CN111979418B - Treatment method of nickel-cobalt-manganese ternary waste - Google Patents
Treatment method of nickel-cobalt-manganese ternary waste Download PDFInfo
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Abstract
The invention provides a method for treating nickel-cobalt-manganese ternary waste. The treatment method of the nickel-cobalt-manganese ternary waste material comprises the following steps: pretreating the nickel-cobalt-manganese ternary waste to obtain a pretreatment solution, extracting by using an extracting agent, and separating to obtain a first organic phase and a first water phase; washing the first organic phase by using materials including the first acid solution, and separating to obtain a second organic phase and a second water phase; carrying out first back extraction on the second organic phase by using materials including the second acid solution, and separating to obtain a third organic phase and a third water phase; and removing oil from the third aqueous phase to obtain a nickel-cobalt-manganese solution. The application provides a processing method of nickel cobalt manganese ternary waste material, impurity in can effectively getting rid of the waste material and the impurity that introduces in the processing procedure, obtain nickel cobalt manganese solution and copper solution that accord with the requirement.
Description
Technical Field
The invention relates to the field of hydrometallurgy, in particular to a treatment method of nickel, cobalt and manganese ternary waste.
Background
The ternary nickel, cobalt and manganese precursor is a positive electrode material of the ternary battery, and with the rapid development of the lithium battery industry, the demand for the high-purity nickel-cobalt-manganese precursor is increasing. In the production process of preparing the ternary nickel-cobalt-manganese precursor, the lithium battery anode material enterprise has waste materials with calcium, magnesium, copper and iron impurities exceeding the standard caused by process pollution, and the waste materials need to be purified and recycled.
In view of this, the present application is specifically made.
Disclosure of Invention
The invention aims to provide a method for treating nickel-cobalt-manganese ternary waste to solve the problems.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a treatment method of nickel-cobalt-manganese ternary waste comprises the following steps:
pretreating the nickel-cobalt-manganese ternary waste to obtain a pretreatment solution, extracting by using an extracting agent, and separating to obtain a first organic phase and a first water phase;
washing the first organic phase by using materials including a first acid solution, and separating to obtain a second organic phase and a second water phase;
carrying out first back extraction on the second organic phase by using materials including a second acid solution, and separating to obtain a third organic phase and a third water phase;
and removing oil from the third aqueous phase to obtain a nickel-cobalt-manganese solution.
Preferably, the pre-treatment comprises: removing iron, calcium and magnesium from the nickel-cobalt-manganese ternary waste to obtain the pretreatment solution;
preferably, the pH value of the pretreatment liquid is 6-7.
In general, the pretreatment solution can be obtained by removing iron by oxidation or alkali addition, or removing calcium and magnesium ions by fluoride, depending on the impurities in the waste. By controlling the pH value of the pretreatment liquid to be 6-7, nickel ions, cobalt ions, manganese ions and copper ions can enter the extractant, and the phase separation efficiency and the extraction rate are improved.
Preferably, the extractant comprises a saponified Mextral V10 extractant.
The extraction agent Mextral V10 after saponification can extract nickel-cobalt-manganese-copper ions into an organic phase through the exchange between sodium ions contained in the extraction agent after saponification and nickel-cobalt-manganese-copper ions, so that most of fluoride ions are left in a water phase, and the separation effect of the extraction agent is better than that of other extraction agents.
Alternatively, the pH of the pretreatment solution may be any one of 6, 6.5, 7, and 6 to 7.
Preferably, the extraction is performed in a multi-stage countercurrent mode;
preferably, the number of stages of extraction is 8-12;
preferably, the volume ratio of the organic phase to the aqueous phase in each stage of extraction is independently (0.5-2): 1.
the extraction is carried out by adopting a multi-stage countercurrent mode, and the extraction stage number and the volume ratio of the organic phase to the water phase are controlled, so that nickel, cobalt, manganese and copper metal ions can enter the extracting agent to the greatest extent, the loss of nickel, cobalt and manganese is reduced, and the yield of valuable metals is improved.
Alternatively, the number of stages of extraction may be any of 8 stages, 9 stages, 10 stages, 11 stages, or 12 stages; the volume ratio of the organic phase to the aqueous phase in each stage independently may be 0.5: 1. 1: 1. 1.5: 1. 2: 1 and (0.5-2): 1, or any value between.
Preferably, the first acid solution comprises an aqueous sulfuric acid solution;
preferably, the concentration of the sulfuric acid aqueous solution is 0.2-1 mol/L;
preferably, the washing is performed in a multi-stage countercurrent mode;
preferably, the number of washing stages is 4 to 7 stages.
Controlling the acid concentration and the number of washing stages reduces the amount of metal ions that enter the aqueous phase during washing (as much as possible to minimize back-extraction).
Alternatively, the concentration of the aqueous sulfuric acid solution may be any value between 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1.0mol/L, and 0.2-1 mol/L; the number of washing stages may be 4 stages, 5 stages, 6 stages, or 7 stages.
Preferably, the second acid solution comprises an aqueous sulfuric acid solution;
preferably, the concentration of the second acid solution is 1-3 mol/L;
preferably, the first stripping is performed in a multi-stage countercurrent mode;
preferably, the first stripping has 7-13 stages;
preferably, the second acid solution is fed from the 2 nd to last, 4 th to last and 6 th to last stages;
preferably, the pH of the third aqueous phase is between 3.5 and 5.
The concentration of the second acid solution, the number of stages of the first stripping, was optimized to allow as much nickel cobalt manganese to enter the aqueous phase as possible. The sulfuric acid is divided into three times to be respectively back-extracted by the penultimate 2-stage, penultimate 4-stage and penultimate 6-stage feeding materials, so that the phenomenon that the sulfuric acid concentration is too high and the acidity is too strong due to one-time feeding of the sulfuric acid can be avoided, and copper ions are back-extracted to a water phase.
Alternatively, the concentration of the second acid solution may be any value between 1mol/L, 2mol/L, 3mol/L, and 1-3 mol/L; the first stripping may be in stages of 7, 8, 9, 10, 11, 12, or 13; the pH of the third aqueous phase may be any of 3.5, 4, 4.5, 5 and 3.5-5.
Preferably, the processing method further comprises:
performing second back extraction on the third organic phase by using materials including a third acid solution, and separating to obtain a fourth organic phase and a fourth aqueous phase;
and removing oil from the fourth aqueous phase to obtain a copper solution.
The purpose of the second back extraction is to obtain a solution containing copper ions, so that the full utilization of materials is realized.
Preferably, the third acid solution comprises an aqueous sulfuric acid solution;
preferably, the concentration of the third acid solution is 1-3 mol/L;
preferably, the second stripping is performed in a multi-stage countercurrent mode;
preferably, the second stripping has 2-8 stages;
preferably, the pH of the fourth aqueous phase is 5.5 to 7.
The optimization of the concentration of the third acid solution, the back extraction by adopting a multi-stage countercurrent mode and the limitation of the pH value of the water phase are both used for improving the extraction efficiency of the copper ions and reducing the process cost.
Alternatively, the concentration of the third acid solution may be any value between 1mol/L, 2mol/L, 3mol/L, and 1-3 mol/L; the second stripping may have 2, 3, 4, 5, 6, 7 or 8 stages; the pH of the fourth aqueous phase may be any of 5.5, 6, 6.5, 7 and between 5.5 and 7.
Preferably, the degreasing is performed using activated carbon.
The residual oil (organic phase) in the water phase is removed by using the adsorption performance of the activated carbon, and most TOC is also removed.
Preferably, the treatment method further comprises the step of performing TOC removal treatment on the nickel-cobalt-manganese solution;
preferably, the TOC removal treatment uses resin removal;
preferably, the pH value of the nickel-cobalt-manganese solution is adjusted to 1-4 before the TOC removal treatment;
preferably, the flow rate of the nickel-cobalt-manganese solution into the resin is 3-8 BV/h.
The risk that TOC exceeds the standard still exists in the nickel-cobalt-manganese solution obtained through oil removal, and the TOC is adsorbed and removed by using resin to obtain a qualified nickel-cobalt-manganese solution; the AF5 resin was removed most effectively.
Optionally, the pH value of the nickel-cobalt-manganese solution before the TOC removal treatment can be any value between 1, 2, 3, 4 and 1-4; the flow rate of the nickel-cobalt-manganese solution into the resin can be any value of 3BV/h, 4BV/h, 5BV/h, 6BV/h, 7BV/h, 8BV/h and 3-8 BV/h.
Compared with the prior art, the invention has the beneficial effects that:
according to the treatment method of the nickel-cobalt-manganese ternary waste, the nickel-cobalt-manganese ternary waste is pretreated, and nickel-cobalt-manganese-copper ions are extracted to an organic phase by using an extracting agent; washing with acid solution to separate impurity element ions such as fluorine ions and sodium ions into water phase; extracting nickel, cobalt and manganese ions into a water phase through first back extraction, and reserving copper ions in an organic phase to obtain a nickel, cobalt and manganese solution; the method is simple to operate, and can effectively separate impurities in the waste material and impurities introduced in the pretreatment to obtain the nickel-cobalt-manganese solution with high purity and good quality.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
Embodiments of the present invention will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
First, some of the reagents used in the examples of the present application will be described:
extraction agent Mextral V10, all named: 2-B2, 5-dimethylhexanoic acid, formula C 10 H 20 O 2 The molecular structural formula is as follows:
AF5 resin was purchased from Langsheng chemical (China) Co.
Example 1
The embodiment provides a method for treating nickel-cobalt-manganese ternary waste, wherein the ternary waste contains impurities such as iron, calcium, magnesium, copper and the like; oxidizing the ternary waste, adding alkali to precipitate to remove aluminum and iron, filtering, and removing calcium and magnesium by using fluoride to obtain a pretreatment solution.
The chemical composition of the pretreatment solution is shown in the following table 1:
TABLE 1 chemical composition of pretreatment solution
And (3) extraction:
using the saponified Mextral V10 extractant, the organic and aqueous phases 1: performing 10-stage countercurrent extraction on the phase ratio (volume ratio) of 1, and separating to obtain a first organic phase and a first water phase;
washing:
carrying out 6-stage countercurrent washing on the first organic phase by adopting 0.5mol/L sulfuric acid, and separating to obtain a second organic phase and a second water phase;
and (3) back extraction for the first time:
carrying out 7-stage countercurrent back extraction on the second organic phase by adopting 2mol/L sulfuric acid, feeding the sulfuric acid from the 2 nd to last stage, the 4 th to last stage and the 6 th to last stage respectively, and separating to obtain a third organic phase and a third water phase; the pH of the third aqueous phase is 5;
and (3) carrying out secondary back extraction:
carrying out 5-stage countercurrent back extraction on the third organic phase by adopting 2mol/L sulfuric acid, and separating to obtain a fourth organic phase and a fourth water phase; the fourth aqueous phase has a pH of 6;
degreasing by using activated carbon:
respectively carrying out activated carbon degreasing on the third water phase and the fourth water phase to obtain a fifth water phase and a copper sulfate solution;
removing TOC:
the pH of the fifth aqueous phase is adjusted to 2.5 by sulfuric acid, TOC adsorption is carried out by AF5 resin (the liquid inlet flow is 4BV/h), the liquid outlet is qualified nickel cobalt manganese sulfate solution, and the detection data of the qualified nickel cobalt manganese sulfate solution are shown in Table 2:
TABLE 2 chemical composition table of qualified nickel cobalt manganese sulfate solution
As can be seen from the comparison between table 1 and table 2, the treatment method of the nickel-cobalt-manganese ternary waste provided by the present application can effectively remove copper, iron, aluminum, magnesium, calcium in the waste and fluorine introduced during the calcium and magnesium removal process.
Example 2
The embodiment provides a method for treating nickel-cobalt-manganese ternary waste, wherein the ternary waste contains impurities such as iron, calcium, magnesium, copper and the like; and (3) oxidizing the ternary waste, adding alkali to precipitate to remove aluminum and iron, filtering, and removing calcium and magnesium by using fluoride to obtain a pretreatment solution.
The chemical composition of the pretreatment solution is shown in table 3 below:
TABLE 3 chemical composition of pretreatment solution
And (3) extraction:
using extraction reagent of Mextral V10 after saponification treatment, and mixing the organic phase and aqueous phase in a ratio of 0.5: carrying out 8-stage countercurrent extraction on the phase ratio (volume ratio) of 1, and separating to obtain a first organic phase and a first water phase;
washing:
carrying out 4-stage countercurrent washing on the first organic phase by using 0.2mol/L sulfuric acid, and separating to obtain a second organic phase and a second water phase;
and (3) carrying out back extraction for the first time:
carrying out 10-stage countercurrent back extraction on the second organic phase by using 1mol/L sulfuric acid, and separating sulfuric acid from penultimate 2, 4 and 6 stages to obtain a third organic phase and a third water phase; the pH of the third aqueous phase was 3.5;
and (3) carrying out secondary back extraction:
2-stage countercurrent back extraction is carried out on the third organic phase by adopting 1mol/L sulfuric acid, and a fourth organic phase and a fourth water phase are obtained through separation; the pH of the fourth aqueous phase is 7;
degreasing by using activated carbon:
respectively carrying out activated carbon degreasing on the third water phase and the fourth water phase to obtain a fifth water phase and a copper sulfate solution;
removing TOC:
the pH of the fifth aqueous phase is adjusted to 4 by sulfuric acid, TOC adsorption is carried out by AF5 resin (the liquid inlet flow is 3BV/h), the liquid outlet is qualified nickel cobalt manganese sulfate solution, and the detection data of the qualified nickel cobalt manganese sulfate solution are shown in the table 4:
TABLE 4 chemical composition table of qualified nickel cobalt manganese sulfate solution
As can be seen from the comparison between tables 3 and 4, the treatment method of the nickel-cobalt-manganese ternary waste provided by the present application can effectively remove copper, iron, aluminum, magnesium, calcium in the waste and fluorine introduced during the calcium and magnesium removal process.
Example 3
The embodiment provides a method for treating nickel-cobalt-manganese ternary waste, wherein the ternary waste contains impurities such as iron, calcium, magnesium, copper and the like; and (3) oxidizing the ternary waste, adding alkali to precipitate aluminum iron, filtering the iron, and removing calcium and magnesium by using fluoride to obtain a pretreatment solution.
The chemical composition of the pretreatment solution is shown in table 5 below:
TABLE 5 chemical composition of pretreatment solution
And (3) extraction:
using the extraction reagent of Mextral V10 after saponification treatment, the extraction reagent was mixed with organic and aqueous phases 2: performing 12-stage countercurrent extraction on the phase ratio (volume ratio) of 1, and separating to obtain a first organic phase and a first water phase;
washing:
carrying out 7-stage countercurrent washing on the first organic phase by adopting 1mol/L sulfuric acid, and separating to obtain a second organic phase and a second water phase;
and (3) carrying out back extraction for the first time:
carrying out 13-stage countercurrent back extraction on the second organic phase by using 3mol/L sulfuric acid, and separating sulfuric acid from penultimate 2, 4 and 6 stages to obtain a third organic phase and a third water phase; the pH of the third aqueous phase is 4;
and (3) carrying out secondary back extraction:
carrying out 8-stage countercurrent back extraction on the third organic phase by using 3mol/L sulfuric acid, and separating to obtain a fourth organic phase and a fourth water phase; the pH of the fourth aqueous phase was 5.5;
degreasing by using activated carbon:
respectively carrying out activated carbon degreasing on the third water phase and the fourth water phase to obtain a fifth water phase and a copper sulfate solution;
removing TOC:
the pH of the fifth aqueous phase is adjusted to 1 by sulfuric acid, TOC adsorption is carried out by AF5 resin (the liquid inlet flow is 8BV/h), the effluent is qualified nickel cobalt manganese sulfate solution, and the detection data of the qualified nickel cobalt manganese sulfate solution are shown in Table 6:
TABLE 6 chemical composition table of qualified nickel cobalt manganese sulfate solution
As can be seen from the comparison between tables 5 and 6, the treatment method of the nickel-cobalt-manganese ternary waste provided by the present application can effectively remove copper, iron, aluminum, magnesium, calcium in the waste and fluorine introduced during the calcium and magnesium removal process.
Comparative example 1
The comparative example provides a nickel-cobalt-manganese ternary waste treatment method, and the ternary waste contains impurities such as iron, calcium, magnesium, copper and the like; oxidizing the ternary waste, adding alkali to precipitate to remove aluminum and iron, filtering, and removing calcium and magnesium by using fluoride to obtain a pretreatment solution.
The chemical composition of the pretreatment solution is shown in table 7 below:
TABLE 7 chemical composition of pretreatment solution
And (3) extraction:
using the saponified Mextral V10 extractant, the organic and aqueous phases 1: performing 10-stage countercurrent extraction on the phase ratio (volume ratio) of 1, and separating to obtain a first organic phase and a first water phase;
and (3) carrying out back extraction for the first time:
carrying out 7-stage countercurrent back extraction on the second organic phase by adopting 2mol/L sulfuric acid, and separating sulfuric acid from the penultimate 2 stage, the penultimate 4 stage and the penultimate 6 stage to obtain a third organic phase and a third water phase; the pH of the third aqueous phase is 5;
and (3) carrying out secondary back extraction:
carrying out 5-stage countercurrent back extraction on the third organic phase by adopting 2mol/L sulfuric acid, and separating to obtain a fourth organic phase and a fourth water phase; the pH of the fourth aqueous phase is 6;
removing oil by using activated carbon:
respectively carrying out activated carbon degreasing on the third water phase and the fourth water phase to obtain a fifth water phase and a copper sulfate solution;
removing TOC:
the pH of the fifth aqueous phase is adjusted to 2.5 by sulfuric acid, TOC adsorption is carried out by AF5 resin (the liquid inlet flow is 4BV/h), the liquid outlet is qualified nickel cobalt manganese sulfate solution, and the detection data of the qualified nickel cobalt manganese sulfate solution are shown in Table 8:
TABLE 8 chemical composition of qualified Ni-Co-Mn sulfate solution
As can be seen from table 8 in comparative example 1 and table 2 in example 2 and comparison, after extraction with the extraction agent Mextral V10 after saponification treatment, no organic-loaded washing is performed, and fluoride ions carried by the organic phase are brought into the nickel-cobalt-manganese sulfate solution along with the first back extraction process, so that the fluoride ions are at an excessive risk.
The treatment method of the nickel-cobalt-manganese ternary waste provided by the application has the advantages that the process flow is short, no new metal impurities are introduced in the purification process, and the obtained nickel-cobalt-manganese ternary solution and copper solution are high in purity and good in quality.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (11)
1. The treatment method of the nickel-cobalt-manganese ternary waste is characterized by comprising the following steps of:
removing iron, calcium and magnesium from the nickel-cobalt-manganese ternary waste to obtain a pretreatment solution, extracting by using an extracting agent, and separating to obtain a first organic phase and a first water phase; the extractant comprises a saponified Mextral V10 extractant; the pH value of the pretreatment liquid is 6-7;
washing the first organic phase by using materials including a first acid solution, and separating to obtain a second organic phase and a second water phase; the first acid solution comprises a sulfuric acid aqueous solution, and the concentration of the first acid solution is 0.2-1 mol/L;
carrying out first back extraction on the second organic phase by using materials including a second acid solution, and separating to obtain a third organic phase and a third water phase; the second acid solution comprises a sulfuric acid aqueous solution, and the concentration of the second acid solution is 1-3 mol/L; the pH value of the third aqueous phase is 3.5-5; the second acid solution is fed from the 2 nd to last stage, the 4 th to last stage and the 6 th to last stage; removing oil from the third aqueous phase to obtain a nickel-cobalt-manganese solution; performing second back extraction on the third organic phase by using materials including a third acid solution, and separating to obtain a fourth organic phase and a fourth aqueous phase; deoiling the fourth aqueous phase to obtain a copper solution; the third acid solution comprises a sulfuric acid aqueous solution, and the concentration of the third acid solution is 1-3 mol/L; the pH value of the fourth aqueous phase is 5.5-7.
2. The process of claim 1, wherein the extraction is carried out in a multistage countercurrent mode;
the extraction stages are 8-12 stages.
3. The process according to claim 2, wherein the volume ratio of the organic phase to the aqueous phase in each stage of extraction is independently (0.5-2): 1.
4. the process of claim 1, wherein the washing is carried out in a multistage countercurrent mode;
the washing stages are 4-7 stages.
5. The process according to claim 1, characterized in that said first stripping is carried out in a multistage countercurrent mode;
the first back extraction stage number is 7-13 stages.
6. The process according to claim 1, characterized in that said second stripping is carried out in a multistage countercurrent mode;
the second back extraction stage number is 2-8 stages.
7. The treatment method according to claim 1, wherein the degreasing is performed using activated carbon.
8. The process according to any one of claims 1 to 7, further comprising subjecting said nickel cobalt manganese solution to a TOC removal treatment.
9. The process of claim 8, wherein the de-TOC treatment uses resin removal.
10. The process according to claim 9, wherein the pH of the nickel cobalt manganese solution is adjusted to 1-4 before the TOC removal treatment.
11. The process according to claim 9, wherein the flow rate of the nickel cobalt manganese solution into the resin is 3 to 8 BV/h.
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