CN115216629A - Method for comprehensively recovering metal elements in tungsten-doped ternary precursor waste - Google Patents
Method for comprehensively recovering metal elements in tungsten-doped ternary precursor waste Download PDFInfo
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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
- C22B7/007—Wet processes by acid leaching
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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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
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
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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
- C22B47/00—Obtaining manganese
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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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- Y02P10/20—Recycling
Abstract
The invention relates to the technical field of battery waste recovery, and discloses a method for comprehensively recovering metal elements in tungsten-doped ternary precursor waste. The method mainly comprises the following steps: carrying out primary acid leaching on the tungsten-doped ternary precursor waste and an acid solution to obtain primary acid leaching solution and primary acid leaching residue containing nickel, cobalt and manganese elements; in the presence of a reducing agent, carrying out second-stage reduction acid leaching on the first-stage acid leaching residue and the acid solution to obtain second-stage acid leaching solution and second-stage acid leaching residue; and adjusting the pH value of the second-stage pickle liquor, filtering, and adsorbing and recovering tungsten elements in the filtrate by using weak-base anion exchange resin to obtain a sodium tungstate product and an adsorbed solution containing nickel, cobalt and manganese elements. The method has the advantages of simple process, convenient operation and low cost, and ensures that the recovery rates of nickel, cobalt, manganese and tungsten elements in the tungsten-doped ternary precursor waste are all over 99 percent.
Description
Technical Field
The invention relates to the technical field of battery waste recovery, in particular to a method for comprehensively recovering metal elements in tungsten-doped ternary precursor waste.
Background
At present, a nickel-cobalt-manganese ternary material has become one of the main anode materials of a lithium ion battery, and is widely applied to electric vehicles, electric bicycles, high-power batteries, medium and low-grade mobile phones and notebook computers.
The precursor product of the ternary composite anode material takes nickel salt, cobalt salt and manganese salt as raw materials, wherein the content ratio (x: y: z) of nickel, cobalt and manganese elements can be adjusted according to actual needs.
In order to improve the electrochemical performance of the cathode material, the precursor is often doped and modified by using elements such as magnesium, aluminum, zirconium, tungsten and the like. During the process of producing the tungsten-doped ternary precursor, tungsten-doped ternary waste materials such as unqualified tungsten-doped centrifugal materials, tungsten-doped slurry tank materials, tungsten-doped sintering materials, tungsten-doped drying materials, ground reclaimed materials and the like can be generated. The nickel element, the cobalt element and the manganese element in the tungsten-doped nickel-cobalt-manganese ternary precursor waste are high in content, and the tungsten-doped ternary precursor waste is directly treated by adopting a reduction acid leaching method, so that the tungsten element is difficult to separate from the nickel element, the cobalt element and the manganese element in the later period, the recovery rates of the nickel element, the cobalt element, the manganese element and the tungsten element are low, and the nickel element, the cobalt element, the manganese element and the tungsten element are not effectively recovered.
However, the method of directly leaching with alkali to obtain tungsten element with high recovery rate consumes a large amount of alkali, which not only has high treatment cost, but also cannot completely separate and purify tungsten from other metal elements, so that the added value of nickel, cobalt, manganese and tungsten metal element products is low.
CN108199106A discloses a recovery process of waste in a nickel-cobalt-manganese ternary precursor production process, which comprises the steps of firstly carrying out acid-soluble reaction on the nickel-cobalt-manganese ternary precursor waste by utilizing a sulfuric acid solution, then carrying out oxidation-reduction reaction on valuable metal active sulfide recovered from a nickel-cobalt-manganese ternary precursor precipitation mother solution and acid-insoluble partial oxide in the nickel-cobalt-manganese ternary precursor waste by utilizing the reducibility of the valuable metal active sulfide, thereby achieving the purpose of recovery. However, the scheme only relates to the recycling of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary precursor waste, and the recycling rates of the nickel, cobalt and manganese are low, so that the comprehensive recycling of metal elements in the tungsten-doped ternary precursor waste cannot be realized through the scheme.
