CN104073637B - A kind of method of the strong acid salt of preparing nickel and cobalt containing zinc ion - Google Patents
A kind of method of the strong acid salt of preparing nickel and cobalt containing zinc ion Download PDFInfo
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- CN104073637B CN104073637B CN201410282644.4A CN201410282644A CN104073637B CN 104073637 B CN104073637 B CN 104073637B CN 201410282644 A CN201410282644 A CN 201410282644A CN 104073637 B CN104073637 B CN 104073637B
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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
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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
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- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The invention provides a kind of method of the strong acid salt of preparing nickel and cobalt containing zinc ion, adopt used Ni-MH battery to make raw material, raw material battery is through disassembling, and---------rare-earth precipitation obtains the aqueous solution after rare earth, and---extraction---obtains after reextraction in battery core dissolving to pulverize battery core. This method technique is simple, and the rate of recovery of nickel cobalt zinc can reach more than 99%, and the strong acid salt of the nickel and cobalt containing zinc ion making, can be directly used in and prepare ball-shape nickel hydroxide, has saved separation and purification crystallisation step, and efficiency is high, and can reduce costs.
Description
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 zinc ion.
Background technology
Ni-MH 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 nickel 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 leachate as the impurity precipitation method or extraction 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 variable concentrations 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 zinc ion. The present invention realizes by following scheme:
Prepare a method for the strong acid salt of nickel and cobalt containing zinc ion, carry out as follows:
(1) battery is disassembled pulverizing: used Ni-MH 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 mixed solution of acid and oxidant, continues to stir 1～5 hour at 50～65 DEG C, obtain leachate;
(3) rare-earth precipitation: with alkali lye adjusting pH of leaching solution to 0.5～2.0, constant temperature stirs at 40～60 DEG C, adds excessive alkali metal sulfates, leaves standstill, and Separation of Solid and Liquid, obtains earth solution;
(4) extraction: will go the pH value of water solution 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 extractant organic solution, standing after by organic phase and aqueous phase separation; Described extractant is the organic matter of the compound that comprises naphthalene sulfonic acids or naphthalene sulfonate and picolinic acid ester, and in compound, the mol ratio of naphthalene sulfonic acids or naphthalene sulfonate and picolinic acid ester is 1:(1～6); The organic solvent that described extractant organic solution adopts is sulfonated kerosene, No. 260 solvent naphthas, aviation kerosine, Escaid110 or C8～13Higher 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 Ni2+、Co2+And Zn2+Strong acid inorganic salt solution.
For improving purity and the rate of recovery of nickel cobalt zinc 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 Ni-MH 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 leachate, 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 loss late 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 pickling2+、Co2+And Zn2+Strong acid inorganic salt solution, without further separation and purification crystallization, can directly be used for producing ball-shape nickel hydroxide, saved a great number of elements separation, the cost of refining crystallization.
Detailed description of the invention
Embodiment 1
Prepare a method for the sulfate of nickel and cobalt containing zinc ion, carry out according to the following steps:
(1) battery core obtaining after used Ni-MH battery broken shell is broken into powder;
(2) getting 1kg battery core powder joins the mixed solution 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 leachate. 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 sulfate, rare earth element can be precipitated out with the form of rare earth sulfate. Leave standstill, Separation of Solid and Liquid, obtains earth solution.
(4) regulate and go earth solution pH value to 2.0 with the NaOH of 4mol/L, be that to add wherein pH value be 3.0 extractant organic solution to 3.5:1 by the volume ratio of organic phase and aqueous phase solution, wherein extractant is the compound being mixed for 1:1.5 in molar ratio with picolinic acid ester by naphthalene sulfonic acids, the organic solvent that extractant 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 sulfuric acid solution 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 Ni2+、Co2+And Zn2+Sulfate liquor.
Use the rate of recovery of the valuable metal nickel cobalt zinc of said method to used Ni-MH battery to reach more than 99%, and the sulfate of the nickel and cobalt containing zinc ion preparing can be directly used in and prepare ball-shape nickel hydroxide.
Embodiment 2
Prepare a method for the sulfate of nickel and cobalt containing zinc ion, its operating procedure is similar with embodiment, and difference is:
1, in step (4), be that to add wherein pH value be 2.8 extractant organic solution to 5:1 by the volume ratio of organic phase and aqueous phase solution, wherein extractant is the compound being mixed for 1:5 in molar ratio with picolinic acid ester by naphthalene sulfonic acids, and the organic solvent that extractant organic solution adopts is No. 260 solvent naphthas;
2, in step (5), organic phase and water volume ratio are 3:1.
Embodiment 3
Prepare a method for the sulfate of nickel and cobalt containing zinc ion, carry out according to the following steps:
(1) battery core obtaining after used Ni-MH battery broken shell is broken into powder;
(2) getting 1kg battery core powder joins the mixed solution 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 leachate. 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 sulfate, rare earth element can be precipitated out with the form of rare earth sulfate. Leave standstill, Separation of Solid and Liquid, obtains earth solution.
(4) regulate and go earth solution pH value to 3.0 with the NaOH of 4mol/L, be that to add wherein pH value be 3.2 extractant organic solution to 6.5:1 by the volume ratio of organic phase and aqueous phase solution, wherein extractant is the compound being mixed for 1:6 in molar ratio with picolinic acid ester by naphthalene sulfonate, the organic solvent that extractant organic solution adopts is aviation kerosine 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 sulfuric acid solution 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 Ni2+、Co2+And Zn2+Sulfate liquor.
Claims (3)
1. prepare the method for the strong acid salt of nickel and cobalt containing zinc ion for one kind, it is characterized in that: adopt used Ni-MH 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 pH value of water solution 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 extractant organic solution---after leaving standstill by organic phase and aqueous phase separation; Described extractant is the organic matter of the compound that comprises naphthalene sulfonic acids or naphthalene sulfonate and picolinic acid ester, and in compound, the mol ratio of naphthalene sulfonic acids or naphthalene sulfonate and picolinic acid ester is 1:(1～6); The organic solvent that described extractant organic solution adopts is sulfonated kerosene, No. 260 solvent naphthas, aviation kerosine, Escaid110 or C8～13Higher 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 Ni2+、Co2+And Zn2+Strong acid inorganic salt solution.
2. the method for the strong acid salt of preparing nickel and cobalt containing zinc 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 zinc 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.
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| CN108277365B (en) * | 2018-02-05 | 2019-06-21 | 中南大学 | The application of trialkyl naphthalene sulfonic acids, the synergic reagent comprising trialkyl naphthalene sulfonic acids and its preparation and application |
| CN108642283B (en) * | 2018-05-25 | 2019-09-27 | 中南大学 | A kind of nickel cobalt synergic reagent and its method separated for nickel cobalt with impurity extraction |
| 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 |
| GB202108372D0 (en) * | 2021-06-11 | 2021-07-28 | 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 |
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Patent Citations (5)
| 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 |
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