CN114686702A - One-pot method for purifying magnesium from serpentine atmospheric sulfuric acid leaching solution - Google Patents

One-pot method for purifying magnesium from serpentine atmospheric sulfuric acid leaching solution Download PDF

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CN114686702A
CN114686702A CN202210356080.9A CN202210356080A CN114686702A CN 114686702 A CN114686702 A CN 114686702A CN 202210356080 A CN202210356080 A CN 202210356080A CN 114686702 A CN114686702 A CN 114686702A
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杨喜云
张宗
陈莹丽
高凌宇
吴玉楼
童丽嵘
苑占永
杨伟光
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Beijing Huaxia Jianlong Mining Science & Technology Co ltd
Central South University
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    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22B26/00Obtaining alkali, alkaline earth metals or magnesium
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    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
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    • C22B34/00Obtaining refractory metals
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    • C22B47/00Obtaining manganese

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Abstract

The invention belongs to the field of mineral resource utilization, and particularly discloses a method for purifying magnesium from a serpentine normal-pressure sulfuric acid leaching solution in one pot, which comprises the steps of carrying out one-pot three-section reaction treatment on the leaching solution obtained by the serpentine normal-pressure sulfuric acid leaching, and then carrying out solid-liquid separation to obtain a purified magnesium solution; the one-pot three-section reaction process comprises the following steps: regulating pH of the leachateA2.0-3.0, adding an oxidant to carry out first-stage oxidation treatment; subsequent control of the pH of the SystemBAdding an oxidant to 4.5-6, and performing second-stage oxidation treatment; readjusting the pH of the SystemCCarrying out a third stage of reaction after the reaction reaches 7-8 ℃; one-pot three-sectionIn the reaction process, the temperature of the first stage oxidation reaction and the second stage oxidation reaction is 60-80 ℃, and the temperature of the third stage oxidation reaction is 80-90 ℃. Under the one-pot three-section treatment process, the invention is matched with the joint control of the reaction type, the pH value and the temperature of each section, can realize the cooperation, can effectively separate magnesium and each ion with high selectivity in one pot, and is beneficial to obtaining high-purity magnesium solution.

Description

蛇纹石常压硫酸浸出液一锅提纯镁的方法One-pot method for purifying magnesium from serpentine atmospheric sulfuric acid leaching solution

技术领域technical field

本发明涉及资源综合利用领域,具体涉及蛇纹石湿法纯镁方法。The invention relates to the field of comprehensive utilization of resources, in particular to a serpentine wet method for pure magnesium.

背景技术Background technique

蛇纹石是含水富镁硅酸盐矿物的总称,其化学组成为3MgO·2SiO2·2H2O,呈暗墨绿色、棕色或黄色,大都有斑点,因磨光面像蛇纹而得名,硬度2~3.5,密度2.2~3.69/cm3。其晶体结构,由一层硅氧四面体与一层氢氧镁石八面体以1:1结合形成双层结构。按矿物结构蛇纹石一般可分为三类:(1)具有圆柱结构的纤蛇纹石(Chrysotile);(2)具有平整结构的利蛇纹石(Lizardite);(3)具有一个交替波状结构的叶蛇纹石(Antigorite)。所有蛇纹石矿物,无论是否具有纤维状特征,都属层状结构,与高岭石类似。矿石中六次配位的Mg2+可以被A13+、Ni2+、Fe2+、Fe3+、Mn2+等所置换,尤其在铝蛇纹石(zoblitzite)、镍蛇纹石(gamierite)和铁蛇纹石(greenallte)等中被置换。通常蛇纹石含有少量的铁、铝、铬、镍、钴、锰等金属。因此,蛇纹石是一种重要的镍、钴潜在资源。Serpentine is a general term for hydrous magnesium-rich silicate minerals. Its chemical composition is 3MgO 2SiO 2 2H 2 O. It is dark green, brown or yellow, and most of them have spots. It is named after the polished surface resembles a snake pattern. , hardness 2~3.5, density 2.2~3.69/cm 3 . Its crystal structure is composed of a layer of silicon-oxygen tetrahedron and a layer of magnesium hydroxide octahedron in a 1:1 combination to form a double-layer structure. Serpentine can be generally divided into three categories according to the mineral structure: (1) Chrysotile with a cylindrical structure; (2) Lizardite with a flat structure; (3) With an alternating wave shape Structure of leaf serpentine (Antigorite). All serpentine minerals, with or without fibrous features, are layered, similar to kaolinite. The Mg 2+ in the six-fold coordination in the ore can be replaced by A1 3+ , Ni 2+ , Fe 2+ , Fe 3+ , Mn 2+ , etc., especially in aluminum serpentine (zoblitzite), nickel serpentine ( gamierite) and iron serpentine (greenallte), etc. are replaced. Usually serpentine contains a small amount of iron, aluminum, chromium, nickel, cobalt, manganese and other metals. Therefore, serpentine is an important potential resource of nickel and cobalt.

蛇纹石的湿法冶炼是资源利用的主要手段,目前行业内涉及的湿法冶炼工艺主要为盐酸酸浸工艺、高压硫酸酸浸工艺,常压硫酸酸浸工艺。盐酸酸浸工艺浸出条件温和、设备投资小、所述的Cl-能有效破坏胶体稳定性,降低溶液粘度,利于操作和分离,但是由于盐酸易挥发、成本高,因此对盐酸的回收有更高的要求,不利于工业的大规模应用。高压硫酸酸浸工艺常应用于镍品位高的蛇纹石矿的冶炼处理,其能够有效控制铁的浸出,常用来提取蛇纹石中的镍;然而,高温浸出工艺能耗高,成本大,对矿石品位要求高。与高压硫酸浸出工艺相比,常压硫酸酸浸工艺常用于低品位蛇纹石的冶炼,其浸出选择性不理想,浸出液金属离子种类多,并呈现高铁、高镁、低镍等特点,该工艺获得的浸出液的元素分离难度大,加上SO4 2-难于破坏胶体结构,在浸出和净化除杂阶段容易成胶,难于操作,且除杂时产生的渣量大、浸出液含SO4 2-多,镍、镁等有价元素的提纯难度大。The hydrometallurgical smelting of serpentine is the main means of resource utilization. At present, the hydrochloric acid leaching process involved in the industry is mainly hydrochloric acid pickling process, high-pressure sulfuric acid pickling process, and atmospheric sulfuric acid pickling process. The hydrochloric acid acid leaching process has mild leaching conditions, small equipment investment, and the Cl- can effectively destroy colloidal stability, reduce solution viscosity, and facilitate operation and separation. requirements, which is not conducive to large-scale industrial applications. High-pressure sulfuric acid leaching process is often used in the smelting treatment of serpentine ore with high nickel grade, which can effectively control the leaching of iron, and is often used to extract nickel in serpentine; however, the high-temperature leaching process has high energy consumption and high cost. High requirements for ore grade. Compared with the high-pressure sulfuric acid leaching process, the atmospheric-pressure sulfuric acid leaching process is often used in the smelting of low-grade serpentine. It is difficult to separate the elements of the leachate obtained by the process, and SO 4 2- is difficult to destroy the colloidal structure. It is easy to form gel during the leaching and purification and removal of impurities, which is difficult to operate, and the amount of slag produced during the removal of impurities is large, and the leachate contains SO 4 2 -Many , the purification of valuable elements such as nickel and magnesium is difficult.

