash is main by SiO2、Al2O3、FeO、Fe2O3、 CaO、TiO2、MgO、MnO2、 P2O5Deng oxide composition.In addition, also containing many very dilute expensive metals, such as Ti (titanium), Ga (gallium), Ge (germanium), chromium, lead, Vanadium, arsenic, uranium etc..At present, the commonsense method handled flyash generally slatterns rare precious metal.
China's flyash is not fully utilized in metal recovery domain variability, only has involved in terms of aluminium element is reclaimed And.But the recovering meanses of aluminium element are all the chemical methodes of application.Substantial amounts of chemical reagent is not only used, and generally Seek very high temperature.In the industrial technique with germanium metal in the germanic flyash of chloride way of distillation enriching and recovering, still-process Need to consume substantial amounts of chloride, hydrolysis temperature and cleansing temp require 650~675 DEG C and 1000~1150 DEG C respectively, and this is right The requirement of the energy and equipment is very high, and the extraction process of this method is also very complicated.
One of the reason for why comprehensive utilization of flyash makes slow progress is that flyash is most in the form of glass bead In the presence of its surface covers one layer of smooth fine and close, firm Si-O-Si, Si-O-Al network structure, its chemical property is in one Individual more stable state, and most metals element contained therein is wrapped in such network structure, it is difficult to it is outer Boundary's contact chemically reacts, and it is difficult to reclaim these metallic elements in flyash to cause conventional metal recovery means.
At present, for the recovery method industrialization also relatively difficult to achieve or production of the rare precious metal such as Ti, Ga, Sr, Zr, Ba Industryization is with high costs.Method such as industrial production Titanium is mainly Kroll process and hunt's method, and both approaches are all present Complex process, cost are high, energy consumption is big, the shortcomings of production cost remains high.Other method such as electrolysis and thermal reduction also exist Experimental stage.Regardless of whether which kind of method (method for including the experimental stage), required temperature is all in 1000K or so, even more high. Also with the presence of many difficulties in terms of the recovery of gallium, when such as full extraction reclaims gallium, there is organic phase has hypertoxic, inflammable, damage Lose the shortcomings of big, production cost is high.Recovery on strontium and zirconium is just more difficult, and metal zirconium does not have individualism in the earth's crust Mineral deposit, often coexisted with the ore deposit such as ferrotianium, monazite, the only separation of zirconium metal is just difficult.There is scholar once from celestine One kind is proposed than more complete extraction process in the half type approval test research for extracting Preparation of Metallic Strontium, but this technological process is tediously long. Sintering temperature is 1100 DEG C, and roasting time 5h is, it is necessary to which substantial amounts of potassium bichromate solution, vapo(u)rizing temperature is also at 1150~1200 DEG C. Later, there is scholar that extraction process is optimized in vacuum thermit reduction prepares high-purity strontium technical study, but optimization The reduction temperature of extraction process still needs in 0.01KPa afterwards, is carried out under the conditions of 1050 ± 20 DEG C.
In summary, the industrial method for extracting the metals such as Titanium, gallium, strontium, zirconium still suffers from many difficulties at present, many Technique still has much room for improvement.But the method for extracting recovery the above metal from the angle of microorganism may is that and solve this One of feasible method of problem, the research on this respect is but rarely reported, the more biological extraction process quilt without a set of completion Propose.
Bioleaching refer to using microorganism itself to the oxidations of mineral or reduction characteristic by mineral oxide or reduction so as to Make dissolving metal therein into leaching mineral solution, or utilize metabolite (such as citric acid, oxalic acid, the Fe of microorganism3+Deng) Make dissolving metal with the metal complex in mineral or mineral oxide, reduction are made into dissolving metal, the valuable metal in mineral is released It is put into the process in solution.Bioleaching is a complicated course of reaction, may include redox reaction, biological oxidation The reactions such as reaction, galvanic interaction, sour molten, complexing, biological adsorption.Most of Bioleaching be a variety of reaction types simultaneously The reaction system of presence.
