CN111961849B - Method for extracting and separating scandium - Google Patents

Method for extracting and separating scandium Download PDF

Info

Publication number
CN111961849B
CN111961849B CN202010907235.4A CN202010907235A CN111961849B CN 111961849 B CN111961849 B CN 111961849B CN 202010907235 A CN202010907235 A CN 202010907235A CN 111961849 B CN111961849 B CN 111961849B
Authority
CN
China
Prior art keywords
scandium
extraction
organic phase
concentration
phase
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010907235.4A
Other languages
Chinese (zh)
Other versions
CN111961849A (en
Inventor
孙国新
彭修静
赵奕铭
崔玉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Jinan
Original Assignee
University of Jinan
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Jinan filed Critical University of Jinan
Priority to CN202010907235.4A priority Critical patent/CN111961849B/en
Publication of CN111961849A publication Critical patent/CN111961849A/en
Application granted granted Critical
Publication of CN111961849B publication Critical patent/CN111961849B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/28Amines
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B59/00Obtaining rare earth metals

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Environmental & Geological Engineering (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

本发明属于钪的萃取提纯技术领域,具体涉及一种利用酰胺荚醚萃取剂分离钪和其他杂质的方法。本发明采用N,N,N’,N’‑四环己基‑3‑氧戊二酰胺为萃取剂从硝酸介质中分离钪,对钪具有高选择性,对Fe、Mg、Ti、Ba、Al、Zr、Mn等杂质萃取能力差,实现钪与杂质元素的分离。本技术操作简单、污染小、对设备要求低。The invention belongs to the technical field of extraction and purification of scandium, and in particular relates to a method for separating scandium and other impurities by utilizing an amide pod ether extractant. The invention adopts N,N,N',N'-tetracyclohexyl-3-oxoglutaramide as extractant to separate scandium from nitric acid medium, has high selectivity to scandium, and has high selectivity to Fe, Mg, Ti, Ba, Al , Zr, Mn and other impurities have poor extraction ability, and realize the separation of scandium and impurity elements. The technology is simple in operation, low in pollution and low in equipment requirements.

Description

一种萃取分离钪的方法A kind of method of extracting and separating scandium

技术领域technical field

本发明属于湿法冶金技术领域,具体涉及一种利用酰胺荚醚萃取剂分离钪和其他杂质的方法。The invention belongs to the technical field of hydrometallurgy, in particular to a method for separating scandium and other impurities by utilizing an amide pod ether extraction agent.

背景技术Background technique

钪的优异性能使其在电光源、宇航、电子工业、核技术、超导技术等领域起着重要作用,但是钪作为稀土元素,分布较散,独立矿床极为稀少。粗氧化钪含有杂质Fe、Mg、Ti、Ba、Al、Zr、Mn等,Sc2O3含量80~90%。在钪的提取过程中如何用较低的成本对钪进行富集,进而获得高纯度的氧化钪是工业难题。The excellent properties of scandium make it play an important role in the fields of electric light source, aerospace, electronic industry, nuclear technology, superconducting technology, etc. However, as a rare earth element, scandium is scattered and independent deposits are extremely rare. Crude scandium oxide contains impurities Fe, Mg, Ti, Ba, Al, Zr, Mn, etc., and the content of Sc 2 O 3 is 80-90%. In the process of extracting scandium, how to enrich scandium with low cost and then obtain high-purity scandium oxide is an industrial problem.

