CN1187855C - Comprehensive recovery and utilization method of waste mercuric battery - Google Patents
Comprehensive recovery and utilization method of waste mercuric battery Download PDFInfo
- Publication number
- CN1187855C CN1187855C CNB001278290A CN00127829A CN1187855C CN 1187855 C CN1187855 C CN 1187855C CN B001278290 A CNB001278290 A CN B001278290A CN 00127829 A CN00127829 A CN 00127829A CN 1187855 C CN1187855 C CN 1187855C
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- battery
- ferrite
- mercury
- metal
- waste
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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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- Manufacture And Refinement Of Metals (AREA)
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Abstract
The present invention provides a comprehensive recovery and utilization method of a waste mercuric battery, which relates to the harmless processing of a waste battery and the reuse technology of substances. A waste mercuric battery is heated in vacuum; mercury, plastics, etc. are gasified, condensed and recovered. Residual gas is processed by active carbon, reaches the standard and is discharged. After the waste battery is pulverized, the waste battery is dissolved by acid, and metal in the waste battery is sufficiently leached out. Leaching solution is filtered, and filtration residue is carbon powder and a small amount of manganese oxide which is not dissolved. After the filtration residue is washed and filtered, the filtration residue can be used as a dry battery or a raw material of other industries. Ferrous sulphate and alkali are added into filtering solution to prepare ferrites. The present invention realizes the integral comprehensive recovery and utilization of various kinds of heavy metal under the identical condition, and has the advantages of simple technological process, low energy consumption, low investment and low operation cost. In addition, the technological process is easily operated. Manufactured ferrite products have strong magnetism, and can be used as a magnetic material with wide application.
Description
One, technical field
The comprehensive reutilization method of mercurous used dry batteries relates to the harmless treatment and the reutilization technology of refuse battery.
Two, background technology
As everyone knows, refuse battery does not add as general rubbish and handles and abandon and pollute the environment the injury human health.Adopted the vacuum metallurgy method to be handled for this reason.Although the vacuum metallurgy method is used for that the energy consumption and the operating cost of harmless treatment of mercurous used dry batteries is low, secondary pollution is little, and this method is not all recycled the utility in the refuse battery, causes the wasting of resources.
Usually, people adopt wet method and two kinds of metallurgical processing methods of pyrogenic process that mercury-containing battery is recycled: hydrometallurgy is divided into roasting-lixiviation process and direct leaching again.Wherein, roasting-lixiviation process be with used dry batteries 600～800 ℃ of following roastings, make Hg
2Cl
2Also reclaim in condensing unit respectively for gas phase Deng volatilization, the high-valency metal oxide is reduced into metal or low oxide, and product of roasting goes out with acidleach, reclaims metal with electrolysis from leachate then; Direct leaching then is to make zinc, manganese dioxide and acid effect in the used dry batteries generate solubility acid, generates metallic zinc and electrolytic manganese dioxide or production chemical product (as zinc oxide), chemical fertilizer etc. through purifying electrolysis again.But all there is long flow path in these two kinds of methods, and secondary pollution is serious, energy consumption height, the quality instability of product, the unmanageable shortcoming of technology.
It is to make the metal in the used dry batteries and the process of compound oxidation, reduction, decomposition and volatilization and condensation thereof under 600～1500 ℃ of high temperature that used dry batteries is handled in pyrometallurgy.Because processing procedure is carried out in atmosphere, air has participated in operation, has long flow path, pollution to weigh the energy and raw materials consumption height, the shortcoming that operating cost is high equally with hydrometallurgical.
Japan Patent " processing method of used dry batteries " (spy opens clear 60-253167,61-74692) discloses two kinds of methods, and a kind of is that the decompression heating makes the mercury gasification, then cooling water-recovering silver and dedusting discharge method.Carry out sorting another kind of used dry batteries is put into different categories by variety classes, broken respectively then, after with magnetic separation process the iron content fragment being reclaimed, residue sieves, and the material that stays on sieve is called for short sieve and goes up screenings, the former is manganese dioxide and cadmia, and the latter is manganese dioxide and carbon dust.The oversize utilization is separated recovery current collecting bar, plastics bits, paper scrap and rolled tin fragment respectively than gravity ore principle.At last screenings is gone out the back with the alkali neutralization with acidleach, reclaim manganese slag, cadmia and carbon-point respectively.A kind ofly before in the method that these two Japan Patents provide only solved the mercury recovery, then a kind ofly adopted physical method to reclaim, reclaimed and the purpose of comprehensive utilization though reached, processing step is numerous and diverse, seriously polluted.
Three, goal of the invention
The purpose of this invention is to provide a kind of comprehensive reutilization that can realize refuse battery, seriously polluted, the recycling used batteries of problem such as energy consumption is high, long flow path that can solve the processing procedure existence of recycling used batteries are simultaneously again utilized method.
