CN115852152A - Method for cooperatively treating battery black powder and nickel-cobalt hydroxide - Google Patents
Method for cooperatively treating battery black powder and nickel-cobalt hydroxide Download PDFInfo
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- CN115852152A CN115852152A CN202310173475.XA CN202310173475A CN115852152A CN 115852152 A CN115852152 A CN 115852152A CN 202310173475 A CN202310173475 A CN 202310173475A CN 115852152 A CN115852152 A CN 115852152A
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- black powder
- manganese
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- 239000000843 powder Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 52
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 title claims abstract description 43
- 238000002386 leaching Methods 0.000 claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000002893 slag Substances 0.000 claims abstract description 45
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 39
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 36
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 30
- 239000011572 manganese Substances 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 17
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 239000004576 sand Substances 0.000 claims abstract description 8
- 239000002699 waste material Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 96
- 239000010941 cobalt Substances 0.000 abstract description 49
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 49
- 229910052759 nickel Inorganic materials 0.000 abstract description 48
- 229910017052 cobalt Inorganic materials 0.000 abstract description 47
- 150000002739 metals Chemical class 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 2
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- POVGIDNLKNVCTJ-UHFFFAOYSA-J cobalt(2+);nickel(2+);disulfate Chemical compound [Co+2].[Ni+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O POVGIDNLKNVCTJ-UHFFFAOYSA-J 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GXMCPHJLTWJFLD-UHFFFAOYSA-L disodium sulfurous acid sulfate Chemical compound S(=O)(=O)([O-])[O-].[Na+].S(=O)(O)O.[Na+] GXMCPHJLTWJFLD-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 159000000002 lithium salts Chemical group 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- -1 nickel/cobalt Chemical class 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The application provides a method for cooperatively processing battery black powder and nickel cobalt hydroxide, and relates to the technical field of battery recycling. The method for the synergistic treatment of the battery black powder and the nickel-cobalt hydroxide specifically comprises the following steps: roasting the battery black powder and a reducing agent to obtain roasted sand; grinding and water leaching the calcine to obtain ore pulp; adding nickel-cobalt hydroxide into the ore pulp, reacting, and carrying out solid-liquid separation to obtain a lithium-rich solution and nickel-cobalt-manganese-rich slag; and performing acid leaching treatment on the nickel-cobalt-manganese-rich slag and sulfuric acid to obtain leaching slag and a nickel-cobalt-manganese-rich leaching solution. According to the method, lithium in the battery black powder can be preferentially extracted, and then elements such as nickel, cobalt and manganese in the battery black powder and the nickel-cobalt hydroxide are enriched and extracted, so that the enrichment and recovery of valuable metals are realized.
Description
Technical Field
The application relates to the technical field of battery recycling, in particular to a method for cooperatively processing battery black powder and nickel-cobalt hydroxide.
Background
With the increase of the popularization of new energy automobiles, as of 2021, the new energy automobiles keep 784 thousands of automobiles, are in a high-speed growth situation, further aggravate the contradiction between supply and demand of resources such as nickel/cobalt/lithium and urgently seek resource supply. Based on the consideration of relevant policies, production cost and other factors, more and more enterprises choose to supplement nickel/cobalt/lithium from an intermediate product, namely nickel-cobalt hydroxide and a secondary resource, namely a waste lithium battery.
At present, in the recovery method of nickel, cobalt and other substances in an intermediate product, namely nickel-cobalt hydroxide, some methods firstly use concentrated sulfuric acid for curing the nickel-cobalt hydroxide, and then reduce and leach the cured leachate to prepare a nickel-cobalt sulfate solution so as to realize the recovery of nickel and cobalt; some methods sequentially carry out the steps of reduction leaching of sulfuric acid-sodium sulfite, neutralization impurity removal, extraction separation of nickel and cobalt and the like, thereby realizing high-purity recovery of nickel and cobalt. Some waste lithium batteries and carbonaceous reducing agents are subjected to carbothermic reduction roasting at a certain temperature to enable lithium to exist in the form of lithium carbonate, and then direct water immersion or CO is adopted to recover valuable metals in the waste batteries 2 Water leaching to realize preferential extraction of lithium; some waste lithium batteries and ammonium sulfate, potassium bisulfate or sodium bisulfate are roasted at a certain temperature, and then the roasted sand is subjected to water leaching to realize the separation of lithium and nickel/cobalt/manganese.
