Differences in the distribution and occurrence of lithium and gallium in the No.11 coal seam from the Antaibao mining district
-
摘要: 为针对性分析煤层中锂、镓的分布赋存特征,选取安太堡11号煤层为研究对象,统计了锂、镓在各灰分级别、硫分级别及纵向分层中的分布特征。通过飞行时间二次离子质谱仪与带能谱的扫描电镜,分析了微区范围内锂、镓与常量元素的结合关系,讨论了煤层中锂、镓赋存状态差异性及影响因素。结果表明,锂富集于高灰煤中,镓在不同灰分级别与硫分级别煤中含量变化不显著。在纵向煤层中,锂在陆源物质供给充分时具有较高含量,镓分布较为均匀未呈现明显变化规律。微区原位分析中,锂的赋存与铝硅酸盐密切相关,镓可赋存于高岭石、勃姆石、黄铁矿、钠盐和钾盐中。煤层中锂与稳定元素锆的相关性系数为0.894,两者主要来源于物源区酸性岩浆岩。镓由于过渡元素的性质显示亲石性与亲硫性,在高灰煤与高硫煤中均具有较高含量,较强的元素迁移性使其在煤分层中趋于均匀分布。Abstract: In order to analyze the distribution and occurrence of lithium (Li) and gallium (Ga) in coal separately, the No.11 coal seam from the Antaibao mining district was collected as research object. The distribution of Li and Ga in different ash fractions, sulfur fractions, and coal column benches was discussed. The relationship between Li and Ga with other major elements in the micro-area was investigated by time-of-flight secondary ion mass spectrometer (TOF-SIMS) and scanning electron microscope with energy dispersive spectrometer (SEM-EDS). The difference in the occurrence of Li and Ga, and the influencing factors were discussed. The results show that Li is enriched in high-ash coal, while Ga does not change significantly in coal samples in various ash and sulfur fractions. In the longitudinal seam, Li is enriched in the coal bench with sufficient supply of terrestrial source material, while Ga is more evenly distributed in the coal seam. In the in-situ regions, Li occurs only in aluminosilicates, while Ga can occur in kaolinite, boehmite, pyrite, chloride, and sylvite. The correlation coefficient between Li and stable element zirconium (Zr) for all samples is 0.894. Both are mainly derived from acidic magmatic rocks in the source area. Gallium is abundant in both high ash coal and high sulfur coal due to its transitional property as a lithophile and sulphophile element. Its mobility makes it tend to be uniformly distributed in the coal seam.
-
Key words:
- coal /
- lithium /
- gallium /
- distribution /
- occurrence
-
表 1 锂、镓在各灰分级别与硫分级别煤中的含量分布
Table 1 Concentration of Li and Ga for coal samples in various ash fractions and sulfur fractions
Fraction Sample Statistics Li/ (μg·g−1) Ga/ (μg·g−1) Fraction Sample Statistics Li/ (μg·g−1) Ga/ (μg·g−1) Ultra-low ash 11-3 range low sulfur 11-6, 11-12, 11-14 range 143−260 19.7−20.7 average 47.2 40.2 average 194 20.2 Low ash 11-4, 11-5, 11-7, 11-8, 11-10, 11-15, 11-16, 11-17 range 57.9−113 14.2−26.3 medium sulfur 11-4, 1-5, 11-9, 11-10, 11-16, 11-17 range 77.6−103 14.2−26.3 average 84.6 19.6 average 86.4 20.2 Medium ash 11-9 range medium to high sulfur 11-7, 11-8, 11-15 range 57.9−113 15−22.7 average 81.2 18.1 average 79.8 17.7 High ash 11-12 range high sulfur 11-3, 11-11 range 42.6−47.2 13.9−40.2 average 260 19.7 average 44.9 27.1 Ultra-high ash 11-14, 11-6, 11-11 range 42.6−179 13.9−20.7 average 122 18.3 -
