Determination of thirty-nine major and minor elements in ilmenite by inductively coupled plasma mass spectrometry with high pressure closed digestion
CHENG Yi, WANG Lin*, ZHANG Fang, LIU Jun, CHEN Haofeng, ZHANG Fan
Henan Province Rock & Mineral Testing Centre, Key Laboratory of Precious Metals Analysis and Exploration Technology Ministry of Land and Resources,Zhengzhou 450012, China
摘要 准确测定钛铁矿中主次元素对提高钛铁矿的选钛技术及有益元素的综合回收具有指导意义。钛铁矿难溶易水解,一般很难实现一次分解多元素同时测定。采用3 mL HF-1 mL HNO3-0.5 mL H2SO4于180 ℃高压密闭消解10 h,用5 mL逆王水180 ℃高压密闭方式溶解盐类5 h,在线引入Rh、Re混合内标,采用标准模式测定Li、Be、Sc、Ti、V、Cr、Mn、Co、Ni、Cu、Zn、Ga、Rb、Sr、Y、Mo、Cd、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、W、Pb、U,动能歧视模式测定Fe、Zr、Nb、La、Ce、Hf、Ta,对于受质谱干扰严重的V、Ni、Cd、Eu、Gd、Tb,通过数学校正方程在线进行校正,建立了电感耦合等离子体质谱法(ICP-MS)测定钛铁矿中39种主次元素的方法。方法校准曲线的相关系数均不小于0.999 6,检出限为0.002~2.4 μg/g,将其应用于钛铁矿成分分析标准物质分析,结果的相对误差(RE)为-10.0%~13.0%,相对标准偏差(RSD,n=12)均不大于3.5%;对主量元素及缺少认定值的元素进行加标回收试验,回收率为96%~104%。采用实验方法对钛铁矿样品进行分析,测得结果的相对标准偏差(RSD,n=12)均不大于4.1%。
Abstract:The accurate determination of major and minor elements in ilmenite had guiding significance to improve the beneficiation technology of ilmenite and the comprehensive recovery of beneficial elements. Ilmenite sample was hardly dissolved and easily hydrolyzed, so it was difficult to realize the simultaneous determination of multiple elements. The sample was digested with 3 mL of HF, 1 mL of HNO3 and 0.5 mL of H2SO4 at 180 ℃ for 10 h with high pressure pressure closed digestion. Then the salts were dissolved with 5 mL of reverse aqua regia at 180 ℃ for 5 h. The mixed internal standard of Rh and Re was introduced on line. Li, Be, Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Mo, Cd, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, W, Pb and U were determined at standard mode (STD), while Fe, Zr, Nb, La, Ce, Hf and Ta were determined at kinetic energy discrimination (KED) mode. For the elements with serious mass spectrometry interference such as V, Ni, Cd, Eu, Gd and Tb, the online correction by mathematical equation was adopted. Consequently, a determination method of 39 major and minor elements in ilmenite by inductively coupled plasma mass spectrometry (ICP-MS) was established. The correlation coefficients of calibration curves of method were all not less than 0.999 6. The limits of detection were between 0.002 μg/g and 2.4 μg/g. The proposed method was applied to analysis of certified reference materials of ilmenite for composition analysis. The relative errors (RE) of results were between -10.0% and 13.0%. The relative standard deviations (RSD, n=12) were not more than 3.5%. The standard recovery tests of major elements and the elements in lack of certified values were conducted. The recoveries were between 96% and 104%. The ilmenite samples were analyzed according to the experimental method, and the RSDs (n=12) of results were not more than 4.1%.
程祎, 王琳, 张芳, 刘军, 陈浩凤, 张帆. 高压密闭消解-电感耦合等离子体质谱法测定钛铁矿中39种主次元素[J]. 冶金分析, 2021, 41(9): 24-33.
CHENG Yi, WANG Lin, ZHANG Fang, LIU Jun, CHEN Haofeng, ZHANG Fan. Determination of thirty-nine major and minor elements in ilmenite by inductively coupled plasma mass spectrometry with high pressure closed digestion. , 2021, 41(9): 24-33.