At present, scientists from the angle of microorganism and extract the rare valuable gold in reclaiming solid waste using microorganism Category has done substantial amounts of research.But, the microorganism extraction being related to is primarily directed to from sulfide mine tailing and discarded circuit Rare precious metal is reclaimed in plate.Wherein using microorganism industry is come into from discarded circuit board and containing copper is reclaimed in copper tailing Metaplasia is produced.The rare precious metal such as Ti, Ga, Sr, Zr, Ba is reclaimed using microbial process from flyash to have not been reported. The not only environmental protection of microorganism absorption method, will not produce secondary hazards, and technique is simple, it is not necessary to use substantial amounts of chemistry examination Agent, i.e., it is economical and environment-friendly.
The content of the invention
In view of the shortcomings of the prior art, it is dilute it is an object of the invention to provide being extracted using Microorganism Leaching from flyash There is the method for precious metal, this method comprises the following steps：
(1) by the use of NaOH as exciting agent, will in advance it be located in the high-temperature high-pressure reaction kettle of flyash under hydrothermal conditions Reason；
(2) production acid domestication is carried out to aspergillus niger；
(3) domestication aspergillus niger obtained by step (2) is added into the culture medium containing various concentrations mortar, by low concentration to highly concentrated Degree, carries out gradient domestication；
(4) by (1) gains the step of domestication aspergillus niger is inoculated in containing culture medium obtained by step (3), cultivated Leach；
The rare precious metal includes at least one of Ti, Ga, Sr, Zr, Ba.
The aspergillus niger is Aspergillus niger DSM 11167.
It is preferred that, in step (1), NaOH concentration is 1~4mol/L.
It is preferred that, in step (1), NaOH addition volume accounts for the 80% of reactor volume.
It is preferred that, in step (1), most in pretreatment, in 150~200 DEG C, 0.476~1.555MPa, reaction 12~ 24h, takes out, is fully filtered with deionized water and wash unnecessary exciting agent, produce hydro-thermal oxygenation pretreatment ash sample.
In step (2), when being illustrated domestication, culture medium used includes PDA culture medium, PSA culture mediums, DOX cultures Base or PCS culture mediums；It is preferred that, used medium is DOX culture mediums.
In step (2), when carrying out domestication culture, in 25~30 DEG C, 165~200rpm is incubated, and pH is detected daily Change, no longer declines to pH.
In step (3), the concentration of the mortar is 1~10%.
It is preferred that, in step (3), the OD600=0.1 of the spore suspension of domestication aspergillus niger obtained by added step (2).
In step (4), the concentration of step (1) gains is 5~10%, the inoculum concentration of domestication aspergillus niger obtained by step (3) For 5%；When being cultivated, in 25~30 DEG C, incubated 7~10 days of 165~200rpm.
For rare precious metal of the present invention, if these metals need to be reclaimed from flyash, how to change The special surface texture of flyash so that these rare precious metals are more easy to leach, and are the keys of problem.
The present invention with physicochemical method pre-treating fly ash, destroys the surface knot of flyash to a certain extent first Structure, is exposed metallic element, recycles the intrinsic advantage of microorganism that metallic element is reduced or is dissolved out.
A variety of methods have been excited on flyash activity, generally activity excitation method have been carried out using acid compound, Also the method for useful microwave calcining carries out activity excitation.Wherein there are some researches show sour concentration is higher, and stimulation effect is better. And be all condition in normal temperature and pressure or less than 100 DEG C in the method pre-processed using acid to flyash for exciting agent Lower progress, it usually needs longer time.
Kinds of culture medium is different, and carbon source, nitrogen source, micronutrient levels can be differed, and the growth metabolism of microorganism can also be deposited In difference.Research shows that aspergillus niger species and content of metabolic type and production organic acid in different culture media are different from.Cause This, screens suitable culture medium, and the acid producing ability and production acid amount for strengthening aspergillus niger are to improve the key point of extraction rate.The present invention Choose PDA (potato sucrose culture medium), PSA (potato dextrose medium), DOX (Czapek's medium), PCS (glucose Corn steep liquor culture medium) it is used as the screening of candidate's culture medium progress extraction culture medium.