中国专利CN108754156A)公开了一种萃取法分离赤泥酸浸出液中铁和钪的方法,采用含长链烷基季铵盐萃取剂对铁配合物离子进行萃取分离,使钪离子留在浸出液中,实现铁与钪的分离。该方法对铁去除率大于95%,说明浸出液中仍残留一定量的铁,影响钪的纯度。中国专利(公开号CN109022810B)公开了一种从钨渣中分离回收有价金属铁、锰和钪的方法,用P204萃取硫酸的浸出液,浸出液中铁、锰及钪的单级萃取率分别为86.1%、82.4%和97.7%,采用不同的反萃液对金属进行反萃,难以得到高纯的钪产品。中国专利(公开号CN109022839A)公开了富集钪的方法,采用不同的萃取剂对钪进行富集,分别采用中性、碱性、有机螯合萃取剂钪进行萃取和反萃,未提到对杂质的分离情况。中国专利(公开号CN1844421A)公开了一种赤泥提钪的方法,采用P204萃取回收赤泥中的钪,在反萃前需先用2.5 mol/L浓硫酸先对负载有机相进行净化,产生大量铁含量较低的浓酸,难以处理。中国专利(公开号CN101182601A)采用不同质量分数的浓盐酸对赤泥进行两次浸渍,利用P204对第二次浸出液进行萃钪,有机相中含有少量杂质铁,影响钪的纯度。Chinese patent CN108754156A) discloses a method for separating iron and scandium in red mud acid leaching solution by an extraction method. The iron complex ions are extracted and separated by using a long-chain alkyl quaternary ammonium salt extractant, so that the scandium ions remain in the leaching solution to realize The separation of iron and scandium. The iron removal rate of this method is greater than 95%, indicating that a certain amount of iron remains in the leaching solution, which affects the purity of scandium. Chinese patent (publication number CN109022810B) discloses a method for separating and recovering valuable metals iron, manganese and scandium from tungsten slag, using P204 to extract the leaching solution of sulfuric acid, and the single-stage extraction rates of iron, manganese and scandium in the leaching solution are 86.1% respectively , 82.4% and 97.7%, it is difficult to obtain high-purity scandium products by using different stripping solutions to strip metals. Chinese patent (publication number CN109022839A) discloses a method for enriching scandium, using different extractants to enrich scandium, respectively using neutral, alkaline, organic chelating extractant scandium for extraction and back-extraction. Separation of impurities. Chinese patent (publication number CN1844421A) discloses a kind of method for extracting scandium from red mud, adopts P204 extraction and reclaims scandium in red mud, and needs to use 2.5 mol/L concentrated sulfuric acid to first purify the loaded organic phase before stripping, resulting in Large amounts of concentrated acid with low iron content are difficult to handle. Chinese patent (publication number CN101182601A) uses concentrated hydrochloric acid of different mass fractions to impregnate red mud twice, and uses P204 to extract scandium from the second leaching solution. The organic phase contains a small amount of impurity iron, which affects the purity of scandium.

上述萃取分离中常用含磷类萃取剂(P204等),萃取过程中加碱,产生含盐、氨氮废水,难以处理,燃烧后有固体废物残留。Phosphorus-containing extractants (P204, etc.) are commonly used in the above-mentioned extraction and separation, and alkali is added during the extraction process, resulting in waste water containing salt and ammonia nitrogen, which is difficult to handle, and solid waste remains after combustion.

发明内容SUMMARY OF THE INVENTION

粗氧化钪中Sc2O3含量80~90%,常用含磷类萃取剂对钪进行提纯,污染环境。本发明设计合成N,N,N’,N’-四环己基-3-氧戊二酰胺萃取剂,该萃取剂分子量大,几乎不溶于水,萃取过程不需要皂化,环境友好。该萃取剂在硝酸以及硝酸和硝酸盐共存的溶液中具有很强的萃取钪的能力,而对共存的杂质离子萃取能力低,利用萃取剂对钪和其他杂质高的分离系数,有效分离钪和其他杂质元素。The content of Sc 2 O 3 in crude scandium oxide is 80-90%, and phosphorus-containing extractants are commonly used to purify scandium, which pollutes the environment. The present invention designs and synthesizes N,N,N',N'-tetracyclohexyl-3-oxoglutaramide extractant, which has a large molecular weight, is almost insoluble in water, does not require saponification in the extraction process, and is environmentally friendly. The extractant has a strong ability to extract scandium in nitric acid and the coexisting solution of nitric acid and nitrate, but has a low ability to extract coexisting impurity ions. The high separation coefficient of the extractant to scandium and other impurities can effectively separate scandium and other impurities. other impurity elements.

本发明以上技术特点通过以下技术方案实施,一种萃取分离钪的方法,由以下步骤组成:The above technical features of the present invention are implemented through the following technical solutions, and a method for extracting and separating scandium is composed of the following steps:

(1)用硝酸溶解钪样品得到杂质包括Fe、Mg、Ti、Ba、Al、Zr、Mn的水溶液,水相中硝酸浓度为0.01~5 mol/L,或硝酸浓度为0.01~1 mol/L和硝酸盐浓度为0.01~4 mol/L,其中钪总浓度为1~200 g/L。(1) Dissolve the scandium sample with nitric acid to obtain an aqueous solution with impurities including Fe, Mg, Ti, Ba, Al, Zr, and Mn. The concentration of nitric acid in the aqueous phase is 0.01~5 mol/L, or the concentration of nitric acid is 0.01~1 mol/L and nitrate concentrations were 0.01-4 mol/L, of which the total scandium concentration was 1-200 g/L.

(2)称量一定质量的N,N,N’,N’-四环己基-3-氧戊二酰胺萃取剂,利用稀释剂稀释到一定浓度为有机相,其中稀释剂为甲苯、二甲苯、二氯甲烷、氯仿或四氯化碳的一种;萃取剂浓度为0.01~2 mol/L。(2) Weigh a certain mass of N,N,N',N'-tetracyclohexyl-3-oxoglutaramide extractant, and dilute it with a diluent to a certain concentration to form the organic phase, wherein the diluent is toluene, xylene , one of dichloromethane, chloroform or carbon tetrachloride; the concentration of extractant is 0.01~2 mol/L.

(3)将一定体积比例(1:10~10:1)的水相和有机相混合搅拌10~120 min,萃取温度为5~60 oC。(3) Mix and stir the aqueous phase and the organic phase in a certain volume ratio (1:10~10:1) for 10~120 min, and the extraction temperature is 5~60 o C.

(4)萃取后的混合溶液静置1~5 min分相,变为澄清透明的两相,即负载钪有机相,杂质留在萃余液水相中。(4) The mixed solution after extraction is left to stand for 1-5 minutes to separate phases, and becomes two clear and transparent phases, namely the organic phase loaded with scandium, and the impurities remain in the aqueous phase of the raffinate.

(5)取一定体积浓度为0.1~1.0 mol/L草酸或者草酸盐水溶液与负载钪有机相混合,搅拌时间为 5~100 min,温度为 5~60 oC,静置分离有机相,过滤水相得到沉淀,120 oC烘干2小时,600 oC煅烧2小时,得到氧化钪。静置分层后的有机相可重复使用。(5) Take a certain volume concentration of 0.1~1.0 mol/L oxalic acid or oxalate aqueous solution and mix it with the organic phase loaded with scandium, the stirring time is 5~100 min, the temperature is 5~60 o C, stand to separate the organic phase, filter The aqueous phase was precipitated, dried at 120 o C for 2 hours, and calcined at 600 o C for 2 hours to obtain scandium oxide. The organic phase after standing and layering can be reused.

与现有技术相比,本发明具有的特点和有益效果是:Compared with the prior art, the present invention has the following characteristics and beneficial effects:

(1)本发明所用萃取剂对钪具有高的识别能力,对钪与杂质元素的分离系数大,有利于钪与杂质的有效分离。(1) The extractant used in the present invention has high identification ability for scandium, and has a large separation coefficient for scandium and impurity elements, which is beneficial to the effective separation of scandium and impurities.

(2)本发明采用的萃取剂热稳定性好,不易挥发,水溶性小,物理化学稳定性好,可重复使用,用的所有试剂低价易得且投入量少,节约成本。(2) The extractant used in the present invention has good thermal stability, low volatility, low water solubility, good physical and chemical stability, and can be reused.

(3)与磷酸类萃取剂相比,本发明采用的萃取剂不需要皂化,属于环境友好型萃取剂。(3) Compared with the phosphoric acid extractant, the extractant used in the present invention does not need saponification, and belongs to the environment-friendly extractant.

(4)本发明操作简便,对设备要求低,容易实现连续工业化生产。(4) The present invention is easy to operate, has low requirements for equipment, and is easy to realize continuous industrial production.

具体实施方法Specific implementation method

萃取率(E)代表萃取前后水相金属浓度的比值。本专利中金属Sc、Fe、Mg、Ti、Ba、Al、Zr、Mn的浓度通过 ICP-AES 测定。The extraction rate (E) represents the ratio of metal concentrations in the aqueous phase before and after extraction. The concentrations of metals Sc, Fe, Mg, Ti, Ba, Al, Zr, Mn in this patent were determined by ICP-AES.

称量36g纯度为85%氧化钪产品,用硝酸加热溶解钪样品,以下工作溶液均由此溶液稀释得到。Weigh 36g of scandium oxide product with a purity of 85%, and heat the scandium sample with nitric acid to dissolve the scandium sample. The following working solutions are all diluted with this solution.

实施例1Example 1

(1)水相中Sc的浓度为5 g/L,硝酸浓度为0.6 mol/L。(1) The concentration of Sc in the aqueous phase is 5 g/L, and the concentration of nitric acid is 0.6 mol/L.

(2)以甲苯为稀释剂,配制0.5 mol/L 的 N,N,N',N'-四环己基-3-氧戊二酰胺为有机相。(2) Using toluene as the diluent, prepare 0.5 mol/L N,N,N',N'-tetracyclohexyl-3-oxoglutaramide as the organic phase.

(3)将水相和有机相各取20 mL 混合,搅拌时间为30 min,萃取温度为10 oC,测定萃余液中Sc的浓度,萃取率为99.89%。(3) The aqueous phase and the organic phase were mixed with 20 mL each, the stirring time was 30 min, the extraction temperature was 10 o C, the concentration of Sc in the raffinate was measured, and the extraction rate was 99.89%.

(4)取20 mL浓度为0.5 mol/L草酸水溶液与萃取后有机相混合,搅拌时间为30min,温度为 30 oC,静置分离有机相,过滤水相得到沉淀,120 oC烘干2小时,600 oC煅烧2小时,得到氧化钪。钪回收率98%以上,钪纯度99.8%以上。(4) Mix 20 mL of oxalic acid aqueous solution with a concentration of 0.5 mol/L with the organic phase after extraction, stir for 30 min, and at a temperature of 30 o C, stand to separate the organic phase, filter the aqueous phase to obtain a precipitate, and dry at 120 o C for 2 calcination at 600 o C for 2 hours to obtain scandium oxide. The recovery rate of scandium is over 98%, and the purity of scandium is over 99.8%.

实施例2Example 2

(1)水相中Sc的浓度为5 g/L,硝酸浓度为0.6 mol/L。(1) The concentration of Sc in the aqueous phase is 5 g/L, and the concentration of nitric acid is 0.6 mol/L.

(2)以甲苯为稀释剂,配制0.5 mol/L 的 N,N,N',N'-四环己基-3-氧戊二酰胺为有机相。(2) Using toluene as the diluent, prepare 0.5 mol/L N,N,N',N'-tetracyclohexyl-3-oxoglutaramide as the organic phase.

(3)将水相和有机相各取20 mL 混合,搅拌时间为30 min,萃取温度为40 oC,测定萃余液中Sc的浓度,萃取率为98.85%。(3) The aqueous phase and the organic phase were mixed with 20 mL each, the stirring time was 30 min, the extraction temperature was 40 o C, the concentration of Sc in the raffinate was measured, and the extraction rate was 98.85%.

(4)取20 mL浓度为0.5 mol/L草酸盐水溶液与萃取后有机相混合,搅拌时间为30min,温度为30 oC,静置分离有机相,过滤水相得到沉淀,120 oC烘干2小时,600 oC煅烧2小时,得到氧化钪。钪回收率97%以上,钪纯度99.3%以上。(4) Take 20 mL of oxalate aqueous solution with a concentration of 0.5 mol/L and mix it with the organic phase after extraction, stir for 30 minutes, and set the temperature to 30 o C, stand to separate the organic phase, filter the aqueous phase to obtain a precipitate, and bake at 120 o C. Dry for 2 hours and calcined at 600 o C for 2 hours to obtain scandium oxide. The recovery rate of scandium is over 97%, and the purity of scandium is over 99.3%.

实施例3Example 3

(1)水相中Sc的浓度为10 g/L,硝酸浓度为3.0 mol/L。(1) The concentration of Sc in the aqueous phase is 10 g/L, and the concentration of nitric acid is 3.0 mol/L.

(2)以甲苯为稀释剂,配制1 mol/L 的 N,N,N',N'-四环己基-3-氧戊二酰胺为有机相。(2) Using toluene as the diluent, prepare 1 mol/L N,N,N',N'-tetracyclohexyl-3-oxoglutaramide as the organic phase.

(3)将水相和有机相各取20 mL 混合,搅拌时间为30 min,萃取温度为20 oC,测定萃余液中Sc的浓度,萃取率为99.98%。(3) The aqueous phase and the organic phase were mixed with 20 mL each, the stirring time was 30 min, the extraction temperature was 20 o C, the concentration of Sc in the raffinate was measured, and the extraction rate was 99.98%.

(4)取20 mL浓度为0.5 mol/L草酸水溶液与萃取后有机相混合,搅拌时间为30min,温度为30 oC,静置分离有机相,过滤水相得到沉淀,120 oC烘干2小时,600 oC煅烧2小时,得到氧化钪。钪回收率98%以上,钪纯度99.9%以上。(4) Mix 20 mL of oxalic acid aqueous solution with a concentration of 0.5 mol/L with the organic phase after extraction, stir for 30 min, and at a temperature of 30 o C, stand to separate the organic phase, filter the aqueous phase to obtain a precipitate, and dry at 120 o C for 2 calcination at 600 o C for 2 hours to obtain scandium oxide. The recovery rate of scandium is over 98%, and the purity of scandium is over 99.9%.

实施例4Example 4

(1)水相中Sc的浓度为10 g/L,硝酸浓度为0.2 mol/L,硝酸锂浓度0.4 mol/L。(1) The concentration of Sc in the aqueous phase is 10 g/L, the concentration of nitric acid is 0.2 mol/L, and the concentration of lithium nitrate is 0.4 mol/L.

(2)以甲苯为稀释剂,配制1 mol/L 的 N,N,N',N'-四环己基-3-氧戊二酰胺为有机相。(2) Using toluene as the diluent, prepare 1 mol/L N,N,N',N'-tetracyclohexyl-3-oxoglutaramide as the organic phase.

(3)将水相和有机相各取20 mL 混合,搅拌时间为30 min,萃取温度为20 oC,测定萃余液中Sc的浓度,萃取率为86.96%。(3) The aqueous phase and the organic phase were mixed with 20 mL each, the stirring time was 30 min, the extraction temperature was 20 o C, and the concentration of Sc in the raffinate was measured, and the extraction rate was 86.96%.

(4)取20 mL浓度为1.0 mol/L草酸盐水溶液与萃取后有机相混合,搅拌时间为 30min,温度为 30 oC,静置分离有机相,过滤水相得到沉淀,120 oC烘干2小时,600 oC煅烧2小时,得到氧化钪。钪回收率85%以上,钪纯度99.7%以上。(4) Take 20 mL of oxalate aqueous solution with a concentration of 1.0 mol/L and mix it with the organic phase after extraction. The stirring time is 30 min and the temperature is 30 o C. The organic phase is separated by standing, and the aqueous phase is filtered to obtain a precipitate. Dry at 120 o C. Dry for 2 hours and calcined at 600 o C for 2 hours to obtain scandium oxide. The recovery rate of scandium is over 85%, and the purity of scandium is over 99.7%.

实施例5Example 5

(1)水相中Sc的浓度为10 g/L,硝酸浓度为0.2 mol/L,硝酸锂浓度3 mol/L。(1) The concentration of Sc in the aqueous phase is 10 g/L, the concentration of nitric acid is 0.2 mol/L, and the concentration of lithium nitrate is 3 mol/L.

(2)以甲苯为稀释剂,配制1 mol/L的N,N,N',N'-四环己基-3-氧戊二酰胺为有机相。(2) Using toluene as the diluent, prepare 1 mol/L of N,N,N',N'-tetracyclohexyl-3-oxoglutaramide as the organic phase.

(3)将水相和有机相各取20 mL 混合,搅拌时间为30 min,萃取温度为20 oC,测定萃余液中Sc的浓度,萃取率为99.68%。(3) The aqueous phase and the organic phase were mixed with 20 mL each, the stirring time was 30 min, the extraction temperature was 20 o C, the concentration of Sc in the raffinate was measured, and the extraction rate was 99.68%.

(4)取20 mL浓度为0.5 mol/L草酸水溶液与萃取后有机相混合,搅拌时间为30min,温度为30 oC,静置分离有机相,过滤水相得到沉淀,120 oC烘干2小时,600 oC煅烧2小时,得到氧化钪。钪回收率98%以上,钪纯度99.7%以上。(4) Mix 20 mL of oxalic acid aqueous solution with a concentration of 0.5 mol/L with the organic phase after extraction, stir for 30 min, and at a temperature of 30 o C, stand to separate the organic phase, filter the aqueous phase to obtain a precipitate, and dry at 120 o C for 2 calcination at 600 o C for 2 hours to obtain scandium oxide. The recovery rate of scandium is over 98%, and the purity of scandium is over 99.7%.

实施例6Example 6

(1)水相中Sc的浓度为5 g/L,硝酸浓度为0.2 mol/L,硝酸锂浓度3 mol/L。(1) The concentration of Sc in the aqueous phase is 5 g/L, the concentration of nitric acid is 0.2 mol/L, and the concentration of lithium nitrate is 3 mol/L.

(2)以甲苯为稀释剂,配制0.5 mol/L的N,N,N',N'-四环己基-3-氧戊二酰胺为有机相。(2) Using toluene as the diluent, prepare 0.5 mol/L N,N,N',N'-tetracyclohexyl-3-oxoglutaramide as the organic phase.

(3)将水相和有机相各取20 mL 混合,搅拌时间为60 min,萃取温度为20 oC,测定萃余液中Sc的浓度,萃取率为99.98%。(3) The aqueous phase and the organic phase were mixed with 20 mL each, the stirring time was 60 min, the extraction temperature was 20 o C, and the concentration of Sc in the raffinate was measured, and the extraction rate was 99.98%.

(4)取20 mL浓度为0.5 mol/L草酸水溶液与萃取后有机相混合,搅拌时间为30min,温度为30 oC,静置分离有机相,过滤水相得到沉淀,120 oC烘干2小时,600 oC煅烧2小时,得到氧化钪。钪回收率98%以上,钪纯度99.6%以上。(4) Mix 20 mL of oxalic acid aqueous solution with a concentration of 0.5 mol/L with the organic phase after extraction, stir for 30 min, and at a temperature of 30 o C, stand to separate the organic phase, filter the aqueous phase to obtain a precipitate, and dry at 120 o C for 2 calcination at 600 o C for 2 hours to obtain scandium oxide. The recovery rate of scandium is over 98%, and the purity of scandium is over 99.6%.

实施例7Example 7

(1)水相中Sc的浓度为10 g/L,硝酸浓度为1 mol/L。(1) The concentration of Sc in the aqueous phase is 10 g/L, and the concentration of nitric acid is 1 mol/L.

(2)以甲苯为稀释剂,配制0.5 mol/L的N,N,N',N'-四环己基-3-氧戊二酰胺为有机相。(2) Using toluene as the diluent, prepare 0.5 mol/L N,N,N',N'-tetracyclohexyl-3-oxoglutaramide as the organic phase.

(3)将水相20 mL和有机相40mL混合,搅拌时间为30 min,萃取温度为20 oC,测定萃余液中Sc的浓度,萃取率为98.32%。(3) Mix 20 mL of the aqueous phase and 40 mL of the organic phase, the stirring time is 30 min, the extraction temperature is 20 o C, the concentration of Sc in the raffinate is determined, and the extraction rate is 98.32%.

(4)取40 mL浓度为0.5 mol/L草酸水溶液与萃取后有机相混合,搅拌时间为30min,温度为30 oC,静置分离有机相,过滤水相得到沉淀,120 oC烘干2小时,600 oC煅烧2小时,得到氧化钪。钪回收率97%以上,钪纯度99.6%以上。(4) Take 40 mL of oxalic acid aqueous solution with a concentration of 0.5 mol/L and mix it with the organic phase after extraction. The stirring time is 30 minutes and the temperature is 30 o C. The organic phase is separated by standing, and the aqueous phase is filtered to obtain a precipitate, and dried at 120 o C for 2 calcination at 600 o C for 2 hours to obtain scandium oxide. The recovery rate of scandium is over 97%, and the purity of scandium is over 99.6%.

实施例8Example 8

(1)水相中Sc的浓度为5 g/L,硝酸浓度为1 mol/L。(1) The concentration of Sc in the aqueous phase is 5 g/L, and the concentration of nitric acid is 1 mol/L.

(2)以甲苯为稀释剂,配制0.5 mol/L的N,N,N',N'-四环己基-3-氧戊二酰胺为有机相。(2) Using toluene as the diluent, prepare 0.5 mol/L N,N,N',N'-tetracyclohexyl-3-oxoglutaramide as the organic phase.

(3)将水相40 mL和有机相20 mL混合,搅拌时间为30 min,萃取温度为20 oC,测定萃余液中Sc的浓度,萃取率为72.56%。(3) Mix 40 mL of the aqueous phase and 20 mL of the organic phase, the stirring time is 30 min, the extraction temperature is 20 o C, the concentration of Sc in the raffinate is determined, and the extraction rate is 72.56%.

(4)取20 mL浓度为0.5 mol/L草酸水溶液与萃取后有机相混合,搅拌时间为 30min,温度为 30 oC,静置分离有机相,过滤水相得到沉淀,120 oC烘干2小时,600 oC煅烧2小时,得到氧化钪。钪回收率70%以上,钪纯度99.7%以上。(4) Mix 20 mL of oxalic acid aqueous solution with a concentration of 0.5 mol/L with the organic phase after extraction, stir for 30 min, and at a temperature of 30 o C, stand to separate the organic phase, filter the aqueous phase to obtain a precipitate, and dry at 120 o C for 2 calcination at 600 o C for 2 hours to obtain scandium oxide. The recovery rate of scandium is over 70%, and the purity of scandium is over 99.7%.

实施例9Example 9

(1)水相中Sc的浓度为5 g/L,硝酸浓度为2 mol/L。(1) The concentration of Sc in the aqueous phase is 5 g/L, and the concentration of nitric acid is 2 mol/L.

(2)以甲苯为稀释剂,配制0.5 mol/L的 N,N,N',N'-四环己基-3-氧戊二酰胺为有机相。(2) Using toluene as the diluent, prepare 0.5 mol/L N,N,N',N'-tetracyclohexyl-3-oxoglutaramide as the organic phase.

(3)将水相80 mL和有机相20 mL混合,搅拌时间为30 min,萃取温度为30 oC,测定萃余液中Sc的浓度,萃取率为45.80%。(3) Mix 80 mL of the aqueous phase and 20 mL of the organic phase, the stirring time is 30 min, the extraction temperature is 30 o C, the concentration of Sc in the raffinate is determined, and the extraction rate is 45.80%.

(4)取20 mL浓度为0.5 mol/L草酸水溶液与萃取后有机相混合,搅拌时间为 30min,温度为 30 oC,静置分离有机相,过滤水相得到沉淀,120 oC烘干2小时,600 oC煅烧2小时,得到氧化钪。钪回收率44%以上,钪纯度99.8%以上。(4) Mix 20 mL of oxalic acid aqueous solution with a concentration of 0.5 mol/L with the organic phase after extraction, stir for 30 min, and at a temperature of 30 o C, stand to separate the organic phase, filter the aqueous phase to obtain a precipitate, and dry at 120 o C for 2 calcination at 600 o C for 2 hours to obtain scandium oxide. The recovery rate of scandium is over 44%, and the purity of scandium is over 99.8%.

实施例10Example 10

(1)水相中Sc的浓度为5 g/L,硝酸浓度为0.6 mol/L。(1) The concentration of Sc in the aqueous phase is 5 g/L, and the concentration of nitric acid is 0.6 mol/L.

(2)以四氯化碳为稀释剂,配制0.5 mol/L 的 N,N,N',N'-四环己基-3-氧戊二酰胺为有机相。(2) Using carbon tetrachloride as the diluent, prepare 0.5 mol/L N,N,N',N'-tetracyclohexyl-3-oxoglutaramide as the organic phase.

(3)将水相和有机相各取20 mL 混合,搅拌时间为30 min,萃取温度为10 oC,测定萃余液中Sc的浓度,萃取率为98.76%。(3) The aqueous phase and the organic phase were mixed with 20 mL each, the stirring time was 30 min, the extraction temperature was 10 o C, and the concentration of Sc in the raffinate was measured. The extraction rate was 98.76%.

(4)取20 mL浓度为0.5 mol/L草酸水溶液与萃取后有机相混合,搅拌时间为30min,温度为 30 oC,静置分离有机相,过滤水相得到沉淀,120 oC烘干2小时,600 oC煅烧2小时,得到氧化钪。钪回收率97%以上,钪纯度99.8%以上。(4) Mix 20 mL of oxalic acid aqueous solution with a concentration of 0.5 mol/L with the organic phase after extraction, stir for 30 min, and at a temperature of 30 o C, stand to separate the organic phase, filter the aqueous phase to obtain a precipitate, and dry at 120 o C for 2 calcination at 600 o C for 2 hours to obtain scandium oxide. The recovery rate of scandium is over 97%, and the purity of scandium is over 99.8%.

Claims (5)

1.一种萃取分离钪的方法,其特征在于所使用的萃取剂为N,N,N’,N’-四环己基-3-氧戊二酰胺,用稀释剂稀释后作为萃取有机相,萃取水相中加硝酸、硝酸盐一种或者两种,经过萃取、反萃得到高纯度钪,其中萃取提纯钪步骤包括:1. a method for extracting and separating scandium, is characterized in that the extraction agent used is N,N,N',N'-tetracyclohexyl-3-oxoglutaramide, after diluting with diluent, as extraction organic phase, One or both of nitric acid and nitrate are added to the extraction water phase, and high-purity scandium is obtained through extraction and back-extraction, wherein the step of extracting and purifying scandium comprises: (1)用硝酸溶解钪样品得到杂质包括Fe、Mg、Ti、Ba、Al、Zr、Mn的水溶液并加入硝酸和硝酸盐的一种或者两种为水相,其中钪总浓度为1~200 g/L,硝酸以及硝酸盐浓度为0.01~5mol/L;(1) Dissolve the scandium sample with nitric acid to obtain an aqueous solution of impurities including Fe, Mg, Ti, Ba, Al, Zr, Mn, and add one or both of nitric acid and nitrate to the aqueous phase, wherein the total concentration of scandium is 1~200 g/L, the concentration of nitric acid and nitrate is 0.01~5mol/L; (2)称量一定质量的萃取剂,利用稀释剂稀释到一定浓度为有机相,其中稀释剂为甲苯、二甲苯、二氯甲烷、氯仿或四氯化碳的一种;萃取剂浓度为0.01~2 mol/L;(2) Weigh a certain quality of extractant, dilute it to a certain concentration with a diluent to form the organic phase, wherein the diluent is one of toluene, xylene, dichloromethane, chloroform or carbon tetrachloride; the concentration of the extractant is 0.01 ~2 mol/L; (3)将一定体积比例的水相和有机相混合搅拌10~120 min,萃取温度为5~60 oC;(3) Mix and stir a certain volume ratio of the aqueous phase and the organic phase for 10-120 min, and the extraction temperature is 5-60 o C; (4)萃取后的混合溶液经静置分相,得到负载钪有机相,杂质留在萃余液中;(4) The mixed solution after extraction is left to stand for phase separation to obtain a scandium-loaded organic phase, and impurities remain in the raffinate; (5)取一定体积浓度为0.1~1.0 mol/L草酸或者草酸盐水溶液与步骤(4)负载钪有机相混合,搅拌时间为 5~100 min,温度为 5~60 oC,静置分离有机相,过滤水相得到沉淀,120oC烘干2小时,600 oC煅烧2小时,得到氧化钪,静置分层后的有机相可重复使用。(5) Take a certain volume concentration of 0.1~1.0 mol/L oxalic acid or oxalate aqueous solution and mix it with the organic phase loaded with scandium in step (4), the stirring time is 5~100 min, the temperature is 5~60 o C, stand for separation The organic phase is filtered and the aqueous phase is filtered to obtain a precipitate, dried at 120 o C for 2 hours, and calcined at 600 o C for 2 hours to obtain scandium oxide, and the organic phase after standing and layering can be reused. 2.根据权利要求 1所述的一种萃取分离钪的方法,其特征在于,所述步骤(3)中,水相与有机相混合体积比为 1:10~10:1。2. a kind of method for extracting and separating scandium according to claim 1, is characterized in that, in described step (3), water phase and organic phase mixing volume ratio is 1:10~10:1. 3.根据权利要求 1所述的一种萃取分离钪的方法,其特征在于,所述步骤(3)中,萃取时间为 20~60 min,萃取温度为 10~50 oC。3. a kind of method for extracting and separating scandium according to claim 1, is characterized in that, in described step (3), extraction time is 20~60 min, and extraction temperature is 10~50 . 4.根据权利要求 1所述的一种萃取分离钪的方法,其特征在于,所述步骤(4)中,静置时间为1~5 min,混合溶液变为澄清透明的两相。4 . The method for extracting and separating scandium according to claim 1 , wherein in the step (4), the standing time is 1 to 5 min, and the mixed solution becomes clear and transparent two-phase. 5 . 5.根据权利要求 1所述的一种萃取分离钪的方法,其特征在于,所述步骤(5)中,反萃剂为草酸或草酸盐溶液,反萃时间为 10~30 min,反萃后的有机相可重复使用。5. The method for extracting and separating scandium according to claim 1, wherein in the step (5), the back-extraction agent is oxalic acid or an oxalate solution, and the back-extraction time is 10 to 30 min. The extracted organic phase can be reused.
CN202010907235.4A 2020-09-02 2020-09-02 Method for extracting and separating scandium Active CN111961849B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010907235.4A CN111961849B (en) 2020-09-02 2020-09-02 Method for extracting and separating scandium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010907235.4A CN111961849B (en) 2020-09-02 2020-09-02 Method for extracting and separating scandium

Publications (2)

Publication Number Publication Date
CN111961849A CN111961849A (en) 2020-11-20
CN111961849B true CN111961849B (en) 2022-04-19

Family

ID=73391653

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010907235.4A Active CN111961849B (en) 2020-09-02 2020-09-02 Method for extracting and separating scandium

Country Status (1)

Country Link
CN (1) CN111961849B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114672650B (en) * 2022-05-06 2023-05-30 济南大学 Method for extracting scandium from titanium white waste acid by using bisphosphonic acid extractant

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3035880B1 (en) * 2015-05-07 2017-06-02 Commissariat Energie Atomique USE OF NOVEL COMPOUNDS FOR THE SELECTIVE EXTRACTION OF RARE EARTHS FROM AQUEOUS SOLUTIONS COMPRISING PHOSPHORIC ACID AND METHOD OF EXTRACTING THE SAME
CN108300878A (en) * 2018-01-26 2018-07-20 中国科学院长春应用化学研究所 A kind of extraction process with acid phosphine enriching and recovering scandium from secondary resource leachate
CN111471860B (en) * 2020-06-17 2021-07-13 济南大学 A method for separating lanthanum and cerium from mixed rare earth by using amide pod ether extractant

Also Published As

Publication number Publication date
CN111961849A (en) 2020-11-20

Similar Documents

Publication Publication Date Title
JP7578803B2 (en) Carboxylic acid compounds, their preparation method and use
CN103055539B (en) Method for extracting lithium salts in lithium-containing brine
CN102627333B (en) Method for refined nickel sulfate
CN103620065B (en) Cobalt extraction method
CN107815542B (en) A kind of synergistic extractant and method for selective extraction of nickel in acidic solution
CN104962743B (en) Method for selectively extracting and recycling gallium, germanium and indium from sulfuric acid leach liquid of zinc displacement residues
CN112662872B (en) Extraction method of oxalic acid-containing solution
Su et al. Recovery of Sm (III), Co (II) and Cu (II) from waste SmCo magnet by ionic liquid-based selective precipitation process
Yu et al. Recovery of rare earth metal oxides from NdFeB magnet leachate by hydrophobic deep eutectic solvent extraction, oxalate stripping and calcination
CN112280982B (en) Method for separating iron from phosphorite leaching solution by utilizing diphosphonic acid extractant
WO2019114815A1 (en) Extraction solvent for lithium element and extraction method therefor
CN110643835B (en) Extraction system, extraction method and application for separating magnesium and extracting lithium from magnesium-containing brine with secondary amide type solvent
CN104822851B (en) Nickel Extraction Method
CN111961849B (en) Method for extracting and separating scandium
CN114853617B (en) Extracting agent for extracting and separating neodymium (III), preparation method and application thereof
CN108998669A (en) A method of using N- octylpyridinium tetrafluoroborate extracting rare-earth element
WO2013069563A1 (en) Cobalt extraction method
CN118598907A (en) A bisphosphonic acid extractant for extracting iron and aluminum, and its preparation method and application
CN109680169B (en) A kind of P204-doped polyaniline solid-phase extractant and method for extracting light rare earth
CN106834681A (en) A kind of method of Fe impurity in use research of Amido Podands Extractant removal Pr
CN113106271A (en) Method for purifying rare earth element gadolinium with high purity by using carboxylic acid functionalized ionic liquid
CN118561910B (en) An extractant for extracting iron and aluminum from wet-process phosphoric acid solution, and its preparation method and application
CN119956084B (en) A composite extraction system and process for extracting lithium from lithium-containing solution
CN115637337B (en) Method for purifying and deironing high-purity hafnium tetrachloride
CN106801154B (en) A method of micro iron tramp is removed from praseodymium using solvent extraction

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant