CN114480364B - Microorganism capsule for recovering valuable metals and preparation method and application thereof - Google Patents

Microorganism capsule for recovering valuable metals and preparation method and application thereof Download PDF

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CN114480364B
CN114480364B CN202210017262.3A CN202210017262A CN114480364B CN 114480364 B CN114480364 B CN 114480364B CN 202210017262 A CN202210017262 A CN 202210017262A CN 114480364 B CN114480364 B CN 114480364B
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solution
carrier
microbial
mixing
mixture
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CN114480364A (en
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黄进
杨振东
马文标
杨博闻
曾丽
王鸿斌
郑旭颖
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Chengdu University
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    • C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
    • C12N11/14—Enzymes or microbial cells immobilised on or in an inorganic carrier
    • C—CHEMISTRY; METALLURGY
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    • C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22B11/00—Obtaining noble metals
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    • C22B13/00—Obtaining lead
    • C22B13/04—Obtaining lead by wet processes
    • C22B13/045—Recovery from waste materials
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B17/00—Obtaining cadmium
    • C22B17/04—Obtaining cadmium by wet processes
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    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22B21/00—Obtaining aluminium
    • C22B21/0015—Obtaining aluminium by wet processes
    • C22B21/0023—Obtaining aluminium by wet processes from waste materials
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    • 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
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • C22B30/04—Obtaining arsenic
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    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
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    • C22B34/22—Obtaining vanadium
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    • C22B34/00—Obtaining refractory metals
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    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B47/00—Obtaining manganese
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    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B59/00—Obtaining rare earth metals
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    • 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
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    • C22B7/02—Working-up flue dust
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Abstract

The invention discloses a microbial capsule for recovering valuable metals, and a preparation method and application thereof. The microbial capsule is prepared through loading microbial strain and microbe homogeneous nutritious matter onto carrier, and coating the carrier with non-toxic polymer material. The invention improves the diversity of functional microorganisms by synthesizing microbiome. The scheme of the invention can promote the substance exchange and information transfer among microorganisms, realize the rapid and directional propagation of microorganisms in the capsule, maintain relative stability and improve the metal recovery efficiency of a biological method.

Description

Microorganism capsule for recovering valuable metals and preparation method and application thereof
Technical Field
The invention belongs to the technical field of metal recovery, and particularly relates to a microbial capsule for valuable metal recovery, and a preparation method and application thereof.
Background
Fly ash is a main solid waste generated after the combustion of the fly ash, and is usually deposited in the fly ash pond near a thermal power plant in the open air, so that not only a large amount of land is occupied, but also harmful substances such as heavy metal elements (lead, chromium, nickel, cobalt and the like) and radioactive elements are leached out after the fly ash contacts with rainwater, so that nearby water bodies or farmlands are polluted, and great threat is caused to the safety of the surrounding ecological environment and the health of human bodies. In addition, the fly ash is used as a novel mineral resource, and valuable elements such as aluminum, iron, titanium, gallium, germanium and the like can be comprehensively extracted. The content of these elements is generally higher than in normal economic deposits. Along with the adjustment and transformation and upgrading of economic structures and energy structures in China, the development of thirteen-five planning in the coal industry brings great demands for the green and efficient utilization of coal. Therefore, the method has the advantages that the coal industry solid waste is well treated, the recovery utilization rate of the fly ash is increased to realize circular economy, and the method is an urgent need for the transformation of the green economy industry in China.
The extraction technology of valuable metals in the fly ash mainly comprises three types of physical separation, chemical extraction and biological leaching. The physical separation energy consumption is high, secondary coal ash can be generated, and the coal ash usually contains high-concentration chloride ions, which is not beneficial to the melting process; the chemical extraction method has the characteristic of low energy consumption, but has the main defects of complex process, large consumption of reagents, easy generation of secondary pollution such as waste liquid, waste residue and the like. In recent years, extraction of valuable metals in fly ash by bioleaching technology has attracted a great deal of attention.
The biological leaching technology is a high-new technology for extracting valuable metals by utilizing inorganic energy nutrition microorganisms, oxidizing and decomposing fly ash, releasing valuable metal ions into solution and further separating, enriching and purifying. However, the extraction of valuable metals by a microbiological method has the problems of difficult colonization, low activity of strains, unstable effect and the like, and severely limits the popularization and application of the microbiological repair technology.
