CN104261480A - Preparation method and use of nano-manganese oxide by utilizing waste battery - Google Patents

Preparation method and use of nano-manganese oxide by utilizing waste battery Download PDF

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Publication number
CN104261480A
CN104261480A CN201410564648.1A CN201410564648A CN104261480A CN 104261480 A CN104261480 A CN 104261480A CN 201410564648 A CN201410564648 A CN 201410564648A CN 104261480 A CN104261480 A CN 104261480A
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nano
gained
filter residue
manganese dioxide
crystal
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CN104261480B (en
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毕建洪
汪宇明
李健
毕文杰
陶文波
李百中
李蒙
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Hunan Qingchong New Material Co ltd
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Hefei Normal University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides; Hydroxides
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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

Abstract

The invention relates to a preparation method and a use of nano-manganese oxide by utilizing a waste battery. The nano-manganese oxide is obtained through the steps such as crushing and screening of the waste battery, acid leaching impurity removal, roasting, leaching, filtering crystallization and hydro-thermal synthesis. According to the preparation method, the waste battery serves as a raw material, the raw material is easily obtained, and the waste battery is secondarily utilized, so that the pollution to the environment is reduced, the preparation method is simple, high in yield and low in cost, and the prepared product nano-manganese oxide is nanowire-shaped; the nano-manganese oxide can serves as a catalyst in the degradation reaction of industrial alkaline magenta dye, is green and environment-friendly, and can be recycled and reutilized.

Description

A kind of utilize old and useless battery to prepare nano-manganese dioxide method and purposes
Technical field
The present invention relates to nano-manganese dioxide preparation field, be specially and a kind ofly from old and useless battery, prepare the method for nano-manganese dioxide and can be used as catalyzer for degrading alkaline rosaniline dyes by nano-manganese dioxide prepared by the method.
Background technology
From the blank of Luigi Galvani proposition galvanic cell in 1780, to the voltaic cell of Alessandro Volta.Again finally, particularly after 1859, after the novel battery appearance such as Zn-Mn drying battery, Li ionization cell, Ag-Zn battery, battery is deep into each corner of people's daily life gradually, and people's life be unable to do without battery.Each component is sealed up for safekeeping at battery case inner by battery in the fabrication process, along with the use of battery, shell is through long-term abrasion and corrosion, inner sealed up for safekeeping material (heavy metal, ionogen, soda acid etc.) and will be leaked, in entered environment, cause the pollution of soil and water, enter human body finally by food chain, cause the obstacle of Human Physiology and metabolism, thus diseases induced.For the harm of old and useless battery, the mode processing old and useless battery at present in the world mainly contains three kinds: solidify buried; Deposit in mine; Recycle.And China at present mainly a part deposit after collecting and do not process, wait technology and equipment to be updated.But depositing in process the secondary pollution problem will noting preventing old and useless battery; Another part burns together with domestic refuse, landfill.But in the protection of burning, landfill process will note environment, landfill easily causes the pollution of underground water, and burning easily causes topsoil.These processes make useful component in old and useless battery less than making full use of, cause waste.Though have the current old and useless battery of report harmless, but that is only mercuryless at battery manufacturing process, does not solve the pollution problem of other heavy metals.
MnO 2the one in both sexes transition metal material, because manganese atom exists different oxidation state (+2 ,+3 ,+4), thus MnO 2there are many excellent electromagnetism, photoelectricity and catalytic performance etc.Research finds that different synthetic methods can obtain the MnO of different structure crystal formation 2, different structures just has different performances, modal MnO 2it is exactly octahedral packed structures.Common 5 kinds main Manganse Dioxide crystal formations have: α type, β type, γ type, δ type, λ type.Common MnO 2particle size is large, and specific surface area is little, and relative reactivity center is few, and nanometer MnO 2due to the nano material characteristic that it is special, be greatly expanded in Application Areas.Nano-manganese dioxide has better chemical property, and make it at ultracapacitor, the fields such as electrochromism become the focus of research.The nano-meter characteristic of nano-manganese dioxide excellence and redox property make it be used widely in catalytic field, and particularly its application in catalysis is developed in recent years, has expanded the Application Areas that it is new.
In recent years, flourish along with printing and dyeing industry, various novel additive, dyestuff are used widely, wherein containing many toxic organicses, some even can make transgenation, canceration etc., also result in great injury while bringing welfare.Simultaneously to account for trade effluent ratio large for waste water from dyestuff, and the organic dye output of China accounts for 27% of world wide production, the features such as the waste water amount of having that it is produced, discharge in dyeing process is large, toxic organic compound content is high, acid-basicity is large, complicated component, difficult degradation are one of generally acknowledged the most difficult waste water.CHINESE FRESHWATER scarcity of resources, organic dye waste water pollutes large.Physical conventional at present has the methods such as absorption method, extraction process and membrane separation technique; Chemical method mainly comprises chemical coagulation process, oxidation style, electrochemical method etc.; Biochemical process and the raw combination process facture of physics and chemistry etc.As: cohesion, solidifying wadding, absorption, ozonize, electrochemical process and fungi decolouring etc.
Summary of the invention
For the problems referred to above, the invention provides a kind of simple, free of contamination method by preparing nano-manganese dioxide in old and useless battery, nano-manganese dioxide prepared by the method can be used as effective catalyst for degrading alkaline rosaniline dyes.
For solving the problem, the invention provides a kind of method utilizing old and useless battery to prepare nano-manganese dioxide, being prepared according to the following steps:
crushing and screening, sieves after old and useless battery fragmentation, obtains black containing manganese mixture, by the H of this black containing manganese mixture 2-4mol/L 2sO 4soak 20-40min, then suction filtration, obtain filter residue;
roasting, by step after suction filtration, the filter residue of gained to send in retort furnace roasting 3-6h at 400-750 DEG C, obtains brown solid powder after cooling;
leach and filter, by step gained brown solid powder is laid on the fresh aluminium flake with NaOH process, and aluminium flake is put into the Na of about 20% of existing preparation 2cO 3in solution, filter after reaction 20-48h, obtain filter residue;
substep crystallization, by step gained filter residue, as in suitable container, adds rare H of 1.5-3mol/L 2sO 4dissolve, rare H to be added 2sO 4to filter residue amount of solid not when reducing, stop adding rare H 2sO 4, and gained solution was carried out filtering filter residue, then by gained filtrate concentrating under reduced pressure at 30-40 DEG C, when having solid to separate out in filtrate, filtrate is cooled to 0 DEG C and separates out Na 2sO 4crystal and Al 2(SO 4) 3filter after crystal, residual filtrate is heated to 90-98 DEG C, after separating out precipitation, obtain MnSO 4crystal;
hydrothermal Synthesis, by step the MnSO of gained 4crystal and oxygenant in mass ratio for 1:1.5-3 mixes, and add deionized water and stir at 80-90 DEG C, and described oxygenant is any one in ammonium persulphate, potassium permanganate; The suspension liquid stirring rear gained is put into withstand voltage still, heats 18h, obtain brownish black suspension liquid at 140 DEG C, the filter residue deionized water after being filtered by brownish black suspension liquid and ethanol are washed till neutrality, then product drying are obtained nano-manganese dioxide.
Further, the nano-manganese dioxide prepared by aforesaid method is adopted to be used for degrading alkaline rosaniline dyes as catalyzer.
Beneficial effect of the present invention is: preparation method of the present invention take old and useless battery as raw material, and raw material is easy to obtain, and has carried out second stage employ to old and useless battery, decreases the pollution to environment; Preparation method of the present invention is simple, and output is high, and cost is low, and prepared product manganese dioxide is nanometer wire, as the catalyzer of degraded industrial alkaline rosaniline dyes, and environmental protection, recyclable recycling.
Accompanying drawing explanation
Be described in further detail with regard to the specific embodiment of the present invention below in conjunction with accompanying drawing, wherein:
Fig. 1 is the FB(flow block) of the inventive method;
Fig. 2 is the XRD diffraction spectrogram of nano-manganese dioxide prepared by the present invention;
Fig. 3 is the SEM phenogram of the nano-manganese dioxide of preparation in the embodiment of the present invention one;
Fig. 4 is the ultraviolet absorptivity comparison diagram of the nano-manganese dioxide catalysis Basic Fuchsin in Aqueous Solution degraded front and back utilizing preparation in the embodiment of the present invention one.
Fig. 5 is the SEM phenogram of the nano-manganese dioxide of preparation in the embodiment of the present invention two;
Fig. 6 is the ultraviolet absorptivity comparison diagram of the nano-manganese dioxide catalysis Basic Fuchsin in Aqueous Solution degraded front and back utilizing preparation in the embodiment of the present invention two.
Fig. 7 is the SEM phenogram of the nano-manganese dioxide of preparation in the embodiment of the present invention three;
Fig. 8 is the ultraviolet absorptivity comparison diagram of the nano-manganese dioxide catalysis Basic Fuchsin in Aqueous Solution degraded front and back utilizing preparation in the embodiment of the present invention three.
 
