WO2020063035A1

WO2020063035A1 - Method for enriching scandium

Info

Publication number: WO2020063035A1
Application number: PCT/CN2019/095692
Authority: WO
Inventors: 王玮玮; 孙宁磊; 付国燕; 刘召波; 刘国; 杜尚超; 李诺
Original assignee: 中国恩菲工程技术有限公司
Priority date: 2018-09-28
Filing date: 2019-07-12
Publication date: 2020-04-02

Abstract

A method for enriching scandium, comprising the following steps: S1, extracting scandium from a scandium-containing inorganic acid solution using an organic extractant or an organic solvent solution containing an organic extractant to obtain an organic phase containing scandium; and S2, back-extracting and precipitating the organic phase containing scandium using a precipitant solution, followed by separation to obtain a precipitate containing scandium, a precipitation mother liquor, and a no-load organic phase. The precipitant solution plays a role in back-extraction and precipitation at the same time, thereby shortening the operation process and reducing the consumption of raw materials.

Description

富集钪的方法Enriched plutonium

技术领域Technical field

本发明涉及冶金技术领域，具体而言，涉及一种富集钪的方法。The invention relates to the field of metallurgical technology, in particular to a method for enriching thorium.

背景技术Background technique

钪是一种商业价值很高的金属，例如，氟化钪可以做光学材料，也是熔盐电解、金属热还原法制备钪金属及其合金的重要原料；氧化钪具有稀土倍半氧化物的立方结构，不溶于水，溶于热酸中，可用作半导体镀层的蒸镀材料，制做可变波长的固体激光器和高清晰度的电视电子枪、金属卤化物灯等。Thallium is a metal with high commercial value. For example, thorium fluoride can be used as an optical material, and it is also an important raw material for the preparation of thallium metal and its alloys by molten salt electrolysis and metal thermal reduction methods. Thallium oxide has a cube of rare earth sesquioxide. Structure, insoluble in water, soluble in hot acid, can be used as a vapor deposition material for semiconductor coatings, to make solid-state lasers with variable wavelengths, high-definition television electron guns, metal halide lamps, etc.

一种传统富集钪的方法，如图1所示，首先利用有机相对含钪料液进行萃取，将钪萃取到有机相；对得到的含钪负载有机相进行洗涤后，通过加入无机酸溶液等反萃剂溶液进行反萃，将负载有机相中的钪从有机相中剥离，将其反萃到反萃液中；再通过加入草酸溶液、碱液等沉淀剂将钪从反萃液中沉淀出来，完成钪的富集。但是该方法操作流程长，反萃剂、水等原料消耗较大，操作费用较高。A traditional method of enriching thorium, as shown in FIG. 1, first uses an organic phase to extract the thorium-containing material solution to extract the thorium into the organic phase; after washing the obtained thorium-containing supported organic phase, adding an inorganic acid solution Back-extract with iso-extractive agent solution, strip the tritium in the supported organic phase from the organic phase, and back-extract it into the back-extract liquid; then add precipitant such as oxalic acid solution, alkaline solution, etc. Precipitate out and complete the enrichment of tritium. However, the method has a long operation process, large consumption of raw materials such as back-extracting agent and water, and high operation cost.

酸性有机磷萃取剂对钪(Sc)有很好的萃取效果，萃取效率高，并且能将钪与杂质元素很好的分离，但是钪(Sc)很难从含酸性有机磷萃取剂的有机溶液中反萃取，往往需要很高的酸度(如600g/L以上的硫酸溶液)以及多次反萃取操作。而且反萃得到的高酸度钪溶液中杂质离子浓度较高，需要进一步纯化操作，常用的方法是加入草酸溶液在较低的酸度下沉淀生成草酸钪沉淀，进而将草酸酸钪沉淀煅烧以生成氧化钪，因此，需要耗费大量的碱溶液进行中和，而且耗用大量价格高的草酸试剂。Acidic organic phosphorus extractant has a good extraction effect on thorium (Sc), high extraction efficiency, and can well separate thorium from impurity elements, but thorium (Sc) is difficult to extract from organic solutions containing acidic organic phosphorus extractant Medium back extraction often requires very high acidity (such as sulfuric acid solution above 600g / L) and multiple back extraction operations. Moreover, the concentration of impurity ions in the high-acidity radon solution obtained by back-extraction is high, and further purification operations are required. A commonly used method is to add an oxalic acid solution to precipitate at a lower acidity to form an oxalate oxalate precipitate, and then calcinate the oxalate oxalate precipitate to generate oxidation. Alas, therefore, a large amount of alkaline solution is needed for neutralization, and a large amount of expensive oxalic acid reagent is consumed.

有机羧酸萃取剂对钪(Sc)有很好的萃取效果，萃取机理为阳离子交换机制，萃取在较低的溶液酸度下时钪萃取效率高，但是，一些杂质离子(如Ca ²⁺、Mg ²⁺、Mn ²⁺、Ni ²⁺、Al ³⁺、Fe ³⁺、Cr ³⁺)一定程度上同时被萃取，即干扰钪与这些离子的分离。为解决这一问题，常用的方法是将负载的有机溶液多次用酸溶液洗涤，但是一方面洗涤杂质效果差，另一方面容易造成钪的损失，并且钪(Sc)很难从其负载的有机溶液中反萃取，往往需要很高的酸度(如4mol/L HCl溶液)以及多次反萃取操作，而且反萃得到的高酸度钪溶液中杂质离子浓度较高，需要进一步纯化操作，常用的方法是加入草酸溶液在较低的酸度下沉淀生成草酸钪沉淀，进而将酸钪沉淀煅烧以生成氧化钪，因此，需要耗费大量的碱溶液进行中和，而且耗用大量价格高的草酸试剂。 Organic carboxylic acid extractants have a good extraction effect on Sc (Sc). The extraction mechanism is a cation exchange mechanism. The extraction efficiency is high when the extraction is performed at a lower solution acidity. However, some impurity ions (such as Ca ²⁺ and Mg) ²⁺ , Mn ²⁺ , Ni ²⁺ , Al ³⁺ , Fe ³⁺ , Cr ³⁺ ) are simultaneously extracted to a certain extent, which interferes with the separation of radon from these ions. In order to solve this problem, the commonly used method is to wash the loaded organic solution with an acid solution multiple times, but on the one hand, the effect of washing impurities is poor, on the other hand, it is easy to cause the loss of tritium, and the tritium (Sc) is difficult to load from it. Back-extraction in organic solutions often requires high acidity (such as 4mol / L HCl solution) and multiple back-extraction operations, and the concentration of impurity ions in the high-acidity radon solution obtained by back-extraction is higher, which requires further purification operations. Commonly used The method is to add an oxalic acid solution to precipitate at a lower acidity to form a lutetium oxalate precipitate, and then calcine the acid ytterbium precipitate to generate ytterbium oxide. Therefore, a large amount of an alkaline solution needs to be neutralized, and a large amount of expensive oxalic acid reagent is consumed.

发明内容Summary of the Invention

本发明旨在提供一种富集钪的方法，以解决现有技术中富集操作流程长、原料消耗大的技术问题。The invention aims to provide a method for enriching thorium to solve the technical problems of long enrichment operation flow and large raw material consumption in the prior art.

为了实现上述目的，根据本发明的一个方面，提供了一种富集钪的方法。该方法包括以下步骤：S1，利用有机萃取剂或含有机萃取剂的有机溶剂溶液对含钪无机酸溶液进行钪萃取，获得含有钪的有机相；S2，利用沉淀剂溶液对含有钪的有机相进行沉淀反萃取处理，固液分离及液液分离后获得含有钪的沉淀，以及沉淀母液和空载的有机相。To achieve the above object, according to one aspect of the present invention, a method for enriching thorium is provided. The method includes the following steps: S1, using an organic extractant or an organic solvent solution containing an organic extractant to perform a rhenium extraction of a rhenium-containing inorganic acid solution to obtain an rhenium-containing organic phase; S2, using a precipitant solution to erbium-containing organic phase After performing precipitation back extraction treatment, solid-liquid separation and liquid-liquid separation, a precipitate containing thorium is obtained, as well as a precipitation mother liquor and an unloaded organic phase.

进一步地，有机萃取剂为选自由酸性有机萃取剂、中性有机萃取剂、碱性有机萃取剂和有机螯合萃取剂组成的组中的一种或多种；Further, the organic extractant is one or more selected from the group consisting of an acidic organic extractant, a neutral organic extractant, a basic organic extractant, and an organic chelate extractant;

优选的，酸性有机萃取剂包括酸性有机磷萃取剂和/或有机羧酸萃取剂；更优选的，酸性有机磷萃取剂为二(2-乙基己基)磷酸和/或2-乙基己基磷酸单-2-乙基己基酯；更优选的，有机羧酸萃取剂为烷烃基羧酸、芳香烃基羧酸和环烷酸中的任一种或多种；进一步优选的，烷烃基羧酸为正己酸，芳香烃基羧酸为仲辛基苯氧基乙酸；Preferably, the acidic organic extractant includes an acidic organic phosphorus extractant and / or an organic carboxylic acid extractant; more preferably, the acidic organic phosphorus extractant is bis (2-ethylhexyl) phosphoric acid and / or 2-ethylhexyl phosphoric acid. Mono-2-ethylhexyl ester; more preferably, the organic carboxylic acid extractant is any one or more of an alkane carboxylic acid, an aromatic carboxylic acid and a naphthenic acid; further preferably, the alkane carboxylic acid is N-hexanoic acid, the aromatic hydrocarbon carboxylic acid is sec-octylphenoxyacetic acid;

优选的，中性有机萃取剂包括中性有机磷(氧)萃取剂和/或长链烷基酯；更优选的，中性有机磷(氧)萃取剂为磷酸三丁酯、甲基膦酸二甲庚酯和三烷基膦氧化物中的任一种或多种；Preferably, the neutral organic extractant includes a neutral organic phosphorus (oxy) extractant and / or a long-chain alkyl ester; more preferably, the neutral organic phosphorus (oxy) extractant is tributyl phosphate, methylphosphonic acid Any one or more of dimethylheptyl ester and trialkylphosphine oxide;

优选的，碱性萃取剂包括有机胺萃取剂；更优选的，有机胺萃取剂为烷基季胺、叔胺、仲胺、伯胺中的任一种或多种；进一步优选的，烷基季胺为氯化甲基三烷基铵，叔胺为三辛胺N235，仲胺为N-十二烯基三烷基甲胺，伯胺为1，1′，1″-三烷基甲胺。Preferably, the alkaline extractant includes an organic amine extractant; more preferably, the organic amine extractant is any one or more of an alkyl quaternary amine, a tertiary amine, a secondary amine, and a primary amine; further preferably, an alkyl amine The quaternary amine is methyltrialkylammonium chloride, the tertiary amine is trioctylamine N235, the secondary amine is N-dodecenyltrialkylmethylamine, and the primary amine is 1,1 ′, 1 ″ -trialkylmethyl amine.

优选的，有机螯合萃取剂包括β-二酮萃取剂；更优选的，β-二酮萃取剂为噻吩甲酰三氟丙酮和/或4-苯甲酰-3-甲基-1-苯基-5-吡唑啉酮。Preferably, the organic chelating extractant includes a β-diketone extractant; more preferably, the β-diketone extractant is thienyltrifluoroacetone and / or 4-benzoyl-3-methyl-1-benzene 5--5-pyrazolone.

进一步地，含有机萃取剂的有机溶剂溶液中的有机溶剂为密度小于水的烷烃类或其混和物、芳香烃类、有机醇、有机醚或有机酯中的至少一种；Further, the organic solvent in the organic solvent solution containing the organic extractant is at least one of alkanes or mixtures thereof, aromatic hydrocarbons, organic alcohols, organic ethers, or organic esters having a density less than water;

优选的，烷烃类或其混和物包括正庚烷、正己烷和煤油；Preferably, the alkanes or mixtures thereof include n-heptane, n-hexane and kerosene;

优选的，芳香烃类包括苯和甲苯；Preferably, the aromatic hydrocarbons include benzene and toluene;

优选的，有机醇包括正己醇和异辛醇；Preferably, the organic alcohol includes n-hexanol and isooctanol;

优选的，有机醚包括***；Preferably, the organic ether includes diethyl ether;

优选的，有机酯包括乙酸乙酯。Preferably, the organic ester includes ethyl acetate.

进一步地，含有机萃取剂的有机溶剂溶液中有机萃取剂的浓度为0.01mol/L～10mol/L。Further, the concentration of the organic extractant in the organic solvent solution containing the organic extractant is 0.01 mol / L to 10 mol / L.

进一步地，含钪无机酸溶液为含钪的硫酸溶液、盐酸溶液或硝酸溶液；任选的，含钪无机酸溶液中含有其它金属离子。Further, the scandium-containing inorganic acid solution is a scandium-containing sulfuric acid solution, a hydrochloric acid solution, or a nitric acid solution; optionally, the scandium-containing inorganic acid solution contains other metal ions.

进一步地，沉淀剂溶液为氢氧化钠、氨水、草酸、氢氟酸、磷酸、草酸钠、碳酸钠、碳酸氢钠、磷酸钠、氟化钠、草酸铵、磷酸铵中一种或多种的水溶液。Further, the precipitant solution is one or more of sodium hydroxide, ammonia, oxalic acid, hydrofluoric acid, phosphoric acid, sodium oxalate, sodium carbonate, sodium bicarbonate, sodium phosphate, sodium fluoride, ammonium oxalate, and ammonium phosphate. Aqueous solution.

进一步地，沉淀剂溶液中的沉淀剂的浓度为0.01mol/L～15mol/L。Further, the concentration of the precipitating agent in the precipitating agent solution is 0.01 mol / L to 15 mol / L.

进一步地，含有机萃取剂的有机溶剂溶液与含钪无机酸溶液的体积比为(1：20)～(1：1)。Further, the volume ratio of the organic solvent solution containing the organic extractant to the rhenium-containing inorganic acid solution is (1:20) to (1: 1).

进一步地，含有钪的有机相与沉淀剂溶液的体积比为(1：20)～(20：1)。Further, the volume ratio of the organic phase containing rhenium to the precipitant solution is (1:20) to (20: 1).

进一步地，空载有机相返回S1中钪萃取处理步骤使用；Further, the unloaded organic phase is returned to S1 in the tritium extraction treatment step for use;

优选的，S1与S2之间还包括对含有钪的有机相进行洗涤的步骤。Preferably, a step of washing the organic phase containing rhenium is further included between S1 and S2.

进一步地，钪萃取和沉淀反萃取处理中均采用机械搅拌的混合方式加快反应进度。Further, in the mash extraction and precipitation back-extraction treatment, mechanical mixing is adopted to accelerate the reaction progress.

进一步地，富集钪的方法所使用的设备为带搅拌混合作用的反应釜、混合澄清萃取槽或管式萃取器，以及离心机、真空过滤器或压滤机，或离心萃取混合分离一体设备，上述设备单独使用或联合使用。Further, the equipment used in the method for enriching thorium is a reaction kettle with agitation and mixing, a clarification extraction tank or a tube extractor, and a centrifuge, a vacuum filter or a filter press, or a centrifugal extraction and mixing integrated equipment The above equipment is used alone or in combination.

进一步地，该方法包括以下步骤：S11，利用含酸性有机磷萃取剂的有机溶剂溶液对含钪无机酸溶液进行钪萃取，获得含有钪的有机相；S12，对含有钪的有机相进行洗涤处理以除去杂质；S13，向除去杂质后的含有钪的有机相中加入浓NaOH或KOH溶液进行反萃取，液液分离后得到钪络阴离子溶液和空载有机相；S14，向钪络阴离子溶液中加入盐酸调节溶液的酸碱度，以生成Sc(OH) ₃沉淀，固液分离后得到Sc(OH) ₃沉淀和沉淀母液；S15，将Sc(OH) ₃沉淀煅烧得到氧化钪。 Further, the method includes the following steps: S11, using an organic solvent solution containing an acidic organic phosphorus extractant to perform a rhenium extraction of the rhenium-containing inorganic acid solution to obtain an organic phase containing rhenium; S12, performing a washing treatment on the organic phase containing rhenium To remove impurities; S13, add concentrated NaOH or KOH solution to the organic phase containing tritium after removing the impurities for back extraction, and obtain the complex anion solution and unloaded organic phase after liquid-liquid separation; S14, add the complex anion solution Hydrochloric acid was added to adjust the pH of the solution to generate Sc (OH) ₃ precipitates. After solid-liquid separation, Sc (OH) ₃ precipitates and mother liquors were obtained. S15, Sc (OH) ₃ precipitates were calcined to obtain hafnium oxide.

进一步地，S13中NaOH或KOH溶液的浓度为4mol/L～8mol/L。Further, the concentration of the NaOH or KOH solution in S13 is 4 mol / L to 8 mol / L.

进一步地，酸性有机磷萃取剂选自由二(2-乙基己基)磷酸、2-乙基己基磷酸单-2-乙基己基酯和Cyanex272萃取剂组成的组中的一种或多种。Further, the acidic organic phosphorus extractant is one or more selected from the group consisting of bis (2-ethylhexyl) phosphoric acid, 2-ethylhexyl phosphate mono-2-ethylhexyl ester, and Cyanex272 extractant.

进一步地，含酸性有机磷萃取剂的有机溶剂溶液中的有机萃取剂为密度小于水的烷烃类或其混和物、芳香烃类、有机醇、有机醚或有机酯中的至少一种；优选的，烷烃类或其混和物包括正庚烷、正己烷和煤油；优选的，芳香烃类包括苯和甲苯；优选的，有机醇包括正己醇和异辛醇；优选的，有机醚包括***；优选的，有机酯包括乙酸乙酯。Further, the organic extractant in the organic solvent solution containing the acidic organic phosphorus extractant is at least one of alkanes or their mixtures, aromatic hydrocarbons, organic alcohols, organic ethers, or organic esters with a density less than water; , Alkanes or mixtures thereof include n-heptane, n-hexane and kerosene; preferably, aromatic hydrocarbons include benzene and toluene; preferably, organic alcohols include n-hexanol and isooctanol; preferably, organic ethers include diethyl ether; preferred Organic esters include ethyl acetate.

进一步地，含酸性有机磷萃取剂的有机溶剂溶液中含酸性有机磷萃取剂的浓度为0.01mol/L～4mol/L。Further, the concentration of the acidic organic phosphorus extractant in the organic solvent solution containing the acidic organic phosphorus extractant is 0.01 mol / L to 4 mol / L.

进一步地，含钪无机酸溶液为含钪的硫酸溶液、盐酸溶液或硝酸溶液。Further, the rhenium-containing inorganic acid solution is a rhenium-containing sulfuric acid solution, a hydrochloric acid solution, or a nitric acid solution.

进一步地，含酸性有机磷萃取剂的有机溶剂溶液与含钪无机酸溶液的体积比为(1：20)～(1：1)。Further, the volume ratio of the organic solvent solution containing the acidic organic phosphorus extractant to the rhenium-containing inorganic acid solution is (1:20) to (1: 1).

进一步地，含酸性有机磷萃取剂的有机溶剂溶液与S13中NaOH或KOH溶液的体积比为(1：20)～(20：1)。Further, the volume ratio of the organic solvent solution containing the acidic organic phosphorus extractant to the NaOH or KOH solution in S13 is (1:20) to (20: 1).

进一步地，S14与S15之间还包括：分别用乙醇和水洗涤Sc(OH) ₃沉淀。 Further, S14 and S15 further include: washing the Sc (OH) ₃ precipitate with ethanol and water, respectively.

进一步地，用乙醇洗涤的温度为20～40℃，用水洗涤的温度为50～90℃。Furthermore, the temperature for washing with ethanol is 20 to 40 ° C, and the temperature for washing with water is 50 to 90 ° C.

进一步地，S12中，洗涤处理所用洗涤液为0.1～4mol/L的盐酸水溶液或0.1～1mol/L的硫酸水溶液。Further, in S12, the washing liquid used for the washing treatment is a 0.1 to 4 mol / L hydrochloric acid aqueous solution or a 0.1 to 1 mol / L sulfuric acid aqueous solution.

进一步地，空载有机相返回S11中钪萃取处理步骤使用。Further, the unloaded organic phase is returned to the step S11 of the tritium extraction treatment step for use.

进一步地，钪萃取和反萃取处理中均采用机械搅拌的混合方式加快反应进度。Further, in the mash extraction and back extraction processing, a mechanical stirring mixing method is adopted to accelerate the reaction progress.

进一步地，反萃取的反应温度为20～90℃，优选为50～70℃。Further, the reaction temperature of the back extraction is 20 to 90 ° C, and preferably 50 to 70 ° C.

进一步地，S14中向钪络阴离子溶液中加入盐酸调节溶液酸碱度，以生成Sc(OH) ₃沉淀，沉淀终点pH为5.0～8.0。 Further, in S14, hydrochloric acid is added to the complex anion solution to adjust the pH of the solution to form a Sc (OH) ₃ precipitate, and the pH of the precipitation end point is 5.0 to 8.0.

进一步地，S15中将Sc(OH) ₃沉淀煅烧以生成氧化钪的温度为400～650℃。 Further, the temperature of Sc (OH) ₃ precipitation and calcination in S15 to generate hafnium oxide is 400-650 ° C.

进一步地，该方法包括以下步骤：S21，利用含有机羧酸萃取剂的有机溶剂溶液对含钪无机酸溶液进行钪萃取，获得含有钪的有机相；S22，向含有钪的有机相中加入浓NaOH或KOH溶液进行反萃取，液液分离后得到钪络阴离子溶液和空载有机相；S23，向钪络阴离子溶液中加入盐酸调节溶液的酸碱度，以生成Sc(OH) ₃沉淀，固液分离后得到Sc(OH) ₃沉淀和沉淀母液；S24，将Sc(OH) ₃沉淀煅烧得到粗氧化钪；S25，将粗氧化钪用盐酸水溶液进行洗涤，去除杂质元素，得到氧化钪。 Further, the method includes the following steps: S21, using an organic solvent solution containing an organic carboxylic acid extractant to perform a rhenium extraction of the rhenium-containing inorganic acid solution to obtain an organic phase containing rhenium; S22, adding a concentrated organic phase to the organic phase containing rhenium NaOH or KOH solution is subjected to back extraction. After the liquid-liquid separation, a complex anion solution and an unloaded organic phase are obtained; S23, hydrochloric acid is added to the complex anion solution to adjust the pH of the solution to form a Sc (OH) ₃ precipitate. Sc (OH) ₃ precipitation and precipitation mother liquor are obtained; S24, Sc (OH) ₃ precipitation is calcined to obtain crude hafnium oxide; S25, crude hafnium oxide is washed with a hydrochloric acid aqueous solution to remove impurity elements to obtain hafnium oxide.

进一步地，S22中NaOH或KOH溶液的浓度为4mol/L～8mol/L。Further, the concentration of the NaOH or KOH solution in S22 is 4 mol / L to 8 mol / L.

进一步地，有机羧酸萃取剂选自由烷烃基羧酸、芳香烃基羧酸和环烷酸组成的组中的一种或多种；优选的，烷烃基羧酸为正己酸；优选的，芳香烃基羧酸为仲辛基苯氧基乙酸。Further, the organic carboxylic acid extractant is one or more selected from the group consisting of an alkane carboxylic acid, an aromatic carboxylic acid, and a naphthenic acid; preferably, the alkane carboxylic acid is n-hexanoic acid; preferably, an aromatic hydrocarbon group The carboxylic acid is sec-octylphenoxyacetic acid.

进一步地，含有机羧酸萃取剂的有机溶剂溶液中的有机萃取剂为密度小于水的烷烃类或其混和物、芳香烃类、有机醇、有机醚或有机酯中的至少一种；优选的，烷烃类或其混和物包括正庚烷、正己烷和煤油；优选的，芳香烃类包括苯和甲苯；优选的，有机醇包括正己醇和异辛醇；优选的，有机醚包括***；优选的，有机酯包括乙酸乙酯。Further, the organic extractant in the organic solvent solution containing the organic carboxylic acid extractant is at least one of alkanes or their mixtures, aromatic hydrocarbons, organic alcohols, organic ethers, or organic esters with a density less than water; , Alkanes or mixtures thereof include n-heptane, n-hexane and kerosene; preferably, aromatic hydrocarbons include benzene and toluene; preferably, organic alcohols include n-hexanol and isooctanol; preferably, organic ethers include diethyl ether; preferred Organic esters include ethyl acetate.

进一步地，含有机羧酸萃取剂的有机溶剂溶液中有机羧酸萃取剂的浓度为0.01mol/L～4mol/L。Further, the concentration of the organic carboxylic acid extractant in the organic solvent solution containing the organic carboxylic acid extractant is 0.01 mol / L to 4 mol / L.

进一步地，含钪无机酸溶液为含钪的硫酸溶液、盐酸溶液或硝酸溶液，任选的，含钪无机酸溶液中含有其它金属离子，其它金属离子为Ca ²⁺、Mg ²⁺、Mn ²⁺、Ni ²⁺、Al ³⁺、Fe ³⁺、Cr ³⁺中的一种或多种。 Further, the rhenium-containing inorganic acid solution is a rhenium-containing sulfuric acid solution, a hydrochloric acid solution, or a nitric acid solution. Optionally, the rhenium-containing inorganic acid solution contains other metal ions, and the other metal ions are Ca ²⁺ , Mg ²⁺ , and Mn ² One or more of ⁺ , Ni2 ⁺ , Al3 ⁺ , Fe3 ⁺ , and Cr3 ⁺ .

进一步地，含有机羧酸萃取剂的有机溶剂溶液与含钪无机酸溶液的体积比为(1：10)～(1：1)；优选的，利用含有机羧酸萃取剂的有机溶剂溶液对含钪无机酸溶液进行钪萃取，用NaOH控制含钪无机酸溶液的终点pH为2～4。Further, the volume ratio of the organic solvent solution containing the organic carboxylic acid extractant to the rhenium-containing inorganic acid solution is (1:10) to (1: 1); preferably, the organic solvent solution containing the organic carboxylic acid extractant is used to The tritium-containing inorganic acid solution was subjected to tritium extraction, and the end pH of the tritium-containing inorganic acid solution was controlled by NaOH to be 2 to 4.

进一步地，含有机羧酸萃取剂的有机溶剂溶液与S22中NaOH或KOH溶液的体积比为(1：10)～(10：1)。Further, the volume ratio of the organic solvent solution containing the organic carboxylic acid extractant to the NaOH or KOH solution in S22 is (1:10) to (10: 1).

进一步地，S23与S24之间还包括：分别用乙醇和水洗涤Sc(OH) ₃沉淀。 Further, S23 and S24 further include: washing the Sc (OH) ₃ precipitate with ethanol and water, respectively.

进一步地，S25中，所用盐酸水溶液的浓度为0.01～0.5mol/L；优选的，将粗氧化钪用盐酸水溶液进行洗涤，温度为10～30℃；优选的，将粗氧化钪用盐酸水溶液进行洗涤后再用水洗涤，然后干燥。Further, in S25, the concentration of the aqueous hydrochloric acid solution used is 0.01 to 0.5 mol / L; preferably, the crude hafnium oxide is washed with an aqueous hydrochloric acid solution at a temperature of 10 to 30 ° C; preferably, the crude hafnium oxide is washed with an aqueous hydrochloric acid solution. After washing, it was washed with water and then dried.

进一步地，空载有机相返回S21中钪萃取处理步骤使用；沉淀母液加入NaOH后返回S22钪反萃取处理步骤中使用。Further, the no-load organic phase is returned to the step S21 in the extraction treatment step; after adding NaOH to the precipitation mother liquor, it is returned to the step S22 in the extraction treatment step.

进一步地，反萃取的反应温度为20～90℃，优选为40～60℃。Further, the reaction temperature of the back extraction is 20 to 90 ° C, and preferably 40 to 60 ° C.

进一步地，S23中向钪络阴离子溶液中加入盐酸调节溶液酸碱度，以生成Sc(OH) ₃沉淀，沉淀终点pH为5.0～8.0。 Further, in S23, hydrochloric acid is added to the complex anion solution to adjust the pH of the solution to form a Sc (OH) ₃ precipitate, and the pH of the precipitation end point is 5.0 to 8.0.

进一步地，S25中将Sc(OH) ₃沉淀煅烧以生成氧化钪的温度为400～650℃。 Further, the temperature of Sc (OH) ₃ precipitation and calcination in S25 to generate hafnium oxide is 400-650 ° C.

根据本发明的另一方面，提供了一种富集金属的方法。该方法包括以下步骤：S1，利用有机萃取剂或含有机萃取剂的有机溶剂溶液对含金属无机酸溶液进行金属萃取，获得含有金属的有机相；S2，利用沉淀剂溶液对含有金属的有机相进行沉淀反萃取处理，固液分离及液液分离后获得含有金属的沉淀，以及沉淀母液和空载的有机相。According to another aspect of the invention, a method for enriching metals is provided. The method includes the following steps: S1, performing a metal extraction on a metal-containing inorganic acid solution using an organic extractant or an organic solvent solution containing an organic extractant to obtain a metal-containing organic phase; S2, using a precipitant solution to the metal-containing organic phase Precipitation back-extraction treatment, solid-liquid separation and liquid-liquid separation are used to obtain a metal-containing precipitate, as well as the mother liquor of precipitation and the unloaded organic phase.

应用本发明的技术方案，将负载有机相中的钪，通过加入沉淀剂溶液，同时起到反萃和沉淀的作用，从有机相中直接得到钪的沉淀，这样缩短了操作流程，使用沉淀剂，不使用反萃剂，减少了反萃剂、水等原料消耗，减少了操作费用。By applying the technical solution of the present invention, the tritium in the supported organic phase is added to the precipitant solution to simultaneously perform back-extraction and precipitation to directly obtain the precipitate of the tritium from the organic phase. This shortens the operation process and uses a precipitant. No back-extracting agent is used, reducing the consumption of back-extracting agent, water and other raw materials, and reducing operating costs.

附图说明BRIEF DESCRIPTION OF THE DRAWINGS

构成本申请的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中：The accompanying drawings, which constitute a part of this application, are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and the descriptions thereof are used to explain the present invention, and do not constitute an improper limitation on the present invention. In the drawings:

图1示出了一种传统富集钪的流程示意图；FIG. 1 shows a schematic flowchart of a conventional enriched plutonium;

图2示出了根据本发明一实施方式的富集钪的流程示意图；FIG. 2 is a schematic flowchart of enriched radon according to an embodiment of the present invention; FIG.

图3示出了根据本发明另一实施方式的富集钪的流程示意图；以及FIG. 3 is a schematic flowchart of enriched radon according to another embodiment of the present invention; and

图4示出了根据本发明又一实施方式的富集钪的流程示意图。FIG. 4 is a schematic flowchart of enriched radon according to another embodiment of the present invention.

具体实施方式detailed description

需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将参考附图并结合实施例来详细说明本发明。It should be noted that, in the case of no conflict, the embodiments in the present application and the features in the embodiments can be combined with each other. The present invention will be described in detail below with reference to the drawings and embodiments.

针对现有技术中提取氧化钪存在的技术问题，本发明提出了下述技术方案：In view of the technical problems existing in the prior art for extracting thorium oxide, the present invention proposes the following technical solutions:

根据本发明一种典型的试试方式，提供一种富集钪的方法。该方法包括以下步骤：S1，利用有机萃取剂或含有机萃取剂的有机溶剂溶液对含钪无机酸溶液进行钪萃取，获得含有钪的有机相；S2，利用沉淀剂溶液对含有钪的有机相进行沉淀反萃取处理，固液分离及液液分离后获得含有钪的沉淀，以及沉淀母液和空载的有机相。According to a typical trial mode of the present invention, a method for enriching thorium is provided. The method includes the following steps: S1, using an organic extractant or an organic solvent solution containing an organic extractant to perform a rhenium extraction of a rhenium-containing inorganic acid solution to obtain an rhenium-containing organic phase; S2, using a precipitant solution to erbium-containing organic phase After performing precipitation back extraction treatment, solid-liquid separation and liquid-liquid separation, a precipitate containing thorium is obtained, as well as a precipitation mother liquor and an unloaded organic phase.

根据本发明一种典型的实施方式，有机萃取剂为选自由酸性有机萃取剂、中性有机萃取剂、碱性有机萃取剂和有机螯合萃取剂组成的组中的一种或多种；优选的，酸性有机萃取剂包括酸性有机磷萃取剂和/或有机羧酸萃取剂；更优选的，酸性有机磷萃取剂为二(2-乙基己基)磷酸(P204萃取剂)和/或2-乙基己基磷酸单-2-乙基己基酯(P507萃取剂)；更优选的，有机羧酸萃取剂为烷烃基羧酸、芳香烃基羧酸和环烷酸中的任一种或多种；进一步优选的，烷烃基羧酸为正己酸，芳香烃基羧酸为仲辛基苯氧基乙酸；优选的，中性有机萃取剂包括中性有机磷(氧)萃取剂和/或长链烷基酯等；更优选的，中性有机磷(氧)萃取剂为磷酸三丁酯(TBP萃取剂)、甲基膦酸二甲庚酯(P350萃取剂)和三烷基膦氧化物(Cyanex923)中的任一种或多种；优选的，碱性萃取剂包括有机胺萃取剂；更优选的，有机胺萃取剂为烷基季胺、叔胺、仲胺、伯胺中的任一种或多种；进一步优选的，烷基季胺为氯化甲基三烷基铵，叔胺为三辛胺N235，仲胺为N-十二烯基三烷基甲胺，伯胺为1，1′，1″-三烷基甲胺。优选的，有机螯合萃取剂包括β-二酮萃取剂；更优选的，β-二酮萃取剂为噻吩甲酰三氟丙酮thenoyl-trifluoroacetone(HTTA)和/或4-苯甲酰-3-甲基-1-苯基-5-吡唑啉酮(1-phenyl-3-methyl-4-benzoyl-pyrazolone-5)。According to a typical embodiment of the present invention, the organic extractant is one or more selected from the group consisting of an acidic organic extractant, a neutral organic extractant, a basic organic extractant, and an organic chelate extractant; preferably The acidic organic extractant includes an acidic organic phosphorus extractant and / or an organic carboxylic acid extractant; more preferably, the acidic organic phosphorus extractant is bis (2-ethylhexyl) phosphoric acid (P204 extractant) and / or 2- Ethylhexyl phosphate mono-2-ethylhexyl ester (P507 extractant); more preferably, the organic carboxylic acid extractant is any one or more of an alkane carboxylic acid, an aromatic carboxylic acid and a naphthenic acid; Further preferably, the alkane carboxylic acid is n-hexanoic acid, and the aromatic hydrocarbon carboxylic acid is sec-octylphenoxyacetic acid. Preferably, the neutral organic extractant includes a neutral organic phosphorus (oxygen) extractant and / or a long-chain alkyl group. Esters, etc .; more preferably, the neutral organic phosphorus (oxygen) extractant is tributyl phosphate (TBP extractant), dimethylheptyl methylphosphonate (P350 extractant), and trialkylphosphine oxide (Cyanex923) Any one or more of them; preferably, the alkaline extractant includes an organic amine extractant; more preferred The organic amine extractant is any one or more of a quaternary alkyl amine, a tertiary amine, a secondary amine, and a primary amine; more preferably, the quaternary alkyl amine is methyltrialkylammonium chloride, and the tertiary amine is trioctyl The amine N235, the secondary amine is N-dodecenyltrialkylmethylamine, and the primary amine is 1,1 ′, 1 ″ -trialkylmethylamine. Preferably, the organic chelating extractant includes a β-diketone extractant ; More preferably, the β-diketone extractant is thenoyl-trifluoroacetone (HTTA) and / or 4-benzoyl-3-methyl-1-phenyl-5-pyrazolinone ( 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5).

根据本发明一种典型的实施方式，含有机萃取剂的有机溶剂溶液中的有机溶剂为密度小于水的烷烃类或其混和物、芳香烃类、有机醇、有机醚或有机酯中的至少一种；优选的，烷烃类或其混和物包括正庚烷、正己烷和煤油；优选的，芳香烃类包括苯和甲苯；优选的，有机醇包括正己醇和异辛醇；优选的，有机醚包括***；优选的，有机酯包括乙酸乙酯。采用上述试剂，能够高效的萃取钪According to a typical embodiment of the present invention, the organic solvent in the organic solvent solution containing the organic extractant is at least one of alkanes or their mixtures, aromatic hydrocarbons, organic alcohols, organic ethers, or organic esters with a density less than water. Species; preferably, alkanes or mixtures thereof include n-heptane, n-hexane, and kerosene; preferably, aromatic hydrocarbons include benzene and toluene; preferably, organic alcohols include n-hexanol and isooctanol; preferably, organic ethers include Diethyl ether; preferably, the organic ester includes ethyl acetate. With the above reagents, it is possible to efficiently extract plutonium

为了进一步优化萃取剂的性能，含有机萃取剂的有机溶剂溶液中有机萃取剂的浓度为0.01mol/L～10mol/L。In order to further optimize the performance of the extractant, the concentration of the organic extractant in the organic solvent solution containing the organic extractant is 0.01 mol / L to 10 mol / L.

根据本发明一种典型的实施方式，含钪无机酸溶液为含钪的硫酸溶液、盐酸溶液或硝酸溶液；任选的，含钪无机酸溶液中含有其它金属离子。According to a typical embodiment of the present invention, the scandium-containing inorganic acid solution is a scandium-containing sulfuric acid solution, a hydrochloric acid solution, or a nitric acid solution; optionally, the scandium-containing inorganic acid solution contains other metal ions.

根据本发明一种典型的实施方式，沉淀剂溶液为氢氧化钠、氨水、草酸、氢氟酸、磷酸、草酸钠、碳酸钠、碳酸氢钠、磷酸钠、氟化钠、草酸铵、磷酸铵中一种或多种的水溶液，具体可以采用哪几种沉淀剂本领域技术人员可以根据本发明的技术教导进行选择。优选的，为了进一步优化沉淀反萃取的性能，沉淀剂溶液中的沉淀剂的浓度为0.01mol/L～15mol/L。According to a typical embodiment of the present invention, the precipitant solution is sodium hydroxide, ammonia, oxalic acid, hydrofluoric acid, phosphoric acid, sodium oxalate, sodium carbonate, sodium bicarbonate, sodium phosphate, sodium fluoride, ammonium oxalate, ammonium phosphate One or more of the aqueous solutions can be selected according to the technical teaching of the present invention. Preferably, in order to further optimize the performance of precipitation back extraction, the concentration of the precipitant in the precipitant solution is 0.01 mol / L to 15 mol / L.

优选的，含有机萃取剂的有机溶剂溶液与含钪无机酸溶液的体积比为(1：20)～(1：1)，在此比例范围内有利于钪被充分并高效的萃取出来；进一步优选的，含有钪的有机相与沉淀剂溶液的体积比为(1：20)～(20：1)。Preferably, the volume ratio of the organic solvent solution containing the organic extractant to the rhenium-containing inorganic acid solution is (1:20) to (1: 1), and the rhenium is fully and efficiently extracted in this ratio range; further Preferably, the volume ratio of the organic phase containing rhenium to the precipitant solution is (1:20) to (20: 1).

根据本发明一种典型的实施方式，空载有机相返回S1中钪萃取处理步骤使用，有利于原料的充分回收利用，降低生产成本；优选的，S1与S2之间还包括对含有钪的有机相进行洗涤的步骤，以除去同时萃取到的杂质。According to a typical embodiment of the present invention, the unloaded organic phase is returned to S1 for use in the plutonium extraction treatment step, which is conducive to the full recycling of raw materials and reduces the production cost. Preferably, S1 and S2 also include organic compounds containing plutonium. The phases are subjected to a washing step to remove impurities that are simultaneously extracted.

根据本发明一种典型的实施方式，钪萃取和沉淀反萃取处理中均采用机械搅拌的混合方式加快反应进度。According to a typical embodiment of the present invention, a mechanical stirring mixing method is used in both the mash extraction and the precipitation back extraction process to accelerate the reaction progress.

根据本发明一种典型的实施方式，富集钪的方法所使用的设备可以是带搅拌混合作用的反应釜、混合澄清萃取槽、管式萃取器等混合设备，以及离心机、真空过滤器、压滤机等分离设备，或者是离心萃取器等混合分离一体设备，这些设备可以单独使用，也可以联合使用。According to a typical embodiment of the present invention, the equipment used in the method for enriching thorium may be a mixing device such as a reaction kettle with stirring function, a mixing and clarifying extraction tank, a tubular extractor, and a centrifuge, a vacuum filter, Separation equipment such as filter presses, or hybrid separation and integration equipment such as centrifugal extractors, these equipment can be used alone or in combination.

根据本发明一种典型的试试方式，如图2所示，该方法包括以下步骤：利用有机萃取剂或含有机萃取剂的有机溶剂溶液对含钪无机酸溶液进行钪萃取，获得含有钪的有机相(含钪负载有机相)；对含有钪的有机相进行洗涤的步骤，以除去同时萃取到的杂质，利用沉淀剂溶液对含有钪的有机相进行沉淀反萃取处理，固液分离及液液分离后获得含有钪的沉淀。According to a typical trial mode of the present invention, as shown in FIG. 2, the method includes the following steps: using an organic extractant or an organic solvent solution containing an organic extractant to perform a rhenium extraction of a rhenium-containing inorganic acid solution to obtain a rhenium-containing Organic phase (containing rhenium-supported organic phase); washing the organic phase containing rhenium to remove impurities extracted at the same time, using a precipitant solution to carry out precipitation back extraction treatment of the organic phase containing rhenium, solid-liquid separation and liquid After the liquid separation, a precipitate containing thallium was obtained.

根据本发明一种典型的实施方式，提供一种富集金属的方法。该方法包括以下步骤：S1，利用有机萃取剂或含有机萃取剂的有机溶剂溶液对含金属无机酸溶液进行金属萃取，获得含有金属的有机相；S2，利用沉淀剂溶液对所述含有金属的有机相进行沉淀反萃取处理，固液分离及液液分离后获得含有金属的沉淀，以及沉淀母液和空载的有机相。According to a typical embodiment of the present invention, a method for enriching metals is provided. The method includes the following steps: S1, performing a metal extraction on a metal-containing inorganic acid solution using an organic extractant or an organic solvent solution containing an organic extractant to obtain a metal-containing organic phase; S2, using a precipitant solution to the metal-containing The organic phase is subjected to precipitation back-extraction treatment. After solid-liquid separation and liquid-liquid separation, a metal-containing precipitate is obtained, as well as a mother liquor and an unloaded organic phase.

也就是说本发明的方法与设备可通用于任何包含液液固三相反应、气液固三相反应的过程；金属不限于稀土(镧(La)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)、镥(Lu)，以及钪(Sc)和钇(Y)共17种元素，称为稀土元素)，也可以是镁(Mg)、(Al)、钙(Ca)、钒(V)、铬(Cr)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、铜(Cu)、锌(Zn)、钛(Ti)、锆(Zr)、铪(Hf)、钡(Ba)、铅(Pb)、锡(Sn)、银(Ag)、钍(Th)等金属；可广泛用于湿法冶金与材料制备，如包含三相的液液反应的溶剂萃取与液固分离的结合、气液反应生成固相产物。That is to say, the method and equipment of the present invention can be universally used in any process including liquid-liquid-solid three-phase reaction and gas-liquid-solid three-phase reaction; the metal is not limited to rare earths (lanthanum (La), europium (Sm), europium (Eu), Thorium (Gd), Thorium (Tb), Thorium (Dy), Thorium (Ho), Thorium (Er), Thorium (Tm), Thorium (Yb), Thorium (Lu), and Thorium (Sc) and Yttrium (Y) A total of 17 elements, called rare earth elements), can also be magnesium (Mg), (Al), calcium (Ca), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt ( Co), nickel (Ni), copper (Cu), zinc (Zn), titanium (Ti), zirconium (Zr), hafnium (Hf), barium (Ba), lead (Pb), tin (Sn), silver ( Ag), thorium (Th) and other metals; can be widely used in wet metallurgy and material preparation, such as the combination of solvent extraction and liquid-solid separation including three-phase liquid-liquid reaction, gas-liquid reaction to produce solid-phase products.

根据本发明一种典型的实施方式，提供一种提取氧化钪的方法。该方法包括以下步骤：S11，利用含酸性有机磷萃取剂的有机溶剂溶液对含钪无机酸溶液进行钪萃取，获得含有钪的有机相；S12，对含有钪的有机相进行洗涤处理以除去杂质；S13，向除去杂质后的含有钪的有机相中加入浓NaOH或KOH溶液进行反萃取，液液分离后得到钪络阴离子溶液和空载有机相；S14向钪络阴离子溶液中加入盐酸调节溶液的酸碱度，以生成Sc(OH) ₃沉淀，固液分离后得到Sc(OH) ₃沉淀和沉淀母液；S15，将Sc(OH) ₃沉淀煅烧得到氧化钪。 According to a typical embodiment of the present invention, a method for extracting thorium oxide is provided. The method includes the following steps: S11, using an organic solvent solution containing an acidic organic phosphorus extractant to perform thorium extraction on a thorium-containing inorganic acid solution to obtain a thallium-containing organic phase; S12, performing a washing treatment on the thallium-containing organic phase to remove impurities ; S13, adding concentrated NaOH or KOH solution to the organic phase containing tritium after removing impurities for back extraction, liquid-liquid separation to obtain tritium anion solution and unloaded organic phase; S14 adding hydrochloric acid to the tritium anion solution to adjust the solution PH to produce Sc (OH) ₃ precipitates. After solid-liquid separation, Sc (OH) ₃ precipitates and precipitated mother liquor; S15, Sc (OH) ₃ precipitates are calcined to obtain hafnium oxide.

在本发明中，“浓NaOH或KOH溶液”是指本领域普通意义上的浓NaOH或KOH溶液，优选的S13中NaOH溶液的浓度为4mol/L～8mol/L。In the present invention, "concentrated NaOH or KOH solution" refers to a concentrated NaOH or KOH solution in the ordinary sense in the art, and the preferred concentration of the NaOH solution in S13 is 4 mol / L to 8 mol / L.

萃取反应为(HA代表萃取剂，脚标 _(o)代表有机相)：Sc ³⁺+3HA _(o)→ScA _3(o)+3H ⁺ The extraction reaction is (HA stands for extractant, subscript _(o) stands for organic phase): Sc ³⁺ + 3HA _(o) → ScA _{3 (o)} + 3H ⁺

反萃取反应为：ScA _3(o)+6NaOH→3NaA _(o)+Sc(OH) ₆ ^3-+3Na ⁺ The back extraction reaction is: ScA _{3 (o)} + 6NaOH → 3NaA _(o) + Sc (OH) ₆ ^3- + 3Na ⁺

沉淀反应为：Sc(OH) ₆ ^3-+3H ³⁺→Sc(OH) ₃↓+3H ₂O The precipitation reaction is: Sc (OH) ₆ ^3- + 3H ³⁺ → Sc (OH) ₃ ↓ + 3H ₂ O

煅烧反应为：2Sc(OH) ₃→Sc ₂O ₃+3H ₂O↑ The calcination reaction is: 2Sc (OH) ₃ → Sc ₂ O ₃ + 3H ₂ O ↑

本发明利用含酸性有机磷萃取剂的有机相(含酸性有机磷萃取剂的有机溶剂溶液)对含钪料液(含钪无机酸溶液)进行钪萃取处理，以便获得含有钪的负载有机相；含有钪的有机相洗涤处理以除去同时萃取的杂质；将上述除杂后的有机相加入浓NaOH溶液进行反萃，以生成可溶性的钪络阴离子溶液，向钪络阴离子溶液中加入盐酸以调节溶液的酸度，以生成Sc(OH) ₃沉淀；将生成的Sc(OH) ₃沉淀煅烧以生成氧化钪。利用该方法可以有效地从含钪溶液中富集提取氧化钪。该方法反萃效率高、沉淀效率高，操作流程缩短，反萃酸、中和碱、水、草酸等原料消耗减少，操作费用减少，利于应用于工业生产。 The present invention uses an organic phase containing an acidic organic phosphorus extractant (an organic solvent solution containing an acidic organic phosphorus extractant) to perform a tritium extraction treatment on a tritium-containing material solution (a tritium-containing inorganic acid solution), so as to obtain a supported organic phase containing tritium; The organic phase containing tritium is washed to remove impurities that are extracted at the same time; the above-removed organic phase is added to a concentrated NaOH solution for back extraction to generate a soluble tritium anion solution, and hydrochloric acid is added to the tritium anion solution to adjust the solution Acidity to produce Sc (OH) ₃ precipitates; the generated Sc (OH) ₃ precipitates are calcined to form osmium oxide. This method can effectively enrich and extract thorium oxide from thorium-containing solution. The method has high back-extraction efficiency, high precipitation efficiency, shortened operation process, reduced consumption of back-extracted acid, neutralized alkali, water, oxalic acid and other raw materials, and reduced operating costs, which is beneficial to industrial production.

优选的，酸性有机磷萃取剂选自由二(2-乙基己基)磷酸(P204萃取剂)、2-乙基己基磷酸单-2-乙基己基酯(P507萃取剂)和Cyanex272萃取剂组成的组中的一种或多种；含酸性有机磷萃取剂的有机溶剂溶液中的有机萃取剂为密度小于水的烷烃类或其混和物、芳香烃类、有机醇、有机醚或有机酯中的至少一种；更优选的，烷烃类或其混和物包括正庚烷、正己烷和煤油；更优选的，芳香烃类包括苯和甲苯；更优选的，有机醇包括正己醇和异辛醇；更优选的，有机醚包括***；更优选的，有机酯包括乙酸乙酯。采用上述试剂，能够高效的萃取钪。Preferably, the acidic organic phosphorus extractant is selected from the group consisting of bis (2-ethylhexyl) phosphoric acid (P204 extractant), 2-ethylhexyl phosphate mono-2-ethylhexyl phosphate (P507 extractant), and Cyanex272 extractant. One or more of the group; the organic extractant in the organic solvent solution containing the acidic organic phosphorus extractant is an alkane or its mixture, aromatic hydrocarbon, organic alcohol, organic ether or organic ester with a density less than water At least one; more preferably, alkanes or mixtures thereof include n-heptane, n-hexane, and kerosene; more preferably, aromatic hydrocarbons include benzene and toluene; more preferably, organic alcohols include n-hexanol and isooctanol; more preferably Preferably, the organic ether includes diethyl ether; more preferably, the organic ester includes ethyl acetate. With the above reagents, radon can be efficiently extracted.

为了进一步优化萃取剂的性能，含酸性有机磷萃取剂的有机溶剂溶液(又称萃取剂)中含酸性有机磷萃取剂的浓度为0.01mol/L～4mol/L。In order to further optimize the performance of the extractant, the concentration of the acidic organic phosphorus extractant in the organic solvent solution (also referred to as the extractant) containing the acidic organic phosphorus extractant is 0.01 mol / L to 4 mol / L.

根据本发明一种典型的实施方式，含钪无机酸溶液为含钪的硫酸溶液、盐酸溶液或硝酸溶液，当然，含钪无机酸溶液中可以含有其它金属离子。According to a typical embodiment of the present invention, the scandium-containing inorganic acid solution is a scandium-containing sulfuric acid solution, a hydrochloric acid solution, or a nitric acid solution. Of course, the scandium-containing inorganic acid solution may contain other metal ions.

优选的，含酸性有机磷萃取剂的有机溶剂溶液与含钪无机酸溶液的体积比为(1：20)～(1：1)，在此比例范围内有利于钪被充分并高效的萃取出来。优选的，含酸性有机磷萃取剂的有机溶剂溶液与S13中NaOH溶液的体积比为(1：20)～(20：1)，在此比例范围内有利于钪被充分并高效的反萃取出来。Preferably, the volume ratio of the organic solvent solution containing the acidic organic phosphorus extractant to the osmium-containing inorganic acid solution is (1:20) to (1: 1), and in this range of ratio, the rhenium is fully and efficiently extracted. . Preferably, the volume ratio of the organic solvent solution containing the acidic organic phosphorus extractant to the NaOH solution in S13 is (1:20) to (20: 1), and in this range of ratio, it is favorable for the radon to be fully and efficiently back-extracted. .

根据本发明一种典型的实施方式，S14与S15之间还包括：分别用乙醇和水洗涤Sc(OH) ₃沉淀，以便于分别除去表面吸附的有机物和水溶性杂质。优选的，乙醇洗涤温度为20～40℃，水洗涤温度为50～90℃。 According to a typical embodiment of the present invention, S14 and S15 further include: washing the Sc (OH) ₃ precipitate with ethanol and water, respectively, so as to remove organic matters adsorbed on the surface and water-soluble impurities, respectively. Preferably, the ethanol washing temperature is 20-40 ° C, and the water washing temperature is 50-90 ° C.

优选的，S12中，所用洗涤液为0.1～4mol/L的盐酸水溶液或0.1～1mol/L的硫酸水溶液。Preferably, in S12, the washing solution used is a 0.1 to 4 mol / L hydrochloric acid aqueous solution or a 0.1 to 1 mol / L sulfuric acid aqueous solution.

根据本发明一种典型的实施方式，将S13中的沉淀母液加入NaOH后返回反萃取处理步骤使用，空载有机相返回S11中钪萃取处理步骤使用，有利于原料的充分回收利用，降低生产成本。According to a typical embodiment of the present invention, the precipitated mother liquor in S13 is added to NaOH and returned to the back-extraction treatment step, and the unloaded organic phase is returned to S11 to be used in the radon extraction treatment step, which is conducive to the full recovery of raw materials and reduces production costs. .

根据本发明一种典型的实施方式，钪萃取和反萃取处理中均采用机械搅拌的混合方式加快反应进度。According to a typical embodiment of the present invention, the mixing process of mechanical stirring is used in both the mash extraction and the back extraction process to accelerate the reaction progress.

优选的，反萃取的反应温度为20～90℃，更优选为50～70℃。Preferably, the reaction temperature of the back extraction is 20 to 90 ° C, and more preferably 50 to 70 ° C.

优选的，向钪络阴离子溶液中加入盐酸调节溶液酸碱度，以生成Sc(OH) ₃沉淀，沉淀终点pH为5.0～8.0。 Preferably, hydrochloric acid is added to the complex anion solution to adjust the pH of the solution to generate a Sc (OH) ₃ precipitate, and the pH of the end point of the precipitation is 5.0-8.0.

优选的，S14中将Sc(OH) ₃沉淀煅烧以生成氧化钪的温度为400～650℃ Preferably, the temperature at which Sc (OH) _{3 is} precipitated and calcined in S14 to generate hafnium oxide is 400-650 ° C.

根据本发明一种典型的实施方式，如图3所示，该方法包括：利用含酸性有机磷萃取剂的有机相对含钪料液进行钪萃取处理，以便获得含有钪的负载有机相，控制萃取剂浓度等反应条件，并使有机相体积小于水相体积，从而使得钪得到富集并与杂质离子(如Ca ²⁺、Mg ²⁺、Zn ²⁺、Mn ²⁺、Ni ²⁺、Co ²⁺、Al ³⁺、Fe ³⁺、Cr ³⁺等)分离；对含有钪的有机相用洗涤处理，可以除去同时萃取或夹带的少量杂质离子，使得钪进一步纯化；将上述除杂后的有机相加入浓NaOH溶液进行反萃，通过控制反萃取剂浓度、温度、有机相：水相体积比等反应条件，以生成可溶性的钪络阴离子Sc(OH) ₆ ^3-溶液，反萃效率高，有机相与水相分离效果好；向钪盐溶液中加入盐酸以调节溶液的酸度，以生成Sc(OH) ₃沉淀，通过控制沉淀终点pH、温度等反应条件，使生成的Sc(OH) ₃沉淀有高的沉淀效率、并利于下步的过滤；将Sc(OH) ₃沉淀分别用乙醇和水在选定的温度下洗涤，以分别除去表面吸附的有机物和水溶性杂质，钪得到进一步纯化，并且洗涤后的Sc(OH) ₃沉淀有更好的被过滤性能；将生成的Sc(OH) ₃沉淀煅烧以生成氧化钪，煅烧温度(400～650℃)较草酸钪煅烧温度(700～800℃)等低，且生成水蒸气而不是温室气体CO ₂。利用该方法可以有效地从含钪溶液中富集提取氧化钪。 According to a typical embodiment of the present invention, as shown in FIG. 3, the method includes: performing an rhenium extraction treatment using an organic relative to a rhenium-containing feed liquid containing an acidic organic phosphorus extractant in order to obtain a supported organic phase containing rhenium and controlling the extraction Reaction conditions such as agent concentration, and the volume of the organic phase is smaller than the volume of the aqueous phase, so that the plutonium is enriched and reacted with impurity ions (such as Ca ²⁺ , Mg ²⁺ , Zn ²⁺ , Mn ²⁺ , Ni ²⁺ , Co ^{2 +} , Al ³⁺ , Fe ³⁺ , Cr ^3+, etc.); washing the organic phase containing rhenium by washing can remove a small amount of impurity ions that are extracted or entrained at the same time, so that the rhenium is further purified; Add concentrated NaOH solution for back extraction, control the reaction conditions such as the concentration of back extractant, temperature, volume ratio of organic phase: water phase, etc., to generate a soluble complex anion Sc (OH) ₆ ^3- solution with high back extraction efficiency. the organic phase and the aqueous phase was separated good effect; scandium salt solution was added hydrochloric acid to adjust the acidity of the solution, to form Sc (OH) ₃ precipitate, by controlling the end of the precipitation pH, temperature and other reaction conditions, so that the resulting Sc (OH) ₃ Precipitation has high precipitation efficiency, Filtered facilitate the next step; and Sc (OH) ₃ precipitate was washed at a selected temperature of ethanol and water, respectively to remove surface adsorbed organic matter and water-soluble impurities, scandium further purification, and after washing Sc (OH ) ₃ precipitate has better filtration performance; the Sc (OH) ₃ precipitate is calcined to generate ytterbium oxide, the calcination temperature (400-650 ° C) is lower than the calcination temperature of osmium oxalate (700-800 ° C), and the Water vapor instead of the greenhouse gas CO ₂ . This method can effectively enrich and extract thorium oxide from thorium-containing solution.

根据本发明一种典型的实施方式，提供一种提取氧化钪的方法。该方法包括以下步骤：S21，利用含有机羧酸萃取剂的有机溶剂溶液对含钪无机酸溶液进行钪萃取，获得含有钪的有机相；S22，向含有钪的有机相中加入浓NaOH或KOH溶液进行反萃取，液液分离后得到钪络阴离子溶液和空载有机相；S23，向钪络阴离子溶液中加入盐酸调节溶液的酸碱度，以生成Sc(OH) ₃沉淀，固液分离后得到Sc(OH) ₃沉淀和沉淀母液；S24，将Sc(OH) ₃沉淀煅烧得到粗氧化钪；S25，将粗氧化钪用盐酸水溶液进行洗涤，去除杂质元素，得到氧化钪。 According to a typical embodiment of the present invention, a method for extracting thorium oxide is provided. The method includes the following steps: S21, using an organic solvent solution containing an organic carboxylic acid extractant to perform thorium extraction on a thorium-containing inorganic acid solution to obtain a thallium-containing organic phase; S22, adding concentrated NaOH or KOH to the thallium-containing organic phase The solution is back-extracted, and the complex anion solution and the unloaded organic phase are obtained after liquid-liquid separation. S23, hydrochloric acid is added to the complex anion solution to adjust the pH of the solution to generate Sc (OH) ₃ precipitate. Sc is obtained after solid-liquid separation. (OH) ₃ precipitation and precipitation mother liquor; S24, Sc (OH) ₃ precipitation is calcined to obtain crude hafnium oxide; S25, crude hafnium oxide is washed with an aqueous hydrochloric acid solution to remove impurity elements to obtain hafnium oxide.

应用本发明的技术方案，反萃效率高、沉淀效率高，操作流程缩短，反萃酸、中和碱、水、草酸等原料消耗减少，操作费用减少，利于应用于工业生产。By applying the technical scheme of the present invention, the stripping efficiency is high, the precipitation efficiency is high, the operation process is shortened, the consumption of raw materials such as stripping acid, neutralizing alkali, water, and oxalic acid is reduced, and the operating cost is reduced, which is beneficial to the application in industrial production.

在本发明中，“浓NaOH或KOH溶液”是指本领域普通意义上的浓NaOH或KOH溶液，优选的S22中NaOH溶液的浓度为4mol/L～8mol/L。In the present invention, "concentrated NaOH or KOH solution" refers to a concentrated NaOH or KOH solution in the ordinary sense in the art, and the preferred concentration of the NaOH solution in S22 is 4 mol / L to 8 mol / L.

本发明利用含有机羧酸萃取剂的有机相(含有机羧酸萃取剂的有机溶剂溶液)对含钪料液(含钪无机酸溶液)进行钪萃取处理，以便获得含有钪的负载有机相；将有机相加入浓NaOH 溶液进行反萃，以生成可溶性的钪络阴离子溶液，向钪络阴离子溶液中加入盐酸以调节溶液的酸度，以生成Sc(OH) ₃沉淀；将生成的Sc(OH) ₃沉淀煅烧以生成粗氧化钪，将粗氧化钪用盐酸水溶液进行洗涤，去除杂质元素，得到氧化钪。利用该方法可以有效地从含钪溶液中富集提取氧化钪。该方法反萃效率高、沉淀效率高，操作流程缩短，反萃酸、中和碱、水、草酸等原料消耗减少，操作费用减少，利于应用于工业生产。 The present invention uses an organic phase containing an organic carboxylic acid extractant (an organic solvent solution containing an organic carboxylic acid extractant) to perform a rhenium extraction treatment on a mash-containing liquid (a fluorene-containing inorganic acid solution) to obtain a supported organic phase containing rhenium; The organic phase is added to a concentrated NaOH solution for back extraction to generate a soluble complex anion solution, and hydrochloric acid is added to the complex anion solution to adjust the acidity of the solution to form a Sc (OH) ₃ precipitate; the generated Sc (OH) _{3 The} precipitate is calcined to generate crude ytterbium oxide, and the crude ytterbium oxide is washed with an aqueous hydrochloric acid solution to remove impurity elements to obtain ytterbium oxide. This method can effectively enrich and extract thorium oxide from thorium-containing solution. The method has high back-extraction efficiency, high precipitation efficiency, shortened operation process, reduced consumption of back-extracted acid, neutralized alkali, water, oxalic acid and other raw materials, and reduced operating costs, which is beneficial to industrial production.

根据本发明一种典型的实施方式，利用经煅烧过的粗氧化钪溶于热的浓盐酸但不溶于或极微量溶于稀盐酸的特性，将生成的粗氧化钪用稀盐酸水溶液在较低温度下进行洗涤，以溶解除去其中的杂质元素，能将钪与杂质元素很好的分离，得到纯化的氧化钪。优选的，S25中，所用盐酸水溶液的浓度为0.01～0.5mol/L；更优选的，将粗氧化钪用盐酸水溶液进行洗涤，温度为10～30℃；进一步优选的，将粗氧化钪用盐酸水溶液进行洗涤后再用水洗涤，然后干燥。According to a typical embodiment of the present invention, the calcined crude ytterbium oxide is soluble in hot concentrated hydrochloric acid but insoluble or very slightly soluble in dilute hydrochloric acid. Washing is performed at a temperature to dissolve and remove the impurity elements therein, and the rhenium and the impurity elements can be well separated to obtain purified erbium oxide. Preferably, the concentration of the aqueous hydrochloric acid solution used in S25 is 0.01 to 0.5 mol / L; more preferably, the crude holmium oxide is washed with an aqueous hydrochloric acid solution at a temperature of 10 to 30 ° C; more preferably, the crude holmium oxide is washed with hydrochloric acid. The aqueous solution was washed with water and then dried.

根据本发明一种典型的实施方式，有机羧酸萃取剂选自由烷烃基羧酸、芳香烃基羧酸和环烷酸组成的组中的一种或多种；优选的，烷烃基羧酸为正己酸；优选的，芳香烃基羧酸为仲辛基苯氧基乙酸。采用上述试剂，能够高效的萃取钪。According to a typical embodiment of the present invention, the organic carboxylic acid extractant is one or more selected from the group consisting of an alkane carboxylic acid, an aromatic carboxylic acid, and a naphthenic acid; preferably, the alkane carboxylic acid is n-hexane Acid; preferably, the aromatic hydrocarbon carboxylic acid is sec-octylphenoxyacetic acid. With the above reagents, radon can be efficiently extracted.

优选的，含有机羧酸萃取剂的有机溶剂溶液中的有机萃取剂为密度小于水的烷烃类或其混和物、芳香烃类、有机醇、有机醚或有机酯中的至少一种；更优选的，烷烃类或其混和物包括正庚烷、正己烷和煤油；更优选的，芳香烃类包括苯和甲苯；更优选的，有机醇包括正己醇和异辛醇；更优选的，有机醚包括***；更优选的，有机酯包括乙酸乙酯。采用上述试剂，能够高效的萃取钪。Preferably, the organic extractant in the organic solvent solution containing the organic carboxylic acid extractant is at least one of alkanes or mixtures thereof, aromatic hydrocarbons, organic alcohols, organic ethers, or organic esters having a density less than water; more preferably Of these, alkanes or mixtures thereof include n-heptane, n-hexane and kerosene; more preferably, aromatic hydrocarbons include benzene and toluene; more preferably, organic alcohols include n-hexanol and isooctanol; more preferably, organic ethers include Diethyl ether; more preferably, the organic ester includes ethyl acetate. With the above reagents, radon can be efficiently extracted.

为了进一步优化萃取剂的性能，含有机羧酸萃取剂的有机溶剂溶液(又称萃取剂)中有机羧酸萃取剂的浓度为0.01mol/L～4mol/L。In order to further optimize the performance of the extractant, the concentration of the organic carboxylic acid extractant in the organic solvent solution (also known as the extractant) containing the organic carboxylic acid extractant is 0.01 mol / L to 4 mol / L.

根据本发明一种典型的实施方式，含钪无机酸溶液为含钪的硫酸溶液、盐酸溶液或硝酸溶液，任选的，含钪无机酸溶液中还可以含有其它金属离子，其它金属离子为Ca ²⁺、Mg ²⁺、Mn ²⁺、Ni ²⁺、Al ³⁺、Fe ³⁺、Cr ³⁺等中的一种或多种。 According to a typical embodiment of the present invention, the scandium-containing inorganic acid solution is a scandium-containing sulfuric acid solution, a hydrochloric acid solution, or a nitric acid solution. Optionally, the scandium-containing inorganic acid solution may further contain other metal ions, and the other metal ions are Ca. One or more of ²⁺ , ^{Mg2 +} , Mn2 ⁺ , Ni2 ⁺ , Al3 ⁺ , Fe3 ⁺ , Cr3 ^+, and the like.

优选的，含有机羧酸萃取剂的有机溶剂溶液与含钪无机酸溶液的体积比为(1：10)～(1：1)，在此比例范围内有利于钪被充分并高效的萃取出来；优选的，利用含有机羧酸萃取剂的有机溶剂溶液对含钪无机酸溶液进行钪萃取，用NaOH控制含钪无机酸溶液的终点pH为2～4。优选的，含有机羧酸萃取剂的有机溶剂溶液与S22中NaOH或KOH溶液的体积比为(1：10)～(10：1)，在此比例范围内有利于钪被充分并高效的反萃取出来。Preferably, the volume ratio of the organic solvent solution containing the organic carboxylic acid extractant to the rhenium-containing inorganic acid solution is (1:10) to (1: 1), and the rhenium is fully and efficiently extracted in this ratio range. Preferably, the rhenium-containing inorganic acid solution is subjected to holmium extraction using an organic solvent solution containing an organic carboxylic acid extractant, and the end pH of the holmium-containing inorganic acid solution is controlled by NaOH to be 2 to 4. Preferably, the volume ratio of the organic solvent solution containing the organic carboxylic acid extractant to the NaOH or KOH solution in S22 is (1:10) to (10: 1). Within this range of ratio, it is favorable for the tritium to be fully and efficiently reacted. Extracted.

根据本发明一种典型的实施方式，S23与S24之间还包括：分别用乙醇和水洗涤Sc(OH) ₃沉淀，以便于分别除去表面吸附的有机物和水溶性杂质。优选的，乙醇洗涤温度为20～40℃，水洗涤温度为50～90℃。 According to a typical embodiment of the present invention, S23 and S24 further include: washing the Sc (OH) ₃ precipitate with ethanol and water, respectively, so as to remove the organic matters and water-soluble impurities adsorbed on the surface, respectively. Preferably, the ethanol washing temperature is 20-40 ° C, and the water washing temperature is 50-90 ° C.

根据本发明一种典型的实施方式，空载有机相返回S21中钪萃取处理步骤使用；沉淀母液加入NaOH后返回S22钪反萃取处理步骤中使用，有利于原料的充分回收利用，降低生产成本。According to a typical embodiment of the present invention, the no-load organic phase is returned to the S21 钪 extraction treatment step for use; the precipitated mother liquor is added to NaOH and returned to the S22 钪 extraction treatment step, which is beneficial to the full recovery of raw materials and reduces production costs.

优选的，反萃取的反应温度为20～90℃，优选为40～60℃。Preferably, the reaction temperature of the back extraction is 20 to 90 ° C, and preferably 40 to 60 ° C.

优选的，S23中向钪络阴离子溶液中加入盐酸调节溶液酸碱度，以生成Sc(OH) ₃沉淀，沉淀终点pH为5.0～8.0。 Preferably, in S23, hydrochloric acid is added to the complex anion solution to adjust the pH of the solution to form a Sc (OH) ₃ precipitate, and the pH of the precipitation end point is 5.0-8.0.

优选的，S25中将Sc(OH) ₃沉淀煅烧以生成氧化钪的温度为400～650℃。 Preferably, the temperature at which Sc (OH) _{3 is} precipitated and calcined in S25 to generate hafnium oxide is 400-650 ° C.

根据本发明一种典型的实施方式，如图4所示，该方法包括：利用有机羧酸萃取剂的有机相对含钪料液进行钪萃取处理，以便获得含有钪的负载有机相，控制萃取剂浓度等反应条件，并使有机相体积小于水相体积，从而使得钪得到富集并与杂质离子(如Ca ²⁺、Mg ²⁺、Zn ²⁺、Mn ²⁺、Ni ²⁺、Co ²⁺、Al ³⁺、Fe ³⁺、Cr ³⁺等)初步分离；将上述有机相加入浓NaOH溶液进行反萃，通过控制反萃取剂浓度、温度、有机相：水相体积比等反应条件，以生成可溶性的钪络阴离子Sc(OH) ₆ ^3-溶液，反萃效率高，有机相与水相分离效果好，并与上述杂质离子进一步分离；向钪盐溶液中加入盐酸以调节溶液的酸度，以生成Sc(OH) ₃沉淀，通过控制沉淀终点pH、温度等反应条件，使生成的Sc(OH) ₃沉淀有高的沉淀效率、并利于下步的过滤；将Sc(OH) ₃沉淀分别用乙醇和水在选定的温度下洗涤，以分别除去表面吸附的有机物和水溶性杂质，钪得到进一步纯化，并且洗涤后的Sc(OH) ₃沉淀有更好的被过滤性能；将生成的Sc(OH) ₃沉淀煅烧以生成粗氧化钪，煅烧温度(400～650℃)较草酸钪煅烧温度(700～800℃)等低，且生成水蒸气而不是温室气体CO ₂；利用经煅烧过的粗氧化钪溶于热的浓盐酸但不溶于或极微量溶于稀盐酸的特性，将生成的粗氧化钪用稀盐酸水溶液在较低温度下进行洗涤，以溶解除去其中的杂质元素，能将钪与杂质元素很好的分离，得到纯化的氧化钪。利用该方法可以有效地从含钪溶液中富集提取氧化钪。 According to a typical embodiment of the present invention, as shown in FIG. 4, the method includes: using an organic organic carboxylic acid extractant to perform a tritium extraction treatment on a tritium-containing feed liquid, so as to obtain a supported organic phase containing tritium and control the extractant Concentration and other reaction conditions, and the volume of the organic phase is smaller than the volume of the aqueous phase, so that the plutonium is enriched and with impurity ions (such as Ca ²⁺ , Mg ²⁺ , Zn ²⁺ , Mn ²⁺ , Ni ²⁺ , Co ²⁺ , Al ³⁺ , Fe ³⁺ , Cr ^3+, etc.) preliminary separation; add the above organic phase to a concentrated NaOH solution for back extraction, and control the reaction conditions such as the concentration of the back extractant, temperature, and volume ratio of the organic phase to the water phase to Generates a soluble complex anion Sc (OH) ₆ ^3- solution, with high back extraction efficiency, good separation of organic and water phases, and further separation from the impurity ions; adding hydrochloric acid to the phosphonium salt solution to adjust the acidity of the solution, In order to generate Sc (OH) ₃ precipitate, by controlling the reaction conditions such as pH and temperature of the end point of the precipitation, the generated Sc (OH) ₃ precipitate has a high precipitation efficiency and is beneficial to the next filtration; Sc (OH) ₃ precipitates separately Wash with ethanol and water at a selected temperature to The organic matter and water-soluble impurities adsorbed on the surface were removed separately, the amidine was further purified, and the washed Sc (OH) ₃ precipitate had better filtering performance; the resulting Sc (OH) ₃ precipitate was calcined to generate crude erbium oxide, The calcination temperature (400-650 ° C) is lower than the calcination temperature of osmium oxalate (700-800 ° C) and generates water vapor instead of greenhouse gas CO ₂ ; the calcined crude osmium oxide is dissolved in hot concentrated hydrochloric acid but insoluble Or it can be dissolved in dilute hydrochloric acid in a very small amount. The resulting crude dysprosium oxide is washed with a dilute aqueous hydrochloric acid solution at a lower temperature to dissolve and remove the impurity elements therein, which can well separate the dysprosium and the impurity elements, and obtain purified Thorium oxide. This method can effectively enrich and extract thorium oxide from thorium-containing solution.

下面将结合实施例进一步说明本发明的有益效果。The beneficial effects of the present invention will be further described below with reference to the embodiments.

实施例1Example 1

在混合澄清萃取槽中，按照有机溶液、含钪溶液体积比为1：1，用含3mol/L磷酸三丁酯萃取剂(TBP萃取剂)的煤油溶液从含0.1mol/L钪盐酸溶液中萃取钪；将负载钪的有机相用1mol/L盐酸水溶液进行洗涤，按照萃取剂有机溶液、沉淀反萃剂溶液的体积比(有机溶液、水溶液体积比)为1：1，将洗涤后的负载钪的有机相与含1mol/L NaOH的沉淀反萃剂水溶液(水相)进行混合，空载钪的有机相与沉淀反萃剂水溶液母液在混合澄清萃取槽中分离，生成氢氧化钪沉淀处于水相中、并与沉淀母液一起从水相出口流出；将生成的氢氧化钪沉淀与沉淀母液通过真空过滤分离，得到富集的氢氧化钪沉淀，钪提取率为80％以上。In a mixed clarification extraction tank, a kerosene solution containing 3 mol / L tributyl phosphate extractant (TBP extractant) was used from a solution containing 0.1 mol / L rhenium hydrochloric acid according to the volume ratio of the organic solution and the rhenium-containing solution to 1: 1. Extraction 钪; washing the organic phase containing 钪 with 1 mol / L hydrochloric acid aqueous solution, according to the volume ratio (organic solution, aqueous solution volume ratio) of the organic solution of the extractant and the precipitation back-extractant solution is 1: 1. The organic phase of rhenium is mixed with an aqueous solution (precipitation phase) of a precipitation and stripping agent containing 1 mol / L NaOH, and the mother liquid of the organic phase of lutetium and the aqueous solution of the precipitation and stripping agent is separated in a mixing and clarifying extraction tank, and the rhenium hydroxide precipitate is formed. The aqueous phase flows out from the aqueous phase outlet together with the precipitation mother liquor; the generated thorium hydroxide precipitate is separated from the precipitation mother liquor by vacuum filtration to obtain an enriched thorium hydroxide precipitate, and the thorium extraction rate is above 80%.

实施例2Example 2

在带搅拌混合作用的反应釜中，按照有机溶液、含钪溶液体积比为1：10，用含1mol/L(二(2-乙基己基)磷酸酯)萃取剂(P204萃取剂)的正庚烷溶液从含0.05mol/L钪硫酸溶液中萃取钪；将负载钪的有机相用0.01mol/L硫酸水溶液进行洗涤，按照萃取剂有机溶液、沉淀反萃剂溶液的体积比(有机溶液：水溶液体积比)为10：1，将洗涤后的负载钪的有机相与含5mol/L NaOH的沉淀反萃剂水溶液(水相)进行混合，空载钪的有机相与沉淀反萃剂水溶液母液在混合澄清萃取槽中分离，生成氢氧化钪沉淀处于水相中、并与沉淀母液一起从水相出口流出；将生成的氢氧化钪沉淀与沉淀母液通过离心机分离，得到富集的氢氧化钪沉淀，钪提取率为70％以上。In a reaction kettle with agitation and mixing, according to the volume ratio of the organic solution and the rhenium-containing solution of 1:10, a positive solution containing 1 mol / L (bis (2-ethylhexyl) phosphate) extractant (P204 extractant) was used. The heptane solution was used to extract rhenium from a sulfuric acid solution containing 0.05 mol / L of rhenium; the organic phase containing rhenium was washed with a 0.01 mol / L sulfuric acid aqueous solution, and the volume ratio of the organic solution of the extractant and the solution of the precipitation back-extracting agent (organic solution: The volume ratio of the aqueous solution) was 10: 1. The washed organic phase containing tritium was mixed with a 5 mol / L NaOH precipitated stripping agent aqueous solution (aqueous phase), and the empty tritium organic phase and the precipitated stripping agent aqueous solution mother liquor were mixed. Separated in a mixed clarification extraction tank, the generated dysprosium hydroxide precipitate is in the water phase, and flows out from the aqueous phase outlet with the precipitation mother liquor; the generated dysprosium hydroxide precipitate and the precipitation mother liquor are separated by a centrifuge to obtain enriched hydroxide The osmium is precipitated and the extraction rate of osmium is more than 70%.

实施例3Example 3

在混合澄清萃取槽中，按照有机溶液、含钪溶液体积比为1：5，用含1mol/L萃取剂环烷酸的甲苯溶液从含0.1mol/L钪盐酸溶液中萃取钪；将负载钪的有机相按照萃取剂有机溶液、沉淀反萃剂溶液的体积比(有机溶液、水溶液体积比)为5：1，将洗涤后的负载钪的有机相与含0.3mol/L草酸的沉淀反萃剂水溶液(水相)进行混合，空载钪的有机相与沉淀反萃剂水溶液母液在混合澄清萃取槽中分离，生成草酸钪沉淀处于水相中、并与沉淀母液一起从水相出口流出；将生成的草酸钪沉淀与沉淀母液通过真空过滤分离，得到富集的草酸钪沉淀，钪提取率为90％以上。In a mixed clarification extraction tank, according to the volume ratio of the organic solution and the rhenium-containing solution of 1: 5, a toluene solution containing 0.1 mol / L of the extractant naphthenic acid was extracted from a 0.1 mol / L hydrazone hydrochloric acid solution; The organic phase was extracted according to the volume ratio (organic solution, aqueous solution volume ratio) of the extractant organic solution and the precipitation back-extractant solution to 5: 1. The washed organic phase loaded with tritium was back-extracted with the precipitate containing 0.3 mol / L oxalic acid. Agent aqueous solution (aqueous phase) is mixed, the organic phase of no-loaded tritium is separated from the mother liquor of the precipitation back-extractant aqueous solution in a mixed clarification extraction tank, and the tritium oxalate precipitate is in the aqueous phase and flows out from the aqueous phase outlet together with the precipitated mother liquid; The generated lutetium oxalate precipitate and the precipitation mother liquor were separated by vacuum filtration to obtain an enriched lutetium oxalate precipitate, and the ytterbium extraction rate was above 90%.

实施例4Example 4

在混合澄清萃取槽中，按照有机溶液、含钪溶液体积比为1：5，用含1mol/L三辛胺(N235萃取剂)的煤油与正己醇溶液从含0.1mol/L钪硝酸溶液中萃取钪；将负载钪的有机相用0.5mol/L硝酸水溶液进行洗涤，按照萃取剂有机溶液、沉淀反萃剂溶液的体积比(有机溶液、水溶液体积比)为20：1，将洗涤后的负载钪的有机相与含10mol/L氟化钠的沉淀反萃剂水溶液(水相)进行混合，空载钪的有机相与沉淀反萃剂水溶液母液在混合澄清萃取槽中分离，生成氟化钪沉淀处于水相中、并与沉淀母液一起从水相出口流出；将生成的氟化钪沉淀与沉淀母液通过真空过滤分离，得到富集的氟化钪沉淀，钪提取率为90％以上。In a mixed clarification extraction tank, according to the volume ratio of the organic solution and the rhenium-containing solution of 1: 5, a kerosene and n-hexanol solution containing 1 mol / L trioctylamine (N235 extractant) was used from a 0.1 mol / L rhenium nitric acid solution. Extracting rhenium; washing the organic phase containing rhenium with a 0.5 mol / L nitric acid aqueous solution, and according to the volume ratio (organic solution, aqueous solution volume ratio) of the organic solution of the extractant and the solution of the precipitation back-extracting agent is 20: 1. The organic phase containing tritium is mixed with a 10 mol / L sodium fluoride precipitated stripping agent aqueous solution (aqueous phase). The no-loaded tritium organic phase and the precipitated stripping agent aqueous solution mother liquor are separated in a mixed clarification extraction tank to generate fluorination. The rhenium precipitate is in the water phase and flows out from the aqueous phase outlet together with the precipitation mother liquor; the generated rhenium fluoride precipitate and the precipitation mother liquor are separated by vacuum filtration to obtain an enriched rhenium fluoride precipitate, and the rhenium extraction rate is above 90%.

实施例5Example 5

在混合澄清萃取槽中，按照有机溶液、含钪溶液体积比为1：5，用含2mol/L三辛胺(N235萃取剂)的煤油与正己醇溶液从含0.5mol/L钪的硝酸溶液中萃取钪；将负载钪的有机相用0.5mol/L硝酸水溶液进行洗涤，按照萃取剂有机溶液、沉淀反萃剂溶液的体积比(有机溶液、水溶液体积比)为10：1，将洗涤后的负载钪的有机相与含1mol/L磷酸铵的沉淀反萃剂水溶液(水相)进行混合，空载钪的有机相与沉淀反萃剂水溶液母液在带搅拌混合作用的反应釜中分离，生成磷酸钪沉淀处于水相中、并与沉淀母液一起从水相出口流出；将生成的磷酸钪沉淀与沉淀母液通过真空过滤分离，得到富集的磷酸钪沉淀，钪提取率为70％以上。In a mixed clarification extraction tank, according to the volume ratio of organic solution and thorium-containing solution of 1: 5, a kerosene and n-hexanol solution containing 2mol / L trioctylamine (N235 extractant) was used to remove a 0.5mol / L thallium nitric acid solution.钪 was extracted from the medium; the lutetium-loaded organic phase was washed with a 0.5 mol / L nitric acid aqueous solution, and the volume ratio (organic solution, aqueous solution volume ratio) of the organic solution of the extractant and the solution of the precipitation-extractive agent was 10: 1. The organic phase containing tritium is mixed with an aqueous solution (precipitation phase) of a precipitated stripping agent containing 1 mol / L ammonium phosphate, and the mother liquid of the organic phase containing no tritium and the aqueous solution of the precipitated stripping agent is separated in a reaction kettle with stirring and mixing. The generated europium phosphate precipitate is in the aqueous phase and flows out from the aqueous phase outlet together with the precipitation mother liquor; the generated europium phosphate precipitate and the precipitation mother liquor are separated by vacuum filtration to obtain an enriched europium phosphate precipitate, and the europium extraction rate is above 70%.

实施例6Example 6

在混合澄清萃取槽中，按照有机溶液、含钪溶液体积比为1：5，用含1mol/L三辛胺(N235萃取剂)与1mol/Lβ-二酮萃取剂(HTTA)的正己醇溶液从含0.2mol/L钪的盐酸溶液中萃取钪；将负载钪的有机相用2mol/L盐酸水溶液进行洗涤，按照萃取剂有机溶液、沉淀反萃剂溶液的体积比(有机溶液、水溶液体积比)为10：1，将洗涤后的负载钪的有机相与含6mol/L氨水的沉淀反萃剂水溶液(水相)进行混合，空载钪的有机相与沉淀反萃剂水溶液母液在带搅拌混合作用的反应釜中分离，生成氢氧化钪沉淀处于水相中、并与沉淀母液一起从水相出口流出；将生成的氢氧化钪沉淀与沉淀母液通过真空过滤分离，得到富集的氢氧化钪沉淀，钪提取率为89％以上。In a mixed clarification extraction tank, an n-hexanol solution containing 1 mol / L trioctylamine (N235 extractant) and 1 mol / L β-diketone extractant (HTTA) was used in accordance with the volume ratio of the organic solution and the rhenium-containing solution to 1: 5. Extract rhenium from a hydrochloric acid solution containing 0.2 mol / L rhenium; wash the organic phase containing rhenium with a 2 mol / L hydrochloric acid aqueous solution, and follow the volume ratio of the organic solution of the extractant and the solution of the precipitation back-extractor (the volume ratio of the organic solution and the aqueous solution) ) Is 10: 1, and the washed organic phase containing tritium is mixed with a 6 mol / L ammonia aqueous precipitation back-extractant aqueous solution (aqueous phase). Separated in a mixing reaction kettle, the generated dysprosium hydroxide precipitate is in the aqueous phase, and flows out from the aqueous phase outlet with the precipitation mother liquor; the generated dysprosium hydroxide precipitate and the precipitation mother liquor are separated by vacuum filtration to obtain enriched hydroxide The osmium is precipitated and the extraction rate of osmium is more than 89%.

实施例7Example 7

在混合澄清萃取槽中，按照有机溶液、含钕溶液体积比为1:5，用含10mol/L的P204从含2mol/L钕的盐酸溶液中萃取钕；将负载钕的有机相用1mol/L盐酸水溶液进行洗涤，按照萃取剂有机溶液、沉淀反萃剂溶液的体积比(有机溶液、水溶液体积比)为1：20，将洗涤后的负载钪的有机相与含6mol/L草酸的沉淀反萃剂水溶液(水相)进行混合。空载钕的有机相与沉淀反萃剂水溶液母液在带搅拌混合作用的反应釜中分离，生成草酸钕沉淀处于水相中、并与沉淀母液一起从水相出口流出；将生成的草酸钕沉淀与沉淀母液通过真空过滤分离，得到富集的草酸钕沉淀。用草酸溶液可以从P204有机相中较好地反萃取沉淀稀土钕，反萃取率在89％以上。In a mixed clarification extraction tank, the neodymium was extracted from a hydrochloric acid solution containing 2 mol / L neodymium with 10 mol / L of P204 according to the volume ratio of organic solution and neodymium-containing solution of 1: 5; the organic phase loaded with neodymium was 1 mol / l L hydrochloric acid aqueous solution was washed, according to the volume ratio (organic solution, aqueous solution volume ratio) of the extractant organic solution and the precipitation back-extractant solution was 1:20, and the washed organic phase loaded with tritium was precipitated with 6 mol / L oxalic acid. The stripping agent aqueous solution (aqueous phase) was mixed. The organic phase of the unloaded neodymium and the mother liquor of the precipitation back-extractant aqueous solution are separated in a reaction kettle with stirring and mixing to form a precipitate of neodymium oxalate which is in the aqueous phase and flows out from the aqueous phase outlet together with the precipitation mother liquor; the resulting neodymium oxalate is precipitated It is separated from the precipitation mother liquor by vacuum filtration to obtain an enriched neodymium oxalate precipitate. The rare earth neodymium can be back-extracted from the organic phase of P204 with oxalic acid solution, and the back-extraction rate is above 89%.

实施例8Example 8

在混合澄清萃取槽中，按照有机溶液、含钕溶液体积比为1:5，用含10mol/L的P204从含0.5mol/L钕的盐酸溶液中萃取钕；将负载钕的有机相用1mol/L盐酸水溶液进行洗涤，按照萃取剂有机溶液、沉淀反萃剂溶液的体积比(有机溶液、水溶液体积比)为1：20，将洗涤后的负载钪的有机相与含15mol/L草酸的沉淀反萃剂水溶液(水相)进行混合。空载钕的有机相与沉淀反萃剂水溶液母液在带搅拌混合作用的反应釜中分离，生成草酸钕沉淀处于水相中、并与沉淀母液一起从水相出口流出；将生成的草酸钕沉淀与沉淀母液通过真空过滤分离，得到富集的草酸钕沉淀。用草酸溶液可以从P204有机相中较好地反萃取沉淀稀土钕，反萃取率在90％左右。In a mixed clarification extraction tank, according to the volume ratio of the organic solution and the neodymium-containing solution of 1: 5, neodymium was extracted from a 0.5 mol / L neodymium hydrochloric acid solution using P204 containing 10 mol / L; 1 mol of the organic phase carrying neodymium was used. / L hydrochloric acid aqueous solution was washed, according to the volume ratio (organic solution, aqueous solution) of the extractant organic solution and the precipitation back-extractant solution was 1:20, and the washed organic phase containing tritium and 15 mol / L oxalic acid was washed. The precipitated stripping agent aqueous solution (aqueous phase) was mixed. The organic phase of the unloaded neodymium and the mother liquor of the precipitation back-extractant aqueous solution are separated in a reaction kettle with stirring and mixing to form a precipitate of neodymium oxalate which is in the aqueous phase and flows out from the aqueous phase outlet together with the precipitation mother liquor; the resulting neodymium oxalate is precipitated It is separated from the precipitation mother liquor by vacuum filtration to obtain an enriched neodymium oxalate precipitate. The rare earth neodymium can be back-extracted from the organic phase of P204 with oxalic acid solution, and the back-extraction rate is about 90%.

从以上的描述中，可以看出，本发明上述的实施例实现了如下技术效果：应用本发明的技术方案，将负载有机相中的钪，通过加入沉淀剂溶液，同时起到反萃和沉淀的作用，从有机相中直接得到钪的沉淀，这样缩短了操作流程，使用沉淀剂，不使用反萃剂，减少了反萃剂、水等原料消耗，减少了操作费用。From the above description, it can be seen that the above-mentioned embodiments of the present invention achieve the following technical effects: By applying the technical solution of the present invention, the tritium in the supported organic phase can be simultaneously back-extracted and precipitated by adding a precipitant solution. The effect is to directly obtain the precipitation of tritium from the organic phase, which shortens the operation process, uses a precipitating agent, does not use a back-extracting agent, reduces the consumption of back-extracting agent, water and other raw materials, and reduces operating costs.

实施例9Example 9

P507萃取剂(2-乙基己基磷酸单-2-乙基己基酯)，NaOH反萃P507 extractant (2-ethylhexyl phosphate mono-2-ethylhexyl ester), NaOH back extraction

在带搅拌混合作用的反应釜中，按照有机溶液、含钪溶液体积比为1：2，用500mL含1mol/L P507萃取剂的煤油溶液从1000mL含钪盐酸溶液中萃取钪，钪的萃取率99.9％；In a reaction kettle with stirring and mixing, according to a volume ratio of organic solution and thorium-containing solution of 1: 2, 500 mL of a kerosene solution containing 1 mol / L P507 extractant was used to extract thallium from 1000 mL of thorium-containing hydrochloric acid solution. 99.9%;

将500mL负载钪的有机相用500mL 1mol/L盐酸水溶液进行洗涤，以除去共同萃取的杂质元素，杂质洗涤率99％以上，钪的洗脱率0.2％；The 500 mL organic phase containing tritium was washed with 500 mL of a 1 mol / L hydrochloric acid aqueous solution to remove the co-extracted impurity elements, the impurity washing rate was more than 99%, and the elution ratio of tritium was 0.2%;

按照萃取剂有机溶液、反萃剂溶液的体积比(有机溶液、水溶液体积比)为1：1，将洗涤后的负载钪的500mL有机相与500mL含5mol/L NaOH的反萃剂水溶液(水相)在反应釜中进行混合，反应温度为50℃，以进行反萃取反应，钪的反萃取率99.1％，生成钪络阴离子处于水相中、并从水相出口流出；空载钪的有机相与钪络阴离子溶液分离，并返回萃取步骤循环使用；According to the volume ratio (organic solution, aqueous solution volume ratio) of the organic solution of the extractant and the stripping agent solution is 1: 1, 500 mL of the organic phase loaded with tritium and 500 mL of a stripping agent aqueous solution containing 5 mol / L NaOH (water Phase) Mix in a reaction kettle at a reaction temperature of 50 ° C to carry out a back-extraction reaction. The back-extraction rate of osmium is 99.1%. The generated anion complex is in the aqueous phase and flows out from the aqueous phase outlet; The phase is separated from the complex anion solution and returned to the extraction step for recycling;

向钪络阴离子溶液中加入240mL含6mol/L HCl的溶液以调节溶液pH至7.0，以生成Sc(OH) ₃沉淀，钪的沉淀率99.5％； 240 mL of a solution containing 6 mol / L HCl was added to the tritium anion solution to adjust the pH of the solution to 7.0 to form a Sc (OH) ₃ precipitate, and the precipitation rate of tritium was 99.5%;

将生成的氢氧化钪沉淀与沉淀母液通过真空过滤分离，得到富集的氢氧化钪Sc(OH) ₃沉淀；将Sc(OH) ₃沉淀分别用乙醇和水洗涤，洗涤温度为20℃和50℃，以分别除去表面吸附的有机物和水溶性杂质。 The generated thorium hydroxide precipitate was separated from the precipitation mother liquor by vacuum filtration to obtain an enriched thorium hydroxide Sc (OH) ₃ precipitate; the Sc (OH) ₃ precipitate was washed with ethanol and water, respectively, at a temperature of 20 ° C and 50 ° C. ℃ to remove organic matter and water-soluble impurities adsorbed on the surface, respectively.

将Sc(OH) ₃沉淀在600℃煅烧以生成氧化钪。钪的总收率98.3％。通过原子发射光谱分析，氧化钪的纯度达到99.0％。 The Sc (OH) ₃ precipitate was calcined at 600 ° C to generate hafnium oxide. The total yield of rhenium was 98.3%. According to atomic emission spectrometry analysis, the purity of europium oxide reached 99.0%.

对比例1：Comparative Example 1:

P507萃取剂(2－乙基己基磷酸单2－乙基己基酯)，HCl反萃、碱沉淀P507 extractant (2-ethylhexyl phosphate mono-2-ethylhexyl ester), HCl back extraction, alkali precipitation

在带搅拌混合作用的反应釜中，按照有机溶液、含钪溶液体积比为1：2，用500mL含1mol/L P507萃取剂的煤油溶液从1000mL含钪盐酸溶液中萃取钪，钪的萃取率99.1％；In a reaction kettle with stirring and mixing, according to a volume ratio of organic solution and thorium-containing solution of 1: 2, 500 mL of a kerosene solution containing 1 mol / L P507 extractant was used to extract thallium from 1000 mL of thorium-containing hydrochloric acid solution. 99.1%;

将500mL负载钪的有机相用500mL 1mol/LHCl盐酸水溶液进行洗涤，以除去共同萃取的杂质元素，杂质洗涤率99％以上，钪的洗脱率0.2％；Wash 500 mL of tritium-loaded organic phase with 500 mL of a 1 mol / L HCl hydrochloric acid aqueous solution to remove co-extracted impurity elements. The impurity washing rate is more than 99%, and the elution rate of tritium is 0.2%;

按照萃取剂有机溶液、反萃剂溶液的体积比(有机溶液、水溶液体积比)为1：1，将洗涤后的负载钪的有机相与500mL含6mol/L HCl的反萃剂水溶液(水相)在反应釜中进行混合，反应温度为50℃，以进行反萃取反应，生成氯化钪反萃液，反萃取率19.1％；According to the volume ratio (organic solution, aqueous solution volume ratio) of the organic solution of the extractant and the stripping agent solution is 1: 1, the washed organic phase loaded with tritium and 500 mL of the stripping agent aqueous solution (water phase containing 6mol / L HCl) ) Mixing in a reaction kettle at a reaction temperature of 50 ° C. to perform a back extraction reaction to generate a thallium chloride back extraction solution with a back extraction rate of 19.1%;

向氯化钪反萃溶液中加入500mL 6mol/L NaOH溶液以调节溶液至pH7.0，以生成Sc(OH) ₃沉淀，钪的沉淀率99.2％；将Sc(OH) ₃沉淀分别用乙醇和水洗涤，洗涤温度为30℃和80℃； 500 mL of a 6 mol / L NaOH solution was added to the rubidium chloride back-extraction solution to adjust the solution to pH 7.0 to generate a Sc (OH) ₃ precipitate with a precipitation rate of 99.2%; the Sc (OH) _{3 was} precipitated with ethanol and Wash with water at 30 ° C and 80 ° C;

将Sc(OH) ₃沉淀在600℃煅烧以生成氧化钪。钪的总收率18.7％。通过原子发射光谱分析，氧化钪的纯度95.5％。 The Sc (OH) ₃ precipitate was calcined at 600 ° C to generate hafnium oxide. The total yield of rhenium was 18.7%. According to atomic emission spectrometry analysis, the purity of europium oxide was 95.5%.

对比例2：Comparative Example 2:

同实施例9的不同之处在于，按照萃取剂有机溶液、反萃剂溶液的体积比(有机溶液、水溶液体积比)为1：1，将洗涤后的负载钪的有机相与500mL含6mol/L H ₂SO ₄的反萃剂水溶液(水相)在反应釜中进行混合，反应温度为50℃，以进行反萃取反应，生成硫酸钪反萃液，反萃取率15.5％； The difference from Example 9 is that, according to the volume ratio (volume ratio of organic solution and aqueous solution) of the organic solution of the extractant and the back-extractant solution is 1: 1, the washed organic phase containing tritium and 500 mL contains 6 mol / The LH ₂ SO ₄ stripping agent aqueous solution (aqueous phase) was mixed in a reaction kettle at a reaction temperature of 50 ° C. to carry out a stripping reaction to generate a tritium sulfate stripping solution with a stripping rate of 15.5%;

向硫酸钪反萃溶液中加入1000mL 6mol/L NaOH溶液以调节溶液至pH7.0，以生成Sc(OH) ₃沉淀，钪的沉淀率98.5％；将Sc(OH) ₃沉淀分别用乙醇和水洗涤，洗涤温度为30℃和80℃； 1000 mL of a 6 mol / L NaOH solution was added to the tritium sulphate back-extraction solution to adjust the solution to pH 7.0 to generate a Sc (OH) ₃ precipitate with a precipitation rate of 98.5%; the Sc (OH) _{3 was} precipitated with ethanol and water, respectively. Washing at 30 ° C and 80 ° C;

将Sc(OH) ₃沉淀在600℃煅烧以生成氧化钪。钪的总收率13.8％。通过原子发射光谱分析，氧化钪的纯度92.5％。 The Sc (OH) ₃ precipitate was calcined at 600 ° C to generate hafnium oxide. The total yield of tritium is 13.8%. According to atomic emission spectrometry, the purity of erbium oxide was 92.5%.

对比例3：Comparative Example 3:

同对比例2的不同之处在于，The difference from Comparative Example 2 is that

向硫酸钪反萃溶液中加入900mL 6mol/L NaOH溶液以调节溶液至pH2.0，向其中加入草酸溶液以生成草酸钪Sc ₂(C ₂O ₄) ₃沉淀，钪的沉淀率98.0％；将Sc ₂(C ₂O ₄) ₃沉淀分别用乙醇和水洗涤，洗涤温度为30℃和80℃； 900 mL of a 6 mol / L NaOH solution was added to the tritium sulphate back-extraction solution to adjust the solution to pH 2.0, and an oxalic acid solution was added thereto to generate Sc ₂ (C ₂ O ₄ ) ₃ oxalate precipitate. The Sc ₂ (C ₂ O ₄ ) ₃ precipitate was washed with ethanol and water at 30 ° C and 80 ° C, respectively;

将Sc ₂(C ₂O ₄) ₃沉淀在800℃煅烧以生成氧化钪。钪的总收率15.0％。通过原子发射光谱分析，氧化钪的纯度98.5％。 The Sc ₂ (C ₂ O ₄ ) ₃ precipitate was calcined at 800 ° C. to generate hafnium oxide. The total yield of rhenium was 15.0%. Analysis by atomic emission spectrometry revealed that the purity of europium oxide was 98.5%.

实施例10Example 10

P204萃取剂(二(2-乙基己基)磷酸)，NaOH反萃P204 extractant (bis (2-ethylhexyl) phosphoric acid), NaOH back extraction

在带搅拌混合作用的反应釜中，按照有机溶液、含钪溶液体积比为1：10，用含0.2mol/L(二(2-乙基己基)磷酸酯)萃取剂(P204萃取剂)的正庚烷溶液从钪硫酸溶液中萃取钪，钪的萃取率99.9％；In a reaction kettle with agitation and mixing, according to the volume ratio of the organic solution and the rhenium-containing solution of 1:10, a solution containing 0.2 mol / L (di (2-ethylhexyl) phosphate) extractant (P204 extractant) was used. N-heptane solution was used to extract rhenium from rhenium sulfuric acid solution, and the extraction rate of rhenium was 99.9%;

将负载钪的有机相用0.5mol/L硫酸水溶液进行洗涤，以除去共同萃取的杂质元素，杂质洗涤率99％以上，钪的洗脱率0.2％；The organic phase containing tritium is washed with a 0.5 mol / L sulfuric acid aqueous solution to remove co-extracted impurity elements, the impurity washing rate is more than 99%, and the tritium elution rate is 0.2%;

按照萃取剂有机溶液、沉淀反萃剂溶液的体积比(有机溶液：水溶液体积比)为10：1，将洗涤后的负载钪的有机相与含7mol/L NaOH的反萃剂水溶液(水相)进行混合，以进行反萃取反应，钪的反萃取率99.9％；According to the volume ratio (organic solution: water solution volume ratio) of the organic solution of the extractant and the precipitation back-extractant solution is 10: 1, the washed organic phase loaded with tritium and the back-extractant aqueous solution (water phase containing 7 mol / L NaOH) ) Mixing to carry out a back extraction reaction, the back extraction rate of rhenium is 99.9%;

向钪络阴离子溶液中加入盐酸以调节溶液至pH6.0，以生成Sc(OH) ₃沉淀；将Sc(OH) ₃沉淀分别用乙醇和水洗涤，洗涤温度为40℃和90℃； Add hydrochloric acid to the complex anion solution to adjust the solution to pH 6.0 to generate a Sc (OH) ₃ precipitate; wash the Sc (OH) ₃ precipitate with ethanol and water, respectively, at 40 ° C and 90 ° C;

将Sc(OH) ₃沉淀在500℃煅烧以生成氧化钪。钪的总收率99.1％。通过原子发射光谱分析，氧化钪的纯度达到99.5％。 The Sc (OH) ₃ precipitate was calcined at 500 ° C to generate hafnium oxide. The total yield of rhenium was 99.1%. According to atomic emission spectrometry, the purity of europium oxide was 99.5%.

对比例1，2，3钪收率远低于实施例9，10，主要在于酸反萃效率低于碱。其中，对比例1中耗酸高于实施例9，但反萃率、钪总收率不如实施例9；对比例2，3，硫酸反萃，反萃效果更差。The yields of Comparative Examples 1, 2, and 3 were much lower than those of Examples 9, 10, mainly because the acid stripping efficiency was lower than that of alkali. Among them, the acid consumption in Comparative Example 1 was higher than that in Example 9, but the back-extraction rate and total ytterbium yield were not as good as those in Example 9; Comparative Examples 2, 3, sulfuric acid back-extraction, the effect of back-extraction was worse.

实施例11Example 11

同实施例9相比其不同之处在于，The difference from Example 9 is that:

其所用的为5mol/L KOH的反萃剂水溶液(水相)，钪的反萃取率99.2％，氧化钪的纯度达到99.3％。钪的总收率98.4％。It uses a 5 mol / L KOH back-extracting agent aqueous solution (aqueous phase), the back extraction rate of rhenium is 99.2%, and the purity of rhenium oxide reaches 99.3%. The total yield of rhenium was 98.4%.

实施例12Example 12

其所用的为8mol/L NaOH的反萃剂水溶液(水相)，钪的反萃取率99.7％。氧化钪的纯度达到99.1％。钪的总收率98.9％。It uses an 8 mol / L NaOH stripping agent aqueous solution (aqueous phase), and the osmium stripping rate is 99.7%. The purity of hafnium oxide reached 99.1%. The total yield of radon was 98.9%.

实施例13Example 13

其所用的反萃反应温度为70℃，钪的反萃取率99.5％，钪的总收率98.7％。The stripping reaction temperature used is 70 ° C., the back extraction rate of rhenium is 99.5%, and the total yield of rhenium is 98.7%.

实施例14Example 14

同实施例9相比其不同之处在于，向钪络阴离子溶液中加入220mL含6mol/L HCl的溶液以调节溶液pH至8.0，以生成Sc(OH) ₃沉淀，钪的沉淀率99.8％；氧化钪的纯度达到99.1％。钪的总收率98.6％。 Compared with Example 9, the difference is that 220 mL of a solution containing 6 mol / L HCl was added to the anion solution of hydrazone to adjust the pH of the solution to 8.0 to generate a Sc (OH) ₃ precipitate. The precipitation rate of rhenium was 99.8%; The purity of hafnium oxide reached 99.1%. The total yield of rhenium was 98.6%.

实施例15Example 15

将Sc(OH) ₃沉淀分别用乙醇和水洗涤，洗涤温度为30℃和80℃；将Sc(OH) ₃沉淀分别用乙醇和水洗涤，洗涤温度为40℃和90℃，以分别除去表面吸附的有机物和水溶性杂质。 The Sc (OH) ₃ precipitate was washed with ethanol and water at 30 ° C and 80 ° C, respectively; the Sc (OH) ₃ precipitate was washed with ethanol and water at 40 ° C and 90 ° C, respectively, to remove the surface Adsorbed organics and water-soluble impurities.

实施例16Example 16

在带搅拌混合作用的反应釜中，按照有机溶剂溶液、含钪无机酸溶液的体积比为1：20，用50mL含4mol/L P507萃取剂的煤油溶液从1000mL含钪盐酸溶液中萃取钪，钪的萃取了99.4％；In a reaction kettle with agitation and mixing, according to a volume ratio of an organic solvent solution and a rhenium-containing inorganic acid solution of 1:20, 50 ml of a kerosene solution containing 4 mol / L P507 extractant was used to extract rhenium from 1000 ml of the HCl-containing hydrochloric acid solution. Rhenium extraction was 99.4%;

将500mL负载钪的有机相用100mL 4mol/L盐酸水溶液进行洗涤，以除去共同萃取的杂志元素，杂质洗涤率达到98％以上，钪的洗脱率为0.3％；The organic phase containing 500 mL of rhenium was washed with 100 mL of a 4 mol / L hydrochloric acid aqueous solution to remove the co-extracted magazine elements. The impurity washing rate reached 98% and the elution rate of rhenium was 0.3%;

按照萃取剂的有机溶液、反萃剂溶液的体积比(有机溶液、水溶液体积比)为1：1，将洗涤后的负载相的500mL有机相与1000mL NaOH的反萃剂水溶液(水相)在反应釜中进行混合，反应温度为50℃，以进行反萃取反应，钪的反萃取率98.9％，生成钪络阴离子处于水相中、并从水相出口流出；空载钪的有机相与钪络阴离子溶液分离，并返回萃取步骤循环使用；According to the volume ratio (organic solution, aqueous solution volume ratio) of the organic solution of the extractant and the stripping agent solution is 1: 1, 500 mL of the organic phase of the washed support phase and 1000 mL of the NaOH stripping agent aqueous solution (aqueous phase) The reaction kettle was mixed at a reaction temperature of 50 ° C to carry out a back-extraction reaction. The back-extraction rate of osmium was 98.9%, and the generated anion complex was in the water phase and flowed out from the aqueous phase outlet. The organic phase and rhenium contained no rhenium. The complex anion solution is separated and returned to the extraction step for recycling;

向钪络阴离子溶液中加入240mL含4mol/L HCl的溶液以调节溶液pH至7.0，以生成Sc(OH) ₃沉淀，钪的沉淀率99.3％； 240 mL of a solution containing 4 mol / L HCl was added to the anion solution to adjust the pH of the solution to 7.0 to form a Sc (OH) ₃ precipitate, and the precipitation rate of the europium was 99.3%;

将Sc(OH) ₃沉淀在600℃煅烧以生成氧化钪。钪的总收率98.3％。通过原子发射光谱分析，氧化钪的纯度达到99.0％。 The Sc (OH) ₃ precipitate was calcined at 600 ° C to generate hafnium oxide. The total yield of rhenium was 98.3%. According to atomic emission spectrometry, the purity of europium oxide was 99.0%.

实施例17Example 17

在带搅拌混合作用的反应釜中，按照有机溶剂溶液、含钪无机酸溶液的体积比为1：2，用500mL含1mol/L P507萃取剂的煤油溶液从1000mL含钪盐酸溶液中萃取钪，钪的萃取了99.1％；In a reaction kettle with stirring and mixing, according to a volume ratio of an organic solvent solution and a thorium-containing inorganic acid solution of 1: 2, 500 ml of a kerosene solution containing 1 mol / L P507 extractant was used to extract thallium from a 1000 ml thorium-containing hydrochloric acid solution. Rhenium extraction was 99.1%;

将500mL负载钪的有机相用500mL 1mol/L盐酸水溶液进行洗涤，以除去共同萃取的杂志元素，杂质洗涤率达到99％以上，钪的洗脱率为0.2％；The 500 mL organic phase containing tritium was washed with 500 mL of a 1 mol / L hydrochloric acid aqueous solution to remove co-extracted magazine elements. The impurity washing rate reached more than 99% and the elution rate of tritium was 0.2%;

按照萃取剂有机溶液、反萃剂溶液的体积比(有机溶液、水溶液体积比)为1：1，将洗涤后的负载钪的1000mL有机相与500mL含5mol/L NaOH的反萃剂水溶液(水相)在反应釜中进行混合，反应温度为50℃，以进行反萃取反应，钪的反萃取率99.3％，生成钪络阴离子处于水相中、并从水相出口流出；空载钪的有机相与钪络阴离子溶液分离，并返回萃取步骤循环使用；According to the volume ratio (volume ratio of organic solution and aqueous solution) of the organic solution of the extractant and the back-extractant solution is 1: 1, the washed 1000 mL organic phase containing the tritium and 500 mL of the back-extractant aqueous solution containing 5 mol / L NaOH (water Phase) Mix in a reaction kettle at a reaction temperature of 50 ° C to perform a back-extraction reaction. The back-extraction rate of osmium is 99.3%, and the generated anion complex is in the aqueous phase and flows out from the aqueous phase outlet; The phase is separated from the complex anion solution and returned to the extraction step for recycling;

向钪络阴离子溶液中加入240mL含6mol/L HCl的溶液以调节溶液pH至7.0，以生成Sc(OH) ₃沉淀，钪的沉淀率99.3％； 240 mL of a solution containing 6 mol / L HCl was added to the tritium anion solution to adjust the pH of the solution to 7.0 to form a Sc (OH) ₃ precipitate, and the precipitation rate of tritium was 99.3%;

将Sc(OH) ₃沉淀在600℃煅烧以生成氧化钪。钪的总收率98.3％。通过原子发射光谱分析，氧化钪的纯度达到99.2％。 The Sc (OH) ₃ precipitate was calcined at 600 ° C to generate hafnium oxide. The total yield of rhenium was 98.3%. According to atomic emission spectrometry, the purity of europium oxide reached 99.2%.

将Sc(OH) ₃沉淀在600℃煅烧以生成氧化钪。通过原子发射光谱分析，氧化钪的纯度达到99.5％。钪的总收率97.8％。从以上的描述中，可以看出，本发明上述的实施例实现了如下技术效果： The Sc (OH) ₃ precipitate was calcined at 600 ° C to generate hafnium oxide. According to atomic emission spectrometry, the purity of europium oxide was 99.5%. The total yield of radon was 97.8%. From the above description, it can be seen that the foregoing embodiments of the present invention achieve the following technical effects:

用浓NaOH溶液进行反萃时，在优化的条件下(包括NaOH浓度、温度、有机相：水相体积比)萃取到有机相中的钪与浓NaOH溶液生成Sc(OH) ₆ ^3-络阴离子，钪以可溶离子的形式进入水相溶液，从而使得反萃效率高，有机相与水相分离效果好，可以应用传统的混合澄清萃取槽进行萃取分离连续操作，因而，利于应用于工业生产。 When back-extracting with concentrated NaOH solution, the osmium and concentrated NaOH solution extracted into the organic phase under optimized conditions (including NaOH concentration, temperature, and organic phase: water phase volume ratio) generate Sc (OH) ₆ ^3- complex anion As a result, rhenium enters the aqueous solution in the form of soluble ions, so that the back extraction efficiency is high, and the organic phase is separated from the water phase. The traditional mixed clarification extraction tank can be used for continuous extraction and separation operations, which is conducive to industrial production. .

将含钪络阴离子盐溶液加入盐酸以中和溶液中的氢氧根OH ^-，可以使得钪络阴离子转变为Sc(OH) ₃沉淀，从而使得钪得以富集，Sc(OH) ₃沉淀可以应用传统的固液分离设备进行分离，因而，也利于应用于工业生产。 Adding the anion salt solution containing tritium anion to hydrochloric acid to neutralize the hydroxide OH ^- in the solution can transform the tritium anion into Sc (OH) ₃ precipitation, so that the tritium can be enriched, and the Sc (OH) ₃ precipitation can be applied. Traditional solid-liquid separation equipment is used for separation, so it is also beneficial to industrial production.

实施例18Example 18

CA-12萃取剂(仲辛基苯氧基取代乙酸)，NaOH反萃CA-12 extractant (sec-octylphenoxy substituted acetic acid), NaOH back extraction

在混合澄清萃取槽中，按照有机溶液、含钪溶液体积比为1：2，用含1mol/L CA-12萃取剂的煤油溶液从含钪盐酸溶液中萃取钪，用NaOH控制含钪溶液终点pH为3；钪的单级萃取率达到85％以上。In the mixed clarification extraction tank, according to the volume ratio of organic solution and thorium-containing solution of 1: 2, thorium was extracted from thorium-containing hydrochloric acid solution with a kerosene solution containing 1 mol / L CA-12 extractant, and the end point of thorium-containing solution was controlled by NaOH The pH is 3; the single-stage extraction rate of rhenium is above 85%.

按照萃取剂有机溶液、反萃剂溶液的体积比(有机溶液、水溶液体积比)为1：1，将洗涤后的负载钪的有机相与含5mol/L NaOH的反萃剂水溶液(水相)在混合澄清萃取槽中进行混合，反应温度为50℃，以进行反萃取反应，生成钪络阴离子处于水相中、并从水相出口流出；空载钪的有机相与钪络阴离子溶液分离，并返回萃取步骤循环使用；According to the volume ratio (organic solution, aqueous solution volume ratio) of the organic solution of the extractant and the stripping agent solution is 1: 1, the washed organic phase loaded with tritium and the stripping agent aqueous solution (aqueous phase) containing 5mol / L NaOH Mix in a clarification extraction tank at a reaction temperature of 50 ° C to perform a back-extraction reaction. The generated anion complex is in the aqueous phase and flows out from the aqueous phase outlet. The organic phase of unloaded tritium is separated from the complex anion solution. And return to the extraction step for recycling;

向钪络阴离子溶液中加入盐酸以调节溶液至pH7.0，以生成Sc(OH) ₃沉淀； Adding hydrochloric acid to the complex anion solution to adjust the solution to pH 7.0 to form a Sc (OH) ₃ precipitate;

将生成的氢氧化钪沉淀与沉淀母液通过真空过滤分离，得到富集的氢氧化钪Sc(OH) ₃沉淀；将Sc(OH) ₃沉淀母液加入NaOH后返回钪反萃取处理步骤使用；将Sc(OH) ₃沉淀分别用乙醇和水洗涤，洗涤温度为30℃和80℃，以分别除去表面吸附的有机物和水溶性杂质。 The generated thorium hydroxide precipitate and the precipitation mother liquor are separated by vacuum filtration to obtain an enriched thorium hydroxide Sc (OH) ₃ precipitate; the Sc (OH) ₃ precipitation mother liquor is added to NaOH and returned to the thorium back extraction treatment step for use; The (OH) ₃ precipitate was washed with ethanol and water at 30 ° C and 80 ° C, respectively, to remove organic matters and water-soluble impurities adsorbed on the surface, respectively.

将Sc(OH) ₃沉淀在500℃煅烧以生成粗氧化钪；将粗氧化钪用0.01mol/L盐酸水溶液进行洗涤，温度为20℃，以除去其中的杂质元素，得到氧化钪；将粗氧化钪用稀盐酸水洗涤后得到的氧化钪用水洗涤，并干燥得到氧化钪产品，钪的提取率达到75％以上。 The Sc (OH) ₃ precipitate was calcined at 500 ° C to generate crude ytterbium oxide; the crude ytterbium oxide was washed with a 0.01 mol / L aqueous hydrochloric acid solution at a temperature of 20 ° C to remove impurity elements therein to obtain ytterbium oxide; the crude oxidized Rhenium oxide obtained after washing with dilute hydrochloric acid water is washed with water and dried to obtain a ytterbium oxide product, and the extraction rate of the rhenium reaches more than 75%.

实施例19Example 19

环烷酸萃取剂，NaOH反萃Naphthenic acid extractant, NaOH back extraction

在带搅拌混合作用的反应釜中，按照有机溶液、含钪溶液体积比为1：10，用含2mol/L环烷酸萃取剂的正庚烷溶液从钪硫酸溶液中萃取钪，用NaOH控制含钪溶液终点pH为3.5；按照萃取剂有机溶液、沉淀反萃剂溶液的体积比(有机溶液：水溶液体积比)为10：1，将洗涤后的负载钪的有机相与含7mol/L NaOH的反萃剂水溶液(水相)进行混合，以进行反萃取反应。向钪络阴离子溶液中加入盐酸以调节溶液至pH6.0，以生成Sc(OH) ₃沉淀；将Sc(OH) ₃沉淀分别用乙醇和水洗涤，洗涤温度为40℃和90℃；将Sc(OH) ₃沉淀在600℃煅烧以生成氧化钪；将粗氧化钪用0.5mol/L盐酸水溶液进行洗涤,温度为30℃，以除去其中的杂质元素，得到氧化钪，钪的总回收率在85％以上。 In a reaction kettle with stirring and mixing, according to the volume ratio of organic solution and thorium-containing solution of 1:10, thorium was extracted from thorium sulfuric acid solution with a n-heptane solution containing 2mol / L naphthenic acid extractant, and controlled by NaOH The final pH of the thorium-containing solution is 3.5; according to the volume ratio (organic solution: water solution volume ratio) of the extractant organic solution and the precipitation back-extractant solution is 10: 1, the washed tritium-containing organic phase and 7 mol / L NaOH The stripping agent aqueous solution (aqueous phase) was mixed to perform a stripping reaction. Hydrochloric acid was added to the complex anion solution to adjust the solution to pH 6.0 to generate a Sc (OH) ₃ precipitate; the Sc (OH) ₃ precipitate was washed with ethanol and water, respectively, at a washing temperature of 40 ° C and 90 ° C; The (OH) ₃ precipitate was calcined at 600 ° C to generate thorium oxide; the crude thorium oxide was washed with a 0.5 mol / L hydrochloric acid aqueous solution at a temperature of 30 ° C to remove the impurity elements therein to obtain thallium oxide. The total recovery of thallium oxide was 85% or more.

实施例20Example 20

VerS2atic10萃取剂(新癸酸)，NaOH反萃VerS2atic10 extractant (neodecanoic acid), NaOH back extraction

按照有机溶液、含钪溶液体积比为1:1，用含2mol/LVerS2atic10萃取剂的磺化煤油溶液从含钪盐酸溶液中萃取钪，用NaOH控制含钪溶液萃取平衡终点pH为3.25；钪的单极萃取率达到90％以上。According to the volume ratio of organic solution and tritium-containing solution was 1: 1, tritium was extracted from tritium-containing hydrochloric acid solution using a sulfonated kerosene solution containing 2mol / LVerS2atic10 extractant, and the final equilibrium pH of the tritium-containing solution was controlled to be 3.25 with NaOH; The unipolar extraction rate is over 90%.

采用pH 3.25的酸溶液按A/O相比1:1洗涤有机相，将洗涤后的负载钪的有机相与含6mol/L NaOH的反萃剂水溶液(水相)在混合澄清萃取槽中按A/O相比1:2进行混合反萃，反应温度为60℃，以进行反萃取反应，生成钪络阴离子处于水相中、并从水相出口流出；空载钪的有机相与钪络阴离子溶液分离，并返回萃取步骤再生后循环使用；向钪络阴离子溶液中加入盐酸以调节溶液至pH 8，以生成Sc(OH) ₃沉淀。 The organic phase was washed with an acid solution of pH 3.25 at A / O ratio of 1: 1, and the washed organic phase loaded with tritium and a stripping agent aqueous solution (aqueous phase) containing 6mol / L NaOH were mixed in a clarification extraction tank according to A / O compared with 1: 2 for mixed back-extraction, the reaction temperature is 60 ° C, to carry out the back-extraction reaction, the complex anion is in the aqueous phase and flows out from the aqueous phase outlet; The anion solution is separated and recycled back to the extraction step for regeneration. Hydrochloric acid is added to the anion solution to adjust the solution to pH 8 to form a Sc (OH) ₃ precipitate.

将Sc(OH) ₃沉淀在400℃煅烧以生成粗氧化钪；将粗氧化钪用0.01mol/L盐酸水溶液进行洗涤，温度为20℃，以除去其中的杂质元素，得到氧化钪；将粗氧化钪用稀盐酸水洗涤后得到的氧化钪用水洗涤，并干燥得到氧化钪产品，钪的总回收率在85％以上。 The Sc (OH) ₃ precipitate was calcined at 400 ° C to generate crude ytterbium oxide; the crude ytterbium oxide was washed with a 0.01 mol / L hydrochloric acid aqueous solution at a temperature of 20 ° C to remove impurity elements therein to obtain ytterbium oxide; the crude oxidized Rhenium oxide obtained after washing with dilute hydrochloric acid water is washed with water and dried to obtain a hafnium oxide product. The total recovery of the hafnium is above 85%.

实施例21Example 21

CA100萃取剂(仲壬基苯氧基乙酸)，NaOH反萃CA100 extractant (sec-nonylphenoxyacetic acid), NaOH back extraction

按照有机溶液、含钪溶液体积比为1:3，用含1mol/L CA100萃取剂的磺化煤油溶液从含钪盐酸溶液中萃取钪，用NaOH控制含钪溶液萃取平衡终点pH为3.2；钪的单级萃取率达到95％以上。According to the volume ratio of organic solution and tritium-containing solution was 1: 3, tritium was extracted from tritium-containing hydrochloric acid solution with a sulfonated kerosene solution containing 1 mol / L CA100 extractant, and the final equilibrium pH of the tritium-containing solution was controlled to be 3.2 with NaOH; The single-stage extraction rate reaches more than 95%.

采用pH 3.25的酸溶液按A/O相比1:1洗涤有机相，将洗涤后的负载钪的有机相与含4mol/L NaOH的反萃剂水溶液(水相)在混合澄清萃取槽中按A/O相比1:2进行混合反萃，反应温度为60℃，以进行反萃取反应，生成钪络阴离子处于水相中、并从水相出口流出；空载钪的有机相与钪络阴离子溶液分离，并返回萃取步骤再生后循环使用；向钪络阴离子溶液中加入盐酸溶液调节溶液至pH 7.5，以生成Sc(OH) ₃沉淀。 The organic phase was washed with an acid solution of pH 3.25 according to A / O ratio 1: 1, and the washed organic phase loaded with tritium and a stripping agent aqueous solution (aqueous phase) containing 4mol / L NaOH were mixed in a clarification extraction tank according to A / O compared with 1: 2 for mixed back-extraction, the reaction temperature is 60 ° C, to carry out the back-extraction reaction, the complex anion is in the aqueous phase and flows out from the aqueous phase outlet; The anion solution is separated and returned to the extraction step for regeneration and recycling; a hydrochloric acid solution is added to the complex anion solution to adjust the solution to pH 7.5 to form a Sc (OH) ₃ precipitate.

将Sc(OH) ₃沉淀在500℃煅烧以生成粗氧化钪；将粗氧化钪用0.01mol/L盐酸水溶液进行洗涤，温度为25℃，以除去其中的杂质元素，得到氧化钪；将粗氧化钪用稀盐酸水洗涤后得到的氧化钪用水洗涤，并干燥得到氧化钪产品，钪的总回收率在80％以上。 The Sc (OH) ₃ precipitate was calcined at 500 ° C to generate crude ytterbium oxide; the crude ytterbium oxide was washed with a 0.01 mol / L aqueous hydrochloric acid solution at a temperature of 25 ° C to remove the impurity elements therein to obtain the ytterbium oxide; the crude oxidized Rhenium oxide obtained after washing with dilute hydrochloric acid water is washed with water and dried to obtain a hafnium oxide product. The total recovery of the hafnium is above 80%.

实施例22Example 22

CA-12萃取剂(仲辛基苯氧基取代乙酸)，KOH为反萃剂CA-12 extractant (secondary octylphenoxy substituted acetic acid), KOH as back extractant

在混合澄清萃取槽中，按照有机溶液、含钪溶液体积比为1：5，用含4mol/l的CA-12萃取剂的煤油溶液从含钪盐酸溶液中萃取钪，用KOH控制含钪溶液终点pH为3；钪的单级萃取率达到85％以上。In a mixed and clarified extraction tank, according to the volume ratio of organic solution and thorium-containing solution of 1: 5, thorium was extracted from thorium-containing hydrochloric acid solution with a kerosene solution containing 4mol / l CA-12 extractant, and thorium-containing solution was controlled by KOH The endpoint pH was 3; the single-stage extraction rate of rhenium reached above 85%.

按照萃取有机溶液、反萃剂溶液的体积比(有机溶液、水溶液体积比)为1：1，将洗涤后的负载钪的有机相与含8mol/l KOH的反萃剂水溶液(水相)在混合澄清萃取槽中进行混合，反应温度为90℃，以进行反萃取反应，生成钪络阴离子处于水相中、并从水相出口流出；空载钪的有机相与钪络阴离子溶液分离，并返回萃取步骤循环使用；According to the volume ratio (volume ratio of organic solution and aqueous solution) of the extracted organic solution and back-extractant solution is 1: 1, the washed organic phase loaded with tritium and the back-extractant aqueous solution (water phase) containing 8 mol / l KOH Mix in a clarification extraction tank at a reaction temperature of 90 ° C to perform a back-extraction reaction. The generated anion complex is in the aqueous phase and flows out from the aqueous phase outlet; the organic phase with no-loaded tritium is separated from the complex anion solution, and Return to the extraction step for recycling;

将生成的氢氧化钪沉淀与沉淀母液通过真空过滤分离，得到富集的氢氧化钪Sc(OH) ₃沉淀；将Sc(OH) ₃沉淀母液加入KOH后返回钪反萃取处理步骤使用；将Sc(OH) ₃沉淀分别用乙醇和水洗涤，洗涤温度为20℃和50℃，以分别除去表面吸附的有机物和水溶性杂质。 The generated thorium hydroxide precipitate and the precipitation mother liquor are separated by vacuum filtration to obtain an enriched thorium hydroxide Sc (OH) ₃ precipitate; the Sc (OH) ₃ precipitation mother liquor is added to KOH and returned to the thorium back extraction treatment step for use; The (OH) ₃ precipitate was washed with ethanol and water at a washing temperature of 20 ° C and 50 ° C, respectively, to remove organic matters and water-soluble impurities adsorbed on the surface, respectively.

将Sc(OH) ₃沉淀在500℃煅烧以生成粗氧化钪；将粗氧化钪用0.01mol/L盐酸水溶液进行洗涤，温度为20℃，以除去其中的杂质元素，得到氧化钪；将粗氧化钪用稀盐酸水洗涤后得到的氧化钪用水洗涤，并干燥得到氧化钪产品，钪的提取率达到80％以上。 The Sc (OH) ₃ precipitate was calcined at 500 ° C to generate crude ytterbium oxide; the crude ytterbium oxide was washed with a 0.01 mol / L aqueous hydrochloric acid solution at a temperature of 20 ° C to remove impurity elements therein to obtain ytterbium oxide; the crude oxidized Rhenium oxide obtained after washing with dilute hydrochloric acid water is washed with water and dried to obtain a hafnium oxide product, and the extraction rate of the hafnium reaches more than 80%.

实施例23Example 23

按照萃取有机溶液、反萃剂溶液的体积比(有机溶液、水溶液体积比)为1：1，将洗涤后的负载钪的有机相与含8mol/l KOH的反萃剂水溶液(水相)在混合澄清萃取槽中进行混合，反应温度为60℃，以进行反萃取反应，生成钪络阴离子处于水相中、并从水相出口流出；空载钪的有机相与钪络阴离子溶液分离，并返回萃取步骤循环使用；According to the volume ratio (volume ratio of organic solution and aqueous solution) of the extracted organic solution and back-extractant solution is 1: 1, the washed organic phase loaded with tritium and the back-extractant aqueous solution (water phase) containing 8 mol / l KOH Mix in a clarification extraction tank with a reaction temperature of 60 ° C to perform a back-extraction reaction. The generated anion complex is in the aqueous phase and flows out from the aqueous phase outlet; the organic phase with no-loaded tritium is separated from the complex anion solution, and Return to the extraction step for recycling;

将Sc(OH) ₃沉淀在500℃煅烧以生成粗氧化钪；将粗氧化钪用0.01mol/L盐酸水溶液进行洗涤，温度为20℃，以除去其中的杂质元素，得到氧化钪；将粗氧化钪用稀盐酸水洗涤后得到的氧化钪用水洗涤，并干燥得到氧化钪产品，钪的提取率达到76％以上。 The Sc (OH) ₃ precipitate was calcined at 500 ° C to generate crude ytterbium oxide; the crude ytterbium oxide was washed with a 0.01 mol / L aqueous hydrochloric acid solution at a temperature of 20 ° C to remove impurity elements therein to obtain ytterbium oxide; the crude oxidized Rhenium oxide obtained after washing with dilute hydrochloric acid water is washed with water and dried to obtain a hafnium oxide product, and the extraction rate of the hafnium reaches more than 76%.

从以上的描述中，可以看出，本发明上述的实施例实现了如下技术效果：From the above description, it can be seen that the foregoing embodiments of the present invention achieve the following technical effects:

利用经煅烧过的粗氧化钪溶于热的浓盐酸但不溶于或极微量溶于稀盐酸的特性，将生成的粗氧化钪用稀盐酸水溶液在较低温度下进行洗涤，以溶解除去其中的杂质元素，能将钪与杂质元素很好的分离，得到纯化的氧化钪。The calcined crude ytterbium oxide is soluble in hot concentrated hydrochloric acid but insoluble or very slightly soluble in dilute hydrochloric acid, and the resulting crude ytterbium oxide is washed with a dilute aqueous hydrochloric acid solution at a lower temperature to dissolve and remove the Impurity elements can well separate rhenium from impurity elements to obtain purified erbium oxide.

以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

一种富集钪的方法，其特征在于，包括以下步骤：A method for enriching radon, which comprises the following steps:

S1，利用有机萃取剂或含有机萃取剂的有机溶剂溶液对含钪无机酸溶液进行钪萃取，获得含有钪的有机相；S1, using an organic extractant or an organic solvent solution containing an organic extractant to perform a rhenium extraction of the rhenium-containing inorganic acid solution to obtain an organic phase containing rhenium;

S2，利用沉淀剂溶液对所述含有钪的有机相进行反萃及沉淀取处理，固液分离及液液分离后获得含有钪的沉淀，以及沉淀母液和空载的有机相。S2: The lutetium-containing organic phase is back-extracted and precipitated by a precipitant solution. After the solid-liquid separation and the liquid-liquid separation, a lutetium-containing precipitate is obtained, and the mother liquor and the unloaded organic phase are precipitated.
根据权利要求1所述的方法，其特征在于，所述有机萃取剂为选自由酸性有机萃取剂、中性有机萃取剂、碱性有机萃取剂和有机螯合萃取剂组成的组中的一种或多种；The method according to claim 1, wherein the organic extractant is one selected from the group consisting of an acidic organic extractant, a neutral organic extractant, a basic organic extractant, and an organic chelating extractant. Or more

优选的，所述酸性有机萃取剂包括酸性有机磷萃取剂和/或有机羧酸萃取剂；更优选的，所述酸性有机磷萃取剂为二(2-乙基己基)磷酸和/或2-乙基己基磷酸单-2-乙基己基酯；更优选的，所述有机羧酸萃取剂为烷烃基羧酸、芳香烃基羧酸和环烷酸中的任一种或多种；进一步优选的，所述烷烃基羧酸为正己酸，所述芳香烃基羧酸为仲辛基苯氧基乙酸；Preferably, the acidic organic extractant comprises an acidic organic phosphorus extractant and / or an organic carboxylic acid extractant; more preferably, the acidic organic phosphorus extractant is bis (2-ethylhexyl) phosphoric acid and / or 2- Ethylhexyl phosphate mono-2-ethylhexyl phosphate; more preferably, the organic carboxylic acid extractant is any one or more of an alkane carboxylic acid, an aromatic carboxylic acid and a naphthenic acid; further preferred , The alkane carboxylic acid is n-hexanoic acid, and the aromatic hydrocarbon carboxylic acid is sec-octylphenoxyacetic acid;

优选的，所述中性有机萃取剂包括中性有机磷(氧)萃取剂和/或长链烷基酯；更优选的，所述中性有机磷(氧)萃取剂为磷酸三丁酯、甲基膦酸二甲庚酯和三烷基膦氧化物中的任一种或多种；Preferably, the neutral organic extractant includes a neutral organic phosphorus (oxy) extractant and / or a long-chain alkyl ester; more preferably, the neutral organic phosphorus (oxy) extractant is tributyl phosphate, Any one or more of dimethylheptyl methylphosphonate and trialkylphosphine oxide;

优选的，所述碱性萃取剂包括有机胺萃取剂；更优选的，所述有机胺萃取剂为烷基季胺、叔胺、仲胺、伯胺中的任一种或多种；进一步优选的，所述烷基季胺为氯化甲基三烷基铵，所述叔胺为三辛胺N235，所述仲胺为N-十二烯基三烷基甲胺，所述伯胺为1，1′，1″-三烷基甲胺；Preferably, the alkaline extractant includes an organic amine extractant; more preferably, the organic amine extractant is any one or more of an alkyl quaternary amine, a tertiary amine, a secondary amine, and a primary amine; further preferred The alkyl quaternary amine is methyltrialkylammonium chloride, the tertiary amine is trioctylamine N235, the secondary amine is N-dodecyltrialkylmethylamine, and the primary amine is 1,1 ′, 1 ″ -trialkylmethylamine;

优选的，所述有机螯合萃取剂包括β-二酮萃取剂；更优选的，所述β-二酮萃取剂为噻吩甲酰三氟丙酮和/或4-苯甲酰-3-甲基-1-苯基-5-吡唑啉酮。Preferably, the organic chelating extractant includes a β-diketone extractant; more preferably, the β-diketone extractant is thienyl trifluoroacetone and / or 4-benzoyl-3-methyl -1-phenyl-5-pyrazolone.
根据权利要求1所述的方法，其特征在于，所述含有机萃取剂的有机溶剂溶液中的有机溶剂为密度小于水的烷烃类或其混和物、芳香烃类、有机醇、有机醚或有机酯中的至少一种；The method according to claim 1, wherein the organic solvent in the organic solvent solution containing the organic extractant is an alkane or a mixture thereof having a density less than water, an aromatic hydrocarbon, an organic alcohol, an organic ether, or an organic solvent. At least one of esters;

优选的，所述烷烃类或其混和物包括正庚烷、正己烷和煤油；Preferably, the alkane or a mixture thereof includes n-heptane, n-hexane and kerosene;

优选的，所述芳香烃类包括苯和甲苯；Preferably, the aromatic hydrocarbons include benzene and toluene;

优选的，所述有机醇包括正己醇和异辛醇；Preferably, the organic alcohol includes n-hexanol and isooctanol;

优选的，所述有机醚包括***；Preferably, the organic ether includes diethyl ether;

优选的，所述有机酯包括乙酸乙酯。Preferably, the organic ester includes ethyl acetate.
根据权利要求1所述的方法，其特征在于，所述含有机萃取剂的有机溶剂溶液中所述有机萃取剂的浓度为0.01mol/L～10mol/L。The method according to claim 1, wherein the concentration of the organic extractant in the organic solvent solution containing the organic extractant is 0.01 mol / L to 10 mol / L.
根据权利要求1所述的方法，其特征在于，所述含钪无机酸溶液为含钪的硫酸溶液、盐酸溶液或硝酸溶液；任选的，所述含钪无机酸溶液中含有其它金属离子。The method according to claim 1, wherein the scandium-containing inorganic acid solution is a scandium-containing sulfuric acid solution, a hydrochloric acid solution, or a nitric acid solution; optionally, the scandium-containing inorganic acid solution contains other metal ions.
根据权利要求1所述的方法，其特征在于，所述沉淀剂溶液为氢氧化钠、氨水、草酸、氢氟酸、磷酸、草酸钠、碳酸钠、碳酸氢钠、磷酸钠、氟化钠、草酸铵、磷酸铵中一种或多种的水溶液。The method according to claim 1, wherein the precipitant solution is sodium hydroxide, ammonia, oxalic acid, hydrofluoric acid, phosphoric acid, sodium oxalate, sodium carbonate, sodium bicarbonate, sodium phosphate, sodium fluoride, An aqueous solution of one or more of ammonium oxalate and ammonium phosphate.
根据权利要求6所述的方法，其特征在于，所述沉淀剂溶液中的沉淀剂的浓度为0.01mol/L～15mol/L。The method according to claim 6, wherein the concentration of the precipitant in the precipitant solution is 0.01 mol / L to 15 mol / L.
根据权利要求1所述的方法，其特征在于，所述含有机萃取剂的有机溶剂溶液与所述含钪无机酸溶液的体积比为(1：20)～(1：1)。The method according to claim 1, wherein a volume ratio of the organic solvent solution containing the organic extractant to the hafnium-containing inorganic acid solution is (1:20) to (1: 1).
根据权利要求1所述的方法，其特征在于，所述含有钪的有机相与所述沉淀剂溶液的体积比为(1：20)～(20：1)。The method according to claim 1, wherein a volume ratio of the organic phase containing rhenium to the precipitant solution is (1:20) to (20: 1).
根据权利要求1所述的方法，其特征在于，所述空载有机相返回S1中钪萃取处理步骤使用；The method according to claim 1, characterized in that the no-load organic phase is returned to S1 in the tritium extraction treatment step for use;

优选的，所述S1与S2之间还包括对所述含有钪的有机相进行洗涤的步骤。Preferably, a step of washing the organic phase containing rhenium is further included between S1 and S2.
根据权利要求1所述的方法，其特征在于，所述钪萃取和沉淀反萃取处理中均采用机械搅拌的混合方式加快反应进度。The method according to claim 1, characterized in that both the mash extraction and the precipitation back-extraction treatment adopt a mixing method of mechanical stirring to accelerate the reaction progress.
根据权利要求1所述的方法，其特征在于，所述富集钪的方法所使用的设备为带搅拌混合作用的反应釜、混合澄清萃取槽或管式萃取器，以及离心机、真空过滤器或压滤机，或离心萃取混合分离一体设备，上述设备单独使用或联合使用。The method according to claim 1, characterized in that the equipment used in the method for enriching thorium is a reaction kettle with agitation, a mixing and clarifying extraction tank or a tube extractor, and a centrifuge, a vacuum filter Or filter press, or centrifugal extraction and mixing integrated equipment, the above equipment is used alone or in combination.
根据权利要求1所述的方法，其特征在于，包括以下步骤：The method according to claim 1, comprising the following steps:

S11，利用含酸性有机磷萃取剂的有机溶剂溶液对含钪无机酸溶液进行钪萃取，获得含有钪的有机相；S11, using a organic solvent solution containing an acidic organic phosphorus extractant to perform thorium extraction on the thorium-containing inorganic acid solution to obtain a thallium-containing organic phase;

S12，对所述含有钪的有机相进行洗涤处理以除去杂质；S12. Wash the organic phase containing rhenium to remove impurities;

S13，向除去杂质后的所述含有钪的有机相中加入浓NaOH或KOH溶液进行反萃取，液液分离后得到钪络阴离子溶液和空载有机相；S13, adding concentrated NaOH or KOH solution to the organic phase containing rhenium after removing impurities to perform back extraction, and obtaining a complex anion solution and an unloaded organic phase after liquid-liquid separation;

S14，向所述钪络阴离子溶液中加入盐酸调节溶液的酸碱度，以生成Sc(OH) ₃沉淀，固液分离后得到Sc(OH) ₃沉淀和沉淀母液； S14. Add hydrochloric acid to the complex anion solution to adjust the pH of the solution to generate a Sc (OH) ₃ precipitate. After solid-liquid separation, a Sc (OH) ₃ precipitate and a precipitation mother liquor are obtained;

S15，将所述Sc(OH) ₃沉淀煅烧得到氧化钪。 S15. Calcining the Sc (OH) ₃ precipitate to obtain hafnium oxide.
根据权利要求13所述的方法，其特征在于，所述S13中NaOH或KOH溶液的浓度为4mol/L～8mol/L。The method according to claim 13, wherein the concentration of the NaOH or KOH solution in the S13 is 4 mol / L to 8 mol / L.
根据权利要求13所述的方法，其特征在于，所述酸性有机磷萃取剂选自由二(2-乙基己基)磷酸、2-乙基己基磷酸单-2-乙基己基酯和Cyanex272萃取剂组成的组中的一种或多种。The method according to claim 13, wherein the acidic organic phosphorus extractant is selected from the group consisting of bis (2-ethylhexyl) phosphoric acid, 2-ethylhexyl phosphate mono-2-ethylhexyl ester, and Cyanex272 extractant. One or more of the group.
根据权利要求13所述的方法，其特征在于，所述含酸性有机磷萃取剂的有机溶剂溶液中的有机萃取剂为密度小于水的烷烃类或其混和物、芳香烃类、有机醇、有机醚或有机酯中的至少一种；The method according to claim 13, characterized in that the organic extractant in the organic solvent solution containing the acidic organic phosphorus extractant is an alkane or a mixture thereof having a density less than water, an aromatic hydrocarbon, an organic alcohol, an organic At least one of an ether or an organic ester;

优选的，所述烷烃类或其混和物包括正庚烷、正己烷和煤油；Preferably, the alkane or a mixture thereof includes n-heptane, n-hexane and kerosene;

优选的，所述芳香烃类包括苯和甲苯；Preferably, the aromatic hydrocarbons include benzene and toluene;

优选的，所述有机醇包括正己醇和异辛醇；Preferably, the organic alcohol includes n-hexanol and isooctanol;

优选的，所述有机醚包括***；Preferably, the organic ether includes diethyl ether;

优选的，所述有机酯包括乙酸乙酯。Preferably, the organic ester includes ethyl acetate.
根据权利要求15或16所述的方法，其特征在于，所述含酸性有机磷萃取剂的有机溶剂溶液中所述含酸性有机磷萃取剂的浓度为0.01mol/L～4mol/L。The method according to claim 15 or 16, wherein the concentration of the acidic organic phosphorus-containing extractant in the organic solvent solution containing the acidic organic phosphorus extractant is 0.01 mol / L to 4 mol / L.
根据权利要求13所述的方法，其特征在于，所述含钪无机酸溶液为含钪的硫酸溶液、盐酸溶液或硝酸溶液。The method according to claim 13, wherein the scandium-containing inorganic acid solution is a scandium-containing sulfuric acid solution, a hydrochloric acid solution, or a nitric acid solution.
根据权利要求13所述的方法，其特征在于，所述含酸性有机磷萃取剂的有机溶剂溶液与所述含钪无机酸溶液的体积比为(1：20)～(1：1)。The method according to claim 13, wherein a volume ratio of the organic solvent solution containing the acidic organic phosphorus extractant to the rhenium-containing inorganic acid solution is (1:20) to (1: 1).
根据权利要求14所述的方法，其特征在于，所述含酸性有机磷萃取剂的有机溶剂溶液与所述S13中NaOH或KOH溶液的体积比为(1：20)～(20：1)。The method according to claim 14, wherein a volume ratio of the organic solvent solution containing the acidic organic phosphorus extractant to the NaOH or KOH solution in S13 is (1:20) to (20: 1).
根据权利要求13所述的方法，其特征在于，所述S14与S15之间还包括：分别用乙醇和水洗涤所述Sc(OH) ₃沉淀。 The method according to claim 13, wherein between S14 and S15 further comprises: washing the Sc (OH) ₃ precipitate with ethanol and water, respectively.
根据权利要求21所述的方法，其特征在于，用乙醇洗涤的温度为20～40℃，用水洗涤的温度为50～90℃。The method according to claim 21, wherein the temperature for washing with ethanol is 20 to 40 ° C, and the temperature for washing with water is 50 to 90 ° C.
根据权利要求13所述的方法，其特征在于，所述S12中，所述洗涤处理所用洗涤液为0.1～4mol/L的盐酸水溶液或0.1～1mol/L的硫酸水溶液。The method according to claim 13, wherein in S12, the washing liquid used for the washing treatment is a 0.1 to 4 mol / L hydrochloric acid aqueous solution or a 0.1 to 1 mol / L sulfuric acid aqueous solution.
根据权利要求13所述的方法，其特征在于，所述空载有机相返回S11中钪萃取处理步骤使用。The method according to claim 13, characterized in that the no-load organic phase is returned to the step of S11 extraction treatment in S11.
根据权利要求13所述的方法，其特征在于，所述钪萃取和反萃取处理中均采用机械搅拌的混合方式加快反应进度。The method according to claim 13, characterized in that the mixing process of mechanical stirring is used in both the mash extraction and the back extraction process to accelerate the reaction progress.
根据权利要求13所述的方法，其特征在于，所述反萃取的反应温度为20～90℃，优选为50～70℃。The method according to claim 13, wherein the reaction temperature of the back extraction is 20 to 90 ° C, preferably 50 to 70 ° C.
根据权利要求13所述的方法，其特征在于，所述S14中向所述钪络阴离子溶液中加入盐酸调节溶液酸碱度，以生成Sc(OH) ₃沉淀，沉淀终点pH为5.0～8.0。 The method according to claim 13, characterized in that, in step S14, hydrochloric acid is added to the complex anion solution to adjust the pH of the solution to form a Sc (OH) ₃ precipitate, and the pH of the precipitation end point is 5.0 to 8.0.
根据权利要求13所述的方法，其特征在于，所述S15中将Sc(OH) ₃沉淀煅烧以生成氧化钪的温度为400～650℃。 The method according to claim 13, characterized in that the temperature at which the Sc (OH) _{3 is} precipitated and calcined in the S15 to generate hafnium oxide is 400-650 ° C.
根据权利要求1所述的方法，其特征在于，包括以下步骤：The method according to claim 1, comprising the following steps:

S21，利用含有机羧酸萃取剂的有机溶剂溶液对含钪无机酸溶液进行钪萃取，获得含有钪的有机相；S21, using an organic solvent solution containing an organic carboxylic acid extractant to perform thorium extraction on the thorium-containing inorganic acid solution to obtain a thallium-containing organic phase;

S22，向所述含有钪的有机相中加入浓NaOH或KOH溶液进行反萃取，液液分离后得到钪络阴离子溶液和空载有机相；S22, adding concentrated NaOH or KOH solution to the organic phase containing rhenium for back extraction, and obtaining a complex anion solution and an unloaded organic phase after liquid-liquid separation;

S23，向所述钪络阴离子溶液中加入盐酸调节溶液的酸碱度，以生成Sc(OH) ₃沉淀，固液分离后得到Sc(OH) ₃沉淀和沉淀母液； S23. Add hydrochloric acid to the complex anion solution to adjust the pH of the solution to generate a Sc (OH) ₃ precipitate. After solid-liquid separation, a Sc (OH) ₃ precipitate and a precipitation mother liquor are obtained;

S24，将所述Sc(OH) ₃沉淀煅烧得到粗氧化钪； S24. The Sc (OH) ₃ precipitate is calcined to obtain crude hafnium oxide;

S25，将所述粗氧化钪用盐酸水溶液进行洗涤，去除杂质元素，得到氧化钪。S25, washing the crude hafnium oxide with an aqueous hydrochloric acid solution to remove impurity elements to obtain hafnium oxide.
根据权利要求29所述的方法，其特征在于，所述S22中NaOH或KOH溶液的浓度为4mol/L～8mol/L。The method according to claim 29, wherein a concentration of the NaOH or KOH solution in the S22 is 4 mol / L to 8 mol / L.
根据权利要求29所述的方法，其特征在于，所述有机羧酸萃取剂选自由烷烃基羧酸、芳香烃基羧酸和环烷酸组成的组中的一种或多种；The method according to claim 29, wherein the organic carboxylic acid extractant is one or more selected from the group consisting of an alkane carboxylic acid, an aromatic carboxylic acid, and a naphthenic acid;

优选的，所述烷烃基羧酸为正己酸；Preferably, the alkanecarboxylic acid is n-hexanoic acid;

优选的，所述芳香烃基羧酸为仲辛基苯氧基乙酸。Preferably, the aromatic hydrocarbon-based carboxylic acid is sec-octylphenoxyacetic acid.
根据权利要求29所述的方法，其特征在于，所述含有机羧酸萃取剂的有机溶剂溶液中的有机萃取剂为密度小于水的烷烃类或其混和物、芳香烃类、有机醇、有机醚或有机酯中的至少一种；The method according to claim 29, wherein the organic extractant in the organic solvent solution containing an organic carboxylic acid extractant is an alkane or a mixture thereof having a density less than water, an aromatic hydrocarbon, an organic alcohol, or an organic solvent. At least one of an ether or an organic ester;

优选的，所述烷烃类或其混和物包括正庚烷、正己烷和煤油；Preferably, the alkane or a mixture thereof includes n-heptane, n-hexane and kerosene;

优选的，所述芳香烃类包括苯和甲苯；Preferably, the aromatic hydrocarbons include benzene and toluene;

优选的，所述有机醇包括正己醇和异辛醇；Preferably, the organic alcohol includes n-hexanol and isooctanol;

优选的，所述有机醚包括***；Preferably, the organic ether includes diethyl ether;

优选的，所述有机酯包括乙酸乙酯。Preferably, the organic ester includes ethyl acetate.
根据权利要求31或32所述的方法，其特征在于，所述含有机羧酸萃取剂的有机溶剂溶液中所述有机羧酸萃取剂的浓度为0.01mol/L～4mol/L。The method according to claim 31 or 32, wherein the concentration of the organic carboxylic acid extractant in the organic solvent solution containing the organic carboxylic acid extractant is 0.01 mol / L to 4 mol / L.
根据权利要求29所述的方法，其特征在于，所述含钪无机酸溶液为含钪的硫酸溶液、盐酸溶液或硝酸溶液，任选的，所述含钪无机酸溶液中含有其它金属离子，所述其它金属离子为Ca ²⁺、Mg ²⁺、Mn ²⁺、Ni ²⁺、Al ³⁺、Fe ³⁺、Cr ³⁺中的一种或多种。 The method according to claim 29, wherein the scandium-containing inorganic acid solution is a scandium-containing sulfuric acid solution, a hydrochloric acid solution, or a nitric acid solution, and optionally, the scandium-containing inorganic acid solution contains other metal ions, The other metal ions are one or more of Ca ²⁺ , Mg ²⁺ , Mn ²⁺ , Ni ²⁺ , Al ³⁺ , Fe ³⁺ , and Cr ³⁺ .
根据权利要求29所述的方法，其特征在于，所述含有机羧酸萃取剂的有机溶剂溶液与所述含钪无机酸溶液的体积比为(1：10)～(1：1)；The method according to claim 29, wherein a volume ratio of the organic solvent solution containing the organic carboxylic acid extractant to the rhenium-containing inorganic acid solution is (1:10) to (1: 1);

优选的，利用含有机羧酸萃取剂的有机溶剂溶液对含钪无机酸溶液进行钪萃取，用NaOH控制所述含钪无机酸溶液的终点pH为2～4。Preferably, the rhenium-containing inorganic acid solution is subjected to holmium extraction using an organic solvent solution containing an organic carboxylic acid extractant, and the end pH of the holmium-containing inorganic acid solution is controlled by NaOH to be 2 to 4.
根据权利要求30所述的方法，其特征在于，所述含有机羧酸萃取剂的有机溶剂溶液与所述S22中NaOH或KOH溶液的体积比为(1：10)～(10：1)。The method according to claim 30, wherein a volume ratio of the organic solvent solution containing the organic carboxylic acid extractant to the NaOH or KOH solution in the S22 is (1:10) to (10: 1).
根据权利要求29所述的方法，其特征在于，所述S23与S24之间还包括：分别用乙醇和水洗涤所述Sc(OH) ₃沉淀。 The method according to claim 29, wherein between S23 and S24 further comprises: washing the Sc (OH) ₃ precipitate with ethanol and water, respectively.
根据权利要求37所述的方法，其特征在于，用乙醇洗涤的温度为20～40℃，用水洗涤的温度为50～90℃。The method according to claim 37, wherein the temperature for washing with ethanol is 20 to 40 ° C, and the temperature for washing with water is 50 to 90 ° C.
根据权利要求29所述的方法，其特征在于，所述S25中，所用盐酸水溶液的浓度为0.01～0.5mol/L；The method according to claim 29, wherein the concentration of the aqueous hydrochloric acid solution used in the S25 is 0.01 to 0.5 mol / L;

优选的，将所述粗氧化钪用盐酸水溶液进行洗涤，温度为10～30℃；Preferably, the crude hafnium oxide is washed with an aqueous hydrochloric acid solution at a temperature of 10 to 30 ° C;

优选的，将所述粗氧化钪用盐酸水溶液进行洗涤后再用水洗涤，然后干燥。Preferably, the crude hafnium oxide is washed with an aqueous solution of hydrochloric acid, then washed with water, and then dried.
根据权利要求29所述的方法，其特征在于，所述空载有机相返回S21中钪萃取处理步骤使用；所述沉淀母液加入NaOH后返回S22钪反萃取处理步骤中使用。The method according to claim 29, wherein the no-load organic phase is returned to the step S21 in the extraction treatment step; after adding NaOH, the precipitation mother liquor is returned to the step S22 in the step of extraction treatment.
根据权利要求29所述的方法，其特征在于，所述钪萃取和反萃取处理中均采用机械搅拌的混合方式加快反应进度。The method according to claim 29, characterized in that the mixing process of mechanical stirring is used in both the mash extraction and the back extraction process to accelerate the reaction progress.
根据权利要求29所述的方法，其特征在于，所述反萃取的反应温度为20～90℃，优选为40～60℃。The method according to claim 29, wherein the reaction temperature of the back extraction is 20 to 90 ° C, preferably 40 to 60 ° C.
根据权利要求29所述的方法，其特征在于，所述S23中向所述钪络阴离子溶液中加入盐酸调节溶液酸碱度，以生成Sc(OH) ₃沉淀，沉淀终点pH为5.0～8.0。 The method according to claim 29, wherein in S23, hydrochloric acid is added to the complex anion solution to adjust the pH of the solution to form a Sc (OH) ₃ precipitate, and the pH of the precipitation endpoint is 5.0 to 8.0.
根据权利要求29所述的方法，其特征在于，所述S25中将Sc(OH) ₃沉淀煅烧以生成氧化钪的温度为400～650℃。 The method according to claim 29, wherein the temperature of Sc (OH) ₃ precipitation and calcination in S25 to generate hafnium oxide is 400-650 ° C.