CN1645656A - Production of Mn-Zn ferrite from waste magnesium dioxide batteries - Google Patents
Production of Mn-Zn ferrite from waste magnesium dioxide batteries Download PDFInfo
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- CN1645656A CN1645656A CNA2005100173228A CN200510017322A CN1645656A CN 1645656 A CN1645656 A CN 1645656A CN A2005100173228 A CNA2005100173228 A CN A2005100173228A CN 200510017322 A CN200510017322 A CN 200510017322A CN 1645656 A CN1645656 A CN 1645656A
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- manganese
- filter
- cadmium
- zinc ferrite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The invention includes hydrothermal method and sol gel method. The hydrothermal includes following steps: leaching; filter; solution composition adjustment; hydrothermal reaction; filter; wash and dry; The sol gel method includes following steps: liquid extraction; filter and insoluble matter remove; solution composition adjustment; sol gel preparation; the xerogel is calcined at 600-650deg.C, or at normal temperature and pressure.
Description
Technical field:
The present invention relates to a kind of preparation method of manganese-zinc ferrite, particularly a kind of method for preparing manganese-zinc ferrite with the spent alkaline manganese dioxide battery.
Background technology:
Being extensive use of of dry cell not only consumed metal materials such as a large amount of manganese, zinc, iron, and abandoning of refuse battery caused severe contamination to environment.Research to the old and useless battery renewable resources becomes a big problem.According to bibliographical information, the laboratory method of old and useless battery resource at present has two kinds, the one, the heat method, the 2nd, liquid leaching method, recyclable part metals and compound thereof, but these two kinds of methods have a common issue with to be, difficulty is big when separating different metal, technology is numerous and diverse, and added value of product is lower, and separation purity is lower.
Summary of the invention:
The technical issues that need to address of the present invention are the metallic elements that utilize in the spent alkaline manganese dioxide battery, directly prepare the method for manganese-zinc ferrite, realize the old and useless battery renewable resources, and its preparation method is simple, and power consumption is few, and cost is low.Technical scheme of the present invention is, a kind of method of utilizing spent alkaline manganese dioxide battery MnZn Ferrite Prepared by Hydrothermal Synthesis, it includes leaching and filter progress, it is characterized in that: the iron powder of contained harmful heavy metal lead, cadmium, mercury amount (molal quantity) in the adding 〉=solution in the solution after above-mentioned leaching is filtered, remove the lead, cadmium, the mercury that cement out; Add an amount of Fe (NO
3)
3, Zn (NO
3)
2, Mn (NO
3)
2Making the metal ion total concentration is 1mol/L, and makes MnO: ZnO: FeO=0.6: 0.4: 1.0 (mol ratio).It is 6-8 that above-mentioned solution is transferred pH value, puts into autoclave, and the filling degree is 60%, and reaction temperature is 200-300 ℃, and the reaction time is 2-3 hour; Reacted solution is filtered at normal temperatures and pressures; The material that filters out is washed with alcohol and distilled water at normal temperatures and pressures; Material after the washing was obtained powdery manganese-zinc ferrite product in dry 2-3 hour under 100 ℃ of conditions.Utilize the spent alkaline manganese dioxide battery to prepare the another kind of method of manganese-zinc ferrite, it includes leaching and filter progress, it is characterized in that: the iron powder of lead, cadmium, mercury content (molal quantity) in the adding 〉=solution in the solution after above-mentioned leaching is filtered, remove by filter the lead, cadmium, the mercury that cement out, add an amount of Fe (NO
3)
3, Zn (NO
3)
2, Mn (NO
3)
2Making the metal ion total concentration is 1mol/L, and makes MnO: ZnO: FeO=0.6: 0.4: 1.0 (mol ratio); Add the citric acid that equates with the metal ion total mole number when mentioned solution is heated to 50-700 ℃, transferring pH value with ammoniacal liquor is 6-8, obtains colloidal sol through slow evaporation moisture, colloidal sol is put into oven drying obtain xerogel; Xerogel is obtained the manganese-zinc ferrite product in 600-650 ℃ of calcining or at normal temperatures and pressures burning.
The present invention is because after adopting liquid leaching method that the MnZn iron substance of old and useless battery is leached out, add suitable material by manganese-zinc ferrite composition proportion requirement and make MnZn ferrite material, this magnetic material is of many uses, consumption is big, thereby has avoided in the old and useless battery renewable resources because of separating the high and low problem of separation purity of energy consumption that MnZn iron causes.
