CN100519786C - Method for extracting indium-zinc alloy from waste mercury-free alkaline zinc-manganese dioxide battery - Google Patents
Method for extracting indium-zinc alloy from waste mercury-free alkaline zinc-manganese dioxide battery Download PDFInfo
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- CN100519786C CN100519786C CNB2007100285222A CN200710028522A CN100519786C CN 100519786 C CN100519786 C CN 100519786C CN B2007100285222 A CNB2007100285222 A CN B2007100285222A CN 200710028522 A CN200710028522 A CN 200710028522A CN 100519786 C CN100519786 C CN 100519786C
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a method for extracting indium-zinc alloy from waste mercury-free alkaline zinc-manganese dioxide batteries, which comprises the following steps: separating and extracting negative electrode substances of the waste mercury-free alkaline zinc-manganese battery, dissolving the negative electrode substances by using a complexing agent of zinc ions, preparing zinc by electrolyzing filtrate, and smelting insoluble substances to obtain the indium-zinc alloy. The method has the advantages that the indium is recovered according to the existence state of the indium in the waste mercury-free alkaline zinc-manganese dioxide batteries and the actual recovery process of the waste mercury-free alkaline zinc-manganese dioxide batteries, the operation process is simple, and the implementation is easy; the recovery rate of indium is high and stable, and the chemical substances added in the recovery process are few, so that secondary pollution is hardly generated; the recovered indium-zinc alloy with the indium content of 0.1-99.9 percent can be used as a raw material for producing a negative electrode material of the mercury-free alkali-manganese battery, namely indium-zinc-containing powder, so that the cyclic regeneration of the negative electrode material of the waste alkali-manganese battery is realized; the value created by the extract is far higher than the recovery and production cost, so the method has better economic benefit and environmental protection value.
Description
Technical Field
The invention relates to a waste battery recovery technology, in particular to a method for extracting indium-zinc alloy from waste mercury-free alkaline zinc-manganese batteries.
Background
China is a large country for producing and consuming zinc-manganese batteries. From 1/2005, the domestic alkaline zinc-manganese battery has reached complete amalgamation, and the production and consumption of the alkaline zinc-manganese battery occupy the dominant position of primary batteries. The main measure of the alkali zinc-manganese battery without mercury is to use a suitable mercury substitute additive. The mercury substitute additive usually comprises inorganic type (such as indium, gallium, thallium, aluminum and other metal elements or compounds) and organic type (such as biphenyl, alcanolamine, amide and other compounds) for achieving the effect of mercury in the battery. There are many combinations of mercury-substituting additives used in literature and production practice, however, regardless of which combination, indium is an essential component. The indium added into the cathode of the alkaline zinc-manganese dioxide battery generally comprises In and In 2 O 3 And In (OH) 3 Three forms. Since indium has a larger electrode potential than zinc, indium added to zinc powder is mostly present In the form of In. Because the utilization rate of the zinc of the cathode is less than 100%, most of the indium In the waste mercury-free alkaline zinc-manganese dioxide battery still exists In the form of In. Although the content of indium in the waste mercury-free alkaline zinc-manganese dioxide battery is small, the indium is less abundant in the earth crust and is a rare precious metal. Therefore, the indium in the waste mercury-free alkaline zinc-manganese dioxide battery is extracted and utilized, so that the harm to environmental water and soil can be reduced, better economic benefit can be obtained, and the method has great significance for the sustainable development of the society.
The recycling of the waste alkaline zinc-manganese dioxide battery has been widely researchedAnd (5) refining. The patent application number of 200510036193.7 of a recycling method of waste alkaline zinc-manganese batteries discloses a recycling method of waste alkaline zinc-manganese batteries, which comprises the following steps: separating and extracting positive and negative electrode substances of the waste alkaline zinc-manganese battery, leaching with alkaline liquor at room temperature, separating zincate, electrolyzing to prepare zinc, preparing potassium manganate, electrolyzing to prepare potassium permanganate and the like. The patent application No. 200510120906.8 'method for extracting metal indium and graphite from waste alkaline zinc-manganese dioxide batteries' discloses a method for extracting metal indium and graphite from waste alkaline zinc-manganese dioxide batteries, which is characterized In that indium is not dissolved In alkaline solution, in 2 O 3 Insoluble In alkaline solution, in (OH) 3 The indium is extracted by the property of difficult dissolution in an alkaline solution with certain alkalinity. However, the method is relatively high in treatment processOxidant (unused anode material MnO) 2 ) Indium may be converted into In (OH) 3 Due to In (OH) 3 The complexity of dissolution in alkaline solutions is liable to lead to loss of indium, and therefore this process has the disadvantage of poor and unstable recovery.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a method for extracting indium-zinc alloy from waste mercury-free alkaline zinc-manganese batteries, which has the advantages of simple process, low cost, high recovery rate and stability.
The purpose of the invention is realized by the following technical scheme: a method for extracting indium-zinc alloy from waste mercury-free alkaline zinc-manganese dioxide batteries comprises the following steps: separating and extracting negative electrode substances of the waste mercury-free alkaline zinc-manganese battery, dissolving a zinc compound in the negative electrode substances by using a zinc ion complexing agent, preparing zinc by electrolyzing the filtrate, and smelting insoluble substances to obtain the indium-zinc alloy.
The zinc complexing agent may be alkali, ammonia water, cyanide, sodium citrate, etc. Wherein, the alkali has better effect as the coordination agent.
The proportion of the negative electrode material to the alkali is as follows by weight percent:
1 to 6 percent of negative electrode material
15 to 38 percent of alkali
56 to 84 percent of water.
The alkali can be sodium hydroxide, potassium hydroxide, etc.
The insoluble substance smelting conditions are as follows: the proportion of the insoluble substances to the alkali is calculated by the following substances in percentage by weight:
40 to 50 percent of insoluble substances
50 to 60 percent of alkali
The alkali can be sodium hydroxide, potassium hydroxide, etc.
The smelting temperature is 400-500 ℃.
The indium content of the indium-zinc alloy obtained by smelting is 0.1-99.9%.
Compared with the prior art, the invention has the following advantages and effects: the method has the advantages that the indium is recovered according to the existing state of the indium in the waste mercury-free alkaline zinc-manganese dioxide batteries and the actual recovery process of the waste mercury-free alkaline zinc-manganese dioxide batteries, the operation process is simple, and the implementation is easy; the recovery rate of indium is high and stable, and the chemical substances added in the recovery process are few, so that secondary pollution is hardly generated; the recovered indium-zinc alloy with the indium content of 0.1-99.9 percent can be used as a raw material for producing a cathode material of the mercury-free alkali-manganese battery, namely indium-zinc powder, thereby realizing the cyclic regeneration of the cathode material of the mercury-free alkali-manganese battery; the value created by the extract is far higher than the recovery and production cost, so the method has better economic benefit and environmental protection value.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Examples
The method for extracting the indium-zinc alloy from the waste mercury-free alkaline zinc-manganese dioxide battery comprises the following steps: the method for separating and extracting the negative electrode material of the waste mercury-free alkaline zinc-manganese dioxide battery can be specifically prepared by adopting the existing method, such as the following steps: the method comprises the steps of adopting a 'recovery processing device of waste alkaline zinc-manganese dioxide batteries' with the patent application number of 200620059353.X to cut the waste mercury-free alkaline manganese dioxide batteries apart, separating a positive electrode and a negative electrode by screening, taking out the negative electrode, and removing a brass nail, a plastic cover and a diaphragm to obtain a negative electrode substance.
After obtaining the above negative electrode material, the following steps were then carried out:
| step (ii) of | Example 1 | Example 2 | Example 3 |
| (1) Alkali soluble | Negative electrode material at room temperature Soaking in sodium hydroxide solution, stirring Dissolving zinc compound, filtering Obtaining zinc-containing solution and filter residue. Is divided into Separating the residue, and adding zinc-containing solution Electrowinning of zinc. Negative electrode material and hydrogen hydroxide The ratio of sodium is determined by The weight percentages are as follows: 1% of negative electrode material Sodium hydroxide 15% Water 84% | The negative electrode material is mixed at room temperature Soaking in sodium hydroxide solution while stirring Dissolving zinc compound, filtering Obtaining a zinc-containing solution and filteringAnd (5) slag. Is divided into Separating the residue, and adding zinc-containing solution Electrowinning of zinc. Negative electrode material and hydrogen hydroxide The ratio of sodium is determined by The weight percentage is as follows: 6 percent of negative electrode material 38 percent of sodium hydroxide 56 percent of water | Negative electrode material at room temperature Soaking in potassium hydroxide solution while stirring Dissolving zinc compound in the solution, filtering Obtaining zinc-containing solution and filter residue. Is divided into Separating the residue, and adding zinc-containing solution Electrowinning of zinc. Negative electrode material and hydrogen hydroxide The proportion of potassium is determined by The weight percentage is as follows: negative electrode material 3% 25 percent of potassium hydroxide 72 percent of water |