CN110607439A discloses a spherical nickel protoxide segmented oxidation acid leaching treatment method, which comprises the steps of carrying out two-stage countercurrent oxidation acid leaching on mechanically activated nickel protoxide to obtain a nickel leaching solution, taking nickel-cobalt-manganese ternary precursor waste as a raw material for consuming residual acid, and using the leaching solution after acid consumption for synthesizing a ternary precursor, preparing a high-purity nickel plate, nickel sulfate, nickel chloride crystals and the like. However, the technical solution disclosed in the prior art does not relate to the recovery rates of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary precursor waste, and the solution cannot realize comprehensive recovery and utilization of metal elements in the tungsten-doped ternary precursor waste.
Therefore, the method for treating the tungsten-doped ternary precursor waste material, which is simple in process, low in cost and high in metal element recovery rate, has important practical significance.
Disclosure of Invention
The invention aims to overcome the defects that the comprehensive recovery of nickel, cobalt, manganese and tungsten elements in the tungsten-doped ternary precursor waste cannot be realized or the recovery rate is low and the separation of the tungsten elements from the nickel, cobalt and manganese elements is difficult in the prior art.
In order to achieve the purpose, the invention provides a method for comprehensively recovering metal elements in tungsten-doped ternary precursor waste, which comprises the following steps:
(1) Carrying out primary acid leaching on the tungsten-doped ternary precursor waste and a first sulfuric acid solution to obtain a primary acid leaching solution I and a primary acid leaching residue;
(2) In the presence of a reducing agent, performing second-stage acid leaching on the first-stage acid leaching residue and a second sulfuric acid solution to obtain a second-stage acid leaching solution I and a second-stage acid leaching residue;
(3) Adjusting the pH value of the second-stage acid leaching solution I to 2-6 by using an alkaline substance I to obtain a second-stage acid leaching solution II, and then filtering the second-stage acid leaching solution II to obtain a second-stage acid leaching solution III;
(4) Selectively adsorbing and recovering the tungsten element in the second-stage pickle liquor III by using ion exchange resin to obtain adsorbed liquor I and ion exchange resin loaded with the tungsten element;
(5) Contacting the ion exchange resin loaded with the tungsten element with an analytic solution to obtain a sodium tungstate solution through analysis;
the method further comprises the following steps: and recycling residual elements contained in the first-stage acid leaching solution I and the adsorbed solution I, wherein the residual elements contained in the first-stage acid leaching solution I and the adsorbed solution I are respectively and independently selected from at least one of nickel element, cobalt element and manganese element.
The invention has at least the following advantages:
(1) The method for comprehensively recovering the metal elements in the tungsten-doped ternary precursor waste can realize the effective separation of three elements of nickel, cobalt and manganese and the tungsten element;
(2) The method for comprehensively recovering the metal elements in the tungsten-doped ternary precursor waste can ensure that the recovery rates of the nickel, the cobalt, the manganese and the tungsten are all over 99 percent;
(3) The method for comprehensively recovering the metal elements in the tungsten-doped ternary precursor waste has the advantages of simple process, convenience in operation and low cost, and has strong practicability and high economic value.
