Ba在络合浸出混合稀土精矿过程中的行为研究
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摘要
Ba元素在包头混合稀土精矿中以氟碳钡铈矿、毒重石、重晶石等形式存在。采用HCl-AlCl_3络合体系浸出50稀土精矿,通过factsage软件对含Ba矿物与络合剂之间的反应进行了热力学计算,以及对稀土精矿与浸出渣分别进行了SEM面扫描及点扫面,发现只有氟碳钡铈矿与毒重石能与络合剂发生反应,剩余留到浸出渣当中的Ba元素主要以重晶石形式存在;通过改变HCl浓度、AlCl_3浓度、反应温度和反应时间等条件,得出络合浸出包头混合稀土精矿的反应条件应当控制到HCl浓度6 mol/L,AlCl_3浓度1 mol/L,反应温度90℃,反应时间150 min的结论,在此条件下,稀土不仅得到很好的浸出效果,Ba也实现了最大化的回收;Ba的浸出是一个缓慢的过程,从而会在一定程度上对稀土的浸出起到抑制作用。
Barium exists mainly in the forms of cordylite,witherite and barite in Baotou mixed rare earth concentrate. In this study,Baotou 50 mixed rare earth concentrate was leached by HCl-AlCl_3 complex system.The thermodynamic data of the reaction btween Ba minerals and comlex system were calculated by Factsage software.Surface analysis for concentrate and leaching residue were conducted with SEM and EDS. The results showed that cordylite and witherite were reaction with complex agent,but barium remained in leaching residue.The influence factors were discussed and the optimum reaction comditions were obtained as follows: HCl concentration shoud be 6.0 mol·L~(-1), temperature 100 ℃,AlCl_3 concentration 1.0 mol·L~(-1), and stirring time 150 min, under the conditions, the best leaching result for rare earth was obtained,and the recovery of barium was maximized.
Barium exists mainly in the forms of cordylite,witherite and barite in Baotou mixed rare earth concentrate. In this study,Baotou 50 mixed rare earth concentrate was leached by HCl-AlCl_3 complex system.The thermodynamic data of the reaction btween Ba minerals and comlex system were calculated by Factsage software.Surface analysis for concentrate and leaching residue were conducted with SEM and EDS. The results showed that cordylite and witherite were reaction with complex agent,but barium remained in leaching residue.The influence factors were discussed and the optimum reaction comditions were obtained as follows: HCl concentration shoud be 6.0 mol·L~(-1), temperature 100 ℃,AlCl_3 concentration 1.0 mol·L~(-1), and stirring time 150 min, under the conditions, the best leaching result for rare earth was obtained,and the recovery of barium was maximized.
引文
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[13] Li M,Zhang X W,Liu Z G,Hu Y H,Wang M T,Liu J,Yang J P.Kinetics of leaching fluoride from mixed rare earth concentrate with hydrochloric acid and aluminum chloride[J].Hydrometallurgy,2013,140:71-76.
[14] Li,Mei,Zhang X W,Liu Z G,Wang M T,Liu J,Yang J P.Mixed rare earth concentrate leaching with HCl-AlCl3 solution[J].Rare Metals,2013,32(3):312-317.
[15] 边雪,吴文远,罗瑶,尹少华,张博.HCl-AlCl3溶液络合浸出稀土氧化物和氟化钙的研究[J].中国稀土学报,2010,28(3):322-329.Bian X,Wu W Y,Luo Y,Yin S H,Zhang B.Coordination leaching of rare earths oxideand CaF2 by HCl-AlCl3[J].Journal of the Chinese Society of Rare Earths,2010,28(3):322-329.
[16] 边雪,尹少华,张丰云,吴文远,涂赣峰.柠檬酸配合浸出分离稀土氧化物与氟化钙[J].材料与冶金学报,2011,10(4):244-248.Bian X,Yin S H,Zhang F Y,Wu W Y,Tu G F.The separation of rare earth oxide and celeium fluoride with the method of citric acid complex leaching[J].Journal of Materials and Metallurgy,2011,10(4):244-248.
[17] 张晓伟,李梅,柳召刚,胡艳宏,刘佳,阳建平.HNO3-Al(NO3)3溶液分离包头混合稀土精矿的研究[J].中国稀土学报,2013,31(5):588-596.Zhang X W,Li M,Liu Z G,Hu Y H,Liu J,Yang J P.Separation of Baotou Mixed Rare Earth Concentrate by HNO3-Al(NO3)3 Solution[J].Journal of the Chinese Society of Rare Earths,2013,31(5):588-596.
[18] 李梅,胡家利,张晓伟,柳召刚,胡艳宏.HCl-AlCl3溶液络合浸出包头50混合稀土精矿的研究[J].稀有金属,2016,40(7):695-697.Li M,Hu J L,Zhang X W,Liu Z G,Hu Y H.Study on the Coordination leaching of Baotou 50 Mixed Rare Earth Concentrate by HCl-AlCl3 Solution[J].Chinese Journal of Rare Metals,2016,40(7):695-697.
[2] 张培善,陶克捷.中国稀土矿主要矿物学特征[J].中国稀土学报,1985,3(3):1-5.Zhang P S,Tao K J.Mineralogical charateristics of rare earth minerals in China[J].Journal of the Chinese Society of Rare Earths,1985,3(3):1-5.
[3] 罗明标,杨枝,郭国林,李伯平,刘峰,刘维.白云鄂博铁矿石中稀土的赋存状态研究[J].中国稀土学报,2007,25:57-60.Luo M B,Yang Z,Guo G L,Li B P,Liu F,Liu W.Research on occurrence state of REE in Bayan Obo iron ore[J].Journal of the Chinese Society of Rare Earths,2007,25:57-60.
