CN104073637A - Method for preparing strong acid salt containing nickel-cobalt-zinc ions - Google Patents

Method for preparing strong acid salt containing nickel-cobalt-zinc ions Download PDF

Info

Publication number
CN104073637A
CN104073637A CN201410282644.4A CN201410282644A CN104073637A CN 104073637 A CN104073637 A CN 104073637A CN 201410282644 A CN201410282644 A CN 201410282644A CN 104073637 A CN104073637 A CN 104073637A
Authority
CN
China
Prior art keywords
nickel
solution
extraction
cobalt
strong acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410282644.4A
Other languages
Chinese (zh)
Other versions
CN104073637B (en
Inventor
王一乔
蒋庆来
杨先锋
齐士博
葛良知
石建珍
张洪涛
欧腾蛟
肖连生
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NATIONAL ENGINEERING RESEARCH CENTER OF ADVANCE ENERGY STORAGE MATERIALS
Original Assignee
NATIONAL ENGINEERING RESEARCH CENTER OF ADVANCE ENERGY STORAGE MATERIALS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NATIONAL ENGINEERING RESEARCH CENTER OF ADVANCE ENERGY STORAGE MATERIALS filed Critical NATIONAL ENGINEERING RESEARCH CENTER OF ADVANCE ENERGY STORAGE MATERIALS
Priority to CN201410282644.4A priority Critical patent/CN104073637B/en
Publication of CN104073637A publication Critical patent/CN104073637A/en
Application granted granted Critical
Publication of CN104073637B publication Critical patent/CN104073637B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/84Recycling of batteries or fuel cells

Abstract

The invention provides a method for preparing strong acid salt containing nickel-cobalt-zinc ions. The method comprises the following steps: by adopting a used nickel-metal hydride battery as a raw material, disintegrating the raw material battery, crushing a cell, dissolving the cell, settling the rare earth to obtain to obtain aqueous solution with the rare earth being removed, extracting, and reverse extracting. The method is simple in process, the recovery rate of the nickel cobalt and zinc can reach more than 99 percent, the strong acid salt containing the nickel-cobalt-zinc ions can be directly used for preparing spherical nickel hydroxide, the separation refining crystallizing step is omitted, the efficiency is high, and the cost can be reduced.

