The Occurrence of Rare Earth and Radioactive Elements in the Associated Minerals with Raw Coal by EDX-SEM and XRD
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摘要: 研究原煤中稀土及放射性元素的赋存形式，对原煤是集中还是分散利用、燃煤过程中粉煤灰的排放截留、从原煤或粉煤灰中提取稀土及放射性元素等方面都具有指导意义。由前人研究可知不同矿区原煤中稀土及放射性元素的赋存形式有差异。本文研究了山西省霍西煤田两个矿区175个煤样中稀土及放射性元素的赋存形式，应用背散射电子图像（BSEI）定位分析区域，应用BSEI、能谱-扫描电镜法（EDX-SEM）中的面分析（EDS-mapping）和粉晶X射线衍射法确定了主要伴生矿物，应用BSEI和EDX-SEM中的点分析（EDS-point）确定了微量伴生矿物。在煤样中发现了铈镧钕钇镝钪六种稀土元素及一种放射性元素钍，其中铈、镧和钕主要以磷酸盐形式伴生于高岭石类矿物中，部分伴生在含氧化铝或氧化硅较多的矿物中，少量存在于碳中；钇、镝以磷酸盐或氧化物形式独立存在于碳中；在部分锆石、独居石中分别发现了钪和钍。研究表明，该矿区煤样中稀土元素主要以细粒自生矿物的形式伴生在其他矿物中，少数以独立矿物的形式存在于碳中，放射性元素钍伴生在独居石中。Abstract:
BACKGROUNDThe study on the occurrences of rare earth and radioactive elements in raw coal is of great significance in terms of whether the raw coal is concentrated or dispersed, the emission of fly ash is intercepted, and the rare earth elements (REEs) and radioactive elements are extracted from raw coal or fly ash. Previous studies showed that the occurrences of rare earth and radioactive elements in raw coal of various mining areas are different. OBJECTIVESTo study the occurrences of rare earth and radioactive elements in 175 coal samples from two mining areas in the Huoxi coalfield of Shanxi Province. METHODSThe analysis region was located by back scattered electron imaging (BSEI), and the main associated minerals were determined by EDS-mapping and powder X-ray diffraction. The trace associated minerals were determined by BSEI and EDS-point methods. RESULTSSix rare earth elements and a radioactive element were determined in the coal samples. Cerium, lanthanum and neodymium were associated with kaolinite minerals in the form of phosphate, partly occuring in minerals containing alumina or silicon oxide, and in carbon to a small degree. Yttrium and dysprosium existed independently in carbon in the form of phosphate or oxide, whereas scandium was found in zircon, and thorium is found in monazite. CONCLUSIONSThe REE in the coal samples of the mining area were associated with other minerals in the form of fine-grained authigenic minerals, and a few occurred as independent minerals in carbon. The radioactive element thorium was associated with monazite. -
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表 1 代表性分析点所属煤样中的元素成分及伴生矿物
Table 1. Elemental composition and associated minerals in representative analysis points of coal samples
原煤样品
图像编号SEM-EDS检出的元素 XRD检出的伴生矿物 图 5-a Al, Si, O; Ca, O; Ca, S, O; P, Ce, O; Fe, O; Ti, O; Si, O; Se, Pb 硅酸铝, 高岭石类矿物, 二氧化硅, 氧化钙, 氧化钛, 三氧化二铁, 磷酸铈, 硒化铅 图 5-b Al, Si, O; Ca, S, O; Ca, C, O; Fe, O; Mg, O; Ca, S, Fe, Mg, O; P, Ce, O 高岭石类矿物, 硫酸钙, 方解石, 磷酸铈, 氧化铁, 氧化镁 图 5-c Ca, C, O; Fe, S; Al, Si, O; O, P, Ce, La, Nd; Ti, O 高岭石类矿物, 碳酸钙, 氧化钛, 硫化铁 图 5-d Al, Si, O; Mg, S, K, Fe; Ti, O; Zr, O; Fe, Mg, Ca, C, O; O, P, Ce, La, W; Fe, Cu, S 氧化铝, 勃姆石, 高岭石类矿物, 低辉铜矿, 硫化钾 图 6-b Ca, C, O; Fe, S; Al, Si, O; Ti, O; Fe, S; O, P, Ce; O, P, Ce, La, Na, W 高岭石类矿物, 方解石, 硫化铁, 磷酸铈, 氧化钛 图 6-a、c Al, Si, O; O, P, Ce, Nd, La, Ca; Ti, O; Fe, S; Ca, C, O; O, P, W; Fe, Cu, S; Ag, Ce, Nd, La, P, O; Ag, Ce, Nd, La, Th, W, P, O 高岭石类矿物, 硫化铁, 氧化钛, 低辉铜矿, 磷酸镧 图 6-d Al, Si, O; Ti, O; Ca, O; Mo, O; O, P, Ce, W; O, P, Y, Dy 高岭石类矿物, 二氧化钛, 氧化钼 图 7-a Al, Si, O; Ti, O; Zr, O, Si; Y, Ir, Ta, Dy, O; O, S, Cu, Zn; O, P, Ce, La, Nd 高岭石类矿物, 硅铝石, 氧化钛, 硫酸锌, 二氧化硅, 锆石, 氧化钕 图 7-b Al, Si, O; Zr, O; Ti, O, K, Fe; Ti, O; Fe, Cu, S; Al, Zr, Sc, Ir, O; O, P, Ce, Nd 高岭石类矿物, 氧化钛, 氧化铁, 硫化亚铜 图 7-c Al, Si, O, K; Ti, O; Zn, S; O, P, Ce, Nd, La; Fe, S; Cu, Fe, S; Zr, Ag, Sc, O; Zr, Ag, Sc, Ir, O 高岭石类矿物, 氧化钛, 硫化铁, 磷酸镧 
