CN102569838A - Method for recycling valuable metals in manganese series waste batteries - Google Patents
Method for recycling valuable metals in manganese series waste batteries Download PDFInfo
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- CN102569838A CN102569838A CN2012100171631A CN201210017163A CN102569838A CN 102569838 A CN102569838 A CN 102569838A CN 2012100171631 A CN2012100171631 A CN 2012100171631A CN 201210017163 A CN201210017163 A CN 201210017163A CN 102569838 A CN102569838 A CN 102569838A
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- 239000010926 waste battery Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000004064 recycling Methods 0.000 title claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 17
- 239000002184 metal Substances 0.000 title claims abstract description 17
- 150000002739 metals Chemical class 0.000 title claims abstract description 16
- 150000002696 manganese Chemical class 0.000 title claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052742 iron Inorganic materials 0.000 claims abstract description 44
- 239000002699 waste material Substances 0.000 claims abstract description 42
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 37
- 239000011572 manganese Substances 0.000 claims abstract description 37
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 27
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011701 zinc Substances 0.000 claims abstract description 25
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 24
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000616 Ferromanganese Inorganic materials 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 17
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011787 zinc oxide Substances 0.000 claims abstract description 13
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 12
- 239000000956 alloy Substances 0.000 claims abstract description 12
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010935 stainless steel Substances 0.000 claims abstract description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 5
- 238000007670 refining Methods 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 43
- 238000003723 Smelting Methods 0.000 claims description 35
- 239000003245 coal Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 10
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910001018 Cast iron Inorganic materials 0.000 claims description 2
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 2
- 229910000617 Mangalloy Inorganic materials 0.000 claims description 2
- 229910001037 White iron Inorganic materials 0.000 claims description 2
- 239000000498 cooling water Substances 0.000 claims description 2
- 239000003546 flue gas Substances 0.000 claims description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 2
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 claims description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000005028 tinplate Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 17
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 5
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000831 Steel Inorganic materials 0.000 abstract description 2
- 239000010959 steel Substances 0.000 abstract description 2
- 239000010405 anode material Substances 0.000 abstract 1
- 238000009853 pyrometallurgy Methods 0.000 abstract 1
- 229960001296 zinc oxide Drugs 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000010812 mixed waste Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- 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
Landscapes
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for recycling valuable metals in manganese series waste batteries, which realizes the comprehensive utilization of manganese, iron, zinc and lithium metal resources in waste zinc-manganese dry batteries, waste alkaline manganese batteries, waste lithium-manganese primary batteries and waste lithium-ion batteries with lithium manganate or lithium manganate derivatives as anode materials by pyrometallurgy to prepare products such as ferromanganese alloy, zinc oxide and the like. The total mass of manganese and iron in the prepared ferromanganese alloy reaches more than 90 percent, and the ferromanganese alloy can be used for steel enterprises and stainless steel enterprises, and the total mass of zinc and lithium in zinc oxide reaches more than 40 percent and can be used for zinc and lithium wet refining. The method has the characteristics of high resource utilization and recovery rate, simple process and high recovery value.
Description
Technical Field
The invention belongs to the field of comprehensive utilization of waste resources, and particularly relates to the field of recycling of valuable metals of waste batteries.
Background
With the increasing use types and quantity of portable electronic appliances, the use amount of batteries is increasing day by day, and the quantity of waste batteries is increasing. As is known, the waste batteries contain alkaline, acidic and organic electrolytes, and contain heavy metals such as lead, mercury, cadmium, nickel, cobalt, manganese, copper and the like, and if the heavy metals cannot be effectively treated, the waste batteries can cause serious pollution to the environment; the water, food and atmosphere enter the human body, and the health of the human body is also seriously threatened; in addition, the waste battery is lost at will and is a waste of resources. Therefore, the method has double meanings of economic value and social benefit when being used for effectively recycling and treating the waste batteries.
