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WO2022048308A1 - 一种从含铜锰钙锌混合溶液中分离铜锰的方法 - Google Patents

一种从含铜锰钙锌混合溶液中分离铜锰的方法 Download PDF

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Publication number
WO2022048308A1
WO2022048308A1 PCT/CN2021/105655 CN2021105655W WO2022048308A1 WO 2022048308 A1 WO2022048308 A1 WO 2022048308A1 CN 2021105655 W CN2021105655 W CN 2021105655W WO 2022048308 A1 WO2022048308 A1 WO 2022048308A1
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Prior art keywords
extraction
extractant
manganese
optionally
zinc
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PCT/CN2021/105655
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English (en)
French (fr)
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王雪
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苏州博萃循环科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/32—Carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B47/00—Obtaining manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • 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.
  • 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.
  • manganese is precipitated to obtain manganese salts such as crude manganese carbonate.
  • 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.
  • 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:
  • 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;
  • 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:
  • 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;
  • step (2) the first organic phase obtained in step (1) is washed and back-extracted successively to obtain a copper-containing solution;
  • step (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 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the first extraction in step (1) includes single-stage extraction or multi-stage countercurrent extraction.
  • 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.
  • 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.
  • 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.
  • 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.
  • the washing in step (2) is multi-stage countercurrent washing.
  • 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.
  • the washing in step (2) is washing with an acid solution.
  • the back extraction in step (2) is to use acid solution for back extraction.
  • 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.
  • the extractant B used in the second extraction in step (3) includes a phosphorus-type extractant and/or a carboxylic acid-type extractant.
  • the phosphorus-based extractant includes C272 and the like.
  • 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.
  • the carboxylic acid extractant in the extractant B includes one carboxylic acid or a mixture of at least two carboxylic acids.
  • 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.
  • 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.
  • the second extraction in step (3) is multi-stage countercurrent extraction.
  • 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.
  • 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.
  • 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.
  • 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.
  • the pH value of the second aqueous phase is 3-4, and the pH value of the second aqueous phase is 5.5-7.5, optionally 5.5-6.8.
  • the extractant B used in the second extraction in step (3) is saponified before use.
  • 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.
  • the washing in step (3) is multi-stage countercurrent washing.
  • 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.
  • the washing in step (3) is washing with an acid solution.
  • 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.
  • the back extraction in step (3) is to use acid solution for back extraction.
  • 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 .
  • the second aqueous phase is sequentially subjected to degreasing and crystallization to obtain sodium sulfate crystals.
  • the crystallization mode is MVR evaporation.
  • the method comprises the following steps:
  • 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;
  • 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:
  • 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;
  • step (2) the first organic phase obtained in step (1) is washed and back-extracted successively to obtain a copper-containing solution;
  • 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;
  • 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:
  • 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.
  • the second organic phase obtained by the second extraction can be returned to the first extraction for copper extraction.
  • the solution after stripping when the mixed solution contains zinc, the solution after stripping will contain zinc.
  • it can be removed by conventional methods before the first extraction or between the first extraction and the second extraction.
  • 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;
  • 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.
  • 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.
  • the solvent may be No. 200 mineral spirits and/or No. 260 mineral spirits.
  • the dodecane may be n-dodecane or the like.
  • 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.
  • the acid solution in washing and stripping is sulfuric acid and/or hydrochloric acid, etc.
  • 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
  • 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
  • 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.
  • 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.
  • 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.
  • reaction equation of the relevant procedure is as follows:
  • M is Cu 2+ , Mn 2+ and other metals.
  • the present application at least has the following beneficial effects:
  • 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.
  • 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%.
  • Example 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.
  • 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 .
  • C272 was used to remove zinc at the beginning of the extraction, and a mixed solution containing copper, manganese, and calcium was obtained.
  • 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.
  • a manganese-rich solution is obtained.
  • 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.
  • This embodiment provides a method for separating copper and manganese from a mixed solution containing copper, manganese, calcium and zinc.
  • Zinc 1.0g/L.
  • 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
  • the first organic phase and the first aqueous phase with pH 5 are obtained after phase separation.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 °C.
  • 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.
  • 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 6.8 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.
  • 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.
  • 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%.
  • Example 1 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.

