用XPS研究新西兰高硫煤热解过程中氮、硫官能团的转变规律

李梅; 杨俊和; 张启锋; 常海洲; 孙慧

用XPS研究新西兰高硫煤热解过程中氮、硫官能团的转变规律

李梅^1,2,
杨俊和^1,,
张启锋³,
常海洲⁴,
孙慧⁴

1.
上海理工大学材料科学与工程学院, 上海 200093;
2.
北方民族大学化学与化学工程学院, 宁夏银川 750021;
3.
宝山钢铁股份有限公司, 上海 201900;
4.
上海理工大学理学院, 上海 200093

基金项目: 国家自然科学基金(21276156)。

详细信息

通讯作者:
杨俊和,Tel:021-55270632,E-mail:jhyang@usst.cn。

中图分类号: TQ530
计量
- 文章访问数: 1507
- HTML全文浏览量: 20
- PDF下载量: 973
- 被引次数: 0
出版历程
- 收稿日期: 2013-04-22
- 修回日期: 2013-06-04
- 刊出日期: 2013-11-30

XPS study on transformation of N- and S-functional groups during pyrolysis of high sulfur New Zealand coal

1.
School of Materials Science and Engineering, University of Shanghai for Science and Technology, Shanghai 200093, China;
2.
School of Chemistry and Chemical Engineering, Beifang University of Nationalities, Yinchuan 750021, China;
3.
Baoshan Iron & Steel Co., Ltd, Shanghai 201900, China;
4.
School of Science, University of Shanghai for Science and Technology, Shanghai 200093, China

摘要

摘要: 选择一种高硫新西兰煤(NXL)作为研究对象,高纯Ar气氛中,以5℃/min的升温速率在管式炉中热解,热解终温为300~1 000℃。用XPS研究煤及不同温度下半焦中氮、硫的赋存形态。将N 1s谱图用Lorentzian-Gaussian拟合分为四个峰:N-6(398.8±0.4)eV、N-5(400.2±0.3)eV、N-Q(401.4±0.3)eV和N-X(402.9±0.5)eV;S 2p谱图分为六个峰:硫铁矿(162.5±0.3)eV、硫化物(163.3±0. 4)eV、噻吩(164.1±0.2)eV、亚砜(166.0±0.5)eV、砜(168.0±0.5)eV和硫酸盐硫(169.5±0.5)eV。结果表明,煤中氮元素的主要存在形式是吡啶、吡咯、质子化吡啶和氮氧化物;低于600℃,半焦中的氮元素主要以吡啶和吡咯形式存在;随温度的升高,吡咯向吡啶转化;当温度超过900℃,氮氧化物这一形态消失。该煤中的硫以有机硫为主,其中,噻吩硫占50%以上;随着热解温度的升高,煤中的硫铁矿硫逐步转化为无机硫化物,600℃时分解完全。
- XPS /
- 高硫煤 /
- 热解 /
- 氮迁移 /
- 硫迁移
Abstract: X-ray photoelectron spectroscopy (XPS) was used to investigate the nitrogen and sulfur functional forms present in New Zealand coal (NXL) and its pyrolysis char prepared under argon atmosphere at 8 different temperatures between 300 and 1 000℃. The N 1s spectra obtained were curve-resolved into 4 peaks: pyridinic-N (398.8±0.4 eV), pyrrolic-N (400.2±0.3 eV), quaternary-N (401.4±0.3 eV) and nitrogen oxides (402.9±0.5 eV); and S 2p peaks into 6 peaks: pyrite (162.5±0.3 eV), sulphidic (163.3±0.4 eV), thiophenic (164.1±0.2 eV), sulfoxide (166.0±0.5 eV), sulfones (168.0±0.5 eV) and sulfate (169.5±0.5 eV). The results show that nitrogen present in coal in pyrrolic forms is converted into pyridinic functionalities upon heat treatment and nitrogen oxides disappeared above 900℃. The major organic sulfur form in NXL is thiophene and its content is over 50%. Pyrite is decomposed completely into troilite at 600℃.
- XPS /
- high sulfur coal /
- pyrolysis /
- nitrogen transformation /
- sulfur transformation

HTML全文

参考文献(21)

GONG B, BUCKLEY A N, LAMB R N, NELSON P F. XPS determination of the forms of nitrogen in coal pyrolysis chars[J]. Sur Int Anal, 1999, 28(1): 126-130.

GORBATY M L, KELEMEN S R. Characterization and reactivity of organically bound sulfur and nitrogen fossil fuels[J]. Fuel Process Technol, 2001, 71(1/3): 71-78.

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.

常海洲, 王传格, 曾凡桂, 李军, 李文英, 谢克昌. 不同还原程度煤显微组分组表面结构XPS对比分析[J]. 燃料化学学报, 2006, 34(4): 389-394. (CHANG Hai-zhou, WANG Chuan-ge, ZENG Fan-gui, LI Jun, LI Wen-ying, XIE Ke-chang. XPS comparative analysis of coal macerals with different reducibility[J]. Journal of Fuel Chemistry and Technology, 2006, 34(4): 389-394.)

刘艳华, 车得福, 徐通模. 利用X射线光电子能谱确定煤及其残焦中硫的形态[J]. 西安交通大学学报, 2004, 38(1): 101-104. (LIU Yan-hua, CHE De-fu, XU Tong-mo. X-Ray photoelectron spectroscopy determination of the forms of sulfur in coal and its chars[J]. Journal of Xi'an JiaoTong University, 2004, 38(1): 101-104.)

WOJTOWICZ M A, PELS J R, MOULIJN J A. The fate of nitrogen functionalities in coal during pyrolysis and combustion[J]. Fuel, 1995, 74(4): 507-516.

SCHMIERS H, FRIEBEL J, STREUBEL P, HESSE R, KOPSEL R. Change of chemical bonding of nitrogen of polymeric N-heterocyclic compounds during pyrolysis[J]. Carbon, 1999, 37(12): 1965-1978.

KAMBARA S, TAKARADA T, YAMAMOTO Y, KATO K. Relation between functional forms of coal nitrogen and formation of nitrogen oxide (NO_x) precursors during rapid pyrolysis[J]. Energy Fuels, 1993, 7(6): 1013-1020.

KAMBARA S, TAKARADA T, TOYOSHIMA M, KATO K. Relation between functional forms of coal nitrogen and NO_x emissions from pulverized coal combustion[J]. Fuel, 1995, 74(9): 1247-1253.

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

KELEMEN S R, GEORGE G N, GORBATY M L. Direct determination and quantification of sulphur forms in heavy petroleum and coals: 1.The X-ray photoelectron spectroscopy (XPS) approach[J]. Fuel, 1990, 69(8): 939-944.

ZHANG Y C, ZHANG J, SHENG C D, CHEN J, LIU Y X, ZHAO L, XIE F. X-ray photoelectron spectroscopy(XPS) investigation of nitrogen functionalities during coal char combustion in O₂/CO₂and O₂/Ar atmospheres[J]. Energy Fuels, 2011, 25(1): 240-245.

PIETRZAK R, GRZYBEK T, WACHOWSKA H. XPS study of pyrite-free coals subjected to different oxidizing agents[J]. Fuel, 2007, 86(16): 2616-2624.

CHEN H K, LI B Q, YANG J L, ZHANG B J. Transformation of sulfur during pyrolysis and hydropyrolysis of coal[J]. Fuel, 1998, 77(6): 487-493.

NELSON P F, KELLY M D, WORNAT M J. Conversion of fuel nitrogen in coal volatiles to NO_x precursors under rapid heating conditions[J]. Fuel, 1991, 70(3): 403-407.

姚明宇, 刘艳华, 车得福. 宜宾煤中氮的形态及其变迁规律研究[J]. 西安交通大学学报, 2003, 37(7): 759-763. (YAO Ming-yu, LIU Yan-hua, CHE De-fu. Investigation of nitrogen functionality in Yibin coal and its char[J]. Journal of Xi'an Jiaotong University, 2003, 37(7): 759-763.)

刘海明, 张军营, 郑楚光, 孟韵. 煤中吡咯型和吡啶型氮热解稳定性研究[J]. 华中科技大学学报(自然科学版), 2004, 32(11): 13-15. (LIU Hai-ming, ZHANG Jun-ying, ZHENG Chu-guang, MENG Yun. Quantum chemical study of the pyrolysis stability of pyrrolic nitrogen and pyridinic nitrogen in coal[J]. Journal of Huazhong University of Science & Technology(Nature Science Edition), 2004, 32(11): 13-15.)

YOSHIHIKO N, DONG Z B. Theoretical study on the thermal decomposition of pyridine[J]. Fuel, 2000, 79(3/4): 449-457.

LIU F R, LI W, CHEN H K, LI B Q. Uneven distribution of sulfurs and their transformation during coal pyrolysis[J]. Fuel, 2007, 86(3): 360-366.

ALVAREZ R, CLEMENTE C, GOMEZ-LIMON D. The influence of nitric acid oxidation of low rank coal and its impact on coal structure[J]. Fuel, 2003, 82(15/17): 2007-2015.

GRYGLEWICZ G, WILK P, YPERMAN J, FRANCO D V, MAES I I, MULLENS J, VAN POUCKE L C. Interaction of the organic matrix with pyrite during pyrolysis of a high-sulfur bituminous coal[J]. Fuel, 1996, 75(13): 1499-1504.

施引文献

资源附件(0)

访问统计