The comprehensive utilization research of the waste batteries in China starts late, the technical research is relatively lagged, the national industrial technical level is uneven, and part of enterprises continue workshop-type production. The current processing technology for manganese batteries is mainly focused on zinc-manganese dry batteries, and the used technology comprises a pyrogenic process and a hydrometallurgical processing method. The prior better technology comprises the steps of crushing, roasting and magnetic separation of waste zinc-manganese batteries, obtaining a raw material of an oxygen body through high-temperature metallurgy, recovering mercury, zinc and cadmium in the waste batteries by utilizing a vacuum smelting technology, recovering mercury and plastics in the waste batteries by utilizing a vacuum distillation technology, leaching residues by utilizing acid, preparing ferrite by utilizing a neutralization method or an oxidation method, and recovering zinc and manganese dioxide by utilizing a leaching method, removing impurities, purifying and electrolyzing. The technical characteristics are that various components of waste zinc-manganese batteries are utilized to prepare zinc-manganese soft magnetic ferrite products with large market capacity and good product marketability, but because the process simultaneously uses a fire method and a wet method, the energy consumption is large, the industrialization investment is large, and a large amount of production wastewater is generated, so the method is not an optimal technical scheme from the aspects of economy, energy conservation and environmental protection.
In addition, as the lead-acid battery shrinks due to policy restrictions, the use amount of manganese lithium ion batteries with high cost performance will increase rapidly, and a large amount of manganese lithium battery waste and waste batteries will be generated in the production and consumption processes, but no report is found on the recovery and treatment technology of manganese waste lithium ion batteries at present.
Disclosure of Invention
The invention aims to overcome the defects of the existing manganese battery recycling technology and discloses a metal recycling method of manganese waste batteries, which can be used for recycling alkali manganese batteries and zinc manganese batteries and can also be used for recycling lithium manganese primary batteries and manganese lithium ion secondary batteries.
The invention discloses a method for recycling valuable metals in manganese series waste batteries, which comprises the following steps:
(1) Preparing materials: crushing and screening manganese waste batteries to obtain a waste battery raw material A with the oversize of 5-30mm, adding a binder, reducing coal and water into fine battery powder with the undersize of less than 5mm, and granulating to 5-30mm to obtain a waste battery raw material B; crushing and screening waste iron to obtain a waste iron raw material A with the oversize product of 5-30mm, adding a binder, reduced coal and water into fine waste iron powder with the undersize product of less than 5mm, and granulating to 5-30mm to obtain a waste iron raw material B;
(2) Fire smelting: melting a waste battery raw material A and a waste battery raw material B in a smelting furnace or melting the waste battery raw material A and the waste battery raw material B in the smelting furnace respectively, and then injecting the waste iron raw material A and/or the waste iron raw material B into the smelting furnace along with pulverized coal by using oxygen-enriched air for smelting to produce ferromanganese alloy;
(3) Collecting the soot: when the manganese series waste battery contains zinc and/or lithium, zinc steam and/or lithium oxide volatilize into flue gas in the smelting process, air is added into a flue, the volatilized zinc steam is converted into zinc oxide, the flue is cooled by using circulating cooling water, and the zinc oxide and/or the lithium oxide are obtained by collecting.
In the waste battery raw material B in the step (1), the weight of the binder is 1-3%, the weight of the reducing coal is 3-6%, and the water content is lower than 10%; in the scrap iron raw material B, the weight of the binder is 1-3%, the weight of the reduced coal is 3-6%, and the water content is lower than 10%.
In the step (2), the temperature in the smelting furnace is controlled to be 1300-1700 ℃, the smelting time is 10-60min, and the mass concentration of oxygen in the oxygen-enriched air is 21-60%.
The mass ratio of manganese to iron in the total amount of the waste iron and the manganese series waste batteries is not lower than 1: 2.
The manganese series waste battery is one or a mixture of more of an alkali manganese battery, a zinc manganese battery, a lithium manganese primary battery and a lithium ion battery with a positive electrode material containing lithium manganese oxide or lithium manganese oxide derivatives. The waste iron resource is one or a mixture of more of waste cast iron, waste horse iron, waste white iron, waste stainless steel and waste alloy with the iron content of more than 50 percent.