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Abstract

本申请涉及一种从含铜锰钙锌混合溶液中分离铜锰的方法，包括：(1)对含铜锰钙锌混合溶液进行第一萃取得到第一有机相和第一水相；其中第一萃取中使用的萃取剂A包括羧酸类萃取剂中的1种或至少2种的组合；(2)第一有机相依次进行洗涤和反萃得到含铜溶液；(3)将第一水相进行第二萃取得到第二有机相和第二水相；第二有机相经依次进行洗涤和反萃得到富锰溶液。

Description

一种从含铜锰钙锌混合溶液中分离铜锰的方法 技术领域
本申请属于湿法冶金领域，涉及一种从含铜锰钙锌混合溶液中分离铜锰的方法。
背景技术
目前，在钴的湿法冶金生产中，钴原料中的杂质离子在P204除杂工序中被除去，形成含大量铜锰钙等杂质金属的氯化物溶液，这些溶液常采用碳酸钠沉淀形成铜锰钙碳酸盐，其中铜和锰含量最多，且价值高。一个大型的钴冶炼厂每年产生的这种碳酸盐渣达数千吨以致上万吨，其中有价金属的价值达数千万。
CN105274352A公开了一种从碳酸铜锰钴钙锌混合物中分离铜锰钴的方法，其先向碳酸铜锰渣中加入硫酸形成硫酸盐溶液，除去硫酸钙沉淀，然后用酮肟或醛肟等萃铜试剂将铜以硫酸铜的形式分离出来，然后调整除铜后的溶液pH值，加入活泼金属粉末将钴还原为钴粉分离出去后，最后向滤液中加入碳酸钠，使锰沉淀下来获得锰碳酸盐。
CN105296754A公开了一种从氯化铜锰钴钙锌除杂溶液中分离铜钴锰的方法，其向铜锰钴钙锌溶液中加入硫酸钠，过滤除去硫酸钙，调节pH值在4.0-6.0，使溶液中铜离子沉淀，过滤分离出铜沉淀，再采用硫酸溶解蒸发结晶后得到硫酸铜晶体，向除铜后液中加入锰粉，使钴离子还原成钴粉分离除去，除钴后液中含有锰及是少量锌钙，通过蒸发结晶或者加入碳酸钠，使锰沉淀下来得到粗碳酸锰等锰盐沉淀。
上述方法操作复杂，其中，所用萃取法成本较高，沉淀法还会造成有价金属夹带损失。
发明内容
本申请的目的在于提供一种从含铜锰钙锌混合溶液中分离铜锰的方法，将铜和锰从溶液中分离开来，操作简单，可以经济有效的将铜锰两种有价金属提取分离。
为达此目的，本申请采用以下技术方案：
本申请提供一种从含铜锰钙锌混合溶液中分离铜锰的方法，所述方法包括如下步骤：
(1)对含铜锰钙锌混合溶液进行第一萃取，得到第一有机相和第一水相；其中，所述第一萃取中使用的萃取剂A包括羧酸类萃取剂中的1种或至少2种的组合；所述羧酸类萃取剂结构通式如下：
Figure PCTCN2021105655-appb-000001
其中，10≤m+n≤22，-C nH 2n+1以及-C mH 2m+1分别独立地为碳原子数为1-21的直链或支链的烷基；所述第一萃取中萃取剂A与含铜锰钙锌混合溶液的体积比为(0.1-10):1；所述第一萃取中所用的萃取剂A使用前进行皂化；所述第一水相的pH为4-5.5；
(2)将步骤(1)得到的第一有机相依次进行洗涤和反萃，得到含铜溶液；
(3)将步骤(1)得到的第一水相进行第二萃取，得到第二有机相和第二水相；所述第二有机相经依次进行的洗涤和反萃得到富锰溶液。
通过本申请提供的方法，将铜锰两种有价金属提取分离，操作简单，同时，羧酸类萃取剂对Cu和Mn提取率均大于99.0％，硫酸反萃率大于99.5％。
本申请中，所述第一萃取中萃取剂A与含铜锰钙锌混合溶液的体积比为 (0.1-10):1，例如可以是0.1:1、0.5:1、1:1、2:1、3:1、4:1、5:1、6:1、7:1、8:1、9:1或10:1等，但不限于所列举的数值，该范围内其他未列举的数值同样适用。
本申请中，所述第一水相的pH为4-5.5，例如可以是4、4.2、4.4、4.6、4.8、5、5.2、5.4或5.5等，但不限于所列举的数值，该范围内其他未列举的数值同样适用。
