WO2022110822A1

WO2022110822A1 - Method for separating copper and manganese, and application thereof

Info

Publication number: WO2022110822A1
Application number: PCT/CN2021/105651
Authority: WO
Inventors: 王雪
Original assignee: 苏州博萃循环科技有限公司
Priority date: 2020-11-24
Filing date: 2021-07-12
Publication date: 2022-06-02
Also published as: CN112575193A

Abstract

A method for separating copper and manganese, comprising the following steps: (1) performing first extraction on a copper-manganese liquid to obtain a first organic phase and a first aqueous phase, wherein an extraction agent A used in the first extraction comprises one or a combination of at least two of carboxylic acid extraction agents; (2) successively performing washing and back extraction on the first organic phase to obtain a copper-containing solution; and (3) performing second extraction on the first aqueous phase to obtain a second organic phase and a second aqueous phase, and successively performing washing and back extraction on the second organic phase to obtain a manganese rich solution.

Description

A kind of separation method of copper and manganese and its application

technical field

The application belongs to the field of hydrometallurgy, and relates to a method for separating copper and manganese and its application.

Background technique

At present, in the hydrometallurgical production of cobalt, the impurity ions in the cobalt raw material are removed in the P204 impurity removal process to form a chloride solution containing a large amount of impurity metals such as copper, manganese, and calcium. These solutions are often precipitated with sodium carbonate to form copper and manganese. Calcium carbonate, of which copper and manganese are most abundant and valuable. A large cobalt smelter produces thousands of tons or even tens of thousands of tons of this carbonate slag every year, and the value of valuable metals is tens of millions.

Solvent extraction technology is an effective technology for separating and extracting various metals from solution. It has the advantages of high separation efficiency, simple process and equipment, continuous operation, and easy automatic control. It has been continuously concerned and developed by many researchers for a long time.

At present, there are many related processes for the separation of copper and manganese, but there are problems such as complicated separation methods, poor separation effect of copper and manganese, and high cost. For example, Chinese patent (publication number CN105274352A) adopts to add sulfuric acid to copper carbonate manganese slag to form sulfate solution, remove calcium sulfate precipitation, then use copper extraction reagents such as ketoxime or aldoxime to separate copper in the form of copper sulfate, and then Adjust the pH value of the solution after copper removal, add active metal powder to reduce cobalt to cobalt powder and separate out, obtain manganese-containing filtrate, add sodium carbonate to the filtrate, and precipitate manganese to obtain manganese carbonate; Chinese patent (CN102888513A ) Precipitate calcium through sulfate, precipitate copper-cobalt-zinc mixture with carbonate and sulfide, obtain manganese chloride crystal concentration, then use inorganic acid to dissolve copper-cobalt-zinc mixture, and add reducing agent to reduce copper, and adjust pH of solution to make solid zinc sulfide. , Cobalt sulfide and Cu ⁺ in the solution undergo a conversion reaction, and then add excess sulfide to make all the copper that does not participate in the reaction to form cuprous sulfide precipitation and remove, and finally adjust the pH of the cobalt-zinc solution and add sodium chloride or pass chlorine gas. Cobalt is oxidized to cobalt hydroxide and separated out.

SUMMARY OF THE INVENTION

The purpose of this application is to provide a method for separating copper and manganese and application thereof, effectively separating copper and manganese in the feed liquid, simple operation, and in addition, the carboxylic acid extractant used has low water solubility and high stability , reduce process cost.

For this purpose, the application adopts the following technical solutions:

The application provides a method for separating copper and manganese and application thereof, the method comprises the following steps:

(1) the first extraction is carried out to the copper-manganese feed liquid to obtain the first organic phase and the first aqueous phase; wherein, the extractant A used in the first extraction comprises one or at least two of the carboxylic acid extractants The combination of species; the general formula of the carboxylic acid extractant is as follows:

Wherein, R ₁ and R ₂ are independently C ₃ -C ₉ straight-chain or branched-chain alkyl groups; the volume ratio of extractant A to copper-manganese feed solution in the first extraction is (0.1-10):1; The extraction agent A used in the first extraction is saponified before use; the pH of the first aqueous phase is 3-4.5;

(2) the first organic phase obtained in step (1) is washed and back-extracted successively to obtain a copper-containing solution;

(3) performing a second extraction on the first aqueous phase obtained in step (1) to obtain a second organic phase and a second aqueous phase; the second organic phase is sequentially washed and back-extracted to obtain a manganese-rich solution.