The manganese-iron alloy prepared by the method has the total mass content of manganese and iron of more than 90 percent, and can be used for manufacturing common manganese steel and manganese-containing stainless steel; the total mass content of zinc and lithium in the mixture of zinc oxide and lithium oxide reaches more than 40 percent, and the zinc oxide and lithium oxide can be used as raw materials for zinc and lithium wet refining.
The invention discloses a method for recycling valuable metals in manganese series waste batteries, which has the following beneficial effects: (1) The method has wide application range, and can be suitable for the recovery treatment and comprehensive utilization of various waste batteries; (2) The comprehensive utilization capacity of elements is strong, various elements such as iron, manganese, zinc, lithium, nickel and the like can be effectively recovered, and the recovery rate is high; (3) Simple process, low cost and high recovery value, belongs to the recycling economy industry, and has economic and social benefits.
Detailed Description
The invention will now be illustrated by means of specific examples.
Example 1:
crushing and screening the waste zinc-manganese battery, and sampling and analyzing the oversize waste zinc-manganese battery raw material with the granularity of 5-30mm, wherein the mass content of zinc in the zinc-manganese battery powder is 28.3%, the mass content of manganese is 18.9%, the mass content of iron is 7.2%, and the mass content of carbon is 28.8%. Firstly, 2000g of zinc-manganese battery powder is melted in a smelting furnace, 400g of scrap iron raw material containing 82% of iron and 9% of manganese is sprayed into the smelting furnace along with 1600g of coal powder by 25% of oxygen-enriched air, the temperature in the smelting furnace is controlled to be 1450-1500 ℃, the smelting is carried out for 20min, ferromanganese alloy with the ferromanganese content reaching 91.5% is produced, and the total recovery rate of ferromanganese reaches 95.6%; the zinc content in the zinc oxide recovered by the flue reaches 63%, and the recovery rate of the zinc reaches 87.8%.
2000g of undersize fine powder smaller than 5mm in the crushed and sieved battery raw materials is taken, 1.5% of binder, 5% of reduced coal and 15% of moisture are added to prepare a raw material of a waste zinc-manganese battery with the size of 5-30mm, the raw material is preheated and dried in a preheating kiln until the moisture content is lower than 10%, and the mass content of zinc, manganese, carbon and iron in the particles is 12.3%, 41.5%, 21.6% and 4.2% through sampling analysis. Firstly, putting the particles into a smelting furnace for melting, then spraying 600g of waste iron raw material containing 82% of iron and 9% of manganese into a volumetric furnace with 2000g of coal powder by 25% of oxygen-enriched air, controlling the temperature in the smelting furnace to be 1450-1500 ℃, and smelting for 20min to produce ferromanganese alloy containing 91.7% of ferromanganese, wherein the total recovery rate of iron and manganese reaches 95.3%; the zinc content in the zinc oxide recovered from the flue reaches 61.8%, and the recovery rate of the zinc reaches 88.4%.
Example 2:
crushing and screening steel shell manganese waste lithium batteries of which the positive electrode material is lithium manganate, and sampling and analyzing oversize product battery residues with the granularity of 5-30mm to obtain the battery residues, wherein the mass content of manganese is 18.9%, the content of lithium is 1.2%, the content of iron is 24.8%, the content of carbon is 10.4%, the content of aluminum is 5.7% and the content of copper is 7.8%. Firstly, melting 2000g of manganese-based waste battery powder in a smelting furnace, then, granulating 200g of waste iron raw material which contains 82% of iron, 9% of manganese and is prepared by granulating fine iron powder which is a undersize product and is less than 5um, wherein the granularity of the waste iron raw material is 5-30um, the water content of the waste iron raw material is less than 10%, spraying 33% of oxygen-enriched air into the smelting furnace along with 1600g of coal powder, controlling the temperature in the smelting furnace to be 1500-1550 ℃, smelting for 15min, producing ferromanganese alloy with the ferromanganese content of 91.8%, and the total recovery rate of ferromanganese reaches 95.6%; the lithium content in the lithium oxide recovered from the flue reaches 41.5%, and the recovery rate of lithium reaches 75.7%.