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表 2 代表性分析点所属煤样中稀土及放射性元素的赋存形式
Table 2. Occurrence modes of rare earth elements and radioactive elements in representative analysis points of coal samples
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[1] Zielinski R A, Budahn J R.Radionuclides in fly ash and bottom ash:Improved characterization based on radiography and low energy gamma-ray spectrometry[J].Fuel, 1998, 77(4):259-267. doi: 10.1016/S0016-2361(97)00194-4
[2] Kizilshtein L Y, Kholodkov Y I.Ecologically hazardous elements in coals of the Donets Basin[J].International Journal of Coal Geology, 1999, 40:189-197. doi: 10.1016/S0166-5162(98)00068-8
[3] Goodarzi F.Assessment of elemental content of milled coal, combustion residues, and stack emitted materials:Possible environmental effects for a Canadian pulverized coal-fired power plant[J].International Journal of Coal Geology, 2006, 65:17-25. doi: 10.1016/j.coal.2005.04.006
[4] Flues M, Camargo I M C, Fiqueiredo F P M, et al.Evaluation of radionuclides concentration in Brazilian coals[J].Fuel, 2007, 86:807-812. doi: 10.1016/j.fuel.2006.09.013
[5] Smolka-Danielowska D.Rare earth elements in fly ashes created during the coal burning process in certain coal-fired power plants operating in Poland-Upper Silesian industrial region[J].Journal of Environmental Radioactivity, 2010, 101:965-968. doi: 10.1016/j.jenvrad.2010.07.001
[6] Seredin V V.Rare earth element-bearing coals from the Russian Far East deposit[J].International Journal of Coal Geology, 1996, 30:101-129. doi: 10.1016/0166-5162(95)00039-9
[7] Seredin V V, Dai S.Coal deposits as potential alternative source of lanthanides and yttrium[J].International Journal of Coal Geology, 2012, 94:67-93. doi: 10.1016/j.coal.2011.11.001
[8] Dai S F, Jiang Y F, Ward C R, et al.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].International Journal of Coal Geology, 2012, 98:10-40. doi: 10.1016/j.coal.2012.03.003
[9] Seredin V V, Dai S F, Sun Y Z, et al.Coal deposits as promising sources of rare metals for alternative power and energy-efficient technologies[J].Applied Geochemistry, 2013, 31:1-11. doi: 10.1016/j.apgeochem.2013.01.009
[10] Funaria V, Bokhari S N H, Vigliotti L, et al.The rare earth elements in municipal solid waste incinerators ash and promising tools for their prospecting[J].Journal of Hazardous Materials, 2016, 301:471-479. doi: 10.1016/j.jhazmat.2015.09.015
[11] Zhang W C, Rezaee M, Bhagavatula A, et al.A review of the occurrence and promising recovery methods of rare earth elements from coal and coal by-products[J].International Journal of Coal Preparation and Utilization, 2015, 35:295-330. doi: 10.1080/19392699.2015.1033097
