CN107236864B - The method of rare precious metals is extracted from flyash using Microorganism Leaching - Google Patents
The method of rare precious metals is extracted from flyash using Microorganism Leaching Download PDFInfo
- Publication number
- CN107236864B CN107236864B CN201710377968.XA CN201710377968A CN107236864B CN 107236864 B CN107236864 B CN 107236864B CN 201710377968 A CN201710377968 A CN 201710377968A CN 107236864 B CN107236864 B CN 107236864B
- Authority
- CN
- China
- Prior art keywords
- domestication
- culture medium
- aspergillus niger
- flyash
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Metallurgy (AREA)
- Geology (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- Microbiology (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention provides the methods for extracting rare precious metal from flyash using Microorganism Leaching comprising following steps: (1) using NaOH as exciting agent, will pre-process in the high-temperature high-pressure reaction kettle of flyash under hydrothermal conditions；(2) aspergillus niger is carried out producing sour domestication；(3) culture medium containing various concentration mortar is added in domestication aspergillus niger obtained by step (2), by low concentration to high concentration, carries out gradient domestication；(4) in the step of domestication aspergillus niger obtained by step (3) being inoculated in containing culture medium (1) gains, 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 rates of this 5 kinds of metals of Ti, Ga, Sr, Zr, Ba；It is environmental-friendly the invention avoids a large amount of uses of organic reagent；The entire technique of the present invention is without too high-temperature, easy to implement and manipulation.
Description
Technical field
The invention belongs to solid waste resource recycling fields, and in particular to be extracted from flyash using Microorganism Leaching
The method of rare precious metal.
Background technique
Flyash is mainly generated by coal-fired industries such as coal fired thermal power plants, with the fast development of power industry, power plant's scale
Constantly expand, leads to the discharge amount sharp increase of China's flyash.The flyash discharge capacity in China in 1985 is 3.769 hundred million tons,
In every 10 years later, the ash discharge amount by 5,600,000 tons every year on average is increasing, and ends 2010, and the ash discharge amount in China is with up to 3,000,000,000
Ton.Utilization rate of the flyash in China be not high, and 2010 annual datas show only 69%, along with sharply increasing for ash discharge amount, gives
The soil in China, water, atmosphere, environment cause huge harm.In China, embankment is concentrated mainly on for the utilization of flyash
In terms of making ground.Flyash is used for construction material, production pulverized fuel ash cement, concrete etc. earliest, and embankment is used in highway construction
Filling, down-hole backfill, also have for fired fly ash brick, fly ash building block.
With the continuous deepening of research, existing research person extracts recycling aluminium oxide with the method for chemistry from flyash,
This respect comes into industrialized production.In addition, manufactured fly ash absorbent there are also researcher, 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 mainly by SiO2、Al2O3、FeO、Fe2O3、CaO、TiO2、MgO、MnO2、
P2O5Equal oxides composition.In addition, also containing many very dilute expensive metals, as Ti (titanium), Ga (gallium), Ge (germanium), chromium, lead,
Vanadium, arsenic, uranium etc..Currently, the commonsense method handled flyash usually slatterns rare precious metal.
China's flyash is not fully utilized in metal recovery domain variability, only has in terms of recycling aluminium element involved
And.But the recovering means of aluminium element are all the chemical methodes of application.A large amount of chemical reagent is not only used, but also is usually wanted
Seek very high temperature.In the industrial technique with germanium metal in the germanic flyash of chloride way of distillation enriching and recovering, distillation process
Need to consume a large amount of chloride, hydrolysis temperature and cleansing temp require 650~675 DEG C and 1000~1150 DEG C respectively, this is right
The requirement of the energy and equipment is very high, and the extraction process of this method is also very complicated.
The reason of why comprehensive utilization of flyash makes slow progress first is that flyash mostly in the form of glass bead
In the presence of surface covers one layer of smooth fine and close, firm Si-O-Si, Si-O-Al network structure, its chemical property is made to be in one
A more stable state, and most metals element contained therein is wrapped in such network structure, be difficult with outside
Boundary's contact chemically reacts, and conventional metal recovery means is caused to be difficult to recycle these metallic elements in flyash.