Taking the crushed and sieved battery raw materials, adding 2.5% of binder, 3% of reduced coal and 15% of water into 2000g of undersize fine powder with the granularity of less than 5mm, preparing into granules with the size of 5-30mm, preheating and drying in a preheating kiln until the water content is less than 10%, and obtaining the waste zinc-manganese battery raw materials. Melting the raw materials of the waste zinc-manganese battery in a smelting furnace, then melting 200g of waste iron raw materials containing 82% of iron, 9% of manganese and 5-30um in granularity prepared by granulating fine iron powder which is a undersize product and is less than 5um, leading the water content to be less than 10%, injecting 1600g of coal powder into the smelting furnace by using 33% of oxygen-enriched air, controlling the temperature in the smelting furnace to be 1500-1550 ℃, smelting for 15min, producing ferromanganese alloy with the ferromanganese content of 92.1%, and leading the total recovery rate of ferromanganese to reach 94.6%; the lithium content in the lithium oxide recovered from the flue reaches 41.5%, and the recovery rate of lithium reaches 75.7%.
Example 3:
a pile of waste batteries containing various types such as zinc-manganese batteries, lithium-manganese primary batteries, manganese-series lithium ion batteries and the like are crushed and sieved to 5-30mm, undersize fine powder smaller than 5mm, 2.5% of binder, 6.5% of reducing coal and 10% of moisture are prepared into waste battery particles with the size of 5-30mm, and the waste battery particles are mixed with oversize products with the size of 5-30mm and then sampled and analyzed, so that the mixed waste battery raw materials contain 39.2% of manganese, 6.7% of zinc, 8.3% of iron, 1.5% of lithium, 0.8% of nickel, 12.8% of carbon, 2.6% of aluminum and 3.3% of copper. Firstly, 2000g of the mixed waste battery raw material is put into a smelting furnace to be melted, 500g of oversize waste iron raw material containing 85% of iron, 7% of manganese and 5-30um in particle size is sprayed into a volumetric furnace with 2000g of coal powder by 25% of oxygen-enriched air, the temperature in the smelting furnace is controlled to be 1600-1700 ℃, smelting is carried out for 30min, ferromanganese alloy containing 93.7% of ferromanganese is produced, and the total recovery rate of iron and manganese reaches 96.2%; the zinc content in the zinc oxide recovered from the flue reaches 62.2%, the recovery rate of zinc reaches 89.2%, and the recovery rate of lithium reaches 76.2%.
In summary, although the present invention has been described in detail with reference to the specific embodiments thereof, it should be understood by those skilled in the art that the foregoing embodiments are merely illustrative of the preferred embodiments of the present invention, and are not intended to limit the scope of the present invention. Variations that are within the skill of one of ordinary skill in the art can be readily envisioned within the scope of the present disclosure.
Claims (10)
1. A method for recycling valuable metals in manganese series waste batteries comprises the following steps:
(1) Preparing materials: crushing and screening manganese series waste batteries to obtain a waste battery raw material A with the oversize being 5-30mm in granularity, adding a binder, reducing coal and water into fine battery powder with the undersize being less than 5mm, and granulating to 5-30mm to obtain a waste battery raw material B; crushing and screening waste iron to obtain a waste iron raw material A with the oversize product of 5-30mm, adding a binder, reduced coal and water into fine waste iron powder with the undersize product of less than 5mm, and granulating to 5-30mm to obtain a waste iron raw material B;
(2) Fire smelting: melting the waste battery raw material A and the waste battery raw material B in a smelting furnace or respectively melting the waste battery raw material A and the waste battery raw material B in the smelting furnace, and then injecting the waste iron raw material A and/or the waste iron raw material B into the smelting furnace along with coal powder by using oxygen-enriched air for smelting to produce the ferromanganese alloy.