[12] Rozelle P L, Khadilkar A B, Pulati N, et al.A study on removal of rare earth elements from U.S. coal byproducts by ion exchange[J].Metallurgical and Materials Transactions E, 2016, 3:6-17. doi: 10.1007/s40553-015-0064-7
[13] Lin R H, Howard B H, Roth E A, et al.Enrichment of rare earth elements from coal and coal by-products by physical separations[J].Fuel, 2017, 200:506-520. doi: 10.1016/j.fuel.2017.03.096
[14] 赵志根, 唐修义, 李宝芳.淮南矿区煤的稀土元素地球化学[J].沉积学报, 2000, 18(3):453-459. doi: 10.3969/j.issn.1000-0550.2000.03.022
Zhao Z G, Tang X Y, Li B F.Geochemistry of rare-earth elements of coal in Huainan mining area[J].Acta Sedimentologica Sinica, 2000, 18(3):453-459. doi: 10.3969/j.issn.1000-0550.2000.03.022
[15] 李大华, 胡礼忠, 陈坤, 等.中国西南煤中的稀土元素[J].中国煤田地质, 2002, 14(1):11-13. doi: 10.3969/j.issn.1674-1803.2002.01.004
Li D H, Hu L Z, Chen K, et al.Rare-earth elements in coal of South-Western China[J].Coal Geology of China, 2002, 14(1):11-13. doi: 10.3969/j.issn.1674-1803.2002.01.004
[16] 代世峰, 任德贻, 李生盛.华北若干晚古生代煤中稀土元素的赋存特征[J].地球学报, 2003, 24(3):273-278. doi: 10.3321/j.issn:1006-3021.2003.03.013
Dai S H, Ren D Y, Li S S.Modes of occurrence of rare earth elements in some Late Paleozoic coals of North China[J].Acta Geoscientia Sinica, 2003, 24(3):273-278. doi: 10.3321/j.issn:1006-3021.2003.03.013
[17] Lashari A A, Kazi T G, Ali J, et al.Evaluation of sequential extraction schemes for the ETAAS determination of cadmium concentrations in coal samples from the Thar Coalfield, Pakistan[J].Atomic Spectroscopy, 2018, 39(5):203-209.
[18] 姜尧发, 王西勃, 赵蕾.大屯矿区太原组煤中稀土元素的赋存特征[J].煤炭科学技术, 2006, 34(1):73-75. doi: 10.3969/j.issn.0253-2336.2006.01.022
Jiang Y F, Wang X B, Zhao L.Distribution characteristics of rare-earth element in coal of Taiyuan group in datum mining area[J].Coal Science and Technology, 2006, 34(1):73-75. doi: 10.3969/j.issn.0253-2336.2006.01.022
[19] Dai S F, Zhao L, Peng S P, et al.Abundances and dis-tribution of minerals and elements in high-alumina coal fly ash from the Jungar Power Plant, Inner Mongolia, China[J].International Journal of Coal Geology, 2010, 81:320-332. doi: 10.1016/j.coal.2009.03.005
[20] Moore F, Esmaeili A.Mineralogy and geochemistry of the coals from the Karmozd and Kiasar coal mines, Mazandaran Province, Iran[J].International Journal of Coal Geology, 2012, 96-97(4):9-21. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=c4ee6eb1106b752f5ead6963f950be71
[21] 赵明坤, 王海泉, 许军, 等.河南省二1煤层稀土元素赋存特征研究[J].煤炭科学技术, 2019, 47(2):176-180. http://d.old.wanfangdata.com.cn/Periodical/mtkxjs201902029
Zhao M K, Wang H Q, Xu J, et al.Study on occurrence features of rare earth elements from Seam B1 in Henan Province[J].Coal Science and Technology, 2019, 47(2):176-180. http://d.old.wanfangdata.com.cn/Periodical/mtkxjs201902029
[22] Vassilev S V, Vassileva C G.Occurrence, abundance and origin of mineral in coals and coal ashes[J].Fuel Processing Technology, 1996, 48:85-106. doi: 10.1016/S0378-3820(96)01021-1
[23] Dai S F, Zhao L, Hower J C, et al.Petrology, mineralogy, and chemistry of size-fractioned fly ash from the Jungar power plant, Inner Mongolia, China, with emphasis on the distribution of rare earth elements[J].Energy Fuel, 2014, 28:1502-1514. doi: 10.1021/ef402184t
[24] 焦汇胜, 李香庭.扫描电镜能谱仪及波谱仪分析技术[M].长春:东北师范大学出版社, 2011:76-80.