Drawings
FIG. 1 is a flow chart of a treatment process of tungsten-doped ternary precursor waste.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the present invention provides a method for comprehensively recovering metal elements from tungsten-doped ternary precursor waste, comprising the following steps:
(1) Carrying out primary acid leaching on the tungsten-doped ternary precursor waste and a first sulfuric acid solution to obtain a primary acid leaching solution I and primary acid leaching slag;
(2) In the presence of a reducing agent, performing second-stage acid leaching on the first-stage acid leaching residue and a second sulfuric acid solution to obtain a second-stage acid leaching solution I and a second-stage acid leaching residue;
(3) Adjusting the pH value of the second-stage acid leaching solution I to 2-6 by using an alkaline substance I to obtain a second-stage acid leaching solution II, and then filtering the second-stage acid leaching solution II to obtain a second-stage acid leaching solution III;
(4) Selectively adsorbing and recovering the tungsten element in the second-stage pickle liquor III by using ion exchange resin to obtain adsorbed liquor I and ion exchange resin loaded with the tungsten element;
(5) Contacting the ion exchange resin loaded with the tungsten element with an analytic solution to obtain a sodium tungstate solution;
the method further comprises the following steps: and recycling residual elements contained in the first-stage acid leaching solution I and the adsorbed solution I, wherein the residual elements contained in the first-stage acid leaching solution I and the adsorbed solution I are respectively and independently selected from at least one of nickel element, cobalt element and manganese element.
In particular, in the step (3), the secondary acid leaching solution II is a solid-liquid mixture containing a small amount of solid particles or colloids.
Preferably, the method further comprises: adjusting the pH value of the primary pickle liquor I to 2-6 by using an alkaline substance II to obtain a primary pickle liquor II, and filtering the primary pickle liquor II to obtain a feed liquor I containing nickel, cobalt and manganese; and (3) using the feed liquid I as a raw material for producing the ternary precursor of nickel, cobalt and manganese for recycling.
Preferably, the method further comprises: and adjusting the pH value of the post-adsorption solution I to 2-6 by using an alkaline substance III to obtain a post-adsorption solution II, concentrating the post-adsorption solution II to obtain a feed liquid II, and using the feed liquid II as a raw material for producing a nickel, cobalt and manganese ternary precursor for recycling.
Preferably, the concentration condition is controlled so that the sum of the mass concentrations of the nickel element, the cobalt element and the manganese element in the feed liquid II is more than or equal to 110g/L.
Preferably, the basic substance I, the basic substance II and the basic substance III according to the present invention are the same or different and each is independently selected from at least one of NaOH solution, ammonia water and KOH solution.
The concentration of the alkaline substance I used in the invention is not particularly required, as long as the secondary pickle liquor I can be adjusted to reach the specified pH value, and the alkaline substance I is a 30wt% NaOH solution.
The concentration of the alkaline substance II used in the invention is not particularly required, as long as the primary pickle liquor I can be adjusted to reach the specified pH value, and the alkaline substance II is ammonia water with the concentration of 25-28wt% as an example.
The concentration of the alkaline substance III used in the present invention is not particularly limited as long as the post-adsorption solution I can be adjusted to reach a specified pH value, and a KOH solution with a concentration of 30wt% is used as the alkaline substance III.
Preferably, in the step (1), the water content in the tungsten-doped ternary precursor waste is 0.2-25wt%.
Preferably, in the step (1), the content of nickel element, the content of cobalt element, the content of manganese element and the content of tungsten element in the tungsten-doped ternary precursor waste material are respectively 20-75wt%, 0.3-15wt%, 0.1-22wt% and 0.05-0.5wt% on a dry basis.
Preferably, in step (1), the concentration of the first sulfuric acid solution is 20 to 35wt%.
Preferably, in step (1), the conditions of the primary acid leaching are controlled so that the pH value of the primary acid leaching solution I is 0-3.
Preferably, in step (1), the conditions of the primary acid leaching are satisfied: the leaching temperature is 40-94 ℃, and the leaching time is 0.5-4h. More preferably, in the step (1), the conditions of the one-stage acid leaching satisfy: the leaching temperature is 70-90 ℃, and the leaching time is 1-2h.
Preferably, in the step (1), the concentration of the first sulfuric acid solution is controlled to be 20-35wt%, and the amount of the first sulfuric acid solution used is 3-6mL per 1g of the tungsten-doped ternary precursor waste.
Preferably, in step (2), the concentration of the second sulfuric acid solution is 5 to 15wt%.
Preferably, in the step (2), the conditions of the secondary acid leaching are controlled so that the pH value of the obtained secondary acid leaching solution I is 0-3.