Disclosure of Invention
Aiming at the prior art, the invention provides a microbial capsule for recovering valuable metals, and a preparation method and application thereof, so as to solve the technical problem of difficult recovery of the valuable metals in fly ash.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the preparation method of the microbial capsule for recovering valuable metals comprises the following steps:
s1: carrying out interlayer domain amplification and surface functionalization treatment on the carrier;
s2: immersing the carrier subjected to the S1 treatment into a microbial nutrient solution, and immersing the carrier by normal pressure or negative pressure to obtain a carrier loaded with nutrient substances;
s3: mixing the bacterial suspension of the functional strain and the bacterial suspension of the auxiliary strain in equal volume, immersing the carrier treated by the S1 into the mixed bacterial solution, and oscillating for 20-25 h at 20-30 ℃ and 180-250 rpm to obtain the carrier loaded with microorganisms; functional strains include iron-reducing bacteria, acidogenic bacteria, and metal-oxidizing-reducing bacteria, auxiliary strains include Ochrobactrum spp, pseudomonas aeruginosa Pseudomonas aeruginosa spp, and Aeromonas spp;
s4: immersing the carrier loaded with nutrient substances and the carrier loaded with microorganisms into MBA solution, and oscillating at a speed of 200-250 rpm for 70-75 h to obtain suspension; adding PES (polyethersulfone) and PVP (polyvinylpyrrolidone) into the suspension, and continuously oscillating at the speed of 200-250 rpm for 70-75 h to obtain a mixture;
s5: coating the mixture on a smooth glass plate, coating the mixture with the thickness of 180-220 mu m, evaporating the mixture at room temperature for 15 seconds, and soaking and curing the mixture in a coagulating bath at the temperature of 17-19 ℃ for 1-3 min to obtain a film; then soaking the film in deionized water for 2 hours, and cutting into slices with the diameter of 1mm to obtain the microbial capsules.
On the basis of the technical scheme, the invention can be improved as follows.
Further, the carrier interlayer domain amplification and surface functionalization treatment comprises the following steps:
SS1: mixing the base material and water according to the feed-liquid ratio of 8-10 g:100mL, and mixing the base material and water according to the feed-liquid ratio of 1.0X10 5 ～1.5×10 5 J, radiating energy ultrasonic for 8-12 min, filtering out the base material and drying at 90-120 ℃ for 5-10 min; the base material is kaolin or montmorillonite;
SS2: calcining the substrate subjected to SS1 treatment under the protection of inert gas, wherein the calcining temperature is 750-850 ℃ and the calcining time is 20-40 s;
SS3: mixing modifier and SS2 treated base material in the weight ratio of 1 to 20-25, and soaking the mixture into 45wt% concentration H 3 PO 4 Soaking in the solution for 24 hours, taking out the base material, drying for 5-10 min at 90-120 ℃ and finishing the carrier treatment; the modifier is prepared by mixing organic quaternary ammonium salt and humic acid according to the mass ratio of 3:1.
Further, the microbial nutrient solution is prepared through the following steps:
SS1: preparing solutions A, B and C; solution a included the following concentrations of components: (NH) 4 ) 2 SO 4 3g/L，KCl 0.2g/L，K 2 HPO 4 1g/L，MgSO 4 .7H 2 O 1g/L，Ca(NO 3 ) 2 0.02g/L；
Solution B included the following concentrations of components: feSO 4 .7H 2 O 177g/L，H 2 SO 4 4g/L；
Solution C included the following concentrations of components: 60g/L of agar, 1.6mL/L of D, L-sodium lactate;
SS2: mixing the solution A, B and the solution C according to the volume ratio of 2:1:1, then adding trace element mother liquor accounting for 2 per mill of the volume of the mixed liquor, and uniformly mixing to obtain a microbial nutrient solution; the microelement mother solution comprises the following components in concentration:
FeCl 3 ·4H 2 O 2000mg/L，CoCl 2 ·6H 2 O 2000mg/L，MnCl 2 ·4H 2 O 500mg/L，CuCl 2 ·2H 2 O 30mg/L，ZnCl 2 50mg/L，H 3 BO 3 50mg/L，(NH 4 ) 6 Mo 7 O 2 ·2H 2 O 90mg/L，Na 2 SeO 3 ·H 2 O 100mg/L，NiCl 2 ·6H 2 O 50mg/L，EDTA 1000mg/L，6％HC1 3ml/L。
further, the iron-reducing bacteria is shiwanella spp; the acid producing bacteria is thiobacillus ferrooxidans (Acidithiobacillus ferrooxidans spp.); the metal redox bacteria is sword bacteria (Ensifer spp.).
Further, the bacterial load in the microorganism-loaded carrier was 1.0X10 10 ～1.0×10 11 CFU/g。
Further, the concentration of the MBA (N, N' -methylenebisacrylamide) solution is 1-2 g/mL; the nutrient-loaded carrier and the microorganism-loaded carrier are immersed in the MBA solution at a feed solution ratio of 1g to 100 mL.
Further, the coagulation bath is deionized water.
The invention also provides a microbial capsule for recovering valuable metals, and the microbial capsule is prepared by the method.
The invention also provides an application of the microbial capsule for recovering valuable metals in recovery of the valuable metals in the fly ash. The application comprises the following steps:
s1: soaking the fly ash in water for 24 hours, then fishing out and draining until the water content is 25% -45%, and then stacking the drained fly ash in a place provided with an impermeable layer;
s2: uniformly mixing the microbial capsules with the fly ash subjected to the S1 treatment in equal mass, spraying water into the mixture, and simultaneously introducing air into the mixture, and controlling the concentration of dissolved oxygen in the mixture to be not lower than 1%; collecting the leaching solution to complete the recovery of valuable metals.
The beneficial effects of the invention are as follows: the invention improves the diversity of functional microorganisms by synthesizing microbiome, loads the microbiome and the substances providing nutrition for the microbiome on the carriers after special treatment, and then wraps the two types of carriers by nontoxic polymer high molecular materials to prepare the microbial capsule. The scheme of the invention can promote the substance exchange and information transfer among microorganisms, realize the rapid and directional propagation of microorganisms in the capsule, maintain relative stability and improve the metal recovery efficiency of a biological method.
Drawings
FIG. 1 shows a microbial capsule structure;
FIG. 2 shows the trend of OD600 over time;
FIG. 3 is a graph of the total leaching rate of minerals;
FIG. 4 is trace metals leaching rate;
fig. 5 is a graph of rare metal leaching rate.
Detailed Description
The following describes the present invention in detail with reference to examples.
Example 1
A microbial capsule for valuable metal recovery, which is prepared by the following steps:
s1: carrying out interlayer domain amplification and surface functionalization treatment on the carrier; the processing specifically comprises the following steps:
SS1: mixing kaolin and water according to the feed-liquid ratio of 9g to 100mL, and mixing the kaolin and water according to the feed-liquid ratio of 1.3X10 5 J, radiating the energy ultrasonic for 10min, filtering out kaolin, and drying at 100 ℃ for 10min;
SS2: placing the kaolin subjected to SS1 treatment in a quartz tube, evacuating helium, and heating in a muffle furnace at 800 ℃ for 30s;
SS3: mixing modifier and SS2 treated kaolin in the weight ratio of 1 to 22.5, and mixingThe mixture was immersed in H at a concentration of 45wt% 3 PO 4 Soaking in the solution for 24 hours, taking out the kaolin, and drying for 10 minutes at 100 ℃ to finish the carrier treatment; the modifier is formed by mixing dialkyl dimethyl quaternary ammonium salt (DHT 21) and humic acid according to the mass ratio of 3:1;
s2: immersing the carrier subjected to the S1 treatment into a microbial nutrient solution, and immersing at normal pressure to obtain a carrier loaded with nutrient substances; the microbial nutrient solution is prepared through the following steps:
SS1: preparing solutions A, B and C; solution a included the following concentrations of components: (NH) 4 ) 2 SO 4 3g/L，KCl 0.2g/L，K 2 HPO 4 1g/L，MgSO 4 .7H 2 O 1g/L，Ca(NO 3 ) 2 0.02g/L；
Solution B included the following concentrations of components: feSO 4 .7H 2 O 177g/L，H 2 SO 4 4g/L；
Solution C included the following concentrations of components: 60g/L of agar, 1.6mL/L of D, L-sodium lactate;
SS2: mixing the solution A, B and the solution C according to the volume ratio of 2:1:1, then adding trace element mother liquor accounting for 2 per mill of the volume of the mixed liquor, and uniformly mixing to obtain a microbial nutrient solution; the microelement mother solution comprises the following components in concentration:
FeCl 3 ·4H 2 O 2000mg/L，CoCl 2 ·6H 2 O 2000mg/L，MnCl 2 ·4H 2 O 500mg/L，CuCl 2 ·2H 2 O 30mg/L，ZnCl 2 50mg/L，H 3 BO 3 50mg/L，(NH 4 ) 6 Mo 7 O 2 ·2H 2 O 90mg/L，Na 2 SeO 3 ·H 2 O 100mg/L，NiCl 2 ·6H 2 O 50mg/L，EDTA 1000mg/L，6％HC1 3ml/L。
s3: dispersing a functional strain in sterile water to form a functional strain bacterial suspension, dispersing an auxiliary strain in sterile water to form an auxiliary strain bacterial suspension, mixing the two bacterial suspensions in equal volume, immersing the carrier subjected to S1 treatment in the mixed bacterial solution, and oscillating for 24 hours at 25 ℃ and 220rpm to obtain a carrier loaded with microorganisms; functional strains include shiso (Shewanella spp.), thiobacillus ferrooxidans (Acidithiobacillus ferrooxidans spp.) and sword bacteria (Ensifer spp.), helper strains include Ochrobactrum spp, pseudomonas aeruginosa Pseudomonas aeruginosa spp.) and Aeromonas sp;
s4: dissolving MBA in a mixed solvent of acetone and water to form an MBA solution with the concentration of 1g/mL, then immersing a carrier loaded with nutrient substances and a carrier loaded with microorganisms into the MBA solution in the feed liquid ratio of 1g to 100mL, and oscillating for 72h at the speed of 220rpm to obtain a suspension; adding PES and PVP into the suspension, and continuously oscillating at a speed of 220rpm for 72 hours to obtain a mixture; the mass concentrations of the added PES and PVP in the suspension are 18% and 8%, respectively;
s5: coating the mixture on a smooth glass plate stuck with a non-woven polypropylene/polyethylene carrier material at a speed of 20mm/s by using a scraper, coating the mixture to a thickness of 200 mu m, evaporating the mixture at room temperature for 15 seconds, and soaking and curing the mixture in deionized water at 18 ℃ for 2 minutes to obtain a film; then soaking the film in deionized water for 2h for solvent exchange, and cutting the film after solvent exchange into slices with the diameter of 1mm to obtain the microbial capsules.
Example 2
A microbial capsule for valuable metal recovery, which is prepared by the following steps:
s1: carrying out interlayer domain amplification and surface functionalization treatment on the carrier; the processing specifically comprises the following steps:
SS1: montmorillonite and water were mixed at a feed-liquid ratio of 8g to 100mL, at a ratio of 1.0X10 5 J, radiating energy ultrasonic for 12min, filtering montmorillonite, and drying at 120 ℃ for 5min;
SS2: placing the montmorillonite subjected to SS1 treatment in a quartz tube, evacuating helium, and heating in a muffle furnace at 750 ℃ for 40s;
SS3: mixing modifier and montmorillonite processed by SS2 according to a mass ratio of 1:20, and immersing the mixture into H with a concentration of 45wt% 3 PO 4 Soaking in the solution for 24h, taking out montmorillonite, drying at 120deg.C for 5min, and finishing carrier treatment; the modifier is dialkyl dimethyl quaternaryThe ammonium salt (DHT 21) and humic acid are mixed according to the mass ratio of 3:1;
s2: immersing the carrier subjected to the S1 treatment into a microbial nutrient solution, and immersing at normal pressure to obtain a carrier loaded with nutrient substances; the microbial nutrient solution is prepared through the following steps:
SS1: preparing solutions A, B and C; solution a included the following concentrations of components: (NH) 4 ) 2 SO 4 3g/L，KCl 0.2g/L，K 2 HPO 4 1g/L，MgSO 4 .7H 2 O 1g/L，Ca(NO 3 ) 2 0.02g/L；
Solution B included the following concentrations of components: feSO 4 .7H 2 O 177g/L，H 2 SO 4 4g/L；
Solution C included the following concentrations of components: 60g/L of agar, 1.6mL/L of D, L-sodium lactate;
SS2: mixing the solution A, B and the solution C according to the volume ratio of 2:1:1, then adding trace element mother liquor accounting for 2 per mill of the volume of the mixed liquor, and uniformly mixing to obtain a microbial nutrient solution; the microelement mother solution comprises the following components in concentration:
FeCl 3 ·4H 2 O 2000mg/L，CoCl 2 ·6H 2 O 2000mg/L，MnCl 2 ·4H 2 O 500mg/L，CuCl 2 ·2H 2 O 30mg/L，ZnCl 2 50mg/L，H 3 BO 3 50mg/L，(NH 4 ) 6 Mo 7 O 2 ·2H 2 O 90mg/L，Na 2 SeO 3 ·H 2 O 100mg/L，NiCl 2 ·6H 2 O 50mg/L，EDTA 1000mg/L，6％HC1 3ml/L。