| (2) Melting | The indium in the step 1 is added Mixing insoluble substance with sodium hydroxide Melting to obtain indium-zinc alloy And (3) gold. Insoluble matter and sodium hydroxide The ratio of (A) to (B) is calculated by weight | The indium in the step 1 is added Mixing insoluble substance with sodium hydroxide Melting to obtain indium-zinc alloy And (3) gold. Insoluble matter and sodium hydroxide The ratio of (A) to (B) is calculated by weight | Adding indium in step 1 Mixing insoluble substance with potassium hydroxide Melting to obtain indium-zinc alloy And (3) gold. Insoluble matter and potassium hydroxide Is prepared from the following materials in percentage by weight |
| The weight percentage is as follows: insoluble matter 40% 60 percent of sodium hydroxide Melting temperature: at 400 deg.c. | The weight percentage is as follows: insoluble matter 60% 40 percent of sodium hydroxide Melting temperature: at 500 ℃. | The weight percentage is as follows: insoluble matter 50% 50 percent of potassium hydroxide Melting temperature: at 450 ℃. |
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. A method for extracting indium-zinc alloy from waste mercury-free alkaline zinc-manganese dioxide batteries is characterized by comprising the following steps: separating and extracting a negative substance of the waste mercury-free alkaline zinc-manganese battery, dissolving a zinc compound in the negative substance by using a zinc ion complexing agent, preparing zinc by electrolyzing filtrate, and smelting insoluble substances to obtain an indium-zinc alloy; the smelting conditions of the insoluble matters are as follows: the proportion of insoluble substances to alkali is calculated by the following substances in percentage by weight:
40 to 50 percent of insoluble substances
50 to 60 percent of alkali.
2. The method for extracting the indium-zinc alloy from the waste mercury-free alkaline zinc-manganese dioxide battery as claimed in claim 1, wherein the method comprises the following steps: the zinc complexing agent is alkali, ammonia water, cyanide or sodium citrate.
3. The method for extracting the indium-zinc alloy from the waste mercury-free alkaline zinc-manganese dioxide battery as claimed in claim 2, wherein the method comprises the following steps: the zinc complexing agent is alkali; the proportion of the negative electrode material to the alkali is as follows by weight percent:
1 to 6 percent of negative electrode material
15 to 38 percent of alkali
56 to 84 percent of water.
4. The method for extracting indium-zinc alloy from waste mercury-free alkaline zinc-manganese dioxide batteries according to claim 3, characterized in that: the alkali is sodium hydroxide or potassium hydroxide.
5. The method for extracting the indium-zinc alloy from the waste mercury-free alkaline zinc-manganese dioxide battery as claimed in claim 1, wherein the method comprises the following steps: the alkali is sodium hydroxide or potassium hydroxide.
6. The method for extracting the indium-zinc alloy from the waste mercury-free alkaline zinc-manganese dioxide battery as claimed in claim 1, wherein the method comprises the following steps: the smelting temperature is 400-500 ℃.
7. The method for extracting indium-zinc alloy from waste mercury-free alkaline zinc-manganese dioxide batteries according to claim 1, characterized in that: the indium content of the indium-zinc alloy is 0.1-99.9%.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2007100285222A CN100519786C (en) | 2007-06-11 | 2007-06-11 | Method for extracting indium-zinc alloy from waste mercury-free alkaline zinc-manganese dioxide battery |
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| CNB2007100285222A CN100519786C (en) | 2007-06-11 | 2007-06-11 | Method for extracting indium-zinc alloy from waste mercury-free alkaline zinc-manganese dioxide battery |
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| CN100519786C true CN100519786C (en) | 2009-07-29 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9555386B2 (en) | 2014-06-20 | 2017-01-31 | Johnson Controls Technology Company | Systems and methods for closed-loop recycling of a liquid component of a leaching mixture when recycling lead from spent lead-acid batteries |
| US9670565B2 (en) | 2014-06-20 | 2017-06-06 | Johnson Controls Technology Company | Systems and methods for the hydrometallurgical recovery of lead from spent lead-acid batteries and the preparation of lead oxide for use in new lead-acid batteries |
| US10062933B2 (en) | 2015-12-14 | 2018-08-28 | Johnson Controls Technology Company | Hydrometallurgical electrowinning of lead from spent lead-acid batteries |
| CN113444253B (en) * | 2020-03-24 | 2022-06-21 | 中国科学院宁波材料技术与工程研究所 | Metal organic framework material and preparation method and application thereof |
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Non-Patent Citations (2)
| Title |
|---|
| 废旧电池的回收利用. 韩东梅等.电源技术，第29卷第2期. 2005 |
| 废旧电池的回收利用. 韩东梅等.电源技术，第29卷第2期. 2005 * |
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