However, the intermediate product, namely the nickel-cobalt hydroxide, is cooperatively treated with the waste lithium battery, so that the recovery method of nickel/cobalt/lithium and other resources is less, and if the method can be combined, the method can be optimized to a certain extent in the aspects of equipment investment, process cost and the like. Therefore, a method for cooperatively treating nickel-cobalt hydroxide and waste lithium batteries is urgently needed to realize the enrichment and recovery of valuable metals.
Disclosure of Invention
The application aims to provide a method for cooperatively processing battery black powder and nickel cobalt hydroxide, lithium in the battery black powder can be preferentially extracted through the cooperative processing method, and then elements such as nickel, cobalt and manganese in the battery black powder and the nickel cobalt hydroxide are enriched and extracted, so that valuable metals are enriched and recovered.
In order to achieve the above purpose, the technical scheme of the application is as follows:
the application provides a method for cooperatively processing battery black powder and nickel cobalt hydroxide, which comprises the following steps:
roasting the battery black powder and a reducing agent to obtain roasted sand;
grinding and water leaching the calcine to obtain ore pulp;
adding nickel-cobalt hydroxide into the ore pulp, reacting, and performing solid-liquid separation to obtain a lithium-rich solution and nickel-cobalt-manganese-rich slag;
and performing acid leaching treatment on the nickel-cobalt-manganese-rich slag and sulfuric acid to obtain leached slag and a nickel-cobalt-manganese-rich leachate.
In some embodiments of the present application, the battery black powder includes at least one of a positive electrode powder of a waste lithium ion battery, and a mixed positive electrode powder and a negative electrode powder of a waste lithium ion battery.
In some embodiments of the present application, the reducing agent includes at least one of carbon powder, hydrogen gas, and metal salt.
In some embodiments of the present application, the temperature of the calcination is 300 ℃ to 800 ℃ and the time is 1h to 6h.
In some embodiments of the present application, the particle size of the calcine after grinding is 200 mesh or larger.
In some embodiments of the present application, at least one of the following conditions is also satisfied:
a. the water leaching process also comprises introducing carbon dioxide;
b. the liquid-solid ratio of water in the water leaching treatment to the calcine is 2mL/g-10mL/g;
c. the temperature of the water immersion treatment is 10-100 ℃, and the time is 0.5-3 h.
In some embodiments of the application, after the nickel cobalt hydroxide is added to the pulp, the pulp has a pH of 10-12;
the reaction temperature is 10-100 ℃, and the reaction time is 1-3 h.
In some embodiments of the present application, the sulfuric acid is concentrated sulfuric acid, and the amount of the sulfuric acid is 1 to 1.5 times of the theoretical amount;
before the acid leaching treatment, the method also comprises the following steps: mixing the nickel-cobalt-rich manganese slag with water, and then adding the sulfuric acid; the liquid-solid ratio of the water to the nickel-cobalt-manganese-rich slag is 3mL/g-10 mL/g.
In some embodiments herein, the acid leaching treatment is at a temperature of 40 ℃ to 90 ℃ for a time of 2h to 6h.
In some embodiments of the present application, the firing is performed in an atmosphere of a protective gas comprising at least one of argon, nitrogen.