Currently, for the recovery method industrialization also relatively difficult to achieve or production of the rare precious metals such as Ti, Ga, Sr, Zr, Ba
Industryization is with high costs.If the method for industrial production Titanium is mainly Kroll process and hunt's method, both methods all exists
The disadvantages of complex process, at high cost, energy consumption is high, and production cost remains high.Other methods such as electrolysis method and thermal reduction also exist
Experimental stage.Regardless of which kind of method (method including the experimental stage), required temperature are even higher all in 1000K or so.?
Also with the presence of many difficulties in terms of the recycling of gallium, when such as full extraction recycles gallium, there is organic phase has hypertoxic, inflammable, loss
Greatly, the disadvantages of high production cost.Recycling about strontium and zirconium is just more difficult, and metal zirconium does not have individualism in the earth's crust
Mineral deposit often coexists with mines such as ferrotianium, monazites, and only the separation of zirconium metal is with regard to difficult.Have in scholar's Zeng Cong celestine and mentions
Take half type approval test of Preparation of Metallic Strontium study in propose a kind of than more complete extraction process, but this process flow is tediously long.Roasting
Burning temperature is 1100 DEG C, calcining time 5h, needs a large amount of potassium bichromate solution, vapo(u)rizing temperature is also at 1150~1200 DEG C.Afterwards
Come, has scholar that extraction process is optimized in vacuum thermit reduction preparation high-purity strontium technical study, but after optimization
There is still a need for carry out the reduction temperature of extraction process under the conditions of 0.01KPa, 1050 ± 20 DEG C.
In conclusion there are still many difficulties for the industrial method for extracting the metals such as Titanium, gallium, strontium, zirconium at present, it is many
Technique still has much room for improvement.However it may is that from the method that the angle of microorganism extracts recycling the above metal and solve this
One of feasible method of problem, the research about this respect are but rarely reported, more without the biological extraction process quilt of a set of completion
It proposes.
Bioleaching refer to using microorganism itself to the oxidations of mineral or reduction characteristic by mineral oxide or reduction to
Make dissolving metal therein into leaching mineral solution, or utilizes 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
The process being put into solution.Bioleaching is a complicated reaction process, 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
Existing reaction system.
Currently, scientists extract the rare valuable gold in recycling solid waste from the angle of microorganism and using microorganism
Category has done a large amount of research.But the microorganism extraction being related to is primarily directed to from sulfide tailing and discarded route
Rare precious metal is recycled in plate.Wherein industry is come into using microorganism from discarded circuit board and containing copper is recycled in copper tailing
Metaplasia produces.The rare precious metal such as Ti, Ga, Sr, Zr, Ba is recycled from flyash using microbial process to have not been reported.
Microorganism absorption method is not only environmentally protective, will not generate secondary hazards, and simple process, does not need using a large amount of chemistry examination
Agent, i.e., it is economical and environmental-friendly.
Summary of the invention
In view of the shortcomings of the prior art, dilute the purpose of the present invention is to provide being extracted from flyash using Microorganism Leaching
There is the method for precious metal, this method comprises the following steps:
(1) using NaOH as exciting agent, will be located in advance in the high-temperature high-pressure reaction kettle of flyash under hydrothermal conditions
Reason；
(2) aspergillus niger is carried out producing sour domestication；
(3) culture medium containing various concentration mortar is added in domestication aspergillus niger obtained by step (2), by low concentration to highly concentrated
Degree carries out gradient domestication；
(4) it in the step of domestication aspergillus niger obtained by step (3) being inoculated in containing culture medium (1) gains, is cultivated
It leaches；
The rare precious metal includes at least one of Ti, Ga, Sr, Zr, Ba.
The aspergillus niger is Aspergillus niger DSM 11167.
Preferably, in step (1), the concentration of NaOH is 1~4mol/L.