Four, technical scheme
The present invention is performed such, and at first various mercurous used dry batteries is mixed, break epidermis after, vacuum heating treatment is 2 hours under 250～400 ℃, 10～20mmHg condition, volatilization gas is used the charcoal treatment qualified discharge after mercury is reclaimed in condensation; Then the battery after the above-mentioned vacuum heating treatment is pulverized; Be 10～50% nitric acid or the nitration mixture of 10% nitric acid and 20% hydrochloric acid or 10～40% sulfuric acid dissolution heavy metal wherein again with 2～6 times of mass percent concentrations to the battery volume; Leachate after then heavy metal fully being leached filters: filter residue is carbon dust and the undissolved manganese oxide of minute quantity, behind washing and filtering, can be used as the raw materials for production of dry cell, filtrate adds ferrous sulfate and aqueous alkali, adopts chemical precipitation method to prepare ferrite under heating or heating aerobic condition; At last, obtain broad-spectrum magnetic material ferrite product by centrifugal and drying, centrifugal effluent reuse disposes in diluted acid.
The chemical precipitation method that the present invention adopts is pressed the chemical reaction mechanism of ferrite forming process, divides neutralisation and two kinds of methods of oxidizing process.Neutralisation adds ferrous sulfate exactly in above-mentioned leachate, according to the refuse battery after pulverizing: FeSO
47H
2O=1: 1～6 part by weight carries out, and with alkali pH=9.5～12.5 that neutralize, generates the metal ion precipitation of hydroxide through chemical reaction again; Be heated to 50～100 ℃ of constant temperature again 0.5～3 hour, precipitation generates ferrite.Its ion-reaction equation can be:
M in the formula
2+Can be Mn
2+, Cu
2+, Ni
2+, Zn
2+, Fe
2+Etc. heavy metal ion, R can be Na
+, K
+, NH
4 +
Also can be:
M in the formula
+Can be Hg
+, Ag
+Etc. heavy metal ion, R can be Na
+, K
+, NH
4 +
Oxidizing process is exactly with the leachate after the above-mentioned filtration, according to the refuse battery after pulverizing: FeSO
47H
2O=1: 1～6 part by weight preparation ferrite prepares liquid, adding strong base solution makes pH=8～9 generate the soliquid of metal ion precipitation of hydroxide, at this moment, be heated to 60～95 ℃, and under said temperature constant temperature 0.5～5.0 hour, regulate pH=9.5～11.5 simultaneously, continue evenly to stir, be blown into the pure air oxygenation, make the suspension oxidation produce ferrite.Its ion-reaction equation is as follows:
M in the formula
2+(M
+) be heavy metal ion, its structural formula is M
2+Fe
2 3+O
4(M
+ 1/2Fe
5/2 3+O
4).
The reaction mechanism of oxidizing process is as follows: when the hydroxide of precipitation generates the divalent metal hydroxo complex of solubility by ionization equilibrium, divalence hydroxo complex and oxygen reaction, generate the hydroxo complex of trivalent, divalence and the interreaction of trivalent metal hydroxo complex then, generate the soliquid of solid solution form and under the heating aerobic condition, be converted into the spinel type ferrite of indissoluble.
Five, the present invention compares the beneficial effect that is had with background technology
1. owing to adopt vacuum heating treatment, avoided air to participate in operation, the exhaust gas volumn that produces is little, is easy to purify, and compares with traditional normal pressure metallurgy method, flue gas treatment scale of the present invention significantly reduces, the content of beary metal for preparing in addition in the water outlet that ferrite produces is lower than discharging standards, and secondary pollution is little, thereby makes process energy consumption of the present invention low, power consumption only is 0.7～0.8KWh/kg refuse battery, and cost of investment and operating cost are also low.
2. because the refuse battery of process heating in vacuum harmless treatment, adding diluted acid after employing is pulverized fully dissolves, leached contained heavy metal, made heavy metal be converted into the ferrite of indissoluble with chemical precipitation method then, insoluble carbon dust after filtration, washing can be used as the raw material of industry.Compare with existing recovery and treatment method, the present invention has realized the whole synthesis recycling under the same conditions of each heavy metal species, so technological process is brief, easy operating and management.
3. the ferrite product performance made from the inventive method is very stable, and not stripping under pH value 3～10 conditions can be widely used in and make the inorganic functional material.