Embodiment
embodiment one
With reference to a kind of method utilizing old and useless battery to prepare nano-manganese dioxide shown in Fig. 1, step is as follows: sieve after spent alkaline batteries fragmentation, obtains black containing manganese mixture, with the H of 3mol/L 2sO 4soak 30min, suction filtration, filter residue is 750 DEG C of roasting 3h in retort furnace, and cooling obtains brown solid powder.20% Na of existing preparation is put into the fresh aluminium flake of NaOH process 2cO 3in solution, be laid on aluminium flake by brown solid powder, reaction 23h, after filtration, uses 1.5mol/L H 2sO 4dissolve filter residue, H to be added 2sO 4time amount of solid constant, stop add H 2sO 4, solids removed by filtration, by filtrate at 30 DEG C of concentrating under reduced pressure, in time having solid to occur, is first cooled to 0 DEG C of removing Na 2sO 4and Al 2(SO 4) 3crystal, is then heated to 95 DEG C and separates out precipitation, obtain MnSO 4crystal, productive rate 87.2%.By gained MnSO 4crystal and oxygenant KMnO 41:2.9 mixing in mass ratio, adds deionized water and stirs at 90 DEG C, gained suspension liquid is put into withstand voltage still, and in 140 DEG C of reaction 18h, obtain brownish black suspension liquid, the filter residue deionized water after filtration and ethanol are washed till neutrality, obtain black MnO after product drying 2particle, productive rate 95.6%.With reference to the XRD diffraction spectrogram of the nano-manganese dioxide shown in Fig. 2, its structure of gained Manganse Dioxide is pure phase square α-MnO 2; With reference to the SEM phenogram of the nano-manganese dioxide shown in Fig. 3, visible products therefrom is made up of a large amount of wire nanometer rod.
Adopt above-mentioned nanometer MnO 2pinkish red as catalyst degrading alkaline, when first to get 2.0mg catalyzer and 5mL concentration be 100mg/L magenta, and add in Erlenmeyer flask with 1mL ethanol together with 17mL water, 30 DEG C of waters bath with thermostatic control, and ceaselessly shake, slowly add the hydrogen peroxide of 2.5mL 3%, dropwise rear continuation reaction 6min, ultraviolet absorptivity contrast as shown in Figure 4 before and after Basic Fuchsin in Aqueous Solution degraded, the pinkish red basic degraded of solution neutral and alkali, degradation rate reaches 99.91%.
embodiment two
With reference to a kind of method utilizing old and useless battery to prepare nano-manganese dioxide shown in Fig. 1, step is as follows: sieve after spent alkaline batteries fragmentation, obtains black containing manganese mixture, with the rare H of 4mol/L 2sO 4soak 20min, suction filtration; Filter residue is 400 DEG C of roasting 6h in retort furnace, and cooling obtains brown solid powder; 20% Na of existing preparation is put into the fresh aluminium flake of NaOH process 2cO 3in solution, be laid on aluminium flake by brown solid powder, reaction 48h, filters; With the rare H of 3mol/L 2sO 4dissolve filter residue, H to be added 2sO 4time amount of solid constant, stop add H 2sO 4, solids removed by filtration, by filtrate at 30 DEG C of concentrating under reduced pressure, in time having solid to occur, is first cooled to 0 DEG C of removing Na 2sO 4and Al 2(SO 4) 3crystal, is then heated to 90 DEG C and separates out precipitation, obtain MnSO 4crystal, productive rate is 82.6%; By MnSO 4the 1:1.5 mixing in mass ratio of crystal and ammonium persulphate, adds deionized water to stirring, stirs at 80 DEG C; Gained suspension liquid is put into withstand voltage still, in 140 DEG C of reacting by heating 18h, obtains brownish black suspension liquid, the filter residue deionized water after filtration and ethanol are washed till neutrality, obtain black Manganse Dioxide particle after product drying, and productive rate is 90.7%.The pattern of products therefrom is nano wire (with reference to Fig. 5).
Adopt above-mentioned nanometer MnO 2pinkish red as catalyst degrading alkaline, first get the Basic Fuchsin in Aqueous Solution of 4.0mg catalyzer and 10mL 100mg/L, and add in Erlenmeyer flask with 2mL ethanol together with 34mL water, 40 DEG C of waters bath with thermostatic control, and ceaselessly shake, slowly add the hydrogen peroxide of 5mL 3%, dropwise rear continuation reaction 2min, degradation rate reaches 91.3%.Ultraviolet correlation curve before and after degraded as shown in Figure 6.
embodiment three
With reference to a kind of method utilizing old and useless battery to prepare nano-manganese dioxide shown in Fig. 1, step is as follows: sieve after spent alkaline batteries fragmentation, obtains black containing manganese mixture, with the H of 2mol/L 2sO 4soak 40min, suction filtration, filter residue is 600 DEG C of roasting 4h in retort furnace, and cooling obtains brown solid powder.20% Na of existing preparation is put into the fresh aluminium flake of NaOH process 2cO 3in solution, be laid on aluminium flake by brown solid powder, reaction 36h, after filtration, uses 2.0mol/L H 2sO 4dissolve filter residue, H to be added 2sO 4time amount of solid constant, stop add H 2sO 4, solids removed by filtration, by filtrate at 40 DEG C of concentrating under reduced pressure, in time having solid to occur, is first cooled to 0 DEG C of removing Na 2sO 4and Al 2(SO 4) 3crystal, is then heated to 98 DEG C and separates out precipitation, obtain MnSO 4crystal, productive rate 84.5%.By gained MnSO 4crystal and oxygenant KMnO 41:3 mixing in mass ratio, adds deionized water and stirs at 85 DEG C, gained suspension liquid is put into withstand voltage still, and in 140 DEG C of reaction 18h, obtain brownish black suspension liquid, the filter residue deionized water after filtration and ethanol are washed till neutrality, obtain black MnO after product drying 2particle, productive rate 94.3%.The pattern of products therefrom is wire nano belt (with reference to Fig. 7).
Adopt above-mentioned nanometer MnO 2pinkish red as catalyst degrading alkaline, when to get 6.0mg catalyzer and 15mL concentration be 100mg/L magenta, and add in Erlenmeyer flask with 3mL ethanol together with 50mL water, 35 DEG C of waters bath with thermostatic control, and ceaselessly shake, slowly add the hydrogen peroxide of 7.5mL 3%, dropwise rear continuation reaction 4min, ultraviolet absorptivity contrast as shown in Figure 8 before and after Basic Fuchsin in Aqueous Solution degraded, the pinkish red basic degraded of solution neutral and alkali, degradation rate reaches 96.75%.
The above; be only the better embodiment of the present invention, but scope is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore scope is as the criterion with the protection domain of claims.

Claims (2)

1. utilize old and useless battery to prepare a method for nano-manganese dioxide, it is characterized in that: be prepared according to the following steps:
crushing and screening, sieves after old and useless battery fragmentation, obtains black containing manganese mixture, by the H of this black containing manganese mixture 2-4mol/L 2sO 4soak 20-40min, then suction filtration, obtain filter residue;
roasting, by step after suction filtration, the filter residue of gained to send in retort furnace roasting 3-6h at 400-750 DEG C, obtains brown solid powder after cooling;
leach and filter, by step gained brown solid powder is laid on the fresh aluminium flake with NaOH process, and aluminium flake is put into the Na of about 20% of existing preparation 2cO 3in solution, filter after reaction 20-48h, obtain filter residue;
substep crystallization, by step gained filter residue, as in suitable container, adds rare H of 1.5-3mol/L 2sO 4dissolve, rare H to be added 2sO 4to filter residue amount of solid not when reducing, stop adding rare H 2sO 4, and gained solution was carried out filtering filter residue, then by gained filtrate concentrating under reduced pressure at 30-40 DEG C, when having solid to separate out in filtrate, filtrate is cooled to 0 DEG C and separates out Na 2sO 4crystal and Al 2(SO 4) 3filter after crystal, residual filtrate is heated to 90-98 DEG C, after separating out precipitation, obtain MnSO 4crystal;
hydrothermal Synthesis, by step the MnSO of gained 4crystal and oxygenant in mass ratio for 1:1.5-3 mixes, and add deionized water and stir at 80-90 DEG C, and described oxygenant is any one in ammonium persulphate, potassium permanganate; The suspension liquid stirring rear gained is put into withstand voltage still, heats 18h, obtain brownish black suspension liquid at 140 DEG C, the filter residue deionized water after being filtered by brownish black suspension liquid and ethanol are washed till neutrality, then product drying are obtained nano-manganese dioxide.
2. can be used as catalyzer for degrading alkaline rosaniline dyes according to a kind of nano-manganese dioxide prepared by method utilizing old and useless battery to prepare nano-manganese dioxide as claimed in claim 1.
CN201410564648.1A 2014-10-22 2014-10-22 A kind of method utilizing old and useless battery to prepare nano-manganese dioxide Active CN104261480B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105886781A (en) * 2016-06-29 2016-08-24 广西桂柳化工有限责任公司 Method for recovering manganese dioxide from electrolytic manganese anode mud
CN106115788A (en) * 2016-06-29 2016-11-16 广西桂柳化工有限责任公司 Method for preparing nano manganese dioxide by using waste battery as raw material
CN106693983A (en) * 2016-11-10 2017-05-24 上海交通大学 Method using waste ternary lithium battery cathode material to prepare methylbenzene degrading catalyst
CN107285395A (en) * 2017-07-12 2017-10-24 合肥梵腾环保科技有限公司 Comprehensive treatment method of waste battery

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105886781A (en) * 2016-06-29 2016-08-24 广西桂柳化工有限责任公司 Method for recovering manganese dioxide from electrolytic manganese anode mud
CN106115788A (en) * 2016-06-29 2016-11-16 广西桂柳化工有限责任公司 Method for preparing nano manganese dioxide by using waste battery as raw material
CN105886781B (en) * 2016-06-29 2018-01-02 广西桂柳化工有限责任公司 Method for recovering manganese dioxide from electrolytic manganese anode mud
CN106693983A (en) * 2016-11-10 2017-05-24 上海交通大学 Method using waste ternary lithium battery cathode material to prepare methylbenzene degrading catalyst
CN107285395A (en) * 2017-07-12 2017-10-24 合肥梵腾环保科技有限公司 Comprehensive treatment method of waste battery

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