Preferably, in step (2), the conditions of the secondary acid leaching include: the leaching temperature is 40-94 ℃, and the leaching time is 0.5-3h. More preferably, in the step (2), the conditions of the two-stage acid leaching satisfy: the leaching temperature is 70-90 ℃, and the leaching time is 1-2h.
Preferably, in the step (2), the concentration of the second sulfuric acid solution is controlled to be 5 to 15wt%, and the amount of the second sulfuric acid solution is 4 to 9mL per 1g of the primary acid-leached residue.
Preferably, in step (2), the reducing agent is selected from at least one of hydrogen peroxide, sodium sulfite, ammonium sulfite, sodium thiosulfate and sodium metabisulfite.
Preferably, in the step (2), the amount of the reducing agent is 3-9g per 100g of the tungsten-doped ternary precursor waste. More preferably, in the step (2), the amount of the reducing agent is 3.6-6.5g per 100g of the tungsten-doped ternary precursor waste.
Preferably, in step (4), the ion exchange resin is a weakly basic anion exchange resin. More preferably, the weakly basic anion exchange resin is selected from at least one of D363, D354 and LSC-486.
In the invention, D363, D354 and LSC-486 represent the types of the weak base anion exchange resin, the D363 represents macroporous acrylic acid series weak base anion resin, the D354 represents macroporous polystyrene weak base anion resin, and the LSC-486 represents macroporous acrylic acid series weak base anion resin.
Particularly preferably, in step (4), the weakly basic anion exchange resin is an LSC-486 resin. The inventor finds that under the preferable condition, the method can further improve the recovery rate of nickel, cobalt, manganese and tungsten elements in the tungsten-doped ternary precursor waste.
Preferably, in the step (4), the conditions for selective adsorption recovery are controlled so that the mass concentration of the tungsten element in the post-adsorption solution I is less than 1mg/L.
Preferably, in the step (5), the resolving solution is a 1-3mol/L NaOH solution.
It should be noted that the method for selective adsorption recovery in step (4) and the method for desorption preferably using 1 to 3mol/L NaOH solution as a desorption solution in step (5) are not particularly limited, and those skilled in the art can perform the method according to the conventional techniques known in the art, and the person skilled in the art should not be construed as limiting the present invention.
In order to achieve higher recovery rate of tungsten element, the invention provides a preferable specific method for selective adsorption recovery and desorption, and the method for selective adsorption recovery and desorption comprises the following steps:
s1: introducing the second-stage leachate III into a single-stage ion exchange resin column filled with LSC-486 weak base anion exchange resin at the speed of 120-360mL/h to perform adsorption reaction to obtain an adsorbed solution I and LSC-486 weak base anion exchange resin I loaded with tungsten element;
s2: introducing water into the single-stage ion exchange resin column of the tungsten element-loaded LSC-486 weakly basic anion exchange resin I obtained in step S1 at a rate of 120-240mL/h to obtain a washing liquid and a tungsten element-loaded LSC-486 weakly basic anion exchange resin II;
s3: and (3) introducing 1-3mol/L NaOH solution into the single-stage ion exchange resin column of the LSC-486 weak base anion exchange resin II loaded with the tungsten element obtained in the step (S2) at the speed of 120-180mL/h to obtain the sodium tungstate solution.
Preferably, the single-stage ion exchange resin column has a height of 15-30cm and a diameter of 2-3cm.
Preferably, in step S1, the conditions of the adsorption reaction satisfy: the adsorption time is 0.5-7h, and the adsorption temperature is 20-40 ℃.
Preferably, in step S2, for every 100cm 3 The amount of the water used in the single-stage ion exchange resin column is 120-300mL.
Preferably, in step S3, for every 100cm 3 The dosage of the 1-3mol/L NaOH solution is 230-450mL.