Description

A kind of method of the strong acid salt of preparing nickel and cobalt containing zine ion
Technical field
The present invention relates to a kind of method of preparing strong acid salt, particularly a kind of method of the strong acid salt of preparing nickel and cobalt containing zine ion.
Background technology
Nickel metal hydride battery is one of the most ripe business-like new forms of energy battery in the market, is extensively being applied among daily life.Along with the progressively exhaustion of the Mineral resources such as nickelous sulfide, be also the raising of environmental requirement and the needs of resource circulation utilization simultaneously, the recovery of old and useless battery appears in face of people as key subjects.But the domestic recovery for old and useless battery, because complex process, efficiency are low, high in cost of production reason, never larger development.
Traditional battery recycling method is that battery is disassembled after pulverizing, and use sulfuric acid leaching, is used as the low price metal in leach liquor as the impurity precipitator method or extraction process is removed, and the metallic solution that leaves the need recovery of valency further separates and be refined into product.The method exists because the removal of impurities mode of different concns different metal impurity has larger difference, thereby causes complicated operation, and efficiency is low, high in cost of production defect.Meanwhile, reclaim the product obtaining and be mainly technical grade nickel salt, cobalt salt etc., great majority have just been realized recycling, and do not come back in battery manufacture.
Summary of the invention
The present invention aims to provide a kind of method of preparing simply, directly, efficiently the strong acid salt of nickel and cobalt containing zine ion.The present invention realizes by following scheme:
Prepare a method for the strong acid salt of nickel and cobalt containing zine ion, carry out as follows:
(1) battery is disassembled pulverizing: used nickel metal hydride battery is disassembled, sub-elected battery core, battery core is broken into powder;
(2) battery core is dissolved: battery core powder is added in the mixing solutions of acid and oxygenant, continues to stir 1~5 hour at 50~65 DEG C, obtain leach liquor;
(3) rare-earth precipitation: with alkali lye adjusting leach liquor pH value to 0.5~2.0, constant temperature stirs at 40~60 DEG C, adds excessive alkali metal sulfates, leaves standstill, and solid-liquid separation, obtains earth solution;
(4) extraction: will go the aqueous ph value after rare earth to be adjusted to 2.0~3.0---be (3~6.5) by the volume ratio of organic phase and aqueous phase solution: 1 to add wherein pH value be 2.5~3.5 extraction agent organic solution, standing after by organic phase and aqueous phase separation; Described extraction agent is the organism of the compound that comprises naphthene sulfonic acid or naphthalenesulfonate and pyridine carboxylic acid ester, and in compound, the mol ratio of naphthene sulfonic acid or naphthalenesulfonate and pyridine carboxylic acid ester is 1:(1~6); The organic solvent that described extraction agent organic solution adopts is sulfonated kerosene, No. 260 solvent oils, aviation kerosene, Escaid110 or C 8~13higher alcohols in one or more;
(5) strip: be (2~4) by organic phase with water volume ratio: 1 adds the inorganic acid aqueous solution to last separation in extraction step in the organic phase solution obtaining, standing after by organic phase and aqueous phase separation, get aqueous phase solution and obtain comprising Ni 2+, Co 2+and Zn 2+strong acid inorganic salt solution.
For improving purity and the rate of recovery of nickel cobalt zine ion, adopt the extraction of 3 grades of above reflux types, adopt the reextraction of 3 grades of above reflux types.
Compared with prior art, advantage of the present invention is as follows:
1. the present invention utilizes used nickel metal hydride battery to be manufactured with non-ferrous metal salt as raw material, has not only solved well old and useless battery and has reclaimed the problem of harmless treatment, but also can prepare valuable metal salt, saves metals resources.
2. the present invention adopts use contrary thinking method, in leach liquor, by the mode of extraction, directly these three kinds of valuable metals of nickel cobalt zinc is extracted, and remaining other low price foreign metal is stayed in the aqueous solution.The method has been avoided the impact on whole system in the time of removal of impurities of different metal impurity, has reduced the removal of impurities rate of loss to valuable metal, simultaneously because organic extractant is can be reusable, this will reduce cost recovery greatly, and this technological operation is simple, and efficiency is high, easily realize whole-course automation.
