Method for preparing nickel/manganese/lithium/cobalt sulfate and tricobalt tetraoxide from battery wastes

Abstract

A method for preparing nickel/manganese/lithium/cobalt sulfate and tricobalt tetraoxide from battery wastes adopts the following process: dissolving battery wastes with acid, removing iron and aluminum, removing calcium, magnesium and copper, carrying extraction separation, and carrying out evaporative crystallization to prepare nickel sulfate, manganese sulfate, lithium sulfate, cobalt sulfate or/and tricobalt tetraoxide. By using the method, multiple metal elements, such as nickel, manganese, lithium and cobalt, can be simultaneously recovered from the battery wastes, the recovered products are high in purity and can reach battery grade, battery-grade tricobalt tetraoxide can also be directly produced. The method is simple in process, low in energy consumption and free in exhaust gas pollution, and can realize zero release of wastewater.

Claims

1. A method for preparing, nickel sulfate, manganese sulfate, lithium sulfate, cobalt sulfate and tricobalt tetraoxide from battery wastes, comprising the following steps: dissolving battery waste with acid, removing iron and aluminum, removing calcium, magnesium and copper, carrying extraction separation, and carrying out, evaporative crystallization to prepare nickel sulfate, manganese sulfate, lithium sulfate, cobalt sulfate and tricobalt tetraoxide; wherein, the evaporative crystallization adopts the following steps: recovering manganese sulfate by extracting pre-extraction solution with a di-2-ethylhexyl phosphoric acid extractant at first so that manganese in the solution is extracted to an organic phase, adding sulfuric acid solution into the organic phase for washing to obtain 150-200 g/L manganese-containing manganese sulfate solution, and carrying out evaporative crystallization and centrifugation on the solution to obtain a manganese sulfate product; recovering cobalt sulfate by extracting di-2-ethylhexyl phosphoric acid extraction raffinate obtained after extraction of manganese in the previous process with mono(2-ethylhexyl) 2-ethylhexyl phosphonate so that cobalt in the solution is extracted to an organic phase, adding sulfuric acid solution into the organic phase for washing to obtain 80-130 g/L cobalt-containing cobalt sulfate solution, and carrying out evaporative crystallization and centrifugation on the solution to obtain a cobalt sulfate product; recovering nickel sulfate by extracting mono(2-ethylhexyl) 2-ethylhexyl phosphonate extraction raffinate obtained after extraction of cobalt in the previous process with di-2-ethylhexyl phosphoric acid again so that nickel in the solution is extracted to an organic phase, adding sulfuric acid solution into the organic phase for washing to obtain 70-130 g/L nickel-containing nickel sulfate solution, and carrying out evaporative crystallization and centrifugation on the solution to obtain a nickel sulfate product; recovering sodium sulfate by evaporating di-2-ethylhexyl phosphoric acid extraction raffinate obtained after extraction of nickel in the previous process with an MRV(mechanical vapor recompression) evaporative crystallization system to form sodium sulfate crystals, and carrying out centrifugal filtration to obtain an anhydrous sodium sulfate byproduct; and recovering lithium carbonate by adding saturated sodium carbonate solution into centrifugation mother liquor obtained after recovery of sodium sulfate to obtain a lithium carbonate precipitate, wherein, a reaction temperature is controlled to 60-100 C., and react lasts, for 0.5-4 h. carrying out centrifugal filtration on the precipitate, washing and drying to obtain a lithium carbonate product.

2. The method for preparing nickel sulfate, manganese sulfate, lithium sulfate, cobalt sulfate and tricobalt tetraoxide from battery wastes according to claim 1, wherein, the dissolving battery wasters with acid is realized by adding acid in the battery wastes with a solid/liquid mass ratio of 1:(2-6), reacting and then filtering to obtain acid dissolved filtrate.

3. The method for preparing nickel sulfate, manganese sulfate, lithium sulfate, cobalt sulfate and tricobalt tetraoxide from battery wastes according to claim 1, wherein, the removing iron and aluminum is realized by adding calcium carbonate and sodium chloride in acid dissolved solution, stirring and then adding sodium carbonate solution, and filtering to obtain iron-removing and aluminum-removing filtrate.

4. The method for preparing nickel sulfate, manganese sulfate, lithium sulfate, cobalt sulfate and tricobalt tetraoxide from battery wastes according to claim 1, wherein, the removing calcium, magnesium and copper is realized by adding sodium fluoride into the iron-removing and aluminum-removing filtrate, stirring and then adding sodium carbonate, and filtering to obtain pre-extraction solution.

5. The method for preparing nickel sulfate, manganese sulfate, lithium sulfate, cobalt sulfate and tricobalt tetraoxide from battery wastes according to claim 1, wherein, the extraction separation comprises the following steps: a. separating a manganese element by extracting and stripping the pre-extraction solution to obtain high-purity and high-concentration anti-manganese liquid; b. separating a cobalt element by allowing extraction raffinate obtained after extraction of manganese to enter an extraction process for separating cobalt, extracting and stripping to obtain high-purity high-concentration anti-cobalt liquid; and c. separating a nickel element by allowing extraction raffinate obtained after extraction of cobalt to enter an extraction process for separating nickel, extracting and stripping to obtain high-purity high-concentration anti-nickel liquid.

6. The method for preparing nickel sulfate, manganese sulfate, lithium sulfate, cobalt sulfate and tricobalt tetraoxide from battery wastes according to claim 5, wherein, a stripping liquid uses 0.5-4N sulfuric acid.