Six, Fa Ming description of drawings
Accompanying drawing 1 is a process flow diagram of the present invention
Accompanying drawing 2 prepares the ferrite process flow diagram for neutralisation of the present invention
Accompanying drawing 3 prepares ferrite I process flow schematic diagram for oxidizing process of the present invention
Accompanying drawing 4 is the image that ferrite product of the present invention is analyzed through X-ray diffraction
Seven, working of an invention mode
Below in conjunction with drawings and Examples the present invention is described in detail
Embodiment 1
See also accompanying drawing 1 and accompanying drawing 2,, comprise that zinc-carbon cell, alkaline manganese battery, silver oxide cell mix at first with various mercurous used dry batteries.Gas expands and meets accident and help the volatilization of gas and carry out simple battery case fragmentation when preventing heat.Then fragmentation contained mercury cell vacuum heating treatment 2 hours in the vacuum furnace under 380～400 ℃, 10mmHg condition, the mercury that refuse battery contained, plastics, paper scrap, organic substance gasify in heat-treatment process or the carbonization volatilization, the mercury of gasification by condensation with separate, reclaim and to obtain thick mercury.Remaining gas becomes the gaseous emission of allow compliance with emission standards through active carbon purifying.Battery after the heat treated obtains battery powder and metal fragment after pulverizing, and placing 2～3 times of volume ratios, concentration is 20～50% nitric acid, and the heavy metal dissolving is leached.Leachate filters the filter residue that obtains and is mainly carbon, can be used as the raw material of industry and uses.Add ferrous sulfate in the filtrate, according to the refuse battery after pulverizing: FeSO
47H
2O=1: 4～6 part by weight carries out, and adds NaOH solution then and regulates pH=9～12, and be heated to 80～90 ℃, and stirring, constant temperature obtained the ferrite crystal precipitation in 0.5～3.0 hour.Through centrifugation, filter residue is through 90 ℃ of dry ferrite products that obtain.The content of beary metal of filtrate is lower than discharging standards, reuse configuration diluted acid.
When heating in vacuum reclaims mercury in the used dry batteries, alkaline manganese battery, silver oxide cell, the mercury rate of recovery reaches more than 95%; Carbon zinc battery, the mercury rate of recovery reaches more than 85%.Please read following table 1.
Table 1 refuse battery changes and the recovery result through the vacuum heating treatment mercury content
| Battery types | Model | Mercury concentration (mg/L) before handling | Handle back mercury concentration (mg/L) | The rate of recovery (%) |
| Carbon zinc battery | UM-1 | 16.4 | 2.24 | Mercury 86.3 |
| Silver oxide cell | SR44 | 14.8 | 1.8 | Mercury 87.8 |
| Alkaline manganese battery (button shaped) | LR1130 | 25 | 2.0 | Mercury 92 |
| Alkaline manganese battery (cylindrical shape) | AM3、 AM4 | 950 | 35.2 | Mercury 96.3 |
The mensuration of mercury concentration: before will handling or the single battery after handling pulverize, fully dissolving in the mixed acid solution of 10% nitric acid and 20% hydrochloric acid, and filtering, filtrate is settled to 200 milliliters, records mercury concentration.The mercury rate of recovery obtains in the variation of handling forward and backward mercury concentration by the single battery of contrast same model.
Embodiment 2
See also accompanying drawing 3, above-mentioned battery process after vacuum heating treatment is pulverized, obtain battery powder and metal fragment, place and be equivalent to 2～4 times of volumes of battery particle, concentration is in the mixed acid solution of 10% nitric acid and 20% hydrochloric acid, heavy metal in refuse battery filters after fully dissolving is leached, and filter residue is carbon and minute quantity manganese oxide mixture, can be used as the raw material of industry and uses.Filtrate adds ferrous sulfate, according to the refuse battery of pulverizing: FeSO
47H
2O=1: 4～6 part by weight carries out, and has been made into ferrite and has prepared liquid.Add ammonia spirit then, regulate the pH=9 of this preparation liquid, kept 75～80 ℃ of heated at constant temperature 1 and a half hours, evenly be blown into air oxygenation 40 minutes simultaneously and continue and evenly stir, generate the ferrite crystal precipitation.Obtain wet ferrite product through filtering and washing.Oven dry makes the thick finished product of ferrite under 90 ℃.At last, the heavy metal concentration that detects in the ferrite solution before and after synthetic finds that the heavy metal in the refuse battery is almost completely recycled.Zn before synthetic
2+Content reduce to 0.098～2.66mg/L after synthetic by 970～1020mg/L; Mn
2+Reduce to 0.96～2.01mg/L by 1258～1520mg/L; Hg
+56～43mg/L reduces to 0, all is lower than discharge standard.But reuse configuration acid solution, the below standard water outlet of certain concentration of heavy metal ion can reflux and continue to handle.Therefore, this technology non-secondary pollution of recycling used batteries.