As shown in the embodiment of the present invention, DOX is adapted to the acidifying domestication of aspergillus niger the most.
Such as preferred technical scheme of the present invention, when second step tames the stage, by freezing for taming on last stage Bacterium solution collects spore after rejuvenation in the medium, and OD600=0.1 spore suspension is made, and is used as inoculation bacterium solution.Prepare first The mortar culture medium of low concentration (1%), seed liquor inoculation mortar culture medium.After collecting spore after bacterial growth, spore is made and hangs Liquid continues to be inoculated with the mortar culture medium of higher concentration, can be in 10% mortar culture medium untill stable growth until bacterium.
It is worthy of note that, the acclimation of the pretreatment of the signified step (1) of the present invention and step (2) to step (3), It is not strict precedence relationship.In fact, described pretreatment and two acclimations can be carried out synchronously, or first carry out Acclimation, then pre-processed.
The invention and utilize hydrothermal method, under high-temperature and high-pressure conditions using NaOH be exciting agent to fine coal Ash is pre-processed, then by the domestication to aspergillus niger, obtain a kind of extraction Ti efficiently from flyash, Ga, Sr, Zr, The method of the rare precious metal such as Ba.
Instant invention overcomes many defects that traditional solid waste reclaims smithcraft, without complicated technological process, extracted Journey is simply controllable.Substantial amounts of chemical reagent and the energy need not be used, the requirement to equipment is not also high, i.e., economic environment friend again It is good.
As the analysis to the technique effect obtained by the present invention, inventor thinks：The present invention is based on the height under hydrothermal condition Warm high pressure base pre-treating fly ash, can effectively destroy the fine and close surface texture of flyash.Make the metal and its chemical combination wherein wrapped up Thing is exposed, and adds the chance that metal and its compound are contacted with microorganism and its metabolin in flyash；The present invention is adopted The method extracted with pretreatment in conjunction with microorganism, substantially increases the leaching of five kinds of metals of Ti, Ga, Sr, Zr, Ba in flyash Go out effect；It is used as control, processing method that is conventional, reducing the pH of flyash, it is difficult to which increase is to of the present invention rare expensive The extraction of heavy metal, for Bi etc., can also suppress its extraction efficiency.
Beneficial effects of the present invention：
(1) the method can significantly improve the extraction rate of this 5 kinds of metals of Ti, Ga, Sr, Zr, Ba.For Ti metals, do not have The biological extraction rate only 8.36% of maximum by pretreatment, after alkali activating pretreatment maximum biology extraction rate improve to 97.5%；Ga extraction rate improves 71.7% by original 39.4%；Metal Sr and metal Zr extraction rate by 18.1%, 12.5% is respectively increased to 72.4%, 87.0%.
(2) used present invention, avoiding a large amount of of organic reagent, it is environment-friendly；
(3) the whole technique of the present invention is without too high-temperature, it is easy to implements and manipulates.
Brief description of the drawings
Fig. 1 is flyash SEM electron microscopes；Wherein, A, B are the flyash before not pre-processing；C, D are at HTHP alkali Reason (i.e. present invention processing) flyash；E, F are HTHP acid treatment flyash；
Fig. 2 is growing state of the aspergillus niger in DOX culture mediums；Wherein, A, B are solid medium, and C, D are Liquid Culture Base；
Fig. 3 is Aspergillus Niger Growth curve after domestication, and this growth curve is measured using biomass-mycelia weight method；
The pH changing rule result figures of different culture media are utilized when Fig. 4 is acid domestication aspergillus niger；
When Fig. 5 is acid domestication aspergillus niger, the content results figure of organic acid is produced in different culture media；
Fig. 6 is result figure of the different disposal method for the maximum biological extraction rate of Ti, Ga, Sr, Zr, Ba and Bi；
Fig. 7 is Bioleaching rate variation rule curve figure of the different disposal method for same metal.