3. the organic phase after extraction step separates can obtain containing Ni by inorganic acid pickling 2+, Co 2+and Zn 2+strong acid inorganic salt solution, without further separation and purification crystallization, can directly be used for producing ball-shape nickel hydroxide, saved macroelement separation, the cost of refining crystallization.
Embodiment
embodiment 1
Prepare a method for the vitriol of nickel and cobalt containing zine ion, carry out according to the following steps:
(1) battery core obtaining after used nickel metal hydride battery broken shell is broken into powder;
(2) getting 1kg battery core powder joins the mixing solutions that 30L is made up of sulfuric acid and oxidants hydrogen peroxide (wherein sulfuric acid concentration is 0.5mol/L, concentration of hydrogen peroxide is 0.8ml/g) in, be heated to 60~65 DEG C, continue to stir 4h, obtain leach liquor.Steep cencentration is: Ni12-17g/L, Co0.5-1.5g/L, Re3-6g/L, Fe0.05-0.3g/L, Zn0.1-0.5g/L, Mn0.1-0.5g/L.PH value is about 0.8-1.0.
(3) regulate pH value to 1.5 with the NaOH of 4mol/L, keep 60 DEG C of constant temperature, add while stirring excessive anhydrous sodium sulphate, rare earth element can be precipitated out with the form of rare earth sulfate.Leave standstill, solid-liquid separation, obtains earth solution.
(4) regulate and remove earth solution pH value to 2.0 with the NaOH of 4mol/L, be that to add wherein pH value be 3.0 extraction agent organic solution to 3.5:1 by the volume ratio of organic phase and aqueous phase solution, wherein extraction agent is the compound being mixed for 1:1.5 in molar ratio with pyridine carboxylic acid ester by naphthene sulfonic acid, the organic solvent that extraction agent organic solution adopts is sulfonated kerosene, adopt 4 stage countercurrent modes to extract, leave standstill, by organic phase and aqueous phase separation.
(5) be that 2:1 finally separates the sulphuric acid soln that adds 0.5mol/L in the organic phase solution obtaining in extraction step by organic phase and water volume ratio, adopt the reextraction of 3 stage countercurrent modes, after leaving standstill, by organic phase and aqueous phase separation, get aqueous phase solution and obtain comprising Ni 2+, Co 2+and Zn 2+sulfate liquor.
Use the rate of recovery of the valuable metal nickel cobalt zinc of aforesaid method to used nickel metal hydride battery to reach more than 99%, and the vitriol of the nickel and cobalt containing zine ion preparing can be directly used in and prepare ball-shape nickel hydroxide.
embodiment 2
Prepare a method for the vitriol of nickel and cobalt containing zine ion, its operation steps is similar with embodiment, and difference is:
1, in step (4), be that to add wherein pH value be 2.8 extraction agent organic solution to 5:1 by the volume ratio of organic phase and aqueous phase solution, wherein extraction agent is the compound being mixed for 1:5 in molar ratio with pyridine carboxylic acid ester by naphthene sulfonic acid, and the organic solvent that extraction agent organic solution adopts is No. 260 solvent oils;
2, in step (5), organic phase and water volume ratio are 3:1.
embodiment 3
Prepare a method for the vitriol of nickel and cobalt containing zine ion, carry out according to the following steps:
(1) battery core obtaining after used nickel metal hydride battery broken shell is broken into powder;
(2) getting 1kg battery core powder joins the mixing solutions that 30L is made up of sulfuric acid and oxidants hydrogen peroxide (wherein sulfuric acid concentration is 0.5mol/L, concentration of hydrogen peroxide is 0.8ml/g) in, be heated to 60~65 DEG C, continue to stir 4h, obtain leach liquor.Steep cencentration is: Ni12-17g/L, Co0.5-1.5g/L, Re3-6g/L, Fe0.05-0.3g/L, Zn0.1-0.5g/L, Mn0.1-0.5g/L.PH value is about 0.8-1.0.
(3) regulate pH value to 1.5 with the NaOH of 4mol/L, keep 50 DEG C of constant temperature, add while stirring excessive anhydrous sodium sulphate, rare earth element can be precipitated out with the form of rare earth sulfate.Leave standstill, solid-liquid separation, obtains earth solution.
(4) regulate and remove earth solution pH value to 3.0 with the NaOH of 4mol/L, be that to add wherein pH value be 3.2 extraction agent organic solution to 6.5:1 by the volume ratio of organic phase and aqueous phase solution, wherein extraction agent is the compound being mixed for 1:6 in molar ratio with pyridine carboxylic acid ester by naphthalenesulfonate, the organic solvent that extraction agent organic solution adopts is aviation kerosene and sulfonated kerosene, adopt 5 stage countercurrent modes to extract, leave standstill, by organic phase and aqueous phase separation.
(5) be that 4:1 finally separates the sulphuric acid soln that adds 1.5mol/L in the organic phase solution obtaining in extraction step by organic phase and water volume ratio, adopt the reextraction of 5 stage countercurrent modes, after leaving standstill, by organic phase and aqueous phase separation, get aqueous phase solution and obtain comprising Ni 2+, Co 2+and Zn 2+sulfate liquor.

Claims (3)

1. prepare the method for the strong acid salt of nickel and cobalt containing zine ion for one kind, it is characterized in that: adopt used nickel metal hydride battery to make raw material, raw material battery is through disassembling that---------rare-earth precipitation obtains the aqueous solution after rare earth, and---extraction---obtains after reextraction in battery core dissolving to pulverize battery core;
Described extraction step: will go the aqueous ph value after rare earth to be adjusted to 2.0~3.0---be (3~6.5) by the volume ratio of organic phase and aqueous phase solution: 1 add wherein pH value be 2.5~3.5 extraction agent organic solution---after leaving standstill by organic phase and aqueous phase separation; Described extraction agent is the organism of the compound that comprises naphthene sulfonic acid or naphthalenesulfonate and pyridine carboxylic acid ester, and in compound, the mol ratio of naphthene sulfonic acid or naphthalenesulfonate and pyridine carboxylic acid ester is 1:(1~6); The organic solvent that described extraction agent organic solution adopts is sulfonated kerosene, No. 260 solvent oils, aviation kerosene, Escaid110 or C 8~13higher alcohols in one or more;
Described strip stage: be in a ratio of with water by organic phase (2~4): 1 adds the inorganic acid aqueous solution to finally separating in extraction step in the organic phase solution obtaining---standing after by organic phase and aqueous phase separation, get aqueous phase solution and obtain comprising Ni 2+, Co 2+and Zn 2+strong acid inorganic salt solution.
2. the method for the strong acid salt of preparing nickel and cobalt containing zine ion as claimed in claim 1, is characterized in that: described extraction step adopts the extraction of 3 grades of above reflux types.
3. the method for the strong acid salt of preparing nickel and cobalt containing zine ion as claimed in claim 1 or 2, is characterized in that: described strip stage adopts the reextraction of 3 grades of above reflux types.
CN201410282644.4A 2014-06-23 2014-06-23 A kind of method of the strong acid salt of preparing nickel and cobalt containing zinc ion Active CN104073637B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410282644.4A CN104073637B (en) 2014-06-23 2014-06-23 A kind of method of the strong acid salt of preparing nickel and cobalt containing zinc ion

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410282644.4A CN104073637B (en) 2014-06-23 2014-06-23 A kind of method of the strong acid salt of preparing nickel and cobalt containing zinc ion

Publications (2)

Publication Number Publication Date
CN104073637A true CN104073637A (en) 2014-10-01
CN104073637B CN104073637B (en) 2016-05-25

Family

ID=51595238

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410282644.4A Active CN104073637B (en) 2014-06-23 2014-06-23 A kind of method of the strong acid salt of preparing nickel and cobalt containing zinc ion

Country Status (1)

Country Link
CN (1) CN104073637B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108277365A (en) * 2018-02-05 2018-07-13 中南大学 The application of trialkyl naphthalene sulfonic acids, the synergic reagent comprising trialkyl naphthalene sulfonic acids and its preparation and application
CN108642283A (en) * 2018-05-25 2018-10-12 中南大学 A kind of nickel cobalt synergic reagent and its method detached with impurity extraction for nickel cobalt
CN110042252A (en) * 2019-05-29 2019-07-23 北京科技大学 A method of scrapping the recycling of nickel-metal hydride battery valuable metal element

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992003853A1 (en) * 1990-08-15 1992-03-05 Nederlandse Organisatie Voor Toegepast- Natuurwetenschappelijk Onderzoek Tno RECOVERY OF Cd AND Ni FROM BATTERIES
CN1171171A (en) * 1994-12-20 1998-01-21 瓦尔达电池股份公司 Process for recovery of metals from used nickel-metal hydride accumulators
CN101787438A (en) * 2009-01-23 2010-07-28 胡建康 Method for precipitating rare earth by adopting carbon dioxide
CN102887855A (en) * 2011-07-18 2013-01-23 海洋王照明科技股份有限公司 Pyridine-ion-containing liquid, preparation method and application thereof
CN103725891A (en) * 2014-01-27 2014-04-16 先进储能材料国家工程研究中心有限责任公司 Method for recycling rare earth from waste nickel-metal hydride battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992003853A1 (en) * 1990-08-15 1992-03-05 Nederlandse Organisatie Voor Toegepast- Natuurwetenschappelijk Onderzoek Tno RECOVERY OF Cd AND Ni FROM BATTERIES
CN1171171A (en) * 1994-12-20 1998-01-21 瓦尔达电池股份公司 Process for recovery of metals from used nickel-metal hydride accumulators
CN101787438A (en) * 2009-01-23 2010-07-28 胡建康 Method for precipitating rare earth by adopting carbon dioxide
CN102887855A (en) * 2011-07-18 2013-01-23 海洋王照明科技股份有限公司 Pyridine-ion-containing liquid, preparation method and application thereof
CN103725891A (en) * 2014-01-27 2014-04-16 先进储能材料国家工程研究中心有限责任公司 Method for recycling rare earth from waste nickel-metal hydride battery