Preferably, in step (5), the method further comprises: and concentrating, crystallizing, centrifuging and drying the sodium tungstate solution in sequence to obtain a sodium tungstate product.
It should be noted that the manner of filtration, concentration, crystallization, centrifugation and drying described in the foregoing is not particularly limited by the present invention, and those skilled in the art can select the filtration, concentration, crystallization, centrifugation and drying according to the techniques known in the art, and the present invention will not be described in detail herein, and those skilled in the art should not be construed as limiting the present invention.
The present invention will be described in detail below by way of examples.
95wt% concentrated sulfuric acid: purchased from kyotong chemicals, ltd.
Hydrogen peroxide: purchased from the national pharmaceutical group chemical agents limited.
LSC-486 weakly basic anion exchange resin: available from seian blue, am, science and technology materials, ltd.
D354 weakly basic anion exchange resin: purchased from Jining Binyi chemical Co., ltd.
D363 weak base anion exchange resin: purchased from Anhui tree chemical sales, inc., anhui, inc.
A precision filter: the model is LFD-1-1P, and the manufacturer is Li Feier Tefilter GmbH in Xinxiang city.
The tungsten-doped ternary precursor waste I (source: hunan Zhongwei New energy science and technology Co., ltd.) consists of: the water content is 15.81wt%, and the content of nickel element, the content of cobalt element, the content of manganese element and the content of tungsten element in the tungsten-doped ternary precursor waste I are respectively 44.77wt%, 4.49wt%, 3.25wt% and 0.079wt% in terms of metal elements on a dry basis.
The tungsten-doped ternary precursor waste II (source: hunan Zhongwei New energy science and technology Co., ltd.) consists of: the water content is 0.48wt%, and the content of nickel element, the content of cobalt element, the content of manganese element and the content of tungsten element in the tungsten-doped ternary precursor waste I are respectively 54.63wt%, 2.45wt%, 3.18wt% and 0.146wt% in terms of metal elements on a dry basis.
The recovery of the metal elements referred to in the following examples is calculated by the formula:
the recovery rate of nickel element (%) = 1-nickel element content in two-stage acid leaching residue/nickel element content in tungsten-doped ternary precursor waste material x 100%;
the recovery rate of the cobalt element (%) = 1-cobalt element content in the two-stage acid leaching residue/cobalt element content in the tungsten-doped ternary precursor waste material is multiplied by 100%;
the recovery rate of manganese element (%) = 1-manganese element content in two-stage acid leaching residue/manganese element content in tungsten-doped ternary precursor waste material is multiplied by 100%;
the recovery rate of tungsten element (%) =1- (the content of tungsten element in the solution I after adsorption and the content of tungsten element in the two-stage acid leaching residue)/the content of tungsten element in the tungsten-doped ternary precursor waste material is multiplied by 100%;
the unit of the contents of nickel, cobalt, manganese and tungsten elements in the above calculation formula is g.
Determining the content of nickel element in the second-stage acid leaching residue by adopting an ICP method after digestion;
determining the content of cobalt element in the second-stage acid leaching residue by adopting an ICP (inductively coupled plasma) method after digestion;
determining the content of manganese element in the second-stage acid leaching residue by adopting an ICP method after digestion;
determining the content of tungsten element in the second-stage acid leaching residue by adopting an ICP method after digestion;
the content of nickel element in the tungsten-doped ternary precursor waste is determined by adopting a dimethylglyoxime-EDTA complexation titration method;
determining the content of cobalt element in the tungsten-doped ternary precursor waste by a post-digestion ICP method;
determining the content of manganese element in the tungsten-doped ternary precursor waste by a post-digestion ICP method;
determining the content of tungsten element in the tungsten-doped ternary precursor waste by a digested ICP (inductively coupled plasma) method;
and measuring the content of the tungsten element in the adsorbed liquid I by adopting an ICP method.
