Structure evolution of oxygen functional groups in Dongsheng long flame coal by <sup>13</sup>C-NMR and FT-IR

SONG Yu; ZHU Yan-ming; LI Wu

Volume 43 Issue 05

May 2015

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SONG Yu, ZHU Yan-ming, LI Wu. Structure evolution of oxygen functional groups in Dongsheng long flame coal by 13C-NMR and FT-IR[J]. Journal of Fuel Chemistry and Technology, 2015, 43(05): 519-529.

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SONG Yu, ZHU Yan-ming, LI Wu. Structure evolution of oxygen functional groups in Dongsheng long flame coal by ¹³C-NMR and FT-IR[J]. Journal of Fuel Chemistry and Technology, 2015, 43(05): 519-529.

SONG Yu, ZHU Yan-ming, LI Wu. Structure evolution of oxygen functional groups in Dongsheng long flame coal by 13C-NMR and FT-IR[J]. Journal of Fuel Chemistry and Technology, 2015, 43(05): 519-529.

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Structure evolution of oxygen functional groups in Dongsheng long flame coal by ¹³C-NMR and FT-IR

SONG Yu^1,2,
ZHU Yan-ming^{1,2
,},
LI Wu^1,2

1.
School of Resources and Earth Science, China University of Mining & Technology, Xuzhou 221116, China;
2.
Key Laboratory of Coalbed Methane Resource & Reservoir Formation Process, Ministry of Education, Xuzhou 221008, China

Received Date: 2014-10-22
Publish Date: 2015-05-30

Abstract

Abstract

Vitrinite was separated and enriched from the 2nd long flame coal seam in Dongsheng coal mine by flotation and centrifugation. Structural parameters of groups were obtained from proximate and ultimate analysis, as well as ¹³C-NMR and FT-IR spectrum. The contents of carboxyl and carbonyl in the vitrain are from 8.91 to 10.90 mol/kg and from 1.61 to 1.79 mol/kg, respectively. Carboxyl is lost rapidly with increasing pyrolysis temperature. Methyl and methylene groups attached in the form of end groups to oxygen in the aliphatic chain or an aliphatic ring structure are removed first, and is basically stable above 350 ℃. The variation in occurrence of oxygen functional groups is the result of competition between aromatic and aliphatic system. Aromatic and aliphatic oxygen in coal pyrolyzed at 510 ℃ are 7.49 and 3.45 mol/kg. The evolution of hydroxyl is closely associated with the occurrence of oxygen. The content of various hydroxyls reduced along with the increasing temperature. Destructive effect on macromolecular network caused by pyrolysis interferes various hydrogen bonds, while the hydroxyl-π effect is enhance. The chemical activity order of oxygen in the coal is [COOH] > [R-O] > [Ar-O-Ar, Ar-O-C, C-O-C] > [C=O]. The contents of inactive and active ether in the vitrain are 0.68 and 0.48 mol/kg, respectively.
- Dongsheng long flame coal,
- pyrolysis,
- oxygen functional groups,
- structure evolution,
- ¹³C-NMR,
- FT-IR

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References(39)

References

LI C Z, SATHE C, KERSHAW J R, PANG Y. Fates and roles of alkali and alkaline earth metals during the pyrolysis of a victorian brown coal[J]. Fuel, 2000, 79(3/4): 427-438.

周剑林, 王永刚, 黄鑫, 张书, 林雄超.低阶煤含氧官能团分布的研究[J]. 燃料化学学报, 2013, 41(2): 134-138.(ZHOU Jian-lin, WANG Yong-gang, HUANG Xin, ZHANG Shu, LIN Xiong-chao. Determination of O-containing functional groups distribution in low-rank coals by chemical titration[J]. J Fuel Chem Technol, 2013, 41(2): 134-138.)

崔丽杰. 煤热解过程中产物组成和官能团转化的研究[D]. 北京: 中国科学院, 2005.(CUI Li-jie. Product distribution and functional group conversion in coal pyrolysis[D]. Beijing: Chinese Academy of Sciences, 2005.)

陈洪博, 李文华, 姜英, 白向飞. 神东煤显微组分与基本结构特征研究[J].煤炭转化, 2006, 29(1): 6-10.(CHEN Hong-bo, LI Wen-hua, JIANG Ying, BAI Xiang-fei. Macerals and structure characteristic parameters of ShenDongcoals[J]. Coal Convers, 2006, 29(1): 6-10.)

艾军, 郭治, 李克健. 神东煤富惰质组加氢液化反应动力学的研究[J]. 煤炭转化, 2008, 31(2): 25-27.(AI Jun, GUO Zhi, LI Ke-jian. Kinetics of hydroliquefaction of ShenDong rich inertinite[J]. Coal Convers, 2008, 31(2): 25-27.)