By the method provided in the present application, the two valuable metals of copper and manganese are separated and extracted, and the operation is simple.

In this application, the volume ratio of extractant A to copper-manganese feed liquid in the first extraction is (0.1-10):1, for example, it can be 0.1:1, 0.5:1, 1:1, 2:1, 3 : 1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, etc., but not limited to the listed values, other unlisted values within this range are also applicable .

In this application, the pH of the first aqueous phase is 3-4.5, such as 3, 3.3, 3.5, 3.8, 4, 4.1, 4.2, 4.3, 4.4 or 4.5, etc., but not limited to the listed values, the The same applies to other non-recited values in the range.

As an optional technical solution of the present application, the metal elements in the copper-manganese feed solution in step (1) include: Cu, Mn, Ca, Fe, Al, Co and Zn.

Optionally, the concentration of Al in the copper-manganese feed solution is ≤1g/L, for example, it can be 1g/L, 0.8g/L, 0.6g/L, 0.4g/L or 0.2g/L, etc., but not limited to Recited values apply equally well to other non-recited values within the range.

As an optional technical solution of the present application, the volume fraction of the extractant A in the first extraction in step (1) is 5-30%, for example, it can be 5%, 10%, 15%, 20%, 25% or 30% %, etc., but not limited to the recited values, other unrecited values within the range are also applicable.

Optionally, the first extraction in step (1) is multi-stage countercurrent extraction.

Optionally, the number of stages of the multi-stage countercurrent extraction is 2-30, for example, it can be 2, 5, 10, 15, 20, 25 or 30, etc., but is not limited to the listed values. The values listed also apply.

Optionally, the stirring speed in the first extraction of step (1) is 100-250r/min, such as 100r/min, 150r/min, 200r/min or 250r/min, etc., but not limited to the listed Numerical values, other non-recited values in the range apply equally.

Optionally, the time of the first extraction described in step (1) is 5-30min, for example, it can be 5min, 10min, 15min, 20min, 25min or 30min, etc., but is not limited to the enumerated numerical values, and others are not listed in this range. The same value applies.

As an optional technical solution of the present application, the saponification of step (1) is carried out by using 6-14mol/L lye, such as 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, 11 mol/L, 12 mol/L, 13 mol/L or 14 mol/L, etc., but not limited to the listed numerical values, and other unlisted numerical values within this range are also applicable.

As an optional technical solution of the present application, the washing in step (2) is multi-stage countercurrent washing.

Optionally, the number of stages of washing described in step (2) is 2-10, such as 2, 3, 4, 5, 6, 7, 8, 9 or 10, etc., but not limited to the listed values, The same applies to other non-recited values within this range.

Optionally, the washing in step (2) is washing with an acid solution.

Optionally, the back extraction in step (2) is to use acid solution for back extraction.

In this application, the volume ratio of the organic phase to the aqueous phase in the washing and stripping of the first organic phase is (0.1-10):1, for example, it can be 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, etc., but not limited to the listed values, and other unlisted values within the range are the same Be applicable.

As an optional technical solution of the present application, the extractant B used in the second extraction in step (3) includes a phosphorus-type extractant and/or a carboxylic acid-type extractant.

In this application, the phosphorus-based extractant includes C272 and the like.

Optionally, the general structural formula of the carboxylic acid extractant is as follows:

Wherein, R ₁ and R ₂ are independently C ₃ -C ₉ straight-chain or branched-chain alkyl groups.

Optionally, the carboxylic acid extractant in the extractant B includes one carboxylic acid or a mixture of at least two carboxylic acids.

Optionally, the volume fraction of the extractant B is 5-30%, such as 5%, 10%, 15%, 20%, 25% or 30%, etc., but not limited to the listed values, the range The same applies to other values not listed here.

As an optional technical solution of the present application, the volume ratio of extractant B to the first aqueous phase in the second extraction described in step (3) is (0.1-10):1, for example, it can be 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, etc., but not limited to the listed values, the The same applies to other non-recited values in the range.

Optionally, the second extraction in step (3) is multi-stage countercurrent extraction.

Optionally, the number of stages of the multi-stage countercurrent extraction is 2-30, for example, it can be 5, 10, 15, 20, 25 or 30, etc., but is not limited to the listed values, and other unlisted values within this range The same applies to numerical values.

Optionally, the stirring speed in the second extraction in step (3) is 100-250r/min, such as 100r/min, 150r/min, 200r/min or 250r/min, etc., but not limited to the listed Numerical values, other non-recited values in the range apply equally.

Optionally, the time of the second extraction described in step (3) is 5-30min, such as 5min, 10min, 15min, 20min, 25min or 30min, etc., but not limited to the enumerated numerical values, other not enumerated in this range. The same value applies.

In this application, the pH value of the second aqueous phase will have different pH value operating ranges due to different extraction agents, which are not specifically limited in this application. For example, when C272 is used, the pH value of the second aqueous phase is 3-4, and the When the carboxylic acid type extractant is used, the pH value of the second aqueous phase is 4.5-6.5, optionally 5-6.5.

As an optional technical solution of the present application, the extractant B used in the second extraction in step (3) is saponified before use.

Optionally, the saponification is carried out using 6-14mol/L lye, such as 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, 11mol/L, 12mol/L, 13mol/L or 14mol/L, etc., but not limited to the listed values, and other unlisted values within this range are also applicable.

As an optional technical solution of the present application, the washing in step (3) is multi-stage countercurrent washing.

Optionally, the number of stages of washing described in step (3) is 2-10, such as 2, 3, 4, 5, 6, 7, 8, 9 or 10, etc., but not limited to the listed values, The same applies to other non-recited values within this range.

Optionally, the washing in step (3) is washing with an acid solution.

Optionally, the volume ratio of the organic phase to the aqueous phase in the washing in step (3) is (0.1-10):1, for example, it can be 0.1:1, 0.5:1, 1:1, 2:1, 3:1: 1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, etc., but not limited to the listed values, and other unlisted values within this range are also applicable.

Optionally, the back extraction in step (3) is to use acid solution for back extraction.

Optionally, the volume ratio of the organic phase and the water phase in the stripping described in step (3) is (0.1-10):1, for example, it can be 0.1:1, 0.5:1, 1:1, 2:1, 3 : 1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, etc., but not limited to the listed values, other unlisted values within this range are also applicable .

Optionally, the second aqueous phase is sequentially subjected to degreasing and crystallization to obtain sodium sulfate crystals.

Optionally, the crystallization mode is MVR evaporation.

As an optional technical solution of the present application, the method comprises the following steps:

Wherein, R ₁ and R ₂ are independently C ₃ -C ₉ straight-chain or branched-chain alkyl groups; in the first extraction, the volume ratio of the extractant A to the copper-manganese feed solution is (0.1-10): 1. The volume fraction of extractant A in the first extraction is 5-30%; the time of the first extraction is 5-30min; the extractant A used in the first extraction is saponified before use; the first aqueous phase The pH is 3-4.5;

(3) the first aqueous phase obtained in step (1) is subjected to the second extraction to obtain the second organic phase and the second aqueous phase; the second organic phase is sequentially washed and back-extracted to obtain a manganese-rich solution; wherein , the extractant B used in the second extraction includes phosphorus type extractant and/or carboxylic acid type extractant; the general formula of the carboxylic acid type extractant is as follows:

Wherein, R ₁ and R ₂ are independently C ₃ -C ₉ linear or branched chain alkyl; the volume fraction of the extractant B is 5-30%; the extractant B and the first water in the second extraction The volume ratio of the phases is (0.1-10): 1; the time of the second extraction is 5-30 min.

In the present application, the second organic phase obtained by the second extraction can be returned to the first extraction for copper extraction.

In this application, when the mixed solution contains zinc, the solution after stripping will contain zinc, which can be removed by conventional methods before the first or second extraction, for example, using phosphorus type and/or carboxylate in step (1). The acid extractant is extracted and removed. When the carboxylic acid extractant is used for extraction, zinc ions can be extracted and removed by controlling the equilibrium pH of the water phase to be 4.5-5; at the same time, if the solution contains iron and aluminum, the existing technology can be used. The iron and aluminum are removed by conventional means such as chemical precipitation, extraction (such as the carboxylic acid extractant in this application), etc., and then the first extraction is performed.

In the present application, the diluent of the extractant includes one or a combination of at least two of mineral spirits, kerosene, Escaid 110, hexane, heptane, and dodecane.

The combination may be a combination of mineral spirits and kerosene, a combination of Escaid 110 and hexane, or a combination of heptane and dodecane, etc., but is not limited to the listed combinations, and other unlisted combinations within the scope are also applicable.

In the present application, the solvent may be No. 200 mineral spirits and/or No. 260 mineral spirits.

In the present application, the dodecane may be n-dodecane or the like.

In the present application, the alkaline solution includes one or a combination of at least two of sodium hydroxide solution, potassium hydroxide solution or ammonia water.

The combination can be a combination of sodium hydroxide solution and potassium hydroxide solution or a combination of potassium hydroxide solution and ammonia water, etc., but is not limited to the listed combinations, and other unlisted combinations within the scope are also applicable.

In this application, the acid solution in washing and stripping is sulfuric acid and/or hydrochloric acid, etc., and the pH of the acid solution used for washing is 1-2, such as 1, 1.2, 1.4, 1.5, 1.8 or 2, etc., but not limited to Enumerated numerical values, other unenumerated numerical values in this range are equally applicable, and the concentration of hydrochloric acid used in back extraction is 1-6mol/L, such as 1mol/L, 1.5mol/L, 2mol/L, 3mol/L, 4mol/L , 5mol/L or 6mol/L, etc., but not limited to the enumerated values, other unenumerated values in this range are also applicable, and the sulfuric acid concentration used in back extraction is 0.5-3.5mol/L, such as 0.5mol/L, 1mol/L L, 2mol/L, 3mol/L, or 3.5mol/L, etc., but not limited to the listed values, and other unlisted values within this range are also applicable.

In the present application, the extractant obtained by back-extraction of the first organic phase can be returned to the extraction operation after saponification.

In this application, the mixture of one or more carboxylic acids of the carboxylic acid extractant, such as extractant BC196 (in the general formula, R ₁ is n-butyl group, R ₂ is a compound corresponding to isononyl), extracts Reagent BC192 (in the general formula, R ₁ is a compound corresponding to n-hexyl, and R ₂ is a compound corresponding to n-nonyl), a mixture of extractants BC196 and BC192.

In this application, the countercurrent extraction is one of the extraction and separation operation methods. The aqueous phase and the organic phase containing the extract are respectively flowed from both ends of the extractor, and flow in opposite directions, and perform continuous multi-stage stirring and contact layering to achieve purpose of separation.

In the present application, the reaction equation of the relevant procedure is as follows:

Carboxylic acid extractant saponification: HA _(org) +NaOH→NaA _(org) +H ₂ O

Carboxylic acid extraction: 2NaA _(org) +MSO ₄ →MA _2(org) +Na ₂ SO ₄

Sulfuric acid stripping: MA _2(org) +H ₂ SO ₄ →2HA _(org) +MSO ₄

Among them: M is Cu ²⁺ , Mn ²⁺ and other metals.

Compared with the prior art solutions, the present application at least has the following beneficial effects:

(1) The method provided by the application has good separation effect on metal ions, effectively separates and extracts copper and manganese in the copper-manganese feed liquid, has simple operation, stable process and low operating cost. Recyclable.

(2) In the recovery method provided by this application, the extraction rate of copper and manganese is greater than or equal to 99.5%, and the reverse extraction rate of sulfuric acid is greater than or equal to 99.5%.

Description of drawings

1 is a schematic diagram of a method for separating copper and manganese from a copper and manganese feed solution in Example 1 of the present application.

The present application is described in further detail below. However, the following examples are only simple examples of the present application, and do not represent or limit the protection scope of the present application. The protection scope of the present application is subject to the claims.

Detailed ways

In order to better illustrate the present application and facilitate the understanding of the technical solutions of the present application, typical but non-limiting examples of the present application are as follows:

Example 1

This embodiment provides a method for separating copper and manganese and its application, as shown in FIG. 1 .

The copper-manganese feed solution in this example comes from P204 extraction and impurity removal solution: manganese 58g/L, copper 15g/L, calcium 0.5g/L, zinc 3.2g/L, iron 0.01g/L.

In this example, in order to obtain a single copper solution and a manganese solution, C272 was used to remove iron and zinc at the beginning of the extraction to obtain a copper-manganese feed solution after the removal of iron, aluminum and zinc.

Using saponified BC196 (volume fraction is 25%, the diluent is Escaid 110, and 6mol/L ammonia solution is used for saponification) to carry out 10-stage countercurrent extraction to the copper and manganese feed liquid after removing iron, aluminum and zinc, extracting agent and iron removing The volume ratio of the copper-manganese material solution after aluminum and zinc is 2:1, the extraction time is 8min, the stirring speed is 150r/min, and the experimental temperature is 25°C. An aqueous phase, after adopting the sulfuric acid of pH 1.5 to carry out 2-level countercurrent washing to the first organic phase, then adopting 2mol/L sulfuric acid to carry out back-extraction 3 times, the volume of the first organic phase and washing solution or back-extraction solution is 8: 1. The obtained copper sulfate solution is concentrated and crystallized after degreasing, and the organic phase after stripping is returned to the saponification process for recycling.

Adopt the BC196 after saponification (volume fraction is 25%, diluent is Escaid 110, carry out saponification with the ammonia solution of 6mol/L) to carry out multistage countercurrent extraction to the first aqueous phase, the number of extraction stages is 8, the extraction agent and the first The volume ratio of the aqueous phase is 4:1, the extraction time is 8 min, the stirring speed is 150 r/min, and the experiment temperature is 25 ° C. The second organic phase and the second aqueous phase with a pH value of 5.7 are obtained respectively. After the second organic phase is washed with 5-stage countercurrent washing with sulfuric acid with a pH of 1.5, 2 mol/L sulfuric acid is used for back-extraction for 5 times. After extraction, a manganese-rich solution is obtained.

In this example, the extraction rates of Cu and Mn were 99.7% and 99.8%, respectively, and the stripping rates were 99.7% and 99.6%, respectively.

Example 2

This embodiment provides a method for separating copper and manganese and its application. In the copper-manganese feed solution in the embodiment, manganese 10g/L, copper 0.01g/L, calcium 0.34g/L, and zinc 1.0g/L.

Adopt BC192 after saponification (volume fraction is 20%, diluent is No. 260 solvent oil, saponify with 10mol/L NaOH solution) to carry out 7-stage countercurrent extraction to copper-manganese feed solution, the volume of extraction agent and copper-manganese feed solution The ratio is 0.2:1, the extraction time is 5min, the stirring speed is 200r/min, the experiment temperature is 20min, and the first organic phase and the first aqueous phase with pH 4 are obtained respectively after phase separation. After carrying out 4-stage countercurrent washing to the first organic phase for 1.2% sulfuric acid, 2 mol/L sulfuric acid was used to carry out back extraction once, and the volume of the first organic phase and the washing solution or the back extraction solution was 10:1. The copper sulfate solution is concentrated and crystallized after degreasing, and the organic phase obtained by back extraction is returned to the saponification process for recycling.

The first aqueous phase was subjected to multi-stage countercurrent extraction using the saponified C272 (volume fraction was 20%, the diluent was No. 260 solvent oil, and the NaOH solution of the saponification agent was 10 mol/L). The volume ratio of an aqueous phase is 0.2:1, the extraction time is 5 min, the stirring speed is 200 r/min, and it is allowed to stand for 20 min. and the first aqueous phase after zinc removal, after carrying out 3-stage countercurrent washing to the zinc-loaded organic phase with sulfuric acid with a pH of 1.2, and then using 2mol/L sulfuric acid to carry out back-extraction 2 times, washing or back-extracting the organic phase and the washing liquid Or the volume of the back-extraction solution is 10:1, and the obtained zinc-rich solution is concentrated and crystallized after degreasing.

Use saponified C272 to perform 5-stage extraction on the first aqueous phase after zinc removal, the volume ratio of the extractant to the first aqueous phase is 1:1, other extraction conditions are the same as above, and the second organic phase and pH value are obtained by phase separation. The second aqueous phase of 4, using pH 1.2 sulfuric acid to carry out 3-level countercurrent washing to the second organic phase, then using 2.5mol/L sulfuric acid to carry out back extraction 4 times, the organic phase in the washing or back extraction and the washing liquid or The volume of the back-extraction solution was 10:1 to obtain a manganese-rich solution.

In this embodiment, the extraction rates of Cu and Mn are 99.6% and 99.7%, respectively, and the stripping rates are 99.7% and 99.8%, respectively.

Example 3

This embodiment provides a method for separating copper and manganese and its application. In the copper-manganese feed solution in the embodiment, manganese is 15g/L, copper is 0.05g/L, calcium is 0.4g/L, and zinc is 1.2g/L.

Adopt BC196 loaded with manganese (derived from the second organic phase after washing) to carry out 4-stage countercurrent extraction to copper-manganese-calcium-zinc solution, the volume ratio of extractant to copper-manganese feed solution is 0.2:1, extraction time is 10min, stirring The speed is 150r/min, and the experiment temperature is 25°C. After the phase separation, the first organic phase and the first aqueous phase with pH value of 4.5 are obtained, respectively. After countercurrent washing, 2.5mol/L sulfuric acid was used to carry out back extraction once again. The volume of the first organic phase and the washing liquid or back extraction liquid was 10:1. The copper sulfate solution obtained by back extraction was concentrated and crystallized after degreasing. The organic phase obtained by extraction is returned to the saponification process for recycling.

Adopt saponified BC196 (volume fraction is 25%, diluent is Escaid 110, carry out saponification with 8mol/L NaOH solution) to extract and remove the zinc in the first water phase, the extraction stage is 9, and the pH of the control water phase is 4.8 , after phase separation, the zinc-loaded organic phase and the first aqueous phase after zinc removal are obtained. After the zinc-loaded organic phase is washed with 5-stage countercurrent with dilute sulfuric acid with pH 1, 2.5 mol/L sulfuric acid is used for back-extraction twice. The volume of the first organic phase and the washing liquid or the back-extraction liquid is 10:1, and the zinc sulfate solution obtained by the back-extraction is concentrated and crystallized after degreasing.

Adopt BC196 after saponification to carry out multistage countercurrent extraction to the first water phase after zinc removal, the number of extraction stages is 7, the volume ratio of extractant to the first water phase is 2:1, the extraction time is 10min, and the stirring speed is 150r/ min, let stand for 10 min, the experimental temperature is 25 °C, and the second organic phase and the second aqueous phase with pH value of 6.5 are obtained respectively. The mol/L sulfuric acid is back-extracted 4 times, and the volume ratio of the second organic phase to the washing liquid or back-extraction liquid is 10:1, and the manganese-rich solution is obtained after back-extraction.

In this example, the extraction rates of Cu and Mn were 99.6% and 99.5%, respectively, and the stripping rates were 99.7% and 99.7%, respectively.

Comparative Example 1

The only difference from Example 1 is that the extraction agent in the first extraction was replaced with a carboxylic acid extraction agent CA-12. After testing, the extraction rates of Cu and Mn were 98.6% and 99.0%, respectively, and the stripping rates were 99.5. % and 99.4%.

The applicant declares that the present application illustrates the detailed structural features of the present application through the above embodiments, but the present application is not limited to the above detailed structural features, which does not mean that the present application must rely on the above detailed structural features for implementation.

The optional embodiments of the present application are described in detail above. However, the present application is not limited to the specific details of the above-mentioned embodiments. Various simple modifications can be made to the technical solutions of the present application within the scope of the technical concept of the present application.

In addition, it should be noted that the specific technical features described in the above-mentioned specific embodiments can be combined in any suitable manner unless they are inconsistent. The combination method will not be specified otherwise.

In addition, the various embodiments of the present application can also be combined arbitrarily, as long as they do not violate the idea of the present application, they should also be regarded as the content disclosed in the present application.

Claims

A kind of separation method of copper and manganese, it comprises the steps:

(1) the first extraction is carried out to the copper-manganese feed liquid to obtain the first organic phase and the first aqueous phase; wherein, the extractant A used in the first extraction comprises one or at least two of the carboxylic acid extractants The combination of species; the general formula of the carboxylic acid extractant is as follows:

Wherein, R 1 and R 2 are independently C 3 -C 9 straight-chain or branched-chain alkyl groups; the volume ratio of extractant A to copper-manganese feed solution in the first extraction is (0.1-10):1; The extraction agent A used in the first extraction is saponified before use; the pH of the first aqueous phase is 3-4.5;

(2) the first organic phase obtained in step (1) is washed and back-extracted successively to obtain a copper-containing solution;

(3) performing a second extraction on the first aqueous phase obtained in step (1) to obtain a second organic phase and a second aqueous phase; the second organic phase is sequentially washed and back-extracted to obtain a manganese-rich solution.
The method of claim 1, wherein the metal elements in the copper-manganese feed solution in step (1) include: Cu, Mn, Ca, Fe, Al, Co, and Zn.
The method of claim 2, wherein the Al concentration in the copper-manganese feed solution is ≤1 g/L.
The method of claim 1 or 2, wherein the volume fraction of the extractant A in the first extraction in step (1) is 5-30%;

Optionally, the first extraction in step (1) is multi-stage countercurrent extraction;

Optionally, the extraction stages of the multistage countercurrent extraction are 2-20;

Optionally, the stirring speed in the first extraction described in step (1) is 100-250r/min;

Optionally, the time of the first extraction described in step (1) is 5-30min;

Optionally, the saponification in step (1) is carried out by using 6-14 mol/L of lye.
The method according to any one of claims 1-4, wherein the washing in step (2) is multi-stage countercurrent washing;

Optionally, the number of stages of washing described in step (2) is 2-10;

Optionally, the washing described in step (2) is to use acid solution to wash;

Optionally, the back extraction in step (2) is to use acid solution for back extraction.
The method according to any one of claims 1-5, wherein the extractant B used in the second extraction in step (3) comprises a phosphorus-type extractant and/or a carboxylic acid-type extractant;

Optionally, the general structural formula of the carboxylic acid extractant is as follows:

wherein, R 1 and R 2 are independently C 3 -C 9 straight-chain or branched-chain alkyl groups;

Optionally, the carboxylic acid extractant in the extractant B comprises one carboxylic acid or a mixture of at least two carboxylic acids;

Optionally, the volume fraction of the extractant B is 5-30%.
The method according to any one of claims 1-6, wherein the volume ratio of extractant B to the first aqueous phase in the second extraction in step (3) is (0.1-10):1;

Optionally, the second extraction in step (3) is multi-stage countercurrent extraction;

Optionally, the number of stages of the multi-stage countercurrent extraction is 2-20;

Optionally, the stirring speed in the second extraction of step (3) is 100-250r/min;

Optionally, the time of the second extraction in step (3) is 5-30min.
The method according to any one of claims 1-7, wherein the extractant B used in the second extraction of step (3) is saponified before use;

Optionally, the saponification is carried out using 6-14 mol/L of lye.
The method according to any one of claims 1-8, wherein the washing in step (3) is multi-stage countercurrent washing;

Optionally, the number of stages of washing described in step (3) is 2-10;

Optionally, the washing described in step (3) is to use acid solution to wash;

Optionally, the volume ratio of the organic phase and the water phase in the washing described in step (3) is (0.1-10): 1;

Optionally, the stripping described in step (3) is to use acid solution to carry out stripping;

Optionally, the volume ratio of organic phase and water phase in the back extraction described in step (3) is (0.1-10): 1;

Optionally, the second aqueous phase is successively subjected to degreasing and crystallization to obtain sodium sulfate crystals;

Optionally, the crystallization mode is MVR evaporation.
The method of any one of claims 1-9, comprising the steps of:

(1) the first extraction is carried out to the copper-manganese feed liquid to obtain the first organic phase and the first aqueous phase; wherein, the extractant A used in the first extraction comprises one or at least two of the carboxylic acid extractants The combination of species; the general formula of the carboxylic acid extractant is as follows:

Wherein, R 1 and R 2 are independently C 3 -C 9 straight-chain or branched-chain alkyl groups; the volume ratio of extractant A to copper-manganese feed solution in the first extraction is (0.1-10):1; The volume fraction of the extractant A in the first extraction is 5-30%; the time of the first extraction is 5-30min; the extractant A used in the first extraction is saponified before use; the first water The pH of the phase is 3-4.5;

(2) the first organic phase obtained in step (1) is washed and back-extracted successively to obtain a copper-containing solution;

(3) performing the second extraction on the first aqueous phase obtained in step (1) to obtain the second organic phase and the second aqueous phase; the second organic phase is washed and back-extracted in sequence to obtain a manganese-rich solution; wherein, The extractant B used in the second extraction includes phosphorus type extractant and/or carboxylic acid type extractant; the general formula of the carboxylic acid type extractant is as follows:

Wherein, R 1 and R 2 are independently C 3 -C 9 linear or branched chain alkyl; the volume fraction of the extractant B is 5-30%; the extractant B and the first water in the second extraction The volume ratio of the phases is (0.1-10): 1; the time of the second extraction is 5-30 min.
An application of the separation method according to any one of claims 1-10, wherein the application is the copper-containing manganese feed liquid obtained by separating P204 by extraction and removal of impurities;
Application of an extraction reagent comprising a carboxylic acid compound having a structure as shown in formula I in separating copper and manganese

Wherein, R 1 and R 2 are independently C 3 -C 9 straight-chain or branched-chain alkyl groups.