7. The method for preparing nickel sulfate, manganese sulfate, lithium sulfate, cobalt sulfate and tricobalt tetraoxide from battery wastes according to claim 1, wherein, in the step of recovering cobalt sulfate, after 80-130 g/L cobalt-containing cobalt sulfate solution is obtained, hydroxy cobalt is synthesized with sodium hydroxide solution, centrifugal filtration is carried out, and firing is carried out at 700-950 C. to prepare tricobalt tetraoxide.

8. The method for preparing nickel sulfate, manganese sulfate, lithium sulfate, cobalt sulfate and tricobalt tetraoxide from battery wastes according to claim 1, wherein, in the step of recovering manganese sulfate, the organic phase is regenerated via acid washing, saponification is carried out with caustic soda solution to restore activity to be recycled, and centrifugation mother liquor is added into the next-batch manganese sulfate solution for evaporative crystallization.

9. The method for preparing nickel sulfate, manganese sulfate, lithium sulfate, cobalt sulfate and tricobalt tetraoxide from battery wastes according to claim 1, wherein, in the step of recovering cobalt sulfate, the organic phase is regenerated via acid washing, saponification is carried out with caustic soda solution to restore activity to be recycled, and centrifugation mother liquor is added into the next-batch cobalt sulfate solution for evaporative crystallization.

10. The method for preparing nickel sulfate, manganese sulfate, lithium sulfate, cobalt sulfate and tricobalt tetraoxide from battery wastes according to claim 1, wherein, in the step of recovering nickel sulfate, the organic phase is regenerated via acid washing, saponification is carried out with caustic soda solution to restore activity to be recycled, and centrifugation mother liquor is added into the next nickel sulfate solution for evaporative crystallization.

11. The method for preparing nickel sulfate, manganese sulfate, lithium sulfate, cobalt sulfate and tricobalt tetraoxide from battery wastes according to claim 1, wherein, in the step of recovering lithium carbonate, the reaction temperature is controlled to 65-95 C., and the reaction time is 1.0-3.5 h.

12. The method for preparing nickel sulfate, manganese sulfate, lithium sulfate, cobalt sulfate and tricobalt tetraoxide from battery wastes according to claim 1, wherein, in the step of recovering lithium carbonate tailwater and washing liquid are returned back to the MVR evaporative crystallization system.

13. The method for preparing nickel sulfate, manganese sulfate, lithium sulfate, cobalt sulfate and tricobalt tetraoxide from battery wastes according to claim 1, wherein, the battery wastes comprise all waste batteries whose shells are stripped, wastes from battery manufacture factories and clearing wastes.

Description

DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a process diagram of pre-extraction solution according to the disclosure; and

(2) FIG. 2 is a process diagram of extraction and evaporative crystallization according to the disclosure.

PREFERRED EMBODIMENTS OF THE DISCLOSURE

(3) Provided is a method for preparing nickel/manganese/lithium/cobalt sulfate and tricobalt tetraoxide from battery wastes, comprising the following steps:

(4) 1) dissolving battery-preparing wastes with acid: adding 9 m.sup.3 washing water or clear water into a 20m.sup.3 acid dissolved baffle, starting stirring, slowly adding 1 m.sup.3 concentrated sulfuric acid, and slowly adding 4 tons of battery wastes; controlling a pH value to 0.5 with concentrated sulfuric acid or a material, and reacting for 3 h; and, filtering and washing, wherein, filtrate enters the next process, the washing liquid is returned back to an acid preparing process, and a filter cake is harmlessly treated.

(5) 2) removing iron and aluminum: pumping 10 m.sup.3 acid solution into a 20 m.sup.3 impurity-removing baffle, heating and stirring; controlling a temperature to 80 C., adding 120 kg of light calcium carbonate; adding sodium chlorate in an amount which is 0.35 time that of divalent iron in the solution; stirring for 30 min; regulating a pH value to 4.5 with 1.0N sodium carbonate solution; and filtering and washing, wherein, filtrate enters the next process, the washing liquid is used for preparing sodium carbonate solution, and a filter cake is harmlessly treated.

(6) 3) removing calcium, magnesium and copper: pumping 18 m.sup.3 iron-removing, filtrate into a 20 m.sup.3 calcium and magnesium-removing baffle, heating and stirring; controlling a temperature to 100 C., and adding sodium fluoride whose amount is 5 times total amount of calcium magnesium; stirring for 40 min; regulating pH to 5.5 with 0.5N sodium carbonate; and filtering and washing, wherein, filtrate, as pre-extraction solution, enters an extraction section, the washing liquid is used for preparing sodium carbonate solution, and a filter cake, as calcium, magnesium and copper residue, is separately treated.

(7) 4) carrying extraction separation, which adopts the following steps:

(8) a. separating a manganese element by extracting and stripping the pre-extraction solution under the following conditions to obtain high-purity and high-concentration anti-manganese liquid; after being repeatedly used, delivering the washing liquid to an acid dissolution workshop for preparing acid; returning the regeneration liquid back to be used as the washing liquid; and allowing extraction raffinate to, enter the next process.

(9) The numbers of grade of extraction can be set as saponification being in grade 1, manganese extraction being in grade 9, washing being in grade 2, stripping being in grade 5 and organic regeneration being in grade 2.

(10) Saponification liquid: 2.0N sodium hydroxide solution; organic composition of P204:TBP:kerosene=15:15:70 (v/v); washing liquid: 4N hydrochloric acid; stripping liquid: 3N sulfuric acid; organic regeneration liquid: 6N hydrochloric acid.

