METHOD FOR RECYCLING NICKEL, COBALT AND MANGANESE FROM FEED LIQUID CONTAINING NICKEL, COBALT AND MANGANESE

Abstract

A method for recycling nickel, cobalt and manganese from a feed liquid containing nickel, cobalt and manganese, the method comprising: (1) subjecting the feed liquid to a first extraction to obtain an aqueous phase 1 and an organic phase 1; (2) subjecting the aqueous phase 1 to a second extraction to obtain an organic phase 2 and an aqueous phase 2 having a pH value of 5-7.5; and (3) successively subjecting the organic phase 2 to washing and reverse extraction to obtain a solution containing nickel, cobalt and manganese, wherein an extractant A used in the second extraction comprises a carboxylic acid extractant.

Claims

1. A method for recycling nickel, cobalt and manganese from a feed solution containing nickel, cobalt and manganese, comprising (1) subjecting the feed solution to a first extraction to obtain an aqueous phase 1 and an organic phase 1; (2) subjecting the aqueous phase 1 obtained in step (1) to a second extraction to obtain an organic phase 2 and an aqueous phase 2 with a pH value of 5-7.5; and (3) subjecting the organic phase 2 obtained in step (2) to washing and back extraction in sequence to obtain a solution containing nickel, cobalt and manganese; wherein an extractant A used in the second extraction comprises a carboxylic acid extractant; the carboxylic acid extractant has the following structural general formula: ##STR00005## wherein 10≤m+n≤22, and —C.sub.nH.sub.2n+1 and —C.sub.mH.sub.2m+1 are each independently linear or branched alkyl with 1-21 carbon atoms.

2. The method according to claim 1, wherein a metal element in the feed solution comprises 1-16 g/L Li, 1-50 g/L Ni, 1-26 g/L Co, 1-30 g/L Mn, less than or equal to 10 g/L of Fe, less than or equal to 1 g/L of Al, less than or equal to 10 g/L of Cu, less than or equal to 5 g/L of Zn, 0.1-0.5 g/L Ca and 0.1-50 g/L Mg.

3. The method according to claim 1, wherein an extractant B used in the first extraction in step (1) comprises one or a combination of at least two of a phosphorus extractant, a carboxylic acid extractant or an oxime extractant.

4. The method according to claim 3, wherein the carboxylic acid extractant has the following structural general formula: ##STR00006## wherein 10≤m+n≤22, and —C.sub.nH.sub.2n+1 and —C.sub.mH.sub.2m+1 are each independently linear or branched alkyl with 1-21 carbon atoms; optionally, the carboxylic acid extractant is one carboxylic acid or a mixture of at least two carboxylic acids; optionally, the extractant B has a volume fraction of 5-30%; optionally, a diluent of the extractant B comprises one or a combination of at least two of solvent oil, kerosene, Escaid 110, hexane, heptane and dodecane; optionally, the extractant B is saponified before use; optionally, the saponification is carried out by using a 6-14 mol/L alkaline solution; optionally, the alkaline solution comprises one or a combination of at least two of a sodium hydroxide solution, a potassium hydroxide solution or aqueous ammonia.

5. The method according to claim 1, wherein the first extraction in step (1) comprises single-stage extraction or multi-stage countercurrent extraction; optionally, the extractant B used in the first extraction in step (1) and the feed solution have a volume ratio of (0.1-10):1; optionally, the first extraction in step (1) has a stirring speed of 100-250 r/min; optionally, the first extraction in step (1) has a mixing time of 5-30 min; optionally, the multi-stage countercurrent extraction has 2-30 stages.

6. The method according to claim 1, wherein the extractant A has a volume fraction of 5-30%; optionally, the carboxylic acid extractant in the extractant A is one carboxylic acid or a mixture of at least two carboxylic acids; optionally, a diluent of the extractant A comprises one or a combination of at least two of solvent oil, kerosene, Escaid 110, hexane, heptane and dodecane; optionally, the extractant A is saponified before use; optionally, the saponification is carried out by using a 6-14 mol/L alkaline solution; optionally, the alkaline solution comprises one or a combination of at least two of a sodium hydroxide solution, a potassium hydroxide solution or aqueous ammonia.

