CN110064407A - Biological preparation method based on zinc-manganese ferrite loaded nano copper sulfide - Google Patents

Biological preparation method based on zinc-manganese ferrite loaded nano copper sulfide Download PDF

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CN110064407A
CN110064407A CN201910268318.0A CN201910268318A CN110064407A CN 110064407 A CN110064407 A CN 110064407A CN 201910268318 A CN201910268318 A CN 201910268318A CN 110064407 A CN110064407 A CN 110064407A
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zinc
manganese
manganese ferrite
copper
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辛宝平
贾纯友
杨书辉
王佳
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Beijing Institute of Technology BIT
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04Sulfides
    • B01J27/043Sulfides with iron group metals or platinum group metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/308Dyes; Colorants; Fluorescent agents

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Environmental & Geological Engineering (AREA)
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  • Compounds Of Iron (AREA)

Abstract

The invention relates to a method for loading nano copper sulfide on zinc-manganese ferrite, in particular to a method for loading nano copper sulfide prepared from copper-containing wastewater by using zinc-manganese ferrite prepared from bioleaching liquid of waste zinc-manganese batteries, belonging to the field of resource treatment of solid wastes. Adding a certain amount of zinc source, manganese source and iron source into a bioleaching solution of the waste zinc-manganese battery to prepare a solution with a corresponding proportion, and synthesizing zinc-manganese ferrite by a hydrothermal method; and fully contacting the extracellular polymer, the copper precursor and the zinc-manganese ferrite, standing for 4 hours, and dropwise adding a sodium sulfide solution into the extracellular polymer, the copper precursor and the zinc-manganese ferrite to obtain the zinc-manganese ferrite loaded nano copper sulfide composite material. The synthesis process takes the waste zinc-manganese batteries and the copper-containing wastewater as raw materials, and realizes the recovery and resource utilization of the zinc-manganese batteries and the copper-containing wastewater; the composite material has good magnetism and photocatalysis, can effectively decompose organic dye in water, is convenient for material recovery, and has good application prospect.

Description

Biological preparation method based on zinc-manganese ferrite loaded nano copper sulfide
Technical Field
The invention relates to a method for loading nano copper sulfide on zinc-manganese ferrite, in particular to a method for loading nano copper sulfide prepared from copper-containing wastewater on zinc-manganese ferrite prepared from bioleaching liquid of a waste zinc-manganese battery, belonging to the field of resource treatment of solid waste.
Background
Copper plays a very important role in the production and life of people, such as the industries of chemical industry, nonferrous smelting, electronic materials and the like, and is generally applied in a large quantity, and the application leads to the generation of copper-containing waste water. If the copper-containing wastewater is directly discharged, not only can the waste of copper resources be caused, but also the environment can be polluted, the crops, the environment and the human body are all greatly harmed, and the large amount of copper has toxic and carcinogenic effects. Therefore, the copper in the copper-containing wastewater must be recovered, so that the environmental pollution and the resource waste are avoided. At present, copper in copper-containing wastewater is mainly recovered by physical or chemical methods, such as chemical precipitation, membrane separation, extraction and ion exchange. These conventional treatment methods are not always feasible due to the high treatment costs, continuous dosing of chemicals. In recent years, biological treatment methods are attracting attention, mainly utilizing biological growth to absorb and fix heavy metal ions, wherein copper in copper-containing wastewater is converted into semiconductor nano material with photocatalytic performance, namely nano copper sulfide, by utilizing a microbial technology, and the treatment of the copper-containing wastewater is changed from harmless treatment to resource treatment.