针对低品位硫酸常压浸出液的元素回收,行业内的主要手段在于分步分类回收,例如,公开号为CN103395796A公开了一种蛇纹石的综合利用方法,步骤为:蛇纹石经硫酸浸出后,过滤得第一滤液;向第一滤液中加入氧化剂;再加入pH值调节剂发生沉淀反应,再过滤得铁铝混合物和第二滤液;向铁铝混合物中加入水和氢氧化钠,后过滤得铁沉淀物和偏铝酸钠溶液;向第二滤液中加入硫化物反应,再过滤得镍钴混合物和第三滤液;向第三滤液中加入氧化剂反应;后加入碱性吸附剂,再过滤得硫酸镁溶液,加氨水制备出氢氧化镁。For the element recovery of low-grade sulfuric acid atmospheric leaching solution, the main method in the industry is to classify and recover in steps. For example, publication number CN103395796A discloses a comprehensive utilization method of serpentine. The steps are: after the serpentine is leached with sulfuric acid , filter to obtain the first filtrate; add an oxidant to the first filtrate; add a pH adjuster to produce a precipitation reaction, and then filter to obtain the iron-aluminum mixture and the second filtrate; add water and sodium hydroxide to the iron-aluminum mixture, and filter Obtain iron precipitate and sodium metaaluminate solution; add sulfide to the second filtrate for reaction, then filter to obtain nickel-cobalt mixture and the third filtrate; add oxidant to the third filtrate for reaction; add alkaline adsorbent, then filter Get magnesium sulfate solution, add ammonia water to prepare magnesium hydroxide.

对于低品位蛇纹石硫酸常压浸出液的冶炼而言,行业内大多都是经过多步分离的工艺分类冶炼,该工艺处理效率低、工艺操作性不强,且目标元素的回收率以及产物纯度有待提高。For the smelting of low-grade serpentine sulfuric acid leaching solution at atmospheric pressure, most of the industry is classified and smelted by a multi-step separation process. This process has low treatment efficiency, poor process operability, and the recovery rate of target elements and product purity. needs improvement.

发明内容SUMMARY OF THE INVENTION

针对蛇纹石常压硫酸浸出液湿法提取镁过程中容易成胶、粘性大、镁回收率和纯度不理想等问题,本发明目的在于,提供一种蛇纹石常压硫酸浸出液(本发明也简称为浸出液)一锅提纯镁的方法,旨在提供一锅体系下实现浸出液中镁离子和其他离子选择性分离,改善镁的回收率和纯度的方法。In view of the problems such as easy gel formation, high viscosity, unsatisfactory magnesium recovery rate and purity in the process of wet extraction of magnesium from serpentine atmospheric sulfuric acid leaching solution, the purpose of the present invention is to provide a serpentine atmospheric sulfuric acid leaching solution (the present invention also Referred to as leachate) one-pot method for purifying magnesium, aiming to provide a method for realizing selective separation of magnesium ions and other ions in leachate under one-pot system, and improving the recovery rate and purity of magnesium.

出于处理价值考量,低品位蛇纹石采用硫酸常压酸浸工艺进行回收,该工艺得到的浸出液为高铁、高镁、低镍、丰富的微量杂质元素的硫酸体系,该类型的浸出液难于实现镁的一锅分离回收,主要在于:(1)体系为高铁硫酸体系,溶液容易形成胶体,且硫酸根离子难于破坏胶体结构,如此将影响镁和其他成分的分离和回收,且工艺操作难度大,例如,难于过滤;(2)该体系下中,存在丰富的金属杂质成分,这些成分难于和镁实现一锅高选择性分离;(3)镁的回收率、纯度和白度不理想。针对蛇纹石硫酸常压酸浸出液难于实现一锅高选择性分离的问题,本发明提供以下改进工艺:For the consideration of processing value, the low-grade serpentine is recovered by the sulfuric acid atmospheric acid leaching process. The leaching solution obtained by this process is a sulfuric acid system with high iron, high magnesium, low nickel and rich trace impurity elements. This type of leaching solution is difficult to achieve. The one-pot separation and recovery of magnesium mainly lies in: (1) the system is a high-iron sulfuric acid system, the solution is easy to form a colloid, and the sulfate ion is difficult to destroy the colloidal structure, which will affect the separation and recovery of magnesium and other components, and the technological operation is difficult , for example, it is difficult to filter; (2) in this system, there are abundant metal impurity components, and these components are difficult to achieve one-pot high-selectivity separation with magnesium; (3) the recovery rate, purity and whiteness of magnesium are not ideal. Aiming at the problem that the serpentine sulfuric acid atmospheric acid leaching solution is difficult to realize one-pot high-selectivity separation, the present invention provides the following improved process:

一种蛇纹石常压硫酸浸出液(本发明也简称为酸浸液)一锅提纯镁的方法,将蛇纹石硫酸常压酸浸的浸出液进行一锅三段反应处理,随后固液分离,得到纯化的镁溶液;A method for purifying magnesium with a serpentine normal-pressure sulfuric acid leaching solution (also referred to as an acid leaching solution in the present invention) in one pot, the leaching solution of the serpentine sulfuric acid normal-pressure acid leaching is subjected to one-pot three-stage reaction treatment, followed by solid-liquid separation, to obtain a purified magnesium solution;

所述的浸出液中溶解有Fe、Cr、Mn和Mg;Fe, Cr, Mn and Mg are dissolved in the leaching solution;

所述的一锅三段反应过程包括:调控浸出液的pHA为2.0~3.0,加入氧化剂进行第一段氧化处理;随后调控体系的pHB至4.5~6,补加氧化剂进行第二段氧化处理;再调控体系的pHC至7~8后进行第三段反应;The one-pot three-stage reaction process includes: adjusting the pH A of the leachate to be 2.0-3.0, adding an oxidant to carry out the first-stage oxidation treatment; then adjusting the pH B of the system to 4.5-6, adding an oxidant to carry out the second-stage oxidation treatment ; Carry out the third stage reaction after adjusting the pH C of the system to 7~8 again;

一锅三段反应过程中,第一段氧化反应、第二段氧化反应的温度为60~80℃,第三段反应的温度为80℃~90℃。In the one-pot three-stage reaction process, the temperature of the first-stage oxidation reaction and the second-stage oxidation reaction is 60-80°C, and the temperature of the third-stage reaction is 80°C-90°C.

针对常压硫酸酸浸液成分特点难于实现一锅提纯镁、工艺操作难度大的问题,本发明创新地提出,在所述的一锅三段处理工艺下,配合各段的反应类型、pH和温度的联合控制,能够实现协同,能够解决常压酸浸体系、高铁、高杂质元素、硫酸体系所致的杂质元素与镁难于一锅高选择性分离的问题,能够有效使镁和各离子一锅高选择性分离,利于获得高纯度的镁溶液,不仅如此,本发明方法还能够有效改善浸出液一锅处理过程中工艺性差(如过滤性差)的问题,利用工业实际放大。Aiming at the problems of difficulty in realizing one-pot purification of magnesium due to the characteristics of the components of the atmospheric sulfuric acid leaching solution and difficult process operation, the present invention innovatively proposes that under the one-pot three-stage treatment process, the reaction type, pH and The joint control of temperature can achieve synergy, and can solve the problem that the impurity elements and magnesium are difficult to be separated in one pot with high selectivity caused by the normal pressure acid leaching system, high iron, high impurity elements, and sulfuric acid system, and can effectively make magnesium and each ion one-pot. The high-selectivity separation of the pot is conducive to obtaining a high-purity magnesium solution. Not only that, the method of the present invention can also effectively improve the problem of poor processability (such as poor filterability) in the one-pot treatment process of the leachate, and can be enlarged by industrial practice.

本发明研究发现,所述的一锅体系下的第一段氧化、第二段氧化以及第三段反应的三段反应工艺以及对各段反应的pH以及温度的联合控制是协同解决常压浸出液难于一锅处理问题、改善镁提取以及提纯效果的关键。According to the research of the present invention, the three-stage reaction process of the first-stage oxidation, the second-stage oxidation and the third-stage reaction under the one-pot system, and the joint control of the pH and temperature of each stage reaction are synergistic solutions to the normal pressure leachate. Difficult to deal with the problem in one pot, improve magnesium extraction and the key to purification.

本发明中,所述的酸浸液由低品位的蛇纹石常压硫酸酸浸得到。In the present invention, the acid leaching solution is obtained by acid leaching of low-grade serpentine at atmospheric pressure with sulfuric acid.

本发明中,所述的浸出液为蛇纹石常压下的硫酸酸浸液。所述的硫酸浓度例如为2~5mol·L-1。所述的常压酸浸的温度例如为80~100℃,优选为80~95℃。In the present invention, the leaching solution is a sulfuric acid leaching solution of serpentine under normal pressure. The sulfuric acid concentration is, for example, 2-5 mol·L -1 . The temperature of the normal-pressure acid leaching is, for example, 80-100°C, preferably 80-95°C.

本发明中,所述的浸出液为高铁、低镍、高镁的硫酸体系。其浓度例如分别为:Fe的浓度为5~18g/L;Mn(II)的浓度为0.2~0.5g/L、Cr(Ⅲ)的浓度为0.10~0.40g/L、Mg的浓度为50~65g/L。进一步优选,Fe的浓度为6~12g/L;Mn(II)的浓度为0.12~0.4g/L、Cr(Ⅲ)的浓度为0.20~0.4g/L、Mg的浓度为50~65g/L。本发明技术方案,对于浸出液的一锅处理能够表现出更优的工业应用价值,但不排除本发明方法对其他浸出液的应用。In the present invention, the leaching solution is a sulfuric acid system with high iron, low nickel and high magnesium. The concentrations thereof are, for example, the concentration of Fe is 5 to 18 g/L, the concentration of Mn(II) is 0.2 to 0.5 g/L, the concentration of Cr(III) is 0.10 to 0.40 g/L, and the concentration of Mg is 50 to 50 g/L. 65g/L. More preferably, the concentration of Fe is 6-12g/L; the concentration of Mn(II) is 0.12-0.4g/L, the concentration of Cr(III) is 0.20-0.4g/L, and the concentration of Mg is 50-65g/L . The technical solution of the present invention can show better industrial application value for the one-pot treatment of the leachate, but does not exclude the application of the method of the present invention to other leachates.

本发明中,酸浸液中,还允许含有镍、钴、铝中的至少一种;其中,所述的浸出液中,Ni的浓度为0.20~0.6g/L;Co的浓度为0.01~0.04g/L;Al的浓度为0.2~2g/L;进一步优选,Ni的浓度例如为0.30~0.6g/L;Co的浓度例如为0.02~0.03g/L;Al的浓度为0.3~1.8g/L。本发明技术方案能够实现镁和铁、锰、铬、镍、铝和钴在硫酸体系下一锅高选择性分离,具有优异的炼镁效果和效率。In the present invention, the acid leaching solution is also allowed to contain at least one of nickel, cobalt and aluminum; wherein, in the leaching solution, the concentration of Ni is 0.20-0.6g/L; the concentration of Co is 0.01-0.04g /L; the concentration of Al is 0.2-2 g/L; more preferably, the concentration of Ni is, for example, 0.30-0.6 g/L; the concentration of Co is, for example, 0.02-0.03 g/L; and the concentration of Al is 0.3-1.8 g/L . The technical scheme of the invention can realize the high selective separation of magnesium and iron, manganese, chromium, nickel, aluminum and cobalt in one pot in a sulfuric acid system, and has excellent magnesium smelting effect and efficiency.

本发明中,一锅三段处理过程中,采用碱性物质调控体系的pH,所述的碱性物质例如为氧化镁、碱金属氢氧化物、氧化钙、氨水中的至少一种。所述的碱性物质可通知固体或者溶液的形式添加使用。In the present invention, in the one-pot three-stage treatment process, the pH of the system is adjusted by using an alkaline substance, such as at least one of magnesium oxide, alkali metal hydroxide, calcium oxide, and ammonia water. The alkaline substance can be added in the form of solid or solution.

本发明中,一锅三段处理过程中,氧化剂为氯酸盐、氧气或过氧化氢中的至少一种。In the present invention, in the one-pot three-stage treatment process, the oxidant is at least one of chlorate, oxygen or hydrogen peroxide.

本发明中,预先向常压浸出液中添加碱性物质,调控体系的pH至需要的pHA,并在所要求的60℃~80℃的温度下通入氧化剂,进行一锅反应中的第一段氧化处理。本发明研究发现,在所述的温度、pH下,如此,能够意外地调控铁的成核行为和形貌,如此能够意外地进一步协同改善一锅体系下的镁和铁以及其他元素的分离选择性,改善一锅处理的加工性能。In the present invention, an alkaline substance is added to the normal pressure leaching solution in advance, the pH of the system is adjusted to the required pH A , and an oxidant is introduced at the required temperature of 60°C to 80°C to carry out the first step in the one-pot reaction. Segment oxidation treatment. The research of the present invention finds that under the described temperature and pH, the nucleation behavior and morphology of iron can be regulated unexpectedly, and the separation and selection of magnesium, iron and other elements in one-pot system can be further improved unexpectedly. improved processing performance in one-pot treatments.

本发明中,第一段氧化反应阶段,氧化剂的用量为将体系中的Fe氧化的理论摩尔量的1.2~1.5倍。作为优选,pHA为2.0~3.0。第一段氧化处理的温度优选为60~70℃,进一步优选为60~65℃。In the present invention, in the first stage of oxidation reaction, the amount of oxidant used is 1.2 to 1.5 times the theoretical molar amount for oxidizing Fe in the system. Preferably, pH A is 2.0 to 3.0. The temperature of the first-stage oxidation treatment is preferably 60 to 70°C, more preferably 60 to 65°C.

本发明中,第一段氧化处理的时间优选为0.5~1.0h。In the present invention, the time for the first-stage oxidation treatment is preferably 0.5 to 1.0 h.

本发明中,第一段氧化处理后,无需进行固液分离,直接调控体系的pH至pHB,并在所要求的60℃~80℃的温度下通入氧化剂,进行一锅反应中的第二段氧化处理。本发明研究发现,在所述的第一段氧化处理的协同前提下,进一步配合第二段氧化处理的工艺和温度的联合控制,能够实现体系中的Mn的选择性氧化,避免体系中的Cr的伴随氧化,如此能够和第一氧化反应联合,协同改善镁和其他成分的一锅分离选择性,改善镁的一锅分离回收率和纯度。In the present invention, after the first stage of oxidation treatment, without solid-liquid separation, the pH of the system is directly adjusted to pH B , and an oxidant is introduced at the required temperature of 60°C to 80°C to carry out the first step in the one-pot reaction. Secondary oxidation treatment. According to the research of the present invention, under the synergistic premise of the first-stage oxidation treatment and the joint control of the process and temperature of the second-stage oxidation treatment, the selective oxidation of Mn in the system can be realized, and the Cr in the system can be avoided. It can be combined with the first oxidation reaction to synergistically improve the one-pot separation selectivity of magnesium and other components, and improve the one-pot separation recovery rate and purity of magnesium.

优选地,第二段氧化反应阶段,氧化剂的用量为将体系中的Mn氧化成Mn(IV)氧化的理论摩尔量的1.2~1.5倍。Preferably, in the second stage of the oxidation reaction, the amount of the oxidant is 1.2 to 1.5 times the theoretical molar amount for oxidizing Mn in the system to Mn(IV) oxidation.

本发明中,第二段氧化反应过程的温度优选为60~70℃。In the present invention, the temperature of the second-stage oxidation reaction process is preferably 60-70°C.

作为优选,pHB为5.0~6.0。Preferably, pH B is 5.0-6.0.

优选地,第二段氧化反应的时间为0.5~1.0h。Preferably, the time of the second-stage oxidation reaction is 0.5-1.0 h.

本发明中,第二段氧化处理后,不进行固液分离,直接调控体系的pH至pHC,并在所要求的80℃~90℃的温度下进行第三段反应,实现除镁以外的其他离子如Cr等其他例如的选择性沉淀,并改善成核行为,如此能够意外地协同改善镁和其他离子的分离效果,改善镁的回收率和纯度,并改善其他元素在渣中的富集效果。In the present invention, after the second-stage oxidation treatment, the solid-liquid separation is not carried out, the pH of the system is directly adjusted to pH C , and the third-stage reaction is carried out at the required temperature of 80°C to 90°C to realize the addition of magnesium. Selective precipitation of other ions such as Cr, and improved nucleation behavior, which can unexpectedly synergistically improve the separation of magnesium and other ions, improve magnesium recovery and purity, and improve the enrichment of other elements in the slag Effect.

作为优选,pHC为7.0~8.0。Preferably, pH C is 7.0-8.0.

优选地,第三段反应的时间为2.0~3.0h。Preferably, the reaction time of the third stage is 2.0-3.0 h.

本发明中,通过所述的一锅三段反应下,配合各段的pH和温度的联合控制,能够实现协同,如此利于控制一锅体系下的元素的成核行为和形貌,且所述条件下构建的渣的形貌有能够和后续的条件协同诱导其他元素的成核选择性,如此利于控制Mg和其他成分的分离选择性,利于改善镁的回收率和纯度,不仅如此,还能够降低过滤难度,改善工艺操作性。In the present invention, through the one-pot three-stage reaction, with the joint control of pH and temperature of each stage, synergy can be achieved, which is beneficial to control the nucleation behavior and morphology of elements in the one-pot system, and the The morphology of the slag constructed under the conditions can synergize with the subsequent conditions to induce the nucleation selectivity of other elements, which is beneficial to control the separation selectivity of Mg and other components, and is beneficial to improve the recovery rate and purity of magnesium. Reduce filtration difficulty and improve process operability.

本发明中,可采用已知的手段对镁溶液进行处理。例如,向镁溶液中添加沉淀剂,进行沉镁反应,制得氢氧化镁。In the present invention, the magnesium solution can be treated by known means. For example, adding a precipitant to a magnesium solution to carry out a magnesium precipitation reaction to produce magnesium hydroxide.

沉淀剂例如为氨水、碱金属氢氧化物中的至少一种。所述的沉淀剂以溶液的形式条件,所述的溶液的浓度例如为1mol·L-1~13mol·L-1The precipitating agent is, for example, at least one of ammonia water and alkali metal hydroxide. The precipitant is in the form of a solution, and the concentration of the solution is, for example, 1 mol·L -1 to 13 mol·L -1 .

优选地,沉镁反应过程及反应终点的pH为8.8~9.5;Preferably, the pH of the magnesium precipitation reaction process and the reaction end point is 8.8 to 9.5;

优选地,沉镁反应过程的温度为70℃~80℃;Preferably, the temperature of the magnesium precipitation reaction process is 70°C to 80°C;

优选地,沉镁反应的时间为1~2h。Preferably, the reaction time of magnesium precipitation is 1-2h.

本发明中,将氢氧化镁置于碱液中进行陈化处理,随后固液分离、洗涤、制得提纯氢氧化镁;In the present invention, the magnesium hydroxide is placed in the alkaline solution for aging treatment, followed by solid-liquid separation, washing, and purified magnesium hydroxide;

优选地,所述的碱液为碱金属氢氧化物的水溶液,优选的溶质的浓度为0.2mol·L-1~0.5mol·L-1Preferably, the alkali solution is an aqueous solution of alkali metal hydroxide, and the preferred concentration of the solute is 0.2 mol·L -1 to 0.5 mol·L -1 ;

优选地,陈化的温度为70℃~80℃;Preferably, the aging temperature is 70°C to 80°C;

优选地,陈化的时间为60~120min。Preferably, the aging time is 60-120 min.

本发明一种优选的利用浸出液制备高纯氢氧化镁的方法,所述方法包括以下步骤:A preferred method for preparing high-purity magnesium hydroxide using leaching solution of the present invention, the method comprises the following steps:

(1)将蛇纹石硫酸浸出液加入碱性物质,调控体系的pH为2.0~3.0;随后添加氧化剂,在60~70℃保温下进行第一段反应;随后无需过滤下,继续补加碱性物质至体系的pH至4.5~6.0,添加氧化剂并在50~60℃保温下进行第二段氧化处理;处理后无需进行过滤,补加碱性物质至体系的pH为7.0~8.0,在80~90℃下保温进行第三段反应;随后经一次过滤,可以得到纯净的硫酸镁溶液。(1) Add alkaline substances to the serpentine sulfuric acid leaching solution, and adjust the pH of the system to 2.0-3.0; then add an oxidant, and carry out the first-stage reaction at a temperature of 60-70 °C; then, without filtration, continue to add alkaline The pH of the system is adjusted to 4.5-6.0, and the oxidizing agent is added and the second-stage oxidation treatment is carried out at a temperature of 50-60 °C; no filtration is required after the treatment, and the pH of the system is 7.0-8.0 by adding an alkaline substance. The third-stage reaction is carried out at a temperature of 90° C.; then a pure magnesium sulfate solution can be obtained after one filtration.

(2)在一定温度下,向过滤后得到的硫酸镁溶液中加入一定量的沉淀剂,进行沉镁反应。控制反应过程的pH为8.8~9.5,温度为70℃~80℃;时间为1~2h,随后经过滤,得到Mg(OH)2。所述步骤(2)硫酸镁溶液和沉淀剂加入的方式为双向滴加。(2) At a certain temperature, add a certain amount of precipitant to the magnesium sulfate solution obtained after filtration to carry out the magnesium precipitation reaction. The pH of the reaction process is controlled to be 8.8-9.5, the temperature is 70°C to 80°C, the time is 1-2 h, and then Mg(OH) 2 is obtained by filtration. The method of adding the magnesium sulfate solution and the precipitant in the step (2) is bidirectional dropwise addition.

(3)用热水洗涤氢氧化镁3~5次。(3) Wash the magnesium hydroxide with hot water 3 to 5 times.

(4)将一定浓度的氢氧化钠溶液加入到氢氧化镁中进行反应,过滤、洗涤,控制反应温度为70℃~80℃,反应时间为60~120min,可制得符合质量标准的高纯氢氧化镁产品。(4) adding a certain concentration of sodium hydroxide solution to magnesium hydroxide for reaction, filtering, washing, controlling the reaction temperature to be 70°C to 80°C, and the reaction time to be 60 to 120min, to obtain high-purity hydroxide that meets quality standards Magnesium products.

相对于现有技术,本发明具有以下优点和有益效果:Compared with the prior art, the present invention has the following advantages and beneficial effects:

针对蛇纹石常压硫酸酸浸的浸出液成分特点难于实现一锅提纯镁、工艺操作难度大的问题,本发明创新地提出,在所述的一锅三段处理工艺下,配合各段的反应类型、pH和温度的联合控制,能够实现协同,能够解决常压酸浸体系高铁、丰富杂质元素所致的与镁难于一锅高选择性分离的问题,能够有效使镁和各离子一锅高选择性分离,利用获得高纯度的镁溶液,改善镁的回收率以及其他成分在渣中的富集回收率,不仅如此,本发明方法还能够有效改善浸出液一锅处理过程中工艺性差(如过滤性差)的问题,利用工业实际放大。Aiming at the problems that the leaching solution of serpentine at atmospheric pressure sulfuric acid leaching is difficult to achieve one-pot purification of magnesium, and the process operation is difficult, the present invention innovatively proposes that under the one-pot three-stage treatment process, the reaction of each stage is coordinated. The joint control of type, pH and temperature can achieve synergy, and can solve the problem that magnesium and magnesium are difficult to separate with high selectivity in one pot caused by high iron and rich impurity elements in the normal pressure acid leaching system, and can effectively make magnesium and various ions high in one pot. Selective separation, utilizing to obtain high-purity magnesium solution, improves the recovery rate of magnesium and the enrichment recovery rate of other components in the slag, not only that, the method of the present invention can also effectively improve the poor processability (such as filtration) in the one-pot treatment process of the leachate. poor performance), using industrial practical amplification.

附图说明Description of drawings

图1为实施例1产品的XRD图;Fig. 1 is the XRD pattern of embodiment 1 product;

图2为实施例1产物的SEM图;Fig. 2 is the SEM image of the product of Example 1;

具体实施方式:Detailed ways:

下面结合实施例对本申请的技术方案进行详细说明:Below in conjunction with embodiment, the technical scheme of the present application is described in detail:

根据工业氢氧化镁的化工行业标准HG/T 3607-2007可知,工业氢氧化镁可分为三类:According to the chemical industry standard HG/T 3607-2007 for industrial magnesium hydroxide, industrial magnesium hydroxide can be divided into three categories:

Ⅰ类:主要用作阻燃剂的原料,[Mg(OH)2]质量分数/%≥97.5;Class I: Mainly used as a raw material for flame retardants, [Mg(OH) 2 ] mass fraction/%≥97.5;

Ⅱ类:主要用作氧化镁和镁盐生产的原料;[Mg(OH)2]质量分数/%≥93Class II: mainly used as raw materials for the production of magnesium oxide and magnesium salts; [Mg(OH) 2 ] mass fraction/%≥93

Ⅲ类:主要用于烟道脱硫,废水处理,农用肥料和土壤改良剂等;[Mg(OH)2]质量分数/%≥92。Class III: Mainly used for flue desulfurization, wastewater treatment, agricultural fertilizers and soil conditioners, etc.; [Mg(OH) 2 ] mass fraction/%≥92.

所以本发明工艺所产的Mg(OH)2的纯度要求符合行业Ⅰ类标准。Therefore, the purity requirements of the Mg(OH) 2 produced by the process of the invention meet the industry class I standard.

以下案例,所述的酸浸液为低品位的蛇纹石经硫酸常压酸浸得到,所述的蛇纹石常压硫酸浸出液中主要元素浓度(g·L-1):Mg 60,Fe 12.89,Al 1.54,Cr(III)0.33,Co(II)0.025,Mn(II)0.40,Ni(II)0.55。In the following cases, the acid leaching solution is obtained from low-grade serpentine by acid leaching with sulfuric acid at atmospheric pressure, and the main element concentration (g·L -1 ) in the serpentine normal pressure sulfuric acid leaching solution: Mg 60, Fe 12.89, Al 1.54, Cr(III) 0.33, Co(II) 0.025, Mn(II) 0.40, Ni(II) 0.55.

为使本发明的目的、技术方案和优点更加清楚明白,下面结合实施例,对本发明作进一步的详细说明,本发明的示意性实施方式及其说明仅用于解释本发明,并不作为对本发明的限定。In order to make the purpose, technical solutions and advantages of the present invention clearer, the present invention will be described in further detail below in conjunction with the examples. limit.

实施例1:Example 1:

步骤(1):一锅处理:Step (1): One-pot treatment:

蛇纹石浸出液(酸浸液)为300mL,用10%MgO浆液将浸出液的pHA调到2.0时,加入铁含量1.3倍的氯酸钠,60℃保温进行第一段氧化处理,氧化30分钟;无需过滤下,继续采用10%MgO浆液将浸出液的pHB调到5.5时,通入氧气(为锰摩尔量的1.3倍),70℃保温进行第二段氧化处理30分钟;无需过滤下继续用10%MgO浆液调节pHC至7.0,80℃保温进行第三段反应2h;The serpentine leaching solution (acid leaching solution) is 300mL. When the pH A of the leaching solution is adjusted to 2.0 with 10% MgO slurry, sodium chlorate with an iron content of 1.3 times is added, and the first stage of oxidation treatment is carried out at 60 °C for 30 minutes. Without filtration, continue to use 10% MgO slurry to adjust the pH B of the leachate to 5.5, introduce oxygen (1.3 times the molar amount of manganese), and carry out the second-stage oxidation treatment at 70 °C for 30 minutes; continue without filtration Adjust pH C to 7.0 with 10% MgO slurry, and conduct the third-stage reaction at 80°C for 2h;

一锅三段处理完成后,进行过滤,过滤的速率为12mg/min·cm2,过滤后滤液中镍的含量为0.13mg·L-1,钴的含量为0.07mg·L-1,锰的含量为0.43mg·L-1,由于铬和铁的含量极低,ICP没有测出;此方法渣中铁的回收率大于99.99%,镍的回收率为99.97%,锰的回收率为99.87%,铬的回收率大于99.99%,镁的损失率低于0.7%。After the one-pot three-stage treatment is completed, the filtration rate is 12 mg/min·cm 2 . The content of nickel in the filtrate after filtration is 0.13 mg·L -1 , the content of cobalt is 0.07 mg·L -1 , and the content of manganese is 0.13 mg·L -1 . The content is 0.43mg·L -1 . Because the content of chromium and iron is extremely low, ICP has not detected it; the recovery rate of iron in the slag by this method is greater than 99.99%, the recovery rate of nickel is 99.97%, and the recovery rate of manganese is 99.87%. The recovery rate of chromium is greater than 99.99%, and the loss rate of magnesium is less than 0.7%.

步骤(2):沉镁以及陈化:Step (2): magnesium precipitation and aging:

将净化除杂后的溶液,滴加氨水进行沉淀反应,反应的温度为70℃,反应过程及反应终点的pH为8.9;反应时间1.0h,经过滤、洗涤得到Mg(OH)2,洗涤得到的Mg(OH)2用0.10mol·L-1NaOH陈化(温度为70℃)1.0h。氢氧化镁的硫含量为0.17%,镁的总回收率为80%,氢氧化镁中未检测到Cr元素,氢氧化镁纯度为98.63%,白度为98.6%。氢氧化镁的XRD图和SEM图如图1和2所示。The purified and impurity-removed solution was added dropwise with ammonia water to carry out precipitation reaction, the reaction temperature was 70°C, the pH of the reaction process and the reaction end point was 8.9; the reaction time was 1.0h, Mg(OH) 2 was obtained by filtration and washing, and washed to obtain Mg(OH) 2 . The Mg(OH) 2 was aged with 0.10 mol·L -1 NaOH (at a temperature of 70 °C) for 1.0 h. The sulfur content of magnesium hydroxide is 0.17%, the total recovery rate of magnesium is 80%, no Cr element is detected in magnesium hydroxide, the purity of magnesium hydroxide is 98.63%, and the whiteness is 98.6%. The XRD pattern and SEM pattern of magnesium hydroxide are shown in Figures 1 and 2.

实施例2:Example 2:

步骤(1):一锅处理:Step (1): One-pot treatment:

蛇纹石浸出液(酸浸液,同实施例1)为300mL,用10%MgO浆液将浸出液的pH调到3时,加入铁含量1.4倍的氯酸钠,60℃保温进行第一段氧化处理,氧化40分钟;10%MgO浆液将浸出液的pH调到6时,再通入锰含量1.4倍的双氧水,60℃保温进行第二段氧化处理40min;继续用10%MgO浆液调节pH,直至将pH调到8,90℃保温进行第三段反应2H;Serpentine leaching solution (acid leaching solution, same as Example 1) was 300 mL, when the pH of the leaching solution was adjusted to 3 with 10% MgO slurry, sodium chlorate with 1.4 times of iron content was added, and the first stage oxidation treatment was carried out at 60° C. , oxidized for 40 minutes; when the pH of the leachate was adjusted to 6 with 10% MgO slurry, hydrogen peroxide with 1.4 times the manganese content was introduced, and the second stage oxidation treatment was carried out at 60 °C for 40 minutes; the pH was adjusted with 10% MgO slurry until the The pH was adjusted to 8, and the third-stage reaction was carried out at 90°C for 2H;

一锅三段处理完成后,进行过滤,过滤的速率为15mg/min·cm2,过滤后滤液中镍的含量为0.074mg·L-1,钴的含量为0.019mg·L-1,锰的含量为1.48mg·L-1,铬的含量为0.041mg·L-1,铁的含量为0.014mg·L-1;此方法中铁的回收率大于99.9%,镍的回收率为99.92%,锰的回收率为99.57%,铬的回收率大于99.99%,镁的损失率低于0.8%After the one-pot three-stage treatment is completed, the filtration rate is 15 mg/min·cm 2 . The content of nickel in the filtrate after filtration is 0.074 mg·L -1 , the content of cobalt is 0.019 mg·L -1 , and the content of manganese is 0.074 mg·L -1 . The content is 1.48mg·L -1 , the content of chromium is 0.041mg·L -1 , the content of iron is 0.014mg·L -1 ; the recovery rate of iron in this method is more than 99.9%, the recovery rate of nickel is 99.92%, and the recovery rate of manganese is 99.92%. The recovery rate is 99.57%, the recovery rate of chromium is more than 99.99%, and the loss rate of magnesium is less than 0.8%

步骤(2):沉镁以及陈化:Step (2): magnesium precipitation and aging:

将净化除杂后的溶液,加入氨水,控制加料温度为30℃,待体系的pH达到9后升温至80℃,控制反应过程和终点的pH为9.2;保温反应时间1.5h,随后经过滤、洗涤得到Mg(OH)2,洗涤得到的Mg(OH)2用0.15mol·L-1NaOH陈化(温度为80℃)1.5h,镁的总回收率为82%,氢氧化镁的硫含量为0.18%,氢氧化镁中未检测到Cr元素,氢氧化镁纯度为98.71%,白度为99.6%。The solution after purification and removal of impurities was added with ammonia water, and the feeding temperature was controlled to be 30 ° C. After the pH of the system reached 9, the temperature was raised to 80 ° C, and the pH of the reaction process and the end point was controlled to be 9.2; Mg(OH) 2 was obtained by washing, and the Mg(OH) 2 obtained by washing was aged with 0.15mol·L -1 NaOH (temperature is 80°C) for 1.5h, the total recovery rate of magnesium was 82%, and the sulfur content of magnesium hydroxide Cr element was not detected in magnesium hydroxide, the purity of magnesium hydroxide was 98.71%, and the whiteness was 99.6%.

实施例3:Example 3:

步骤(1):一锅处理(中试处理):Step (1): One-pot treatment (pilot test treatment):

蛇纹石浸出液(酸浸液,同实施例1)为300L,用10%MgO浆液将浸出液的pH调到2.5时,加入铁含量1.5倍的氯酸钠,65℃保温进行第一段氧化处理,氧化50分钟;10%MgO浆液将浸出液的pH调到5时,再通入锰含量1.5倍的氧气,65℃保温进行第二段氧化处理50分钟;继续用10%MgO浆液调节pH,直至将pH调到7.5,85℃保温进行第三段反应2h;Serpentine leaching solution (acid leaching solution, same as Example 1) was 300L, when the pH of the leaching solution was adjusted to 2.5 with 10% MgO slurry, sodium chlorate with 1.5 times of iron content was added, and the first stage oxidation treatment was carried out at 65° C. , oxidized for 50 minutes; when the pH of the leachate was adjusted to 5 with 10% MgO slurry, oxygen with 1.5 times the manganese content was introduced, and the second-stage oxidation treatment was carried out at 65 °C for 50 minutes; continue to adjust pH with 10% MgO slurry until The pH was adjusted to 7.5, and the third-stage reaction was carried out at 85 °C for 2 h;

一锅三段处理完成后,进行过滤,过滤的速率为73g/h·dm2,过滤后滤液中镍的含量为0.11mg·L-1,钴的含量为0.09mg·L-1,锰的含量为0.41mg·L-1,铬的含量为0.85mg·L-1,由于铁的含量极低,ICP没有测出;此方法中铁的回收率大于99.9%,镍的回收率为99.98%,锰的回收率为99.89%,铬的回收率为99.7%,镁的损失率为1.2%。After the one-pot three-stage treatment is completed, the filtration rate is 73 g/h·dm 2 . The content of nickel in the filtrate after filtration is 0.11 mg·L -1 , the content of cobalt is 0.09 mg·L -1 , and the content of manganese is 0.11 mg·L -1 . The content of iron was 0.41mg·L -1 , and the content of chromium was 0.85mg·L -1 . Due to the extremely low content of iron, ICP was not detected. The recovery of manganese was 99.89%, the recovery of chromium was 99.7%, and the loss of magnesium was 1.2%.

步骤(2):沉镁以及陈化:Step (2): magnesium precipitation and aging:

步骤(1)净化除杂后的溶液中加入氨水,控制加料温度为40℃,当体系的pH达到8.8后升温至75℃保温反应,控制反应过程及反应终点的pH为9.1,反应时间2.0h,随后经过滤、洗涤得到Mg(OH)2,洗涤得到的Mg(OH)2用0.20mol·L-1NaOH陈化(温度为75℃)2.0h,镁的总回收率为75%,氢氧化镁的硫含量为0.16%,氢氧化镁中未检测到Cr元素,氢氧化镁纯度为98.5%,白度为99.3%。Step (1) Add ammonia water to the solution after purification and removal of impurities, control the feeding temperature to 40 ° C, when the pH of the system reaches 8.8, heat up to 75 ° C and keep the reaction, control the pH of the reaction process and the reaction end point to be 9.1, and the reaction time is 2.0h , and then filtered and washed to obtain Mg(OH) 2 , and the obtained Mg(OH) 2 was aged with 0.20 mol·L -1 NaOH (at a temperature of 75° C.) for 2.0 h. The total recovery rate of magnesium was 75%, and the hydrogen The sulfur content of the magnesium oxide was 0.16%, and no Cr element was detected in the magnesium hydroxide. The purity of the magnesium hydroxide was 98.5% and the whiteness was 99.3%.

对比例1:Comparative Example 1:

和实施例1相比,区别仅在于,一锅处理过程中的第一段氧化过程的温度为50℃;其他操作和参数同实施例1。Compared with Example 1, the only difference is that the temperature of the first stage oxidation process in the one-pot treatment process is 50°C; other operations and parameters are the same as those of Example 1.

结果为:步骤(1)中,过滤效率为6mg/min·cm2;铁的回收率为80%,镍的回收率为95%,锰的回收率为96%;铬的回收率为94%;镁的损失率为10%;步骤(2)中,氢氧化镁的总回收收率为70%,纯度为98.5%,白度为98.6%;氢氧化镁中Cr元素为0.0334%,硫含量为0.2%。工艺的过滤性能、产物质量如纯度、白度等性能均不及实施例1。The results are: in step (1), the filtration efficiency is 6 mg/min·cm 2 ; the recovery rate of iron is 80%, the recovery rate of nickel is 95%, the recovery rate of manganese is 96%; the recovery rate of chromium is 94% The loss rate of magnesium is 10%; in step (2), the total recovery yield of magnesium hydroxide is 70%, the purity is 98.5%, and the whiteness is 98.6%; Cr element in the magnesium hydroxide is 0.0334%, and the sulfur content is 0.0334%. is 0.2%. The filtering performance and product quality of the process, such as purity and whiteness, are not as good as those of Example 1.

对比例2:Comparative Example 2:

和实施例1相比,区别仅在于,一锅处理过程中的第二段氧化处理过程的温度为50℃;其他操作和参数同实施例1。Compared with Example 1, the only difference is that the temperature of the second-stage oxidation treatment process in the one-pot treatment process is 50°C; other operations and parameters are the same as those of Example 1.

结果为:步骤(1)中,铁的回收率为98.8%,镍的回收率为97.5%,锰的回收率为70%,铬的回收率为94%;镁的损失率低于0.8%;步骤(2)中,镁的总收率为79%,纯度为96.8%,白度为89%;硫含量为0.18%,Cr元素为0.0771%。The results are: in step (1), the recovery rate of iron is 98.8%, the recovery rate of nickel is 97.5%, the recovery rate of manganese is 70%, and the recovery rate of chromium is 94%; the loss rate of magnesium is less than 0.8%; In step (2), the total yield of magnesium is 79%, the purity is 96.8%, and the whiteness is 89%; the sulfur content is 0.18%, and the Cr element is 0.0771%.

对比例3:Comparative Example 3:

和实施例1相比,区别仅在于,一锅处理过程中的第二段氧化处理的为90℃;其他操作和参数同实施例1。Compared with Example 1, the only difference is that the oxidation treatment of the second stage in the one-pot treatment process is 90°C; other operations and parameters are the same as those of Example 1.

结果为:步骤(1)中,铁的回收率为97.7%,镍的回收率为98%,锰的回收率为96%;铬的回收率为80%,镁的损失率低于0.8%;步骤(2)中,镁的总收率为76%,纯度为95.4%,白度为87%;氢氧化镁中硫含量为0.21%、Cr元素为0.0419%。The results are: in step (1), the recovery rate of iron is 97.7%, the recovery rate of nickel is 98%, and the recovery rate of manganese is 96%; the recovery rate of chromium is 80%, and the loss rate of magnesium is less than 0.8%; In step (2), the total yield of magnesium is 76%, the purity is 95.4%, and the whiteness is 87%; the sulfur content in the magnesium hydroxide is 0.21%, and the Cr element is 0.0419%.

对比例4:Comparative Example 4:

和实施例1相比,区别仅在于,一锅处理过程中的第三段处理的为60℃;其他操作和参数同实施例1。Compared with Example 1, the only difference is that the third stage of the one-pot treatment process is treated at 60°C; other operations and parameters are the same as those of Example 1.

结果为:步骤(1)中,铁的回收率为97%,镍的回收率为96.4%,锰的回收率为94%;铬的回收率为95%;镁的损失率为3%;步骤(2)中,镁的总收率为77%,纯度为97.5%,白度为98%;氢氧化镁中硫含量为0.18%。The results are: in step (1), the recovery rate of iron is 97%, the recovery rate of nickel is 96.4%, the recovery rate of manganese is 94%, the recovery rate of chromium is 95%, and the loss rate of magnesium is 3%; In (2), the total yield of magnesium is 77%, the purity is 97.5%, and the whiteness is 98%; the sulfur content in magnesium hydroxide is 0.18%.

对比例5:Comparative Example 5:

和实施例1相比,区别仅在于,步骤(1)的一锅第二段过程中,pHB为4.0。其他参数同实施例1。Compared with Example 1, the only difference is that in the one-pot second stage process of step (1), pH B is 4.0. Other parameters are the same as in Example 1.

结果为:步骤(1)中,铁的回收率为98%,镍的回收率为97%,锰的回收率为73%,铬的回收率为94%;镁的损失率为1%。The results were: in step (1), the recovery rate of iron was 98%, the recovery rate of nickel was 97%, the recovery rate of manganese was 73%, the recovery rate of chromium was 94%, and the loss rate of magnesium was 1%.

步骤(2)中,镁的总回收率为80%,氢氧化镁的硫含量为0.2%,氢氧化镁纯度为96.4%,白度为87%。In step (2), the total recovery rate of magnesium is 80%, the sulfur content of magnesium hydroxide is 0.2%, the purity of magnesium hydroxide is 96.4%, and the whiteness is 87%.

对比例6:Comparative Example 6:

和实施例1相比,区别仅在于,步骤(1)的一锅第二段过程中,pHB为6.5。Compared with Example 1, the only difference is that in the one-pot second stage process of step (1), pH B is 6.5.

结果为:步骤(1)中,铁的回收率为96%,镍的回收率为97%,铬的回收率为82%,锰的回收率为96%;镁的损失率为0.9%。The results are: in step (1), the recovery rate of iron is 96%, the recovery rate of nickel is 97%, the recovery rate of chromium is 82%, the recovery rate of manganese is 96%, and the loss rate of magnesium is 0.9%.

步骤(2)中,镁的总回收率为78%;氢氧化镁纯度为95.1%,硫含量为0.23%,白度为88%。In step (2), the total recovery rate of magnesium is 78%; the purity of magnesium hydroxide is 95.1%, the sulfur content is 0.23%, and the whiteness is 88%.

Claims (10)

1.蛇纹石常压硫酸浸出液一锅提纯镁的方法,其特征在于,将蛇纹石硫酸常压酸浸的浸出液进行一锅三段反应处理,随后固液分离,得到纯化的镁溶液;1. the method for purifying magnesium in one pot of serpentine normal pressure sulfuric acid leachate, it is characterized in that, the leachate of serpentine sulfuric acid normal pressure acid leaching is carried out one pot three-stage reaction processing, subsequently solid-liquid separation, obtains the magnesium solution of purification; 所述的浸出液中溶解有Fe、Mn、Cr和Mg;Fe, Mn, Cr and Mg are dissolved in the leaching solution; 所述的一锅三段反应过程包括:调控浸出液的pHA为2.0~3.0,加入氧化剂进行第一段氧化处理;随后调控体系的pHB至4.5~6,补加氧化剂进行第二段氧化处理;再调控体系的pHC至7~8后进行第三段反应;The one-pot three-stage reaction process includes: adjusting the pH A of the leachate to be 2.0-3.0, adding an oxidant to carry out the first-stage oxidation treatment; then adjusting the pH B of the system to 4.5-6, adding an oxidant to carry out the second-stage oxidation treatment ; Carry out the third stage reaction after adjusting the pH C of the system to 7~8 again; 一锅三段反应过程中,第一段氧化反应、第二段氧化反应的温度为60~80℃,第三段反应的温度为80℃~90℃。In the one-pot three-stage reaction process, the temperature of the first-stage oxidation reaction and the second-stage oxidation reaction is 60-80°C, and the temperature of the third-stage reaction is 80°C-90°C. 2.如权利要求1所述的蛇纹石常压硫酸浸出液一锅提纯镁的方法,其特征在于,常压硫酸酸浸过程的硫酸浓度为2~5mol·L-1;酸浸过程的温度为80~100℃。2. the method for one-pot purifying magnesium of serpentine atmospheric sulfuric acid leaching solution as claimed in claim 1, it is characterized in that, the sulfuric acid concentration of normal pressure sulfuric acid leaching process is 2~5mol L -1 ; The temperature of acid leaching process It is 80~100 ℃. 3.如权利要求1所述的蛇纹石常压硫酸浸出液一锅提纯镁的方法,其特征在于,所述的浸出液中,Fe的浓度为5~18g/L;Mn的浓度为0.2~0.5g/L、Cr的浓度为0.10~0.40g/L、Mg的浓度为50~65g/L。3. the method for purifying magnesium in one pot of serpentine atmospheric sulfuric acid leachate as claimed in claim 1, is characterized in that, in described leachate, the concentration of Fe is 5~18g/L; The concentration of Mn is 0.2~0.5 The concentration of g/L and Cr is 0.10 to 0.40 g/L, and the concentration of Mg is 50 to 65 g/L. 4.如权利要求1所述的蛇纹石常压硫酸浸出液一锅提纯镁的方法,其特征在于,酸浸液中,还含有镍、钴、铝中的至少一种;4. the method for one-pot purifying magnesium of serpentine atmospheric sulfuric acid leaching solution as claimed in claim 1, is characterized in that, in acid leaching solution, also contains at least one in nickel, cobalt, aluminum; 优选地,所述的浸出液中,Ni的浓度为0.20~0.6g/L;Co的浓度为0.01~0.04g/L;Al的浓度为0.2~2g/L。Preferably, in the leaching solution, the concentration of Ni is 0.20-0.6 g/L; the concentration of Co is 0.01-0.04 g/L; the concentration of Al is 0.2-2 g/L. 5.如权利要求1所述的蛇纹石常压硫酸浸出液一锅提纯镁的方法,其特征在于,一锅三段处理过程中,采用碱性物质调控体系的pH,所述的碱性物质为氧化镁、氧化钙、碱金属氢氧化物、氨水中的至少一种。5. the method for one-pot purifying magnesium of serpentine atmospheric sulfuric acid leachate as claimed in claim 1, is characterized in that, in one-pot three-stage treatment process, adopts the pH of alkaline substance control system, described alkaline substance It is at least one of magnesium oxide, calcium oxide, alkali metal hydroxide and ammonia water. 6.如权利要求1所述的蛇纹石常压硫酸浸出液一锅提纯镁的方法,其特征在于,一锅三段处理过程中,氧化剂为氯酸盐、氧气、过氧化氢中的至少一种。6. the method for one-pot purifying magnesium of serpentine atmospheric sulfuric acid leachate as claimed in claim 1, is characterized in that, in one-pot three-stage treatment process, oxidant is at least one of chlorate, oxygen, hydrogen peroxide kind. 7.如权利要求1所述的蛇纹石常压硫酸浸出液一锅提纯镁的方法,其特征在于,第一段氧化反应阶段,氧化剂的用量为将体系中的Fe2+氧化的理论摩尔量的1.2~1.5倍;7. the method for one-pot purifying magnesium of serpentine atmospheric sulfuric acid leachate as claimed in claim 1, is characterized in that, the first stage oxidation reaction stage, the consumption of oxidant is by Fe in the system The theoretical molar weight of oxidation 1.2 to 1.5 times of ; 优选地,第二段氧化反应阶段,氧化剂的用量为将体系中的Mn(Ⅱ)氧化成Mn(IV)氧化的理论摩尔量的1.2~1.5倍。Preferably, in the second stage of oxidation reaction, the dosage of the oxidant is 1.2-1.5 times the theoretical molar amount for oxidizing Mn(II) in the system to Mn(IV) oxidation. 8.如权利要求1所述的蛇纹石常压硫酸浸出液一锅提纯镁的方法,其特征在于,第一段氧化反应的时间为0.5~1h;8. the method for one-pot magnesium purification of serpentine atmospheric sulfuric acid leaching solution as claimed in claim 1, is characterized in that, the time of first-stage oxidation reaction is 0.5~1h; 优选地,第二段氧化反应的时间为0.5~1h;Preferably, the time of the second-stage oxidation reaction is 0.5-1 h; 优选地,第三段反应的时间为2.0~3.0h。Preferably, the reaction time of the third stage is 2.0-3.0 h. 9.如权利要求1所述的蛇纹石常压硫酸浸出液一锅提纯镁的方法,其特征在于,向镁溶液中添加沉淀剂,进行沉镁反应,制得氢氧化镁;9. the method for one-pot purifying magnesium of serpentine atmospheric sulfuric acid leachate as claimed in claim 1, is characterized in that, in magnesium solution, add precipitating agent, carry out magnesium precipitation reaction, make magnesium hydroxide; 优选地,沉镁反应过程和终点的pH为8.8~9.5;Preferably, the pH of the magnesium precipitation reaction process and the end point is 8.8 to 9.5; 优选地,沉镁反应过程的温度为70℃~80℃;Preferably, the temperature of the magnesium precipitation reaction process is 70°C to 80°C; 优选地,沉镁反应的时间为1~2h。Preferably, the reaction time of magnesium precipitation is 1-2h. 10.如权利要求9所述的蛇纹石常压硫酸浸出液一锅提纯镁的方法,其特征在于,将氢氧化镁置于碱液中进行陈化处理,随后固液分离、洗涤、制得提纯氢氧化镁;10. the method for one-pot purifying magnesium of serpentine atmospheric sulfuric acid leaching solution as claimed in claim 9, is characterized in that, magnesium hydroxide is placed in lye to carry out ageing treatment, subsequently solid-liquid separation, washing, making Purified magnesium hydroxide; 优选地,所述的碱液为碱金属氢氧化物的水溶液,优选的溶质的浓度为0.2mol·L-1~0.5mol·L-1Preferably, the alkali solution is an aqueous solution of alkali metal hydroxide, and the preferred concentration of the solute is 0.2 mol·L -1 to 0.5 mol·L -1 ; 优选地,陈化的温度为70℃~80℃;Preferably, the aging temperature is 70°C to 80°C; 优选地,陈化的时间为60~120min。Preferably, the aging time is 60-120 min.
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