[1] 梁虎珍, 曾凡桂, 相建华, 李美芬. 伊敏褐煤中微量元素的地球化学特征及其无机-有机亲和性分析[J]. 燃料化学学报, 2013, 41(10): 1173–1183.LIANG Hu-zhen, ZENG Fan-gui, XIANG Jian-hua, LI Mei-fei. Geochemical characteristics and inorganic-organic affinity of the trace elements in Yimin lignite[J]. J Fuel Chem Technol, 2013, 41(10): 1173–1183. [2] 杨建业, 张卫国, 赵洲, 汪广恒. 微量元素与煤有机质的结合关系浅探—以太原西山矿区8号煤层为例[J]. 燃料化学学报, 2014, 42(6): 662-670.YANG Jian-ye, ZHANG Wei-guo, ZHAO Zhou, WANG Guang-heng. Preliminary study about combination between trace elements and organic matter in coal-An example of 8# coal seam from Taiyuan Xishan[J]. J Fuel Chem Technol, 2014, 42(6): 662–670. [3] 吕海亮, 陈皓侃, 李文, 李宝庆. 义马煤中几种微量污染元素的赋存状态研究[J]. 燃料化学学报,2003,31(1):31−34. doi: 10.3969/j.issn.0253-2409.2003.01.007LǙ Hai-liang, CHEN Hao-kan, LI Wen, LI Bao-qing. Mode of occurrence of several harmful trace elements in Yima coal[J]. J Fuel Chem Technol,2003,31(1):31−34. doi: 10.3969/j.issn.0253-2409.2003.01.007 [4] 宁树正, 邓小利, 李聪聪, 秦国红, 张建强, 朱士飞, 乔军伟, 陈磊, 章伟. 中国煤中金属元素矿产资源研究现状与展望[J]. 煤炭学报,2017,42(9):2214−2225.NING Shu-zheng, DENG Xiao-li, LI Cong-cong, QIN Guo-hong, ZHANG Jian-qiang, ZHU Shi-fei, QIAO Jun-wei, CHEN Lei, ZHANG Wei. Research status and prospect of metal element mineral resources in China[J]. J China Coal Soc,2017,42(9):2214−2225. [5] 李钟模. 锂-2l世纪的“元素新星”[J]. 中国化工,1997,11:33−57.LI Zhong-mo. Lithium: "Elemental Nova" of the 21st century[J]. China Nat Chem,1997,11:33−57. [6] DAI S F, JIANG Y F, WARD C R, GU L D, SEREDIN V V, LIU H S, ZHOU D, WANG X B, SUN Y Z, ZOU J H, REN D Y. Mineralogical and geochemical compositions of the coal in the Guanbanwusu Mine, Inner Mongolia, China: Further evidence for the existence of an Al (Ga and REE) ore deposit in the Jungar Coalfield[J]. Int J Coal Geol,2012,98:10−40. doi: 10.1016/j.coal.2012.03.003 [7] FINKELMAN R B, PALMER C A, WANG P P. Quantification of the modes of occurrence of 42 elements in coal[J]. Int J Coal Geol,2018,185:138−160. doi: 10.1016/j.coal.2017.09.005 [8] WILLIS J P. Some aspects of the geochemistry of gallium in silicate rocks and stony meteorites[D]. Cape Town, The Republic of South Africa: University of Cape Town, 1979. [9] WEN X Q, ZENG F G, ZHANG H. Geochemical characteristics of the coal gangues from the Du’erping coal mine, Xishan coalfield, North China[J]. Chin J Geochem,2013,32(2):227−234. doi: 10.1007/s11631-013-0626-2 [10] SUN Y Z, ZHAO C L, ZHANG J Y, YANG J J, ZHANG Y Z, YUAN Y, XU J, DUAN D J. Concentrations of valuable elements of the coals from the Pingshuo Mining District, Ningwu Coalfield, northern China[J]. Energy Explor Exploit,2013,31(5):727−744. doi: 10.1260/0144-5987.31.5.727 [11] 李华, 许霞, 杨恺. 山西平朔矿区4号煤中锂、镓资源成矿地质特征研究[J]. 中国煤炭地质,2014,26(12):17−19. doi: 10.3969/j.issn.1674-1803.2014.12.04LI Hua, XU Xia, YANG Kai. Lithium and gallium resources metallogenic geological characteristics in coal No. 4, Pingshuo mining area, Shanxi[J]. Coal Geology China,2014,26(12):17−19. doi: 10.3969/j.issn.1674-1803.2014.12.04 [12] 刘汉斌, 马志斌, 郭彦霞, 程芳琴. 太原西山煤田煤系锂镓赋存特征及工业前景[J]. 洁净煤技术,2018,24(5):26−32.LIU Han-bin, MA Zhi-bin, GUO Yan-xia, CHENG Fang-qin. Occurrence characteristics and industrial prospects of lithium and gallium in coal in Taiyuan Xishan coalfield[J]. Clean Coal Technol,2018,24(5):26−32. [13] 廖家隆, 张福强, 韦梦蝶, 梁兴东. 广西晚二叠世典型聚煤盆地中锂, 镓丰度及富集因素[J]. 