作为本申请可选的技术方案，步骤(1)所述含铜锰钙锌混合溶液中的金属元素包括：Cu、Mn、Ca、Fe、Al、Co及Zn。
可选地，所述含铜锰钙锌混合溶液中Fe的浓度≤10g/L，例如可以是10g/L、9g/L、8g/L、7g/L、6g/L、5g/L、4g/L或3g/L等，但不限于所列举的数值，该范围内其他未列举的数值同样适用。
可选地，所述含铜锰钙锌混合溶液中Al的浓度≤1g/L，例如可以是1g/L、0.8g/L、0.6g/L、0.4g/L或0.2g/L等，但不限于所列举的数值，该范围内其他未列举的数值同样适用。
作为本申请可选的技术方案，步骤(1)所述第一萃取中萃取剂A的体积分数为5-30％，例如可以是5％、10％、15％、20％、25％或30％等，但不限于所列举的数值，该范围内其他未列举的数值同样适用。
可选地，步骤(1)所述第一萃取包括单级萃取或多级逆流萃取。
可选地，所述多级逆流萃取的级数为2-30级，例如可以是2、5、10、15、20、25或30等，但不限于所列举的数值，该范围内其他未列举的数值同样适用。
可选地，步骤(1)所述第一萃取中的搅拌速度为100-250r/min，例如可以是100r/min、150r/min、200r/min或250r/min等，但不限于所列举的数值，该范围内其他未列举的数值同样适用。
可选地，步骤(1)所述第一萃取的时间为5-30min，例如可以是5min、10min、15min、20min、25min或30min等，但不限于所列举的数值，该范围内其他未列举的数值同样适用。
作为本申请可选的技术方案，步骤(1)所述皂化采用6-14mol/L的碱液进行，例如可以是6mol/L、7mol/L、8mol/L、9mol/L、10mol/L、11mol/L、12mol/L、13mol/L或14mol/L等，但不限于所列举的数值，该范围内其他未列举的数值同样适用。
作为本申请可选的技术方案，步骤(2)所述洗涤为多级逆流洗涤。
可选地，步骤(2)所述洗涤的级数为2-10级，例如可以是2、3、4、5、6、7、8、9或10等，但不限于所列举的数值，该范围内其他未列举的数值同样适用。
可选地，步骤(2)所述洗涤为采用酸液进行洗涤。
可选地，步骤(2)所述反萃为采用酸液进行反萃。
本申请中，第一有机相的洗涤和反萃中有机相和水相的体积比为(0.1-10):1，例如可以是0.1:1、0.5:1、1:1、2:1、3:1、4:1、5:1、6:1、7:1、8:1、9:1或10:1等，但不限于所列举的数值，该范围内其他未列举的数值同样适用。
作为本申请可选的技术方案，步骤(3)所述第二萃取中所用的萃取剂B包括包括磷型萃取剂和/或羧酸类萃取剂。
本申请中，所述磷型萃取剂包括C272等。
可选地，所述羧酸类萃取剂结构通式如下：
Figure PCTCN2021105655-appb-000002
其中，10≤m+n≤22，-C nH 2n+1以及-C mH 2m+1分别独立地为碳原子数为1-21的直链或支链的烷基。
可选地，所述萃取剂B中的羧酸类萃取剂包括1种羧酸或至少2种羧酸的混合物。
可选地，所述萃取剂B的体积分数为5-30％，例如可以是5％、10％、15％、20％、25％或30％等，但不限于所列举的数值，该范围内其他未列举的数值同样适用。
作为本申请可选的技术方案，步骤(3)所述第二萃取中萃取剂B与第一水相的体积比为(0.1-10):1，例如可以是0.1:1、0.5:1、1:1、2:1、3:1、4:1、5:1、6:1、7:1、8:1、9:1或10:1等，但不限于所列举的数值，该范围内其他未列举的数值同样适用。
可选地，步骤(3)所述第二萃取为多级逆流萃取。