The beneficial effect of this application:
in the method, after the battery black powder is reduced by the reducing agent, the nickel/cobalt exists in a metal form, and the lithium exists in a lithium salt form which is easily soluble in water. After the ore pulp is prepared by water leaching, the nickel-cobalt hydroxide has certain alkalinity and can be used as a neutralizer for impurity removal, nickel/cobalt/manganese ions in the ore pulp exist in solid slag after solid-liquid separation in the form of hydroxide which is difficult to dissolve in water, and then a purified lithium-rich solution is obtained, wherein the nickel/cobalt/manganese/aluminum/copper ions can be reduced to below 10ppm, and the requirement for preparing an aqueous solution from battery-grade lithium carbonate can be met only by removing impurities aiming at partial ions subsequently. In the process of acid leaching treatment, metals such as nickel/cobalt and the like obtained from the calcine can be used as reducing agents of high-valence cobalt, so that the high-valence cobalt in the nickel-cobalt hydroxide is subjected to oxidation reduction reaction under the action of sulfuric acid, other reducing agents are not required to be added, the high-efficiency leaching of the nickel/cobalt/manganese can be realized, and the leaching rate can reach more than 99%. Compared with a method for independently treating waste batteries and a method for independently treating nickel-cobalt hydroxide, the method has the advantages of higher cost and is beneficial to industrialized popularization and application.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present invention, and therefore should not be considered as limiting the scope of the present invention.
Fig. 1 is an XRD phase analysis diagram of calcine obtained by roasting battery black powder and reducing agent carbon powder at different temperatures.
Detailed Description
The terms as used herein:
"by 8230; \ 8230; preparation" is synonymous with "comprising". As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains" or any other variation thereof, 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 823070, 8230composition" 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 8230' \8230"; composition "appears in a clause of the subject matter of the claims and not 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 a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4," "1 to 3," "1 to 2 and 4 to 5," "1 to 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 an arbitrary 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).
The application provides a method for cooperatively processing battery black powder and nickel cobalt hydroxide, which comprises the following steps:
s1, roasting battery black powder and a reducing agent to obtain roasted sand;
s2, grinding and water leaching the calcine to obtain ore pulp;
s3, adding nickel-cobalt hydroxide into the ore pulp, reacting, and carrying out solid-liquid separation to obtain a lithium-rich solution and nickel-cobalt-manganese-rich slag;
and S4, carrying out acid leaching treatment on the nickel-cobalt-manganese-rich slag and sulfuric acid to obtain leaching slag and a nickel-cobalt-manganese-rich leaching solution.
In some optional embodiments of the present application, the battery black powder in S1 includes at least one of a waste lithium ion battery positive electrode powder and a waste lithium ion battery positive-negative electrode mixed powder.
It can be understood that the battery black powder can be purchased directly, or obtained by overdischarging, disassembling, crushing and separating a waste lithium ion battery, wherein the disassembled battery black powder is mainly an active positive electrode material and also contains some negative electrode carbon materials. The waste lithium ion battery can be a unitary lithium ion battery containing any one of nickel, cobalt and manganese or a binary lithium ion battery containing any two of nickel, cobalt and manganese, and can also be a ternary lithium ion battery containing nickel, manganese and cobalt or nickel, cobalt and aluminum.
It should be noted that, the battery black powder in the present application S1 may also be replaced by battery positive electrode powder, and the battery positive electrode powder mainly comes from unqualified products generated in the production process of the positive electrode material.
In some optional embodiments of the present application, the reducing agent in S1 includes at least one of carbon powder, hydrogen gas, and metal salt.
It is understood that if the battery black powder in S1 itself contains a substance such as carbon powder, the carbon powder contained in itself can also be used as a reducing agent for reduction. If the battery black powder is subjected to carbothermic reduction roasting, the nickel/cobalt compound is reduced into nickel/cobalt metal, and lithium exists in the form of lithium carbonate dissolved in water, and the specific reaction mechanism is as follows:
specifically, the inventor of the application carries out roasting treatment on the battery black powder and the reducing agent carbon powder at different temperatures, and other conditions are kept consistent except the temperature. Finally, the calcine obtained at different temperatures is subjected to XRD detection, and the corresponding XRD pattern is shown in figure 1. As can be seen from the figure, at temperatures of 550 ℃ and above 550 ℃, the calcined product has a Ni/Co simple substance.
If the battery black powder is reduced by hydrogen, nickel/cobalt exists in the calcine in a metal form, and lithium exists in a lithium hydroxide form which is easy to dissolve in water, and the specific reaction mechanism is as follows:
during the roasting process, metal sulfate (such as nickel/cobalt/manganese sulfate) can be used as a reducing agent, wherein the metal can be replaced with lithium in the waste lithium battery, the rest metal exists basically in the form of metal oxide, and the metal exists in the form of reduced metal due to the fact that the raw material contains a little negative electrode material C, so that the preferential extraction of lithium can be realized by adopting direct water leaching.