At last, see also accompanying drawing 3, the Performance Detection of ferrite product is as follows: ferrite product the analysis showed that through X-ray diffraction, and the product that two embodiment synthesize all presents tangible spinelle diffraction maximum, and promptly product is a spinel type ferrite.Product all has certain magnetic, according to pulverizing refuse battery: FeSO
47H
2O=1: the synthetic ferrite product of 6 part by weight has than ferromagnetism.
Claims (2)
1. the comprehensive reutilization method of mercurous used dry batteries, it is characterized in that: at first various mercurous used dry batteries are mixed, broke behind the epidermis under 250～400 ℃, 10～20mmHg condition vacuum heating treatment 2 hours, mercury, plastics, paper scrap, organic substance gasification or carbonization volatilization, gas is used the charcoal treatment qualified discharge after mercury metal is reclaimed in condensation; Refuse battery after the vacuum heating treatment is pulverized, and is 10～50% nitric acid or the nitration mixture of 10% nitric acid and 20% hydrochloric acid or 10～40% sulfuric acid to leach heavy metal wherein again with 2～6 times of mass percent concentrations to the refuse battery volume; Then metal is filtered by the leachate after fully leaching: filter residue is carbon dust and the undissolved manganese oxide of minute quantity; Filtrate prepares ferrite by neutralisation, is exactly according to the refuse battery after pulverizing: FeSO in the leachate after above-mentioned filtration
47H
2O=1: 1～6 part by weight adds ferrous sulfate, regulate with NaOH, KOH or ammoniacal liquor aqueous slkali again and make pH=9.5～12.5, when chemical reaction generates the metal ion precipitation of hydroxide, be heated to 50～100 ℃ and constant temperature 0.5～3.0 hour, precipitation generates ferrite,, dry down at 90 ℃ again and making ferrite product after washing and suction filtration obtain moist ferrite product.
2. the comprehensive reutilization method of mercurous used dry batteries, it is characterized in that: at first various mercurous used dry batteries are mixed, broke behind the epidermis under 250～400 ℃, 10～20mmHg condition vacuum heating treatment 2 hours, mercury, plastics, paper scrap, organic substance gasification or carbonization volatilization, gas is used the charcoal treatment qualified discharge after mercury metal is reclaimed in condensation; Refuse battery after the vacuum heating treatment is pulverized, and is 10～50% nitric acid or the nitration mixture of 10% nitric acid and 20% hydrochloric acid or 10～40% sulfuric acid to leach heavy metal wherein again with 2～6 times of mass percent concentrations to the refuse battery volume; Then metal is filtered by the leachate after fully leaching: filter residue is carbon dust and the undissolved manganese oxide of minute quantity; Filtrate prepares ferrite by oxidizing process, is exactly according to the battery particle after pulverizing: FeSO in the leachate after above-mentioned filtration
47H
2O=1: 1～6 part by weight adds ferrous sulfate, add NaOH, KOH again or the ammoniacal liquor aqueous slkali makes pH=8～9, formed the soliquid of metal ion precipitation of hydroxide, be heated to 60～95 ℃ then, and under said temperature constant temperature 0.5～5.0 hour, be blown into the pure air oxygenation 20～90 minutes, regulate pH=9.5～11.5 simultaneously, continue evenly to stir, make the precipitation of hydroxide oxidation generate ferrite,, dry down at 90 ℃ again and making ferrite product after washing and suction filtration obtain moist ferrite product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001278290A CN1187855C (en) | 2000-12-08 | 2000-12-08 | Comprehensive recovery and utilization method of waste mercuric battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001278290A CN1187855C (en) | 2000-12-08 | 2000-12-08 | Comprehensive recovery and utilization method of waste mercuric battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1357936A CN1357936A (en) | 2002-07-10 |
| CN1187855C true CN1187855C (en) | 2005-02-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001278290A Expired - Fee Related CN1187855C (en) | 2000-12-08 | 2000-12-08 | Comprehensive recovery and utilization method of waste mercuric battery |
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Families Citing this family (6)
| 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 |
| CN101604606A (en) * | 2009-06-30 | 2009-12-16 | 惠州市奥美特环境科技有限公司 | Resource recycle method for waste tubes |
| CN102189092A (en) * | 2010-03-01 | 2011-09-21 | 王自新 | Method for realizing comprehensive recycling of mercury-containing waste |
| CN109193003B (en) * | 2018-09-03 | 2020-08-14 | 丁柳朋 | Vacuum heating equipment for waste battery recycling convenient for mercury recycling |
| CN111106359B (en) * | 2020-01-17 | 2020-10-16 | 三门踱哒环保设备有限公司 | Automatic metal collecting device in waste battery |
| CN112501426B (en) * | 2020-11-12 | 2021-12-14 | 中南大学 | Method for separating micro-fine copper particles from lithium iron phosphate battery waste electrode powder |
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2000
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