Transformation of nitrogen during pyrolysis of Na-loaded Shengli brown coal

ZHENG Pan-pan; WANG Yong-gang; WU Xin; LIU Chen; BAI Yan-ping; LIN Xiong-chao

Volume 45 Issue 4

Apr. 2017

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Article Navigation > Journal of Fuel Chemistry and Technology > 2017 > 45(4): 418-426

ZHENG Pan-pan, WANG Yong-gang, WU Xin, LIU Chen, BAI Yan-ping, LIN Xiong-chao. Transformation of nitrogen during pyrolysis of Na-loaded Shengli brown coal[J]. Journal of Fuel Chemistry and Technology, 2017, 45(4): 418-426.

Citation:

ZHENG Pan-pan, WANG Yong-gang, WU Xin, LIU Chen, BAI Yan-ping, LIN Xiong-chao. Transformation of nitrogen during pyrolysis of Na-loaded Shengli brown coal[J]. Journal of Fuel Chemistry and Technology, 2017, 45(4): 418-426.

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Transformation of nitrogen during pyrolysis of Na-loaded Shengli brown coal

School of Chemical and Environmental Engineering, China University of Mining and Technology (Beijing), Beijing 100083, China

Funds:

the National Natural Science Foundation of China 21406261

the Plan of National Science and Technology Support 2012BAA04B02

Received Date: 2016-12-17
Rev Recd Date: 2017-03-01

Available Online: 2021-01-23

Publish Date: 2017-04-10

Abstract

Abstract

The impact of Na content on nitrogen transformation during the pyrolysis of Shengli raw coal and the Na-loaded coal in a fixed-bed/fluidized-bed quartz reactor was investigated. The quantification of NH₃ and HCN in gas product was carried out using an ultraviolet-visible spectrophotometer while the occurrence modes of nitrogen in the solid chars were detected by X-ray photoelectron spectroscopy (XPS). The results indicate that the transformation of coal-N to NH₃ can be catalytically enhanced by certain amount of Na at low temperature. When the final pyrolysis temperature is relatively high, the presence of Na appears to inhibit the formation of NH₃. Meanwhile, for any given pyrolysis temperature, the production of HCN will be suppressed by Na. When the pyrolysis temperature is high, the increase of Na content in coal causes the reduction of nitrogen remaining in char and promotes quaternary nitrogen formation, whereas, the effect is negligible at low temperature.
- brown coal,
- pyrolysis,
- Na,
- nitrogen

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References(35)