(11) b. separating a cobalt element by allowing extraction raffinate after extraction of manganese to enter an extraction process for separating cobalt, and extracting and stripping under the following conditions to obtain high-purity high-concentration anti-cobalt liquid; after being repeatedly used, delivering the washing liquid to an acid dissolved workshop for preparing acid; returning regeneration liquid back to be used as the washing liquid; and allowing extraction raffinate to enter the next process.

(12) The numbers of grade of extraction can be set as: saponification being in grade 1, cobalt extraction being in grade 5, washing being in grade 2, stripping being in grade 5, and organic regeneration being in grade 1.

(13) Saponification liquid: 2.0N sodium hydroxide solution; organic composition of P204:TBP:kerosene=20:20:60 (v/v); washing liquid: 4N hydrochloric acid; stripping liquid: 4N sulfuric acid; organic regeneration liquid: 6N hydrochloric acid.

(14) c. separating a nickel element by allowing extraction raffinate obtained after extraction of cobalt to enter an extraction process for separating nickel, and extracting and stripping under the following conditions to obtain high-purity high-concentration anti-nickel liquid; after being repeatedly used, delivering the washing liquid to an acid dissolved workshop for preparing acid; allowing the regeneration liquid return to back to be used as the washing liquid; and allowing extraction raffinate to enter an MVR evaporative crystallization process, and crystallizing and separating sodium sulfate in the extraction raffinate adopting a heat crystallization to achieve an objective of concentrating lithium sulfate.

(15) The numbers of grade of extraction can be set as saponification being in grade 1, cobalt extraction being in grade 5, washing being in grade 2, stripping being in grade 5, and organic regeneration being in grade 1.

(16) Saponification liquid: 2.0N sodium hydroxide solution; organic composition of P204:TBP:kerosene=10:10:80 (v/v); the washing liquid: 3N hydrochloric acid; the stripping liquid: 3N sulfuric acid; the organic regeneration liquid: 6N hydrochloric acid.

(17) 5) carrying out evaporative crystallization, which adopts the following steps:

(18) a. recovering manganese sulfate by extracting pre-extraction solution with a P204 extractant at first so that manganese in the solution is extracted to an organic phase, adding sulfuric acid into the organic phase for washing to obtain 200 g/L manganese-containing manganese sulfate solution, and carrying out evaporative crystallization and centrifugation on the solution to obtain a manganese sulfate product; regenerating the organic phase via acid washing, and saponifying with caustic soda solution to restore activity to be recycled; and adding a few amount of centrifugation mother liquor into the next-batch manganese sulfate solution for evaporative crystallization.

(19) b. recovering cobalt sulfate by extracting P204 extraction raffinate obtained after extraction of manganese in the previous process with P507 so that cobalt in the solution is extracted to an organic phase, adding sulfuric acid into the organic phase for washing to obtain 110 g/L cobalt-containing cobalt sulfate solution, and carrying out evaporative crystallization and centrifugation on the solution to obtain a cobalt sulfate product; regenerating the organic phase via acid washing, and saponifying with caustic soda solution to restore activity to be recycled; and adding a few amount of centrifugation mother liquor into the next-batch manganese sulfate solution for evaporative crystallization; alternatively, synthesizing 110 g/L cobalt-containing cobalt sulfate solution into hydroxy cobalt with sodium hydroxide solution, and after centrifugal filtration, firing at 800 C. to prepare tricobalt tetraoxide.

(20) c. recovering nickel sulfate by extracting P507 extraction raffinate obtained after extraction of cobalt in the previous process with P204 again so that nickel in the solution is extracted to an organic phase, adding sulfuric acid into the organic phase for washing to obtain 100 g/L nickel-containing nickel sulfate solution, and carrying out evaporative crystallization and centrifugation on the solution to obtain a nickel sulfate product; regenerating the organic phase via acid washing, and saponifying with caustic soda solution to restore activity to be recycled; and adding a few amount of centrifugation mother liquor into the next-batch manganese sulfate solution for evaporative crystallization.

(21) d. recovering sodium sulfate and lithium carbonate: evaporating P204 extraction raffinate obtained after extraction of nickel in the previous process with an MRV evaporative crystallization system, wherein, the P204 extraction raffinate contains about 1-4 g/L lithium and about15-20 g/L sodium which, are present in the solution in forms of sodium sulfate and lithium carbonate, until the extraction raffinate contains 15-20 g/L lithium so as to generate a large amount of sodium sulfate crystals; and carrying out centrifugal filtration to obtain an anhydrous sodium sulfate byproduct.

(22) e. recovering lithium sulfate: adding saturated sodium carbonate solution into centrifugation mother liquor, which is saturated sodium sulfate solution containing about 15 g/L lithium, of the sodium sulfate recovery process to obtain a lithium carbonate precipitate, wherein, a reaction temperature is controlled to100 C., and reaction time is 3 h; and carrying out centrifugal filtration on the precipitate, washing and drying to obtain a lithium carbonate product.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

(23) The disclosure will be further described in combination with embodiments.

(24) Example 1: a method for preparing nickel/manganese/lithium/cobalt sulfate and tricobalt tetraoxide from battery waste comprises the following steps:

(25) 1) dissolving battery-preparing wastes with acid: in an acid dissolved baffle, preparing sulfuric acid into 4N, and adding battery wastes in a solid-liquid mass ratio of 1:5; controlling a temperature to100 C., and reacting for 1 h; filtering and washing, wherein, filtrate enters the next process, the washing liquid is returned back to an acid preparing process, and a filter cake is harmlessly treated.