Preferably, in step (1), the addition volume of NaOH accounts for the 80% of reaction kettle volume.
Preferably, in step (1), most in pretreatment, in 150~200 DEG C, 0.476~1.555MPa, reaction 12~
For 24 hours, it takes out, is sufficiently filtered with deionized water and wash extra exciting agent to get hydro-thermal oxygenation pretreatment ash sample.
In step (2), when being illustrated domestication, culture medium used includes PDA culture medium, PSA culture medium, DOX culture
Base or PCS culture medium；Preferably, used medium is DOX culture medium.
In step (2), when carrying out domestication culture, in 25~30 DEG C, 165~200rpm constant temperature incubation detects pH daily
Variation, until pH no longer declines.
In step (3), the concentration of the mortar is 1~10%.
Preferably, 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)
It is 5%；When being cultivated, in 25~30 DEG C, 165~200rpm constant temperature incubation 7~10 days.
For rare precious metal of the present invention, if these metals need to be recycled from flyash, how to change
The special surface texture of flyash, so that these rare precious metals are easier to leach, it is the key that problem.
The present invention uses physicochemical method pre-treating fly ash first, destroys the surface knot of flyash to a certain extent
Metallic element is exposed in structure, recycles the intrinsic advantage of microorganism that metallic element is restored or is dissolved out.
Excitation about flyash activity is there are many kinds of method, usually using acid compound progress activity excitation method,
Also the method for useful microwave calcining carries out activity excitation.Wherein some researches show that sour concentration is higher, and stimulation effect is better.
And flyash is carried out all being the condition in normal temperature and pressure or lower than 100 DEG C in pretreated method for exciting agent using acid
Lower progress, it usually needs longer time.
Kinds of culture medium is different, and carbon source, nitrogen source, micronutrient levels can not be identical, and the growth metabolism of microorganism can also be deposited
In difference.Studies have shown that the type and content of metabolic type and production organic acid are different from aspergillus niger in different medium.Cause
This, screens suitable culture medium, and enhancing the acid producing ability of aspergillus niger and producing acid amount is 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 pulp culture medium) screening of extraction culture medium is carried out as candidate culture medium.
As shown in the embodiment of present invention, DOX is suitble to the acidification domestication of aspergillus niger the most.
As a preferred technical solution of the invention freezes when second step tames the stage by what is tamed on last stage
Bacterium solution collects spore after rejuvenation in the medium, and the spore suspension of OD600=0.1 is made, as inoculation bacterium solution.It prepares first low
The mortar culture medium of concentration (1%), seed liquor are inoculated with mortar culture medium.Spore is collected after bacterial growth, and spore suspension is made
Continue the mortar culture medium for being inoculated with higher concentration, until bacterium can stablize growth in 10% mortar culture medium.
It is worth noting that the signified step (1) of the present invention pretreatment and step (2) to step (3) acclimation,
It is not stringent precedence relationship.In fact, the pretreatment synchronous can be carried out with two acclimations, 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 flyash
It is pre-processed, then by the domestication to aspergillus niger, obtains one kind and extract Ti, Ga, Sr, Zr, Ba efficiently from flyash
Etc. the method for rare precious metal.
The present invention overcomes many defects of traditional solid waste recycling smithcraft, not complicated process flow, extracteds
Journey is simply controllable.The requirement not needed using a large amount of chemical reagent and the energy, to equipment is not also high, i.e., economic environment friend again
It is good.
By the analysis to the resulting technical effect of 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 surface texture of flyash densification.Make the metal wherein wrapped up and its chemical combination
Object is exposed, and increases the chance that metal and its compound are contacted with microorganism and its metabolin in flyash；The present invention adopts
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
Effect；As control, the processing method of pH reduction conventional, by flyash, it is difficult to increase to of the present invention rare valuable
The extraction of metal can also inhibit its extraction efficiency for Bi etc..
