草酸沉淀法分离Sm~(3+)和Zn~(2+)
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摘要
在SmCl_3和ZnCl_2的混合溶液中添加NH_4Cl,研究了用草酸沉淀法分离Sm~(3+)和Zn~(2+),并对料液中NH_4Cl、SmCl_3、ZnCl_2浓度、沉淀母液pH和沉淀温度对Sm_2O_3产品中ZnO含量影响进行了分析与讨论。结果表明,料液中SmCl_3、ZnCl_2和NH_4Cl浓度分别为0.60 mol·L~(-1)～0.75 mol·L~(-1)、≤0.18 mol·L~(-1)和4 mol·L~(-1),沉淀母液pH为5～6,反应温度80℃,得到的Sm_2O_3产品中ZnO含量小于0.0025%。本工艺已实现产业化,操作简单,产品质量稳定。
The separartion of Sm~(3+) and Zn~(2+) was studied with the precipitation method of oxalic acid by adding NH_4Cl in the SmCl_3 solution containing ZnCl_2, and the influence of the concentration SmCl_3, ZnCl_2 and NH_4Cl in the feed liquid, pH of mother liquor and reaction temperature on the content of ZnO in Sm_2O_3 products were discussed. The results show that the optimal process parameters were that the concentration of SmCl_3, ZnCl_2 and NH_4Cl were 0.60 mol·L~(-1)～0.75 mol·L~(-1), ≤0.18 mol·L~(-1) and 4 mol·L~(-1) in the feed liuquid respectively, pH of mother liquor was 5～6, the precipitation temperature was 80 ℃. The content of ZnO in Sm_2O_3 products was less than 0.0025%. In addition, the process has achieved industrialization, simple operation and stable product quality.
The separartion of Sm~(3+) and Zn~(2+) was studied with the precipitation method of oxalic acid by adding NH_4Cl in the SmCl_3 solution containing ZnCl_2, and the influence of the concentration SmCl_3, ZnCl_2 and NH_4Cl in the feed liquid, pH of mother liquor and reaction temperature on the content of ZnO in Sm_2O_3 products were discussed. The results show that the optimal process parameters were that the concentration of SmCl_3, ZnCl_2 and NH_4Cl were 0.60 mol·L~(-1)～0.75 mol·L~(-1), ≤0.18 mol·L~(-1) and 4 mol·L~(-1) in the feed liuquid respectively, pH of mother liquor was 5～6, the precipitation temperature was 80 ℃. The content of ZnO in Sm_2O_3 products was less than 0.0025%. In addition, the process has achieved industrialization, simple operation and stable product quality.
引文
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[15] 丁治英,尹周澜,肖忠良,张平民,胡慧萍,陈启元.氧化锌氨性浸出体系的平衡热力学研究[J].中国稀土学报,2010,28(S1):6-11.Ding Z Y,Yin Z L,Xiao Z L,Zhang P M,Hu H P,Chen Q Y.Study on the equilibrium thermodynamics of zinc oxide in ammonia leaching system[J].Journal of the Chinese Society of Rare Earths,2010,28(S1):6-11.
[16] 施民梅.焓变与熵变对化学反应的影响[J].沧州师范专科学校学报,2003,19(1):44-45.Shi M M.Environmental change and the change in enthalpy versus chemical reactions[J].Journal of Changzhou Teachers college,2003,19(1):44-45.
[17] 杨永斌,张鑫,李骞,江涛,白国华.氨法一步沉淀法制备碱式碳酸锌结晶行为特征[J].矿冶工程,2013,33(2):101-104.Yang Y B,Zhang X,Li Q,Jiang T,Bai G H.Characteristics of crystallization behavior of basic zinc carbonate in preparation by ammonia process[J].Mining and Metallurgical Engineering,2013,33(2):101-104.
[2] 李慧琴,陈敏璇,韩强,马显东,胡珊珊,赵永志,张瑞祥.矿化剂对黄色颜料Sm0.3Ce0.66Mo0.04O(1.85+δ)光学性能影响[J].稀土,2014,35(6):6-10.Li H Q,Chen M X,Han Q,Ma X D,Hu S S,Zhao Y Z,Zhang R X.Effect of mineralizer on optical properties of yellow pigment of Sm0.3Ce0.66Mo0.04O(1.85+δ)[J].Chinese Rare Earths,2014,35(6):6-10.
[3] Sayed S A,Rabie K A,Salama I E.Studies on europium separation from a middle rare earth concentrate by in situ zinc reduction technique[J].Separation and Purification Technology,2005,46(3):145-154.
[4] 郑昌琼,冉均国,杨云志,尹光福,刘耀敏.草酸盐共沉淀法制取优质锰锌铁氧体微细粉末的热力学分析[J].稀有金属,1997,21(2):101-104.Zheng C Q,Ran J G,Yang Y Z,Yi G F,Liu Y M.Thermodynamic analysis on preparation of high quality MnZn ferrite powders with oxalate coprecipitation method[J].Chinese Journal of Rare Metals,1997,21(2):101-104.
[5] 李慧琴,张瑞祥,刘海旺,王士智.锌与稀土分离及碱式碳酸锌的制备[J].稀土,2007,27(6):62-64.Li H Q,Zhang R X,Liu H W,Wang S Z.Separation of Zn-RE and preparation of zinc subcarbonate[J].Chinese Rare Earths,2007,27(6):62-64.
[6] 王军,李向阳,郝先库,张瑞祥,胡珊珊,马显东.锌与钐的萃取分离工艺研究[J].稀土,2015,36(5):102-106.Wang J,Li X Y,Hao X K,Zhang R X,Hu S S,Ma X D.Study on the extraction seperation process of zinc and samarium[J].Chinese Rare Earths,2015,36(5):102-106.
[7] 王军,郝先库,李向阳,赵永志,马显东,张瑞祥.添加NH4Cl的洗液对负载有机相中Zn2+洗涤率的影响[J].稀土,2016,37(4):74-80.Wang J,Hao X K,Li X Y,Zhao Y Z,Ma X D,Zhang R X.Effect of the washing with NH4Cl on the washing rate of Zn2+ in the loaded organic phase[J].Chinese Rare Earths,2016,37(4):74-80.
[8] 王军,郝先库,李向阳,张瑞祥,赵永志,刘海旺.料液中添加NH4Cl对Sm3+和Zn2+萃取性能的影响[J].稀土,2017,38(1):13-19.Wang J,Hao X K,Li X Y,Zhang R X,Zhao Y Z,Liu H W.Effect of adding NH4Cl to feed liquid on the extraction performance of Sm3+ and Zn2+[J].Chinese Rare Earths,2017,38(1):13-19.
[9] Masatoshi K,Toshiro Y.Methods for separation of rare earth from zinc[P].Japan:JP 2001151743,2001-06-05.
[10] 李慧琴,郑超,刘全,郝先库,张瑞祥,郭瑞华.在SmCl3和ZnCl2溶液中加入NH4Cl制备Sm2O3[J].稀土,2016,37(5):66-71.Li H Q,Zheng C,Liu Q,Hao X K,Zhang R X,Guo R H.Preparation of Sm2O3 from the mixed solution of ZnCl2 and SmCl3 with NH4Cl[J].Chinese Rare Earths,2016,37(5):66-71.
[11] 王艳,周春山,王歆燕.阴离子交换色谱法分离含钴溶液中锌、镉、铜等杂质[J].过程工程学报,2001,1(4):356-359.Wang Y,Zhou C S,Wang Y Y.Separation of cobalt from zinc,cadmium and copper by anion-exchange chromatography[J].The Chinese Journal of Process Engineering,2001,1(4):356-359.
[12] Ding Z Y,Chen Q Y,Yin Z L,Liu K.Predominance diagrams for Zn(II)-NH3-Cl--H2O system[J].Transactions of Nonferrous Metals Society of China,2013,23(3):832-840.
[13] Limpo J L,Luis A.Solubility of zinc chloride in ammoniacal ammonium chloride solutions[J].Hydrometallurgy,1993,32(2):247-260.
[14] 李伯刚,尹光福,韩纪梅,郑昌琼.制备软磁锰锌铁氧体粉的共沉淀条件的热力学分析[J].稀有金属,1999,23(6):421-424.Li B G,Yin G F,Han J M,Zheng C Q.Thermodynamic analysis on preparation of MnZn ferrite powders with coprecipitation process[J].Chinese Journal of Rare Metals,1999,23(6):421-424.
[15] 丁治英,尹周澜,肖忠良,张平民,胡慧萍,陈启元.氧化锌氨性浸出体系的平衡热力学研究[J].中国稀土学报,2010,28(S1):6-11.Ding Z Y,Yin Z L,Xiao Z L,Zhang P M,Hu H P,Chen Q Y.Study on the equilibrium thermodynamics of zinc oxide in ammonia leaching system[J].Journal of the Chinese Society of Rare Earths,2010,28(S1):6-11.
[16] 施民梅.焓变与熵变对化学反应的影响[J].沧州师范专科学校学报,2003,19(1):44-45.Shi M M.Environmental change and the change in enthalpy versus chemical reactions[J].Journal of Changzhou Teachers college,2003,19(1):44-45.
[17] 杨永斌,张鑫,李骞,江涛,白国华.氨法一步沉淀法制备碱式碳酸锌结晶行为特征[J].矿冶工程,2013,33(2):101-104.Yang Y B,Zhang X,Li Q,Jiang T,Bai G H.Characteristics of crystallization behavior of basic zinc carbonate in preparation by ammonia process[J].Mining and Metallurgical Engineering,2013,33(2):101-104.