Embodiment:
After existing old and useless battery renewable resources adopts liquid leaching method or heat method that the metallic element in the old and useless battery and other impurity are separated, again the metal of separating is separated and purify, owing to separate different metals, when particularly purity is higher, separating difficulty is big, the normal at present electrolysis separation and Extraction metal that adopts, its energy consumption is big, and cost height and purity are lower.The zinc-manganese ferrite is a kind of magnetic material of function admirable, is widely used in transformer, each side such as radio communication and space flight, and its consumption is big, and its main component is a manganese-zinc ferrite.Thereby after can utilizing these technique known of leaching method that the insoluble impurity with other of the MnZn iron in the spent alkaline manganese dioxide battery is separated, require the MnZn iron of separating is carried out the ratio adjustment according to the ferritic component ratio of zinc-manganese, adopt hydro thermal method or Prepared by Sol Gel Method manganese-zinc ferrite magnetic material.
Hydro thermal method technology is:
(1) leaching operation: the spent alkaline manganese dioxide battery is immersed in the nitric acid liquid, and liquid-solid ratio is 12-14, H
2O
2Concentration is 2.0-3.0%, (H
2O
2Weight/solution weight), reaction temperature is 50-70 ℃, reaction time 20-40 minute.
(2) filter operation: remove by filter insoluble matter at normal temperatures and pressures.
(3) add than lead, cadmium, the slightly high iron powder of mercury content (molal quantity) in the solution, remove the lead, cadmium, the mercury that cement out.
(4) each elementary composition ratio is adjusted operation: add a certain amount of Fe (NO
3)
3, Zn (NO
3)
3, Mn (NO
3)
2Making the metal ion total concentration is 1mol/L, and makes MnO: ZnO: FeO=0.6: 0.4: 1.0 (mol ratio).
(5) water heating process: the accent pH value is 9-10, and solution is put into autoclave, and compactedness is 60%, and reaction temperature is 200-300 ℃, and the reaction time is 2-3 hour.
(6) filter operation: filter at normal temperatures and pressures, leach the product material in the solution.
(7) washing procedure: with alcohol and distilled water the above-mentioned material that leaches is washed at normal temperatures and pressures.
(8) drying process: descended dry 2-3 hour at 100 ℃, make powdery manganese-zinc ferrite product.
Sol-gal process technology is:
(1) leaching operation: the spent alkaline manganese dioxide battery is immersed in the nitric acid liquid, and liquid-solid ratio is 12-14, H
2O
2Concentration is 2.0-3.0%, (H
2O
2Weight/solution weight), reaction temperature is 50-70 ℃, reaction time 20-40 minute.
(2) filter operation: remove by filter insoluble matter at normal temperatures and pressures.
(3) add than lead, cadmium, the slightly high iron powder of mercury content (molal quantity) in the solution, remove the lead, cadmium, the mercury that cement out.
(4) each elementary composition ratio is adjusted operation: add a certain amount of Fe (NO
3)
3, Zn (NO
3)
3, Mn (NO
3)
2Making the metal ion total concentration is 1mol/L, and makes MnO: ZnO: FeO=0.6: 0.4: 1.0 (mol ratio).
(5) add the citric acid that equates with the metal ion total mole number.
(6) collosol and gel preparation section: transferring pH value with ammoniacal liquor is 6-8, obtains colloidal sol through slow transpiring moisture, colloidal sol is put into oven drying obtain xerogel.
(7) finished product operation: xerogel is obtained the manganese-zinc ferrite product in 600-650 ℃ of calcining or burning at normal temperatures and pressures.
Claims (2)
1. method of utilizing the spent alkaline manganese dioxide battery to prepare manganese-zinc ferrite, it includes leaching and filter progress, it is characterized in that: the iron powder of leaded in the adding 〉=solution in the solution after above-mentioned leaching is filtered, cadmium, mercury amount (molal quantity) removes by filter the lead, cadmium, the mercury that cement out; Add an amount of Fe (NO
3)
3, Zn (NO
3)
2, Mn (NO
3)
2Making the metal ion total concentration is 1mol/L, and makes MnO: ZnO: FeO=0.6: 0.4: 1.0 (mol ratio); It is 6-8 that mentioned solution is transferred pH value, puts into autoclave, and the filling degree is 60%, and reaction temperature is 200-300 ℃, and the reaction time is 2-3 hour; Reacted solution is filtered at normal temperatures and pressures; The material that filters out is washed with alcohol and distilled water at normal temperatures and pressures; Material after the washing was obtained powdery manganese-zinc ferrite product in dry 2-3 hour under 100 ℃ of conditions.
2, a kind of method of utilizing the spent alkaline manganese dioxide battery to prepare manganese-zinc ferrite, it includes leaching and filter progress, it is characterized in that: the iron powder of lead, cadmium, mercury content (molal quantity) in the adding 〉=solution in the solution after above-mentioned leaching is filtered, remove by filter the lead, cadmium, the mercury that cement out, add an amount of Fe (NO
3)
3, Zn (NO
3)
2, Mn (NO
3)
2Making the metal ion total concentration is 1mol/L, and makes MnO: ZnO: FeO=0.6: 0.4: 1.0 (mol ratio); Add the citric acid that equates with the metal ion total mole number when mentioned solution is heated to 50-70 ℃, transferring pH value with ammoniacal liquor is 6-8, obtains colloidal sol through slow evaporation moisture, colloidal sol is put into oven drying obtain xerogel; Xerogel is obtained the manganese-zinc ferrite product in 600-650 ℃ of calcining or at normal temperatures and pressures burning.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100173228A CN1266793C (en) | 2005-01-17 | 2005-01-17 | Production of Mn-Zn ferrite from waste magnesium dioxide batteries |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100173228A CN1266793C (en) | 2005-01-17 | 2005-01-17 | Production of Mn-Zn ferrite from waste magnesium dioxide batteries |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006100551226A Division CN1880273A (en) | 2005-01-17 | 2005-01-17 | Method for preparing manganese-zinc ferrite using waste alkaline manganese bioxide battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1645656A true CN1645656A (en) | 2005-07-27 |
| CN1266793C CN1266793C (en) | 2006-07-26 |
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ID=34875634
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100173228A Expired - Fee Related CN1266793C (en) | 2005-01-17 | 2005-01-17 | Production of Mn-Zn ferrite from waste magnesium dioxide batteries |
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|---|---|
| CN (1) | CN1266793C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515763A (en) * | 2011-11-10 | 2012-06-27 | 哈尔滨工业大学 | Preparation method for perovskite structural ceramic sol |
| CN103570344A (en) * | 2013-11-04 | 2014-02-12 | 河南师范大学 | Method for preparing manganese-zinc ferrite by using waste zinc-manganese battery |
| CN103441315B (en) * | 2013-09-05 | 2015-05-20 | 北京理工大学 | Method for preparing manganese-zinc ferrite soft magnet by taking biological leachate of waste zinc-manganese battery as raw material |
| CN106435189A (en) * | 2016-08-30 | 2017-02-22 | 江苏省冶金设计院有限公司 | Treatment method and system for metalized pellets |
| CN107188293A (en) * | 2017-06-08 | 2017-09-22 | 武汉大学 | Method for degrading organic pollutants by using manganese-zinc ferrite activated persulfate prepared from waste batteries |
| CN112259754A (en) * | 2020-10-22 | 2021-01-22 | 上海交通大学 | Method for recycling manganese from waste zinc-manganese dry battery positive electrode material and application |
| CN116116867A (en) * | 2022-09-07 | 2023-05-16 | 北京科技大学 | Cooperative treatment system and method for waste dry batteries and kitchen waste |
-
2005
- 2005-01-17 CN CNB2005100173228A patent/CN1266793C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515763A (en) * | 2011-11-10 | 2012-06-27 | 哈尔滨工业大学 | Preparation method for perovskite structural ceramic sol |
| CN102515763B (en) * | 2011-11-10 | 2013-05-22 | 哈尔滨工业大学 | Preparation method for perovskite structural ceramic sol |
| CN103441315B (en) * | 2013-09-05 | 2015-05-20 | 北京理工大学 | Method for preparing manganese-zinc ferrite soft magnet by taking biological leachate of waste zinc-manganese battery as raw material |
| CN103570344A (en) * | 2013-11-04 | 2014-02-12 | 河南师范大学 | Method for preparing manganese-zinc ferrite by using waste zinc-manganese battery |
| CN106435189A (en) * | 2016-08-30 | 2017-02-22 | 江苏省冶金设计院有限公司 | Treatment method and system for metalized pellets |
| CN107188293A (en) * | 2017-06-08 | 2017-09-22 | 武汉大学 | Method for degrading organic pollutants by using manganese-zinc ferrite activated persulfate prepared from waste batteries |
| CN107188293B (en) * | 2017-06-08 | 2020-02-18 | 武汉大学 | Method for degrading organic pollutants by using manganese-zinc ferrite activated persulfate prepared from waste batteries |
| CN112259754A (en) * | 2020-10-22 | 2021-01-22 | 上海交通大学 | Method for recycling manganese from waste zinc-manganese dry battery positive electrode material and application |
| CN116116867A (en) * | 2022-09-07 | 2023-05-16 | 北京科技大学 | Cooperative treatment system and method for waste dry batteries and kitchen waste |
| CN116116867B (en) * | 2022-09-07 | 2023-10-13 | 北京科技大学 | Cooperative treatment system and method for waste dry batteries and kitchen waste |
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| Publication number | Publication date |
|---|---|
| CN1266793C (en) | 2006-07-26 |
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