7. The method according to of claim 1, wherein the second extraction in step (2) is multi-stage countercurrent extraction; optionally, the extractant A used in the second extraction in step (2) and the aqueous phase 1 have a volume ratio of (0.1-10):1; optionally, the second extraction in step (2) has a stirring speed of 100-250 r/min; optionally, the second extraction in step (2) has a mixing time of 5-30 min; optionally, the multi-stage countercurrent extraction of the second extraction has 5-30 stages.

8. The method according to claim 1, wherein the method further comprises subjecting the organic phase 1 in step (1) to multi-stage countercurrent washing and then back extraction to obtain a solution containing metal ions and an organic phase 3; optionally, the washing has 2-10 stages; optionally, the organic phase 3 is returned to be used as an extractant.

9. The method according to claim 1, wherein the method comprises subjecting the aqueous phase 2 in step (2) to oil removal and crystallization in sequence to obtain sodium sulfate crystals; optionally, the crystallization is carried out in a manner of MVR evaporation.

10. The method according to claim 1, wherein the washing in step (3) is multi-stage countercurrent washing; optionally, the washing has 2-10 stages.

11. The method according to claim 1, comprising (1) subjecting the feed solution to a first extraction to obtain an aqueous phase 1 and an organic phase 1; wherein an extractant B used in the first extraction comprises one or a combination of at least two of a phosphorus extractant, a carboxylic acid extractant or an oxime extractant; the carboxylic acid extractant has the following structural general formula: ##STR00007## wherein 10≤m+n≤22, and —C.sub.nH.sub.2n+1 and —C.sub.mH.sub.2m+1 are each independently linear or branched alkyl with 1-21 carbon atoms; the extractant B has a volume fraction of 5-30%; the first extraction comprises single-stage extraction or multi-stage countercurrent extraction; the extractant B used in the first extraction and the feed solution have a volume ratio of (0.1-10):1; the first extraction has a stirring speed of 100-250 r/min; the first extraction has a mixing time of 5-30 min; the multi-stage countercurrent extraction has 2-30 stages; (2) subjecting the aqueous phase 1 obtained in step (1) to a second extraction to obtain an organic phase 2 and an aqueous phase 2 with a pH value of 5-7.5; wherein an extractant A used in the second extraction comprises a carboxylic acid extractant; the carboxylic acid extractant has the following structural general formula: ##STR00008## wherein 10≤m+n≤22, and —C.sub.nH.sub.2n+1 and —C.sub.mH.sub.2m+1 are each independently linear or branched alkyl with 1-21 carbon atoms; the extractant A has a volume fraction of 5-30%; the second extraction is multi-stage countercurrent extraction; the extractant A used in the second extraction and the aqueous phase 1 have a volume ratio of (0.1-10):1; the second extraction has a stirring speed of 100-250 r/min; the second extraction has a mixing time of 5-30 min; the multi-stage countercurrent extraction of the second extraction has 5-30 stages; and (3) subjecting the organic phase 2 obtained in step (2) to washing and back extraction in sequence to obtain a solution containing nickel, cobalt and manganese; wherein the washing is multi-stage countercurrent washing; the washing has 2-10 stages.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0080] FIG. 1 is a schematic diagram of a recovery method in Example 1 of the present application.

[0081] The present application will be further described in detail hereinafter. However, the following embodiments are only simple examples of the present application, and do not represent or limit the protection scope of the claims of the present application. The protection scope of the present application is defined by the appended claims.

DETAILED DESCRIPTION

[0082] For both a better explanation of the present application and a better understanding of the technical solutions of the present application, the typical but non-limiting embodiments of the present application are described below.

Example 1

[0083] This example provides a method for recycling nickel, cobalt and manganese from a feed solution containing nickel, cobalt and manganese, as shown in FIG. 1.