Beneficial effects of the present invention:
(1) the method can significantly improve the extraction rates of this 5 kinds of metals of Ti, Ga, Sr, Zr, Ba.For Ti metal, do not have
By pretreated maximum biological extraction rate only 8.36%, after alkali activating pretreatment maximum biology extraction rate improve to
97.5%；The extraction rate of Ga improves 71.7% by original 39.4%；The extraction rate of metal Sr and metal Zr by 18.1%,
12.5% is respectively increased to 72.4%, 87.0%.
(2) environmental-friendly the invention avoids a large amount of uses of organic reagent；
(3) the entire technique of the present invention is without too high-temperature, easy to implement and manipulation.
Detailed description of the invention
Fig. 1 is flyash SEM electron microscope；Wherein, A, B are the flyash before not pre-processing；C, D is high temperature and pressure alkali process
(i.e. present invention processing) flyash；E, F is high temperature and pressure acid treated coal ash；
Fig. 2 is growing state of the aspergillus niger in DOX culture medium；Wherein, A, B are solid medium, and C, D are Liquid Culture
Base；
Fig. 3 is Aspergillus Niger Growth curve after domestication, this growth curve is measured using biomass-mycelia weight method；
The pH changing rule result figure of different culture medium is 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 medium；
Fig. 6 is the result figure of different disposal method biological extraction rate maximum for Ti, Ga, Sr, Zr, Ba and Bi；
Fig. 7 is Bioleaching rate variation rule curve figure of the different disposal method for same metal.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that following embodiment is only used
It is further detailed in the present invention, should not be understood as limiting the scope of the invention, which 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
Object Institute for Research and Technology.
Embodiment 1
Flyash pre-processes concrete operation step:
(1) NaOH (alkali-activator) and saturation Na of 4mol/L is selected in the pretreatment of flyash respectively2SO4(acid exciting
Agent) it is used as exciting agent.
(2) appropriate flyash is added in high-temperature high-pressure reaction kettle under the conditions of hydrothermal pretreatment in 200ml, respectively plus
It is appropriate to enter soda acid exciting agent.Reacting total volume is 70%.150 DEG C of reaction temperature, system pressure is 0.476MPa, and reaction takes for 24 hours
Out.
(3) excessive moisture is filtered, and with deionized water repeated flushing, removes the Na of high concentration+.Total water consumption presses every 100g
Ash sample 2L deionized water meter.
(4) ash sample after pre-processing is made after silicon wafer sample and tabletting carries out SEM, XRF detection respectively.
(5) it can be seen that without the glass bead structure spherical in shape by pretreated flyash under Electronic Speculum.Through peracid,
After the pretreatment of alkali-activator high temperature and pressure, spherical glass bead structure division is shown as being crushed, sky occurs in spherome surface by broken ring
Hole (such as Fig. 1), preprocess method can reach expected purpose；Flyash is according to its different mineral composition and change in source, the place of production
Composition is learned to differ greatly.According to XRF measurement result, flyash chemical composition such as table 1 used in the present invention, wherein Al2O3、SiO2Contain
Amount accounts for 90% or more.After peracid, oxygenation pretreatment, a constituent of ash sample decreases (except SO in alkali process3Outside).
The chemical composition of 1 flyash of table
Embodiment 2
Extract the screening and acid producing ability domestication of culture medium
(1) formula of candidate culture medium is as follows:
PDA: taking fresh potato 200.0g, peeled, be sliced after boil 30.0min, with double gauze filter removal potato
Glucose 20.0g is added into filtered fluid for slag, and adding distilled water to total volume is 1.0L, stirs and evenly mixs, pH is naturally, 121
High pressure sterilization 20.0min under the conditions of DEG C.
PSA: taking fresh potato 200.0g, peeled, be sliced after boil 30.0min, with double gauze filter removal potato
Sucrose 20.0g is added into filtered fluid for slag, and adding distilled water to total volume is 1.0L, stirs and evenly mixs, pH is naturally, at 121 DEG C
Under the conditions of high pressure sterilization 20.0min.
