CN1187862C - Comprehensive recovery and utilization method of waste NiCd battery - Google Patents
Comprehensive recovery and utilization method of waste NiCd battery Download PDFInfo
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- CN1187862C CN1187862C CNB001278304A CN00127830A CN1187862C CN 1187862 C CN1187862 C CN 1187862C CN B001278304 A CNB001278304 A CN B001278304A CN 00127830 A CN00127830 A CN 00127830A CN 1187862 C CN1187862 C CN 1187862C
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- cadmium
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- 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
Abstract
The present invention provides a comprehensive recovery and utilization method of waste nickel-cadmium batteries, which relates to a harmless processing and reusing technology for waste nickel-cadmium batteries and nickel-hydrogen accumulators. The method comprises the following steps: disassembling or breaking the outer shell of a waste nickel-cadmium battery for vacuum heating; making cadmium, plastic, etc. gasified and volatilized; condensing gas, and purifying the gas by active carbon to reach the discharge standard after the gas is condensed, and the cadmium is recovered. The waste battery is thoroughly leached and filtered by acid after being pulverized; filtered residue is a small amount of undissolved metal, and is returned for redissolution. Filtrate is heated or heated and oxygenated to prepare ferrite by an oxidizing method or a neutralizing method, and the integral recovery and utilization of various heavy metals in the waster battery can be realized. The present invention has the advantages of simple manufacturing process, easy operation and management, low energy consumption and no secondary pollution. The prepared ferrite which is insoluble within a Ph value from 3 to 10 can be used as industrial raw materials.
Description
One, the technical field
A comprehensive recycling method of waste nickel-cadmium batteries relates to a harmless treatment and recycling technology of nickel-cadmium and nickel-hydrogen batteries.
Second, background Art
As is known to all, the waste batteries are discarded without being treated, so that the environment is polluted, and particularly, toxic heavy metal cadmium contained in the nickel-cadmium batteries is easy to enrich in plants, so that the human health is easily injured by food through water, soil and the like. The method adopts a simple vacuum metallurgy method for treatment, and has low energy consumption and operation cost and small secondary pollution, but the method does not recycle the useful substances in the waste batteries, thereby causing resource waste.
Therefore, people adopt two treatment methods of pyrometallurgy and hydrometallurgy to recycle nickel-cadmium waste batteries. Wherein the pyrometallurgical treatment method of the catalyst chemical company of Guanxi Japan mainly utilizes the characteristic of high vapor pressure of cadmium and oxides thereof and nickel separation. And (3) after the coating layer on the surface of the battery is stripped, oxidizing roasting is carried out at 900-1200 ℃, so that the nickel is separated into nickel cinder and cadmium oxide concentrated solution, the nickel cinder is used as a steel smelting raw material, and the cadmium oxide concentrated solution is leached and purified to be prepared into various cadmium salts or metals. Various crushed nickel cadmium cells were treated with a rotary furnace at 1260 ℃ by INMETCO, usa, and the collected gas was sprayed with water. The residue in the water, which contains lead and zinc in addition to a large amount of cadmium, is sent to a cadmium refinery for purification. The iron-nickel residue in the furnace is sent into an electric arc furnace to be melted to prepare iron-nickel alloy, and the non-toxic residue can be sold as building aggregate. In the hydrometallurgical treatment method, Tokyo resource company firstly peels off and crushes the battery coating layer, and leaches the battery coating layer and sludge slag together with sulfuric acid to remove impurities such as iron and the like. Then hydrogen sulfide is blown into the nickel-cadmium solution to form cadmium sulfide precipitate for separation, and sodium carbonate is added into the nickel-cadmium solution from which cadmium is removed to form nickel carbonate for sale. The waste nickel-cadmium battery hydrometallurgical recovery treatment of Dutch research institute is to crush and screen waste nickel-cadmium batteries, the coarse particles mainly comprise iron shells, plastics and paper, the coarse particles are divided into iron and non-iron parts through magnetic separation, then the iron and non-iron parts are respectively cleaned by hydrochloric acid, iron fragments adhered with cadmium are taken out to produce iron-nickel alloy, and the non-iron fragments are disposed of as dangerous objects due to the cadmium. Leaching the fine particles with acid solution, disposing the residue as hazardous waste, and extracting cadmium from the filtrate with solvent. The cadmium-containing extract is re-extracted with dilute hydrochloric acid to produce a cadmium chloride solution. Finally, the cadmium is recovered by an electrolytic method.