Embodiment
The present invention is specifically described below by embodiment, it is necessary to it is pointed out here that be following examples be use It is further detailed in the present invention, it is impossible to be interpreted as limiting the scope of the invention, the field is skilled in technique Some nonessential modifications and adaptations that personnel are made according to foregoing invention content, still fall within protection scope of the present invention.
Aspergillus niger used in following embodiments (Aspergillus niger DSM 11167), be purchased from Beijing North receive wound connection life Thing Institute for Research and Technology.
Embodiment 1
Flyash pre-processes concrete operation step：
(1) 4mol/L NaOH (alkali-activator) and saturation Na is selected in the pretreatment of flyash respectively2SO4(acidity swashs Hair agent) it is used as exciting agent.
(2) appropriate flyash is added in the high-temperature high-pressure reaction kettle under the conditions of the hydrothermal pretreatment in 200ml, added respectively Enter soda acid exciting agent appropriate.It is 70% to react cumulative volume.150 DEG C of reaction temperature, system pressure is 0.476MPa, and reaction 24h takes Go out.
(3) excessive moisture is filtered, and is rinsed repeatedly with deionized water, the Na of high concentration is removed+.Total water consumption is pressed per 100g Ash sample 2L deionized water meters.
(4) ash sample after pretreatment terminates is made after silicon chip sample and tabletting carries out SEM, XRF detection respectively.
(5) it can be seen that without the glass bead structure spherical in shape of the flyash by pretreatment under Electronic Speculum.Through peracid, After the pretreatment of alkali-activator HTHP, spherical glass bead structure division by broken ring, show as crushing, spherome surface occur it is empty Hole (such as Fig. 1), preprocess method can reach expected purpose；Flyash is according to different its mineral composition and change in source, the place of production Composition is learned to differ greatly.According to XRF measurement results, the present invention flyash chemical composition such as table 1, wherein Al used2O3、SiO2Contain Amount accounts for more than 90%.After peracid, oxygenation pretreatment, the individual constituent of ash sample, which decreases, (removes SO in alkali process3Outside).
The chemical composition of the flyash of table 1
Embodiment 2
Extract the screening and acid producing ability domestication of culture medium
(1) formula of candidate's culture medium is as follows：
PDA：Fresh potato 200.0g is taken, 30.0min is boiled after peeling, cutting into slices, potato is removed with double gauze filtering Slag, glucose 20.0g is added into filtered fluid, and it is 1.0L to add distilled water to cumulative volume, is stirred and evenly mixed, pH is naturally, 121 Autoclaving 20.0min under the conditions of DEG C.
PSA：Fresh potato 200.0g is taken, 30.0min is boiled after peeling, cutting into slices, potato is removed with double gauze filtering Slag, sucrose 20.0g is added into filtered fluid, and it is 1.0L to add distilled water to cumulative volume, is stirred and evenly mixed, pH is naturally, at 121 DEG C Under the conditions of the min of autoclaving 20.0.
DOX：NaNO3 3.0g, K2HPO4 1.0g, KCl 0.5g, MgSO4.7H2O 0.5.0g, FeSO4 0.01g, sugarcane Sugared 30.0g, agar 15.0-20.0g, distilled water 1000.0ml, pH 7.3 ± 0.2.
PCS：Take corn flour 10.0g to boil 30.0min, filtered with double gauze, collect filtered fluid, Portugal is added into filtrate Grape sugar 30.0g, yeast extract 1.0g, KH2PO41.0g、 Mg SO4.7H201.0g, adding distilled water to cumulative volume is 1.0L, is stirred and evenly mixed, pH naturally, under the conditions of 121 DEG C autoclaving 20.0min.
(2) PDA, PSA, DOX, PCS culture medium are prepared respectively, and the spore suspension of domesticated strain is inoculated with by 1% inoculum concentration, It is 30 DEG C, incubated under the conditions of 165rpm.The pH changes of sampling detection daily, until pH not untill reduction.Different culture media pH Value changes such as Fig. 4.
(3) zymotic fluid is collected, centrifugation is crossed after 0.45um miillpore filters with UPLC and IC to the oxalic acid in zymotic fluid, lemon Acid, acetic acid, malic acid, α-ketoglutaric acid, butanedioic acid carry out qualitative and quantitative.