The copper sulfide nano particles are used as a semiconductor material, have unique optical and electrical properties, and have wide application in the aspects of solar batteries, solar controllers, solar radiation absorbers, catalysts, nanoscale switches, high-capacity cathode materials, lithium ion batteries and the like. The preparation method of the CuS nano material is mainly a chemical method, and the chemical method can prepare the nano material with high stability and controllable particle size, but the preparation process needs to use various organic and inorganic reagents, has certain biological toxicity, pollutes the environment and limits the further application of the nano material. And the copper-containing waste water is used as a raw material to synthesize the nano copper sulfide, so that the synthesis is basically impossible. The biosynthesis method is a synthesis method which is gradually raised in recent years, and the biosynthesis quantum dots have natural biocompatibility, low biotoxicity, mild reaction conditions, low cost and wide application prospect. If the biosynthesis method is used for synthesizing the nano copper sulfide by using the copper-containing wastewater as a copper source, the copper-containing wastewater can inhibit the growth of bacteria, and the purification of products by components such as a culture medium of the biosynthesis method can increase the difficulty, so that the problems need to be solved.
Nanometer copper sulfide is used as a photocatalytic material, and when CuS nanoparticles are excited by visible light to absorb light in a visible light region, electrons from a valence band are excited to a conduction band to form photo-generated electron-hole pairs. Electrons from the conduction band are transferred to the catalyst surface, O 2 Reduction to O 2 - . Holes in the valence band and H on the catalyst surface, on the other hand 2 The O reacts to form hydroxyl radicals. Due to the generation of hydroxyl radicals and superoxide anions, the recombination of photogenerated electrons and holes in the CuS quantum dots is inhibited, the hydroxyl radicals and the superoxide anions can further react with methylene blue dye molecules, and finally, organic dyes such as methylene blue and the like are oxidized into inorganic micromolecule non-toxic products. Besides studying the photocatalytic activity, the stability of the material, i.e. whether the photocatalyst can be recycled, is another important problem faced by the practical application of the photocatalyst. In the photocatalytic reaction, the performance of the photocatalyst is reduced due to the photo-corrosion or the catalyst contamination, and particularly in practical applications, the recovery and reuse of the photocatalyst is one of the important problems.
Zinc-manganese dry batteries are widely used due to their low cost, small size, and portability. But it results in a large amount of waste of the zinc-manganese battery due to its shorter life than the secondary battery, and is largely discarded in the environment. As the production and export of manganese-zinc batteries in China and also the consumption of the countries, the technology of treating and recycling waste batteries is still in the starting stage, thereby not only causing the waste of resources, but also seriously influencing the ecological environment. Therefore, the research on the disposal and recycling of waste batteries is urgent.
Disclosure of Invention
The invention aims to solve the problems of high cost and low resource utilization of the treatment of the copper-containing wastewater; the method for loading nano copper sulfide on zinc-manganese ferrite is provided.
The purpose of the invention is realized by the following technical scheme.
The invention discloses a method for loading nano copper sulfide on zinc-manganese ferrite. The method comprises the following specific steps:
step one, preparation of zinc-manganese ferrite
(1) Measuring the contents of zinc ions, manganese ions and iron ions in the bioleaching solution of the waste zinc-manganese batteries in the laboratory; and a manganese source, a zinc source and an iron source are supplemented, so that the total concentration of the three ions is 1.5-4.5mol/L, wherein the ratio of the concentration of manganese ions to the concentration of zinc ions is controlled to be 1-2, and the ratio of manganese ions to zinc ions to iron ions is controlled to be 0.4-1;
(2) Supplementing a manganese source, a zinc source and an iron source according to the requirements in the step one (1), and stirring for 12-24h at room temperature by using a magnetic stirrer;