(26) 2) removing iron and aluminum: pumping acid solution into an impurity-removing baffle, heating and stirring; controlling a temperature to 80 C., adding 20 kg of light calcium carbonate per m.sup.3; adding sodium chlorate in an amount which is 0.3 time that of divalent iron in the solution; stirring for 30 min; regulating a pH value to 3.5 with 1.0N sodium carbonate solution; and filtering and washing, wherein, filtrate enters the next process, the washing liquid is used for preparing sodium carbonate solution, and a filter cake is harmlessly treated.

(27) 3) removing calcium, magnesium and copper: pumping iron-removing filtrate into a calcium and magnesium-removing baffle, heating and stirring; controlling a temperature to 100 C., and adding sodium fluoride whose amount is 5 times total amount of calcium magnesium; stirring for 30 min; regulating pH to 5.5 with 0.5N sodium carbonate; and filtering and washing, wherein, filtrate, as pre-extraction solution, enters an extraction section, the washing liquid is used for preparing sodium carbonate solution; and a filter cake, as calcium, magnesium and copper residue, is separately treated.

(28) 4) carrying extraction separation, which adopts the following steps:

(29) a. separating a manganese element by extracting and stripping the pre-extraction solution under the following conditions to obtain high-purity and high-concentration anti-manganese liquid; after being repeatedly used, allowing the washing liquid to enter an acid dissolution workshop for preparing acid; returning the regeneration liquid back to be used as the washing liquid; and allowing extraction raffinate to enter the next process.

(30) The numbers of grade of extraction can be set as saponification in being grade 1, manganese extraction being in grade 9, washing being in grade 2, grade 5 stripping being in grade 5 and organic regeneration being in grade 2.

(31) Saponification liquid: 2.0N sodium hydroxide solution; organic composition of P204:TBP:kerosene=10:10:80 (v/v); washing liquid: 2N hydrochloric acid; stripping liquid: 4N sulfuric acid; organic regeneration liquid: 6N hydrochloric acid.

(32) b. separating a cobalt element by allowing extraction raffinate obtained after extraction of manganese to enter an extraction process for separating cobalt, and extracting and stripping under the following conditions to obtain high-purity high-concentration anti-cobalt liquid; after being repeatedly used, delivering the washing liquid to an acid dissolved workshop for preparing acid; returning regeneration liquid back to be used as the washing liquid; and allowing extraction raffinate to enter the next process.

(33) The numbers of grade of extraction can be set as saponification being in grade 1, cobalt extraction being in grade 5, washing being in grade 2, stripping being in grade 5, and organic regeneration being in grade 1.

(34) Saponification liquid: 2.0N sodium hydroxide solution; organic composition of P204:TBP:kerosene 15:15:70 (v/v); washing liquid: 6N hydrochloric acid; stripping liquid: 4N sulfuric acid; organic regeneration liquid: 6N hydrochloric acid.

(35) c. separating a nickel element by allowing extraction raffinate obtained after extraction of cobalt to enter an extraction process for separating nickel, and extracting and stripping under the following conditions to obtain high-purity high-concentration anti-nickel liquid; after being repeatedly used, delivering the washing liquid to an acid dissolved workshop for preparing acid; returning the regeneration liquid back to be used as the washing liquid; and allowing extraction raffinate to enter an MVR evaporative crystallization process, and crystallizing and separating sodium sulfate in the extraction raffinate adopting a heat crystallization to achieve an objective of concentrating lithium sulfate.

(36) The numbers of grade of extraction can be set as saponification being in grade 1, cobalt extraction being in grade 5, washing being in grade 2, stripping being in grade 5, and organic regeneration being in grade 1.

(37) Saponification liquid: 1.0N sodium hydroxide solution; organic composition of P204:TBP:kerosene=15:15:70 (v/v); the washing liquid: 4N hydrochloric acid; the stripping liquid: 3N sulfuric acid; the organic regeneration liquid: 6N hydrochloric acid.

(38) 5) carrying out evaporative crystallization, which adopts the following steps:

(39) a. recovering manganese sulfate by extracting pre-extraction solution with a P204 extractant at first so that manganese in the solution is extracted to an organic phase, adding sulfuric acid into the organic phase for washing to obtain 200 g/L manganese-containing manganese sulfate solution, and carrying out evaporative crystallization and centrifugation on the solution to obtain a manganese sulfate product; regenerating the organic phase via acid washing, and saponifying with caustic soda solution to restore activity to be recycled; and adding a few amount of centrifugation mother liquor into the next-batch manganese sulfate solution for evaporative crystallization.

(40) b. recovering cobalt sulfate by extracting P204 extraction raffinate obtained after extraction of manganese in the previous process with P507 so that cobalt in the solution is extracted to an organic phase, adding sulfuric acid into the organic phase for washing to obtain 110 g/L cobalt-containing cobalt sulfate solution, and carrying out evaporative crystallization and centrifugation on the solution to obtain a cobalt sulfate product; regenerating the organic phase via acid washing, and saponifying with caustic soda solution to restore activity to be recycled; and adding a few amount of centrifugation mother liquor into the next-batch manganese sulfate solution for joint evaporative crystallization; alternatively, synthesizing 110 g/L cobalt-containing cobalt sulfate solution into hydroxy cobalt with sodium hydroxide solution, and after centrifuging, firing at 800 C. to prepare tricobalt tetraoxide.

(41) c. recovering nickel sulfate by extracting P507 extraction raffinate obtained after extraction of cobalt in the previous process with P204 again so that nickel in the solution is extracted to an organic phase, adding sulfuric acid into the organic phase for washing to obtain 100 g/L nickel-containing nickel sulfate solution, and carrying out evaporative crystallization and centrifugation on the solution to obtain a nickel sulfate product; regenerating the organic phase via acid washing, and saponifying with caustic soda solution to restore activity to be recycled; and adding a few amount of centrifugation mother liquor into the next-batch manganese sulfate solution for joint evaporative crystallization.

(42) d. recovering sodium sulfate and lithium carbonate: evaporating P204 extraction raffinate obtained after extraction of nickel in the previous process with an MRV evaporative crystallization system, wherein, the P204 extraction raffinate contains about 1-4 g/L lithium and about15-20 g/L sodium which are present in the solution in forms of sodium sulfate and lithium carbonate, until the extraction raffinate contains 15-20 g/L lithium so as to generate a large amount of sodium sulfate crystals; carrying out centrifugal filtration to obtain an anhydrous sodium sulfate byproduct.

(43) e. recovering lithium carbonate by adding saturated sodium carbonate solution into centrifugation mother liquor, which is saturated sodium sulfate solution containing 15-20 g/L lithium, of the sodium sulfate recovery process to obtain a lithium carbonate precipitate, wherein, reaction temperature is controlled to 100 C., and reaction time is 3 h; and carrying out centrifugal filtration on the precipitate, washing and, drying to obtain a lithium carbonate product.

(44) Example 2: a method for preparing nickel/manganese/lithium/cobalt sulfate and tricobalt tetraoxide from battery waste comprises the following steps:

(45) 1) dissolving battery waste with acid: in an acid dissolved baffle, preparing sulfuric acid into 4N, and adding battery wastes in a solid-liquid mass ratio of 1:5; controlling a temperature to 80 C., and reacting for 3 h; and filtering and washing, wherein, filtrate enters the next process, the washing liquid is returned back to an acid preparing process, and a filter cake is harmlessly treated.

(46) 2) removing iron and aluminum: pumping acid solution into an impurity-removing baffle, heating and stirring; controlling a temperature to 80 C., adding 50 kg of light calcium carbonate per m.sup.3; adding sodium chlorate in an amount 0.5 time that of divalent iron in the solution; stirring for 30 min; regulating a pH value to 4.0 with 2.0N sodium carbonate solution; and filtering and washing, wherein, filtrate enters the next process, the washing liquid is used for preparing sodium carbonate solution, and a filter cake is harmlessly treated.

(47) 3) removing calcium, magnesium and copper: pumping iron-removing filtrate into a calcium and magnesium-removing baffle, heating and stirring; controlling a temperature to 100 C., and adding sodium fluoride whose amount is 6 times total amount of calcium magnesium; stirring, for 40 min; regulating pH to 5.0 with 1.0N sodium carbonate; and filtering and washing, wherein, filtrate, as pre-extraction solution, enters an extraction section, the washing liquid is used for preparing sodium carbonate solution, and separately treating a filter cake, as calcium, magnesium and copper residue, is separately treated.

(48) 4) carrying extraction separation, which adopts the following steps:

(49) a. separating a manganese element by extracting and stripping the pre-extraction solution under the following conditions to obtain high-purity and high-concentration anti-manganese liquid; after being repeatedly used, allowing the washing liquid to enter an acid dissolution workshop for preparing acid; returning the regeneration liquid back to be used as the washing liquid; and allowing extraction raffinate to enter the next process.

(50) The numbers of grade of extraction can be set as saponification being in grade 1, cobalt extraction being in grade 9, washing being in grade 2, stripping being in grade 5, and organic regeneration being in grade 2.

(51) Saponification liquid: 0.5-2.0N sodium hydroxide solution; organic composition of P204:TBP:kerosene=20:20:60 (v/v); washing liquid: 4N hydrochloric acid; stripping liquid: 3N sulfuric acid; organic regeneration liquid: 6N hydrochloric acid.

(52) b. separating a cobalt element by allowing extraction raffinate obtained after extraction of, manganese to enter an extraction process for separating cobalt, and extracting and stripping under the following conditions to obtain high-purity high-concentration anti-cobalt liquid; after being repeatedly used, delivering the washing liquid to an acid dissolved workshop for preparing acid; returning regeneration liquid back to be used as the washing liquid; and allowing extraction raffinate to enter the next process.

(53) The numbers of grade of extraction can be set as saponification being in grade 1, cobalt extraction being in grade 5, washing being in grade 2, stripping being in grade 5, and organic regeneration being in grade 1.

(54) Saponification liquid: 2.0N sodium hydroxide solution; organic composition of P507:TBP; kerosene=20:20:60 (v/v); washing liquid: 4N hydrochloric acid; stripping liquid: 4N sulfuric acid; organic regeneration liquid: 6N hydrochloric acid.

(55) c. separating a nickel element by allowing extraction raffinate obtained after extraction of cobalt to enter an extraction process for separating nickel, and extracting and stripping under the following conditions to obtain high-purity high-concentration anti-nickel liquid; after being repeatedly used, delivering the washing liquid to an acid dissolved workshop for preparing acid; returning the regeneration liquid back to be used as the washing liquid; and allowing extraction raffinate to enter an MVR evaporative crystallization process, and crystallizing and separating sodium sulfate in the extraction raffinate adopting a heat crystallization to achieve an objective of concentrating lithium sulfate.

(56) The numbers of grade of extraction can be set as saponification being in grade 1, cobalt extraction being in grade 5, washing being in grade 2, stripping being in grade 5, and organic regeneration being in grade 1.

(57) Saponification liquid: 2.0N sodium hydroxide solution; organic composition of P204:TBP:kerosene=10:10:80 (v/v); the washing liquid: 3N hydrochloric acid; the stripping liquid: 3N sulfuric acid; the organic regeneration liquid: 6N hydrochloric acid.