李文华, 霍卫东, 舒歌平, 白向飞, 戴和武. 马家塔煤及其显微组分的加氢液化特征[J]. 燃料化学学报, 2001, 29(2): 104-107.(LI Wen-hua, HUO Wei-dong, SHU Ge-ping, BAI Xiang-fei, DAI He-wu. Hydroliquefaction characteristics of Majiata coal and its maceralscomponents[J]. J Fuel ChemTechnol, 2001, 29(2): 104-107.)

赵鹏, 史士东. 胜利褐煤中氧在液化预反应中脱除的研究[J]. 煤炭学报, 2004, 29(2): 230-233.(ZHAO Peng, SHI Shi-dong. Study on the release of oxygen functional group in Shengli lignite during preliquefaction[J]. J Chin Coal Soc, 2004, 29(2): 230-233.)

陈洪博, 郭治. 神东煤不同显微组分加氢液化性能及转化规律[J]. 煤炭转化, 2006, 29(4): 9-12.(CHEN Hong-bo, GUO Zhi. Study on hydroliquefaction behavior and rules of ShenDong coal macerals[J]. Coal Convers, 2006, 29(4): 9-12.)

SCHAFER H N S. Determination of the total acidity of low rank coals[J]. Fuel, 1970, 49(2): 271-280.

SCHAFER H N S. Determination of carboxyl groups in low rank coals[J]. Fuel, 1984, 63(5): 723-726.

ALLARDICE D J, CLEMOW L M, JACKSON W R. Determination of the acid distribution and total acidity of low rank coals and coal derived materials by an improved barium exchange technique[J]. Fuel, 2003, 82(1): 35-40.

张蓬洲, 李丽云, 叶朝辉. 用固体高分辨核磁共振研究煤结构[J]. 燃料化学学报, 1993, 21(3): 310-316.(ZHANG Peng-zhou, LI Li-yun, YE Chao-hui. Solid state ¹³ C-NMR study of Chinese coals[J]. J Fuel Chem Technol, 1993, 21(3): 310-316.)

罗陨飞, 李文华, 陈亚飞. 中低变质程度煤显微组分结构的¹³C-NMR研究[J]. 燃料化学学报, 2005, 33(5): 540-543.(LUO Yun-fei, LI Wen-hua, CHEN Ya-fei. ¹³ C-NMR analysis on different macerals of several low to medium rank coals[J]. J Fuel Chem Technol, 2005, 33(5): 540-543.)

贾建波, 曾凡桂, 孙蓓蕾. 神东2^-2煤镜质组大分子结构模型¹³C-NMR谱的构建于修正[J]. 燃料化学学报, 2011, 39(9): 653-657.(JIA Jian-bo, ZENG Fan-gui, SUN Bei-lei. Construction and modification of macromolecular structure model for vitrinite from ShenDong 2^-2 coal[J]. J Fuel Chem Technol, 2011, 39(9): 653-657.)

KELEMEN S R, AFEWOK M, GORBATY M L, COHEN A D. Characterization of organically bound oxygen forms in lignite, peats, and pyrolyzed peats by X ray photoelectron spectroscopy (XPS) and solid state ¹³C-NMR methods[J]. Energy Fuels, 2002, 16(6): 1450-1462.

KOZLOWSKI M. XPS study of reductively and non-reductively modified coals[J]. Fuel, 2004, 83(3): 259-265.

SUPALUKNARI S, LARKINS F P, REDLICH P, JACKSON W R. An FT-IR study of australian coals: Characterization of oxygen functional groups[J]. Fuel Process Technol, 1988, 19(2): 123-140.

KUEHN D W, SNYDER R W, DAVIS A, PAINTER P C. Characterization of vitrinite concentrates Fourier transform infrared studies[J]. Fuel, 1982, 61(8): 682-694.

戴中蜀, 郑钧晖, 马立红. 低煤化度煤热解脱氧后结构的变化[J]. 燃料化学学报, 1999, 27(3): 256-261.(DAI Zhong-shu, ZHENG Jun-hui, MA Li-hong. Structural change of low rank coal by deoxygen under pyrolysis at low temperature[J]. J Fuel Chem Technol, 1999, 27(3): 256-261.)

张卫, 曾凡桂. 中等变质程度煤中羟基的红外光谱分析[J]. 太原理工大学学报, 2005, 36(5): 545-548.(ZHANG Wei, ZENG Fan-gui. FT-IR analysis of hydrogen bond in middle maturate coals[J]. J Taiyuan Univ Technol, 2005, 36(5): 545-548.)

郑庆荣, 曾凡桂, 张世同. 中变质煤结构演化的FT-IR分析[J]. 燃料化学学报, 2011, 36(3): 481-486.(ZHENG Qing-rong, ZENG Fan-gui, ZHANG Shi-tong. FT-IR study on structure evolution of middle maturate coals[J]. J Fuel Chem Technol, 2011, 36(3): 481-486.)

WU L, YAN M Z, YU S, MENG W. Study of a vitrinite macromolecular structure evolution control mechanism of the energy barrier in hydrocarbon generation[J]. Energy Fuels, 2014, 28(1): 500-509.

WU L, YAN M Z. Structural characteristics of coal vitrinite during pyrolysis[J]. Energy Fuels, 2014, 28(6): 3645-3654.

王永刚, 周剑林, 陈艳巨, 胡秀秀, 张书, 林雄超. ¹³C固体核磁共振分析煤中含氧官能团的研究[J].燃料化学学报, 2013, 41(12):1422-1426.(WANG Yong-gang, ZHOU Jian-lin, CHEN Yan-ju, HU Xiu-xiu, ZHANG Shu, LIN Xiong-chao. Contents of O-containing functional groups in coals by ¹³C-NMR analysis[J]. J Fuel Chem Technol, 2013, 41(12): 1422-1426.)

MURATA S, HOSOKAW A M, KIDENA K, NOMURAW. Analysis of oxygen-functional groups in brown coals[J]. Fuel Process Technol, 2000, 67(3): 231-243.

USP-NF24, Methoxy determination[S].

王三跃. 褐煤结构的分子动力学模拟与量子化学研究[D]. 太原: 太原理工大学, 2007.(WANG San-yue. Study of lignite structure by molecular dynamics simulation and quantum chemistry[D]. Taiyuan: Taiyuan University of Technology, 2007.)

张莉, 曾凡桂, 向建华. 内蒙五牧场矿区11 号煤层原煤大分子结构特征及其形成机制[J]. 燃料化学学报, 2013, 41(11): 1295-1302.(ZHANG Li, ZENG Fan-gui, XIANG Jian-hua. Macromolecular structure and formation mechanism of raw coal in coal seam 11 of Wumuchang district, Inner Mongolia[J]. J Fuel Chem Technol, 2013, 41(11): 1295-1302.)

王丽, 张蓬洲, 郑敏. 用固体核磁共振和电子能谱研究我国高硫煤的结构[J]. 燃料化学学报, 1996, 24(6): 539-543.(WANG Li, ZHANG Peng-zhou, ZHENG Min. Study on structural characterization of three Chinese coals of high organic sulphur content using XPS and solid-state NMR spectroscopy[J]. J Fuel Chem Technol, 1996, 24(6): 539-543.)

THOMASK M. The release of nitrogen oxides during char combustion[J]. Fuel, 1997, 76(6): 457-473.

JOHNSON J E. Formation and reduction of nitrogen oxides in fluidized-bed combustion[J]. Fuel, 1994, 73(9): 1398-1415.

HÄMÄLÄINEN J P, AHOM J. Conversion of fuel nitrogen through HCN and NH₃ to nitrogen oxides at elevated pressure[J]. Fuel, 1996, 75(12): 1377-1386.

陶建红. 褐煤中含氧官能团的测定与研究[J]. 河南化工, 2010, 27(4): 8-10.(TAO Jian-hong. Research and measurement on oxygen-containing functional groups in brown coal[J]. Henan Chem Ind, 2010, 27(4): 8-10.)

MURATA S, HOSOKAWA M, KIDENA K, NOMURA M. Analysis of oxygen functional groups in brown coals[J]. Fuel Process Technol, 2000, 67(3): 231-243.

庄书贤, 季明荣, ROVIDA G. 酚在P_d(110)上的吸附于分解[J]. 化学物理学报, 1994, 7(4): 558-565.(ZHUANG Shu-xian, JI Ming-rong, ROVIDA G. Adsorption and decomposition of phenol on Pd(110) surface[J]. Chin J Chem Phys, 1994, 7(4): 558-565.)

刘生玉. 中国典型动力煤及含氧模型化合物热解过程的化学基础研究[D]. 太原: 太原理工大学, 2004.(LIU Sheng-yu. Fundamental study on pyrolysis of Chinese steam coals and model compounds containing oxygen[D]. Taiyuan: Taiyuan University of Technology, 2004.)

降文平, 王传格, 晋香兰, 田新娟, 李小彦.不同变质程度煤的液化差异及其分子结构研究[J].煤炭转化, 2012, 35(1): 33-36.(JIANG Wen-ping, WANG Chuan-ge, JIN Xiang-lan, TIAN Xin-juan, LI Xiao-yan. Study on the liquefaction difference and molecule structure on different rank coals[J]. Coal Convers, 2012, 35(1): 33-36.)

马博文. 褐煤加氢液化过程中酚羟基反应行为研究[D]. 北京: 煤炭科学研究总院, 2014.(MA Bo-wen. Study on reaction behaviors of phenolic hydroxyl through hydrogenation liquefaction process of lignite[D]. Beijing: CCRI, 2014.)

陈永健. 含氧官能团模型化合物对煤直接液化的影响研究[D]. 太原: 太原理工大学, 2013.(CHEN Yong-jian. The effect of oxygenated model compounds on direct coal liquefaction[D]. Taiyuan: Taiyuan University of Technology, 2013.)

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