[0084] The feed solution in this example is a battery feed solution containing nickel, cobalt and manganese, the feed solution has a pH value of 4.46, and the components are as follows:

TABLE-US-00001 Element Fe Al Zn Cu Ni Co Mn Ca Mg Li Content (g/L) 0.001 0.001 0.5 0.8 46 22 20 0.4 0.3 9

[0085] In this example, the copper in the feed solution was extracted by using the saponified Mextral 984H extractant (a volume fraction was 15%, a diluent was solvent oil No. 260, and an 8 mol/L NaOH solution was used for the saponification) before a first extraction, the extraction had 1 stage, the organic phase and the feed solution had a volume ratio of 0.25:1, a mixing time was 10 min, a stirring speed was 120 r/min, the system was allowed to stand for 10 min, an experimental temperature was 25° C., and a pH of the aqueous phase was controlled at 2.5. After phase separation, a copper-loaded organic phase and a copper-removed feed solution were obtained separately. The copper-loaded organic phase was subjected to one-stage countercurrent washing by using a dilute sulfuric acid at pH 1, and then subjected to back extraction twice by using a 2 mol/L sulfuric acid. The organic phase 1 and the washing solution or the organic phase 1 and the back extraction solution had a volume ratio of 10:1. The obtained copper sulfate solution was subjected to oil removal and then concentration and crystallization.

[0086] In this example, the first extraction adopted C272 as the extractant, a volume fraction was 15%, and a diluent was solvent oil No. 260, and the extractant was saponified by an 8 mol/L NaOH solution.

[0087] The copper-removed feed solution was subjected to multi-stage countercurrent extraction by using the saponified C272, the extraction had 2 stages, the organic phase and the copper-removed feed solution had a volume ratio of 0.25:1, a mixing time was 10 min, a stirring speed was 120 r/min, and an experimental temperature was 25° C. After phase separation, an organic phase 1 and an aqueous phase 1 at pH 3 were obtained separately, and the organic phase 1 was subjected to four-stage countercurrent washing by using a dilute sulfuric acid at pH 1, and then subjected to back extraction twice by using a 2 mol/L sulfuric acid. The organic phase 1 and the washing solution or the organic phase 1 and the back extraction solution had a volume ratio of 10:1. The obtained zinc sulfate solution was subjected to oil removal and then concentration and crystallization. The organic phase was returned to the saponification process for recycling.

[0088] The aqueous phase 1 was subjected to multi-stage countercurrent extraction by using the saponified Mextral BC191 extractant (a volume fraction was 25%, a diluent was solvent oil No. 260, and a 14 mol/L NaOH solution was used for the saponification), the extraction had 15 stages, the organic phase and the aqueous phase 1 had a volume ratio of 3:1, a mixing time was 10 min, a stirring speed was 120 r/min, the system was allowed to stand for 10 min, an experimental temperature was 25° C., and an organic phase 2 and an aqueous phase 2 at pH 6 were obtained separately. The organic phase 2 was subjected to five-stage countercurrent washing by using a dilute sulfuric acid at pH 1, and then subjected to back extraction six times by using a 2 mol/L sulfuric acid. The organic phase 2 and the washing solution or the organic phase 2 and the back extraction solution had a volume ratio of 9:1. Thus a solution rich in nickel, cobalt and manganese was obtained.

[0089] In this example, the impurity removal rate is 99.2%, the extraction rates of Ni, Co and Mn are 99.8%, 99.7% and 99.6% respectively, and the back extraction rates are 99.5%, 99.6% and 99.6% respectively.

Example 2

[0090] This example provides a method for recycling nickel, cobalt and manganese from a feed solution containing nickel, cobalt and manganese, the feed solution in this example is a battery 15 feed solution containing nickel, cobalt and manganese, the feed solution has a pH value of 1.59, and the components are as follows:

TABLE-US-00002 Element Fe Al Zn Cu Ni Co Mn Ca Mg Li Content (g/L) 0.5 0.01 0.3 0.6 48 22 18 0.5 0.5 10

[0091] In this example, BC196 was used as the extractant, a volume fraction was 25%, and a diluent was Escaid 110, and the extractant was saponified by a 6 mol/L NaOH solution.

[0092] The feed solution containing nickel, cobalt and manganese was subjected to eight-stage countercurrent extraction by using the saponified BC196, the extractant and the battery feed solution had a volume ratio of 0.2:1, a mixing time was 8 min, a stirring speed was 150 r/min, and an experimental temperature was 25° C. After phase separation, the organic phase 1 and the aqueous phase 1 at pH 5.7 were obtained separately. The organic phase 1 was subjected to eight-stage countercurrent washing by using a dilute sulfuric acid at pH 1.5, and then subjected to back extraction thrice by using a 2.5 mol/L sulfuric acid. The organic phase 1 and the washing solution or the organic phase 1 and the back extraction solution had a volume ratio of 10:1. The obtained mixing solution of ferric sulfate, copper sulfate, zinc sulfate and aluminum sulfate was subjected to oil removal and then concentration and crystallization. The organic phase was returned to the saponification process for recycling.

[0093] The aqueous phase 1 was subjected to multi-stage countercurrent extraction by using the saponified BC196, the extraction had 8 stages, the organic phase and the aqueous phase 1 had a volume ratio of 4:1, a mixing time was 8 min, a stirring speed was 150 r/min, the system was allowed to stand for 15 min, an experimental temperature was 25° C., and an organic phase 2 and an aqueous phase 2 at pH 6.4 were obtained separately. The organic phase 2 was subjected to seven-stage countercurrent washing by using a dilute sulfuric acid at pH 1.5, and then subjected to back extraction five times by using a 2.5 mol/L sulfuric acid. The organic phase 2 and the washing solution or the organic phase 2 and the back extraction solution had a volume ratio of 10:1. Thus a solution rich in nickel, cobalt and manganese was obtained.

[0094] In this example, the impurity removal rate is 99.4%, the extraction rates of Ni, Co and Mn are 99.8%, 99.6% and 99.5% respectively, and the back extraction rates are 99.7%, 99.7% and 99.6% respectively.

Example 3

[0095] This example provides a method for recycling nickel, cobalt and manganese from a feed solution containing nickel, cobalt and manganese, the feed solution in this example is a battery feed solution containing nickel, cobalt and manganese, the feed solution has a pH value of 4.3, and the components are as follows:

TABLE-US-00003 Element Fe Al Zn Cu Ni Co Mn Ca Mg Li Content (g/L) 0.001 0.001 0.5 0.7 48 24 20 0.5 0.5 10

[0096] In this example, the copper in the feed solution was extracted by using the saponified CP50 extractant (a volume fraction was 20%, a diluent was sulfonated kerosene, and a saponifier was an 8 mol/L NaOH solution) before a first extraction, the extraction had 1 stage, a ratio was 0.25:1, a mixing time was 5 min, a stirring speed was 200 r/min, the system was allowed to stand for 20 min, an experimental temperature was 20° C., and a pH of the aqueous phase was controlled at 2.5. After phase separation, a copper-loaded organic phase and a copper-removed feed solution were obtained separately. The copper-loaded organic phase was subjected to one-stage countercurrent washing by using a dilute sulfuric acid at pH 1, and then subjected to back extraction twice by using a 2 mol/L sulfuric acid. The organic phase 1 and the washing solution or the organic phase 1 and the back extraction solution had a volume ratio of 10:1. The obtained copper sulfate solution was subjected to oil removal and then concentration and crystallization.

[0097] In this example, the first extraction adopted P204 as the extractant, a volume fraction was 20%, and a diluent was sulfonated kerosene, and the extractant was saponified by an 8 mol/L NaOH solution.