In some alternative embodiments of the present application, the calcination in S1 is performed at a calcination temperature of 300 ℃ to 800 ℃, for example, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃ or at any value between 300 ℃ and 800 ℃, and the calcination time is 1h to 6h, for example, 1h, 2h, 3h, 4h, 5h, 6h or at any value between 1h and 6h.
In some alternative embodiments of the present application, the firing in S1 is also performed under an atmosphere of a protective gas, and the protective gas includes at least one of argon and nitrogen.
In some alternative embodiments of the present application, the calcine particle size after grinding in S2 is 200 mesh or larger. It is understood that the lithium-containing compound in the calcine is more soluble in water when stirred in water after grinding.
In some optional embodiments of the present application, the step of performing the water leaching treatment in S2 further comprises introducing carbon dioxide.
It is to be understood that the solubility of the lithium carbonate formed after thermal reductive calcination with carbon is not so high, and therefore the conversion of lithium carbonate to lithium bicarbonate that is more soluble in water is achieved by passing carbon dioxide through an aqueous leaching solution.
In some alternative embodiments of the present application, the liquid-solid ratio of water used for the water-leaching treatment to the calcine in S2 is 2mL/g to 10mL/g, and may be, for example, 2mL/g, 3mL/g, 4mL/g, 5mL/g, 6mL/g, 7mL/g, 8mL/g, 9mL/g, 10mL/g, or any value between 2mL/g and 10mL/g.
Further, the temperature of the water immersion treatment is 10 ℃ to 100 ℃, for example, 10 ℃, 20 ℃, 40 ℃, 70 ℃, 100 ℃ or any value between 10 ℃ and 100 ℃, and the time is 0.5h to 3h, for example, 0.5h, 1h, 1.5h, 2h, 2.5h, 3h or any value between 0.5h and 3h. After water immersion at room temperature, solid-liquid separation was not necessary.
In some alternative embodiments of the present application, after the nickel cobalt hydroxide is added to the pulp in S3, the pulp has a pH of 10-12.
The nickel-cobalt hydroxide can be purchased directly, or can be prepared by using laterite-nickel ore as a raw material and then performing a high-pressure acid leaching technology, or can be prepared by using battery black powder.
Nickel cobalt hydroxide (MHP), also known as nickel cobalt hydroxide, is an intermediate product of nickel, and can be used for preparing nickel sulfate and further preparing an anode material of an electrode. The nickel-cobalt hydroxide contains a large amount of alkaline substances, so that free metal ions in the ore pulp can be hydrolyzed and precipitated, nickel/cobalt/manganese ions in the ore pulp are enriched in slag in the form of hydroxide which is insoluble in water, and the effective separation of lithium and other metal impurities is realized. The amount of the nickel-cobalt hydroxide added into the ore pulp is based on the optimal leaching rate of nickel/cobalt/manganese in the leaching liquid after the nickel-cobalt-manganese slag is subjected to acid leaching treatment.
In some alternative embodiments of the present application, the slurry is added to S3, and the reaction is performed at a temperature of 10 ℃ to 100 ℃, more preferably at room temperature, and for a time of 1h to 3h, which may be, for example, 1h, 1.5h, 2h, 2.5h, 3h, or any value between 1h and 3h.
In some optional embodiments of the present application, the sulfuric acid used in S4 is concentrated sulfuric acid, and the amount of the concentrated sulfuric acid is 1 to 1.5 times of the theoretical amount, so that leaching of each element in the nickel-cobalt-manganese rich slag can be promoted. Further, the mass fraction of the concentrated sulfuric acid is 98%.