[4] 杜长顺,李梅,柳召刚,常宏涛,胡艳宏.包头稀土精矿处理现状及建议[J].湿法冶金,2010,29(1):1-4.Du C S,Li M,Liu Z G,Chang H T,Hu Y H.Present situation and suggestions for treatment of Baotou’s rare earth concentrate[J].Hydrometallurgy of China,2010,29(1):1-4.
[5] 许涛,彭会清,林忠,吕保义.稀土固体废物的成因、成分分析及综合利用[J].稀土,2010,(2):34-39.Xu T,Peng H Q,Lin Z,Lu B Y.Formation cause,composition analysis and comprehensive utilization of rare earth solid wastes[J].Chinese Rare Earths,2010,(2):34-39.
[6] Shi W Z,Zhu G C,Hua J,Xu S M,Chi Y A.Recovery of RE from Baotou rare earth concentrate with chlorination roasting[J].Trans Nonferrous Met Soc China,2003,13(2):438-442.
[7] 姜楠,邢娇娇,李勇,何金桂.稀土冶炼中氟的影响及其解决办法[J].辽宁化工,2013,42(6):637-640.Jiang N,Xing J J,Li Y,He J G.Influence of fluorine on rare earth smelting and its solution[J].Liaoning Chemical Industry,2013,42(6):637-640.
[8] 王满合,曾明,王良士,周继海,崔大立,王全根,翁荣贵,陈雪松.氟碳铈矿氧化焙烧-盐酸催化浸出新工艺研究[J].中国稀土学报,2013,31(2):148-154.Wang M H,Zeng M,Wang L S,Zhou J H,Cui D L,Wang Q G,Weng R G,Chen X S.Catalytic leaching process of bastnaesite with hydrochloric acid after oxidation roasting pretreatment [J].Journal of the Chinese Society of Rare Earths,2013,31(2):148-154.
[9] 李解,李成元,李保卫,王少炳,韩继铖,王介良.微波加热低品位稀土精矿酸浸实验研究[J].稀有金属,2014,(5):107-113.Li J,Li C Y,Li B W,Wang S B,Han J C,Wang J L.Acid leaching of low grade rare earth concentrate by microwave heating[J].Chinese Journal of Rare Metals,2014,(5):107-113.
[10] 马莹,许延辉,常叔,乔军,王晶晶,王宝荣.包头稀土精矿浓硫酸低温焙烧工艺技术研究[J].稀土,2010,(2):20-23.Ma Y,Xu Y H,Chang S,Qiao J,Wang J J,Wang B R.Study on the decomposition of Baotou rare earth concentrate[J].Chinese Rare Earths,2010,(2):20-23.
[11] 王秀艳,张丽萍,张军,白彦,许延辉,郝先库.包头稀土精矿硫酸低温焙烧分解工艺研究[J].稀土,2003,(4):29-31.Wang X Y,Zhang L P,Zhang J,Bai Y,Xu Y H,Hao X K.New technique of decomposition of rare earth concentrate[J].Chinese Rare Earths,2003,(4):29-31.
[12] 付红扬,魏莹莹,李勇,何金桂.铝盐配位分离氟碳铈矿酸浸液中氟和铈[J].中国稀土学报,2013,31(4):393-398.Fu H Y,Wei Y Y,Li Y,He J G.Separation of fluoride/cerium by aluminum salt coordination from bastnasite sulfuric acid leaching solution[J].Journal of the Chinese Society of Rare Earths,2013,31(4):393-398.
[13] Li M,Zhang X W,Liu Z G,Hu Y H,Wang M T,Liu J,Yang J P.Kinetics of leaching fluoride from mixed rare earth concentrate with hydrochloric acid and aluminum chloride[J].Hydrometallurgy,2013,140:71-76.
[14] Li,Mei,Zhang X W,Liu Z G,Wang M T,Liu J,Yang J P.Mixed rare earth concentrate leaching with HCl-AlCl3 solution[J].Rare Metals,2013,32(3):312-317.
[15] 边雪,吴文远,罗瑶,尹少华,张博.HCl-AlCl3溶液络合浸出稀土氧化物和氟化钙的研究[J].中国稀土学报,2010,28(3):322-329.Bian X,Wu W Y,Luo Y,Yin S H,Zhang B.Coordination leaching of rare earths oxideand CaF2 by HCl-AlCl3[J].Journal of the Chinese Society of Rare Earths,2010,28(3):322-329.
[16] 边雪,尹少华,张丰云,吴文远,涂赣峰.柠檬酸配合浸出分离稀土氧化物与氟化钙[J].材料与冶金学报,2011,10(4):244-248.Bian X,Yin S H,Zhang F Y,Wu W Y,Tu G F.The separation of rare earth oxide and celeium fluoride with the method of citric acid complex leaching[J].Journal of Materials and Metallurgy,2011,10(4):244-248.
[17] 张晓伟,李梅,柳召刚,胡艳宏,刘佳,阳建平.HNO3-Al(NO3)3溶液分离包头混合稀土精矿的研究[J].中国稀土学报,2013,31(5):588-596.Zhang X W,Li M,Liu Z G,Hu Y H,Liu J,Yang J P.Separation of Baotou Mixed Rare Earth Concentrate by HNO3-Al(NO3)3 Solution[J].Journal of the Chinese Society of Rare Earths,2013,31(5):588-596.
[18] 李梅,胡家利,张晓伟,柳召刚,胡艳宏.HCl-AlCl3溶液络合浸出包头50混合稀土精矿的研究[J].稀有金属,2016,40(7):695-697.Li M,Hu J L,Zhang X W,Liu Z G,Hu Y H.Study on the Coordination leaching of Baotou 50 Mixed Rare Earth Concentrate by HCl-AlCl3 Solution[J].Chinese Journal of Rare Metals,2016,40(7):695-697.
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