Determination of fluorine and chlorine in iron ores bypyrohydrolysis- ion chromatography
LI Ying-na1,XU Zhi-bin*2,ZHANG Zhi-wei2
1.Department of Environmental and Chemical Engineering,Tangshan College, Tangshan 063000, China; 2.Technical Center,Hebei Entry-exit Inspection and Quarantine,Tangshan 063611,China
Abstract：The iron ore sample was pretreated by self-made pyrohydrolysis device.The simultaneous determination method of fluorine and chlorine in iron ore by ion chromatography was established. The influence of sample mass, hydrolysis temperature and time, catalyst type and dosage, oxygen and water flow rate on hydrolysis effect was investigated. The optimal temperature hydrolysis conditions were obtained: the sample mass was 0.5 g, the hydrolysis temperature was 1 100 ℃, the hydrolysis time was 30 min, the mass ratio of sample and catalyst (V2O5) was 1∶1, the oxygen flow rate was 300 mL/min, and the peristaltic pump flow rate was 1.5 mL/min. Two groups of water were used as absorbent. The mass concentration of fluorine and chlorine in range of 1.00-20.00 μg/mL was linear to the peak area. The linear correlation coefficients (R2) of calibration curves were higher than 0.999 5. The detection limit of fluorine and chlorine in proposed method was 3.7 μg/g and 4.9 μg/g, respectively. The proposed method was applied to the determination of fluorine and chlorine in iron ore certified reference materials. The relative standard deviations (RSD, n=6) were between 1.0% and 2.1%. The determination results were consistent with the certified values.
李颖娜,徐志彬,张志伟. 高温水解-离子色谱法测定铁矿石中氟和氯[J]. 冶金分析, 2016, 36(6): 23-28.
LI Ying-na,XU Zhi-bin,ZHANG Zhi-wei. Determination of fluorine and chlorine in iron ores bypyrohydrolysis- ion chromatography. , 2016, 36(6): 23-28.
Ando M,Tadano M,S Yamamoto,et al.Health effects of fluoride pollution caused by coal burning[J].Science of the Total Environment,2001,271(1-3):107-116.
[2]
LIU Guo-rui,ZHENG Ming-hui,CAI Zong-wei,et al.Dioxin analysis in China[J].TrAC Trends in Analytical Chemistry,2013,46(6):178.
[3]
刘卫国,彭子成,肖应凯.硼、氯同位素测定方法及地球化学研究进展[J].地球科学进展,1998,13(6):547-554.LIU Wei-guo,PENG Zi-cheng,XIAO Ying-kai.Boron and chlorine isotopic determinations and applications for earth science[J].Advance in Earth Science,1998,13(6):547-554.
[4]
Eastoe C J,Guilbert J M,Kaufmann R S.Preliminary evidence for fractionation of stable chlorine isotopes in ore-forming hydrothermal systems[J].Geology,1989,17(3):285-288.
[5]
窦怀智,陆彩霞,侯晋.离子色谱法测定镍矿中氟和氯[J].冶金分析,2012,32(8):59-62.DOU Huai-zhi,LU Cai-xia,HOU Jin. Determination of fluoride and chloride in nickel ore by ion chromatography[J].Metallurgical Analysis,2012,32(8):59-62.
[6]
胡德新,马德起,安鹏升,等.超声提取-离子色谱法测定铁矿石中水溶性氟氯溴及硝酸根[J].岩矿测试,2012,31(2):287-290.HU De-xin,MA De-qi,AN Peng-sheng,et al.Determination of water soluble fluoride,chloride,bromide and nitrate in iron ores by supersonic extraction ion chromatograph[J].Rock and Mineral Analysis,2012,31(2):287-290.
[7]
张媛媛,林学辉,贺行良,等.离子色谱法同时测定海洋沉积物中氯和硫[J].分析科学学报,2015,31(2):249-252.ZHANG Yuan-yuan,LIN Xue-hui,HE Xing-liang,et al.Determination of chlorine and sulfur in marine sediment by ion chromatography [J].Journal of Analytical Science,2015,31(2):249-252.
[8]
刘建权,赵峰华,刘璟,等.氧弹燃烧-离子色谱法测定煤中氯含量[J].分析化学,2009,37(8):1152-1156.LIU Jian-quan,ZHAO Feng-hua,LIU Jing,et al.Determination of chlorine in coal by oxygen bomb-ion chromatography[J]. Chinese Journal of Analytical Chemistry,2009,37(8):1152-1156.
[9]
彭炳先,吴代赦.高温热水解离子色谱法快速同时测定粘土中的卤素[J].分析化学,2013,41(10):1499-1504.PENG Bing-xian,WU Dai-he.Simultaneous determination of halogens in clay using pyrohydrolysis combined with ion chromatography[J].Chinese Journal of Analytical Chemistry,2013,41(10):1499-1504.
[10]
阳兆鸿,李华昌,于力,等.水蒸气蒸馏-离子色谱法测定硫化矿石中氟和氯[J].冶金分析,2015,35(4):34-38. YANG Zhao-hong,LI Hua-chang,YU Li,et al.Determination of fluorine and chlorine in solution of wet zinchydrometallurgy by steam distillation-ion chromatography[J].Metallurgical Analysis,2015,35(4):34-38.
[11]
Warf J C,Cline W D,Tevebaugh R D.Pyrohydrolysis in determination of fluoride and other halides[J].Anal. Chem.,1954,26(2):342-346.
[12]
Warf H C,Cline W D,Tevebaugh R D.Pyrohydrolysis in determination of fluoride fluorine, chlorine, bromine and iodine in six geochemical reference materials using pyrohydrolysis,ion chromatography and inductively coupled plasma-mass spectrometry[J].Geostandards and Geoanalytical Research,2009,33(4):477-485.
[13]
Wang Qiaoyun,Makishima Akio,Nakamura Eizo.Determination of fluorine and chlorine by pyrohydrolysis and ion chromatography:Comparison with alkaline fusion digestion and ion chromatography[J].Geostandards and Geoanalytical Research,2010,34(2):175-183.
[14]
李映日,邓双,王红梅,等.高温燃烧水解-淋洗液在线发生离子色谱法同时测定煤中氟和氯[J].环境工程,2011,29(5):130-134.LI Ying-ri,DENG Shuang,WANG Hong-mei,et al.Simultaneous determination of fluorine and chlorine in coal by high temperature combustion hyderolysis-ion chromatography with on-line eluent generator[J].Environmental Engineering,2011,29(5):130-134.
[15]
Schnetger B,Muramatsu Y.Determination of halogens,with special reference to iodine, in geological and biological samples using pyrohydrolysis for preparation and inductively coupled plasma mass spectrometry and ion chromatography for measurement [J].Analyst,1996,121(11):1627-1631.
[16]
李权斌.氧弹燃烧-电位滴定法测定煤中氯[J].岩矿测试,2006,25(1):79-81. LI Quan-bin.Determination of chlorine in coal by combustion bomb-potentiometric titration[J].Rock and Mineral Analysis,2006,25(1):79-81.
[17]
Flores M M,Mesko M F,Moraes D P,et al.Determination of Halogens in coal after digestion using the microwave-induced combustion technique[J].Anal. Chem.,2008,80(6):1865-1870.
[18]
Goisa S de,Pereiraa R,Welz B.Simultaneous determination of bromine and chlorine in coal using electrothermal vaporization inductively coupled plasma mass spectrometry and direct solid sample analysis[J].Anal.,Chim.Acta,2014,852:82-87.
[19]
Boulyga S F,Heilmann J,Prohaska T,et al.Development of an accurate, sensitive, and robust isotope dilution laser ablation ICP-MS method for simultaneous multi-element analysis (chlorine,sulfur,and heavy metals) in coal samples[J].Analytical and Bioanalytical Chemistry,2007(3):697-706.
[20]
Shimizu K,Suzuki K,Saitoh M,et al.Simultaneous determinations of fluorine,chlorine,and sulfur in rock samples by ion chromatography combined with pyro hydrolysis [J].Geochemical Journal,2015(49):113-124.
[21]
Michel A,Villemant B.Determination of halogens (F,Cl,Br,I),sulfur and water in seventeen geologicalreference materials [J].Geostandards Newsletter,2003,27(2):163-171.