2. The method for recycling valuable metals from manganese-based waste batteries according to claim 1, wherein the method comprises the following steps: the manganese waste battery contains zinc and/or lithium, zinc steam and/or lithium oxide volatilize into flue gas in the smelting process, air is added into a flue, the volatilized zinc steam is converted into zinc oxide, the flue is cooled by using circulating cooling water, and the zinc oxide and/or lithium oxide is obtained by collecting.
3. The method for recycling valuable metals from manganese-based waste batteries according to claim 1, wherein the method comprises the following steps: in the waste battery raw material B in the step (1), the weight of the binder is 1-3%, the weight of the reducing coal is 3-6%, and the water content is lower than 10%.
4. The method for recycling valuable metals from manganese-based waste batteries according to claim 1, wherein the method comprises the following steps: in the scrap iron raw material B in the step (1), the weight of the binder is 1-3%, the weight of the reduced coal is 3-6%, and the water content is lower than 10%.
5. The method for recycling valuable metals from manganese-based waste batteries according to claim 1, wherein the method comprises the following steps: in the step (2), the temperature in the smelting furnace is controlled to be 1300-1700 ℃, the smelting time is 10-60min, and the mass concentration of oxygen in the oxygen-enriched air is 21-60%.
6. The method for recycling valuable metals from manganese-based waste batteries according to claim 1, wherein the method comprises the following steps: the mass ratio of manganese to iron in the total amount of the waste iron and manganese series waste batteries is not lower than 1: 2.
7. The method for recycling valuable metals from manganese-based waste batteries according to claim 1, wherein the method comprises the following steps: the manganese series waste battery is one or a mixture of more of an alkali manganese battery, a zinc manganese battery, a lithium manganese primary battery and a lithium ion battery with a positive electrode material containing lithium manganese oxide or lithium manganese oxide derivatives.
8. The method for recycling valuable metals from manganese-based waste batteries according to claim 1, wherein the method comprises the following steps: the scrap iron is one or a mixture of more of scrap cast iron, scrap tinplate, scrap white iron, scrap stainless steel and scrap alloy with the iron content of more than 50%.
9. The method for recycling valuable metals from manganese-based waste batteries according to claim 1, wherein the method comprises the following steps: the manganese-iron alloy has the total mass content of manganese and iron of more than 90 percent and can be used for manufacturing common manganese steel and manganese-containing stainless steel.
10. The method for recycling valuable metals from manganese-based waste batteries according to claim 2, wherein the method comprises the following steps: the total mass content of zinc and lithium in the mixture of zinc oxide and lithium oxide reaches more than 40 percent, and the zinc oxide and lithium oxide can be used as raw materials for zinc and lithium wet refining.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210017163.1A CN102569838B (en) | 2012-01-18 | 2012-01-18 | Method for recycling valuable metals in manganese series waste batteries |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210017163.1A CN102569838B (en) | 2012-01-18 | 2012-01-18 | Method for recycling valuable metals in manganese series waste batteries |
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| Publication Number | Publication Date |
|---|---|
| CN102569838A true CN102569838A (en) | 2012-07-11 |
| CN102569838B CN102569838B (en) | 2015-08-26 |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103219561A (en) * | 2013-03-28 | 2013-07-24 | 四川天齐锂业股份有限公司 | Method for recovering lithium manganate battery anode material |