Example 1
(1) Carrying out primary acid leaching on the tungsten-doped ternary precursor waste I and a first sulfuric acid solution to obtain primary acid leaching solution I and primary acid leaching residue;
(2) Carrying out second-stage acid leaching on all the obtained first-stage acid leaching residues, the reducing agent and the second sulfuric acid solution to obtain second-stage acid leaching solution I and second-stage acid leaching residues;
(3) Adjusting the pH value of the second-stage acid leaching solution I by using a NaOH solution with the concentration of 30wt% to obtain a second-stage acid leaching solution II, and filtering by using a precision filter to obtain a second-stage acid leaching solution III with solid particles smaller than 15 mu m;
(4) Selectively adsorbing and recovering the tungsten element in the second-stage pickle liquor III by using weak-base anion exchange resin to obtain adsorbed liquor I and weak-base anion exchange resin II loaded with the tungsten element;
the selective adsorption recovery method comprises the following steps:
s1: introducing the second-stage leachate III into a single-stage ion exchange resin column filled with a weak base anion exchange resin to perform adsorption reaction to obtain an adsorbed solution I and a tungsten element-loaded weak base anion exchange resin I;
s2: introducing water into the single-stage ion exchange resin column of the tungsten element-loaded weak base anion exchange resin I obtained in the step S1 to obtain a washing liquid and a tungsten element-loaded weak base anion exchange resin II;
(5) Introducing a NaOH solution into the single-stage ion exchange resin column of the tungsten element-loaded weak-base anion exchange resin II obtained in the step S2 to obtain a sodium tungstate solution;
(6) Sequentially concentrating, crystallizing, centrifuging and drying the sodium tungstate solution to obtain a sodium tungstate product;
(7) Adjusting the pH value of the first-stage acid leaching solution I by using a NaOH solution with the concentration of 30wt% to obtain a first-stage acid leaching solution II, filtering the first-stage acid leaching solution II by using a precision filter to obtain a feed liquid I containing nickel, cobalt and manganese, wherein the solid particles of the nickel, cobalt and manganese are smaller than 15 microns, and recycling the feed liquid I as a raw material for producing a nickel, cobalt and manganese ternary precursor; and the number of the first and second groups,
adjusting the pH value of the post-adsorption solution I by using a NaOH solution with the concentration of 30wt% to obtain a post-adsorption solution II, concentrating the post-adsorption solution II to obtain a feed liquid II containing nickel elements, cobalt elements and manganese elements, and recycling the feed liquid II as a raw material for producing a nickel, cobalt and manganese ternary precursor;
the sum of the mass concentrations of the nickel element, the cobalt element and the manganese element in the feed liquid II is 110g/L.
See table 1 for other specific parameters related in this example;
the recovery of the metal elements in this example is shown in table 2.
Example 2
This example was carried out using a similar procedure to example 1, except that in this example: the types of materials and process parameters used are different and are shown in table 1.
The recovery of the metal elements in this example is shown in table 2.
Example 3
This example was carried out using a similar procedure to example 1, except that in this example: the types of materials and process parameters used are different and are shown in table 1.
The recovery of the metal elements in this example is shown in table 2.
Example 4
This example was carried out using a similar procedure to example 1, except that in this example:
the amount of the reducing agent is 3.5g per 100g of the tungsten-doped ternary precursor waste I.
The rest is the same as in example 1.
See table 1 for other specific parameters related in this example;
the recovery of the metal elements in this example is shown in table 2.
Example 5
This example was carried out using a similar procedure to example 1, except that in this example:
the resin used in the selective adsorption recovery process is D363 weak base anion exchange resin.
The rest is the same as in example 1.
See table 1 for other specific parameters related in this example;
the recovery of the metal elements in this example is shown in table 2.
Comparative example 1
The metal elements in the tungsten-doped ternary precursor waste are recovered by adopting a one-stage acid leaching method.