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: taking corn flour 10.0g to boil 30.0min, filtered with double gauze, collects 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 total volume is
1.0L is stirred and evenly mixed, pH naturally, under the conditions of 121 DEG C high pressure sterilization 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,
30 DEG C, constant temperature incubation under the conditions of 165rpm.Daily sample detection pH variation, until pH not until reduction.Different culture medium pH
Value variation such as Fig. 4.
(3) fermentation liquid is collected, centrifugation is crossed after 0.45um miillpore filter with UPLC and IC to the oxalic acid in fermentation liquid, lemon
Acid, acetic acid, malic acid, α-ketoglutaric acid, succinic acid carry out qualitative and quantitative.
(4) obtained according to Fig. 4, Fig. 5: pH the biggest drop of DOX culture medium 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 12.671mg/ml.Therefore DOX culture medium is selected to soak mine culture medium as aspergillus niger.
2 aspergillus niger of table produces the content of organic acid in different medium
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.(agar is added in solid medium
15.0-20.0g)
(2) bacterium solution will be frozen and collect spore after rejuvenation in the medium, the spore suspension of OD600=0.1 is made, as connecing
Kind 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 observes bacteria living situation and carries out spore count.Collect the bacterium of survival
Spore suspension is made in spore.
(4) the domestication culture medium of 5% mortar concentration is prepared.The spore suspension that inoculation step (3) obtains.When cultivating one section
Between, it observes bacteria living situation and carries out spore count.The bacterial spore for collecting survival, is made spore suspension.
(5) step (4) are repeated repeatedly, if the domestication culture medium strain of higher concentration cannot survive, it is dense reduces mortar
Degree.Until strain can stablize growth.
(6) repeatedly repeatedly, until fungi can stablize growth in the culture medium of 10% mortar concentration.Collect spore
Spore suspension is made in son, and protective agent is added and saves in -80 DEG C, both obtains the aspergillus niger of resisting high-concentration (10%) flyash.
(7) the aspergillus niger seed liquor for being resistant to 10% mortar concentration has been obtained by training repeatedly, and in solid (in Fig. 2
A, B) and liquid (C, D in Fig. 2) culture medium in can stablize growth.By growth curve (Fig. 3) it is found that domestication after aspergillus niger
Enter logarithmic growth phase within the 3rd day in culture, reaches the growth platform phase within the 5th day.
Embodiment 4
The foundation of microorganism acid soil
(1) according to the selection result, select DOX culture medium as leaching culture medium.
(2) 250.0ml culture medium is filled in 500.0ml conical flask, weighs 25.0g former ash, the activation of high temperature and pressure alkali respectively
Ash, high temperature and pressure 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.In 30 DEG C, constant temperature incubation 8d under the conditions of 165rpm.It takes daily
Sample measures 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 the formalin bacteriostatic agent (0.5% formalin ethanol solution) of 0.5% (v/v).
(4) result: the result shows that, the method that pretreatment combines Bioleaching, which can increase, is permitted polymetallic leaching in flyash
Rate.Wherein, it is most representative that metal is planted in Ti, Ga, Sr, Zr, Ba etc. 5.As seen from Figure 6, in addition to metal Bi, high temperature and pressure
Acid, oxygenation pretreatment method can significantly improve the leaching rate of Ti, Ga, Sr, Zr, Ba.Wherein, and belong to the pretreated effect of alkali activator most
It is significant.For Ti metal, by pretreated maximum biological extraction rate only 8.36%, after acid, alkali activating pretreatment
Maximum biology extraction rate is respectively increased to 15.2% and 97.5%.The extraction rate of Ga is also respectively increased by original 39.4%
57.6% and 71.7%.The case where metal Sr and metal Zr, is roughly the same, and the processing of high temperature and pressure acid influences less its extraction rate,
Extraction rate is respectively increased by 18.1%, 12.5% to 72.4%, 87.0% when alkali process.
In the extraction period of 8d by a definite date, the Leaching Rule of metal Ti 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 also sharply increases, and maximum value is reached when reaching plateau within the 6th day
(97.6%)；The Leaching Rule of metal Ga (B in Fig. 7) are as follows: three kinds of ash samples all changed at first 5 days of bacterial growth, alkali
The leaching rate of processing ash is higher than sour processing ash and former ash, overall in increase, constant, downward trend；Metal Sr (C in Fig. 7)
Leaching Rule are as follows: alkali process ash shows the similar rule of same bacterial growth, culture the 1st day after start to increase.Leaching rate
After reaching 65.2%, change unobvious, the 8th day when reaches 72.4%；Metal Zr (D in Fig. 7) in alkali process ash sample with
The growth of bacterium, leaching rate gradually increase, and reach maximum value 87.0% within the 7th day；The leaching rate of Ba (E in Fig. 7), which increases, to be concentrated
Between the 1 to 5th day, sour, sode ash sample maximum leaching rate is respectively 29%, 45.6%；Metal Bi (F in Fig. 7) is then showed
Different changing rule out, at first 5 days of culture, acid, oxygenation pretreatment made the leaching rate of Bi lower than the leaching rate of former ash instead.
The maximum leaching rate difference 86.6%, 60.9%, 43.0% of former ash, alkali process ash, acid processing ash.
Claims (11)
1. the method for rare precious metal is extracted from flyash using Microorganism Leaching, which is characterized in that the method includes
Following steps:
(1) it using NaOH as exciting agent, will be pre-processed in the high-temperature high-pressure reaction kettle of flyash under hydrothermal conditions；
(2) aspergillus niger is carried out producing sour domestication；
(3) culture medium containing various concentration mortar is added in domestication aspergillus niger obtained by step (2), by low concentration to high concentration,
Carry out gradient domestication；
(4) in the step of domestication aspergillus niger obtained by step (3) being inoculated in containing culture medium (1) gains, culture leaching is carried out；
The rare precious metal includes at least one of Ti, Ga, Sr, Zr, Ba.
2. the method according to claim 1, wherein the aspergillus niger is Aspergillus niger
DSM11167。
3. method according to claim 1 or 2, which is characterized in that in step (1), the concentration of NaOH is 1~4mol/L.
4. according to the method described in claim 3, it is characterized in that, the addition volume of NaOH accounts for reaction kettle volume in step (1)
80%.
5. according to the method described in claim 4, it is characterized in that, in step (1), in pretreatment, in 150~200 DEG C,
0.476~1.555MPa, reaction 12~for 24 hours, it takes out, is sufficiently filtered with deionized water and wash extra exciting agent to get hydro-thermal
Oxygenation pretreatment ash sample.
6. the method according to claim 1, wherein in step (2), when being illustrated domestication, culture used
Base includes PDA culture medium, PSA culture medium, DOX culture medium or PCS culture medium.
7. according to the method described in claim 6, it is characterized in that, used medium is DOX culture medium.
8. the method according to claim 1, wherein in step (2), when carrying out domestication culture, in 25~30
DEG C, 165~200rpm constant temperature incubation detects pH variation, until pH no longer declines daily.
9. the method according to claim 1, wherein the concentration of the mortar is 1~10% in step (3).
10. the method according to claim 1, wherein taming black song obtained by added step (2) in step (3)
The OD600=0.1 of mould spore suspension.
11. the method according to claim 1, wherein in step (4), the concentration of step (1) gains is 5~
10%, the inoculum concentration of step (3) gained domestication aspergillus niger is 5%；When being cultivated, in 25~30 DEG C, 165~200rpm is permanent
Temperature culture 7~10 days.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710377968.XA CN107236864B (en) | 2017-05-25 | 2017-05-25 | The method of rare precious metals is extracted from flyash using Microorganism Leaching |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710377968.XA CN107236864B (en) | 2017-05-25 | 2017-05-25 | The method of rare precious metals is extracted from flyash using Microorganism Leaching |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107236864A CN107236864A (en) | 2017-10-10 |
| CN107236864B true CN107236864B (en) | 2019-05-10 |
Family
ID=59984463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710377968.XA Active CN107236864B (en) | 2017-05-25 | 2017-05-25 | The method of rare precious metals is extracted from flyash using Microorganism Leaching |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107236864B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108130421B (en) * | 2018-01-26 | 2019-06-18 | 宁波华成阀门有限公司 | A kind of manufacturing method of the brass extracted from useless radiator |
| CN108285981B (en) * | 2018-02-09 | 2020-05-19 | 南华大学 | Method for extracting uranium from fly ash of fire coal |
| CN110408788B (en) * | 2019-09-04 | 2020-12-22 | 贵州理工学院 | Method for leaching acidolysis slag containing rare earth and recovering rare earth |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4567026A (en) * | 1984-10-24 | 1986-01-28 | Internorth, Inc. | Method for extraction of iron aluminum and titanium from coal ash |
| JP2001017942A (en) * | 1999-07-09 | 2001-01-23 | Agency Of Ind Science & Technol | Process for removing lead compound from incineration ash |
| CN105969994B (en) * | 2016-06-23 | 2019-04-05 | 中国神华能源股份有限公司 | A method of extracting lanthanum from flyash |
-
2017
- 2017-05-25 CN CN201710377968.XA patent/CN107236864B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107236864A (en) | 2017-10-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Vakilchap et al. | Role of Aspergillus niger in recovery enhancement of valuable metals from produced red mud in Bayer process | |
| Eisele et al. | Review of reductive leaching of iron by anaerobic bacteria | |
| CN107236864B (en) | The method of rare precious metals is extracted from flyash using Microorganism Leaching | |
| Muddanna et al. | A comparative study of the extraction of metals from the spent fluid catalytic cracking catalyst using chemical leaching and bioleaching by Aspergillus niger | |
| CN100554444C (en) | A kind of bioleaching process of ore of cobalt nickel oxide | |
| CN101434909B (en) | Penicillium, as well as preparation method and application | |
| CN102002588B (en) | Bioleaching method-uranium leaching from fungus | |
| Tzeferis | Leaching of a low grade hematitic laterite ore using fungi and biologically produced acid metabolites | |
| CN113337409B (en) | Aspergillus niger strain 738Y-15MJ and application thereof | |
| CN111304096A (en) | Penicillium oxalicum and culture method and application thereof | |
| CN102560114A (en) | Method for bioleaching and extracting valuable metal ions in waste batteries | |
| Shah et al. | Enhanced bio-recovery of aluminum from low-grade bauxite using adapted fungal strains | |
| Wang et al. | Green recovery of vanadium from vanadium-bearing shale under the biological action by Bacillus mucilaginosus and its effect on mineral dissolution | |
| CN101837962A (en) | Method for leaching phosphorus from low-grade phosphate ore by thiobacillus thiooxidans | |
| CN101748080A (en) | Ore leaching bacteria and selectivity organism extraction process of low grade zinc sulfide ore | |
| CN1827805A (en) | Sulfide ore treatment technology by thermoacidophile | |
| He et al. | Mobilization and fractionation of rare earth elements during experimental bio-weathering of granites | |
| CN104531990B (en) | Biological gold extraction process of antimony-bearing complex refractory gold ore and microorganism used in same | |
| CN108913889A (en) | A kind of method of Microorganism Leaching vanadium and selective enrichment vanadium | |
| Lee et al. | Microbial removal of Fe (III) impurities from clay using dissimilatory iron reducers | |
| Kar et al. | Bioleaching of lateritic nickel ore by ultrasound | |
| CN108300856A (en) | The bioleaching process of indium metal in a kind of waste liquid crystal display | |
| Ventura et al. | Bioreduction of iron compounds by Aeromonas hydrophila | |
| CN110408801B (en) | Method for recovering rare earth by heap leaching and leaching phosphogypsum containing rare earth | |
| CN105803194B (en) | A kind of method that arsenic-bearing refractory gold ore microbe-preoxidation gold is carried out using high arsenic ion tolerance leaching microbacteria |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |