CN87102008A - From waste zinc manganese dry battery, extract the method for Manganse Dioxide and zinc - Google Patents
From waste zinc manganese dry battery, extract the method for Manganse Dioxide and zinc Download PDFInfo
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- CN87102008A CN87102008A CN198787102008A CN87102008A CN87102008A CN 87102008 A CN87102008 A CN 87102008A CN 198787102008 A CN198787102008 A CN 198787102008A CN 87102008 A CN87102008 A CN 87102008A CN 87102008 A CN87102008 A CN 87102008A
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- zinc
- manganse dioxide
- cadmia
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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
From waste zinc manganese dry battery, extract the method for Manganse Dioxide and zinc, belong to the useful material regeneration of refuse battery field one time.The present invention is Manganse Dioxide material and metal cadmia or the zinc sulfide concentrates leaching simultaneously in sulphuric acid soln that will sub-elect after the refuse battery fragmentation, utilize the redox effect of Manganse Dioxide and zinc, doing promotor reinforcement with iron leaches, thereby improved the leaching yield of Manganse Dioxide and zinc, comprehensive reclaim zinc-manganese in the refuse battery and the zinc in the metal cadmia, and saved the calcining process of ordinary method, eliminate secondary pollution, improve metal recovery rate, reduced cost.The present invention is applicable to and handles various waste zinc manganese dry batteries.
Description
The invention belongs to the useful material regeneration of refuse battery field one time.Usually the refuse battery that contains a large amount of useful metals is abandoned by the user, is great waste from resource view.In order from refuse battery, to reclaim Manganse Dioxide and zinc, the clear 52-7813 of Japan special permission and BeiJing, China's mining and metallurgy are studied in " roasting one electrodeposition method is handled waste zinc manganese dry battery " article (seeing " non-ferrous metal " 1985 NO2) that total institute delivers and have been proposed " roasting-leaching-purification-electrolysis " technology respectively, and its principle process is seen accompanying drawing 1.It is made of following four road master operations:
(1) roasting-refuse battery was through after the fragmentation under 500-1000 ℃ temperature roasting 3-20 hour, and combustiblematerialss such as carbon rod, pitch, plastics are all burnt in roasting, and Manganse Dioxide becomes suboxide, and metallic zinc is melted.
(2) leach-material after the roasting is removed the copper cap and zinc granule leaches with sulphuric acid soln again.
(3) purification-leach liquor carries out deironing, copper, cadmium and nickel.
(4) electrolysis-through solution electrolysis in electrolyzer of above-mentioned processing.Anode is black with stone, the negative electrode aluminium sheet.Separate out Manganse Dioxide at anode during electrolysis, negative electrode precipitating metal zinc.
Its advantage is: 1. by roasting, can reclaim the ammonium oxide solution of high density from furnace gas; 2. roasting can reduce the inventory of next step wet processing.But aforesaid method exists: 1. roasting process produces a large amount of hydrocarbon polymer obnoxious flavoures, serious environment pollution; 2. the battery cadmia is pure zinc, and it is very uneconomical all to enter roasting, leaching, purification, electrolytic process; 3. the spelter leaching velocity is slow in the calcining; 4. for satisfying the electrolysis simultaneously of zinc-dioxy manganese, the zinc-manganese dioxide ratio is difficult to shortcomings such as control in the leach liquor.
The present invention is exactly at the problems referred to above, proposes a kind ofly can eliminate secondary pollution, again can comprehensive treating process metal cadmia or the regeneration Manganse Dioxide from refuse battery of zinc sulfide concentrates and the method for zinc.
Feature of the present invention is that the Manganse Dioxide material that refuse battery sub-elects after fragmentation is placed sulphuric acid soln, evenly adds metal cadmia or zinc sulfide concentrates under agitation condition, does promotor with iron, and controls suitable temperature, and time and liquid-solid ratio leach.Leach liquor purifies and electrolysis.
Principle process of the present invention as shown in Figure 2, its master operation comprises:
(1) fragmentation-, cell cathode mixture and anode zinc tube are exposed with refuse battery pulverizer fragmentation.
(2) refuse battery of sorting-fragmentation is selected cadmia, iron sheet, copper cap, paper and plastics respectively.
(3) leach-the Manganse Dioxide material of sorting is placed sulphuric acid soln, under agitation condition, evenly add metal cadmia or zinc sulfide concentrates, leach as promotor with iron.The leaching process reaction formula is:
Leaching condition is: temperature 65-100 ℃, and optimum temps 70-90 ℃; Time 2-15 hour, Best Times 4-10 hour; Liquid-solid ratio 3-12: 1, best liquid-solid ratio 4-9: 1; Iron 1-6g/l, residual sour 12-30g/l.
(4) contain impurity such as a certain amount of chlorine, iron, copper, cobalt in the purification-leach liquor, unfavorable to electrolytic process, can adopt ordinary method to remove.The ferruginous purification slag of part returns the leaching operation.
(5) solution after electrolysis-purification enters electrolyzer, and anode electrolytic cell carbon rod, negative electrode aluminium sheet, zinc and Manganse Dioxide carry out electrolysis simultaneously in same groove.Its reaction formula is:
Electrolytic production is electrolytic zinc and electrolytic manganese dioxide.
Waste electrolyte returns leaching process.
Usually, because the MnO in the refuse battery
2And Mn
2O
3Therefore when having reductive agent to exist, can not be dissolved in acid, will make them be dissolved in acid and must give and earlier it is carried out reducing roasting.On the other hand, when leaching the metal cadmia separately, metallic zinc is separated out a large amount of hydrogen when acid is molten, and the leaching process sluggish.The present invention combines both redox leaching process, utilizes the MnO in the zinc reduction refuse battery in the metal cadmia
2And Mn
2O
3, to reach the purpose that zinc, manganese leach simultaneously.
The metal cadmia can be zinc-plated slag or refining cadmia or metallic zinc bits or zinc sulfide concentrates among the present invention.Realize for the dynamic conditions that guarantees reaction (1) and (2), must have promotor in the leaching process.The present invention adopts iron as promotor, and its reaction is as follows in leaching process:
Advantage of the present invention is: 1. removed the calcining process in the common process of recycling used batteries, eliminated secondary pollution; (2) refuse battery can directly reclaim through the zinc metal sheet that cracking and sorting goes out, and has both improved the rate of recovery of zinc, can reduce production costs again; 3. in the process of recycling used batteries both condensation handled the metal cadmia, improved the leaching speed of response again; 4. the ratio of zinc and Manganse Dioxide can satisfy electrolytic requirement in the leach liquor.The present invention also has the metal recovery rate height in addition, cost is low and advantage such as good product quality.
The present invention is applicable to that zinc and the Manganse Dioxide in the various waste zinc manganese dry batteries reclaims.
Example 1. waste zinc manganese dry battery 34kg, behind (1) and (2) two-step: refuse battery Manganse Dioxide material 17.63kg; Zinc metal sheet 7.15kg: paper scrap, plastics, copper cap, iron sheet 4.39kg.Refuse battery Manganse Dioxide material major ingredient following (%):
Zn????15.98????Mn????19.10
Fe????2.77????Cu????0.63
The scum 2.0kg of above-mentioned Manganse Dioxide material 7.1kg and iron content 8-15g/l is put into sulphuric acid soln, and adding while stirring contains zinc 72.5% zinc-plated slag 2.0kg and leaches.80 ℃ of extraction temperatures, liquid-solid ratio 4.35: 1, residual sour 20g/l, 7 hours time, leach liquor composition following (g/l):
Zn????71.33????Mn????32.38
Fe????1.78????Cu????0.507
The leaching yield of zinc is 96%, and the leaching yield of manganese is 91%.
The composition of leach liquor after purifying is (g/l):
Zn????73.63????Mn????44.18
Fe????0.001????Cu????0.00035
Co????0.00066
Quality product following (%) after the scavenging solution electrolysis:
Cu????Cd????Fe????Pb
Electrolytic zinc 0.00095 0.00031 0.00074 0.0031
MnO
20.0023 0.025 0.007
Example 2: the Manganse Dioxide material 71kg and the scum 23kg that will be same as in the example 1 add in the sulphuric acid soln, evenly add 12kg metallic zinc bits then.70 ℃ of extraction temperatures.Residual sour 14.67g/l, liquid-solid ratio stirs 9 hour at 8: 1.The leach liquor composition is (g/l):
Zn????83.16????Mn????28.86
Fe????1.92????Cu????0.57
Composition is (g/l) behind the purification of leaching liquor:
Zn????66.71????Mn????22.39????Fe????0.05
Cu????0.0005????Co????0.0018
Quality product following (%) after the scavenging solution electrolysis:
Cu????Cd????Fe????Pb
Electrolytic zinc 0.00095 0.00031 0.00074 0.0031
MnO
20.0068 0.025 0.03
Example 3: the Manganse Dioxide material 308g that will be same as in the example 1 puts into sulfuric acid liquid, adds zinc sulfide concentrates 124g while stirring, and the zinc sulfide concentrates composition is as follows:
Zn????50.38????Fe????11.25????S????29.96
Pb????1.72????Cu????0.28????Cd????0.28
Co????0.0035
90 ℃ of extraction temperatures, residual sour 28g/l, churning time 4 hours.The leach liquor composition is (g/l)
Zn????92.5????Mn????42.4????Fe????6.82
Cu????0.39
Purifying the back composition is (g/l):
Zn????87.4????Mn????37.5????Fe????0.009
Cu????0.0002????Co????0.0006
Quality product is (%) after the scavenging solution electrolysis:
Cu????Cd????Fe????Pb
Electrolytic zinc 0.00098 0.002 0.0021 0.005
MnO
20.0013 0.014 0.012
Claims (3)
1, from waste zinc manganese dry battery, extracts the method for Manganse Dioxide and zinc, constitute by fragmentation, leaching, purification, electrowinning process, it is characterized in that the Manganse Dioxide material that to sub-elect after the refuse battery fragmentation, add the part scum and place sulphuric acid soln, under agitation condition, evenly add metal cadmia or zinc sulfide concentrates, 65-100 ℃ of control condition temperature, liquid-solid ratio 3-12: 1, extraction time 2-12 hour.
2, method according to claim 1 is characterized in that extraction temperature 70-90 ℃, iron 1-6g/l, and residual sour 12-30g/l, liquid-solid ratio 4-9: 1, time 4-10 hour.
3, method according to claim 1 is characterized in that the metal cadmia can be zinc-plated slag or refining cadmia or metallic zinc bits.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN198787102008A CN87102008A (en) | 1987-03-27 | 1987-03-27 | From waste zinc manganese dry battery, extract the method for Manganse Dioxide and zinc |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN198787102008A CN87102008A (en) | 1987-03-27 | 1987-03-27 | From waste zinc manganese dry battery, extract the method for Manganse Dioxide and zinc |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN87102008A true CN87102008A (en) | 1988-10-19 |
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ID=4813719
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN198787102008A Pending CN87102008A (en) | 1987-03-27 | 1987-03-27 | From waste zinc manganese dry battery, extract the method for Manganse Dioxide and zinc |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN87102008A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321224C (en) * | 2004-08-02 | 2007-06-13 | 西安建筑科技大学 | Method for separating and purifying zinc and manganese dioxide in comprehensive treatment of waste batteries |
| CN100428547C (en) * | 2005-05-30 | 2008-10-22 | 上海电力学院 | Method for preparing manganese-zinc ferrite by using waste dry batteries |
| CN101935068A (en) * | 2010-10-18 | 2011-01-05 | 湘潭县永晟再生资源有限公司 | Process for producing manganese dioxide by using zinc sulfate oxidized waste mud containing manganese |
| CN102168284A (en) * | 2011-03-18 | 2011-08-31 | 北京中航长力能源科技有限公司 | Method for recovering and electrolyzing zinc electrode of insert-block-type zinc air battery |
| CN107180977A (en) * | 2017-07-05 | 2017-09-19 | 内蒙古科技大学 | The recoverying and utilizing method of zinc-manganese in old and useless battery |
| CN110752384A (en) * | 2019-09-16 | 2020-02-04 | 东南大学 | Recycling method of waste zinc-manganese battery |
| CN114196839A (en) * | 2021-11-05 | 2022-03-18 | 陈康明 | Equipment for refining metal zinc from waste battery |
-
1987
- 1987-03-27 CN CN198787102008A patent/CN87102008A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321224C (en) * | 2004-08-02 | 2007-06-13 | 西安建筑科技大学 | Method for separating and purifying zinc and manganese dioxide in comprehensive treatment of waste batteries |
| CN100428547C (en) * | 2005-05-30 | 2008-10-22 | 上海电力学院 | Method for preparing manganese-zinc ferrite by using waste dry batteries |
| CN101935068A (en) * | 2010-10-18 | 2011-01-05 | 湘潭县永晟再生资源有限公司 | Process for producing manganese dioxide by using zinc sulfate oxidized waste mud containing manganese |
| CN102168284A (en) * | 2011-03-18 | 2011-08-31 | 北京中航长力能源科技有限公司 | Method for recovering and electrolyzing zinc electrode of insert-block-type zinc air battery |
| CN107180977A (en) * | 2017-07-05 | 2017-09-19 | 内蒙古科技大学 | The recoverying and utilizing method of zinc-manganese in old and useless battery |
| CN110752384A (en) * | 2019-09-16 | 2020-02-04 | 东南大学 | Recycling method of waste zinc-manganese battery |
| CN114196839A (en) * | 2021-11-05 | 2022-03-18 | 陈康明 | Equipment for refining metal zinc from waste battery |
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