可选地，所述多级逆流萃取的级数为5-30级，例如可以是5、10、15、20、25或30等，但不限于所列举的数值，该范围内其他未列举的数值同样适用。
可选地，步骤(3)所述第二萃取中的搅拌速度为100-250r/min，例如可以是100r/min、150r/min、200r/min或250r/min等，但不限于所列举的数值，该范围内其他未列举的数值同样适用。
可选地，步骤(3)所述第二萃取的时间为5-30min，例如可以是5min、10min、15min、20min、25min或30min等，但不限于所列举的数值，该范围内其他未列举的数值同样适用。
本申请中，第二水相的pH值由于萃取剂不同会有不同的pH值作业区间，本申请中不做具体限定，如采用C272时，第二水相的pH值为3-4，采用所述 羧酸类萃取剂时，第二水相的pH值为5.5-7.5，可选为5.5-6.8。
作为本申请可选的技术方案，步骤(3)所述第二萃取中所用的萃取剂B使用前进行皂化。
可选地，所述皂化为采用6-14mol/L的碱液进行，例如可以是6mol/L、7mol/L、8mol/L、9mol/L、10mol/L、11mol/L、12mol/L、13mol/L或14mol/L等，但不限于所列举的数值，该范围内其他未列举的数值同样适用。
作为本申请可选的技术方案，步骤(3)所述洗涤为多级逆流洗涤。
可选地，步骤(3)所述洗涤的级数为2-10级，例如可以是2、3、4、5、6、7、8、9或10等，但不限于所列举的数值，该范围内其他未列举的数值同样适用。
可选地，步骤(3)所述洗涤为采用酸液进行洗涤。
可选地，步骤(3)所述洗涤中有机相和水相的体积比为(0.1-10):1，例如可以是0.1:1、0.5:1、1:1、2:1、3:1、4:1、5:1、6:1、7:1、8:1、9:1或10:1等，但不限于所列举的数值，该范围内其他未列举的数值同样适用。
可选地，步骤(3)所述反萃为采用酸液进行反萃。
可选地，步骤(3)所述反萃中有机相和水相的体积比为(0.1-10):1，例如可以是0.1:1、0.5:1、1:1、2:1、3:1、4:1、5:1、6:1、7:1、8:1、9:1或10:1等，但不限于所列举的数值，该范围内其他未列举的数值同样适用。
可选地，所述第二水相依次经除油和结晶，得到硫酸钠晶体。
可选地，所述结晶的方式为MVR蒸发。
作为本申请可选的技术方案，所述方法包括如下步骤：
(1)对含铜锰钙锌混合溶液进行第一萃取，得到第一有机相和第一水相； 其中，所述第一萃取中使用的萃取剂A包括羧酸类萃取剂中的1种或至少2种的组合；所述羧酸类萃取剂结构通式如下：
Figure PCTCN2021105655-appb-000003
其中，10≤m+n≤22，-C nH 2n+1以及-C mH 2m+1分别独立地为碳原子数为1-21的直链或支链的烷基；所述第一萃取中萃取剂A与含铜锰钙锌混合溶液的体积比为(0.1-10):1所述第一萃取中萃取剂A的体积分数为5-30％；所述第一萃取的时间为5-30min；所述第一萃取中所用的萃取剂A使用前进行皂化；所述第一水相的pH为4-5.5；
(2)将步骤(1)得到的第一有机相依次进行洗涤和反萃，得到含铜溶液；
(3)将步骤(1)得到的第一水相进行第二萃取，得到第二有机相和第二水相；所述第二有机相经依次进行的洗涤和反萃得到富锰溶液；其中，所述第二萃取中所用的萃取剂B包括包括磷型萃取剂和/或羧酸类萃取剂；所述羧酸类萃取剂结构通式如下：
Figure PCTCN2021105655-appb-000004
其中，10≤m+n≤22，-C nH 2n+1以及-C mH 2m+1分别独立地为碳原子数为1-21的直链或支链的烷基；所述萃取剂B的体积分数为5-30％；所述第二萃取中萃取剂B与第一水相的体积比为(0.1-10):1；所述第二萃取的时间为5-30min。
本申请中，第二萃取得到的第二有机相可以返回第一萃取进行萃铜。
本申请中，当混合溶液中含锌时，反萃后的溶液中会含有锌，为了得到单一的锰溶液可在第一萃取前或在第一萃取和第二萃取间采用常规方法进行去 除，例如采用磷型和/或步骤(1)中羧酸类萃取剂萃取除去，采用所述羧酸类萃取剂进行萃取时，可通过控制水相平衡pH在5-6将锌离子萃取除去；同时若溶液中含有铁铝时，可采用现有技术中常规的手段如化学沉淀，萃取(如本申请中的羧酸类萃取剂)等方法去除铁铝，然后再进行第一萃取。上述过程并不会对铜和锰的分离造成影响。
本申请中，萃取剂的稀释剂包括溶剂油、煤油、Escaid110、己烷、庚烷、十二烷中的1种或至少2种的组合。
所述组合可以是溶剂油和煤油的组合，Escaid110和己烷的组合或庚烷和十二烷的组合等，但不限于所列举的组合，该范围内其他未列举的组合同样适用。
本申请中，所述溶剂可以是200号溶剂油和/或260号溶剂油。
本申请中，所述十二烷可以是正十二烷等。
本申请中，所述碱液包括氢氧化钠溶液、氢氧化钾溶液或氨水中的1种或至少2种的组合。
所述组合可以是氢氧化钠溶液和氢氧化钾溶液的组合或氢氧化钾溶液和氨水的组合等，但不限于所列举的组合，该范围内其他未列举的组合同样适用。
本申请中，洗涤和反萃中的酸液为硫酸和/或盐酸等，洗涤采用酸液pH为1-2，例如可以是1、1.2、1.4、1.5、1.8或2等，但不限于所列举的数值，该范围内其他未列举的数值同样适用，反萃采用盐酸浓度为1-4mol/L，例如可以是1mol/L、1.5mol/L、2mol/L、2.5mol/L、3mol/L或4mol/L等，但不限于所列举的数值，该范围内其他未列举的数值同样适用，反萃所用硫酸浓度为0.5-3.5mol/L，例如0.5mol/L、1mol/L、2mol/L、3mol/L或3.5mol/L等，但不限于所列举的数值，该范围内其他未列举的数值同样适用。
本申请中，有机相1经反萃得到的萃取剂经皂化后可返回萃取作业中，萃取剂皂化后也可由钠皂转为锰皂。
本申请中，所述的羧酸类萃取剂可为一种或多种羧酸的混合物，例如萃取剂BC196(通式中m＝8，n＝8所对应的化合物)，萃取剂BC191(通式中m＝8，n＝10所对应的化合物)，萃取剂BC196和BC191的混合物，萃取剂BC199(通式中m＝8，n＝2、m＝7，n＝9、m＝10，n＝8和m＝10，n＝10所对应的化合物以体积比1:1:1:1混合)。
本申请中，所述逆流萃取是萃取分离操作法之一，含有被萃取物的水相及有机相分别从萃取器的两端流入，以相反方向流动，进行连续多级搅拌接触分层而达到分离的目的。
本申请中，相关工序的反应方程式如下：
羧酸类萃取剂皂化：HA (org)+NaOH→NaA (org)+H 2O
羧酸类萃取剂萃取：2NaA (org)+MSO 4→MA 2(org)+Na 2SO 4
硫酸反萃：MA 2(org)+H 2SO 4→2HA (org)+MSO 4
其中：M为Cu 2+、Mn 2+等金属。
与现有技术方案相比，本申请至少具有以下有益效果：
(1)本申请提供的方法，对金属离子分离效果好，将铜锰钙锌渣中铜锰实现分离净化，操作简单，工艺稳定，运行成本低。
(2)本申请提供的回收方法中铜、锰提取率≥99％，硫酸反萃率≥99.5％。
附图说明
图1是本申请实施例1中的从含铜锰钙锌混合溶液中分离铜锰的方法的示意图。
下面对本申请进一步详细说明。但下述的实例仅仅是本申请的简易例子，并不代表或限制本申请的权利保护范围，本申请的保护范围以权利要求书为准。
具体实施方式
为更好地说明本申请，便于理解本申请的技术方案，本申请的典型但非限制性的实施例如下：
实施例1