(58) 5) carrying out evaporative crystallization, which adopts the following steps:

(59) a. recovering manganese sulfate by extracting pre-extraction solution with a P204 extractant at first so that manganese in the solution is extracted to an organic phase, adding sulfuric acid into the organic phase for washing to obtain 200 g/L manganese-containing manganese sulfate solution, and carrying out evaporative crystallization and centrifugation on the solution to obtain a manganese sulfate product; regenerating the organic phase via acid washing, and saponifying with caustic soda solution to restore activity to be recycled; and adding a few amount of centrifugation mother liquor into the next-batch manganese sulfate solution for evaporative crystallization.

(60) b. recovering cobalt sulfate by extracting P204 extraction raffinate obtained after extraction of manganese in the previous process with P507 so that cobalt in the solution is extracted to an organic phase, adding sulfuric acid into the organic phase for washing to obtain 110 g/L cobalt-containing cobalt sulfate solution, synthesizing hydroxy cobalt with sodium hydroxide solution, and after centrifuging, firing at 800 C. to prepare tricobalt tetraoxide.

(61) c. recovering nickel sulfate by extracting P507 extraction raffinate obtained after extraction of cobalt in the previous process with P204 again so that nickel in the solution is extracted to an organic phase, adding sulfuric acid into the organic phase for washing to obtain 100 g/L nickel-containing nickel sulfate solution, and carrying out evaporative crystallization and centrifugation on the solution to obtain a nickel sulfate product; regenerating the organic phase via acid washing, and saponifying with caustic soda solution to restore activity to be recycled; and adding a few amount of centrifugation mother liquor into the next-batch manganese sulfate solution for evaporative crystallization.

(62) d. recovering sodium sulfate by evaporating P204 extraction raffinate obtained after extraction of nickel in the previous process with an MRV evaporative crystallization system, wherein, the P204 extraction raffinate contains about 1-4 g/L lithium and about 15-20 g/L sodium which are present in the solution in forms of sodium sulfate and lithium carbonate, until the extraction raffinate contains 15-20 g/L lithium so as to generate a large amount of sodium sulfate crystals; and carrying out centrifugal filtration to obtain an anhydrous sodium sulfate byproduct.

(63) e. recovering lithium carbonate by adding saturated sodium carbonate solution into centrifugation mother liquor, which is saturated sodium sulfate solution containing 15-20 g/L lithium, of the sodium sulfate recovery process to obtain a lithium carbonate precipitate, wherein, reaction temperature is controlled to 100 C., and reaction time is 2 h; and carrying out centrifugal filtration on the precipitate, washing and drying to obtain a lithium carbonate product.

(64) Example 3: a method for preparing nickel/manganese/lithium/cobalt sulfate and tricobalt tetraoxide from battery waste comprises the following steps:

(65) 1) dissolving battery-preparing wastes with acid: adding 9 m.sup.3 washing water or clear water into a 20 m.sup.3 acid dissolved baffle, starting stirring, slowly adding 1 m.sup.3 concentrated sulfuric acid, and slowly adding 4 tons of battery wastes; controlling a pH value to 0.5 with concentrated sulfuric acid or a material, and reacting for 3 h; and filtering and washing, wherein, filtrate enters the next process, the washing liquid is returned back to an acid preparing process, and a filter cake is harmlessly treated.

(66) 2) removing iron and aluminum: pumping 10 m.sup.3 acid solution into an 20 m.sup.3 impurity-removing baffle, heating and stirring; controlling a temperature to 80 C., adding 120 kg of light calcium carbonate; adding sodium chloride in an amount 0.35 time that of divalent iron in the solution; stirring for 30 min; regulating a pH value to 4.5 with 1.0N sodium carbonate solution; and filtering and washing, wherein, filtrate enters the next process, the washing liquid is used for preparing sodium carbonate solution, and a filter cake is harmlessly treated.

(67) 3) removing calcium, magnesium and copper: pumping 18 m.sup.3 iron-removing filtrate into a calcium and magnesium-removing baffle, heating and stirring; controlling a temperature to 100 C., and adding sodium fluoride whose amount is 4.5 times total amount of calcium magnesium; stirring for 40 min; regulating pH to 5.5 with 0.5N sodium carbonate; and filtering and washing, wherein, filtrate, as pre-extraction solution, enters an extraction process, the washing liquid is used for preparing sodium carbonate solution, and a filter cake, as calcium, magnesium and copper residue, is separately treated.

(68) 4) carrying extraction separation, which adopts the following steps:

(69) a. separating a manganese element by extracting and stripping the pre-extraction solution under the following conditions to obtain high-purity and high-concentration anti-manganese liquid; after being repeatedly used, allowing the washing liquid to enter an acid dissolution workshop for preparing acid; returning the regeneration liquid back to be used as the washing liquid; and allowing extraction raffinate to enter the next process.

(70) The numbers of grade of extraction can be set as saponification being in grade 1, cobalt extraction being in grade 9, washing being in grade 2, stripping being in grade 5, and organic regeneration being in grade 2.

(71) Saponification liquid: 2.0N sodium hydroxide solution; organic composition of P204:TBP:kerosene=15:15:70 (v/v); washing liquid: 4N hydrochloric acid; stripping liquid: 3N sulfuric acid; organic regeneration liquid: 6N hydrochloric acid.

(72) b. separating a cobalt element by allowing extraction raffinate obtained after extraction of, manganese to enter an extraction process for separating cobalt, and extracting and stripping under the following conditions to obtain high-purity high-concentration anti-cobalt liquid; after being repeatedly used, delivering the washing liquid to an acid dissolved workshop for preparing acid; returning regeneration liquid back to be used as the washing liquid; and allowing extraction raffinate to enter the next process.

