CN113061730A - Method for removing iron in waste ternary lithium battery recovery process - Google Patents
Method for removing iron in waste ternary lithium battery recovery process Download PDFInfo
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- CN113061730A CN113061730A CN202110306268.8A CN202110306268A CN113061730A CN 113061730 A CN113061730 A CN 113061730A CN 202110306268 A CN202110306268 A CN 202110306268A CN 113061730 A CN113061730 A CN 113061730A
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- ternary lithium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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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
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The invention discloses a method for removing iron in a waste ternary lithium battery recovery process, which comprises the steps of copper removal, water bath heating, stirring, drying and the like. The method for preparing the iron oxide yellow is applied to impurity removal of the acid leaching solution of the waste ternary lithium battery mainly containing Ni, Co and Mn, and the application scene of preparing the iron oxide yellow is expanded. The step of preparing the seed crystal in advance for preparing the iron oxide yellow is omitted.
Description
Technical Field
The invention particularly relates to a method for removing iron in a recovery process of a waste ternary lithium battery, which is mainly used in the field of recovery of battery materials.
Background
The recovery process of valuable elements of the waste ternary lithium battery generally comprises the steps of firstly carrying out acid leaching on powder of a positive electrode or a battery cell, then removing impurities such as Al, Fe, Cu and the like, and finally recovering the valuable elements through precipitation or extraction. At present, the iron removal method commonly used in the recovery process of the waste ternary lithium battery comprises an extraction method, a precipitation method and the like. The extraction method has the problems that the price of an organic solvent is high, secondary pollution is easy to cause and the like, so that the precipitation method is a main iron removal method in the recovery process of the waste ternary lithium battery. The common method for removing iron by precipitation method is Fe (OH)3Precipitation, sulfide precipitation, jarosite precipitation, and the like. Fe (OH)3The precipitation method is usually carried out with H2O2As an oxidizing agent, Fe2+Oxidation to Fe3+By adjusting the pH to form amorphous Fe (OH)3And (4) precipitating. But amorphous Fe (OH)3Is a typical colloid, and has a problem of poor filtering performance. The sulfide precipitation method is to utilize heavy metal ions to react with S2-to generate relatively stable sulfide precipitates, so as to achieve the separation of metal ions such as Fe, Cu and the like. However, the sulfide precipitation method has long precipitation period, needs a coagulant aid, and is easy to generate toxic gas H2S and the like. The iron removal by the jarosite method is carried out by using H2O2Or NaClO3Oxidizing with an oxidant to obtain Fe2+Oxidation to Fe3+Then NaOH is added to adjust the pH value, and the reaction is carried out at the temperature of more than 90 ℃ to generate the jarosite precipitate. The sodium jarosite has good filtering performance, but the reaction conditions are harsh, and the alum forming rate is unstable.
According to the research on the process for preparing iron yellow pigment by using a dripping method [ J ]. inorganic salt industry, 2004(06):49-51, Hemsan, Severe schoenoprass and air oxidation method [ J ]. Chinese powder technology, 2006(05):32-34, Wupenghui, Jiadingtian, Schwenjie, Li Art Chun, Li Mingyu, titanium white by-product ferrous sulfate to prepare iron oxide yellow [ J ]. process engineering bulletin, 2016,16(02):310 and 316, Dingjie, Hoxinyang and Liuyan Yan, the research on the iron yellow pigment by using the hydrochloric acid method titanium white waste liquid [ J ]. chemical research and application, 2008 and 934, etc., it can be seen that at present, seed crystal is generally required to be prepared by using a solution containing a large amount of Fe2+ as a raw material to prepare iron yellow, the method is not applied to the scene of removing iron impurities in the solution, and the application range is limited.