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108277365A (en) * 2018-02-05 2018-07-13 中南大学 The application of trialkyl naphthalene sulfonic acids, the synergic reagent comprising trialkyl naphthalene sulfonic acids and its preparation and application
CN108642283A (en) * 2018-05-25 2018-10-12 中南大学 A kind of nickel cobalt synergic reagent and its method detached with impurity extraction for nickel cobalt
CN110042252A (en) * 2019-05-29 2019-07-23 北京科技大学 A method of scrapping the recycling of nickel-metal hydride battery valuable metal element
CN110042252B (en) * 2019-05-29 2020-07-31 北京科技大学 Method for recycling valuable metal elements of scrapped nickel-metal hydride battery

Also Published As

Publication number Publication date
CN104073637B (en) 2016-05-25

Similar Documents

Publication Publication Date Title
CN107267759B (en) A kind of comprehensive recovering process of anode material for lithium-ion batteries
CN102244309B (en) Method for recovering lithium from lithium power battery of electric automobile
CN101886178B (en) Comprehensive recovery method for nickel-hydrogen waste battery
CN102285673B (en) Method for recovering lithium and iron from lithium iron phosphate power battery for electromobile
CN106319228A (en) Method for recycling nickel, cobalt and manganese synchronously from waste residues containing nickel, cobalt and manganese
CN104659438B (en) A kind of method that utilization refuse battery prepares ternary anode material precursor
CN103326088A (en) Comprehensive recycling method of waste and old lithium-ion battery
CN105886767B (en) A kind of recovery method of copper indium gallium selenide waste material
CN104745823B (en) Method for recycling lithium from waste lithium ion battery
CN102956936A (en) Method for treating lithium iron phosphate cathode material of waste and old power lithium battery of automobile
CN105087935B (en) The method of copper, indium and gallium is separately recovered in a kind of gallium waste target from copper and indium
CN101613803A (en) A kind of method of recovering lead from lead paste of waste lead-acid battery
CN107416908B (en) A kind of method that low cost prepares high-purity sulphuric acid manganese solution
CN109097581A (en) The recovery method of valuable metal in waste and old nickel cobalt manganese lithium ion battery
CN109666799A (en) The method and its application of valuable metal are separated and recovered from waste lithium cell material
CN104073637B (en) A kind of method of the strong acid salt of preparing nickel and cobalt containing zinc ion
CN109439914A (en) A method of the Selective Separation lithium from waste lithium ion cell anode material extract
CN109088115A (en) Waste lithium ion cell anode closed matereial cycle prepares tertiary cathode material method
CN106229577A (en) The method that the mixing of a kind of waste nickel hydrogen battery both positive and negative polarity material is leached
CN109095481A (en) A kind of comprehensive recovering process of the useless powder of LiFePO4
CN103233123A (en) Integrated recovery method of waste and old rare earth capacitance battery
CN109536728A (en) A method of recycling nickel cobalt from battery electrode material leachate
CN104073638B (en) A kind of method that adopts used Ni-MH battery to prepare ball-shape nickel hydroxide
CN104928476B (en) A kind of processing method of cobalt-copper alloy Water Quenching Slag
CN109055746A (en) A method of recycling valuable metal from nickelic lithium ion cell anode waste

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant