WO2024103568A1 - Method for preparing high-purity manganese sulfate from manganese solution containing calcium, copper, chromium and silicon - Google Patents

Method for preparing high-purity manganese sulfate from manganese solution containing calcium, copper, chromium and silicon Download PDF

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WO2024103568A1
WO2024103568A1 PCT/CN2023/079180 CN2023079180W WO2024103568A1 WO 2024103568 A1 WO2024103568 A1 WO 2024103568A1 CN 2023079180 W CN2023079180 W CN 2023079180W WO 2024103568 A1 WO2024103568 A1 WO 2024103568A1
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manganese
chromium
organic phase
copper
extraction
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PCT/CN2023/079180
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French (fr)
Chinese (zh)
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张荣荣
刘黄华
刘勇奇
巩勤学
李长东
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
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Publication of WO2024103568A1 publication Critical patent/WO2024103568A1/en

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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
    • C22B47/00—Obtaining manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/10—Sulfates
    • 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
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3842—Phosphinic acid, e.g. H2P(O)(OH)
    • 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
    • C22B3/40—Mixtures
    • 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 present application relates to the field of hydrometallurgy, and in particular to a method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon.
  • manganese plays a special and important role in the development of the national economy.
  • it generally involves the process of extracting and removing impurities with P204. Its purpose is to purify the nickel-cobalt-manganese solution and remove impurities such as calcium, copper, zinc, cadmium, magnesium, and aluminum from the nickel-cobalt-manganese solution.
  • impurities such as calcium, copper, zinc, cadmium, magnesium, and aluminum
  • CN113072487A discloses a pyridyl-containing calix[4] aromatic hydrocarbon derivative and its preparation method and use as a manganese ion extractant.
  • the method uses a pyridyl-containing calix[4] aromatic hydrocarbon derivative and P204 to extract the manganese ion.
  • the organic phase is mixed to improve the selectivity for manganese ions and to achieve the separation of manganese from nickel, cobalt, magnesium and lithium.
  • P204 in this method can enhance the selectivity of manganese and improve the phase separation effect, the extraction rate of impurities such as calcium, zinc, copper, chromium and cadmium will also be enhanced, especially calcium.
  • the quality of the obtained manganese sulfate stripping solution is extremely low and cannot be directly used for precursor synthesis.
  • the above scheme has the problems of poor phase separation of the extractant, large organic loss, impurity content in the manganese sulfate solution obtained by the one-step method cannot meet the requirements of battery-grade manganese sulfate, and low economic benefits.
  • the purpose of the present application is to provide a method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon.
  • the present application adopts two extractants, HBL116 and di(2,4,4-trimethylpentyl)phosphinic acid, for synergistic extraction, which solves the problems of high extraction rate of calcium, copper and zinc by HBL116 but poor phase separation and high cost of di(2,4,4-trimethylpentyl)phosphinic acid but high extraction rate of silicon, chromium and the like.
  • the present application has the advantages of high extraction efficiency, large separation coefficient of manganese from elements such as calcium, copper, silicon and chromium, low water solubility, low organic loss, high stripping rate, efficient short-range recovery, recyclable organic phase after stripping, organic stability, short process flow, low production cost, low equipment investment, etc.
  • Advantages It realizes the resource utilization of manganese in wastewater and improves the recovery rate of manganese.
  • this application includes the following contents:
  • a method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon comprising the following steps:
  • step (2) using the extracted organic phase obtained in step (1) to extract the manganese solution containing calcium, copper, chromium and silicon to obtain a loaded organic phase and a raffinate aqueous phase;
  • the washed loaded organic phase is stripped with a stripping agent to obtain a high-purity manganese sulfate solution, thereby achieving efficient separation of manganese from impurity ions such as calcium, copper, chromium, silicon, magnesium, and sodium.
  • the synergistic extractant HBL116 was purchased from Hunan Hongbang Material Technology Co., Ltd.; the extraction order of HBL116 extractant in aqueous solution is Fe 3+ >Mn ion>Ca 2+ >Mg 2+ , and the performance parameters are as follows: color: red-brown oily liquid, specific gravity 0.94-0.97g/cm 3 , viscosity ⁇ 24mPa ⁇ s, content ⁇ 98%, flash point ⁇ 70°C.
  • the volume proportion of the extractant di(2,4,4-trimethylpentyl)phosphinic acid is 15%-25%; specifically, the volume proportion of the extractant di(2,4,4-trimethylpentyl)phosphinic acid can be 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24% or 25%, etc.
  • the volume proportion of the co-extractant HBL116 is 5%-10%, specifically 5%, 6%, 7%, 8%, 9% or 10%.
  • the diluent in step (1) is any one of kerosene, sulfonated kerosene, Escaid110, heptane, hexane, and dodecane, or a combination of at least two thereof;
  • the volume proportion of the combined extractant is It is 20%-35%, specifically it can be 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, or 35%, etc.
  • the volume proportion of the diluent is 65%-80%, specifically 65%, 67%, 69%, 71%, 73%, 75%, 77%, 78% or 80%, etc.
  • the extracted organic phase in step (2) is subjected to saponification treatment before extraction;
  • the saponifying agent for the saponification treatment is an alkaline solution;
  • the alkaline solution is any one of sodium hydroxide, ammonia water, potassium hydroxide, magnesium hydroxide, etc., or a combination of at least two thereof;
  • the concentration of the alkaline solution is 5-12 mol/L, specifically 5 mol/L, 6 mol/L, 7 mol/L, 8 mol/L, 9 mol/L, 10 mol/L, 11 mol/L or 12 mol/L, etc.
  • the saponification degree of the saponification treatment is 0%-50%, specifically 0%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50%, etc., wherein a saponification degree of 0% means no saponification treatment is performed.
  • the volume ratio of the extracted organic phase to the manganese solution containing calcium, copper, chromium and silicon is 1:(0.05-15), specifically 1:0.05, 1:0.1, 1:1.5, 1:2, 1:2.5, 1:3, 1:4, 1:10 or 1:15, etc.
  • the extraction in step (2) is a single-stage extraction or a multi-stage countercurrent extraction, preferably a multi-stage countercurrent extraction;
  • the multi-stage countercurrent extraction stages are 3-10, specifically 3, 4, 5, 6, 7, 8, 9 or 10 stages, etc.
  • the pH value of the aqueous phase in the extraction section of step (2) is controlled at 2-6, specifically 2, 3, 4, 5 or 6.
  • the manganese solution containing calcium, copper, chromium and silicon in step (2) is a stripping solution produced by leaching battery waste, removing iron, aluminum and copper, and then extracting and removing impurities with P204, wherein the manganese concentration is 25-55g/L,
  • the calcium concentration is 1.5-6 g/L
  • the magnesium concentration is 0.5-2 g/L
  • the copper concentration is 0.05-1 g/L
  • the chromium concentration is 0.05-1 g/L
  • the silicon concentration is 0.02-0.8 g/L
  • the sodium concentration is 2-5 g/L
  • the pH of the feed solution is 2-3.5.
  • the loaded organic phase obtained in step (2) is washed with a washing liquid, wherein the washing liquid is any one or more of a sulfuric acid solution, a hydrochloric acid solution, a phosphoric acid solution or an oxalic acid solution;
  • the H + concentration of the washing solution is 0-1 mol/L; specifically, it can be 0, 0.2 mol/L, 0.4 mol/L, 0.6 mol/L, 0.8 mol/L or 1 mol/L, etc.
  • the volume ratio of the washing liquid to the loaded organic is (0.05-0.5):1, specifically 0.05:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1 or 0.5:1, etc.
  • the washing process is multi-stage countercurrent washing
  • the number of stages of the multi-stage countercurrent washing is 2-8, for example: 2, 3, 4, 5, 6, 7 or 8, etc.
  • the washing liquid used in step (3) is used to wash the loaded organic phase, and the washed organic phase is stripped using a stripping agent to obtain a high-purity manganese sulfate solution and a blank organic phase, and the blank organic phase is returned for saponification and reused.
  • the stripping agent for the stripping treatment in step (3) is a sulfuric acid solution and/or a hydrochloric acid solution;
  • the H + concentration in the stripping agent is 3-5 mol/L, for example, 3 mol/L, 3.5 mol/L, 4 mol/L, 4.5 mol/L or 5 mol/L.
  • the volume ratio of the stripping agent to the washed loaded organic phase is (0.05-0.5):1, such as 0.05:1, 0.1:1, 0.15:1, 0.2:1, 0.25:1, 0.3:1 or 0.5:1, etc.
  • the number of stages of the stripping treatment is 1-6, for example: 1, 2, 3, 4, 5 or 6, etc.
  • the preferred solution of this application comprises the following steps:
  • step (2) using an alkaline solution with a concentration of 5-12 mol/L to saponify the extracted organic phase prepared in step (1) to obtain a saponified organic phase; using the saponified organic phase to extract the calcium, copper, chromium, silicon and manganese solution under the condition that the pH value of the aqueous phase in the extraction section is 2-6 to obtain a loaded organic phase and a raffinate aqueous phase;
  • step (3) using a washing solution with an H + concentration of 0-1 mol/L to perform a 2-8 level washing treatment on the loaded organic phase obtained in step (2); using a stripping agent with an H + concentration of 3-5 mol/L to strip the loaded organic phase obtained in step (2) to obtain a high-purity manganese sulfate solution.
  • the present application adopts a synergistic extraction method to prepare high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon.
  • the extractant di(2,4,4-trimethylpentyl)phosphinic acid and the synergist HBL116 used have excellent selectivity, low water solubility, low organic loss and stable extraction performance.
  • the method provided in the present application can solve the problems of high extraction rate of calcium, copper and zinc by HBL116, poor phase separation, high cost of di(2,4,4-trimethylpentyl)phosphinic acid and high extraction rate of silicon, chromium and the like.
  • the present application After synergistic extraction, the present application has the advantages of high extraction efficiency, large separation coefficient of manganese from elements such as calcium, copper, silicon and chromium, short process flow, low production cost and low equipment investment.
  • the present application realizes the resource utilization of manganese in wastewater, improves the recovery rate of manganese, has high economic benefits and is suitable for industrial application.
  • the method disclosed in the present application obtains a high-purity manganese sulfate solution, and the manganese recovery rate can reach 99%.
  • manganese sulfate solution manganese>120g/L, copper ⁇ 0.5ppm, magnesium ⁇ 3ppm, chromium ⁇ 2ppm, silicon ⁇ 8ppm, calcium ⁇ 2ppm, and sodium ⁇ 100ppm are contained, and the one-step method meets the requirements of battery-grade manganese sulfate.
  • FIG1 is a flow chart of a method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon according to an embodiment of the present application.
  • This embodiment provides a method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon, comprising the following steps:
  • the pH value of the feed solution is 2.7
  • the volume ratio of the manganese solution containing calcium, copper, chromium and silicon to the saponified organic phase is 1:4, and 6-stage countercurrent extraction is performed. After standing for 5 minutes, the upper organic phase and the lower aqueous phase are separated to obtain a loaded organic phase;
  • This embodiment provides a method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon, comprising the following steps:
  • the pH value of the feed solution is 3.0
  • the volume ratio of the manganese solution containing calcium, copper, chromium and silicon to the saponified organic phase is 1:4, and 6-stage countercurrent extraction is performed. After standing for 5 minutes, the upper organic phase and the lower aqueous phase are separated to obtain a loaded organic phase;
  • This embodiment provides a method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon, comprising the following steps:
  • the pH value of the feed solution is 3.0
  • the volume ratio of the manganese solution containing calcium, copper, chromium and silicon to the saponified organic phase is 1:4, and 6-stage countercurrent extraction is performed. After standing for 5 minutes, the upper organic phase and the lower aqueous phase are separated to obtain a loaded organic phase;
  • Example 2 The difference between Example 2 and Example 1 is that the pH of the liquid is slightly higher and the saponification rate is higher.
  • the data show that the separation rate of the organic and aqueous phases slows down with the increase of the saponification rate, and the manganese load is increased, but the extraction rate of calcium chromium silicon is also increased.
  • the increase will increase the washing cost and the risk of the stripping solution manganese sulfate solution not meeting the standard. Therefore, it is advisable to control the saponification rate at about 40%.
  • Example 3 The difference between Example 3 and Example 1 is that the proportion of the extractant bis(2,4,4-trimethylpentyl)phosphonic acid is increased.
  • the data show that the manganese load is improved by increasing the proportion of the extractant. Due to the increase in the sodium salt of bis(2,4,4-trimethylpentyl)phosphonic acid after saponification, the turbidity of the organic phase increases. Under the condition of unchanged washing conditions, the chromium and silicon contents in the stripping liquid manganese sulfate solution increase, and the product quality is at risk.
  • the manganese content in the raffinate is less than 150 mg/L, the manganese recovery rate reaches 99%, the manganese in the stripping solution manganese sulfate solution is greater than 120 g/L, copper is less than 0.5 ppm, magnesium is less than 3 ppm, chromium is less than 2 ppm, silicon is less than 8 ppm, calcium is less than 2 ppm, and sodium is less than 100 ppm, and the one-step method meets the requirements of battery-grade manganese sulfate.
  • Example 1 The difference between this comparative example and Example 1 is that the synergist HBL116 is replaced with an equal amount of Escaid110, that is, without adding a synergist, manganese and silicon chromium cannot be effectively separated;
  • Example 1 The difference between this comparative example and Example 1 is that the extractant bis(2,4,4-trimethylpentyl)phosphonic acid is replaced with an equal amount of Escaid110, that is, without adding an extractant, manganese and calcium, copper and zinc cannot be effectively separated;
  • the method provided by the present application can realize the one-step preparation of a high-purity manganese sulfate solution from a manganese solution containing calcium, copper, chromium and silicon through the synergistic extraction effect of the extractant di(2,4,4-trimethylpentyl)phosphonic acid and the synergistic extraction agent HBL116.
  • the manganese sulfate solution in the stripping liquid contains manganese>120 g/L, copper ⁇ 0.5 ppm, magnesium ⁇ 3 ppm, chromium ⁇ 2 ppm, silicon ⁇ 8 ppm, calcium ⁇ 2 ppm, and sodium ⁇ 100 ppm, and the recovery rate of manganese reaches 99%.

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Abstract

A method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon. The method comprises the following steps: (1) formulating a combined extraction agent from an extraction agent, i.e. bis(2,4,4-trimethylpentyl)phosphinic acid and a synergistic extraction agent, i.e. HBL116, and adding a diluent thereto to formulate an organic extraction phase; (2) extracting a solution containing calcium, copper, chromium, silicon and manganese by using the organic extraction phase, so as to obtain a loaded organic phase and a raffinate water phase; and (3) washing the loaded organic phase by using a washing solution, and performing a reverse extraction treatment on the washed loaded organic phase by using a reverse extraction agent. By means of the synergistic extraction effect of the double extraction agents, the problems of the high extraction rate of calcium, copper and zinc and the poor phase separation of HBL116, and the high cost and high extraction rate of silicon, chromium, etc. of bis(2,4,4-trimethylpentyl)phosphinic acid are solved; the method has the advantages of a high extraction efficiency, a large separation coefficient of manganese from the other elements, a short process flow, low production costs, etc.; and the method improves the recovery rate of manganese, has relatively great economic benefits, and has industrial application prospects.

Description

一种从含钙铜铬硅的锰溶液中制备高纯硫酸锰的方法A method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon 技术领域Technical Field
本申请涉及湿法冶金领域，特别涉及一种从含钙铜铬硅的锰溶液中制备高纯硫酸锰的方法。The present application relates to the field of hydrometallurgy, and in particular to a method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon.
背景技术Background technique
近年来，得益于我国政府不断的政策扶持，社会大众的环保意识的逐步加强，以及国内高校、科研单位及企业在动力电池、电池管理系统等方面的研发的持续努力，我国的电动汽车市场得到了快速发展。随着新能源车的快速产业化，其销量将突飞猛进，锂离子电池的保有量也将会随之呈几何级数增长，与此同时，废旧锂离子动力电池的污染问题和合理资源化回收利用的问题成为当今乃至今后国内外普遍关注和亟待解决的难题。In recent years, thanks to the continuous policy support from the Chinese government, the gradual strengthening of the public's environmental awareness, and the continuous efforts of domestic universities, scientific research institutions and enterprises in the research and development of power batteries, battery management systems, etc., my country's electric vehicle market has developed rapidly. With the rapid industrialization of new energy vehicles, their sales will increase by leaps and bounds, and the number of lithium-ion batteries will also increase exponentially. At the same time, the pollution problem of waste lithium-ion power batteries and the problem of reasonable resource recycling have become a common concern and urgent problem to be solved at home and abroad today and in the future.
锰作为重要的战略物资，在国民经济发展中有着特殊的重要地位。湿法冶金回收镍钴锰时一般都会涉及到用P204萃取除杂的工艺，其目的是将镍钴锰溶液净化，去除镍钴锰溶液中的钙、铜、锌、镉、镁、铝等杂质，但是当除杂时由于锰与杂质分离系数较小，除杂过程中会损失一部分锰，造成锰的回收率普遍低于镍和钴。目前P204锰反萃液中除钙、铜、铬、硅、锌等比较困难，一般企业都采用沉淀法处理，但沉淀时锰与杂质离子一起沉淀形成的渣只能作为危废渣处理或者折价给其他公司处理，造成锰的回收率低，危废产生量大、生产成本高，不利于锰的资源化和可持续发展。As an important strategic material, manganese plays a special and important role in the development of the national economy. When recovering nickel, cobalt and manganese by hydrometallurgy, it generally involves the process of extracting and removing impurities with P204. Its purpose is to purify the nickel-cobalt-manganese solution and remove impurities such as calcium, copper, zinc, cadmium, magnesium, and aluminum from the nickel-cobalt-manganese solution. However, due to the small separation coefficient between manganese and impurities during impurity removal, a part of manganese will be lost during the impurity removal process, resulting in a generally lower manganese recovery rate than nickel and cobalt. At present, it is difficult to remove calcium, copper, chromium, silicon, zinc, etc. from P204 manganese stripping solution. Generally, enterprises use precipitation method for treatment. However, the slag formed by the precipitation of manganese and impurity ions can only be treated as hazardous waste slag or sold at a discount to other companies for treatment, resulting in a low manganese recovery rate, a large amount of hazardous waste, and high production costs, which is not conducive to the resource utilization and sustainable development of manganese.
CN113072487A公开了这一种含吡啶基杯[4]芳香烃衍生物及其制备方法和作为锰离子萃取剂的应用，该方法采用含吡啶基杯[4]芳香烃衍生物与P204的 混合有机相来提高对锰离子的选择性，实现锰和镍、钴、镁、锂的分离，该方法加入P204虽然可以增强锰的选择性，改善分相效果，但对杂质钙、锌、铜、铬、镉的萃取率也会加强，尤其是钙，得到的硫酸锰反萃液质量极低，不能直接用于前驱体合成。CN113072487A discloses a pyridyl-containing calix[4] aromatic hydrocarbon derivative and its preparation method and use as a manganese ion extractant. The method uses a pyridyl-containing calix[4] aromatic hydrocarbon derivative and P204 to extract the manganese ion. The organic phase is mixed to improve the selectivity for manganese ions and to achieve the separation of manganese from nickel, cobalt, magnesium and lithium. Although the addition of P204 in this method can enhance the selectivity of manganese and improve the phase separation effect, the extraction rate of impurities such as calcium, zinc, copper, chromium and cadmium will also be enhanced, especially calcium. The quality of the obtained manganese sulfate stripping solution is extremely low and cannot be directly used for precursor synthesis.
论文“Cyanex272采取分离锰与钙镁的试验研究”，采用Cyanex272对模拟只含钙镁的硫酸锰溶液进行锰与钙镁的分离探究，在最佳条件下锰的萃取率可以达到99.42％，镁的去除率可以达到99.52％，钙的去除率可以达到99.68％，钙镁可以达到电池级硫酸锰的要求，但实验发现Cyanex272在萃锰的同时对杂质硅、铬、锌的萃取也较强，在实验条件下反萃液硫酸锰溶液中硅、铬、锌等杂质无法满足电池级硫酸锰的要求，而且Cyanex272萃取剂价格在20万元/吨左右，是P204、P507等膦酸类萃取剂价格的5-10倍，经济效益差。The paper "Experimental Study on Separation of Manganese from Calcium and Magnesium by Cyanex272" uses Cyanex272 to separate manganese from calcium and magnesium in a simulated manganese sulfate solution containing only calcium and magnesium. Under optimal conditions, the manganese extraction rate can reach 99.42%, the magnesium removal rate can reach 99.52%, and the calcium removal rate can reach 99.68%. Calcium and magnesium can meet the requirements of battery-grade manganese sulfate. However, the experiment found that Cyanex272 also has strong extraction of impurities such as silicon, chromium, and zinc while extracting manganese. Under experimental conditions, impurities such as silicon, chromium, and zinc in the stripping solution of manganese sulfate cannot meet the requirements of battery-grade manganese sulfate. In addition, the price of Cyanex272 extractant is about 200,000 yuan/ton, which is 5-10 times the price of phosphonic acid extractants such as P204 and P507, and the economic benefits are poor.
上述方案存在萃取剂分相不佳、有机损耗大，一步法得到的硫酸锰溶液中杂质含量无法满足电池级硫酸锰要求、经济效益低等问题。The above scheme has the problems of poor phase separation of the extractant, large organic loss, impurity content in the manganese sulfate solution obtained by the one-step method cannot meet the requirements of battery-grade manganese sulfate, and low economic benefits.
发明内容Summary of the invention
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.
本申请的目的在于提供一种从含钙铜铬硅的锰溶液中制备高纯硫酸锰的方法，本申请采用HBL116和二(2,4,4-三甲基戊基)次膦酸两种萃取剂协同萃取，解决了HBL116对钙铜锌萃取率高分相不佳和二(2,4,4-三甲基戊基)次膦酸成本高对硅、铬等萃取率高的问题，协同萃取后具有萃取效率高，锰与钙铜硅铬等元素分离系数大，水溶性低，有机损耗少，反萃率高，可高效短程回收，反萃后的有机相可循环利用，有机稳定，工艺流程短，生产成本低，设备投资少等 优点；实现了废水中锰的资源化，提高了锰的回收率。The purpose of the present application is to provide a method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon. The present application adopts two extractants, HBL116 and di(2,4,4-trimethylpentyl)phosphinic acid, for synergistic extraction, which solves the problems of high extraction rate of calcium, copper and zinc by HBL116 but poor phase separation and high cost of di(2,4,4-trimethylpentyl)phosphinic acid but high extraction rate of silicon, chromium and the like. After synergistic extraction, the present application has the advantages of high extraction efficiency, large separation coefficient of manganese from elements such as calcium, copper, silicon and chromium, low water solubility, low organic loss, high stripping rate, efficient short-range recovery, recyclable organic phase after stripping, organic stability, short process flow, low production cost, low equipment investment, etc. Advantages: It realizes the resource utilization of manganese in wastewater and improves the recovery rate of manganese.
具体地，本申请包括以下内容：Specifically, this application includes the following contents:
一种从含钙铜铬硅的锰溶液中制备高纯硫酸锰的方法，所述方法包括如下步骤：A method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon, the method comprising the following steps:
(1)将萃取剂二(2,4,4-三甲基戊基)次膦酸和协萃剂HBL116配制成组合萃取剂，加入稀释剂配制成萃取有机相；(1) preparing a combined extractant by mixing di(2,4,4-trimethylpentyl)phosphinic acid as an extractant and HBL116 as a co-extractant, and adding a diluent to prepare an extracted organic phase;
(2)使用步骤(1)所得的萃取有机相萃取含钙铜铬硅的锰溶液，得到负载有机相和萃余水相；(2) using the extracted organic phase obtained in step (1) to extract the manganese solution containing calcium, copper, chromium and silicon to obtain a loaded organic phase and a raffinate aqueous phase;
(3)使用反萃剂对洗涤后的负载有机相进行反萃处理，得到高纯硫酸锰溶液，实现锰与钙、铜、铬、硅、镁、钠等杂质离子的高效分离。(3) The washed loaded organic phase is stripped with a stripping agent to obtain a high-purity manganese sulfate solution, thereby achieving efficient separation of manganese from impurity ions such as calcium, copper, chromium, silicon, magnesium, and sodium.
其中，所述协萃剂HBL116购买于湖南宏邦材料科技有限公司；HBL116萃取剂在水溶液中的萃取顺序为Fe3+>Mn离子＞Ca2+＞Mg2+，性能参数如下：颜色：红棕色油状液体、比重0.94-0.97g/cm3、粘度≥24mPa·s、含量≥98％、闪点≥70℃。The synergistic extractant HBL116 was purchased from Hunan Hongbang Material Technology Co., Ltd.; the extraction order of HBL116 extractant in aqueous solution is Fe 3+ >Mn ion>Ca 2+ >Mg 2+ , and the performance parameters are as follows: color: red-brown oily liquid, specific gravity 0.94-0.97g/cm 3 , viscosity ≥24mPa·s, content ≥98%, flash point ≥70°C.
可选地，以步骤(1)所述组合萃取剂的体积为100％计，所述萃取剂二(2,4,4-三甲基戊基)次膦酸的体积占比为15％-25％；具体地，所述萃取剂二(2,4,4-三甲基戊基)次膦酸的体积占比可以为15％、16％、17％、18％、19％、20％、21％、22％、23％、24％或25％等。Optionally, based on the volume of the combined extractant in step (1) as 100%, the volume proportion of the extractant di(2,4,4-trimethylpentyl)phosphinic acid is 15%-25%; specifically, the volume proportion of the extractant di(2,4,4-trimethylpentyl)phosphinic acid can be 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24% or 25%, etc.
可选地，所述协萃剂HBL116的体积占比为5％-10％，具体可以是5％、6％、7％、8％、9％或10％等。Optionally, the volume proportion of the co-extractant HBL116 is 5%-10%, specifically 5%, 6%, 7%, 8%, 9% or 10%.
可选地，步骤(1)所述稀释剂为煤油、磺化煤油、Escaid110、庚烷、己烷、十二烷中的任意一种或至少两种的组合；Optionally, the diluent in step (1) is any one of kerosene, sulfonated kerosene, Escaid110, heptane, hexane, and dodecane, or a combination of at least two thereof;
可选地，以所述萃取有机相的体积为100％计，所述组合萃取剂的体积占比 为20％-35％，具体可以是20％、22％、24％、26％、28％、30％、32％、34％、或35％等。Optionally, based on the volume of the extracted organic phase as 100%, the volume proportion of the combined extractant is It is 20%-35%, specifically it can be 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, or 35%, etc.
可选地，所述稀释剂的体积占比为65％-80％，具体可以是65％、67％、69％、71％、73％、75％、77％、78％或80％等。Optionally, the volume proportion of the diluent is 65%-80%, specifically 65%, 67%, 69%, 71%, 73%, 75%, 77%, 78% or 80%, etc.
可选地，步骤(2)所述的萃取有机相在萃取前进行皂化处理；所述皂化处理的皂化剂为碱性溶液；所述碱性溶液为氢氧化钠、氨水、氢氧化钾、氢氧化镁等中的任意一种或至少两种的组合；Optionally, the extracted organic phase in step (2) is subjected to saponification treatment before extraction; the saponifying agent for the saponification treatment is an alkaline solution; the alkaline solution is any one of sodium hydroxide, ammonia water, potassium hydroxide, magnesium hydroxide, etc., or a combination of at least two thereof;
可选地，所述碱性溶液的浓度为5-12mol/L，具体可以是5mol/L、6mol/L、7mol/L、8mol/L、9mol/L、10mol/L、11mol/L或12mol/L等。Optionally, the concentration of the alkaline solution is 5-12 mol/L, specifically 5 mol/L, 6 mol/L, 7 mol/L, 8 mol/L, 9 mol/L, 10 mol/L, 11 mol/L or 12 mol/L, etc.
可选地，所述皂化处理的皂化度为0％-50％，具体可以是0％、5％、10％、15％、20％、25％、30％、35％、40％、45％或50％等，其中，皂化度为0％即不进行皂化处理。Optionally, the saponification degree of the saponification treatment is 0%-50%, specifically 0%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50%, etc., wherein a saponification degree of 0% means no saponification treatment is performed.
可选地，步骤(2)所述萃取操作中萃取有机相和含钙铜铬硅的锰溶液的体积比为1：(0.05-15)，具体可以是1:0.05、1:0.1、1:1.5、1:2、1:2.5、1:3、1:4、1:10或1:15等。Optionally, in the extraction operation of step (2), the volume ratio of the extracted organic phase to the manganese solution containing calcium, copper, chromium and silicon is 1:(0.05-15), specifically 1:0.05, 1:0.1, 1:1.5, 1:2, 1:2.5, 1:3, 1:4, 1:10 or 1:15, etc.
可选地，步骤(2)所述萃取为单级萃取或多级逆流萃取，优选为多级逆流萃取；Optionally, the extraction in step (2) is a single-stage extraction or a multi-stage countercurrent extraction, preferably a multi-stage countercurrent extraction;
可选地，所述多级逆流萃取级数为3-10级，具体可以是3级、4级、5级、6级、7级、8级、9级或10级等。Optionally, the multi-stage countercurrent extraction stages are 3-10, specifically 3, 4, 5, 6, 7, 8, 9 or 10 stages, etc.
可选地，步骤(2)所述萃取段水相的pH值控制在2-6，具体可以是2、3、4、5或6等。Optionally, the pH value of the aqueous phase in the extraction section of step (2) is controlled at 2-6, specifically 2, 3, 4, 5 or 6.
本申请所公开的方法中，步骤(2)所述的含钙铜铬硅的锰溶液为电池废料经浸出、除铁铝铜后经P204萃取除杂产生的反萃液，其中锰浓度为25-55g/L、 钙浓度为1.5-6g/L、镁浓度为0.5-2g/L、铜浓度为0.05-1g/L、铬浓度为0.05-1g/L、硅浓度为0.02-0.8g/L、钠浓度为2-5g/L，料液的pH为2-3.5。In the method disclosed in the present application, the manganese solution containing calcium, copper, chromium and silicon in step (2) is a stripping solution produced by leaching battery waste, removing iron, aluminum and copper, and then extracting and removing impurities with P204, wherein the manganese concentration is 25-55g/L, The calcium concentration is 1.5-6 g/L, the magnesium concentration is 0.5-2 g/L, the copper concentration is 0.05-1 g/L, the chromium concentration is 0.05-1 g/L, the silicon concentration is 0.02-0.8 g/L, the sodium concentration is 2-5 g/L, and the pH of the feed solution is 2-3.5.
可选地，步骤(3)所述反萃处理之前使用洗涤液对步骤(2)所得的负载有机相进行洗涤处理，所述洗涤液为硫酸溶液、盐酸溶液、磷酸溶液或草酸溶液中的任意一种或多种的组合；Optionally, before the stripping treatment in step (3), the loaded organic phase obtained in step (2) is washed with a washing liquid, wherein the washing liquid is any one or more of a sulfuric acid solution, a hydrochloric acid solution, a phosphoric acid solution or an oxalic acid solution;
可选地，所述洗涤液的H+浓度为0-1mol/L；具体可以是0、0.2mol/L、0.4mol/L、0.6mol/L、0.8mol/L或1mol/L等。Optionally, the H + concentration of the washing solution is 0-1 mol/L; specifically, it can be 0, 0.2 mol/L, 0.4 mol/L, 0.6 mol/L, 0.8 mol/L or 1 mol/L, etc.
可选地，所述洗涤液与所述负载有机的体积比为(0.05-0.5):1，具体可以是0.05:1、0.1:1、0.2:1、0.3:1、0.4:1或0.5:1等。Optionally, the volume ratio of the washing liquid to the loaded organic is (0.05-0.5):1, specifically 0.05:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1 or 0.5:1, etc.
可选地，所述洗涤处理为多级逆流洗涤；Optionally, the washing process is multi-stage countercurrent washing;
可选地，所述多级逆流洗涤的级数为2-8级，例如：2级、3级、4级、5级、6级、7级或8级等。Optionally, the number of stages of the multi-stage countercurrent washing is 2-8, for example: 2, 3, 4, 5, 6, 7 or 8, etc.
本申请中，所述步骤(3)中所使用洗涤液对负载有机相进行洗涤，使用反萃剂对洗涤后的有机相进行反萃得到高纯硫酸锰溶液和空白有机相，空白有机相返回皂化后重复使用。In the present application, the washing liquid used in step (3) is used to wash the loaded organic phase, and the washed organic phase is stripped using a stripping agent to obtain a high-purity manganese sulfate solution and a blank organic phase, and the blank organic phase is returned for saponification and reused.
可选地，步骤(3)所述反萃处理的反萃剂为硫酸溶液和/或盐酸溶液；Optionally, the stripping agent for the stripping treatment in step (3) is a sulfuric acid solution and/or a hydrochloric acid solution;
可选地，所述反萃剂中H+浓度为3-5mol/L，例如3mol/L、3.5mol/L、4mol/L、4.5mol/L或5mol/L。Optionally, the H + concentration in the stripping agent is 3-5 mol/L, for example, 3 mol/L, 3.5 mol/L, 4 mol/L, 4.5 mol/L or 5 mol/L.
可选地，所述反萃剂与洗涤后的负载有机相的体积比为(0.05-0.5):1，例如0.05:1、0.1:1、0.15:1、0.2:1、0.25:1、0.3:1或0.5:1等。Optionally, the volume ratio of the stripping agent to the washed loaded organic phase is (0.05-0.5):1, such as 0.05:1, 0.1:1, 0.15:1, 0.2:1, 0.25:1, 0.3:1 or 0.5:1, etc.
可选地，所述反萃处理的级数为1-6级，例如：1级、2级、3级、4级、5级或6级等。Optionally, the number of stages of the stripping treatment is 1-6, for example: 1, 2, 3, 4, 5 or 6, etc.
本申请的优选方案，包括以下步骤： The preferred solution of this application comprises the following steps:
(1)将体积占比为15％-25％的萃取剂二(2,4,4-三甲基戊基)次膦酸和体积占比为5％-10％的协萃剂HBL116配制成组合萃取剂；将稀释剂和组合萃取剂配制成萃取有机相，所述萃取有机相中组合萃取剂的体积占比为20％-35％，所述稀释剂的体积占比为65％-80％；(1) preparing a combined extractant by 15% to 25% by volume of an extractant di(2,4,4-trimethylpentyl)phosphinic acid and a co-extractant HBL116 by 5% to 10% by volume; preparing an organic phase for extraction by a diluent and the combined extractant, wherein the combined extractant by volume in the organic phase accounts for 20% to 35% and the diluent by volume accounts for 65% to 80%;
(2)使用浓度为5-12mol/L的碱性溶液对步骤(1)配制的萃取有机相进行皂化处理，得到皂化有机相；使用皂化有机相在萃取段水相的pH值为2-6的条件下萃取含钙铜铬硅锰溶液，得到负载有机相和萃余水相；(2) using an alkaline solution with a concentration of 5-12 mol/L to saponify the extracted organic phase prepared in step (1) to obtain a saponified organic phase; using the saponified organic phase to extract the calcium, copper, chromium, silicon and manganese solution under the condition that the pH value of the aqueous phase in the extraction section is 2-6 to obtain a loaded organic phase and a raffinate aqueous phase;
(3)使用H+浓度为0-1mol/L的洗涤液对步骤(2)得到的负载有机相进行2-8级洗涤处理；使用H+浓度为3-5mol/L的反萃剂对步骤(2)得到的负载有机相进行反萃处理，得到高纯硫酸锰溶液。(3) using a washing solution with an H + concentration of 0-1 mol/L to perform a 2-8 level washing treatment on the loaded organic phase obtained in step (2); using a stripping agent with an H + concentration of 3-5 mol/L to strip the loaded organic phase obtained in step (2) to obtain a high-purity manganese sulfate solution.
相对于现有技术，本申请具有以下有益效果：Compared with the prior art, this application has the following beneficial effects:
(1)本申请采用协同萃取的方法从含钙铜铬硅的锰溶液中制备高纯硫酸锰，采用的萃取剂二(2,4,4-三甲基戊基)次膦酸和协萃剂HBL116有优越的选择性，水溶性低，有机损耗小，萃取性能稳定；并且，通过本申请提供的方法可以解决HBL116对钙铜锌萃取率高、分相不佳和二(2,4,4-三甲基戊基)次膦酸成本高、对硅、铬等萃取率高的问题，协同萃取后具有萃取效率高，锰与钙铜硅铬等元素分离系数大，工艺流程短，生产成本低，设备投资少等优点；实现了废水中锰的资源化，提高了锰的回收率，具有较高的经济效益，具备工业化应用。(1) The present application adopts a synergistic extraction method to prepare high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon. The extractant di(2,4,4-trimethylpentyl)phosphinic acid and the synergist HBL116 used have excellent selectivity, low water solubility, low organic loss and stable extraction performance. In addition, the method provided in the present application can solve the problems of high extraction rate of calcium, copper and zinc by HBL116, poor phase separation, high cost of di(2,4,4-trimethylpentyl)phosphinic acid and high extraction rate of silicon, chromium and the like. After synergistic extraction, the present application has the advantages of high extraction efficiency, large separation coefficient of manganese from elements such as calcium, copper, silicon and chromium, short process flow, low production cost and low equipment investment. The present application realizes the resource utilization of manganese in wastewater, improves the recovery rate of manganese, has high economic benefits and is suitable for industrial application.
(2)本申请公开的方法得到高纯硫酸锰溶液，锰的回收率可以达到99％，硫酸锰溶液中锰＞120g/L、铜＜0.5ppm、镁＜3ppm、铬＜2ppm、硅＜8ppm、钙＜2ppm、钠＜100ppm，一步法达到电池级硫酸锰的要求。(2) The method disclosed in the present application obtains a high-purity manganese sulfate solution, and the manganese recovery rate can reach 99%. In the manganese sulfate solution, manganese>120g/L, copper<0.5ppm, magnesium<3ppm, chromium<2ppm, silicon<8ppm, calcium<2ppm, and sodium<100ppm are contained, and the one-step method meets the requirements of battery-grade manganese sulfate.
在阅读并理解了附图和详细描述后，可以明白其他方面。 Other aspects will be apparent upon reading and understanding the drawings and detailed description.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
本申请的上述或附加的方面和优点从结合下面附图对实施例的描述中将变得明显和容易理解，其中，图1是根据本申请一个实施例从含钙铜铬硅的锰溶液中制备高纯硫酸锰的方法的流程图。The above or additional aspects and advantages of the present application will become apparent and easily understood from the description of the embodiments in conjunction with the following drawings, wherein FIG1 is a flow chart of a method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon according to an embodiment of the present application.
具体实施方式Detailed ways
为了对本申请进行深入的理解，下面结合实例和附图对本申请优选实验方案进行描述，以进一步的说明本申请的特点和优点，任何不偏离本申请主旨的变化或者改变能够为本领域的技术人员理解，本申请的保护范围由所属权利要求范围确定。In order to have a deeper understanding of the present application, the preferred experimental scheme of the present application is described below in combination with examples and drawings to further illustrate the characteristics and advantages of the present application. Any changes or modifications that do not deviate from the main purpose of the present application can be understood by technicians in this field. The scope of protection of the present application is determined by the scope of the claims.
实施例1Example 1
本实施例提供了一种从含钙铜铬硅的锰溶液中制备高纯硫酸锰的方法，包括如下步骤：This embodiment provides a method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon, comprising the following steps:
(1)分别将萃取剂双(2,4,4-三甲基戊基)膦酸和协萃剂HBL116按照体积比20％:5％的比例配制成组合萃取剂；(1) preparing a combined extractant by mixing an extractant bis(2,4,4-trimethylpentyl)phosphonic acid and a co-extractant HBL116 in a volume ratio of 20%:5% respectively;
(2)将组合萃取剂与稀释剂Escaid110配制成组合萃取剂浓度(体积浓度)为25％的萃取有机相；(2) preparing a combined extractant and a diluent Escaid 110 to prepare an organic phase with a combined extractant concentration (volume concentration) of 25%;
(3)使用浓度为10mol/L的氢氧化钠对萃取有机相进行皂化，皂化度为40％；(3) saponifying the extracted organic phase using sodium hydroxide at a concentration of 10 mol/L, with a saponification degree of 40%;
(4)料液pH值为2.7，含钙铜铬硅的锰溶液与皂化有机相的体积比为1:4，进行6级逆流萃取，静置5min后分相将上层有机相和下层水相分出，得到负载有机相；(4) The pH value of the feed solution is 2.7, the volume ratio of the manganese solution containing calcium, copper, chromium and silicon to the saponified organic phase is 1:4, and 6-stage countercurrent extraction is performed. After standing for 5 minutes, the upper organic phase and the lower aqueous phase are separated to obtain a loaded organic phase;
(5)采用0.5mol/L的稀盐酸按照洗涤液与负载有机相体积比为1:10的条件下进行4级逆流洗涤，得到洗后有机相；使用2.5mol/L的硫酸按照硫酸与洗 后有机相体积比1:16的条件下进行4级逆流反萃，得到高纯硫酸锰溶液和空白有机。(5) Using 0.5 mol/L dilute hydrochloric acid at a volume ratio of 1:10 for washing liquid to loaded organic phase, four-stage countercurrent washing was performed to obtain a washed organic phase; using 2.5 mol/L sulfuric acid at a volume ratio of 1:10 for washing liquid to loaded organic phase, Then, four-stage countercurrent stripping was carried out under the condition of organic phase volume ratio of 1:16 to obtain high-purity manganese sulfate solution and blank organic phase.
检测料液、反萃液的数据如表1所示。The data of the test solution and stripping solution are shown in Table 1.
实施例2Example 2
本实施例提供了一种从含钙铜铬硅的锰溶液中制备高纯硫酸锰的方法，包括如下步骤：This embodiment provides a method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon, comprising the following steps:
(1)分别将萃取剂双(2,4,4-三甲基戊基)膦酸和协萃剂HBL116按照体积比20％:5％的比例配制成组合萃取剂；(1) preparing a combined extractant by mixing an extractant bis(2,4,4-trimethylpentyl)phosphonic acid and a co-extractant HBL116 in a volume ratio of 20%:5% respectively;
(2)将组合萃取剂与稀释剂Escaid110配制成组合萃取剂浓度(体积浓度)为25％的萃取有机相；(2) preparing a combined extractant and a diluent Escaid 110 to prepare an organic phase with a combined extractant concentration (volume concentration) of 25%;
(3)使用浓度为10mol/L的氢氧化钠对萃取有机相进行皂化，皂化度为50％；(3) saponifying the extracted organic phase using sodium hydroxide at a concentration of 10 mol/L, with a saponification degree of 50%;
(4)料液pH值为3.0，含钙铜铬硅的锰溶液与皂化有机相的体积比为1:4，进行6级逆流萃取，静置5min后分相将上层有机相和下层水相分出，得到负载有机相；(4) The pH value of the feed solution is 3.0, the volume ratio of the manganese solution containing calcium, copper, chromium and silicon to the saponified organic phase is 1:4, and 6-stage countercurrent extraction is performed. After standing for 5 minutes, the upper organic phase and the lower aqueous phase are separated to obtain a loaded organic phase;
(5)采用0.5mol/L的稀盐酸按照洗涤液与负载有机相体积比为1:10的条件下进行4级逆流洗涤，得到洗后有机相；使用2.5mol/L的硫酸按照硫酸与洗后有机相体积比1:16的条件下进行4级逆流反萃，得到高纯硫酸锰溶液和空白有机。(5) using 0.5 mol/L dilute hydrochloric acid at a volume ratio of 1:10 between the washing liquid and the loaded organic phase to perform four-stage countercurrent washing to obtain a washed organic phase; using 2.5 mol/L sulfuric acid at a volume ratio of 1:16 between the sulfuric acid and the washed organic phase to perform four-stage countercurrent stripping to obtain a high-purity manganese sulfate solution and a blank organic phase.
检测料液、反萃液的数据如表1所示。The data of the test solution and stripping solution are shown in Table 1.
实施例3Example 3
本实施例提供了一种从含钙铜铬硅的锰溶液中制备高纯硫酸锰的方法，包括如下步骤：This embodiment provides a method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon, comprising the following steps:
(1)分别将萃取剂双(2,4,4-三甲基戊基)膦酸和协萃剂HBL116按照体 积比25％：5％的比例配制成组合萃取剂；(1) The extractant bis(2,4,4-trimethylpentyl)phosphonic acid and the synergist HBL116 were respectively mixed according to the volume The combined extractant is prepared in a ratio of 25%:5%;
(2)将组合萃取剂与稀释剂Escaid110配制成组合萃取剂浓度为30％的萃取有机相；(2) preparing a combined extractant and a diluent Escaid 110 to prepare an extracted organic phase with a combined extractant concentration of 30%;
(3)使用浓度为10mol/L的氢氧化钠对萃取有机相进行皂化，皂化度为40％；(3) saponifying the extracted organic phase using sodium hydroxide at a concentration of 10 mol/L, with a saponification degree of 40%;
(4)料液pH值为3.0，含钙铜铬硅的锰溶液与皂化有机相的体积比为1:4，进行6级逆流萃取，静置5min后分相将上层有机相和下层水相分出，得到负载有机相；(4) The pH value of the feed solution is 3.0, the volume ratio of the manganese solution containing calcium, copper, chromium and silicon to the saponified organic phase is 1:4, and 6-stage countercurrent extraction is performed. After standing for 5 minutes, the upper organic phase and the lower aqueous phase are separated to obtain a loaded organic phase;
(5)采用0.5mol/L的稀盐酸按照洗涤液与负载有机相体积比为1:10的条件下进行4级逆流洗涤，得到洗后有机相；使用2.5mol/L的硫酸按照硫酸与洗后有机相体积比1:16的条件下进行4级逆流反萃，得到高纯硫酸锰溶液和空白有机。(5) using 0.5 mol/L dilute hydrochloric acid at a volume ratio of 1:10 between the washing liquid and the loaded organic phase to perform four-stage countercurrent washing to obtain a washed organic phase; using 2.5 mol/L sulfuric acid at a volume ratio of 1:16 between the sulfuric acid and the washed organic phase to perform four-stage countercurrent stripping to obtain a high-purity manganese sulfate solution and a blank organic phase.
检测料液、反萃液的数据如表1所示。The data of the test solution and stripping solution are shown in Table 1.
表1.皂化率对元素萃取的影响
Table 1. Effect of saponification rate on element extraction
实施例2与实施例1区别在于料液pH稍高且皂化率高，数据表明提高皂化率有机和水相分相速度变慢，锰的负载有所提升，但钙铬硅的萃取率也有所 增加，增加洗涤成本和反萃液硫酸锰溶液不达标风险，因此，皂化率控制在40％左右为宜。The difference between Example 2 and Example 1 is that the pH of the liquid is slightly higher and the saponification rate is higher. The data show that the separation rate of the organic and aqueous phases slows down with the increase of the saponification rate, and the manganese load is increased, but the extraction rate of calcium chromium silicon is also increased. The increase will increase the washing cost and the risk of the stripping solution manganese sulfate solution not meeting the standard. Therefore, it is advisable to control the saponification rate at about 40%.
实施例3与实施例1区别在于增加了萃取剂双(2,4,4-三甲基戊基)膦酸的比例，数据表明提高萃取剂的比例，锰的负载有所提升，由于双(2,4,4-三甲基戊基)膦酸皂化后的钠盐增多，有机相浑浊度增加，在洗涤条件不变的情况下，反萃液硫酸锰溶液中铬和硅含量升高，产品质量存在风险。The difference between Example 3 and Example 1 is that the proportion of the extractant bis(2,4,4-trimethylpentyl)phosphonic acid is increased. The data show that the manganese load is improved by increasing the proportion of the extractant. Due to the increase in the sodium salt of bis(2,4,4-trimethylpentyl)phosphonic acid after saponification, the turbidity of the organic phase increases. Under the condition of unchanged washing conditions, the chromium and silicon contents in the stripping liquid manganese sulfate solution increase, and the product quality is at risk.
上述实施例中萃余液中锰含量均小于150mg/L，锰的回收率达到99％，反萃液硫酸锰溶液中锰＞120g/L、铜＜0.5ppm、镁＜3ppm、铬＜2ppm、硅＜8ppm、钙＜2ppm、钠＜100ppm，一步法达到电池级硫酸锰的要求。In the above embodiments, the manganese content in the raffinate is less than 150 mg/L, the manganese recovery rate reaches 99%, the manganese in the stripping solution manganese sulfate solution is greater than 120 g/L, copper is less than 0.5 ppm, magnesium is less than 3 ppm, chromium is less than 2 ppm, silicon is less than 8 ppm, calcium is less than 2 ppm, and sodium is less than 100 ppm, and the one-step method meets the requirements of battery-grade manganese sulfate.
对比例1Comparative Example 1
本对比例与实施例1区别仅把协萃剂HBL116换为等量的Escaid110，即不加协萃剂，锰与硅铬无法有效分离；The difference between this comparative example and Example 1 is that the synergist HBL116 is replaced with an equal amount of Escaid110, that is, without adding a synergist, manganese and silicon chromium cannot be effectively separated;
对比例2Comparative Example 2
本对比例与实施例1区别仅把萃取剂双(2,4,4-三甲基戊基)膦酸换为等量的Escaid110，即不加萃取剂，锰与钙铜锌无法有效分离；The difference between this comparative example and Example 1 is that the extractant bis(2,4,4-trimethylpentyl)phosphonic acid is replaced with an equal amount of Escaid110, that is, without adding an extractant, manganese and calcium, copper and zinc cannot be effectively separated;
检测料液、反萃液的数据如表2所示。The data of the test solution and stripping solution are shown in Table 2.
表2.萃取剂和协萃剂对元素萃取的影响

Table 2. Effects of extractants and synergists on element extraction

通过上述实施例和对比例的结果可知，本申请提供的方法，通过萃取剂双(2,4,4-三甲基戊基)膦酸与协萃剂HBL116的协同萃取作用，可实现从含钙铜铬硅的锰溶液中一步法制备高纯硫酸锰溶液，反萃液硫酸锰溶液中锰＞120g/L、铜＜0.5ppm、镁＜3ppm、铬＜2ppm、硅＜8ppm、钙＜2ppm、钠＜100ppm，锰的回收率达到99％。It can be seen from the results of the above embodiments and comparative examples that the method provided by the present application can realize the one-step preparation of a high-purity manganese sulfate solution from a manganese solution containing calcium, copper, chromium and silicon through the synergistic extraction effect of the extractant di(2,4,4-trimethylpentyl)phosphonic acid and the synergistic extraction agent HBL116. The manganese sulfate solution in the stripping liquid contains manganese>120 g/L, copper<0.5 ppm, magnesium<3 ppm, chromium<2 ppm, silicon<8 ppm, calcium<2 ppm, and sodium<100 ppm, and the recovery rate of manganese reaches 99%.
以上对本申请提供的一种从含钙铜铬硅的锰溶液中制备高纯硫酸锰的方法进行了详细的介绍，本文中应用了具体实施例对本申请的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本申请的方法及其核心思想，包括最佳方式，并且也使得本领域的任何技术人员都能够实践本申请，包括制造和使用任何装置或系统，和实施任何结合的方法。应当指出，对于本技术领域的普通技术人员来说，在不脱离本申请原理的前提下，还可以对本申请进行若干改进和修饰，这些改进和修饰也落入本申请权利要求的保护范围内。本申请专利保护的范围通过权利要求来限定，并可包括本领域技术人员能够想到的其他实施例。如果这些其他实施例具有不是不同于权利要求文字表述的结构要素，或者如果它们包括与权利要求的文字表述无实质差异的等同结构要素，那么这些其他实施例也应包含在权利要求的范围内。 The above is a detailed introduction to a method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon provided by the present application. Specific examples are used herein to illustrate the principles and implementation methods of the present application. The description of the above examples is only used to help understand the method and its core ideas of the present application, including the best mode, and also enables any technician in the field to practice the present application, including the manufacture and use of any device or system, and the implementation of any combined method. It should be pointed out that for ordinary technicians in this technical field, without departing from the principles of the present application, several improvements and modifications can be made to the present application, and these improvements and modifications also fall within the scope of protection of the claims of the present application. The scope of patent protection of the present application is defined by the claims and may include other embodiments that can be thought of by those skilled in the art. If these other embodiments have structural elements that are not different from the literal expression of the claims, or if they include equivalent structural elements that are not substantially different from the literal expression of the claims, then these other embodiments should also be included in the scope of the claims.

Claims (12)

  1. 一种从含钙铜铬硅的锰溶液中制备高纯硫酸锰的方法，其中，所述方法包括如下步骤：A method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon, wherein the method comprises the following steps:
    (1)将萃取剂二(2,4,4-三甲基戊基)次膦酸和协萃剂HBL116配制成组合萃取剂，加入稀释剂配制成萃取有机相；(1) preparing a combined extractant by mixing di(2,4,4-trimethylpentyl)phosphinic acid as an extractant and HBL116 as a co-extractant, and adding a diluent to prepare an extracted organic phase;
    (2)使用步骤(1)所得的萃取有机相萃取含钙铜铬硅的锰溶液，得到负载有机相和萃余水相；(2) using the extracted organic phase obtained in step (1) to extract the manganese solution containing calcium, copper, chromium and silicon to obtain a loaded organic phase and a raffinate aqueous phase;
    (3)使用反萃剂对洗涤后的负载有机相进行反萃处理，得到高纯硫酸锰溶液。(3) using a stripping agent to strip the washed loaded organic phase to obtain a high-purity manganese sulfate solution.
  2. 根据权利要求1所述的一种从含钙铜铬硅的锰溶液中制备高纯硫酸锰的方法，其中，以步骤(1)所述组合萃取剂的体积为100％计，所述萃取剂二(2,4,4-三甲基戊基)次膦酸的体积占比为15％-25％。A method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon according to claim 1, wherein, based on the volume of the combined extractant in step (1) being 100%, the volume proportion of the extractant di(2,4,4-trimethylpentyl)phosphinic acid is 15%-25%.
  3. 根据权利要求2所述的一种从含钙铜铬硅的锰溶液中制备高纯硫酸锰的方法，其中，所述协萃剂HBL116的体积占比为5％-10％。A method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon according to claim 2, wherein the volume proportion of the synergist HBL116 is 5%-10%.
  4. 根据权利要求1-3任一项所述的从含钙铜铬硅的锰溶液中制备高纯硫酸锰的方法，其中，步骤(1)所述稀释剂为煤油、磺化煤油、Escaid110、庚烷、己烷、十二烷中的任意一种或至少两种的组合；所述稀释剂的体积占比为65％-80％。The method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon according to any one of claims 1 to 3, wherein the diluent in step (1) is any one of kerosene, sulfonated kerosene, Escaid 110, heptane, hexane and dodecane, or a combination of at least two thereof; the volume proportion of the diluent is 65%-80%.
  5. 根据权利要求1-3任一项所述的从含钙铜铬硅的锰溶液中制备高纯硫酸锰的方法，其中，步骤(2)所述的萃取有机相在萃取前进行皂化处理，所述皂化处理的皂化剂为碱性溶液，所述碱性溶液为氢氧化钠、氨水、氢氧化钾、氢氧化镁等中的任意一种或至少两种的组合。The method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon according to any one of claims 1 to 3, wherein the extracted organic phase in step (2) is subjected to saponification treatment before extraction, and the saponifying agent for the saponification treatment is an alkaline solution, and the alkaline solution is any one of sodium hydroxide, ammonia water, potassium hydroxide, magnesium hydroxide, etc., or a combination of at least two thereof.
  6. 根据权利要求5所述的一种从含钙铜铬硅的锰溶液中制备高纯硫酸锰的方法，其中，所述碱性溶液的浓度为5-12mol/L；所述皂化处理的皂化度为0％-50％。 A method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon according to claim 5, wherein the concentration of the alkaline solution is 5-12 mol/L; and the saponification degree of the saponification treatment is 0%-50%.
  7. 根据权利要求1-3任一项所述的从含钙铜铬硅的锰溶液中制备高纯硫酸锰的方法，其中，步骤(2)所述萃取操作中萃取有机相和含钙铜铬硅的锰溶液的体积比为1：(0.05-15)。The method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon according to any one of claims 1 to 3, wherein the volume ratio of the extracted organic phase to the manganese solution containing calcium, copper, chromium and silicon in the extraction operation of step (2) is 1: (0.05-15).
  8. 根据权利要求1-3任一项所述的从含钙铜铬硅的锰溶液中制备高纯硫酸锰的方法，其中，步骤(2)所述萃取为单级萃取或多级逆流萃取。The method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon according to any one of claims 1 to 3, wherein the extraction in step (2) is a single-stage extraction or a multi-stage countercurrent extraction.
  9. 根据权利要求1-3任一项所述的从含钙铜铬硅的锰溶液中制备高纯硫酸锰的方法，其中，步骤(2)所述萃取段水相的pH值控制在2-6。The method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon according to any one of claims 1 to 3, wherein the pH value of the aqueous phase in the extraction section in step (2) is controlled at 2-6.
  10. 根据权利要求1-3任一项所述的从含钙铜铬硅的锰溶液中制备高纯硫酸锰的方法，其中，步骤(3)所述反萃处理之前使用洗涤液对步骤(2)所得的负载有机相进行洗涤处理；所述洗涤处理所用的洗涤液为硫酸溶液、盐酸溶液、磷酸溶液或草酸溶液中的任意一种或多种的组合；所述洗涤液的H+浓度为0-1mol/L；所述洗涤液与所述负载有机的体积比为(0.05-0.5):1；所述洗涤处理为多级逆流洗涤。The method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon according to any one of claims 1 to 3, wherein, before the stripping treatment in step (3), the loaded organic phase obtained in step (2) is washed with a washing liquid; the washing liquid used for the washing treatment is any one or more of a sulfuric acid solution, a hydrochloric acid solution, a phosphoric acid solution or an oxalic acid solution; the H + concentration of the washing liquid is 0-1 mol/L; the volume ratio of the washing liquid to the loaded organic phase is (0.05-0.5):1; and the washing treatment is a multi-stage countercurrent washing.
  11. 根据权利要求1-3任一项所述的从含钙铜铬硅的锰溶液中制备高纯硫酸锰的方法，其中，步骤(3)所述反萃处理的反萃剂为硫酸溶液和/或盐酸溶液；所述反萃剂中H+浓度为3-5mol/L；所述反萃剂与洗涤后的负载有机相的体积比为(0.05-0.5):1；所述反萃处理的级数为1-6级。The method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon according to any one of claims 1 to 3, wherein the stripping agent for the stripping treatment in step (3) is a sulfuric acid solution and/or a hydrochloric acid solution; the H + concentration in the stripping agent is 3-5 mol/L; the volume ratio of the stripping agent to the washed loaded organic phase is (0.05-0.5):1; and the number of stages of the stripping treatment is 1-6.
  12. 根据权利要求1-3任一项所述的从含钙铜铬硅的锰溶液中制备高纯硫酸锰的方法，其中，所述方法包括以下步骤：The method for preparing high-purity manganese sulfate from a manganese solution containing calcium, copper, chromium and silicon according to any one of claims 1 to 3, wherein the method comprises the following steps:
    (1)将体积占比为15％-25％的萃取剂二(2,4,4-三甲基戊基)次膦酸和体积占比为5％-10％的协萃剂HBL116配制成组合萃取剂；将稀释剂和组合萃取剂配制成萃取有机相，所述萃取有机相中组合萃取剂的体积占比为20％-35％，所述稀释剂的体积占比为65％-80％； (1) preparing a combined extractant by 15% to 25% by volume of an extractant di(2,4,4-trimethylpentyl)phosphinic acid and a co-extractant HBL116 by 5% to 10% by volume; preparing an organic phase for extraction by a diluent and the combined extractant, wherein the combined extractant by volume in the organic phase accounts for 20% to 35% and the diluent by volume accounts for 65% to 80%;
    (2)使用浓度为5-12mol/L的碱性溶液对步骤(1)配制的萃取有机相进行皂化处理，得到皂化有机相；使用皂化有机相在萃取段水相的pH值为2-6的条件下下萃取含钙铜铬硅锰溶液，得到负载有机相和萃余水相；(2) using an alkaline solution with a concentration of 5-12 mol/L to saponify the extracted organic phase prepared in step (1) to obtain a saponified organic phase; using the saponified organic phase to extract the calcium, copper, chromium, silicon and manganese solution under the condition that the pH value of the aqueous phase in the extraction section is 2-6 to obtain a loaded organic phase and a raffinate aqueous phase;
    (3)使用H+浓度为0-1mol/L的洗涤液对步骤(2)得到的负载有机相进行2-8级洗涤处理；使用H+浓度为3-5mol/L的反萃剂对步骤(2)得到的负载有机相进行反萃处理，得到高纯硫酸锰溶液。 (3) using a washing solution having an H + concentration of 0-1 mol/L to perform a 2-8 level washing treatment on the loaded organic phase obtained in step (2); using a stripping agent having an H + concentration of 3-5 mol/L to strip the loaded organic phase obtained in step (2) to obtain a high-purity manganese sulfate solution.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103122409A (en) * 2012-10-26 2013-05-29 中南大学 Extraction agent capable of effectively improving manganese extraction effect and extraction method
KR20150094412A (en) * 2014-02-11 2015-08-19 타운마이닝캄파니(주) Method for recovering valuable metals from cathodic active material of used lithium battery
CN109097599A (en) * 2018-09-27 2018-12-28 中南大学 A kind of method of synergic solvent extraction separation manganese and calcium, magnesium
CN109797294A (en) * 2019-02-02 2019-05-24 广东芳源环保股份有限公司 The method of nickel, cobalt is recycled in a kind of magnesium water
CN112281001A (en) * 2020-10-22 2021-01-29 北京博萃循环科技有限公司 Method for preparing manganese salt by using manganese-containing waste liquid
CN113072487A (en) * 2021-03-26 2021-07-06 中南大学 Pyridyl-containing calix [4] arene derivative, preparation method thereof and application of derivative as manganese ion extracting agent
CN113881846A (en) * 2021-10-12 2022-01-04 昆明理工大学 Method for improving rare earth element separation performance of extractant
CN115159578A (en) * 2022-06-16 2022-10-11 荆门市格林美新材料有限公司 Method for producing battery-grade manganese sulfate by recycling manganese through ternary synergistic extraction system

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040050212A1 (en) * 2000-09-15 2004-03-18 Cheng Chu Yong Solvent extraction process for recovering nickel and cobalt from each solutions
JP5541336B2 (en) * 2011-10-24 2014-07-09 住友金属鉱山株式会社 Method for producing high purity cobalt sulfate aqueous solution
CN109868373A (en) * 2019-02-02 2019-06-11 广东芳源环保股份有限公司 A method of substep leaching nickel, cobalt from nickel, cobalt, manganese mixture
CN110066925A (en) * 2019-04-28 2019-07-30 浙江天能新材料有限公司 The recovery method of valuable metal in a kind of waste and old nickel-cobalt-manganese ternary lithium battery
CA3141478A1 (en) * 2019-05-22 2020-11-26 Nemaska Lithium Inc. Processes for preparing hydroxides and oxides of various metals and derivatives thereof
CN110372038A (en) * 2019-08-15 2019-10-25 衢州华友资源再生科技有限公司 A kind of method of raw material containing manganese preparation LITHIUM BATTERY manganese sulfate and its LITHIUM BATTERY manganese sulfate of preparation
CN114134322B (en) * 2020-09-04 2023-03-14 苏州博萃循环科技有限公司 Method for separating copper and manganese from copper-manganese-calcium-zinc-containing mixed solution
CN114561541A (en) * 2020-11-27 2022-05-31 北京博萃循环科技有限公司 Method for synchronously recycling nickel, cobalt and manganese from battery positive plate leachate

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103122409A (en) * 2012-10-26 2013-05-29 中南大学 Extraction agent capable of effectively improving manganese extraction effect and extraction method
KR20150094412A (en) * 2014-02-11 2015-08-19 타운마이닝캄파니(주) Method for recovering valuable metals from cathodic active material of used lithium battery
CN109097599A (en) * 2018-09-27 2018-12-28 中南大学 A kind of method of synergic solvent extraction separation manganese and calcium, magnesium
CN109797294A (en) * 2019-02-02 2019-05-24 广东芳源环保股份有限公司 The method of nickel, cobalt is recycled in a kind of magnesium water
CN112281001A (en) * 2020-10-22 2021-01-29 北京博萃循环科技有限公司 Method for preparing manganese salt by using manganese-containing waste liquid
CN113072487A (en) * 2021-03-26 2021-07-06 中南大学 Pyridyl-containing calix [4] arene derivative, preparation method thereof and application of derivative as manganese ion extracting agent
CN113881846A (en) * 2021-10-12 2022-01-04 昆明理工大学 Method for improving rare earth element separation performance of extractant
CN115159578A (en) * 2022-06-16 2022-10-11 荆门市格林美新材料有限公司 Method for producing battery-grade manganese sulfate by recycling manganese through ternary synergistic extraction system

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