In the obtained nickel-cobalt-manganese slag, there are elementary metals such as nickel/cobalt, so these metals can be used as a reducing agent, and the high-valence cobalt in the nickel-cobalt-manganese slag is subjected to oxidation reduction reaction under the action of concentrated sulfuric acid, so that the cobalt element is leached sufficiently and efficiently, for example, co (OH) 3 can react with cobalt in a concentrated sulfuric acid system, specifically:
further, before the acid leaching treatment in S4, the method further includes: and mixing the nickel-cobalt-rich manganese slag with water, and then mixing the mixture with sulfuric acid for acid leaching treatment. The liquid-solid ratio of the water to the nickel-cobalt-manganese-rich slag is 3mL/g to 10mL/g, and can be any value between 3mL/g, 4mL/g, 5mL/g, 6mL/g, 7mL/g, 8mL/g, 9mL/g, 10mL/g or 3mL/g to 10mL/g, for example.
In some alternative embodiments of the present application, the temperature of the acid leaching treatment in S4 is 40 ℃ to 90 ℃, for example, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or any value between 40 ℃ to 90 ℃, and the time is 2h to 6h, for example, 2h, 3h, 4h, 5h, 6h or any value between 2h to 6h. After acid leaching treatment, leaching residue and nickel-cobalt-manganese-rich acid leaching liquid can be obtained through solid-liquid separation.
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.
Example 1
The embodiment provides a method for cooperatively processing battery black powder and nickel cobalt hydroxide, which comprises the following steps:
(1) Discharging the waste nickel-cobalt-manganese ternary battery, disassembling to obtain a positive plate, crushing the positive plate, dissolving the crushed positive plate in N-methyl pyrrolidone to remove a current collector, and then cleaning and drying to obtain battery black powder containing positive powder.
(2) Weighing 50g of battery black powder, introducing hydrogen at 600 ℃ in an argon protective atmosphere, roasting for 5 hours, and cooling to obtain roasted sand.
(3) Grinding the calcine obtained in the step (2) to 200 meshes, weighing 10g of calcine, adding 50mL of water, performing water immersion treatment at room temperature, and stirring for 2 hours to obtain ore pulp.
(4) And (3) slowly adding the nickel-cobalt hydroxide into the ore pulp obtained in the step (3), testing the pH value of the slurry, stopping adding when the pH value is 10-11, stirring at room temperature, reacting for 2 hours, and performing solid-liquid separation to obtain a lithium-rich solution and nickel-cobalt-manganese-rich slag.
(5) And (3) drying a small amount of the nickel-cobalt-manganese-rich slag obtained in the step (4), analyzing the water content and the metal content such as nickel, cobalt and manganese in the slag, further obtaining the water content and the metal content such as nickel, cobalt and manganese in all the nickel-cobalt-manganese-rich slag according to the result, and then adding water to prepare the nickel-cobalt-manganese-rich slag with a liquid-solid ratio of 5mL:1g of ore pulp is added with concentrated sulfuric acid (98%) with the theoretical mass of 1.1 times, the mixture is stirred at the temperature of 50 ℃, and after 6 hours of reaction, solid-liquid separation is carried out to obtain leaching slag and a nickel-cobalt-manganese-rich leaching solution.
In the step (4) of this example, the leaching rate of lithium is 98.15%, and nickel/cobalt/manganese is not leached basically; acid leaching process in the step (5): the leaching rates of nickel/cobalt/manganese are respectively 98.23%, 98.65% and 96%.
Example 2
The embodiment provides a method for cooperatively processing battery black powder and nickel cobalt hydroxide, which comprises the following steps:
(1) Discharging the waste nickel-cobalt-manganese ternary battery, disassembling to obtain a positive plate and a negative plate, crushing, dissolving in N-methyl pyrrolidone to remove a current collector, and cleaning and drying to obtain battery black powder containing positive and negative mixed powder.
(2) Weighing 50g of battery black powder and 10g of carbon powder, uniformly mixing, roasting for 3 hours at 800 ℃ in an argon atmosphere, and cooling to obtain roasted product.
(3) Grinding the calcine obtained in the step (2) to 200 meshes, weighing 10g of the calcine, adding 30mL of water, performing water leaching treatment at room temperature, introducing excessive carbon dioxide, and stirring for 2 hours to obtain ore pulp.