(4) obtained according to Fig. 4, Fig. 5：PH the biggest drop of DOX culture mediums, it produces oxalic acid, citric acid, acetic acid, α -one penta 2 The amount of acid is most.The content of its mesoxalic acid is up to 12.671 mg/ml.Therefore selection DOX culture mediums soak ore deposit culture as aspergillus niger Base.
The aspergillus niger of table 2 produces the content of organic acid in different culture media
Embodiment 3
The domestication of enduring high-concentration mortar cultivating system
(1) domestication culture medium is Czapek's medium：NaNO3 3.0g、K2HPO4 1.0g、KCl 0.5g、MgSO4.7H2O 0.5g、FeSO40.01g, sucrose 30.0g, distilled water 1000.0ml, pH 7.3 ± 0.2.(solid medium adds agar 15.0-20.0g)
(2) bacterium solution will be frozen and collect spore after rejuvenation in the medium, OD600=0.1 spore suspension is made, as It is inoculated with bacterium solution.
(3) Czapek's medium is prepared, a certain amount of flyash is added, the domestication culture medium of 1% mortar concentration is made.By 10% Inoculum concentration inoculating spores suspension.Culture a period of time, observe bacteria living situation and carry out spore count.Collect the bacterium of survival Spore, is made spore suspension.
(4) the domestication culture medium of 5% mortar concentration is prepared.The spore suspension that inoculation step (3) is obtained.When cultivating one section Between, observe bacteria living situation and carry out spore count.The bacterial spore of survival is collected, spore suspension is made.
(5) repeatedly, if the domestication culture medium strain of higher concentration can not survive, reduction mortar is dense for repeat step (4) Degree.Untill strain can be stablized and grow.
(6) it is so repeated multiple times, can be in the culture medium of 10% mortar concentration untill stable growth until fungi.Collect spore Son, is made spore suspension, adds protective agent in -80 DEG C of preservations, both obtains the aspergillus niger of resisting high-concentration (10%) flyash.
(7) obtained being resistant to the aspergillus niger seed liquor of 10% mortar concentration by training repeatedly, and in solid (in Fig. 2 A, B) and liquid (C, D in Fig. 2) culture medium in can stablize grow.From growth curve (Fig. 3), aspergillus niger after domestication Enter within the 3rd day exponential phase in culture, reach the growth platform phase within the 5th day.
Embodiment 4
The foundation of microorganism acid soil
(1) according to the selection result, selection DOX culture mediums are used as leaching culture medium.
(2) 250.0ml culture mediums are filled in 500.0ml conical flasks, 25.0g former ash, the activation of HTHP alkali are weighed respectively Ash, HTHP acid activation ash shake up the cultivating system for both obtaining 10% mortar concentration in culture medium.Adjustment pH to 7.3 ± 0.2,121 DEG C of sterilizing 15.0min.
(3) 5% inoculum concentration inoculating spores suspension is pressed after cooling down.In 30 DEG C, incubated 8d under the conditions of 165rpm.Take daily Sample determines tenor, pH, biomass.The moisture of evaporation is supplemented using constant weight method with distilled water.One group of blank pair is set simultaneously According to blank group is inoculated with 0.5% (v/v) formalin bacteriostatic agent (0.5% formalin ethanol solution).
(4) result：As a result show, the method that pretreatment combines Bioleaching can increase perhaps polymetallic in flyash leach Rate.Wherein, metal is planted in Ti, Ga, Sr, Zr, Ba etc. 5 most representative.As seen from Figure 6, in addition to metal Bi, HTHP Acid, oxygenation pretreatment method can significantly improve Ti, Ga, Sr, Zr, Ba leaching rate.Wherein, the effect that category alkali activator is pre-processed again is most To be notable.For Ti metals, not by the maximum biological extraction rate only 8.36% of pretreatment, after acid, alkali activating pretreatment Maximum biology extraction rate is respectively increased to 15.2% and 97.5%.Ga extraction rate is also respectively increased by original 39.4% 57.6% and 71.7%.Metal Sr is roughly the same with metal Zr situation, and HTHP acid treatment influences little to its extraction rate, Extraction rate is respectively increased to 72.4%, 87.0% by 18.1%, 12.5% during alkali process.
