郝国强,胡社荣
HAO Guoqiang,HU Sherong

• 1:河北工程大学矿业与测绘工程学院
• 2:河北省高校煤炭资源开发与建设研发中心
• 3:中国矿业大学(北京)地球科学与测绘工程学院

摘要(Abstract)：

氮是煤中的常见元素之一,煤中氮的赋存形态多样且随煤阶发生变化。以邯郸–峰峰矿区为例,利用X射线光电子能谱(XPS)实验,研究不同变质程度煤(R_(ran)=1.08%～3.67%)中有机氮的赋存形态,探讨煤中各形态有机氮相对含量随煤阶的变化规律。结果表明:按N 1s XPS谱图分峰峰值的结合能可将煤中氮的形态归为N-6、N-5、N-Q和N-X四种;研究区煤中N-5的相对含量最高,且随着煤阶的增高而降低;N-Q的相对含量随着煤阶的增高而增高;煤中N-6的相对含量随煤阶呈"增–减–稳"的变化规律;N-X的相对含量为9.1%～35.1%,其与煤阶关系不明显;在煤阶R_(ran)=1.08%～1.47%的范围内,煤的N 1s XPS谱图中缺失N-Q分峰,表明褐煤中相对含量最高的质子化吡啶氮在此阶段已几乎全部去质子化而转化为吡啶氮。不同变质阶段氮的赋存形态变化特征对燃煤发电及煤化工领域煤化学参数选取提供参考。
Nitrogen is one of the common elements in coal. The occurrence forms of nitrogen in coal are various and vary with coal rank. Based on X-ray photoelectron spectroscopy(XPS), taking Handan-Fengfeng mining area as an example, organic nitrogen forms of different rank coals(R_(ran) = 1.08%–3.67%) were studied, and the variation of the relative abundance of each organic nitrogen with rank was further discussed. The results show that four kinds of nitrogen forms are considered for the coals according to binding energies of N 1 s XPS sub-peaks, corresponding to N-6, N-5, N-Q and N-X. N-5 is the most abundant organic nitrogen and its relative abundance decreases as coal rank increases, while N-Q shows opposite trend. The variation of the relative abundance of N-6 with rank shows "increasing-decreasing-stable" trend, and N-X accounts for 9.1%–35.1% of the total organic nitrogen, whose changing with coal rank is not obvious. Protonated pyridinic nitrogen, a type of N-Q, which dominates in lignite, almost disappears at a coal rank range from R_(ran) 1.08% to R_(ran) 1.47% due to the loss of oxygen groups and deprotonation, resulting in the absence of N-Q sub-peaks in the XPS spectra.

关键词(KeyWords)： 有机氮;赋存形态;煤阶;X射线光电子能谱;邯郸–峰峰矿区
organic nitrogen;nitrogen forms;coal rank;X-ray photoelectron spectroscopy;Handan-Fengfeng mining area

Abstract:

Keywords:

基金项目(Foundation): 国家自然科学基金项目(41072119)~~

作者(Author): 郝国强,胡社荣
HAO Guoqiang,HU Sherong

参考文献(References)：

• [1]刘钦甫，徐占杰，崔晓南，等.不同煤化程度煤的热解及氮的释放行为[J].煤炭学报，2015,40(2):450-455.LIU Qinfu,XU Zhanjie,CUI Xiaonan,et al.Release behavior of nitrogen in different rank coals during pyrolysis[J].Journal of China Coal Society,2015,40(2):450-455.
• [2]BURCHILL P,WELCH L S.Variation of nitrogen content and functionality with rank for some UK bituminous coals[J].Fuel,1989,68(1):100-104.
• [3]刘艳华，车得福，李荫堂，等.X射线光电子能谱确定铜川煤及其焦中氮的形态[J]．西安交通大学学报，2001,35(7):661-665.LIU Yanhua,CHE Defu,LI Yintang,et al.X-Ray photoelectron spectroscopy determination of the forms of nitrogen in Tongchuan coal and its chars[J].Journal of Xi’an Jiaotong University,2001,35(7):661-665.
• [4]PELS J R,KAPTEIJN F,MOULIJN J A,et al.Evolution of nitrogen functionalities in carbonaceous materials during pyrolysis[J].Carbon N Y,1995,33(11):1641-1653.
• [5]KELEMEN S R,GORBATY M L,KWIATEK P J.Quantification of nitrogen forms in Argonne Premium coals[J].Energy&Fuels,1994,8(4):896-906.
• [6]KELEMEN S R,FREUND H,GORBATY M L,et al.Thermal chemistry of nitrogen in kerogen and low-rank coal[J].Energy&Fuels,1999,13(2):529-538.
• [7]KELEMEN S R,AFEWORKI M,GORBATY M L,et al.Thermal transformations of nitrogen and sulfur forms in peat related to coalification[J].Energy&Fuels,2006,20(2):635-652.
• [8]BOUDOU J P,SCHIMMELMANN A,ADER M,et al.Organic nitrogen chemistry during low-grade metamorphism[J].Geochimica et Cosmochimica Acta,2008,72:1199-1221.
• [9]VALENTIM B,GUEDES A,BOAVIDA D.Nitrogeon functionality in“oil window”rank range vitrinite rich coals and chars[J].Organic Geochemistry,2011,42(5):502-509.
• [10]FRIEBEL J,K?PSEL R F W.The fate of nitrogen during pyrolysis of German low rank coals:A parameter study[J].Fuel,1999,78(8):923-932.
• [11]曹代勇，占文峰，张军，等．邯郸-峰峰矿区新构造特征及其煤炭资源开发意义[J].煤炭学报，2007,32(2):141-145.CAO Daiyong,ZHAN Wenfeng,ZHANG Jun,et al.Neotectonic character of Handan-Fengfeng mining area and its significance for coal resource exploitation[J].Journal of China Coal Society,2007,32(2):141-145.
• [12]ZHU Q,MONEY S L,RUSSELL A E,et al.Determination of the fate of nitrogen functionality in carbonaceous materials during pyrolysis and combustion using X-ray absorption near edge structure spectroscopy[J].Langmuir,1997,13(7):2149-2157.
• [13]HANSSON K M，?MAND L E,HABERMANN A,et al.Pyrolysis of poly-L-leucine under combustion-like conditions[J].Fuel,2003,82(6):653-660.
• [14]BUCKLEY A N,KELLY M D,NELSON P F,et al.Inorganic nitrogen in Australian semi-anthracites:Implications for determining organic nitrogen functionality in bituminous coals by X-ray photoelectron spectroscopy[J].Fuel Process.Technology,1995,43(1):47-60.
• [15]GONG B,PIGRAM P J,LAMB R N.Identification of inorganic nitrogen in an Australian bituminous coal using X-ray photoelectron spectroscopy(XPS)and time-of-flight secondary ion mass spectrometry(TOFSIMS)[J].International Journal of Coal Geology,1997,34(1):53-68.
• [16]刘钦甫，张鹏飞，丁树理，等.华北石炭二叠纪含煤地层中的铵伊利石[J].科学通报，1996,41(8):717-719.LIU Qinfu,ZHANG Pengfei,DING Shuli,et al.Ammonium illite in the coal-bearing strata of Carboniferous-Permian in Northern China[J].Chinese Science Bulletin,1996,41(8):717-719.
• [17]梁绍暹，王水利，任大伟，等.华北石炭二叠纪煤层含铵云母黏土岩夹矸研究[J].煤田地质与勘探，1996,24(3):11-18.LIANG Shaoxian,WANG Shuili,REN Dawei,et al.Study on tobelite-bearing tonsteins of Carboniferous-Permian coal measures in North China[J].Coal Geology&Exploration,1996,24(3):11-18．
• [18]郑启明，刘钦甫，伍泽广，等.山西晋城地区含煤地层中的铵伊利石/蒙脱石间层矿物[J].煤炭学报，2012,37(2):231-236.ZHENG Qiming,LIU Qinfu,WU Zeguang,et al.Ammonium-illite smectite interlayer clay minerals in coal-bearing strata in Jincheng district of Shanxi Province[J].Journal of China Coal Society,2012,37(2):231-236.
• [19]ZHENG Q,LIU Q,SHI S.Mineralogy and geochemistry of ammonian illite in intra-seam partings in Permo-Carboniferous coal of the Qinshui coalfield,North China[J].International Journal of Coal Geology,2016,153:1-11.
• [20]MITRA-KIRTLEY S,MULLINS O C,BRANTHAVER J F,et al.Nitrogen chemistry of kerogens and bitumens from X-ray absorption near-edge structure spectroscopy[J].Energy and Fuels,1993,7(6):1128-1134.
• [21]GENG W,KUMABE Y,NAKAJIMA T,et al.Analysis of hydrothermally treated and weathered coals by X-ray photoelectron spectroscopy(XPS)[J].Fuel,2009,88:644-649.

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