References

[1]	WU Z H, SUGIMOTO Y, KAWASHIMA H. The influence of mineral matter and catalyst on nitrogen release during slow pyrolysis of coal and related material:A comparative study[J]. Energy Fuels, 2002, 16(2):451-456. doi: 10.1021/ef010183q
[2]	FRIEBEL J, KÖPSEL R F. The fate of nitrogen during pyrolysis of German low rank coals-a parameter study[J]. Fuel, 1999, 78(8):923-932. doi: 10.1016/S0016-2361(99)00008-3
[3]	WU Z H, SUGIMOTO Y, KAWASHIMA H. Effect of demineralization and catalyst addition on N₂ formation during coal pyrolysis and on char gasification[J]. Fuel, 2003, 82(15/17):2057-2064. http://www.sciencedirect.com/science/article/pii/S001623610300187X
[4]	TSUBOUCHI N, OHTSUKA Y. Formation of N₂ during pyrolysis of Ca-loaded coals[J]. Fuel, 2002, 81(11/12):1423-1431. https://www.mysciencework.com/publication/show/e86ecee908767991c6038d697097b963
[5]	OHTSUKA Y, WU Z, EDWARD F. Effect of alkali and alkaline metals on nitrogen release during temperature programmed pyrolysis of coal[J]. Fuel, 1997, 76(14/15):1361-1367. https://www.researchgate.net/publication/263600839_Effect_of_alkali_and_alkaline_earth_metals_on_nitrogen_release_during_temperature_programmed_pyrolysis_of_coal
[6]	胡俊豪, 黎阳, 杨海平, 杨晴, 邵敬爱, 王贤华, 陈汉平.煤热解过程中含氮产物的析出及金属离子的催化特性研究[J].燃料化学学报, 2014, 42(8):913-921. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18465.shtml HU Jun-hao, LI Yang, YANG Hai-ping, YANG Qing, SHAO Jing-ai, WANG Xian-hua, CHEN Han-ping. Release of nitrogenous products and the catalytic characteristics of metal ions during coal pyrolysis[J]. J Fuel Chem Technol, 2014, 42(8):913-921. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18465.shtml
[7]	孟丽莉, 付春慧, 王美军, 常丽萍.碱金属碳酸盐对褐煤程序升温热解过程中H₂S和NH₃生成的影响[J].燃料化学学报, 2012, 40(2):138-142. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17874.shtml MENG Li-li, FU Chun-hui, WANG Mei-Jun, CHANG Li-ping. Effect of alkali carbonates on the formation of H₂S and NH₃ during temperature programmed pyrolysis of brown coal[J]. J Fuel Chem Technol, 2012, 40(2):138-142. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17874.shtml
[8]	赵宗彬, 李文, 李保庆, 陈皓侃.钠、钙、铁对模型化合物热解及燃烧过程中氮逸出规律的影响[J].燃料化学学报, 2002, 30(4):294-299. http://www.cnki.com.cn/Article/CJFDTOTAL-RLHX200204001.htm ZHAO Zong-bin, LI Wen, LI Bao-qing, CHEN Hao-kan. Effect of Na, Ca and Fe on evolution of fuel-nitrogen during pyrolysis and combustion of model compound[J]. J Fuel Chem Technol, 2002, 30(4):294-299. http://www.cnki.com.cn/Article/CJFDTOTAL-RLHX200204001.htm
[9]	ZHAO Z B, LI W, QIU J S, LI B Q. Effect of Na、Ca and Fe on the evolution of nitrogen species during pyrolysis and combustion of model chars[J]. Fuel, 2003, 82(15/17):1839-1844.
[10]	秦玲丽. 金属化合物对煤热解过程中氮、硫转化的影响[D]. 太原: 太原理工大学, 2007. QIN Ling-li. Effect of metal compound on the transformation of coal-N and coal-S during coal pyrolysis[D]. Taiyuan:Taiyuan University of Technology, 2007.
[11]	王永刚, 郑盼盼, 杨萨莎, 张书, 白艳萍, 贾晓璐.酸洗脱矿对胜利褐煤热解过程中N迁移转化的影响[J].燃料化学学报, 2014, 42(5):519-526. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18404.shtml WANG Yong-gang, ZHENG Pan-pan, YANG Sa-sha, BAI Yan-ping, JIA Xiao-lu. Influence of demineralization using acid wash on N migration and transformation during pyrolysis of Shengli brown coal[J]. J Fuel Chem Technol, 2004, 42(5):519-526. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18404.shtml
[12]	许慎启, 周志杰, 代正华, 于广锁, 龚欣.碱金属及灰分对煤焦炭微晶结构及气化反应特性的影响[J].高校化学工程学报, 2010, 24(1):64-70. http://www.cnki.com.cn/Article/CJFDTOTAL-GXHX201001013.htm XU Shen-qi, ZHOU Zhi-jie, DAI Zheng-hua, YU Guang-suo, GONG Xin. Effects of alkalimetal and ash on crystallite structure of coal char during pyrolysis and on gasification reactivity[J]. J Chem Eng Chin Univ, 2010, 24(1):64-70. http://www.cnki.com.cn/Article/CJFDTOTAL-GXHX201001013.htm
[13]	LI C Z. Some recent advances in the understanding of the pyrolysis gasification behavior of Victorian brown coal[J]. Fuel, 2007, 86(12/13):1664-1683. https://www.researchgate.net/publication/222034353_Some_recent_advances_in_the_understanding_of_the_pyrolysis_and_gasification_behaviour_of_Victorian_brown_coal
[14]	WOOD B J, SANCIER K M. The mechanism of the catalytic gasification of coal char:A critical review[J]. Catal Rev, 1984, 26(2):233-279. doi: 10.1080/01614948408078065
[15]	VERNAGLIA B A, WORNAT M J, LI C Z, NELSON P F. The effects of pyrolysis temperature and ion-exchanged metals on the composition of brown coal tars produced in a fluidized-bed reactor[J]. Symp Combust, 1996, 26(2):3287-3294. doi: 10.1016/S0082-0784(96)80175-5
[16]	李春柱.维多利亚褐煤褐煤科学进展[M].北京:化学工业出版社, 2009. LI Chun-zhu. Advance in the Science of Victorian Brown Coal[M]. Beijing:Chemical Industry Press, 2009.
[17]	ZHANG S, HAYASHI J I, LI C Z. Volatilisation and catalytic effects of alkali and alkaline earth metallic species during the cytolysis and gasification of Victorian brown coal. Part IX. Effects of volatile-char interactions on char-H₂O and char-O₂ reactivities[J].Fuel, 2011, 90(4):1655-1661. doi: 10.1016/j.fuel.2010.11.008
[18]	张书, 白艳萍, 米亮, 郑盼盼, 陈绪军, 许德平, 王永刚.升温速率对胜利褐煤热解过程中N迁移转化的影响[J].燃料化学学报, 2013, 41(10):1153-1159. doi: 10.1016/S1872-5813(13)60048-1 ZHANG Shu, BAI Yan-ping, MI Liang, ZHENG Pan-pan, CHEN Xu-jun, XU De-ping, WANG Yong-gang. Effect of heating rate on the migration and transformation of N during pyrolysis of Shengli brown coal[J]. J Fuel Chem Technol, 2013, 41(10):1153-1159. doi: 10.1016/S1872-5813(13)60048-1
[19]	秦玲丽, 崔银萍, 徐明艳, 常丽萍.煤氮催化转化研究中的主要影响因素分析[J].现代化工, 2006, 26(2):382-385. http://www.cnki.com.cn/Article/CJFDTOTAL-XDHG2006S2106.htm QIN Ling-li, CUI Yin-ping, XU Ming-yan, CHANG Li-ping. Main influencing factors in the, research on catalytic conversion of coal-nitrogen[J]. Mod Chem Ind, 2006, 26(2):382-385. http://www.cnki.com.cn/Article/CJFDTOTAL-XDHG2006S2106.htm
[20]	MANZOORI A R, AGARWAL P K. The fate of organically bound inorganic elements and sodium chloride during fluidized bed combustion of high sodium, high sulphur low rank coals[J]. Fuel, 1992, 71(5):513-522. doi: 10.1016/0016-2361(92)90148-H
[21]	YAN X, CHE D F, XU T M. Effect of rank, temperature and inherent minerals on nitrogen emissions during coal pyrolysis in a fixed bed reactor[J]. Fuel Process Technol, 2005, 86(7):739-756. doi: 10.1016/j.fuproc.2004.08.005
[22]	闫晓, 车得福, 徐通模.煤热解过程中焦炭氮变化规律的试验研究[J].西安交通大学学报, 2004, 38(9):980-984. http://www.cnki.com.cn/Article/CJFDTOTAL-XAJT200409024.htm YAN Xiao, CHE De-fu, XU Tong-mo. Experimental investigation on char nitrogen conversion during coal pyrolysis[J]. J Xi'an Jiaotong Univ, 2004, 38(9):980-984. http://www.cnki.com.cn/Article/CJFDTOTAL-XAJT200409024.htm
[23]	LI C Z, NELSON P F. Interaction of quarts, zircon sand and stainless steel with ammonia implications for the measurement of ammonia at high temperature[J]. Fuel, 1996, 75(4):525-526. doi: 10.1016/0016-2361(95)00256-1