本实施例提供一种从含铜锰钙锌混合溶液中分离铜锰的方法，如图1所示。
本实施例中的含铜锰钙锌溶液来源于P204除杂后离子硫酸盐混合液：锰58g/L，铜15g/L，钙0.5g/L，锌3.2g/L，铁0.01g/L。
本实施例中为了得到单一的铜溶液和锰溶液，在萃取开始时进行了采用C272进行除锌，得到含铜锰钙混合溶液
采用皂化后的BC196(体积分数为25％，稀释剂为Escaid 110，用6mol/L的氨水溶液进行皂化)对含铜锰钙混合溶液进行10级逆流萃取，萃取剂与含铜锰钙溶液的体积比为2:1，萃取时间为8min，搅拌速度为150r/min，实验温度为25℃，分相后分别获得第一有机相和pH值为4.5的第一水相，采用pH为1.5的硫酸对第一有机相进行2级逆流洗涤后，再采用2mol/L硫酸进行反萃3次，第一有机相与洗涤液或反萃液的体积为8:1，得到硫酸铜溶液经除油后浓缩结晶，反萃后的有机相返回皂化工序循环使用。
采用皂化后的BC196(体积分数为25％，稀释剂为Escaid 110，用6mol/L的氨水溶液进行皂化)对第一水相进行多级逆流萃取，萃取级数8级，萃取剂与第一水相的体积比为4:1，萃取时间为8min，搅拌速度为150r/min，静置15min， 实验温度为25℃，分别获得第二有机相和pH值为6.3的第二水相，采用pH为1.5的硫酸对第二有机相进行5级逆流洗涤后，再采用2mol/L的硫酸进行反萃5次，第二有机相与洗涤液或反萃液的体积比为2:1，反萃后得到富锰溶液。
本实施例中Cu和Mn的提取率分别为99.7％和99.6％，反萃率分别为99.7％和99.7％。
实施例2
本实施例提供一种从含铜锰钙锌混合溶液中分离铜锰的方法，实施例中的含铜锰钙锌溶液中：锰10g/L，铜0.01g/L，钙0.34g/L，锌1.0g/L。
采用皂化后的BC191(体积分数为20％，稀释剂为260号溶剂油，用10mol/L的NaOH溶液进行皂化)对含铜锰溶液进行7级逆流萃取，萃取剂与含铜锰钙锌溶液的体积比为0.2:1，萃取时间为5min，搅拌速度为200r/min，静置20min，实验温度为25℃，分相后分别获得第一有机相和pH值为5的第一水相，采用pH为1.2的硫酸对第一有机相进行4级逆流洗涤后，再采用2mol/L硫酸进行反萃1次，第一有机相与洗涤液或反萃液的体积为10:1，反萃得到的硫酸铜溶液经除油后浓缩结晶，反萃得到的有机相返回皂化工序循环使用。
采用皂化后的C272(体积分数为20％，稀释剂为260号溶剂油，皂化剂10mol/L的NaOH溶液)对第一水相进行多级逆流萃取，萃取级数5级，萃取剂与第一水相的体积比为0.2:1，萃取时间为5min，搅拌速度为200r/min，静置20min，实验温度为常规温度25℃，控制水相pH值2.5，分相，获得负载锌有机相和除锌后第一水相，采用pH为1.2的硫酸对负载锌有机相进行3级逆流洗涤后，再采用2mol/L硫酸进行反萃2次，洗涤或反萃中的有机相与洗涤液或反萃液的体积为10:1，得到富锌溶液经除油后浓缩结晶。
采用皂化后的C272对除锌后第一水相进行5级萃取，萃取剂与第一水相的体积比为1:1，其它萃取条件同上，分相分别获得第二有机相和pH值为4的第二水相，采用pH为1.2的硫酸对第二有机相进行3级逆流洗涤后，再采用2.5mol/L硫酸进行反萃4次，洗涤或反萃中的有机相与洗涤液或反萃液的体积为10:1，得到富锰溶液。
本实施例中Cu和Mn的提取率分别为99.7％和99.8％，反萃率分别为99.6％和99.7％。
实施例3
本实施例提供一种从含铜锰钙锌混合溶液中分离铜锰的方法，实施例中的含铜锰钙锌溶液中：锰15g/L，铜0.05g/L，钙0.4g/L，锌1.2g/L。