In the extraction cycle of 8d by a definite date, metal Ti Leaching Rule is as shown in the A in Fig. 7.In alkali process ash sample, with Bacterial growth enters logarithmic phase, and the leaching rate of titanium is also sharply increased, and when reaching plateau within the 6th day up to maximum (97.6%)；Metal Ga (B in Fig. 7) Leaching Rule is：Three kinds of ash samples all changed at first 5 days of bacterial growth, alkali The leaching rate of processing ash is overall in increase, constant, downward trend higher than acid treatment ash and former ash；Metal Sr (C in Fig. 7) Leaching Rule be：Alkali process ash shows the similar rule of same bacterial growth, starts increase after cultivating the 1st day.Leaching rate After reaching 65.2%, change unobvious, 72.4% is reached at the 8th day；Metal Zr (D in Fig. 7) in alkali process ash sample with The growth of bacterium, leaching rate gradually increases, and reaches maximum 87.0% within the 7th day；Ba (E in Fig. 7) leaching rate increase is concentrated Between the 1 to 5th day, acid, the maximum leaching rate of sode ash sample are respectively 29%, 45.6%；Metal Bi (F in Fig. 7) is then showed Go out different changing rules, at first 5 days of culture, acid, oxygenation pretreatment caused Bi leaching rate to be less than the leaching rate of former ash on the contrary. The maximum leaching rate difference 86.6%, 60.9%, 43.0% of former ash, alkali process ash, acid treatment ash.

Claims (10)

1. the method for rare precious metal is extracted from flyash using Microorganism Leaching, it is characterised in that methods described includes Following steps：
(1) by the use of NaOH as exciting agent, it will be pre-processed in the high-temperature high-pressure reaction kettle of flyash under hydrothermal conditions；
(2) production acid domestication is carried out to aspergillus niger；
(3) domestication aspergillus niger obtained by step (2) is added into the culture medium containing various concentrations mortar, by low concentration to high concentration, Carry out gradient domestication；
(4) by (1) gains the step of domestication aspergillus niger is inoculated in containing culture medium obtained by step (3), culture leaching is carried out；
The rare precious metal includes at least one of Ti, Ga, Sr, Zr, Ba.
2. according to the method described in claim 1, it is characterised in that the aspergillus niger is Aspergillus niger DSM 11167。
3. method according to claim 1 or 2, it is characterised in that in step (1), NaOH concentration is 1~4mol/L.
4. method according to claim 3, it is characterised in that in step (1), NaOH addition volume accounts for reactor volume 80%.
5. method according to claim 4, it is characterised in that in step (1), most in pretreatment, in 150~200 DEG C, 0.476~1.555MPa, reacts 12~24h, takes out, is fully filtered with deionized water and wash unnecessary exciting agent, produce hydro-thermal Oxygenation pretreatment ash sample.
6. according to the method described in claim 1, it is characterised in that in step (2), when being illustrated domestication, culture used Base includes PDA culture medium, PSA culture mediums, DOX culture mediums or PCS culture mediums；It is preferred that, used medium is DOX culture mediums.
7. according to the method described in claim 1, it is characterised in that in step (2), when carrying out domestication culture, in 25~30 DEG C, 165~200rpm is incubated, and detection pH changes, no longer decline to pH daily.
8. according to the method described in claim 1, it is characterised in that in step (3), the concentration of the mortar is 1~10%.
9. according to the method described in claim 1, it is characterised in that in step (3), the black song of domestication obtained by added step (2) The OD600=0.1 of mould spore suspension.
10. according to the method described in claim 1, it is characterised in that in step (4), the concentration of step (1) gains be 5~ 10%, the inoculum concentration of domestication aspergillus niger is 5% obtained by step (3)；When being cultivated, in 25~30 DEG C, 165~200rpm is permanent Temperature culture 7~10 days.
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