(73) The numbers of grade of extraction can be set as saponification being in grade 1, cobalt extraction being in grade 5, washing being in grade 2, stripping being in grade 5, and organic regeneration being in grade 1.

(74) Saponification liquid: 2.0N sodium hydroxide solution; organic composition, of P507:TBP:kerosene=20:20:60 (v/v); washing liquid: 4N hydrochloric acid; stripping liquid: 4N sulfuric acid; organic regeneration liquid: 6N hydrochloric acid.

(75) c. separating a nickel element by allowing extraction raffinate obtained after extraction cobalt to enter an extraction process for separating nickel, and extracting and stripping under the following conditions to obtain high-purity high-concentration anti-nickel liquid; after being repeatedly used, delivering the washing liquid to an acid dissolved workshop for preparing acid; returning the regeneration liquid back to be used as the washing liquid; and allowing extraction raffinate to enter an MVR evaporative crystallization process, and crystallizing and separating sodium sulfate in the extraction raffinate adopting a heat crystallization to achieve an objective of concentrating lithium sulfate.

(76) The numbers of grade of extraction can be set as saponification being in grade 1, cobalt extraction being in grade 5, washing being in grade 2, stripping being in grade 5, and organic regeneration being in grade 1.

(77) Saponification liquid: 2.0N sodium hydroxide solution; organic composition of P204:TBP:kerosene=10:10:80 (v/v); the washing liquid: 3N hydrochloric acid; the stripping liquid: 3N sulfuric acid; the organic regeneration liquid: 6N hydrochloric acid.

(78) 5) carrying out evaporative crystallization, which adopts the following steps:

(79) a. recovering manganese sulfate by extracting pre-extraction solution with a P204 extractant at first so that manganese in the solution is extracted to an organic phase, adding sulfuric acid into the organic phase for washing to obtain 200 g/L manganese-containing manganese sulfate solution, and carrying out evaporative crystallization and centrifugation on the solution to obtain a manganese sulfate product; regenerating the organic phase via acid washing, and saponifying with caustic soda solution to restore activity to be recycled; and adding a few amount of centrifugation mother liquor into the next-batch manganese sulfate solution for evaporative crystallization.

(80) b. recovering cobalt sulfate by extracting P204 extraction raffinate obtained after extraction of manganese in the previous process with P507 so that cobalt in the solution is extracted to an organic phase, adding sulfuric acid into the organic phase for washing to obtain 110 g/L cobalt-containing cobalt sulfate solution, carrying out evaporative crystallization and centrifugation on the solution to obtain a cobalt sulfate product; regenerating the organic phase via acid washing, and saponifying with caustic soda to restore activity to be recycled; adding a few amount of centrifugation mother liquor into the next-batch cobalt sulfate solution for joint evaporative crystallization; alternatively, synthesizing 110 g/L cobalt-containing cobalt sulfate solution into hydroxy cobalt with sodium hydroxide solution, and after centrifuging, firing at 800 C. to prepare tricobalt tetraoxide.

(81) c. recovering nickel sulfate by extracting P507 extraction raffinate obtained after extraction of cobalt in the previous process with P204 again so that nickel in the solution is extracted to an organic phase, adding sulfuric acid into the organic phase for washing to obtain 100 g/L nickel-containing nickel sulfate solution, and carrying out evaporative crystallization and centrifugation on the solution to obtain a nickel sulfate product; regenerating the organic phase via acid washing, and saponifying with caustic soda solution to restore activity to be recycled; and adding a few amount of centrifugation mother liquor into the next-batch manganese sulfate solution for evaporative crystallization.

(82) d. recovering sodium sulfate: evaporating P204 extraction raffinate obtained after extraction of nickel in the previous process with an MRV evaporative crystallization system, wherein, the P204 extraction raffinate contains about 1-4 g/L lithium and about 15-20 g/L sodium which are present in the solution in forms of sodium sulfate and lithium carbonate, until the extraction raffinate contains 15-20 g/L lithium so as to generate a large amount of sodium sulfate crystals; and carrying out centrifugal filtration to obtain an anhydrous, sodium sulfate byproduct.

(83) e. recovering lithium carbonate by adding saturated sodium carbonate solution into centrifugation mother liquor, which is saturated sodium sulfate solution containing about 15 g/L lithium, of the sodium sulfate recovery process to obtain a lithium carbonate precipitate, wherein, reaction temperature is controlled to 100 C., and reaction time is 4 h; and carrying out centrifugal filtration on the precipitate, washing and drying to obtain a lithium carbonate product.

(84) Embodiments of the disclosure are only limited to the above examples, each technological factor point within a parameter range and near a parameter range in the technical solution of the disclosure and technical features obtained by those skilled in the art via inference, expansion, permutation and combination are all included within the scope exemplified by embodiments of the disclosure.