(4) And (4) slowly adding the nickel-cobalt hydroxide into the ore pulp obtained in the step (3), testing the pH value in the pulp, stopping adding when the pH value is 10-11, stirring at room temperature, reacting for 2 hours, and performing solid-liquid separation to obtain a lithium-rich solution and nickel-cobalt-manganese-rich slag.
(5) And (5) drying a small amount of the wet slag rich in nickel, cobalt and manganese in the step (4), analyzing the water content and the metal content of nickel, cobalt, manganese and the like in the wet slag, further obtaining the water content and the metal content of nickel, cobalt, manganese and the like in all the wet slag rich in nickel, cobalt and manganese according to the result, and then adding water to prepare the wet slag rich in nickel, cobalt and manganese with a liquid-solid ratio of 5mL:1g of ore pulp is added with concentrated sulfuric acid (98%) with the theoretical mass of 1.1 times, the mixture is stirred at the temperature of 50 ℃, and after 6 hours of reaction, solid-liquid separation is carried out to obtain leaching slag and a nickel-cobalt-manganese-rich leaching solution.
In the step (4) of this example, the leaching rate of lithium is 80.12%, and nickel/cobalt/manganese is not leached basically; the acid leaching process of the step (5): the leaching rates of nickel/cobalt/manganese are respectively 99.14%, 98.13% and 95.84%.
Example 3
The embodiment provides a method for cooperatively processing battery black powder and nickel cobalt hydroxide, which comprises the following steps:
(1) Discharging the waste nickel-cobalt-manganese ternary battery, disassembling to obtain a positive plate and a negative plate, crushing, dissolving in N-methylpyrrolidone to remove a current collector, and cleaning and drying to obtain battery black powder containing positive and negative mixed powder.
(2) Weighing 50g of battery black powder and 60g of nickel sulfate hexahydrate, roasting at 800 ℃ for 5 hours under the protection of argon gas, and cooling to obtain roasted sand.
(3) Grinding the calcine obtained in the step (2) to 200 meshes, weighing 10g of the calcine, adding 50mL of water, performing water leaching treatment at room temperature, and stirring for 2 hours to obtain ore pulp.
(4) And (3) slowly adding the nickel-cobalt hydroxide into the ore pulp obtained in the step (3), testing the pH value of the slurry, stopping adding when the pH value is 10-11, stirring at room temperature, reacting for 2 hours, and performing solid-liquid separation to obtain a lithium-rich solution and nickel-cobalt-manganese-rich slag.
(5) And (3) drying a small amount of the nickel-cobalt-manganese-rich wet slag obtained in the step (4), analyzing the water content and the metal content of nickel, cobalt, manganese and the like in the wet slag, further obtaining the water content and the metal content of nickel, cobalt, manganese and the like in all the nickel-cobalt-manganese-rich wet slag according to the result, and then adding water to prepare the nickel-cobalt-manganese-rich wet slag with a liquid-solid ratio of 5mL:1g of ore pulp is added with concentrated sulfuric acid (98%) with the theoretical mass of 1.1 times, the mixture is stirred at 50 ℃, and after 6 hours of reaction, solid-liquid separation is carried out to obtain leaching slag and nickel-cobalt-manganese-rich leaching liquid.
In the step (4) of this example, the leaching rate of lithium is 99.58%, and nickel/cobalt/manganese is not leached basically; the acid leaching process of the step (5): the leaching rates of nickel/cobalt/manganese are respectively 99.35%, 99.24% and 98%.
Comparative example 1
The present comparative example provides a method of treating battery black powder, comprising:
(1) Discharging the waste nickel-cobalt-manganese ternary battery, disassembling to obtain a positive plate, crushing the positive plate, dissolving the crushed positive plate in N-methyl pyrrolidone to remove a current collector, and then cleaning and drying to obtain battery black powder containing positive powder.
(2) Weighing 50g of battery black powder and 60g of nickel sulfate hexahydrate, roasting at 800 ℃ for 5 hours under the protection atmosphere of argon, and cooling to obtain roasted sand.
(3) Grinding the calcine obtained in the step (2) to 200 meshes, weighing 10g of calcine, adding 30mL of water, performing water leaching treatment at room temperature, stirring for 2 hours, and performing solid-liquid separation to obtain a lithium-rich solution and solid slag.
(4) And (3) mixing the solid slag obtained in the step (3) with water in a liquid-solid ratio of 5mL:1g of the mixture is prepared into ore pulp, sulfuric acid (98%) is added, stirring is carried out at 50 ℃, after 6 hours of reaction, solid-liquid separation is carried out, and leaching residue and nickel-cobalt-manganese-rich leaching liquid are obtained.
The water leaching process of step (3) of this comparative example: the leaching rate of lithium is 99.15 percent, and the leaching rates of nickel/cobalt/manganese are respectively 3.13 percent, 0.21 percent and 13.25 percent; acid leaching process in the step (4): the leaching rates of nickel/cobalt/manganese are 82.14%, 86.37% and 89.24%, respectively.
Comparing the leaching rates of examples 1 to 3 and comparative example 1, it can be seen that, in the process of extracting lithium by water leaching preferentially, a considerable part of nickel/manganese enters into the aqueous solution along with lithium, the separation is not complete, and the leaching rate of nickel/cobalt/manganese is low because the obtained solid slag does not contain reducing agents such as nickel/cobalt simple substance metals.
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 (10)
1. A method for cooperatively processing battery black powder and nickel cobalt hydroxide is characterized by comprising the following steps:
roasting the battery black powder and a reducing agent to obtain roasted sand;
grinding and water leaching the calcine to obtain ore pulp;
adding nickel-cobalt hydroxide into the ore pulp, reacting, and carrying out solid-liquid separation to obtain a lithium-rich solution and nickel-cobalt-manganese-rich slag;
and performing acid leaching treatment on the nickel-cobalt-manganese-rich slag and sulfuric acid to obtain leaching slag and a nickel-cobalt-manganese-rich leaching solution.
2. The method according to claim 1, wherein the battery black powder comprises at least one of a positive electrode powder of a waste lithium ion battery and a mixed positive and negative electrode powder of the waste lithium ion battery.
3. The method according to claim 1, wherein the reducing agent comprises at least one of carbon powder, hydrogen gas, and metal salt.
4. The method of claim 1, wherein the baking is performed at a temperature of 300 ℃ to 800 ℃ for 1h to 6h.
5. The method for co-processing battery black powder and nickel cobalt hydroxide according to claim 1, wherein the particle size of the calcine after grinding is not less than 200 mesh.
6. The method for co-processing battery black powder and nickel cobalt hydroxide according to claim 1, wherein at least one of the following conditions is also satisfied:
a. the water leaching process also comprises introducing carbon dioxide;
b. the liquid-solid ratio of water in the water leaching treatment to the calcine is 2mL/g-10mL/g;
c. the temperature of the water immersion treatment is 10-100 ℃, and the time is 0.5-3 h.
7. The method for co-processing battery black powder and nickel cobalt hydroxide according to claim 1, wherein after the nickel cobalt hydroxide is added to the pulp, the pulp has a pH of 10 to 12;
the reaction temperature is 10-100 ℃, and the reaction time is 1-3 h.
8. The method for co-processing battery black powder and nickel cobalt hydroxide according to claim 1, wherein the sulfuric acid is concentrated sulfuric acid, and the amount of the sulfuric acid is 1 to 1.5 times of the theoretical amount;
before the acid leaching treatment, the method also comprises the following steps: mixing the nickel-cobalt-rich manganese slag with water, and then adding the sulfuric acid; the liquid-solid ratio of the water to the nickel-cobalt-manganese-rich slag is 3mL/g-10 mL/g.
9. The method for co-processing battery black powder and nickel cobalt hydroxide according to claim 1, wherein the acid leaching treatment is performed at a temperature of 40 ℃ to 90 ℃ for 2h to 6h.
10. The method of co-processing battery black powder and nickel cobalt hydroxide according to any one of claims 1 to 9, wherein the firing is performed in an atmosphere of a protective gas comprising at least one of argon, nitrogen.
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