新型萃取剂NA萃取中重混合稀土的研究
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摘要
研究了一种新型酸性磷类萃取剂NA萃取中重混合稀土的性能,探讨了萃取过程中有机相的皂化度、有机相组成、混合稀土料液中杂质含量、料液初始p H对新型萃取剂萃取饱和容量的影响以及反萃过程中反萃酸度对反萃性能的影响,同时还探讨了新型萃取剂的损耗率。试验结果表明,控制混合稀土料液浓度与铝浓度比≥222,与铁浓度比≥2543、有机相的皂化度0.64~0.68 mol·L~(-1)、有机相中磺化煤油∶新型萃取剂=1∶1(新型萃取剂浓度为1.45 mol·L~(-1))及混合稀土料液初始p H=1.2的工艺条件下,萃取过程分相效果好,新型萃取剂的饱和容量大于0.20 mol·L~(-1),比传统萃取剂P507的最佳萃取饱和容量高15%~20%左右,新型萃取剂的损耗率为0.42%~0.45%;反萃过程,采用盐酸作为反萃剂,只要控制盐酸浓度为3.0 mol·L~(-1)时,负载有机相的单级反萃率即可达到98%以上;研究结果表明,该新型萃取剂,具有萃取饱和容量大、溶解损失少、循环使用性能好、反萃酸度低的特点,可以大大降低槽体有机积存量、稀土积存量和酸耗量,减少投资成本,改善工作环境,具有广泛的应用前景。
The present work proposed the extraction behaviors of a new acidic phosphorus extractant NA in solvent extraction of heavy mixed rare earth. The factors influencing the extraction saturation capacity of extractant NA were studied,such as saponification degree of organic phase,organic phase compositions,impurity contents in rare earth solution and initial p H value of rare earth solution. The attrition rate of extractant NA was also discussed. The results showed that the saturation capacity of new extractant exceeded 0. 20mol·L~(-1)and the attrition rate was 0. 42% ~ 0. 45% when the concentration of mischmetal to that of aluminum ratio was more than 222,while the concentration of mischmetal to that of iron ratio was more than 2543,the saponification degree of organic phase was 0. 64 ~0. 68 mol·L~(-1),the initial p H value was 1. 2,the proportion between sulfonated kerosene and new extractant in organic phase was 1∶ 1(extractant NA was 1. 45 mol·L~(-1)). In the same condition,the saturation capacity of new extractant was 15%~ 20% higher than the best result of P507. During stripping process,the re-extraction rate of organics loaded was above 98% when the hydrochloric acid concentration was 3. 0 mol·L~(-1),used as a stripping agent. This study indicated that the new extractant NA had a high saturation capacity with low dissolution loss and re-extraction acidity. It could greatly reduce the amount of accumulation of organic and rare earth,acid consumption,investment cost and improve working environment. The new extractant had a wide application prospect.
The present work proposed the extraction behaviors of a new acidic phosphorus extractant NA in solvent extraction of heavy mixed rare earth. The factors influencing the extraction saturation capacity of extractant NA were studied,such as saponification degree of organic phase,organic phase compositions,impurity contents in rare earth solution and initial p H value of rare earth solution. The attrition rate of extractant NA was also discussed. The results showed that the saturation capacity of new extractant exceeded 0. 20mol·L~(-1)and the attrition rate was 0. 42% ~ 0. 45% when the concentration of mischmetal to that of aluminum ratio was more than 222,while the concentration of mischmetal to that of iron ratio was more than 2543,the saponification degree of organic phase was 0. 64 ~0. 68 mol·L~(-1),the initial p H value was 1. 2,the proportion between sulfonated kerosene and new extractant in organic phase was 1∶ 1(extractant NA was 1. 45 mol·L~(-1)). In the same condition,the saturation capacity of new extractant was 15%~ 20% higher than the best result of P507. During stripping process,the re-extraction rate of organics loaded was above 98% when the hydrochloric acid concentration was 3. 0 mol·L~(-1),used as a stripping agent. This study indicated that the new extractant NA had a high saturation capacity with low dissolution loss and re-extraction acidity. It could greatly reduce the amount of accumulation of organic and rare earth,acid consumption,investment cost and improve working environment. The new extractant had a wide application prospect.
引文
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[2]Zhao W J,Wang D J.Development of rare earth separation technology in today's world and the process of China's rare earth extraction industry[J].Rare Earth Information,2015,(3):28.(赵文静,王东杰.当今世界稀土分离技术的发展与中国稀土萃取工业进程[J].稀土信息,2015,(3):28.)
[3]Wu W Y.Rare Earth Metallurgy[M].Beijing:Chemical Industry Press,2005.71.(吴文远.稀土冶金学[M].北京:化学工业出版社,2005.71.)
[4]Parhi P K,Park K H,Nam C W,Park J T.Liquidliquid extraction and separation of total rare earth(RE)metals from polymetallic manganese nodule leaching solution[J].Journal of Rare Earths,2015,33(2):207.
[5]Chang H T,Wu W Y,Tu G F,Zhao Z H,Li D,Sang X Y.Study on La and Ce distribution ratio and separation factor in P204-HCl-H3cit system[J].Chinese Rare Earths,2008,29(3):18.(常宏涛,吴文远,涂赣峰,赵治华,李东,桑晓云.P204-HCl-H3cit体系萃取分离轻稀土的研究[J].稀土,2008,29(3):18.)
[6]Zhang C.The Mechanism Study of Rare Earth from Chloride Medium with Synergistic Systems of the Acidic Phosphorus-Containing Extractant[D].Beijing:General Research Institute for Nonferrous Metals,2014.30.(张灿.盐酸介质下酸性磷(膦)类萃取剂对稀土元素的协同萃取机理研究[D].北京有色金属研究总院,2014.30.)
[7]He H W,Meng J.Recycling rare earth from spent FCC catalyst using P507(HEH/EHP)as extractant[J].Journal of Central South University(Science and Technology),2011,42(9):2651.(何捍卫,孟佳.采用P507(HEH/EHP)从废FCC催化剂中回收稀土[J].中南大学学报(自然科学版),2011,42(9):2651.)
[8]Ye X Y,Wu L,Yang M,Wu D,Yang Y M,Nie H P,Jiao Y F.Stripping process in P507-N235 dual solvent extraction system[J].Journal of the Chinese Society of Rare Earths,2013,31(6):695.(叶信宇,吴龙,杨明,吴迪,杨幼明,聂华平,焦芸芬.P507-N235双溶剂萃取体系反萃工艺研究[J].中国稀土学报,2013,31(6):695.)
[9]Wang M,Yang Q Z.Process design for ion-absorbed rare earth ore[J].Rare Metals and Cemented Carbides,2015,(3):16.(王明,杨庆珠.离子型稀土矿分离的工艺设计[J].稀有金属与硬质合金,2015,(3):16.)
[10]Yang Y M,Huang Z H,Deng S H,Shen W M,Zhou W F,Zhong Y G.Recycle of complex organic phase of P507-N235 system[J].Chinese Journal of Rare Metals,2014,38(2):300.(杨幼明,黄振华,邓声华,沈文明,周武风,钟杨根.P507-N235体系复合有机相的再生与循环[J].稀有金属,2014,38(2):300.)
[11]Feng X P.Study and application on separating P204and P350[J].Journal of the Chinese Society of Rare Earths,2002,20(S2):170.(冯新培.萃取剂P204与P350分离的研究与应用[J].中国稀土学报,2002,20(S2):170.)
[12]Mou M M,Chen G,Luo X.Research status and progress of the novel extractants of rare earth[J].Conservation and Utilization of Mineral Resources,2015,(4):73.(牟苗苗,陈广,罗兴.新型稀土萃取剂研究现状与进展[J].矿产保护与利用,2015,(4):73.)
