电喷雾质谱法示踪钨回收过程离子的转化路径

doi:10.12034/j.issn.1009-606X.219158

过程工程学报 ›› 2019, Vol. 19 ›› Issue (6): 1135-1142.DOI: 10.12034/j.issn.1009-606X.219158

电喷雾质谱法示踪钨回收过程离子的转化路径

蔺淑洁^1,2，温嘉玮¹，曹宏斌¹，宁朋歌^1*，张懿¹

1. 北京市过程污染控制工程技术研究中心，中国科学院过程工程研究所湿法冶金清洁生产技术国家工程实验室，北京 100190 2. 中国科学院大学化学工程学院，北京 100049

收稿日期:2019-03-18 修回日期:2019-04-07 出版日期:2019-12-22 发布日期:2019-12-22
通讯作者: 宁朋歌 pgning@ipe.ac.cn
基金资助:
杰出青年基金;青促会基金

Tracking transformation pathway of tungsten recovery process by electrospray ionization time-of-flight mass spectrometry

Shujie LIN^1,2, Jiawei WEN¹, Hongbin CAO¹, Pengge NING^1*, Yi ZHANG¹

1. Beijing Engineering Research Center of Process Pollution Control, National Engineering Laboratory for Hydrometallurgical Cleaner Production & Technology, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China 2. School of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2019-03-18 Revised:2019-04-07 Online:2019-12-22 Published:2019-12-22

摘要/Abstract

摘要： 将环隙式离心萃取器(ACCs)与电喷雾飞行时间质谱(ESI-TOF-MS)相结合，在线监测了回收过程中的钨萃取行为(宏观)和钨形态的转化路径(微观)，发现宏观萃取反应和微观离子形态转化同时发生并相互补充。伯胺N1923萃取钨在144 s内即可达到萃取平衡，萃取率高达98%以上，同时，酸钨比n(H)/n(W)是一个关键变量，当酸钨比n(H)/n(W)=2.4时，全流程钨回收率超过93%。最后，得到了基于钨形态监测的萃取机理，同时，减少原料液中W1含量，增加W10含量，可有效提高钨回收效率。

关键词: 钨, 伯胺N1923, 形态转化, ESI-TOF-MS

Abstract: Tungsten is an important rare metal, which is widely used in the fields of national defense, chemical industry, electronics and metallurgy. Solvent extraction has been widely used for tungsten recovery because of its simple operation, good continuity and high recovery rate. Previous researches have always focused on the development of new extractants while ignoring the role of tungsten ion morphology in the extraction process. In fact, ion morphology will affect the way of combining with the extractant and the extraction process. Therefore, in-depth study of ion morphology in the extraction process can better understand the extraction mechanism of tungsten, and thus provide a basis for the separation of tungsten and molybdenum. In this study, annular centrifugal contactors (ACCs) were combined with electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS) to study the transformation pathway of tungsten species in the recovery process by online monitoring method. It was found that the extraction of tungsten by primary amine N1923 was very fast and effective. Within 144 s, more than 98% of the tungsten could be extracted into the organic phase. At the same time, n(H)/n(W) was a key variable. When the acid ratio was 2.4, the whole tungsten recovery rate exceeded 93%. Finally, the extraction mechanism based on tungsten morphology monitoring was obtained. The macroscopic extraction reaction and the micro-ion exchange reaction occurred simultaneously and complemented each other. As the initial pH decreased, W2, W6 and W10 became active forms in sequence and were preferentially extracted into the organic phase, respectively. In addition, W10 was more active than any other species during the whole process. W1 was an inactive substance that only participated in the tungsten ion balance reaction to adjust the tungsten form and pH. As a result, reducing W1 and increasing W10 as much as possible would be conducive to improve tungsten extraction efficiency in solution.

Key words: tungsten recovery, primary amine N1923, tungsten transformation pathway, ESI-TOF-MS

蔺淑洁温嘉玮曹宏斌宁朋歌张懿. 电喷雾质谱法示踪钨回收过程离子的转化路径[J]. 过程工程学报, 2019, 19(6): 1135-1142.

Shujie LIN Jiawei WEN Hongbin CAO Pengge NING Yi ZHANG. Tracking transformation pathway of tungsten recovery process by electrospray ionization time-of-flight mass spectrometry[J]. Chin. J. Process Eng., 2019, 19(6): 1135-1142.

参考文献

[1] Nguyen T H, Lee M S. A review on the separation of molybdenum, tungsten, and vanadium from leach liquors of diverse resources by solvent extraction [J]. Geosystem Engineering, 2016, 19(5): 247-259.
[2] Zhao Z W, Cao C F, Chen X Y. Separation of macro amounts of tungsten and molybdenum by precipitation with ferrous salt [J]. Transactions of Nonferrous Metals Society of China, 2011, 21(12): 2758-2763.
[3] Pagnanelli F, Ferella F, De Michelis I, et al. Adsorption onto activated carbon for molybdenum recovery from leach liquors of exhausted hydrotreating catalysts [J]. Hydrometallurgy, 2011, 110(1-4): 67-72.
[4] Nguyen T H, Lee M S. Separation of molybdenum (VI) and tungsten (VI) from sulfuric acid solution by ion exchange with TEVA resin [J]. Separation Science and Technology, 2015, 50(13): 2060-2065.
[5] Zhao Z W, Zhang J L, Chen X Y, et al. Separation of tungsten and molybdenum using macroporous resin: Equilibrium adsorption for single and binary systems [J]. Hydrometallurgy, 2013, 140: 120-127.
[6] Wang L P, Zhang G Q, Guan W J, et al. Complete removal of trace vanadium from ammonium tungstate solutions by solvent extraction [J]. Hydrometallurgy, 2018, 179: 268-273.
[7] Liao Y L, Zhao Z W. Comparison of 2-Octanol and tributyl phosphate in recovery of tungsten from sulfuric–phosphoric acid leach solution of scheelite [J]. Jom, 2018, 70(4): 581-586.
[8] Ning P G, Cao H B, Zhang Y. Selective extraction and deep removal of tungsten from sodium molybdate solution by primary amine N1923 [J]. Separation and Purification Technology, 2009, 70(1): 27-33.
[9] Redkin A F, Bondarenko G V. Raman spectra of tungsten-bearing solutions [J]. Journal of Solution Chemistry, 2010, 39(10): 1549-1561.
[10] Himeno S, Kitazumi I. Capillary electrophoretic study on the formation and transformation of isopolyoxotungstates in aqueous and aqueous-CH3CN media [J]. Inorganica Chimica Acta, 2003, 355: 81-86.
[11] Hastings J J, Howarth O W. A 183W, 1H and 17O nuclear magnetic resonance study of aqueous isopolytungstates [J]. Journal of the Chemical Society-Dalton Transactions, 1992, (2): 209-215.
[12] Fedotov M A, Maksimovskaya R I. NMR structural aspects of the chemistry of V, Mo, W polyoxometalates [J]. Journal of Structural Chemistry, 2006, 47(5): 952-978.
[13] Xu W, Ning P G, Cao H B,et al. Thermodynamic model for tungstic acid extraction from sodium tungstate in sulfuric acid medium by primary amine N1923 diluted in toluene [J]. Hydrometallurgy, 2014, 147-148: 170-177.
[14] Zhang J J, Zhao Z W, Chen X Y, et al. Thermodynamic analysis for separation of tungsten and molybdenum in W-Mo-H2O system [J]. The Chinese Journal of Nonferrous Metals, 2013, 23(5): 1463-1470.
[15] Zhang C, Howell R C, Scotland K B, et al. Aqueous speciation studies of europium(III) phosphotungstate [J]. Inorganic Chemistry, 2004, 43: 7691-7701.
[16] Aureliano M, Ohlin C A, Vieira M O, et al. Characterization of decavanadate and decaniobate solutions by raman spectroscopy [J]. Dalton Trans, 2016, 45(17): 7391-7399.
[17] Scancar J, Berlinger B, Thomassen Y, et al. Simultaneous speciation analysis of chromate, molybdate, tungstate and vanadate in welding fume alkaline extracts by HPLC-ICP-MS [J]. Talanta, 2015, 142: 164-169.
[18] Schramel P, Wendler I, Angerer J. The determination of metals (antimony, bismuth, lead, cadmium, mercury, palladium, platinum, tellurium, thallium, tin and tungsten) in urine samples by inductively coupled plasma-mass spectrometry [J]. Int Arch Occup Environ Health, 1997, 69(3): 219-223.
[19] Mohajerin T J, Helz G R, White C D, et al. Tungsten speciation in sulfidic waters: determination of thiotungstate formation constants and modeling their distribution in natural waters [J]. Geochimica et Cosmochimica Acta, 2014, 144: 157-172.
[20] Long D L, Streb C, Song Y F, et al. Unravelling the complexities of polyoxometalates in solution using mass spectrometry: Protonation versus heteroatom inclusion [J]. Journal of the American Chemical Society, 2008, 130(6): 1830-1832.
[21] Jia Q D, Cao J, Duan Y P, et al. The solution chemistry and reactivity of lacunary Keggin silicotungstates monitored in real-time by a combination of mass spectrometry and electrochemistry [J]. Dalton Transactions, 2015, 44 (2): 553-559.
[22] Jing X H, Ning P G, Cao H B, et al. Separation of V(V) and Cr(VI) in leaching solution using annular centrifugal contactors [J]. Chemical Engineering Journal, 2017, 315: 373-381.
[23] Wen J W, Ning P G, Cao H B, et al. Recovery of high-purity vanadium from aqueous solutions by reusable primary amines N1923 associated with semiquantitative understanding of vanadium species [J]. ACS Sustainable Chemistry & Engineering, 2018, 6(6): 7619-7626.
[24] Zhao H, Liu H J, Qu J H. Aluminum speciation of coagulants with low concentration: Analysis by electrospray ionization mass spectrometry [J]. Colloids and Surfaces A-Physicochemical and Engineering Aspects, 2011, 379 (1-3), 43-50.
[25] Truebenbach C S, Houalla M, Hercules D M. Characterization of isopoly metal oxyanions using electrospray time-of-flight mass spectrometry [J]. Journal of the Mass Spectrom, 2000, 35(9): 1121-1127.
[26] Walanda D A, Burns R C, Lawrance G A, et al. Electrospray mass spectrometry of aqueous solutions of Isopolyoxotungstates [J]. Journal of Cluster Science, 2000, 11: 5-28.
[27] Deery M J, Howarth O W, Jennings K R. Application of electrospray ionisation mass spectrometry to the study of dilute aqueous oligomeric anions and their reactions [J]. Journal of the Chemical Society-Dalton Trans, 1997, 4783-4788.

电喷雾质谱法示踪钨回收过程离子的转化路径

Tracking transformation pathway of tungsten recovery process by electrospray ionization time-of-flight mass spectrometry

PDF

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

[1]	武文粉李会泉孟子衡王晨晔王兴瑞赵晨. 碱溶法回收废SCR脱硝催化剂中的二氧化钛[J]. 过程工程学报, 2019, 19(S1): 72-80.
[2]	蔺淑洁宁朋歌张懿. 含氧酸根检测方法的研究现状及质谱法在钨钼分离中的应用前景[J]. 过程工程学报, 2019, 19(5): 910-918.
[3]	刘云竹符晓芳高丽华雷连彩王轶博. 1,3-二乙酸咪唑磷钨酸盐的制备及其对甲基红的光催化降解性能[J]. 过程工程学报, 2018, 18(S1): 146-152.
[4]	周秋生李栋朱志成李小斌齐天贵. 钨酸铵-硝酸铵溶液体系结晶制备仲钨酸铵过程中钠/钾的析出行为[J]. 过程工程学报, 2018, 18(1): 118-125.
[5]	高良军陈平. 六方介孔氧化硅负载磷钨酸的催化性能[J]. 过程工程学报, 2016, 16(3): 522-528.
[6]	刘强徐瑞东何世伟. 钨粉表面化学镀铜沉积过程中的开路电位[J]. 过程工程学报, 2015, 15(6): 1012-1017.
[7]	周文刘雅兰王长福刘峙嵘. 氯化钆在熔盐LiCl-KCl中的电化学性质[J]. 过程工程学报, 2015, 15(4): 698-702.
[8]	丁冲王晓辉何超然郑诗礼谢华张盈. 黑钨渣硫酸浸钪及浸出过程中草黄铁矾法抑制铁浸出[J]. , 2014, 14(6): 907-914.
[9]	范兴祥行卫东董海刚赵家春吴跃东刘杨付光强. 从废旧高温合金的硫酸浸出渣中浸出分离钨钼铼[J]. , 2013, 13(6): 969-973.
[10]	李金辉谢芳浩乔珊杨幼明. 酸性溶液中钨钼离子的电化学行为[J]. , 2013, 13(1): 73-77.
[11]	杨得岭宁朋歌曹宏斌张懿. 伯胺N1923络合萃取苯酚[J]. , 2012, 12(4): 569-575.
[12]	周华锋刘玉萍张丽清. 介孔二氧化钛负载硅钨杂多酸的制备及其催化性能[J]. , 2012, 12(3): 522-526.
[13]	曾坚贤孙霞辉周虎贺勤程李书. 聚电解质强化超滤技术处理钨(VI)[J]. , 2011, 11(3): 396-400.
[14]	黄惠郭忠诚李具康陈步明. 锌电积过程中聚苯胺/碳化钨阳极的结构变化及失效行为[J]. , 2010, 10(5): 1020-1024.
[15]	张莉王聪卓馨陶淑华. 12-磷钨酸体系水热法制备金颗粒及其表征[J]. , 2010, 10(1): 155-160.