Disclosure of Invention
The invention aims to provide a method for removing iron in the recovery process of waste ternary lithium batteries, which removes Fe in the acid leaching solution of the waste ternary lithium batteries in the form of iron yellow, solves the problems that precipitates in the prior acid leaching solution for removing Fe in the waste ternary lithium batteries are difficult to filter, organic solvents are easy to cause secondary pollution and the like, and also improves the added value of products. The method for preparing the iron oxide yellow is applied to impurity removal of the acid leaching solution of the waste ternary lithium battery mainly containing Ni, Co and Mn, and the application scene of preparing the iron oxide yellow is expanded. The step of preparing the seed crystal in advance for preparing the iron oxide yellow is omitted.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for removing iron in the recovery process of waste ternary lithium batteries is characterized by comprising the following steps:
(1) copper removal: adding excessive iron powder into acid leaching solution of the anode/battery core powder of the waste ternary lithium battery, and removing copper by a displacement method;
(2) heating in a water bath, controlling the temperature to be 30-40 ℃, adding a flocculating agent into the copper-removed acid leaching solution of the waste ternary lithium battery according to 0.5-3% of the mass of the iron element in the stirring process, adjusting the pH value to 1-2.5, and stirring for 0.5-2 h;
(3) raising the temperature of the water bath to 40-70 ℃, introducing air at the aeration rate of 2-6L/min, adjusting the pH value to 3-5, and stirring for 1-3 h;
(4) filtering, washing the precipitate, and drying to obtain the iron oxide yellow product.
The substitution method comprises the following specific steps: stirring for 0.5h at 55 ℃, and filtering to obtain the copper-removed pickle liquor.
The flocculating agent is one of polyacrylamide, polyethyleneimine and sodium carboxymethylcellulose.
The reagent for adjusting pH comprises one or more of ammonia water, ethylenediamine and glycine.
The invention has the advantages that:
1. the iron yellow precipitation method is adopted to remove iron in the acid leaching solution of the waste ternary lithium battery, the formed precipitate iron yellow has good filtering performance, and meanwhile, the iron yellow can be sold as pigment, so that the added value of the impurity-removed product is improved.
The existing method for removing iron from the pickle liquor of the waste ternary lithium battery comprises the following steps:
(1) fe (oh)3 precipitation processes typically oxidize Fe2+ to Fe3+ using H2O2 as the oxidant, and produce amorphous Fe (oh)3 precipitates by adjusting the pH. However, amorphous Fe (OH)3 is a typical colloid and has a problem of poor filtering properties.
(2) The sulfide precipitation method is to utilize heavy metal ions to react with S2-to generate relatively stable sulfide precipitates, so as to achieve the separation of metal ions such as Fe, Cu and the like. However, the sulfide precipitation method has the problems of long precipitation period, need of a coagulant aid, easy generation of toxic gas H2S and the like.
(3) The method for removing iron by using the jarosite method comprises the steps of oxidizing Fe2+ into Fe3+ by using an oxidant such as H2O2 or NaClO3, adding NaOH to adjust the pH value, and reacting at the temperature of over 90 ℃ to generate the jarosite precipitate. The sodium jarosite has good filtering performance, but the reaction conditions are harsh, and the alum forming rate is unstable.
2. The process of preparing the iron oxide yellow by adding the organic flocculant does not need to prepare seed crystals separately.
The existing preparation method of iron oxide yellow requires that ferrous sulfate solution is firstly used for preparing iron oxide yellow seed crystal.
3. Ammonia water, ethylenediamine or glycine is used as a precipitator, so that Ni, Co and Mn ions are complexed with NH3, and the loss of valuable elements such as Ni, Co and Mn in the impurity removal process is reduced.
In the existing method, NaOH is usually used as a precipitator in the impurity removal process, so that the loss of Ni, Co and Mn is easily caused.
Detailed Description
Example 1:
1. and adding excessive iron powder into the pickle liquor of the anode/battery cell powder of the waste ternary lithium battery, stirring for 0.5h at 55 ℃, and filtering to obtain the pickle liquor after copper removal (see table 1).
2. Heating in water bath, and controlling the temperature at 30 ℃. And in the stirring process, adding a flocculating agent polyacrylamide according to 0.5 percent of the mass of the iron element into the copper-removed pickle liquor of the waste ternary lithium battery, adding ammonia water with a certain concentration to adjust the pH value to 1, and stirring for 2 hours.
3. The temperature of the water bath is raised to 40 ℃, air is introduced at the aeration rate of 6L/min, ammonia water with certain concentration is added to adjust the pH value to 3, and the mixture is stirred for 3 hours.