采用锰皂后的BC196(体积分数为25％，稀释剂为Escaid 110，先采用10moL/L氢氧化钠溶液处理，然后采用2g/L的硫酸锰溶液处理得到锰皂)对含铜锰钙锌溶液进行4级逆流萃取，萃取剂与含铜锰溶液的体积比为0.2:1，萃取时间为10min，搅拌速度为150r/min，静置10min，实验温度为25℃，分相后分别获得第一有机相和pH值为5.3的第一水相，采用pH为1的硫酸对第一有机相进行5级逆流洗涤后，再采用2.5mol/L硫酸进行反萃1次，第一有机相与洗涤液或反萃液的体积为10:1，反萃得到的硫酸铜溶液经除油后浓缩结晶，反萃得到的有机相返回皂化工序循环使用。
采用皂化的BC196(体积分数为25％，稀释剂为Escaid 110，用8mol/L的NaOH溶液进行皂化)将第一水相中的锌萃取除去，萃取级数9级，控制水相pH为5.6，分相后获得负载锌有机相和除锌后第一水相，采用pH为1的稀硫酸对负载锌有机相进行5级逆流洗涤后，再采用2.5mol/L硫酸进行反萃2次，第 一有机相与洗涤液或反萃液的体积为10:1，反萃得到的硫酸锌溶液经除油后浓缩结晶。
采用皂化后的BC196对除锌后第一水相进行多级逆流萃取，萃取级数7级，萃取剂与第一水相的体积比为2:1，萃取时间为10min，搅拌速度为150r/min，静置10min，实验温度为25℃，分别获得第二有机相和pH值为6.8的第二水相，采用pH为1的硫酸对第二有机相进行7级逆流洗涤后，再采用2.5mol/L的硫酸进行反萃4次，第二有机相与洗涤液或反萃液的体积比为10:1，反萃后得到富锰溶液。
本实施例中Cu和Mn的提取率分别为99.8％和99.7％，反萃率分别为99.7％和99.7％。
对比例1
与实施例1的区别仅在于将第一萃取中的萃取剂替换为羧酸类萃取剂CA-100，经检测，Cu和Mn的提取率分别为78％和75％，反萃率分别为99.4％和99.3％。
对比例2
与实施例1的区别仅在于将第一萃取中的萃取剂替换为羧酸类萃取剂Versatic 10，水溶性较大，萃取不稳定，分离效果差，成本高。
申请人声明，本申请通过上述实施例来说明本申请的详细结构特征，但本申请并不局限于上述详细结构特征，即不意味着本申请必须依赖上述详细结构特征才能实施。
以上详细描述了本申请的可选实施方式，但是，本申请并不限于上述实施方式中的具体细节，在本申请的技术构思范围内，可以对本申请的技术方案进 行多种简单变型。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本申请对各种可能的组合方式不再另行说明。
此外，本申请的各种不同的实施方式之间也可以进行任意组合，只要其不违背本申请的思想，其同样应当视为本申请所公开的内容。

Claims (13)

  1. 一种从含铜锰钙锌混合溶液中分离铜锰的方法，其包括如下步骤：
    (1)对含铜锰钙锌混合溶液进行第一萃取，得到第一有机相和第一水相；其中，所述第一萃取中使用的萃取剂A包括羧酸类萃取剂中的1种或至少2种的组合；所述羧酸类萃取剂结构通式如下：
    Figure PCTCN2021105655-appb-100001
    其中，10≤m+n≤22，-C nH 2n+1以及-C mH 2m+1分别独立地为碳原子数为1-21的直链或支链的烷基；所述第一萃取中萃取剂A与含铜锰钙锌混合溶液的体积比为(0.1-10):1；所述第一萃取中所用的萃取剂A使用前进行皂化；所述第一水相的pH为4-5.5；
    (2)将步骤(1)得到的第一有机相依次进行洗涤和反萃，得到含铜溶液；
    (3)将步骤(1)得到的第一水相进行第二萃取，得到第二有机相和第二水相；所述第二有机相经依次进行洗涤和反萃得到富锰溶液。
  2. 如权利要求1所述的方法，其中，步骤(1)所述第一萃取中萃取剂A的体积分数为5-30％.