[13]Chen G,Wang J L,Zhang Q,Xu S M,Li L Y.A new extractant(2,3-methyl two Ding Ji(three)2,4,4'-methyl pentyl)phosphinic acid(INET-3)synthesis and extraction performance of heavy rare earth[J].Nonferrous Metals Engineering,2014,4(5):29.(陈广,王俊莲,张覃,徐盛明,李林艳.新型萃取剂(2,3-二甲基丁基)(2,4,4'-三甲基戊基)次膦酸(INET-3)的合成及其萃取重稀土的性能[J].有色金属工程,2014,4(5):29.)
[14]Mowafy E A,Mohamed D.Extraction and separation of Nd(Ⅲ),Sm(Ⅲ),Dy(Ⅲ),Fe(Ⅲ),Ni(Ⅱ),and Cs(Ⅰ)from concentrated chloride solutions with N,N,N',N'-tetra(2-ethylhexyl)diglycolamide as new extractant[J].Journal of Rare Earths,2015,33(4):432.
[15]Xu X,Yang X W,Wu Y X,Zhong Y M,Li Y X.Extraction and separation properties of zirconium(IV)and hafnium(IV)using P507[J].Chinese Journal of Rare Metals,2008,32(3):355.(徐欣,杨新伟,邬元旭,钟月明,李永绣.P507萃取锆和铪及分离性能[J].稀有金属,2008,32(3):355.)
[16]Liu R J,Zhao Z H,Sang X Y,Xu H,Gao Y.Dicussion of saponification process in rare earth extraction separation and utilization of waste water[J].Chinese Rare Earths,2015,(4):132.(刘瑞金,赵治华,桑晓云,许慧,高媛.稀土萃取分离皂化工艺及其废水资源化探讨[J].稀土,2015,(4):132.)
[17]Zhou J Y,Chen D Y,Yang X H,Lai L P,Wu X G.Ammonia-free continuous saponification of organic phase in rare earths extraction[J].Hydrometallurgy of China,2015,34(1):43.(周洁英,陈冬英,杨新华,赖兰萍,吴新根.稀土萃取有机相的无氨连续皂化试验研究[J].湿法冶金,2015,34(1):43.)
[2]Zhao W J,Wang D J.Development of rare earth separation technology in today's world and the process of China's rare earth extraction industry[J].Rare Earth Information,2015,(3):28.(赵文静,王东杰.当今世界稀土分离技术的发展与中国稀土萃取工业进程[J].稀土信息,2015,(3):28.)
[3]Wu W Y.Rare Earth Metallurgy[M].Beijing:Chemical Industry Press,2005.71.(吴文远.稀土冶金学[M].北京:化学工业出版社,2005.71.)
[4]Parhi P K,Park K H,Nam C W,Park J T.Liquidliquid extraction and separation of total rare earth(RE)metals from polymetallic manganese nodule leaching solution[J].Journal of Rare Earths,2015,33(2):207.
[5]Chang H T,Wu W Y,Tu G F,Zhao Z H,Li D,Sang X Y.Study on La and Ce distribution ratio and separation factor in P204-HCl-H3cit system[J].Chinese Rare Earths,2008,29(3):18.(常宏涛,吴文远,涂赣峰,赵治华,李东,桑晓云.P204-HCl-H3cit体系萃取分离轻稀土的研究[J].稀土,2008,29(3):18.)
[6]Zhang C.The Mechanism Study of Rare Earth from Chloride Medium with Synergistic Systems of the Acidic Phosphorus-Containing Extractant[D].Beijing:General Research Institute for Nonferrous Metals,2014.30.(张灿.盐酸介质下酸性磷(膦)类萃取剂对稀土元素的协同萃取机理研究[D].北京有色金属研究总院,2014.30.)
[7]He H W,Meng J.Recycling rare earth from spent FCC catalyst using P507(HEH/EHP)as extractant[J].Journal of Central South University(Science and Technology),2011,42(9):2651.(何捍卫,孟佳.采用P507(HEH/EHP)从废FCC催化剂中回收稀土[J].中南大学学报(自然科学版),2011,42(9):2651.)
[8]Ye X Y,Wu L,Yang M,Wu D,Yang Y M,Nie H P,Jiao Y F.Stripping process in P507-N235 dual solvent extraction system[J].Journal of the Chinese Society of Rare Earths,2013,31(6):695.(叶信宇,吴龙,杨明,吴迪,杨幼明,聂华平,焦芸芬.P507-N235双溶剂萃取体系反萃工艺研究[J].中国稀土学报,2013,31(6):695.)
[9]Wang M,Yang Q Z.Process design for ion-absorbed rare earth ore[J].Rare Metals and Cemented Carbides,2015,(3):16.(王明,杨庆珠.离子型稀土矿分离的工艺设计[J].稀有金属与硬质合金,2015,(3):16.)
[10]Yang Y M,Huang Z H,Deng S H,Shen W M,Zhou W F,Zhong Y G.Recycle of complex organic phase of P507-N235 system[J].Chinese Journal of Rare Metals,2014,38(2):300.(杨幼明,黄振华,邓声华,沈文明,周武风,钟杨根.P507-N235体系复合有机相的再生与循环[J].稀有金属,2014,38(2):300.)
[11]Feng X P.Study and application on separating P204and P350[J].Journal of the Chinese Society of Rare Earths,2002,20(S2):170.(冯新培.萃取剂P204与P350分离的研究与应用[J].中国稀土学报,2002,20(S2):170.)
[12]Mou M M,Chen G,Luo X.Research status and progress of the novel extractants of rare earth[J].Conservation and Utilization of Mineral Resources,2015,(4):73.(牟苗苗,陈广,罗兴.新型稀土萃取剂研究现状与进展[J].矿产保护与利用,2015,(4):73.)
[13]Chen G,Wang J L,Zhang Q,Xu S M,Li L Y.A new extractant(2,3-methyl two Ding Ji(three)2,4,4'-methyl pentyl)phosphinic acid(INET-3)synthesis and extraction performance of heavy rare earth[J].Nonferrous Metals Engineering,2014,4(5):29.(陈广,王俊莲,张覃,徐盛明,李林艳.新型萃取剂(2,3-二甲基丁基)(2,4,4'-三甲基戊基)次膦酸(INET-3)的合成及其萃取重稀土的性能[J].有色金属工程,2014,4(5):29.)
[14]Mowafy E A,Mohamed D.Extraction and separation of Nd(Ⅲ),Sm(Ⅲ),Dy(Ⅲ),Fe(Ⅲ),Ni(Ⅱ),and Cs(Ⅰ)from concentrated chloride solutions with N,N,N',N'-tetra(2-ethylhexyl)diglycolamide as new extractant[J].Journal of Rare Earths,2015,33(4):432.
[15]Xu X,Yang X W,Wu Y X,Zhong Y M,Li Y X.Extraction and separation properties of zirconium(IV)and hafnium(IV)using P507[J].Chinese Journal of Rare Metals,2008,32(3):355.(徐欣,杨新伟,邬元旭,钟月明,李永绣.P507萃取锆和铪及分离性能[J].稀有金属,2008,32(3):355.)
[16]Liu R J,Zhao Z H,Sang X Y,Xu H,Gao Y.Dicussion of saponification process in rare earth extraction separation and utilization of waste water[J].Chinese Rare Earths,2015,(4):132.(刘瑞金,赵治华,桑晓云,许慧,高媛.稀土萃取分离皂化工艺及其废水资源化探讨[J].稀土,2015,(4):132.)
[17]Zhou J Y,Chen D Y,Yang X H,Lai L P,Wu X G.Ammonia-free continuous saponification of organic phase in rare earths extraction[J].Hydrometallurgy of China,2015,34(1):43.(周洁英,陈冬英,杨新华,赖兰萍,吴新根.稀土萃取有机相的无氨连续皂化试验研究[J].湿法冶金,2015,34(1):43.)