WO2022048308A1

WO2022048308A1 - Method for separating copper and manganese from mixed solution containing copper, manganese, calcium and zinc

Info

Publication number: WO2022048308A1
Application number: PCT/CN2021/105655
Authority: WO
Inventors: 王雪
Original assignee: 苏州博萃循环科技有限公司
Priority date: 2020-09-04
Filing date: 2021-07-12
Publication date: 2022-03-10
Also published as: CN114134322B; CN114134322A

Abstract

The present application relates to a method for separating copper and manganese from a mixed solution containing copper, manganese, calcium and zinc, the method comprising: (1) subjecting the mixed solution containing copper, manganese, calcium and zinc to first extraction to obtain a first organic phase and a first aqueous phase, wherein an extractant A used in the first extraction comprises one or a combination of at least two of carboxylic acid extractants; (2) successively subjecting the first organic phase to washing and reverse extraction to obtain a copper-containing solution; and (3) subjecting the first aqueous phase to second extraction to obtain a second organic phase and a second aqueous phase, and successively subjecting the second organic phase to washing and reverse extraction to obtain a manganese-rich solution.

Description

A kind of method for separating copper and manganese from copper-manganese-calcium-zinc mixed solution

technical field

The application belongs to the field of hydrometallurgy, and relates to a method for separating copper and manganese from a mixed solution containing copper, manganese, calcium and zinc.

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.

CN105274352A discloses a method for separating copper-manganese-cobalt from copper-manganese-cobalt-cobalt-calcium-zinc mixture of carbonate-copper-manganese-carbonate. It firstly adds sulfuric acid to copper-manganese carbonate slag to form a sulfate solution, removes calcium sulfate precipitation, and then extracts it with ketoxime or aldoxime. The copper reagent separates copper in the form of copper sulfate, then adjusts the pH value of the solution after copper removal, adds active metal powder to reduce cobalt to cobalt powder and separates it out, and finally adds sodium carbonate to the filtrate to precipitate manganese to obtain manganese. carbonate.

CN105296754A discloses a method for separating copper, manganese, cobalt, calcium and zinc from copper chloride, manganese, cobalt, calcium and zinc impurities removal solution. The method adds sodium sulfate to the copper, manganese, cobalt, calcium and zinc solution, removes calcium sulfate by filtration, and adjusts the pH value between 4.0 and 6.0. The copper ions in the solution are precipitated, the copper precipitates are separated by filtration, and then the copper sulfate crystals are obtained after dissolving, evaporating and crystallizing with sulfuric acid, and manganese powder is added to the solution after removing copper, so that the cobalt ions are reduced to cobalt powder and separated and removed. It contains manganese and a small amount of zinc and calcium. By evaporating crystallization or adding sodium carbonate, manganese is precipitated to obtain manganese salts such as crude manganese carbonate.

The operation of the above method is complicated, wherein the extraction method used is expensive, and the precipitation method can also cause entrainment loss of valuable metals.

SUMMARY OF THE INVENTION

The purpose of this application is to provide a method for separating copper and manganese from a mixed solution containing copper, manganese, calcium and zinc, separate copper and manganese from the solution, the operation is simple, and the two valuable metals of copper and manganese can be extracted economically and effectively. separation.

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

The application provides a method for separating copper and manganese from a mixed solution containing copper, manganese, calcium and zinc, the method comprising the following steps:

(1) the first extraction is carried out to the mixed solution containing copper, manganese, calcium and zinc to obtain the first organic phase and the first aqueous phase; wherein, the extraction agent A used in the first extraction includes one of the carboxylic acid extraction agents Or a combination of at least 2 kinds; the general formula of the carboxylic acid extractant is as follows:

Wherein, 10≤m+n≤22, -C _n H _2n+1 and -C _m H _2m+1 are independently a straight-chain or branched alkyl group with 1-21 carbon atoms; the first In the extraction, the volume ratio of extractant A and the mixed solution containing copper, manganese, calcium and zinc is (0.1-10): 1; the extractant A used in the first extraction is saponified before use; the pH of the first water phase is 4-5.5;

(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 extracted and separated, and the operation is simple.

In this application, the volume ratio of the extractant A to the mixed solution containing copper, manganese, calcium and zinc 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 the range The same applies to numerical values.

In this application, the pH of the first aqueous phase is 4-5.5, for example, it can be 4, 4.2, 4.4, 4.6, 4.8, 5, 5.2, 5.4 or 5.5, etc., but not limited to the listed values, within this range Other non-recited values also apply.

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

Optionally, the concentration of Fe in the mixed solution containing copper, manganese, calcium and zinc is ≤ 10g/L, for example, it can be 10g/L, 9g/L, 8g/L, 7g/L, 6g/L, 5g/L, 4g /L or 3g/L, etc., but not limited to the listed values, and other unlisted values within this range are also applicable.

Optionally, the concentration of Al in the mixed solution containing copper, manganese, calcium and zinc 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 the recited values, other non-recited values within the range are equally applicable.

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) includes single-stage extraction or 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 values, and other unlisted 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, 10≤m+n≤22, -C _n H _2n+1 and -C _m H _2m+1 are each independently a linear or branched alkyl group having 1 to 21 carbon atoms.

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 5-30, 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-based extractant is used, the pH value of the second aqueous phase is 5.5-7.5, optionally 5.5-6.8.

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, 10≤m+n≤22, -C _n H _2n+1 and -C _m H _2m+1 are independently a straight-chain or branched alkyl group with 1-21 carbon atoms; the first In the extraction, the volume ratio of the extractant A and the mixed solution containing copper, manganese, calcium and zinc 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 extraction agent A used in the first extraction is saponified before use; the pH of the first aqueous phase is 4-5.5;

(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, 10≤m+n≤22, -C _n H _2n+1 and -C _m H _2m+1 are respectively a straight-chain or branched alkyl group with 1-21 carbon atoms; the extractant The volume fraction of B is 5-30%; the volume ratio of extractant B to the first aqueous phase in the second extraction 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. In order to obtain a single manganese solution, it can be removed by conventional methods before the first extraction or between the first extraction and the second extraction. For example, the phosphorus type and/or the carboxylic acid type extractant in step (1) is used for extraction and removal, and when the carboxylic acid type extractant is used for extraction, the zinc ions can be extracted and removed at 5-6 by controlling the equilibrium pH of the water phase; If the solution contains iron and aluminum, conventional means in the prior art such as chemical precipitation, extraction (such as the carboxylic acid extractant in this application) can be used to remove iron and aluminum, and then the first extraction is performed. The above process does not affect the separation of copper and manganese.

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 also applicable, and the concentration of hydrochloric acid used in back extraction is 1-4mol/L, such as 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L L or 4mol/L, etc., but not limited to the listed values, other unlisted values within this range are also applicable, and the concentration of sulfuric acid used in back extraction is 0.5-3.5mol/L, such as 0.5mol/L, 1mol/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 organic phase 1 can be returned to the extraction operation after saponification, and the extractant can also be converted from sodium soap to manganese soap after saponification.

In this application, the carboxylic acid extractant may be a mixture of one or more carboxylic acids, such as extractant BC196 (compound corresponding to m=8 and n=8 in the general formula), extractant BC191 (general formula Compounds corresponding to m=8 and n=10 in the formula), a mixture of extractants BC196 and BC191, extractants BC199 (m=8, n=2, m=7, n=9, m=10 in the general formula, n=8 and m=10, the compounds corresponding to n=10 were mixed in a volume ratio of 1:1:1:1).

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 present application has good separation effect on metal ions, realizes separation and purification of copper and manganese in copper-manganese-calcium-zinc slag, and has simple operation, stable process and low operating cost.

(2) In the recovery method provided by this application, the extraction rate of copper and manganese is greater than or equal to 99%, 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 mixed solution containing copper, manganese, calcium and zinc 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 description

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 from a mixed solution containing copper, manganese, calcium and zinc, as shown in FIG. 1 .

The copper-containing manganese-calcium-zinc solution in this example comes from the mixed solution of ionic sulfate after P204 impurity removal: 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 zinc at the beginning of the extraction, and a mixed solution containing copper, manganese, and calcium was obtained.

Using saponified BC196 (volume fraction is 25%, the diluent is Escaid 110, and 6 mol/L ammonia solution is used for saponification) to carry out 10-stage countercurrent extraction to the mixed solution containing copper, manganese and calcium. The volume ratio was 2:1, the extraction time was 8 min, the stirring speed was 150 r/min, and the experimental temperature was 25 °C. After phase separation, the first organic phase and the first aqueous phase with pH 4.5 were obtained respectively. After 2-stage countercurrent washing of the first organic phase with sulfuric acid, 2 mol/L sulfuric acid is used to carry out back-extraction 3 times, the volume of the first organic phase and the washing liquid or the back-extraction liquid is 8:1, and the copper sulfate solution is obtained after degreasing. After concentrating and crystallization, 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 was 4:1, the extraction time was 8 min, the stirring speed was 150 r/min, the temperature was allowed to stand for 15 min, and the experimental temperature was 25 ° C to obtain the second organic phase and the second aqueous phase with a pH value of 6.3, 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 are 99.7% and 99.6%, respectively, and the stripping rates are 99.7% and 99.7%, respectively.

Example 2

This embodiment provides a method for separating copper and manganese from a mixed solution containing copper, manganese, calcium and zinc. Zinc 1.0g/L.

Using saponified BC191 (volume fraction is 20%, the diluent is No. 260 solvent oil, and 10mol/L NaOH solution is used for saponification), the copper-manganese solution is subjected to 7-stage countercurrent extraction. The volume ratio is 0.2:1, the extraction time is 5min, the stirring speed is 200r/min, the temperature is 25°C, and the first organic phase and the first aqueous phase with pH 5 are obtained after phase separation. After the first organic phase was washed with a 4-stage countercurrent with sulfuric acid with a pH of 1.2, 2 mol/L sulfuric acid was used for back extraction once. The volume of the first organic phase and the washing solution or the back extraction solution was 10:1. The obtained 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 example, the extraction rates of Cu and Mn were 99.7% and 99.8%, respectively, and the stripping rates were 99.6% and 99.7%, respectively.

Example 3

This embodiment provides a method for separating copper and manganese from a mixed solution containing copper, manganese, calcium and zinc. Zinc 1.2g/L.

BC196 after using manganese soap (volume fraction is 25%, the diluent is Escaid 110, first treated with 10moL/L sodium hydroxide solution, and then treated with 2g/L manganese sulfate solution to obtain manganese soap) has a strong effect on copper, manganese, calcium and zinc. The solution was subjected to 4-stage countercurrent extraction, the volume ratio of the extractant to the copper-manganese-containing solution was 0.2:1, the extraction time was 10 min, the stirring speed was 150 r/min, and the experiment temperature was 25 ℃. an organic phase and a first aqueous phase with a pH value of 5.3, after the first organic phase is washed with a 5-stage countercurrent with sulfuric acid with a pH of 1, and then back-extracted once with 2.5 mol/L sulfuric acid, the first organic phase and the The volume of washing liquid or back-extraction liquid is 10:1, the copper sulfate solution obtained by back-extraction is concentrated and crystallized after degreasing, and the organic phase obtained by back-extraction is returned to the saponification process for recycling.

Adopt saponified BC196 (the volume fraction is 25%, the diluent is Escaid 110, and the 8mol/L NaOH solution is used for saponification) to extract and remove the zinc in the first aqueous phase, the extraction stage is 9, and the pH of the controlled aqueous phase is 5.6 , 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 ℃, and the second organic phase and the second aqueous phase with pH value of 6.8 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 99.8% and 99.7%, 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-100. After testing, the extraction rates of Cu and Mn were 78% and 75%, respectively, and the stripping rates were 99.4 % and 99.3%.

Comparative Example 2

The difference with Example 1 is only that the extraction agent in the first extraction is replaced with a carboxylic acid type extraction agent Versatic 10, which has larger water solubility, unstable extraction, poor separation effect and high cost.

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 to be implemented.

The optional embodiments of the present application are described in detail above, but the present application is not limited to the specific details in the above-mentioned embodiments, and within the scope of the technical concept of the present application, various simple modifications can be made to the technical solutions 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 method for separating copper and manganese from a mixed solution containing copper, manganese, calcium and zinc, comprising the steps of:

(1) the first extraction is carried out to the mixed solution containing copper, manganese, calcium and zinc to obtain the first organic phase and the first aqueous phase; wherein, the extraction agent A used in the first extraction includes one of the carboxylic acid extraction agents Or a combination of at least 2 kinds; the general formula of the carboxylic acid extractant is as follows:

Wherein, 10≤m+n≤22, -C n H 2n+1 and -C m H 2m+1 are independently a straight-chain or branched alkyl group with 1-21 carbon atoms; the first In the extraction, the volume ratio of extractant A and the mixed solution containing copper, manganese, calcium and zinc is (0.1-10): 1; the extractant A used in the first extraction is saponified before use; the pH of the first water phase is 4-5.5;

(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 according to claim 1, wherein, the volume fraction of extractant A in the first extraction of step (1) is 5-30%.
The method according to claim 1 or 2, wherein the first extraction in step (1) comprises single-stage extraction or multi-stage countercurrent extraction.
The method of claim 3, wherein the number of stages of the multi-stage countercurrent extraction is 2-30.
The method according to claim 1, wherein, the stirring speed in the first extraction of step (1) is 100-250r/min;

Optionally, the time of the first extraction in step (1) is 5-30min.
The method according to any one of claims 1-5, wherein the metal elements in the mixed solution containing copper, manganese, calcium and zinc in step (1) include: Cu, Mn, Ca, Fe, Al, Co and Zn;

Optionally, the concentration of Fe in the mixed solution containing copper, manganese, calcium and zinc is less than or equal to 10g/L;

Optionally, the concentration of Al in the mixed solution containing copper, manganese, calcium and zinc is less than or equal to 1 g/L.
The method according to any one of claims 1-6, wherein the saponification of step (1) is carried out with 6-14 mol/L of lye.
The method according to any one of claims 1-7, 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 for washing;

Optionally, the back extraction in step (2) is to use acid solution for back extraction.
The method according to any one of claims 1-8, 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, 10≤m+n≤22, -C n H 2n+1 and -C m H 2m+1 are independently a straight-chain or branched alkyl group with 1-21 carbon atoms;

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 1-9, wherein, in the second extraction of step (3), the volume ratio of extractant B to the first aqueous phase 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 5-30;

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 1-10, 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 1-11, 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 organic phase and 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 water 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 1-12, comprising the steps of:

(1) the first extraction is carried out to the mixed solution containing copper, manganese, calcium and zinc to obtain the first organic phase and the first aqueous phase; wherein, the extraction agent A used in the first extraction includes one of the carboxylic acid extraction agents Or a combination of at least 2 kinds; the general formula of the carboxylic acid extractant is as follows:

Wherein, 10≤m+n≤22, -C n H 2n+1 and -C m H 2m+1 are independently a straight-chain or branched alkyl group with 1-21 carbon atoms; the first In the extraction, the volume ratio of the extractant A and the mixed solution containing copper, manganese, calcium and zinc 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 extraction agent A used in the first extraction is saponified before use; the pH of the first aqueous phase is 4-5.5;

(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, 10≤m+n≤22, -C n H 2n+1 and -C m H 2m+1 are respectively a straight-chain or branched alkyl group with 1-21 carbon atoms; the extractant The volume fraction of B is 5-30%; the volume ratio of extractant B to the first aqueous phase in the second extraction is (0.1-10):1; the time of the second extraction is 5-30 min.