  3. 如权利要求1或2所述的方法，其中，步骤(1)所述第一萃取包括单级萃取或多级逆流萃取。
  4. 如权利要求3所述的方法，其中，所述多级逆流萃取的级数为2-30级。
  5. 如权利要求1-4然一项所述的方法，其中，步骤(1)所述第一萃取中的搅拌速度为100-250r/min；
    可选地，步骤(1)所述第一萃取的时间为5-30min。
  6. 如权利要求1-5任一项所述的方法，其中，步骤(1)所述含铜锰钙锌 混合溶液中的金属元素包括：Cu、Mn、Ca、Fe、Al、Co及Zn；
    可选地，所述含铜锰钙锌混合溶液中Fe的浓度≤10g/L；
    可选地，所述含铜锰钙锌混合溶液中Al的浓度≤1g/L。
  7. 如权利要求1-6任一项所述的方法，其中，步骤(1)所述皂化采用6-14mol/L的碱液进行。
  8. 如权利要求1-7任一项所述的方法，其中，步骤(2)所述洗涤为多级逆流洗涤；
    可选地，步骤(2)所述洗涤的级数为2-10级；
    可选地，步骤(2)所述洗涤为采用酸液进行洗涤；
    可选地，步骤(2)所述反萃为采用酸液进行反萃。
  9. 如权利要求1-8任一项所述的方法，其中，步骤(3)所述第二萃取中所用的萃取剂B包括包括磷型萃取剂和/或羧酸类萃取剂；
    可选地，所述羧酸类萃取剂结构通式如下：
    Figure PCTCN2021105655-appb-100002
    其中，10≤m+n≤22，-C nH 2n+1以及-C mH 2m+1分别独立地为碳原子数为1-21的直链或支链的烷基；
    可选地，所述萃取剂B中的羧酸类萃取剂包括1种羧酸或至少2种羧酸的混合物；
    可选地，所述萃取剂B的体积分数为5-30％。
  10. 如权利要求1-9任一项所述的方法，其中，步骤(3)所述第二萃取中萃取剂B与第一水相的体积比为(0.1-10):1；
    可选地，步骤(3)所述第二萃取为多级逆流萃取；
    可选地，所述多级逆流萃取的级数为5-30级；
    可选地，步骤(3)所述第二萃取中的搅拌速度为100-250r/min；
    可选地，步骤(3)所述第二萃取的时间为5-30min。
  11. 如权利要求1-10任一项所述的方法，其中，步骤(3)所述第二萃取中所用的萃取剂B使用前进行皂化；
    可选地，所述皂化为采用6-14mol/L的碱液进行。
  12. 如权利要求1-11任一项所述的方法，其中，步骤(3)所述洗涤为多级逆流洗涤；
    可选地，步骤(3)所述洗涤的级数为2-10级；
    可选地，步骤(3)所述洗涤为采用酸液进行洗涤；
    可选地，步骤(3)所述洗涤中有机相和水相的体积比为(0.1-10):1；
    可选地，步骤(3)所述反萃为采用酸液进行反萃；
    可选地，步骤(3)所述反萃中有机相和水相的体积比为(0.1-10):1；
    可选地，所述第二水相依次经除油和结晶，得到硫酸钠晶体；
    可选地，所述结晶的方式为MVR蒸发。
  13. 如权利要求1-12任一项所述的方法，其包括如下步骤：
    (1)对含铜锰钙锌混合溶液进行第一萃取，得到第一有机相和第一水相；其中，所述第一萃取中使用的萃取剂A包括羧酸类萃取剂中的1种或至少2种的组合；所述羧酸类萃取剂结构通式如下：
    Figure PCTCN2021105655-appb-100003
    其中，10≤m+n≤22，-C nH 2n+1以及-C mH 2m+1分别独立地为碳原子数为1-21的直链或支链的烷基；所述第一萃取中萃取剂A与含铜锰钙锌混合溶液的体积比为(0.1-10):1所述第一萃取中萃取剂A的体积分数为5-30％；所述第一萃取的时间为5-30min；所述第一萃取中所用的萃取剂A使用前进行皂化；所述第一水相的pH为4-5.5；
    (2)将步骤(1)得到的第一有机相依次进行洗涤和反萃，得到含铜溶液；
    (3)将步骤(1)得到的第一水相进行第二萃取，得到第二有机相和第二水相；所述第二有机相经依次进行洗涤和反萃得到富锰溶液；其中，所述第二萃取中所用的萃取剂B包括包括磷型萃取剂和/或羧酸类萃取剂；所述羧酸类萃取剂结构通式如下：
    Figure PCTCN2021105655-appb-100004
    其中，10≤m+n≤22，-C nH 2n+1以及-C mH 2m+1分别独立地为碳原子数为1-21的直链或支链的烷基；所述萃取剂B的体积分数为5-30％；所述第二萃取中萃取剂B与第一水相的体积比为(0.1-10):1；所述第二萃取的时间为5-30min。
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CN115058597B (zh) * 2022-06-30 2024-06-04 盛隆资源再生（无锡）有限公司 一种含钙、铁、钴、镍的电镀污泥的回收处理方法
CN115893497A (zh) * 2022-11-14 2023-04-04 广东邦普循环科技有限公司 一种从含钙铜铬硅的锰溶液中制备高纯硫酸锰的方法

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