(1) Carrying out primary acid leaching on the tungsten-doped ternary precursor waste I and a first sulfuric acid solution to obtain primary acid leaching solution I and primary acid leaching residue;
(2) And (2) adjusting the pH value of the first-stage acid leaching solution I by using a NaOH solution with the concentration of 30wt% to obtain a first-stage acid leaching solution II, filtering the first-stage acid leaching solution II by using a precision filter to obtain a feed liquid containing nickel elements, cobalt elements and manganese elements and solid particles with the particle size of less than 15 micrometers, and recycling the feed liquid as a raw material for producing a nickel, cobalt and manganese ternary precursor.
The remaining specific parameters referred to in this comparative example are shown in table 1;
the recovery rates of the metal elements in the comparative examples are shown in Table 2.
Comparative example 2
The method combines the first-stage reduction acid leaching and the adsorption recovery of the tungsten element by the ion exchange resin to recover the metal element in the tungsten-doped ternary precursor waste.
(1) Carrying out primary acid leaching on the tungsten-doped ternary precursor waste I, hydrogen peroxide and a first sulfuric acid solution to obtain primary acid leaching solution I and primary acid leaching residue;
(2) Adjusting the pH value of the first-stage acid leaching solution I by using a NaOH solution with the concentration of 30wt% to obtain a first-stage acid leaching solution II, and filtering by using a precision filter to obtain a first-stage acid leaching solution III with solid particles smaller than 15 mu m;
(3) Selectively adsorbing and recovering the tungsten element in the first-stage pickle liquor III by using weak-base anion exchange resin to obtain adsorbed liquor I and weak-base anion exchange resin II loaded with the tungsten element;
the selective adsorption recovery method comprises the following steps:
s1: introducing the first-stage leachate III into a single-stage ion exchange resin column filled with weakly basic anion exchange resin to perform adsorption reaction to obtain an adsorbed solution I and a tungsten element-loaded weakly basic anion exchange resin I;
s2: introducing water into the single-stage ion exchange resin column of the tungsten element-loaded weak base anion exchange resin I obtained in the step S1 to obtain a washing liquid and a tungsten element-loaded weak base anion exchange resin II;
(4) Introducing a NaOH solution into the single-stage ion exchange resin column of the tungsten element-loaded weak-base anion exchange resin II obtained in the step S2 to obtain a sodium tungstate solution;
(5) Sequentially concentrating, crystallizing, centrifuging and drying the sodium tungstate solution to obtain a sodium tungstate product;
(6) With H at a concentration of 5% by weight 2 SO 4 Adjusting the pH value of the post-adsorption solution I by using the solution to obtain a post-adsorption solution II, and concentrating the post-adsorption solution II to obtain the solution containing nickelThe method comprises the following steps of taking feed liquid of elements, cobalt elements and manganese elements as raw materials for producing the nickel, cobalt and manganese ternary precursor for recycling.
The remaining specific parameters referred to in this comparative example are shown in table 1;
the recovery rates of the metal elements in the comparative examples are shown in Table 2.
Comparative example 3
This comparative example was carried out using a similar procedure to example 1, except that in this comparative example: the pH of the secondary pickle liquor II was adjusted to 1, and the rest was the same as in example 1.
The recovery rates of the metal elements in the comparative examples are shown in Table 2.
TABLE 1
The recovery rates of the metal elements in the tungsten-doped ternary precursor waste are shown in table 2.