s3: dispersing a functional strain in sterile water to form a functional strain bacterial suspension, dispersing an auxiliary strain in sterile water to form an auxiliary strain bacterial suspension, mixing the two bacterial suspensions in equal volume, immersing the carrier subjected to S1 treatment in the mixed bacterial solution, and oscillating for 24 hours at 20 ℃ and 250rpm to obtain a carrier loaded with microorganisms; functional strains include shiso (Shewanella spp.), thiobacillus ferrooxidans (Acidithiobacillus ferrooxidans spp.) and sword bacteria (Ensifer spp.), helper strains include Ochrobactrum spp, pseudomonas aeruginosa Pseudomonas aeruginosa spp.) and Aeromonas sp;
s4: dissolving MBA in a mixed solvent of acetone and water to form an MBA solution with the concentration of 2g/mL, then immersing a carrier loaded with nutrient substances and a carrier loaded with microorganisms into the MBA solution in a feed liquid ratio of 1g to 100mL, and oscillating for 75 hours at a speed of 200rpm to obtain a suspension; adding PES and PVP into the suspension, and continuously oscillating at a speed of 200rpm for 75 hours to obtain a mixture; the mass concentrations of the added PES and PVP in the suspension are 18% and 8%, respectively;
s5: coating the mixture on a smooth glass plate stuck with a non-woven polypropylene/polyethylene carrier material at a speed of 20mm/s by using a scraper, coating the mixture to a thickness of 220 mu m, evaporating the mixture at room temperature for 15 seconds, and soaking and curing the mixture in deionized water at 17 ℃ for 3 minutes to obtain a film; then soaking the film in deionized water for 2h for solvent exchange, and cutting the film after solvent exchange into slices with the diameter of 1mm to obtain the microbial capsules.
Example 3
A microbial capsule for valuable metal recovery, which is prepared by the following steps:
s1: carrying out interlayer domain amplification and surface functionalization treatment on the carrier; the processing specifically comprises the following steps:
SS1: kaolin was mixed with water at a feed to water ratio of 8g to 100mL at 1.5X10 5 J, radiating energy ultrasonic for 8min, filtering out kaolin, and drying at 90 ℃ for 10min;
SS2: placing the kaolin subjected to SS1 treatment in a quartz tube, evacuating helium, and heating in a muffle furnace at 850 ℃ for 20s;
SS3: mixing modifier and kaolin subjected to SS2 treatment according to a mass ratio of 1:25, and immersing the mixture into H with a concentration of 45wt% 3 PO 4 Soaking in the solution for 24 hours, taking out the kaolin, and drying for 10 minutes at 90 ℃ to finish the carrier treatment; the modifier is formed by mixing dialkyl dimethyl quaternary ammonium salt (DHT 21) and humic acid according to the mass ratio of 3:1;
s2: immersing the carrier subjected to the S1 treatment into a microbial nutrient solution, and immersing at normal pressure to obtain a carrier loaded with nutrient substances; the microbial nutrient solution is prepared through the following steps:
SS1: preparing solutions A, B and C; solution a included the following concentrations of components: (NH) 4 ) 2 SO 4 3g/L，KCl 0.2g/L，K 2 HPO 4 1g/L，MgSO 4 .7H 2 O 1g/L，Ca(NO 3 ) 2 0.02g/L；
Solution B included the following concentrations of components: feSO 4 .7H 2 O 177g/L，H 2 SO 4 4g/L；
Solution C included the following concentrations of components: 60g/L of agar, 1.6mL/L of D, L-sodium lactate;
SS2: mixing the solution A, B and the solution C according to the volume ratio of 2:1:1, then adding trace element mother liquor accounting for 2 per mill of the volume of the mixed liquor, and uniformly mixing to obtain a microbial nutrient solution; the microelement mother solution comprises the following components in concentration:
FeCl 3 ·4H 2 O 2000mg/L，CoCl 2 ·6H 2 O 2000mg/L，MnCl 2 ·4H 2 O 500mg/L，CuCl 2 ·2H 2 O 30mg/L，ZnCl 2 50mg/L，H 3 BO 3 50mg/L，(NH 4 ) 6 Mo 7 O 2 ·2H 2 O 90mg/L，Na 2 SeO 3 ·H 2 O 100mg/L，NiCl 2 ·6H 2 O 50mg/L，EDTA 1000mg/L，6％HC1 3ml/L。
s3: dispersing a functional strain in sterile water to form a functional strain bacterial suspension, dispersing an auxiliary strain in sterile water to form an auxiliary strain bacterial suspension, mixing the two bacterial suspensions in equal volume, immersing the carrier subjected to S1 treatment in the mixed bacterial solution, and oscillating for 24 hours at 30 ℃ and 200rpm to obtain a carrier loaded with microorganisms; functional strains include shiso (Shewanella spp.), thiobacillus ferrooxidans (Acidithiobacillus ferrooxidans spp.) and sword bacteria (Ensifer spp.), helper strains include Ochrobactrum spp, pseudomonas aeruginosa Pseudomonas aeruginosa spp.) and Aeromonas sp;
