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 PDFInfo
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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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- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 70
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052802 copper Inorganic materials 0.000 claims abstract description 30
- 239000010949 copper Substances 0.000 claims abstract description 30
- 230000001699 photocatalysis Effects 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000012691 Cu precursor Substances 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 claims abstract description 19
- 239000002351 wastewater Substances 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 238000011068 loading method Methods 0.000 claims abstract description 15
- 239000002699 waste material Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011572 manganese Substances 0.000 claims abstract description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 239000011701 zinc Substances 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 8
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 241000894006 Bacteria Species 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 21
- 239000006228 supernatant Substances 0.000 claims description 17
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 12
- 229910001437 manganese ion Inorganic materials 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000000502 dialysis Methods 0.000 claims description 10
- 239000001963 growth medium Substances 0.000 claims description 10
- -1 iron ions Chemical class 0.000 claims description 10
- 239000002086 nanomaterial Substances 0.000 claims description 10
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 8
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000287 crude extract Substances 0.000 claims description 5
- 238000012258 culturing Methods 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 230000001502 supplementing effect Effects 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 241000193464 Clostridium sp. Species 0.000 claims description 2
- 240000004808 Saccharomyces cerevisiae Species 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000002910 solid waste Substances 0.000 abstract description 2
- 230000005389 magnetism Effects 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 239000002096 quantum dot Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 229940041514 candida albicans extract Drugs 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 239000012138 yeast extract Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000006100 radiation absorber Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- 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
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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