| CN103526035A (en) * | 2013-10-31 | 2014-01-22 | 长沙矿冶研究院有限责任公司 | Method for recycling valuable metals from waste lithium ion batteries and/or other materials |
| CN103545538A (en) * | 2013-11-06 | 2014-01-29 | 安徽工业大学 | A method of using waste zinc-manganese dry batteries to prepare raw materials for manganese-based ferroalloys |
| RU2531911C1 (en) * | 2013-12-06 | 2014-10-27 | Федеральное государственное казенное учреждение "33 Центральный научно-исследовательский испытательный институт" Министерства обороны Российской Федерации | Method of recycling expired lithium cells |
| CN105811041A (en) * | 2016-05-19 | 2016-07-27 | 株洲鼎端装备股份有限公司 | Recycling and disposal system for waste lithium-ion power battery |
| CN105846006A (en) * | 2016-04-05 | 2016-08-10 | 江门市长优实业有限公司 | Method for recycling lithium metal from batteries of waste vehicle through electric arc furnace |
| CN105992829A (en) * | 2013-12-10 | 2016-10-05 | 菲戴管理有限公司 | Method for recycling used or discarded portable electrical batteries |
| JP2018184622A (en) * | 2017-04-24 | 2018-11-22 | Ｊｆｅ条鋼株式会社 | Method of recovering manganese |
| 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 |
| CN113728118A (en) * | 2019-04-19 | 2021-11-30 | 尤米科尔公司 | Method for preparing precursor compound of lithium battery cathode |
| CN114107678A (en) * | 2021-12-03 | 2022-03-01 | 万循材料科技有限公司 | Method for recovering zinc and manganese metals from waste mercury-free zinc-manganese dry batteries |
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| TWI614938B (en) * | 2015-11-30 | 2018-02-11 | 朝陽科技大學 | Method for refining of zinc or manganese from regrind materials of waste battery |
| EP3511431A1 (en) * | 2018-01-10 | 2019-07-17 | Fiday Gestion | Method and facility for reclamation of used batteries and storage cells |
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| CN103219561A (en) * | 2013-03-28 | 2013-07-24 | 四川天齐锂业股份有限公司 | Method for recovering lithium manganate battery anode material |
| CN103526035A (en) * | 2013-10-31 | 2014-01-22 | 长沙矿冶研究院有限责任公司 | Method for recycling valuable metals from waste lithium ion batteries and/or other materials |
| CN103545538A (en) * | 2013-11-06 | 2014-01-29 | 安徽工业大学 | A method of using waste zinc-manganese dry batteries to prepare raw materials for manganese-based ferroalloys |
| RU2531911C1 (en) * | 2013-12-06 | 2014-10-27 | Федеральное государственное казенное учреждение "33 Центральный научно-исследовательский испытательный институт" Министерства обороны Российской Федерации | Method of recycling expired lithium cells |
| CN105992829A (en) * | 2013-12-10 | 2016-10-05 | 菲戴管理有限公司 | Method for recycling used or discarded portable electrical batteries |
| US20160315330A1 (en) * | 2013-12-10 | 2016-10-27 | Fiday Gestion | Method for recycling used or discarded portable electric batteries |
| US11417893B2 (en) | 2013-12-10 | 2022-08-16 | Fiday Gestion | Method for recycling used or discarded portable electric batteries |
| EP3080316B1 (en) * | 2013-12-10 | 2023-02-22 | Erasteel | Method for recycling used or discarded portable electrical batteries |
| CN105846006A (en) * | 2016-04-05 | 2016-08-10 | 江门市长优实业有限公司 | Method for recycling lithium metal from batteries of waste vehicle through electric arc furnace |
| CN105811041A (en) * | 2016-05-19 | 2016-07-27 | 株洲鼎端装备股份有限公司 | Recycling and disposal system for waste lithium-ion power battery |
| JP2018184622A (en) * | 2017-04-24 | 2018-11-22 | Ｊｆｅ条鋼株式会社 | Method of recovering manganese |
| CN113728118A (en) * | 2019-04-19 | 2021-11-30 | 尤米科尔公司 | Method for preparing precursor compound of lithium battery cathode |
| 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 |
| CN114107678A (en) * | 2021-12-03 | 2022-03-01 | 万循材料科技有限公司 | Method for recovering zinc and manganese metals from waste mercury-free zinc-manganese dry batteries |
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