[1] 孙赛军,廖仁强,丛亚楠,等.钛的地球化学性质与成矿[J].岩石学报,2020,36(1):68-76. SUN Saijun,LIAO Renqiang,CONG Yanan,et al.Geochemistry and mineralization of titanium[J].Acta Petrologica Sinica,2020,36(1):68-76. [2] 尹明,李家熙.岩石矿物分析:第2分册[M].4版.北京:地质出版社,2011:752-753. [3] 朱忠平,李国会.熔融制样-X射线荧光光谱法测定钛铁矿中主次组分[J].冶金分析,2013,33(6):32-36. ZHU Zhongping,LI Guohui.Determination of major and minor components in ilmenite by X-ray fluorescence spectrometry with fusion sample preparation[J].Metallurgical Analysis,2013,33(6):32-36. [4] 李小莉,刘斌,徐进力,等.压片法和熔融片法制样-X射线荧光光谱法测定钛矿石中的18种组分[J].理化检验(化学分册),2020,56(11):1188-1192. LI Xiaoli,LIU Bin,XU Jinli,et al.Determination of 18 components in titanium ores by X-ray fluorescence spectrometry with sample preparation of tablet compression method and fusion tablet method[J].Physical Testing and Chemical Analysis (Part B:Chemical Analysis),2020,56(11):1188-1192. [5] 黄康,刘菊琴,邵晓龙,等.X-射线荧光光谱法测定钛铁矿中的主次量元素[J].甘肃冶金,2020,42(2):93-96. HUANG Kang,LIU Juqin,SHAO Xiaolong,et al.Determination of major-minor elements in ilmenite by X-ray fluorescence spectrometry[J].Gansu Metallurgy,2020,42(2):93-96. [6] 黄康,李仲夏,朱文静,等.熔融制样-X射线荧光光谱法测定金红石中主次组分[J].冶金分析,2020,40(3):68-72. HUANG Kang,LI Zhongxia,ZHU Wenjing,et al.Determination of major and minor components in rutile by X-ray fluorescence spectrometry with fusion sample preparation[J].Metallurgical Analysis,2020,40(3):68-72. [7] 马海萍,马玲,刘瑱,等.电感耦合等离子体原子发射光谱法在钒钛磁铁矿中钒化学物相分析中的应用[J].冶金分析,2019,39(8):61-66. MA Haiping,MA Ling,LIU Zhen,et al.Application of inductively coupled plasma atomic emission spectrometry in chemical phase analysis of vanadium in vanadium-titanium magnetite[J].Metallurgical Analysis,2019,39(8):61-66. [8] 赵伟,王卿,张会堂,等.电感耦合等离子体发射光谱法测定钛铁矿中主、微量元素[J].山东国土资源,2018,34(5):107-110. ZHAO Wei,WANG Qing,ZHANG Huitang,et al.Determination of main and trace elements in ilmenite by using inductively coupled plasma atomic emission spectrometry method[J].Shandong Land and Resources,2018,34(5):107-110. [9] 周学富,周晓晶.盐酸对钛铁矿岩矿和沙矿的溶解作用[J].四川师范大学学报(自然科学版),1998(1):115-117. ZHOU Xuefu,ZHOU Xiaojing.Acidolysis of the rock-forming and the powder-forming ilmenite in HCl[J].Journal of Sichuan Normal University (Natural Science),1998(1):115-117. [10] 宋茂生,张鑫,范鹏飞,等.阴离子交换分离-电感耦合等离子体质谱法测定钛铁矿中的铀、钍[J].理化检验(化学分册),2020,56(6):650-654. SONG Maosheng,ZHANG Xin,FAN Pengfei,et al.ICP-MS determination of uranium and thorium in ilmenite with separation by anion-exchange[J].Physical Testing and Chemical Analysis (Part B:Chemical Analysis),2020,56(6):650-654. [11] 赵昕,严慧,禹莲玲,等.过氧化钠碱熔-电感耦合等离子体发射光谱法测定钛铁矿中的高含量钛[J].岩矿测试,2020,39(3):459-466. ZHAO Xin,YAN Hui,YU Lianling,et al.Determination of high content of titanium in ilmenite by inductively coupled plasma-optical emission spectrometry with sodium peroxide alkali fusion[J].Rock and Mineral Analysis,2020,39(3):459-466. [12] 王卿,赵伟,张会堂,等.过氧化钠碱熔-电感耦合等离子体发射光谱法测定钛铁矿中铬磷钒[J].岩矿测试,2012,31(6):971-974. WANG Qing,ZHAO Wei,ZHANG Huitang,et al.Determination of Cr, V and P in ilmenite by inductively coupled plasma-atomic emission spectrometry with sodium peroxide fusion[J].Rock and Mineral Analysis,2012,31(6):971-974. [13] 李蓉,王劲榕.ICP-AES法测定金红石及钛铁矿中锆[J].云南冶金,2013,42(5):98-100. LI Rong,WANG Jinrong.The determination of zirconium in rutile and ilmenite by ICP-AES method[J].Yunnan Metallurgy,2013,42(5):98-100. [14] 张歌,刘叶楠,段宁,等.高压密闭消解-电感耦合等离子体质谱法测定锰矿石中钛钒锶[J].冶金分析,2014,34(12):39-43. ZHANG Ge,LIU Yenan,DUAN Ning,et al.Determination of titanium, vanadium and strontium in manganese ore by inductively coupled plasma mass spectrometry with high-pressure closed digestion[J].Metallurgical Analysis,2014,34(12):39-43. [15] 于亚辉,王琳,王明军,等.电感耦合等离子体质谱法测定地球化学样品中痕量铑的干扰消除方法探讨[J].冶金分析,2017,37(9):25-32. YU Yahui,WANG Lin,WANG Mingjun,et al.Discussion on elimination of interference in determination of trace rhodium in geochemical sample by inductively coupled plasma mass spectrometry[J].Metallurgical Analysis,2017,37(9):25-32. [16] 程祎,李志伟,于亚辉,等.高压密闭消解-电感耦合等离子体质谱法测定地质样品中铌、钽、锆、铪和16种稀土元素[J].理化检验(化学分册),2020,56(7):782-787. CHENG Yi,LI Zhiwei,YU Yahui,et al.ICP-MS Determination of Nb, Ta, Zr, Hf and 16 rare earth elements in geological samples with high pressure closed digestion[J].Physical Testing and Chemical Analysis (Part B:Chemical Analysis),2020,56(7):782-787. [17] 任冬,陈宇豪,张廷忠.高压密闭消解技术在土壤有效态样品前处理中的应用[J].岩矿测试2020,39(1):143-149. REN Dong,CHEN Yuhao,ZHANG Tingzhong.Application of high pressure closed digestion in pretreatment of effective soil samples[J].Rock and Mineral Analysis,2020,39(1):143-149. [18] 周晓东,张云梅.钛铁矿常压微波消解溶样方法研究[J].冶金分析,2007,27(8):69-72. ZHOU Xiaodong,ZHANG Yunmei.Research on microwave digestion of titanic iron ore under atmospheric pressure[J].Metallurgical Analysis,2007,27(8):69-72.