It can be seen from the above recovery method of nickel cadmium battery that in both methods, except for the high energy consumption caused by the high heating temperature required by pyrometallurgical treatment, cadmium has toxicity, and the generated cadmium-containing waste gas and waste water must be strictly treated, so both methods have the disadvantages of long flow, high investment and operating cost, easy generation of serious secondary pollution, and low comprehensive benefit.
Third, the invention
The invention aims to provide a method for recycling and comprehensively utilizing nickel-cadmium and nickel-hydrogen storage batteries with less pollution and low energy consumption.
The invention is carried out by mixing various waste nickel-cadmium batteries together, and breaking the shell; the nickel-hydrogen storage battery is disassembled. Then, the battery is subjected to vacuum heating treatment for 2 hours at the temperature of 600-750 ℃ and under the condition of 20-30 mmHg, cadmium, plastics and the like are gasified and volatilized, and the gas is condensed to recover cadmium and then is subjected to activated carbon purification treatment to reach the standard and be discharged; then, in order to recover other metals in the waste battery, crushing the battery after vacuum heating treatment, and dissolving heavy metals such as nickel, iron and the like in the crushed battery by using nitric acid with the mass percentage concentration of 10-50%, sulfuric acid with the mass percentage concentration of 10-40%, or mixed acid of nitric acid with the mass percentage concentration of 10% and hydrochloric acid with the mass percentage concentration of 20% which is 1-6 times of the weight of the battery to form leachate; then filtering the leaching solution, wherein filter residues are a small amount of undissolved metals, and continuously adding the acid into the leaching solution for further digesting the metals; adding alkali and ferrous sulfate into the filtrate, and preparing ferrite by chemical precipitation. Finally, obtaining the ferrite product with wide application by centrifugation and drying. The centrifuged effluent is reused for dissolving the dilute acid configuration of the waste battery.
The invention adoptsChemical precipitation methods refer to oxidation and neutralization methods. The oxidation method is that ferrous sulfate is added into the filtrate of the leachate of the waste battery according to the quantity of the crushed waste battery and FeSO4·7H2And (3) neutralizing with alkali until the pH value is 8-9 to generate colloidal suspension containing metal ion hydroxide precipitate, adjusting the pH value to 10.0-12.0, heating at 60-100 ℃ for 0.5-5.0 hours, and uniformly blowing pure air for 20-90 minutes to oxidize intermediate precipitate to generate ferrite. The ion reaction equation is as follows:
in the formula M2+Or M+Is heavy metal ion Ni2+、Cd2+Etc. of the structural formula M2+Fe3+O4Or M+ 1/2Fe5/2 3+O4. R is Na+、K+、NH4 +。
The reaction mechanism of the oxidation process is as follows: when the precipitated hydroxide generates soluble divalent metal hydroxy complex through ionization equilibrium, the divalent hydroxy complex reacts with oxygen to generate trivalent hydroxy complex, and then the divalent and trivalent metal hydroxy complexes react with each other to generate colloidal suspension in the form of solid solution, and under the condition of heating or heating oxygenation, the colloidal suspension is converted into the spinel-type ferrite which is difficult to dissolve.
The neutralization method comprises adding ferrous sulfate into the filtrate obtained by filtering the leachate, and pulverizing the waste battery according to the proportion of FeSO4·7H2Preparing ferrite preparation liquid by using O in a weight ratio of 1: 2-6, adding a strong base solution, adjusting the pH value of the preparation liquid to 9.0-12.5, heating to 50-100 ℃, keeping the temperature for 0.5-3 hours, continuously stirring to obtain ferrite crystal precipitate, washing and filtering to obtain a wet ferrite product, and drying at 90 ℃ to obtain the ferrite product.
Compared with the background technology, the invention has the following beneficial effects:
1. because the vacuum heating treatment is adopted, air is prevented from participating in the operation, the generated flue gas amount is small, the purification is easy, the flue gas treatment scale is greatly reduced, and the secondary pollution is small. The centrifugal effluent is circulated, so that the standard discharge treatment cost is reduced, and the investment cost and the operation cost are reduced. The process of the invention has low energy consumption, and the power consumption for processing the nickel-cadmium battery is 1.0 KWh/kg.
2. Because the acid solution is adopted to leach the metal in the waste battery after heating and crushing, the filtrate filtered by the leaching solution is adopted to prepare the ferrite by adopting a chemical precipitation method, and the integral recycling of the metal is really realized. The invention has high recovery rate of waste batteries, and almost all substances can be recycled as resources except organic matters such as plastics and the like.
3. The composite ferrite product prepared by the method canbe used as a magnetic material, has stable performance and is not dissolved out under the condition of pH value of 3-10.
Description of the drawings
FIG. 1 is a schematic view of the process of the present invention
FIG. 2 is a schematic diagram of the process flow of preparing ferrite by neutralization method of the invention
FIG. 3 is a schematic diagram of the process flow of preparing ferrite by oxidation method of the present invention
FIG. 4 is an X-ray diffraction image of a ferrite product of the present invention
Fifth, detailed description of the invention
The invention is described in detail below with reference to the figures and examples
Example 1
Referring to fig. 1 and 2, various nickel-cadmium batteries and nickel-metal hydride batteries are first mixed together.In order to prevent the gas from expanding unexpectedly when heated at high temperature, the simple crushing of the shell is carried out in favor of the volatilization of the gas. Then vacuum heating the crushed batteries in a vacuum heating furnace at 750 ℃ and 20mmHg for 2 hours, carbonizing and volatilizing plastics and organic matters contained in the waste batteries in the heating process, and activating generated gasThe carbon is purified into gas which meets the emission standard. The gasified cadmium and the cadmium after the decomposition of the cadmium oxide are condensed and separated to obtain cadmium powder. Crushing the battery subjected to vacuum heating treatment to obtain battery powder and heavy metal chips such as nickel, iron and the like, and putting the battery powder and the heavy metal chips into nitric acid with the mass percentage concentration of 20-50% which is 2-4 times of the volume of the battery powder to dissolve and leach the heavy metals. And a small amount of undissolved metal scrap filter residue obtained by filtering the leaching solution can be continuously dissolved by adding acid. Adding FeSO (ferric oxide) which is 4-6 times of the weight of the crushed waste battery into the filtrate4·7H2And O, preparing a ferrite preparation solution, adding a NaOH solution to adjust the pH value to 9.0-12.5, heating to 80-90 ℃, keeping the temperature for 2 hours, continuously stirring to obtain ferrite precipitate, performing centrifugal separation to obtain a product, wherein the heavy metal content of effluent basically meets the discharge standard, the product can be recycled, and effluent which does not meet the standard is refluxed and continuously treated.
The nickel-cadmium battery is heated for 2 hours under the conditions of 750 ℃ and 20mmHg, and the cadmium recovery rate reaches more than 95 percent. Taking a button-shaped nickel-cadmium battery (NF-H) as an example, the concentration of cadmium in the battery digestion solution before treatment is 11075mg/L, the concentration of cadmium in the battery digestion solution after treatment is 332mg/L, and the recovery rate of cadmium reaches 97 percent.
The nickel-cadmium battery after vacuum heating basically realizes harmlessness because most of cadmium is recycled. Plastics, organic matters and other volatile matters contained in the waste batteries are removed in the heating treatment process.
Example 2
Referring to fig. 2, the process for preparing ferrite by oxidation method is as follows: firstly, crushing the battery subjected to vacuum heating treatment to obtain battery powder and metal scraps, placing the battery powder and the metal scraps into a sulfuric acid solution with the volume being 1-4 times that of the battery scraps and the mass percentage concentration being 20-30%, dissolving and leaching the metal under the condition of normal temperature stirring, filtering the leachate to obtain a small amount of undissolved metal scraps as filter residues, and continuously adding the small amount of undissolved metal scraps into the leachate for dissolution. Adding ferrous sulfate into the filtrate according to the crushed waste battery amount: FeSO4·7H2And O is carried out according to the weight ratio of 1: 2-6 to prepare the ferrite preparation liquid. Adding KOH solution, adjusting the pH of the preparation solution to 9 to prepare a colloidal suspension, and then adjusting the pH to 10.5-11.5 to 75EHeating at 80 deg.C for 3 hr, blowing purified air uniformly for 60 min to oxidize colloidal suspended matter to obtain ferrite precipitate, washing, vacuum filtering, and drying at 90 deg.C to obtain ferrite crude product.
And finally, detecting the concentration of the heavy metal in the battery digestion filtrate to find that the heavy metal in the waste battery is almost completely recycled. The content of cadmium before and after synthesis is reduced to 0.098-0.35 mg/L from 689 mg/L; the concentration of nickel 4083mg/L is reduced to 0.35-0.59 mg/L. The filtrate separated by centrifugation or suction filtration can be recycled to prepare acid solution, and the effluent with the concentration of heavy metal ions not reaching the standard can be refluxed for continuous treatment. Therefore, the recovery process of the waste nickel-cadmium battery has no secondary pollution.
Referring to the attached figure 3, the performance detection of the ferrite product shows that the products synthesized from the nickel-cadmium battery raw materials have obvious ferrite spinel diffraction peak shapes through X-ray diffraction analysis, namely the products are spinel type ferrites. The product has certain magnetism according to the waste nickel-cadmium battery quantity: FeSO4·7H2The ferrite product synthesized by the weight ratio of 1: 5-6 has stronger magnetism.
A toxic heavy metal leaching test of the ferrite product shows that toxic heavy metal cadmium is not dissolved out under the condition that the pH value is 3-10.
Claims (2)
1. The comprehensive recycling method of the waste nickel-cadmium battery is characterized by comprising the following steps: firstly, mixing various waste nickel-cadmium batteries and nickel-hydrogen storage batteries together, breaking or disassembling a shell, then carrying out vacuum heating treatment on the waste nickel-cadmium batteries and the nickel-hydrogen storage batteries at the temperature of 600-750 ℃ for 2 hours under the condition of 20-30 mmHg, gasifying and volatilizing cadmium and plastics, condensing and recycling the gas to recover the cadmium, and then purifying the gas by using activated carbon to reach the standard and discharging the gas; then crushing the battery after vacuum heating treatment, dissolving heavy metals such as nickel, cadmium and iron in the battery by using nitric acid with the mass percentage concentration of 10-50%, sulfuric acid with the mass percentage concentration of 10-40% or mixed acid consisting of nitric acid with the mass percentage concentration of 10% and hydrochloric acid with the mass percentage concentration of 20% which is 1-6 times of the weight of the battery, and then fully leaching the heavy metals in leachateFiltering, wherein the filter residue is a small amount of undissolved metal and returns to be dissolved again; preparing ferrite from the filtrate by a neutralization method, namely, adding the filtrate into FeSO accordingto the quantity of the crushed waste batteries4·7H2Adding ferrous sulfate into the ferrite preparation solution according to the weight ratio of 1: 2-6, then adding NaOH solution, adjusting the pH of the preparation solution to 9.0-12.5, heating to 50-100 ℃, keeping the temperature for 0.5-3.0 hours, continuously stirring to obtain ferrite crystal precipitate, washing and filtering to obtain a wet ferrite product, drying at 90 ℃ to obtain a crude ferrite product, and finally centrifuging and drying to obtain the ferrite product with wide application.