[24]	张双全.煤化学[M]. 2版.徐州:中国矿业大学出版社, 2010. ZHANG Shuang-quan. Coal Chemistry[M]. 2nd ed. Xuzhou:China University of Mining and Technology Press, 2010.
[25]	刘艳华, 车得福, 李荫堂, 惠世恩, 徐通模. 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. http://www.cnki.com.cn/Article/CJFDTOTAL-XAJT200107000.htm LIU Yan-hua, CHE De-fu, LI Yin-tang, HUI Shi-en, XU Tong-mo. X-ray photoelectron spectroscopy determination of the forms of nitrogen in Tongchuan coal and its chars[J]. J Xi'an Jiaotong Univ, 2001, 35(7):661-665. http://www.cnki.com.cn/Article/CJFDTOTAL-XAJT200107000.htm
[26]	吴婷, 凌凤香, 马波, 王少军, 吴洪新. GC-MS分析低温煤焦油酸性组分及碱性组分[J].石油化工高等学校学报, 2013, 26(3):44-52. http://www.cnki.com.cn/Article/CJFDTOTAL-SYHX201303009.htm WU Ting, LING Feng-xiang, MA Bo, WANG Shao-jun, WU Hong-xin. Analysis of acidcomposition and base composition from low-temperature coal tar by GC-MS[J]. J Petrochem Univ, 2013, 26(3):44-52. http://www.cnki.com.cn/Article/CJFDTOTAL-SYHX201303009.htm
[27]	张喜亮, 贾德民. 炭黑表面的化学结构模型[C]. 全国高分子学术论文报告会, 2001. ZHANG Xi-liang, JIA De-min. Chemical model of carbon black surface[C]. Nation Polymer Academic Paper Report, 2001.
[28]	王道宏, 王日杰, 张继炎, 何菲. X光电子能谱法研究色素碳黑的表面化学性质[J].天津大学学报, 2004, 37(7):634-638. http://www.cnki.com.cn/Article/CJFDTOTAL-TJDX200407015.htm WANG Dao-hong, WANG Ri-jie, ZHANG Ji-yan, HE Fei. Study on surface chemical property of carbon black pigments by x-ray photoelectronic spectroscopy[J]. J Tianjin Univ, 2004, 37(7):634-638. http://www.cnki.com.cn/Article/CJFDTOTAL-TJDX200407015.htm
[29]	朱廷钰, 汤忠, 黄戒介, 张建民, 汪洋.煤温和气化特性的热重研究[J].燃料化学学报, 1999, 27(5):420-423. http://www.cnki.com.cn/Article/CJFDTOTAL-RLHX199905008.htm ZHU Ting-yu, TANG Zhong, HUANG Jie-jie, ZHANG Jian-min, WANG Yang. Thermo-gravimetric study of coal mild gasification[J]. J Fuel Chem Technol, 1999, 27(5):420-423. http://www.cnki.com.cn/Article/CJFDTOTAL-RLHX199905008.htm
[30]	TIAN F J, YU J L, MCKENZIE L J, HAYASHI J I, LI C Z. Formation of NO_x precursors during the pyrolysis of coal and biomass. Part IX. Effect of coal ash and externally loaded-Na on fuel-N conversion during the reforming of coal and biomass in steam[J]. Fuel, 2006, 85(10/11):1411-1417.
[31]	LI C Z, LI L T. Formation of NO_x and SO_x precursors during the pyrolysis of coal and biomass. Part III. Further discussion on the formation of HCN and NH₃ during pyrolysis[J]. Fuel, 2000, 79(15):1899-1906. doi: 10.1016/S0016-2361(00)00008-9
[32]	熊杰, 周志杰, 许慎启, 于广锁.碱金属对煤热解和气化反应速率的影响[J].化工学报, 2011, 62(1):192-198. http://www.cnki.com.cn/Article/CJFDTOTAL-HGSZ201101031.htm XIONG JIE, ZHOU Zhi-jie, XU Shen-qi, YU Guang-suo. Effect of alkali metal on rate of coal pyrolysis and gasification[J]. CIESC J, 2011, 62(1):192-198. http://www.cnki.com.cn/Article/CJFDTOTAL-HGSZ201101031.htm
[33]	KAPTEIGIN F, MOULIGIN J A, MATZNER S, BOEHMB H P. The development of nitrogen functionality in model chars during gasification in CO₂ and O₂[J]. Carbon, 1999, 37(7):1143-1150. doi: 10.1016/S0008-6223(98)00312-1
[34]	SCHMIER S H, FRIEBEL J, STREUBEL P, HESSEB R K, PSELA R. Change of chemical bonding of nitrogen of polymeric N-heterocyclic compounds during pyrolysis[J]. Carbon, 1999, 37(12):1965-1978. doi: 10.1016/S0008-6223(99)00071-8
[35]	XU M X, LI S Y, WU Y H, JIA L F, LU Q G. Effects of CO₂ on the fuel nitrogen conversion during coal rapid pyrolysis[J]. Fuel, 2016, 184:430-439. doi: 10.1016/j.fuel.2016.06.130