4. Filtering, washing the precipitate, and drying to obtain iron yellow product (see table 2).
TABLE 1 composition of solution after iron removal Table (unit: g/L)
TABLE 2 iron oxide yellow Property Table
Example 2:
1. and adding excessive iron powder into the pickle liquor of the anode/battery cell powder of the waste ternary lithium battery, stirring for 0.5h at 55 ℃, and filtering to obtain the pickle liquor after copper removal (see table 3).
2. Heating in water bath, and controlling the temperature at 35 ℃. And in the stirring process, 1.7 percent of the copper-removed waste ternary lithium battery pickle liquor by mass of the iron element is added with flocculating agent polyethyleneimine, ammonia water with certain concentration is added to adjust the pH value to 1.7, and the mixture is stirred for 1 hour.
3. The temperature of the bath was raised to 55 ℃ and air was introduced at an aeration rate of 4L/min, and a certain concentration of ammonia was added to adjust the pH to 4 and stirred for 2h (see Table 4).
4. Filtering, washing the precipitate, and drying to obtain the iron oxide yellow product.
TABLE 3 composition of solution after iron removal Table (unit: g/L)
TABLE 4 iron oxide yellow Property Table
Example 3:
1. and adding excessive iron powder into the pickle liquor of the anode/battery cell powder of the waste ternary lithium battery, stirring for 0.5h at 55 ℃, and filtering to obtain the pickle liquor after copper removal (see table 5).
2. Heating in water bath, and controlling the temperature at 40 ℃. And in the stirring process, adding a flocculating agent polyethyleneimine into the copper-removed waste ternary lithium battery pickle liquor according to 1% of the mass of the iron element, adding ammonia water with a certain concentration to adjust the pH value to 2.5, and stirring for 0.5 h.
3. The temperature of the water bath is raised to 70 ℃, air is introduced at the aeration rate of 2L/min, ammonia water with certain concentration is added to adjust the pH value to 5, and the mixture is stirred for 1 hour.
4. Filtering, washing the precipitate, and drying to obtain iron yellow product (see Table 6).
TABLE 5 composition of solution after iron removal Table (unit: g/L)
TABLE 6 iron oxide yellow Property Table
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (4)
1. A method for removing iron in the recovery process of waste ternary lithium batteries is characterized by comprising the following steps:
(1) copper removal: adding excessive iron powder into acid leaching solution of the anode/battery core powder of the waste ternary lithium battery, and removing copper by a displacement method;
(2) heating in a water bath, controlling the temperature to be 30-40 ℃, adding a flocculating agent into the copper-removed acid leaching solution of the waste ternary lithium battery according to 0.5-3% of the mass of the iron element in the stirring process, adjusting the pH value to 1-2.5, and stirring for 0.5-2 h;
(3) raising the temperature of the water bath to 40-70 ℃, introducing air at the aeration rate of 2-6L/min, adjusting the pH value to 3-5, and stirring for 1-3 h;
(4) filtering, washing the precipitate, and drying to obtain the iron oxide yellow product.
2. The method for removing iron in the recovery process of the waste ternary lithium battery as claimed in claim 1, wherein the replacement method comprises the following specific steps: stirring for 0.5h at 55 ℃, and filtering to obtain the copper-removed pickle liquor.
3. The method for removing iron in the recovery process of the waste ternary lithium battery as claimed in claim 1, wherein the flocculant is one of polyacrylamide, polyethyleneimine and sodium carboxymethylcellulose.
4. The method for removing iron in the recovery process of the waste ternary lithium battery as claimed in claim 1, wherein the reagent for adjusting the pH comprises one or more of ammonia water, ethylenediamine and glycine.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023242129A1 (en) * | 2022-06-13 | 2023-12-21 | Mecaware Sas | Process for selectively capturing chemical elements from a polymetallic sample |
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2021
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Patent Citations (9)
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| US20040028585A1 (en) * | 2000-09-13 | 2004-02-12 | Francois Cardarelli | Method for recycling spent lithium metal polymer rechargeable batteries and related materials |
| CN102381789A (en) * | 2011-10-08 | 2012-03-21 | 昆明理工大学 | Method for treating smelting wastewater containing heavy metals |
| CN103145194A (en) * | 2011-12-06 | 2013-06-12 | 北京三聚环保新材料股份有限公司 | Method of preparing iron oxide yellow by using titanium dioxide by-product |
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Application publication date: 20210702 |