TABLE 2
In conclusion, the method for comprehensively recovering the metal elements in the tungsten-doped ternary precursor waste material can ensure that the recovery rates of the nickel element, the manganese element, the cobalt element and the tungsten element are all over 99 percent, and the method provided by the invention can also greatly reduce the consumption of the reducing agent, reduce the adsorption time and has important significance for reducing the production cost, saving the resources and improving the production efficiency.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A method for comprehensively recovering metal elements in tungsten-doped ternary precursor waste is characterized by comprising the following steps:
(1) Carrying out primary acid leaching on the tungsten-doped ternary precursor waste and a first sulfuric acid solution to obtain a primary acid leaching solution I and a primary acid leaching residue;
(2) In the presence of a reducing agent, performing second-stage acid leaching on the first-stage acid leaching residue and a second sulfuric acid solution to obtain a second-stage acid leaching solution I and a second-stage acid leaching residue;
(3) Adjusting the pH value of the second-stage acid leaching solution I to 2-6 by using an alkaline substance I to obtain a second-stage acid leaching solution II, and then filtering the second-stage acid leaching solution II to obtain a second-stage acid leaching solution III;
(4) Selectively adsorbing and recovering the tungsten element in the second-stage pickle liquor III by using ion exchange resin to obtain adsorbed liquor I and ion exchange resin loaded with the tungsten element;
(5) Contacting the ion exchange resin loaded with the tungsten element with an analytic solution to obtain a sodium tungstate solution through analysis;
the method further comprises the following steps: and recycling residual elements contained in the first-stage acid leaching solution I and the adsorbed solution I, wherein the residual elements contained in the first-stage acid leaching solution I and the adsorbed solution I are respectively and independently selected from at least one of nickel element, cobalt element and manganese element.
2. The process according to claim 1, wherein in step (1), the conditions of the primary acid leach are controlled such that the pH of the primary acid leach solution I obtained is in the range of 0-3; and/or the presence of a gas in the gas,
the conditions of the first-stage acid leaching are as follows: the leaching temperature is 40-94 ℃, and the leaching time is 0.5-4h.
3. The process according to claim 1 or 2, wherein in step (2), the conditions of the secondary acid leach are controlled such that the obtained secondary acid leach solution I has a pH value between 0 and 3; and/or the presence of a gas in the gas,
the conditions of the two-stage acid leaching comprise: the leaching temperature is 40-94 ℃, and the leaching time is 0.5-3h.
4. The method according to any one of claims 1 to 3, wherein, in step (2), the reducing agent is used in an amount of 3 to 9g per 100g of the tungsten-doped ternary precursor waste.
5. The method according to any one of claims 1 to 4, wherein, in step (2), the reducing agent is selected from at least one of hydrogen peroxide, sodium sulfite, ammonium sulfite, sodium thiosulfate and sodium metabisulfite.
6. The process according to any one of claims 1 to 5, wherein, in step (4), the ion exchange resin is a weakly basic anion exchange resin;
preferably, the weakly basic anion exchange resin is selected from at least one of D363, D354 and LSC-486.
7. The method according to any one of claims 1 to 6, wherein in the step (4), the conditions of the selective adsorption recovery are controlled so that the mass concentration of the tungsten element in the post-adsorption solution I is less than 1mg/L.
8. The method according to any one of claims 1 to 7, wherein in step (5), the resolving liquid is a 1-3mol/L NaOH solution.
9. The method according to any one of claims 1-8, wherein the method further comprises: and (5) sequentially concentrating, crystallizing, centrifuging and drying the sodium tungstate solution obtained in the step (5) to obtain a sodium tungstate product.
10. The method according to any one of claims 1-9, wherein the method further comprises: adjusting the pH value of the primary pickle liquor I to 2-6 by using an alkaline substance II to obtain a primary pickle liquor II, and filtering the primary pickle liquor II to obtain a feed liquor I containing nickel, cobalt and manganese; and then the feed liquid I is used as a raw material for producing a ternary precursor of nickel, cobalt and manganese so as to realize the recycling.
11. The method according to any one of claims 1-10, wherein the method further comprises: and adjusting the pH value of the post-adsorption solution I to 2-6 by using an alkaline substance III to obtain a post-adsorption solution II, concentrating the post-adsorption solution II to obtain a feed liquid II, and then using the feed liquid II as a raw material for producing a nickel, cobalt and manganese ternary precursor to realize the recycling.
12. The method according to claim 11, wherein the concentration condition is controlled so that the sum of the mass concentrations of the nickel element, the cobalt element and the manganese element in the feed liquid II is more than or equal to 110g/L.
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