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

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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
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solution
nickel
strong acid
organic phase
cobalt
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CN201410282644.4A
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CN104073637B (en
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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
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NATIONAL ENGINEERING RESEARCH CENTER OF ADVANCE ENERGY STORAGE MATERIALS
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NATIONAL ENGINEERING RESEARCH CENTER OF ADVANCE ENERGY STORAGE MATERIALS
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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

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  • Manufacture And Refinement Of Metals (AREA)

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)

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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
GB2607991A (en) * 2021-06-11 2022-12-21 Johnson Matthey Plc A recycling method for battery and catalyst materials

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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 (6)

* 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
GB2607991A (en) * 2021-06-11 2022-12-21 Johnson Matthey Plc A recycling method for battery and catalyst materials
GB2607991B (en) * 2021-06-11 2024-07-31 Gelion Tech Pty Ltd A recycling method for battery and catalyst materials

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