煤田地质与勘探,2020,48(1):77−84. doi: 10.3969/j.issn.1001-1986.2020.01.011LIAO Jia-long, ZHANG Fu-qiang, WEI Meng-die, LIANG Xing-dong. Lithium and gallium abundance and enrichment factors in typical Late Permian coal-accumulating basin in Guangxi[J]. Coal Geol Explor,2020,48(1):77−84. doi: 10.3969/j.issn.1001-1986.2020.01.011 [14] YANG N, TANG S H, ZHANG S H, CHEN Y Y. Modes of occurrence and abundance of trace elements in Pennsylvanian coals from the Pingshuo Mine, Ningwu Coalfield, Shanxi Province, China[J]. Minerals,2016,6(2):40. doi: 10.3390/min6020040 [15] DAI S F, LIU J J, WARD C R, HOWER J C, FRENCH D, JIA S H, HOOD M M, GARRISON T M. Mineralogical and geochemical compositions of Late Permian coals and host rocks from the Guxu Coalfield, Sichuan Province, China, with emphasis on enrichment of rare metals[J]. Int J Coal Geol,2016,166:71−95. doi: 10.1016/j.coal.2015.12.004 [16] 王文峰, 秦勇, 刘新花, 赵建岭, 王钧漪, 吴国代, 刘炯天. 内蒙古准格尔煤田煤中镓的分布赋存与富集成因[J], 中国科学: 地球科学, 2011, 41(2): 181–196.WANG Wen-feng, QIN Yong, LIU Xin-hua, ZHAO Jian-ling, WANG Jun-yi, Wu Guo-dai, LIU Jiong-tian. Distribution, occurrence and enrichment causes of gallium in coals from the Jungar Coalfield, Inner Mongolia[J]. Sci China Earth Sci, 2011, 41(2): 181–196. [17] 衣姝, 王金喜. 安家岭矿9号煤中锂的赋存状态和富集因素分析[J]. 煤炭与化工,2014,37(9):7−10.YI Shu, WANG Jin-xi. Lithium occurrences and enrichment factor law in No. 9 coal seam of Anjialing mine[J]. Coal Chem Ind,2014,37(9):7−10. [18] 朱华雄, 陈寒勇, 章伟, 宁树正, 韩亮. 华北煤中金属矿产的种类和分布特征[J]. 煤炭学报,2016,41(2):303−309.ZHU Hua-xiong, CHEN Han-yong, ZHANG Wei, NING Shu-zheng, HAN Liang. Metal mineral types and distribution characteristics in coal in Northern China[J]. J China Coal Soc,2016,41(2):303−309. [19] WANG W F, QIN Y, SANG S X, JIANG B, ZHU Y M, GUO Y H. Sulfur variability and element geochemistry of the No. 11 coal seam from the Antaibao mining district, China[J]. Fuel,2007,86(5/6):777−784. doi: 10.1016/j.fuel.2006.09.017 [20] LIU D M, YANG Q, TANG D Z, KANG X, HUANG W H. Geochemistry of sulfur and elements in coals from the Antaibao surface mine, Pingshuo, Shanxi Province, China[J]. Int J Coal Geol,2001,46(1):51−64. doi: 10.1016/S0166-5162(00)00040-9 [21] 秦勇, 王文峰, 宋党育, 张晓东. 山西平朔矿区上石炭统太原组11号煤层沉积地球化学特征及成煤微环境[J]. 古地理学报,2005,7(2):249−260.QIN Yong, WANG Wen-feng, SONG Dang-yu, ZHANG Xiao-dong. Geochemistry characteristics and sedimentary micro-environments of No. 11 coal seam of the Taiyuan formation of upper carboniferous in Pingshuo mining district, Shanxi Province[J]. Palaeography,2005,7(2):249−260. [22] 宋党育, 王文峰, 秦勇. 安太堡11#煤元素地球化学特征及环境效应[J]. 煤炭转化,2003,26(1):41−44. doi: 10.3969/j.issn.1004-4248.2003.01.009SONG Dang-yu, WANG Wen-feng, QIN Yong. Element geochemistry and its environment effect from coalbed No. 11 in Antaibao mine[J]. Coal Convers,2003,26(1):41−44. doi: 10.3969/j.issn.1004-4248.2003.01.009 [23] DAI S F, WANG X B, ZHOU Y P, HOWER J C, LI D H, CHEN W M, ZHU X W, ZOU J H. Chemical and mineralogical compositions of silicic, mafic, and alkali tonsteins in the late Permian coals from the Songzao Coalfield, Chongqing, Southwest China[J]. Chem Geol,2011,282(1-2):29−44. doi: 10.1016/j.chemgeo.2011.01.006 [24] QI L, HU J, GREGOIRE D C. Determination of trace elements in granites by inductively coupled plasma mass spectrometry[J]. Talanta,2000,51(3):507−513. doi: 10.1016/S0039-9140(99)00318-5 [25] 程伟, 杨瑞东, 张覃, 崔玉朝, 高军波. 