[0098] The copper-removed feed solution containing nickel, cobalt and manganese was subjected to seven-stage countercurrent extraction by using the saponified P204, the extractant and the copper-removed feed solution had a volume ratio of 0.25:1, a mixing time was 5 min, a stirring speed was 200 r/min, and an experimental temperature was 20° C. After phase separation, an organic phase 1 and an aqueous phase 1 at pH 2 were obtained separately, and the organic phase 1 was subjected to four-stage countercurrent washing by using hydrochloric acid at pH 1, and then subjected to back extraction twice by using a 4 mol/L hydrochloric acid. The organic phase 1 and the washing solution or the organic phase 1 and the back extraction solution had a volume ratio of 10:1. The obtained mixing solution of calcium chloride and zinc chloride was subjected to oil removal and then concentration and crystallization. The organic phase was returned to the saponification process for recycling.

[0099] The aqueous phase 1 was subjected to a second extraction by using the saponified BC194 (a volume fraction was 30%, a diluent was Escaid 110, and a saponifier was a 10 mol/L NaOH solution), the extraction was multi-stage countercurrent extraction with 7 stages, the BC194 extractant and the aqueous phase 1 had a volume ratio of 3:1, a mixing time was 5 min, a stirring speed was 200 r/min, an experimental temperature was 20° C., and an organic phase 2 and an aqueous phase 2 at pH 6.8 were obtained separately. The organic phase 2 was subjected to eight-stage countercurrent washing by using sulfuric acid at pH 1, and then subjected to back extraction six times by using a 2 mol/L sulfuric acid. The organic phase 2 and the washing solution or the organic phase 2 and the back extraction solution had a volume ratio of 9:1. Thus a solution rich in nickel, cobalt and manganese was obtained.

[0100] In this example, the impurity removal rate is 99.3%, the extraction rates of Ni, Co and Mn are 99.8%, 99.7% and 99.6% respectively, and the back extraction rates are 99.7%, 99.6% and 99.5% respectively.

Example 4

[0101] The only difference from Example 1 is that the pH of the aqueous phase 2 was controlled at 7.5. In this example, the impurity removal rate is 99.3%, the extraction rates of Ni, Co and Mn are 99.7%, 99.8% and 99.6% respectively, and back extraction rates are 99.7%, 99.6% and 99.6% respectively. The washing processes were increased, and the washing cost was increased.

Comparative Example 1

[0102] The only difference from Example 1 is that the pH of the aqueous phase 2 obtained in the second extraction was controlled at 5. The single-stage extraction rates of Ni, Co and Mn are all less than 10%.

Comparative Example 2

[0103] The only difference from Example 1 is that the extractant in the second extraction was replaced with the same amount of P204, and the nickel, cobalt and manganese could not be extracted synchronously.

Comparative Example 3

[0104] The difference from Example 1 is that the extractant in the second extraction was replaced by carboxylic acid extractant CA-100. The extraction rates of Ni, Co and Mn are 78.8%, 74.5% and 73% respectively.

[0105] According to the results of the above examples and comparative examples, the method provided in the present application realizes synchronous extraction and recovery of nickel, cobalt and manganese from the leachate of waste lithium-ion battery positive electrode materials by using the coupling effect of extractant and extraction pH, which is not affected by impurity metal ions such as calcium and magnesium. The method has simple operation, and reduces the separation cost of separately recovering nickel, cobalt and manganese and the extraction and purification cost of impurity metal ions. Meanwhile, the impurity removal rate of the carboxylic acid extractant is more than or equal to 99.0%, and the sulfuric acid back extraction rate is more than or equal to 99.5%.

[0106] The applicant has stated that the detailed structural features of the present application are illustrated by the above embodiments, but the present application is not limited to the above detailed structural features, which means that the present application is not necessarily rely on the above detailed structural features to be implemented.

[0107] Although the optional embodiments of the present application have been described above in detail, the present application is not limited to details of the above embodiments, and various simple modifications can be made to the technical solutions of the present application without departing from the technical concept of the present application.

[0108] In addition, it should be noted that if not in collision, the specific technical features described in the above embodiments may be combined in any suitable manner. To avoid unnecessary repetition, the present application does not further specify any of various combinations.

[0109] In addition, the different embodiments of the present application can also be combined in any manner, and those combinations should also be regarded as the content disclosed in the present application without departing from the idea of the present application.