the manganese source, the zinc source and the iron source are respectively MnSO 4 、ZnSO 4 、Fe 2 SO 4
(3) Transferring the solution obtained in the step one (2) into a high-pressure reaction kettle, adding a coprecipitator to enable the pH value of the coprecipitator to be 8-11, and fully stirring;
the coprecipitator is NaOH, ammonia water or the mixture of the two
(4) Reacting the high-pressure reaction kettle in the step one (3) at the temperature of 160-200 ℃ for 6-10h; after the reaction is finished, aging for 20-40h at room temperature; then carrying out suction filtration or centrifugation to obtain a sample; washing with distilled water until pH is about 7-9, centrifuging or vacuum filtering, oven drying at 50-70 deg.C, and grinding for later use;
step two, preparation of zinc-manganese ferrite loaded nano copper sulfide material
(1) Culturing sulfate reducing bacteria; preparing a culture medium; the solute is: 0.1-0.8g/L lactic acid, 0.5-1.5g/LNH 4 Cl,0.2-0.8gl/L MgSO 4 ,0.1-0.5g/L CaCl 2 ,0.5-1.0g/L KH 2 PO 4 0.5-1.0g/L yeast powder and 10-28g/L Na 2 SO 4 . Subsequently, the pH value of the culture is adjusted to 6-8 by using 6mol/LNaOH, and the growth temperature is increasedThe temperature is 20-40 ℃; inoculating sulfate reducing bacteria (Clostridium sp.) into a sulfate reducing bacteria culture medium, and placing the sulfate reducing bacteria culture medium at the temperature of 20-40 ℃ for anaerobic culture;
(2) Extraction of Extracellular Polymers (EPS); centrifuging at 4-20 deg.C to obtain crude extracellular polymer extractive solution, filtering with filter membrane, dialyzing the filtrate in dialysis bag, and purifying extracellular polymer in dialysis bag at 4 deg.C for later use;
the extraction of the extracellular polymer of the sulfate reducing bacteria is to centrifuge the sulfate reducing bacteria for 10-20min at 4-20 ℃ at 6000-8000rpm/min, discard the supernatant, re-suspend the precipitate with ultrapure water, centrifuge for 10-20min at 6000-8000rpm/min, discard the supernatant, re-suspend the precipitate with ultrapure water, centrifuge for 10-25min at 16000-18000rpm/min to obtain a crude extract of the extracellular polymer, filter the crude extract with a 0.22um filter membrane, put the filtrate into a 3500-4500KDa dialysis bag, dialyze with ultrapure water overnight, put the purified extracellular polymer of the sulfate reducing bacteria in the dialysis bag at 4 ℃ for later use
(3) Preparing a copper precursor and a sulfur precursor; measuring the copper content in the copper-containing wastewater, and preparing 0.05-0.1mol/L by using copper sulfate; preparing 0.05-0.1mol/L sodium sulfide solution with sodium sulfide;
(4) Preparing a zinc-manganese ferrite loaded nano copper sulfide material; mixing the EPS in the step two (2), the copper precursor in the step two (3) and the zinc-manganese ferrite in the step one (4), performing ultrasonic treatment for 5 minutes by using an ultrasonic instrument, and vibrating for 2-6 hours to fully contact the EPS, the copper precursor in the step two (3) and the zinc-manganese ferrite; under the magnetic force of a magnet, pouring out the supernatant, and washing with deionized water for 2-5 times; adding the sulfur source in the step two (3) into the solution, and oscillating for 2-4h; pouring out the supernatant under the attraction of a magnet and washing the supernatant with deionized water for 2 to 5 times; centrifuging, and drying at 50-70 ℃ to obtain the zinc-manganese ferrite loaded nano copper sulfide material.
(5) And (3) photocatalytic test: and (3) photocatalytic test: 25mg/L methylene blue solution (MB) 100ml,40mg composite nanomaterial, 5ml H 2 O 2 Under the irradiation of visible light, samples were taken every two hours to determine the MB content of the solution.
The mixing amount of EPS, copper precursor and zinc-manganese ferrite is 0.5-1.0g of zinc-manganese ferrite, 20-50ml of EPS20, 5-10ml of copper precursor and 10-15ml of sulfur precursor respectively
Advantageous effects
1. The method for loading nano copper sulfide on zinc-manganese ferrite takes copper-containing wastewater as a copper source and sodium sulfide as a sulfur source, and synthesizes the nano copper sulfide through regulation and control of extracellular polymer generated by sulfate reducing bacteria, so that the recovery and resource utilization of copper in the wastewater are realized to the maximum extent, and the synthesized nano copper sulfide has good crystal phase, uniform particle size and good dispersion.
2. According to the method for loading nano copper sulfide on the zinc-manganese ferrite, disclosed by the invention, the zinc-manganese ferrite is prepared by using the bioleaching solution of the waste zinc-manganese battery and a hydrothermal method, the method can effectively recover and utilize valuable metals in the waste zinc-manganese battery, and the hydrothermal method for synthesizing the zinc-manganese ferrite has the advantages of mild condition, low energy consumption, no use of a dispersing agent in the synthesis process and low environmental pollution.
3. According to the method for loading the nano copper sulfide on the zinc-manganese ferrite, disclosed by the invention, the nano copper sulfide is loaded on the zinc-manganese ferrite by taking the extracellular polymer generated by the sulfate reducing bacteria as the linking agent, the process is carried out at normal temperature and normal pressure, and the method is free of the use of a chemical linking agent, low in cost, small in pollution and low in energy consumption.
4. According to the method for loading the nano copper sulfide on the zinc-manganese ferrite, disclosed by the invention, the composite material can be quickly recovered by using the nano copper sulfide loaded on the zinc-manganese ferrite under the adsorption of a magnet, so that the waste of the material can be effectively avoided.
5. The method for loading the nano copper sulfide on the zinc-manganese ferrite has stronger photocatalysis property, stable performance and reusability, and the nano copper sulfide loaded on the zinc-manganese ferrite is convenient to recover after organic dye is degraded.
Drawings
FIG. 1 XRD Pattern of embodiment 1 Nano copper sulfide
FIG. 2 XRD patterns of Zn-Mn ferrite in example 1
FIG. 3 TEM image of 1 nm copper sulfide as an embodiment
FIG. 4 is a graph showing the photocatalytic effect of the composite material of embodiment 1
FIG. 5 example 1 photocatalytic cycle diagram of composite material
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1: step one, preparation of zinc-manganese ferrite
(1) Measuring the contents of zinc ions, manganese ions and iron ions in the bioleaching solution of the waste zinc-manganese batteries in the laboratory; and a manganese source, a zinc source and an iron source are supplemented, so that the total concentration of the three ions is 4.5mol/L, wherein the ratio of the concentrations of manganese ions and zinc ions is controlled to be 1.5, and the ratio of manganese ions, zinc ions and iron ions is controlled to be 0.5.
(2) And (2) supplementing a manganese source, a zinc source and an iron source according to the requirements in the step one (1), and stirring for 24 hours at room temperature by using a magnetic stirrer.
The manganese source, the zinc source and the iron source are respectively MnSO 4 、ZnSO 4 、Fe 2 SO 4
(3) Transferring the solution obtained in the step one (2) into a high-pressure reaction kettle, adding a coprecipitator to enable the pH value of the solution to be 10, and fully stirring.
The coprecipitator is NaOH
(4) Reacting the high-pressure reaction kettle in the step one (3) at the temperature of 180 ℃ for 6 hours; after the reaction is finished, aging is carried out for 24 hours at room temperature; then carrying out suction filtration or centrifugation to obtain a sample; washing with distilled water until the pH of the sample is about 7, centrifuging or suction filtering, drying the sample at 55 ℃, and grinding for later use.
Step two, preparation of zinc-manganese ferrite loaded nano copper sulfide material
(1) Culturing sulfate reducing bacteria; preparing a culture medium; the solute is: 0.2mol/L lactic acid, 14.28g/L Na 2 SO 4 ,1.0g/LNH 4 Cl,0.5g/LKH 2 PO 4 ,0.5g/L MgSO 4 ,0.1g/L CaCl 2 0.5g/L yeast extract powder, followed by adjusting the pH of the medium to 7 using 6mol/L NaOH.
(2) Extracting Extracellular Polymeric Substance (EPS); centrifuging sulfate reducing bacteria at 4 ℃ and 8000rpm/min for 10min, discarding supernatant, re-suspending precipitate with ultrapure water, centrifuging at 18000rpm/min for 25min to obtain crude extracellular polymer extract, filtering the crude extract with 0.22um filter membrane, placing filtrate in 3500KDa dialysis bag, dialyzing with ultrapure water overnight, and placing purified sulfate reducing bacteria extracellular polymer in the dialysis bag at 4 ℃ for later use.
(3) Preparing a copper precursor and a sulfur precursor; measuring the copper content in the copper-containing wastewater, and preparing 0.1mol/L copper sulfate; sodium sulfide is used to prepare 0.1mol/L sodium sulfide solution.
(4) Preparing a zinc-manganese ferrite loaded nano copper sulfide material; mixing the EPS in the step two (2), the copper precursor in the step two (3) and the zinc-manganese ferrite in the step one (4), and carrying out ultrasonic treatment for 5 minutes by using an ultrasonic instrument and shaking for 4 hours to fully contact the EPS, the copper precursor in the step two (3) and the zinc-manganese ferrite; under the magnetic force of a magnet, the supernatant is poured off and washed for 5 times by deionized water; adding the sulfur source in the step two (3) into the mixture, and oscillating for 4 hours; the supernatant was decanted under the attraction of a magnet and washed 4 times with deionized water; centrifuging and drying at 55 ℃ to obtain the zinc-manganese ferrite loaded nano copper sulfide material.
XRD analysis is carried out on the nano copper sulfide and the zinc manganese ferrite in the composite material (figures 1 and 2), the result shows that the nano copper sulfide is matched with a standard card JCPDS NO.65-3561, the zinc manganese ferrite is matched with a standard card JCPDS NO.87-1171, TEM analysis is carried out on the nano copper sulfide in a sample (figure 3), and the result shows that the average grain diameter is 8.98nm, the size of quantum dots is met, the grain diameter distribution is in accordance with normal distribution, and the grain diameters are relatively uniform.
(5) And (3) photocatalytic test: and (3) photocatalytic test: 25mg/L methylene blue solution (MB) 100ml,40mg composite nanomaterial, 5ml H 2 O 2 Under the irradiation of visible light, samples were taken every two hours to determine the MB content in the solution.
The photocatalytic test shows that the composite material has good catalytic effect (figure 4), the degradation rate reaches more than 83% in 12h, and the cycle test shows that the degradation rates of four cycle tests in 12h are respectively as follows: 83%,75%,67%,59%, good stability.
Example 2: step one, preparation of zinc-manganese ferrite
(1) The same as step one (1) in embodiment 1.
(2) The same as step one (2) in embodiment 1.
(3) The same as in step one (3) of embodiment 1.
(4) The same as in step one (4) of embodiment 1.
Step two, preparation of zinc-manganese ferrite loaded nano copper sulfide material
(1) Culturing sulfate reducing bacteria; preparing a culture medium; the solute is: 0.6mol/L lactic acid, 14.28g/L Na 2 SO 4 ,1.0g/L NH 4 Cl,0.5g/L KH 2 PO 4 ,0.5g/L MgSO 4 ,0.1g/L CaCl 2 0.5g/L yeast extract powder, followed by adjusting the pH of the medium to 7 using 6mol/L NaOH.
(2) The same as (2) of step two in embodiment 1.
(3) The same as (3) of step two in embodiment 1.
(4) Preparing a zinc-manganese ferrite loaded nano copper sulfide material; mixing the EPS in the step two (2), the copper precursor in the step two (3) and the zinc-manganese ferrite in the step one (4), performing ultrasonic treatment for 5 minutes by using an ultrasonic instrument, and vibrating for 4 hours to fully contact the EPS, the copper precursor in the step two (3) and the zinc-manganese ferrite; under the magnetic force of a magnet, the supernatant is poured off and washed for 5 times by deionized water; adding the sulfur source in the step two (3) into the mixture, and oscillating for 4 hours; the supernatant was decanted off under the attraction of a magnet and washed 4 times with deionized water; centrifuging and drying at 55 ℃ to obtain the zinc-manganese ferrite loaded nano copper sulfide material.
XRD analysis is carried out on the nano copper sulfide and the zinc manganese ferrite in the composite material (figures 1 and 2), the result shows that the nano copper sulfide is matched with a standard card JCPDS NO.65-3561, the zinc manganese ferrite is matched with a standard card JCPDS NO.87-1171, TEM analysis is carried out on the nano copper sulfide in a sample (figure 3), and the result shows that the average grain diameter is 7.54nm, the size of quantum dots is met, the grain diameter distribution is in accordance with normal distribution, and the grain diameters are relatively uniform.
(5) And (3) photocatalytic test: and (3) photocatalytic test: 25mg/L methylene blue solution (MB) 100ml,40mg composite nanomaterial, 5ml H 2 O 2 Under the irradiation of visible light, samples were taken every two hours to determine the MB content in the solution.
The photocatalytic test shows that the composite material has good catalytic effect, the degradation rate in 12h reaches more than 82%, and the cycle test shows that the degradation rates in four cycle tests in 12h are respectively as follows: 83%,74.5%,64%,59%, good stability.
Example 3: step one, preparation of zinc-manganese ferrite
(1) Measuring the contents of zinc ions, manganese ions and iron ions in the bioleaching solution of the waste zinc-manganese batteries in the laboratory; and supplementing a manganese source, a zinc source and an iron source to ensure that the total concentration of the three ions is 3mol/L, wherein the ratio of the concentrations of manganese ions and zinc ions is controlled to be 2, and the ratio of the concentrations of manganese ions, zinc ions and iron ions is controlled to be 0.6.
(2) The same as step one (2) in embodiment 1.
(3) The same as in step one (3) of embodiment 1.
(4) The same as step one (4) in embodiment 1.
Step two, preparation of zinc-manganese ferrite loaded nano copper sulfide material
(1) The same as (1) of step two in embodiment 1.
(2) The same as step two (2) in embodiment 1.
(3) The same as in step two (3) of embodiment 1.
(4) Preparing a zinc-manganese ferrite loaded nano copper sulfide material; mixing the EPS in the step two (2), the copper precursor in the step two (3) and the zinc-manganese ferrite in the step one (4), performing ultrasonic treatment for 5 minutes by using an ultrasonic instrument, and vibrating for 3 hours to fully contact the EPS, the copper precursor in the step two (3); under the magnetic force of a magnet, the supernatant is poured off and washed for 3 times by deionized water; adding the sulfur source in the step two (3) into the mixture, and oscillating for 3 hours; the supernatant was decanted off under the attraction of a magnet and washed 3 times with deionized water; centrifuging and drying at 55 ℃ to obtain the zinc-manganese ferrite loaded nano copper sulfide material.
XRD analysis is carried out on the nano copper sulfide and the zinc manganese ferrite in the composite material (figures 1 and 2), the result shows that the nano copper sulfide is matched with a standard card JCPDS NO.65-3561, the zinc manganese ferrite is matched with a standard card JCPDS NO.87-1171, TEM analysis is carried out on the nano copper sulfide in a sample (figure 3), the result shows that the average particle size is 8.98nm, the size accords with the size of a quantum dot, the particle size distribution accords with normal distribution, and the particle sizes are relatively uniform.
(5) And (3) photocatalytic test: and (3) photocatalytic test: 25mg/L methylene blue solution (MB) 100ml,40mg composite nanomaterial, 5ml H 2 O 2 Under the irradiation of visible light, samples were taken every two hours to determine the MB content of the solution.