毕节地区晚二叠世煤中微量元素的分布赋存规律及控因分析[J]. 煤炭学报,2013,38(1):103−113.CHENG Wei, YANG Rui-dong, ZHANG Qin, CUI Yu-chao, GAO Jun-bo. Distribution characteristics, occurrence modes and controlling factors of trace elements in Late Permian coal from Bijie City, Guizhou Province[J]. J China Coal Soc,2013,38(1):103−113. [26] VAN DER FLIER E, Fyfe W S. Uranium-thorium systematics of two Canadian coals[J]. Int J Coal Geol,1985,4(4):335−353. doi: 10.1016/0166-5162(85)90019-9 [27] SHAO L Y, JONES T, GAYER R, DAI S F, Li S S, JIANG Y F, ZHANG P F. Petrology and geochemistry of the high-sulphur coals from the Upper Permian carbonate coal measures in the Heshan Coalfield, southern China[J]. Int J Coal Geol,2003,55(1):1−26. doi: 10.1016/S0166-5162(03)00031-4 [28] 林治家, 陈多福, 刘芊. 海相沉积氧化还原环境的地球化学识别指标[J]. 矿物岩石地球化学通报,2008,27(1):72−80. doi: 10.3969/j.issn.1007-2802.2008.01.012LIN Zhi-jia, CHEN Duo-fu, LIU Qian. Geochemical indices for redox conditions of marine sediments[J]. Bull Mineral, Petrol Geochem,2008,27(1):72−80. doi: 10.3969/j.issn.1007-2802.2008.01.012 [29] STARKEY H C. The Role of Clays in Fixing Lithium[M]. Washington: US Government Printing Office, 1982: 3. [30] GOLDSCHMIDT V M. The principles of distribution of chemical elements in minerals and rocks[J]. Chem Soc,1937,655−673. [31] HEIER K S, ADAMS J A. The geochemistry of the alkali metals[J]. Phys Chem Earth,1964,5(64):253−381. [32] DAI S F, REN D Y, LI S S. Discovery of the super large gallium ore deposit in Jungar, Inner Mongolia, North China[J]. Sci Bull,2006,51(18):2243−2252. doi: 10.1007/s11434-006-2113-1 [33] DAI S F, ZOU J H, JIANG Y F, WARD C R, WANG X B, LI T, XUE W F, LIU S D, TIAN H M, SUN X H, ZHOU D. Mineralogical and geochemical compositions of the Pennsylvanian coal in the Adaohai Mine, Daqingshan Coalfield, Inner Mongolia, China: Modes of occurrence and origin of diaspore, gorceixite, and ammonian illite[J]. Int J Coal Geol,2012,94:250−270. doi: 10.1016/j.coal.2011.06.010 [34] 陈家怀, 陈善庆, 赵时久. 滇东田坝黔西土城晚二叠世煤系上段沉积相和煤中硫成因探讨[J]. 中国地质科学院宜昌地质矿产研究所所刊,1990,15:31−67.CHEN Jia-huai, CHEN Shan-qing, ZHAO Shi-jiu. On the sedimentary facies and origin of sulfur in coal of the upper member of the late permian coal measures in Tianba (Eastern Yunnan) and Tuchen (Western Guizhou)[J]. Bull Yichang Inst Geol Min Res,1990,15:31−67. [35] 刘帮军, 林明月, 褚光琛. 山西平朔矿区4#煤中镓的分布规律与富集机理[J]. 中国煤炭,2014,40(11):25−29. doi: 10.3969/j.issn.1006-530X.2014.11.007LIU Bang-jun, LIN Ming-yue, CHU Guang-chen. Distribution law and enrichment mechanism of Ga in 4# coal seam in Pingshuo mining area in Shanxi province[J]. China Coal,2014,40(11):25−29. doi: 10.3969/j.issn.1006-530X.2014.11.007 [36] BARDI U. Extracting minerals from seawater: An energy analysis[J]. Sustainability,2010,2(4):980−992. doi: 10.3390/su2040980 [37] KARAYIĞIT A I, OSKAY R G, CHRISTANIS K, TUNOĞLU C, TUNCER A, BULUT Y. Palaeoenvironmental reconstruction of the Çardak coal seam, SW Turkey[J]. Int J Coal Geol,2015,139:3−16. doi: 10.1016/j.coal.2014.04.009 [38] 王华. 