s4: dissolving MBA in a mixed solvent of acetone and water to form an MBA solution with the concentration of 1g/mL, then immersing a carrier loaded with nutrient substances and a carrier loaded with microorganisms into the MBA solution in the feed liquid ratio of 1g to 100mL, and oscillating at the speed of 250rpm for 70h to obtain a suspension; adding PES and PVP into the suspension, and continuously oscillating at the speed of 250rpm for 70 hours to obtain a mixture; the mass concentrations of the added PES and PVP in the suspension are 18% and 8%, respectively;
s5: coating the mixture on a smooth glass plate attached with a non-woven polypropylene/polyethylene carrier material at a speed of 20mm/s by using a scraper, coating the mixture to a thickness of 180 mu m, evaporating the mixture at room temperature for 15 seconds, and soaking and curing the mixture in deionized water at a temperature of 19 ℃ for 1min to obtain a film; then soaking the film in deionized water for 2h for solvent exchange, and cutting the film after solvent exchange into slices with the diameter of 1mm to obtain the microbial capsules.
Experimental example
The microbial capsule prepared by the invention has a structure shown in figure 1. The recovery effect of valuable metals is illustrated by the microbial capsules prepared in example 1.
The fly ash was milled in a ball mill for 1 hour and sieved to 0.037-0.074 mm (200-400 mesh screen). The pulverized coal ash after grinding is washed by 2M HCl, distilled water and pure ethanol in sequence, dried and placed in a 125mL vacuum drier, and used for the subsequent metal recovery experiment at room temperature.
The moisture content and mineral content of the fly ash are characterized: 1) Drying the sample in an oven at 103 ℃ to constant weight; 2) The dried sample was placed in an oven at 550 ℃ and calcined for 6 hours (the nonflammable component was considered to be a mineral).
100mL of sterilized 0.9% physiological saline was poured into the shake flask, and the flask was autoclaved at 121℃for 20 minutes.
The fly ash sample was autoclaved at 110℃for 40 minutes, and then 5g was mixed with physiological saline in a shake flask.
5g of the biocapsules were added to the shake flask and mixed well, and placed on a shaker (120 rpm) for 7 days, three replicates were set and a blank (no biocapsules added) was set.
Samples were taken every day for 5mL of test OD600, and the results of the test with the added bio-capsules are shown in fig. 2, from which it can be seen that biomass rapidly accumulated from day 1 to day 3, with the OD600 average increasing from initial 0.51 to 0.70. After day 3, the OD600 values remained stable, with an average value of between 0.70-0.71. The results show that the biological capsules can rapidly accumulate biomass and realize stable growth in the process of leaching the fly ash. Three biological replicates of the experiment showed a large difference after day 3, with standard deviations ranging from 0.04 to 0.06, indicating that the biocapsules had divergent growth characteristics after undergoing log phase, but did not affect their overall effect.
After 7 days all samples were filtered through a 0.45 μm membrane filter to separate the solids from the liquids. The solid was then washed with 50mL of distilled water and deionized water, dried in an oven at 105 ℃ to constant weight to measure total solids content, and then calcined in a muffle furnace at 550 ℃ for 6 hours to measure mineral content, and the total leaching rate of minerals was calculated based on the measurement results, as shown in fig. 3, and the results show that the total leaching rate of minerals in the experimental group using the biocapsules was as high as 64.3%, which is far higher than 7.6% of the blank experimental group, indicating that the biocapsules were excellent. Three groups of biological repeated experiments show that the total leaching rate has a certain floating degree, and the standard deviation reaches 14.0%, which is consistent with the result of fig. 2.