Jiao H S, Li X T.Analysis Technology in Scanning Electron Microscope-Energy Dispersive Spectrometer and Spectrometer[M].Changchun:Northeast Normal University Press, 2011:76-80.
[25] 赵文宽.仪器分析实验[M].北京:高等教育出版社, 2011:55-61.
Zhao W K.Instrumental Analysis[M].Beijing:Higher Education Press, 2011:55-61.
[26] 胡勇平, 于学峰, 郑林伟, 等.高分辨扫描电镜和X射线能谱Mapping技术研究碲矿物的成分和形态特征[J].岩矿测试, 2015, 34(6):643-651. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.2015.06.007
Hu Y P, Yu X F, Zheng L W, et al.Application of high-resolution scanning electron microscope and X-ray energy dispersive spectroscope mapping technique to study the composition and morphology of tellurium minerals[J].Rock and Mineral Analysis, 2015, 34(6):643-651. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.2015.06.007
[27] 王含, 周征宇, 钟倩, 等.电子微探针-X射线衍射-扫描电镜研究老挝石岩石矿物学特征[J].岩矿测试, 2016, 35(1):56-61. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.2016.01.010
Wang H, Zhou Z Y, Zhong Q, et al.Study on petrological and mineralogical characteristics of Laos Stone by EMPA-XRD-SEM[J].Rock and Mineral Analysis, 2016, 35(1):56-61. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.2016.01.010
[28] 刘亚非, 王立社, 魏小燕, 等.应用电子微探针-扫描电镜-拉曼光谱-电子背散射衍射研究一种未知Ti-Zr-U氧化物的矿物学特征[J].岩矿测试, 2016, 35(1):48-55. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.2016.01.009
Liu Y F, Wang L S, Wei X Y, et al.Study on the mineralogical properties of an unknown Ti-Zr-U oxide using EMPA, SEM, Raman spectroscopy and EBSD techniques[J].Rock and Mineral Analysis, 2016, 35(1):48-55. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.2016.01.009
[29] 李春辉, 宋党育, 宋播艺, 等.豫西裴沟矿二叠系构造煤中稀土元素分布与赋存特征[J].地球化学, 2017, 46(7):435-457. http://d.old.wanfangdata.com.cn/Periodical/dqhx201704005
Li C H, Song D Y, Song B Y, et al.Distribution and occurrence of REE in the Permian tectonically deformed coals from the Peigou Mine, Western Henan Province[J].Geochimica, 2017, 46(7):435-457. http://d.old.wanfangdata.com.cn/Periodical/dqhx201704005
[30] 林龙斌.河东煤田北部主采煤中稀土元素地球化学特征[J].中国煤炭地质, 2018, 30(11):18-23. doi: 10.3969/j.issn.1674-1803.2018.11.05
Lin L B.REE Geochemical features of main mineable coal seams in Northern Hedong Coalfield[J].Coal Geology of China, 2018, 30(11):18-23. doi: 10.3969/j.issn.1674-1803.2018.11.05
[31] 殷晓.扫描电镜能谱法测定独居石中铈、镧、钍等元素的含量[J].地质与资源, 2015, 24(5):501-506. doi: 10.3969/j.issn.1671-1947.2015.05.017
Yin X.Content determination of cerium, lanthanum, thorium and other elements in monazite with SEM-EDS analysis[J].Geology and Resources, 2015, 24(5):501-506. doi: 10.3969/j.issn.1671-1947.2015.05.017
[32] 沈明联, 杨瑞东.煤中稀土元素研究综述[J].中国煤炭地质, 2016, 28(9):18-20. doi: 10.3969/j.issn.1674-1803.2016.09.04
Shen M L, Yang R D.Summarization of REE in coal[J].Coal Geology of China, 2016, 28(9):18-20. doi: 10.3969/j.issn.1674-1803.2016.09.04
[33] 黄文辉, 久博, 李媛.煤中稀土元素分布特征及其开发利用前景[J].煤炭学报, 2019, 44(1):287-294. http://d.old.wanfangdata.com.cn/Periodical/mtxb201901029
Huang W H, Jiu B, Li Y.Distribution characteristics of rare earth elements in coal and its prospects on development and exploitation[J].Journal of China Coal Society, 2019, 44(1):287-294. http://d.old.wanfangdata.com.cn/Periodical/mtxb201901029
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