The photocatalytic test shows that the composite material has good catalytic effect, the degradation rate in 12h reaches more than 83%, and the cycle test shows that the degradation rates in the four cycle tests in 12h are respectively as follows: 83%,75%,67%,59%, good stability.
Example 4: step one, preparation of zinc-manganese ferrite
(1) The same as step one (1) in embodiment 3.
(2) The same as step one (2) in embodiment 1.
(3) Transferring the solution in the step one (2) into a high-pressure reaction kettle, adding a coprecipitator to enable the pH value of the coprecipitator to be 10, and fully stirring;
the coprecipitator is ammonia water
(4) The same as step one (1) in embodiment 1.
Step two, preparation of zinc-manganese ferrite loaded nano copper sulfide material
(1) Culturing sulfate reducing bacteria; preparation of culture mediumPreparing; the solute is: 0.8mol/L lactic acid, 14.28g/L Na 2 SO 4 ,1.0g/L NH 4 Cl,0.5g/L KH 2 PO 4 ,0.5g/L MgSO 4 ,0.1g/L CaCl 2 0.5g/L yeast extract, followed by adjusting the pH of the medium to 7 using 6mol/L NaOH;
(2) The same as step two (2) in embodiment 1.
(3) The same as (3) of step two in embodiment 1.
(4) The same as in step two (4) of embodiment 1.
XRD analysis is carried out on the nano copper sulfide and the zinc manganese ferrite in the composite material (figures 1 and 2), the result shows that the nano copper sulfide is matched with a standard card JCPDS NO.65-3561, the zinc manganese ferrite is matched with a standard card JCPDS NO.87-1171, TEM analysis is carried out on the nano copper sulfide in a sample (figure 3), and the result shows that the average grain diameter is 8.98nm, the size of quantum dots is met, the grain diameter distribution is in accordance with normal distribution, and the grain diameters are relatively uniform.
(5) And (3) photocatalytic test: and (3) photocatalytic test: 25mg/L methylene blue solution (MB) 100ml,40mg composite nanomaterial, 5ml H 2 O 2 Under the irradiation of visible light, samples were taken every two hours to determine the MB content of the solution.
The photocatalytic test shows that the composite material has good catalytic effect, the degradation rate in 12h reaches more than 80%, and the cycle test shows that the degradation rates in the four cycle tests in 12h are respectively as follows: 80%,72%,65% and 57%, and has good stability.

Claims (5)

1. A method for loading nano copper sulfide on zinc-manganese ferrite is characterized by comprising the following steps: the method comprises the following specific steps:
step one, preparing zinc-manganese ferrite: measuring the contents of zinc ions, manganese ions and iron ions in the bioleaching solution of the waste zinc-manganese battery in the laboratory; and supplementing a manganese source, a zinc source and an iron source to ensure that the total concentration of the three ions is 1.5-4.5mol/L, wherein the ratio of the concentrations of manganese ions and zinc ions is controlled to be 1-2mol/L, and the ratio of manganese ions, zinc ions and iron ions is controlled to be 0.4-1mol/L; after the manganese source, the zinc source and the iron source are supplemented, stirring for 12-24 hours at room temperature by using a magnetic stirrer; transferring the solution into a high-pressure reaction kettle, adding a coprecipitator to enable the pH value of the solution to be 8-11, and fully stirring; the high-pressure reaction kettle reacts for 6 to 10 hours at the temperature of 160 to 200 ℃; after the reaction is finished, aging for 20-40h at room temperature; then carrying out suction filtration or centrifugation to obtain a sample; washing with distilled water until pH is about 7-9, centrifuging or vacuum filtering, oven drying at 50-70 deg.C, and grinding for later use;
step two, preparing the zinc-manganese ferrite loaded nano copper sulfide material:
(1) Culturing sulfate reducing bacteria; preparing a culture medium; the solute is: 0.1-0.8g/L lactic acid, 0.5-1.5g/L NH 4 Cl,0.2-0.8gl/L MgSO 4 ,0.1-0.5g/L CaCl 2 ,0.5-1.0g/L KH 2 PO 4 0.5-1.0g/L yeast powder and 10-28g/L Na 2 SO 4 . Then, adjusting the pH value of the culture medium to 6-8 by using 6mol/L NaOH, wherein the growth temperature is 20-40 ℃; inoculating sulfate reducing bacteria (Clostridium sp.) into a sulfate reducing bacteria culture medium, and placing the sulfate reducing bacteria culture medium at the temperature of 20-40 ℃ for anaerobic culture;
(2) Extraction of Extracellular Polymers (EPS); centrifuging at 4-20 deg.C to obtain crude extracellular polymer extractive solution, filtering with filter membrane, dialyzing the filtrate in dialysis bag, and purifying extracellular polymer in dialysis bag at 4 deg.C for later use;
(3) Preparing a copper precursor and a sulfur precursor; measuring the copper content in the copper-containing wastewater, and preparing 0.05-0.1mol/L by using copper sulfate; preparing 0.05-0.1mol/L sodium sulfide solution with sodium sulfide;
(4) Preparing a zinc-manganese ferrite loaded nano copper sulfide material; mixing the EPS in the step two (2), the copper precursor in the step two (3) and the zinc-manganese ferrite in the step one, and carrying out ultrasonic treatment for 5 minutes by using an ultrasonic instrument and shaking for 2-6 hours to fully contact the EPS, the copper precursor in the step two (3); under the magnetic force of a magnet, pouring out the supernatant, and washing with deionized water for 2-5 times; adding the sulfur source in the step two (3) into the mixture, and oscillating for 2-4h; pouring out the supernatant under the attraction of a magnet and washing the supernatant for 2 to 5 times by using deionized water; centrifuging, and drying at 50-70 ℃ to obtain the zinc-manganese ferrite loaded nano copper sulfide material.
(5) And (3) photocatalytic test: and (3) photocatalytic test: 25mg/L methylene blue solution (MB) 100ml,40mg composite nanomaterial, 5ml H 2 O 2 Under the irradiation of visible light, samples were taken every two hours to determine the MB content in the solution.
2. The method for preparing nano copper sulfide loaded on zinc-manganese ferrite according to claim 1, which is characterized in that: the manganese source, the zinc source and the iron source in the step one are respectively MnSO 4 、ZnSO 4 、FeSO 4
3. The method for loading nano copper sulfide on zinc-manganese ferrite as claimed in claim 1, wherein: the coprecipitator in the first step is NaOH, ammonia water or a mixture of the NaOH and the ammonia water.
4. The method for loading nano copper sulfide on zinc-manganese ferrite as claimed in claim 1, wherein: and (2) the extraction of the extracellular polymer of the sulfate reducing bacteria is to centrifuge the sulfate reducing bacteria for 10-20min at 4-20 ℃ and 6000-8000rpm/min, discard the supernatant, re-suspend the precipitate with ultrapure water, centrifuge for 10-20min at 6000-8000rpm/min, discard the supernatant, re-suspend the precipitate with ultrapure water, centrifuge for 10-25min at 16000-18000rpm/min to obtain a crude extract of the extracellular polymer, filter the crude extract with a 0.22um filter membrane, place the filtrate in a 3500-4500KDa dialysis bag, dialyze with ultrapure water overnight, and place the purified extracellular polymer of the sulfate reducing bacteria in the dialysis bag at 4 ℃ for later use.
5. The method for loading nano copper sulfide on zinc-manganese ferrite as claimed in claim 1, wherein: and in the second step (4), the mixing amount of the EPS, the copper precursor and the zinc-manganese ferrite is 0.5-1.0g of the zinc-manganese ferrite, 20-50ml of the EPS20, 5-10ml of the copper precursor and 10-15ml of the sulfur precursor respectively.
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