Subsequently, the individual metal contents were analyzed by ICP-MS: the fly ash and the residual ash sample after 550 ℃ in the furnace are analyzed. The sample was digested in a diluted mixture of nitric acid and hydrochloric acid and extracted at 95 ℃ under reflux for 30 minutes. After cooling to room temperature, the samples were diluted and analyzed by ICP-MS. The leaching rates of the individual metals are shown in figures 4 and 5. The results show that the leaching effect of trace metals is generally better. Wherein, the leaching rates of Cd, as and Fe are the highest, and the average values are 87.4%, 85.9% and 72.7% respectively; be. U, th has the lowest leaching rate and average values of 28.4%, 28.4% and 27.8% respectively. Trace metals with leaching rates greater than 50% are 10, including Fe, mn, zn, cu, V, as, mo, ag, cd, pb. The leaching rate of Al is only 42.9%, but its concentration in minerals is as high as 35242.8mg/g, so that its leaching effect is considered to be good. Overall, the leaching rate of rare metals is lower than trace metals. Wherein, the leaching rate of Se, dy, gd, yb is highest, and the average value is 61.2%, 53.8% and 53.4% respectively; la, ce, nd, pr has the lowest leaching rate and the average values of 25.2%, 26.7%, 28.2% and 28.6% respectively. The leaching rate is more than 50 percent, and the rare metals are only 4, namely Se, dy, gd, Y
Application example
According to the analysis in experimental examples, the microbial capsules have a good leaching effect on metals in the fly ash, so that the microbial capsules can be used for recovering valuable metals in the fly ash. The recovery method comprises the following steps:
s1: soaking the fly ash in water for 24 hours, then fishing out and draining until the water content is 25% -45%, and then stacking the drained fly ash in a place provided with an impermeable layer;
s2: uniformly mixing the microbial capsules with the fly ash subjected to the S1 treatment in equal mass, spraying water into the mixture, and simultaneously introducing air into the mixture, and controlling the concentration of dissolved oxygen in the mixture to be not lower than 1%; collecting the leaching solution to complete the recovery of valuable metals.
Under the action of microbial capsule, the valuable metal in flyash is converted from insoluble/insoluble form (sulfide, organic combination state, etc.) into soluble ion state or weak acid combination state, and leached from flyash. And finally collecting the leaching solution to realize the efficient and low-consumption recovery of valuable metals.
While specific embodiments of the invention have been described in detail in connection with the examples, it should not be construed as limiting the scope of protection of the patent. Various modifications and variations which may be made by those skilled in the art without the creative effort are within the scope of the patent described in the claims.

Claims (5)

1. The preparation method of the microbial capsule for recycling the valuable metal of the fly ash is characterized by comprising the following steps of:
s1: carrying out interlayer domain amplification and surface functionalization treatment on the carrier; the carrier interlayer domain amplification and surface functionalization treatment comprises the following steps:
SS1: mixing the base material with water according to the feed-liquid ratio of 8-10 g to 100mL, and mixing the base material with water according to the feed-liquid ratio of 1.0X10 5 ~1.5×10 5 Energy of JUltrasonic radiation is measured for 8-12 min, and then the base material is filtered out and dried for 5-10 min at the temperature of 90-120 ℃; the base material is kaolin or montmorillonite;
SS2: calcining the substrate subjected to SS1 treatment under the protection of inert gas, wherein the calcining temperature is 750-850 ℃ and the calcining time is 20-40 s;
SS3: mixing a modifier with the substrate subjected to SS2 treatment according to a mass ratio of 1:20-25, and immersing the mixture into H with a concentration of 45wt% 3 PO 4 Soaking in the solution for 24 hours, taking out the substrate, and drying at 90-120 ℃ for 5-10 min to finish the carrier treatment; the modifier is formed by mixing dialkyl dimethyl quaternary ammonium salt and humic acid according to the mass ratio of 3:1;
s2: immersing the carrier subjected to the S1 treatment into a microbial nutrient solution, and immersing the carrier by normal pressure or negative pressure to obtain a carrier loaded with nutrient substances; the microbial nutrient solution is prepared through the following steps:
SS1: preparing solutions A, B and C; the solution a comprises the following components in concentration: (NH) 4 ) 2 SO 4 3g/L，KCl 0.2g/L，K 2 HPO 4 1g/L，MgSO 4 .7H 2 O 1g/L，Ca(NO 3 ) 2 0.02g/L；
The solution B comprises the following components in concentration: feSO 4 .7H 2 O 177g/L，H 2 SO 4 4g/L；
The solution C comprises the following concentration components: 60g/L of agar, 1.6mL/L of D, L-sodium lactate;
SS2: mixing the solution A, B and the solution C according to the volume ratio of 2:1:1, then adding trace element mother liquor accounting for 2 per mill of the volume of the mixed liquor, and uniformly mixing to obtain a microbial nutrient solution; the trace element mother solution comprises the following components in concentration:
FeCl 3 ·4H 2 O 2000 mg/L，CoCl 2 ·6H 2 O 2000 mg/L，MnCl 2 ·4H 2 O 500 mg/L，CuCl 2 ·2H 2 O 30mg/L，ZnCl 2 50mg/L，H 3 BO 3 50mg/L，(NH 4 ) 6 Mo 7 O 2 ·2H 2 O 90mg/L，Na 2 SeO 3 ·H 2 O 100mg/L，NiCl 2 ·6H 2 O 50mg/L，EDTA 1000 mg/L，6%HC1 3ml/L；
s3: mixing the bacterial suspension of the functional strain and the bacterial suspension of the auxiliary strain in equal volume, immersing the carrier treated by the S1 in the mixed bacterial solution, and oscillating for 20-25 h at 20-30 ℃ and 180-250 rpm to obtain the carrier loaded with the microorganism; the functional strains comprise iron-reducing bacteria, acidogenic bacteria and metal redox bacteria, and the auxiliary strains comprise ochrobactrum, pseudomonas aeruginosa and aeromonas; the iron reducing bacteria are Shewanella; the acidogenic bacteria are thiobacillus ferrooxidans; the metal redox bacteria are Sword bacteria;
s4: immersing a carrier loaded with nutrient substances and a carrier loaded with microorganisms into an N, N' -methylene bisacrylamide solution, and oscillating at a speed of 200-250 rpm for 70-75 hours to obtain a suspension; the concentration of the N, N '-methylene bisacrylamide solution is 1-2 g/mL, and the carrier loaded with nutrient substances and the carrier loaded with microorganisms are immersed into the N, N' -methylene bisacrylamide solution according to the feed liquid ratio of 1g to 100 mL; then polyether sulfone and polyvinylpyrrolidone are added into the suspension, and the mixture is obtained by continuing to oscillate for 70-75 hours at the speed of 200-250 rpm;
s5: coating the mixture on a smooth glass plate, wherein the coating thickness is 180-220 mu m, evaporating for 15 seconds at room temperature, and soaking and curing in a coagulating bath at 17-19 ℃ for 1-3 min to obtain a film; then soaking the film in deionized water for 2 hours, and cutting into slices with the diameter of 1mm to obtain the microbial capsules.
2. The method of manufacturing according to claim 1, characterized in that: the microorganism-loaded carrier has a bacterial load of 1.0X10 10 ~1.0×10 11 CFU/g。
3. The method of manufacturing according to claim 1, characterized in that: the coagulating bath is deionized water.
4. A microbial capsule for recovery of valuable metal of fly ash, which is prepared by the preparation method of any one of claims 1 to 3.
5. The method for recycling the valuable metal of the fly ash is characterized by comprising the following steps of:
s1: soaking the fly ash in water for 24 hours, then fishing out and draining until the water content is 25% -45%, and then stacking the drained fly ash in a place provided with an impermeable layer;
s2: uniformly mixing the microbial capsules according to claim 4 with the fly ash subjected to S1 treatment in equal mass, spraying water into the mixture, and simultaneously introducing air into the mixture, and controlling the concentration of dissolved oxygen in the mixture to be not lower than 1%; collecting the leaching solution to complete the recovery of valuable metals.
CN202210017262.3A 2022-01-07 2022-01-07 Microorganism capsule for recovering valuable metals and preparation method and application thereof Active CN114480364B (en)

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CN109504672A (en) * 2019-01-17 2019-03-22 中南大学 A kind of acidophilus leaching microbacteria embedding body and preparation method thereof
CN110004136A (en) * 2019-04-16 2019-07-12 中南大学 A kind of embedding body, preparation method and cultural method loading leaching microbacteria

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CN109504672A (en) * 2019-01-17 2019-03-22 中南大学 A kind of acidophilus leaching microbacteria embedding body and preparation method thereof
CN110004136A (en) * 2019-04-16 2019-07-12 中南大学 A kind of embedding body, preparation method and cultural method loading leaching microbacteria

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