2. The comprehensive recycling method of the waste nickel-cadmium battery is characterized by comprising the following steps: firstly, mixing various waste nickel-cadmium batteries and nickel-hydrogen storage batteries together, breaking or disassembling a shell, then carrying out vacuum heating treatment on the waste nickel-cadmium batteries and the nickel-hydrogen storage batteries at the temperature of 600-750 ℃ for 2 hours under the condition of 20-30 mmHg, gasifying and volatilizing cadmium and plastics, condensing and recycling the gas to recover the cadmium, and then purifying the gas by using activated carbon to reach the standard and discharging the gas; crushing the battery subjected to vacuum heating treatment, dissolving heavy metals such as nickel, cadmium and iron in the battery by using nitric acid with the mass percentage concentration of 10-50%, sulfuric acid with the mass percentage concentration of 10-40% or mixed acid consisting of nitric acid with the mass percentage concentration of 10% and hydrochloric acid with the mass percentage concentration of 20% which is 1-6 times of the weight of the battery, filtering leachate after the heavy metals are fully leached, and returning filter residues which are a small amount of undissolved metals to be redissolved; preparing ferrite from filtrate by adopting an oxidation method, namely adding thefiltrate according to the crushed waste battery amount: FeSO4·7H2Adding ferrous sulfate into the mixture according to the weight ratio of 1: 2-6 to prepare ferrite preparation liquid, then adding NaOH solution, adjusting the pH of the preparation liquid to 8-9 to prepare colloidal suspension containing metal ion hydroxide precipitate, adjusting the pH to 10-12, heating to 60-100 ℃, keeping the temperature for 0.5-5.0 hours, uniformly blowing pure air for 20-90 minutes to oxidize the precipitate to generate ferrite precipitate, washing and filtering to obtain a wet ferrite product, and drying at 90 ℃ to prepare a ferrite crude product.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB001278304A CN1187862C (en) | 2000-12-08 | 2000-12-08 | Comprehensive recovery and utilization method of waste NiCd battery |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB001278304A CN1187862C (en) | 2000-12-08 | 2000-12-08 | Comprehensive recovery and utilization method of waste NiCd battery |
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| CN1357938A CN1357938A (en) | 2002-07-10 |
| CN1187862C true CN1187862C (en) | 2005-02-02 |
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Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN100389520C (en) * | 2005-10-08 | 2008-05-21 | 罗爱平 | Method for removing sodium ion from recovered nickle sulfate solution of waste nickle-hydrogen and nickle-cadmium |
| CN101613804B (en) * | 2009-07-28 | 2011-04-20 | 北京科技大学 | Method for recovering cadmium from waste nickel-cadmium battery |
| CN101775496B (en) * | 2010-03-12 | 2011-03-16 | 兰州理工大学 | Metal recycling method with waste cadmium-nickel battery purified fume |
| CN102324592A (en) * | 2011-07-27 | 2012-01-18 | 上海交通大学 | Method for recovering cadmium, ferrum, nickel and cobalt from used nickel-cadmium battery |
| CN103468958B (en) * | 2013-09-23 | 2014-12-10 | 陈启松 | Tailings harmless treatment method for laterite nickel ore hydrometallurgical process |
| CN103757255A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Leaching method of nickel-cadmium waste battery positive electrode material |
| CN103757357A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Leaching method of nickel-cadmium waste battery positive electrode material |
| US9533273B2 (en) | 2014-06-20 | 2017-01-03 | Johnson Controls Technology Company | Systems and methods for isolating a particulate product 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 |
| CN104773763A (en) * | 2015-03-30 | 2015-07-15 | 河南师范大学 | Method for preparing nanometer crystalline nickel cobalt ferrite by using waste nickel-hydrogen battery |
| US10062933B2 (en) | 2015-12-14 | 2018-08-28 | Johnson Controls Technology Company | Hydrometallurgical electrowinning of lead from spent lead-acid batteries |
| CN108011146B (en) * | 2017-11-17 | 2021-04-23 | 四川长虹电器股份有限公司 | Recycling method of waste lithium battery |
| CN108899605B (en) * | 2018-06-29 | 2020-10-30 | 马鞍山冠成科技信息咨询有限公司 | Waste nickel-hydrogen battery dissolving and recycling equipment |
| CN108963370A (en) * | 2018-07-10 | 2018-12-07 | 深圳市华慧品牌管理有限公司 | Waste lithium cell handles recovery method |
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