(85) Detection data of process flow at various stages in Examples of the disclosure is as follows:

(86) TABLE-US-00001 a. Detection Table of Battery wastes Items Co Ni Mn Li Fe Al Cu Ca Mg Battery 15.61 6.61 8.36 4.15 0.21 14.35 4.21 0.35 0.18 wastes 1 (%) Battery 24.35 0.21 0.18 4.56 0.35 15.21 3.86 0.44 0.24 wastes 2 (%)

(87) TABLE-US-00002 b. Acid Decomposition Process Detection Items Co Ni Mn Li Fe Al Cu Ca Mg Acid 34.60 13.57 18.57 9.01 0.45 31.77 9.27 0.71 0.40 decomposition liquid g/L Decomposition 0.32 0.15 0.11 0.10 0.14 0.21 0.12 residue % Leaching rate 98.3 99.1 99.3 98.10 97.40 (%)

(88) TABLE-US-00003 c. Iron-Removing and Aluminum-Removing Process Detection Items Co Ni Mn Li Fe Al Cu Ca Mg Iron- 30.25 12.22 16.54 8.24 0.01 0.01 8.35 removing liquid g/L Iron and 0.38 0.22 0.44 0.01 16.11 34.02 0.23 Aluminum residue

(89) TABLE-US-00004 d. Calcium/Magnesium/Copper-Removing Process Detection Items Co Ni Mn Li Fe Al Cu Ca Mg Pre-extraction 29.14 11.65 15.88 3.21 0.001 0.001 0.01 0.002 0.002 solution g/L Calcium and 4.36 1.21 1.0 4.65 2.11 2.15 8.21 15.11 11.21 magnesium residue

(90) TABLE-US-00005 e. Manganese-Extracting Process Detection Items Co Ni Mn Li Fe Al Cu Ca Mg Anti-manganese 0.001 0.001 112.5 0.001 0.001 0.001 0.001 0.001 0.001 liquid g/L Manganese 28.15 11.11 0.001 2.55 0.001 0.001 0.001 0.001 0.001 extraction raffinate g/L

(91) TABLE-US-00006 f. Cobalt-Extracting Process Detection Items Co Ni Mn Li Fe Al Cu Ca Mg Anti-cobalt 110.2 10.50 0.001 0.001 0.001 0.001 0.001 0.001 0.001 liquid g/L Cobalt 0.001 0.001 0.001 2.32 0.001 0.001 0.001 0.001 0.001 extraction raffinate g/L

(92) TABLE-US-00007 g. Nickel-Extracting Process Detection Items Co Ni Mn Li Fe Al Cu Ca Mg Anti-nickel 0.001 100.50 0.001 0.001 0.001 0.001 0.001 0.001 0.001 liquid g/L Nickel 0.001 0.001 0.001 2.22 0.001 0.001 0.001 0.001 0.001 extraction raffinate g/L

(93) TABLE-US-00008 h. MVP Evaporative Crystallization Process Detection Items Co Ni Mn Li Fe Al Cu Ca Mg Concentrated 0.01 0.01 0.01 20.15 0.01 0.01 0.01 0.01 0.01 mother liquor g/L Anhydrous 0.001 0.001 0.001 0.1 0.001 0.001 0.001 0.01 0.01 sodium sulfate % Condensed 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 water (%)

INDUSTRIAL APPLICABILITY

(94) According to the disclosure, through pilot scale test, the yield of cobalt is 95% the yield of nickel is 96%, and the yield of lithium is 90%.

(95) TABLE-US-00009 Quality detection indexes of various products after a pilot scale test in the disclosure Nickel Cobalt Manganese Lithium Elements sulfate sulfate sulfate carbonate (%) Standard Product Standard Product Standard Product Standard Product Note Co 0.05 0.005 20.50 20.52 0.0020 0.0010 0.0005 0.0005 Ni 21.5 21.24 0.0010 0.0005 0.0020 0.002 0.0005 0.0001 Mn 0.0005 0.0003 0.0005 0.0004 31.80 31.82 0.0005 0.0002 Cu 0.0005 0.0001 0.0005 0.0002 0.0020 0.0008 0.0005 0.0002 Fe 0.0005 0.0003 0.0005 0.0002 0.0005 0.0001 0.0005 0.0003 Al 0.0005 0.0001 0.0005 0.0002 0.0005 0.0002 0.0001 0.0001 Na 0.001 0.0005 0.0010 0.0005 0.001 0.0007 0.0010 0.0008 Mg 0.0005 0.0001 0.0005 0.0002 0.0015 0.0006 0.0010 0.0005 Ca 0.0005 0.0003 0.0005 0.0004 0.002 0.0008 0.0010 0.0005 Pb 0.0001 0.0001 0.0001 0.0001 0.0020 0.0001 0.0005 0.0005 Cr 0.0005 0.0002 0.0005 0.0001 0.0001 0.0001 0.0005 0.0004 Cd 0.0005 0.0002 0.0005 0.0002 0.0001 0.0001 0.0005 0.0002 Zn 0.0005 0.0003 0.0005 0.0003 0.0005 0.0001 0.0005 0.0003

(96) TABLE-US-00010 Detection indexes of battery-grade tricobalt tetraoxide in the disclosure Items Detection name Index Detection result Physical index Appearance Dark grey powder Dark grey powder Central grain size 7.3 0.5 7.71 D50 (m) Tap density T.D 2.30 2.31 (g/m.sup.2) Water content (%) 0.080 0.044 Micromorphology Spherical shape or Spherical shape or spherical-like shape spherical-like shape Magnetic foreign Fe + Ni + Cr + Zn 2 matters (ppm) Detection Detection Detection Detection Items name Index result Items name Index result Element Cobalt (Co) 72.8 72.98 Element Plumbum 0.003 0.0021 content content (Pb) (%) Copper 0.005 0.0004 (%) Sodium 0.005 0.0033 (Cu) (Na) Calcium 0.01 0.0046 Chrome (Cr) 0.002 0.0017 (Ca) Manganese 0.002 0.0007 Zinc (Zn) 0.005 0.0006 (Mn) Nickel (Ni) 0.005 0.0021 Chlorine 0.005 0.002 (Cl) Ferrum 0.005 0.0035 Hydrargyrum 0.001 0.0008 (Fe) (Hg) Magnesium 0.005 0.0036 (Mg)