陕北侏罗纪煤中微量元素赋存形态及迁移规律研究[D]. 西安: 西安科技大学, 2017.WANG Hua. Study on the mode of occurrence and migration of trace elements in Shanbei Jurassic coals[D]. Xi’an: Xi’an University of Science and Technology, 2017. [39] SWAINE D J. Trace Elements in Coal[M]. Oxford: Butterworth-Heinemann Ltd, 1990: 44. [40] ZHENG Q M, SHI S L, LIU Q F, XU Z J. Modes of occurrences of major and trace elements in coals from Yangquan Mining District, North China[J]. J Geochem Explor,2017,175:36−47. doi: 10.1016/j.gexplo.2016.12.008 [41] MASTALERZ M, DROBNIAK A. Gallium and germanium in selected Indiana coals[J]. Int J Coal Geol,2012,94:302−313. doi: 10.1016/j.coal.2011.09.007 [42] SHAW D M. The geochemistry of gallium, indium, thallium-a review[J]. Phys Chem Earth,1957,2:164−211. doi: 10.1016/0079-1946(57)90009-5 [43] SUN Y Z, LI Y H, ZHAO C L, LIN M Y, WANG J X, QIN S J. Concentrations of lithium in Chinese coals[J]. Energy Explor Exploit,2010,28(2):97−104. doi: 10.1260/0144-5987.28.2.97 [44] 黄文辉, 杨起, 汤达祯. 枣庄煤田太原组煤中微量元素地球化学特征[J]. 现代地质,2000,14(1):61−68.HUANG Wen-hui, YANG Qi, TANG Da-zhen. Trace elements geochemistry of the coals in the Taiyuan formation from Zaozhuang coal field[J]. Geoscience,2000,14(1):61−68. [45] WINCHESTER J A, FLOYD P A. Geochemical discrimination of different magma series and their differentiation products using immobile elements[J]. Chem Geol,1977,20:325−343. doi: 10.1016/0009-2541(77)90057-2 [46] TYRRELL S, HAUGHTON P D W, DALY J S, SHANNON P M. The Pb isotopic composition of detrital K-feldspar: A tool for constraining provenance, sedimentary processes and paleodrainage[Z]. Quantitative mineralogy and microanalysis of sediments and sedimentary rocks mineralogical association of Canada, Short Course Series, 2012, 42: 203–217. [47] 魏迎春, 华芳辉, 何文博, 宁树正, 张宁, 秦云虎, 曹代勇. 峰峰矿区2号煤中微量元素富集特征差异性研究[J]. 煤炭学报,2020,45(4):1473−1487.WEI Ying-chun, HUA Fang-hui, HE Wen-bo, NING Shu-zheng, ZHANG Ning, QIN Yun-hu, CAO Dai-yong. Difference of trace elements characteristics of No. 2 coal in Fengfeng mining area[J]. J China Coal Soc,2020,45(4):1473−1487. [48] SUN Y Z, ZHAO C L, LI Y H, WANG J X, LIN M Y. Li distribution and mode of occurrences in Li-bearing coal seam #6 from the Guanbanwusu Mine, Inner Mongolia, Northern China[J]. Energy Explor Exploit,2012,30(1):109−130. doi: 10.1260/0144-5987.30.1.109 [49] 李聪聪, 宁树正, 乔军伟, 魏云迅. 重庆南武矿区煤中镓赋存规律及控制因素[J]. 煤田地质与勘探,2018,46(3):15−20. doi: 10.3969/j.issn.1001-1986.2018.03.004LI Cong-cong, NING Shu-zheng, QIAO Jun-wei, WEI Yun-xun. Occurrence regularity and controlling factors of gallium in coal of Nanwu mining area, Chongqing[J]. Coal Geol Explor,2018,46(3):15−20. doi: 10.3969/j.issn.1001-1986.2018.03.004 [50] 刘桂建, 彭子成, 杨萍玥, 王桂梁, 张威. 煤中微量元素富集的主要因素分析[J]. 煤田地质与勘探,2001,29(4):1−4. doi: 10.3969/j.issn.1001-1986.2001.04.001LIU Gui-jian, PENG Zi-cheng, YANG Ping-yue, WANG Gui-liang, ZHANG Wei. Main Factors controlling concentration of trace element in coal[J]. Coal Geol Explor,2001,29(4):1−4. doi: 10.3969/j.issn.1001-1986.2001.04.001