张嘉航,朱建国
ZHANG Jiahang,ZHU Jianguo

• 1:中国科学院工程热物理研究所
• 2:中国科学院大学

摘要(Abstract)：

煤炭是我国主要能源,然而煤炭燃烧释放的SO_2等污染物影响环境。煤中有机硫结构复杂、形式多样,研究相对困难,因此研究煤中有机硫转化特性可为燃煤SO_2污染物排放控制提供理论支撑。在30 kW预热燃烧试验平台上对神木烟煤开展了预热燃烧试验,试验过程中对于测量点进行固体取样,利用X射线光电子能谱技术(XPS)和X射线衍射(XRD)对神木烟煤及预热半焦中的有机硫进行分析。结果表明:神木烟煤中有机硫的主要形态可分为4种:硫醇和硫醚(32.6%)、噻吩(16.0%)、亚砜(15.9%)和砜类(15.3%),无机硫有CaSO_4、FeS_2;当循环流化床的预热温度达到800℃以上时,预热半焦中硫形态及含量与原煤相比发生较大变化,表现为预热半焦中无机硫除原有种类外出现了CaS,预热半焦中的有机硫随着预热中空气当量比的增加分解程度加深,其中硫醇和硫醚因分解而减少最多,噻吩、亚砜类次之,砜类物质相对含量增大。砜类物质相对含量增大的原因一方面与其他有机硫形态分解有关,另一方面可能存在硫醇、硫醚等向砜类物质的转化。
Coal is a major pillar of our national energy, however, the SO_2 and other pollutants released by coal combustion have caused serious damage to the environment. The organic sulfur in coal has a complex structure and diverse forms so that the research is relatively difficult. Therefore, the research on the conversion characteristics of organic sulfur in coal can provide theoretical support for the control of SO_2 pollutant emissions and achieve clean coal combustion. In order to study the conversion of organic sulfur forms in coal during the preheating process, a preheating combustion test of Shenmu bituminous coal was carried out on a 30 kW preheating combustion experiment platform. During the experiment, solid samples were taken at the measurement points, and X-ray photoelectron spectroscopy technology(XPS)and diffraction of X-rays(XRD)was used to analyze Shenmu bituminous coal and preheated semi-coke. The results show that the main forms of organic sulfur in Shenmu bituminous coal can be divided into four types: mercaptans and thioethers(32.6%),thiophenes(16.0%),sulfoxides(15.9%)and sulfones(15.3%). Inorganic sulfur includes CaSO_4,FeS_2. When the preheating temperature reaches above 800 ℃,the sulfur form and content in the preheated semi-coke change greatly compared with that in the raw coal. The inorganic sulfur in the preheated semi-coke has CaS in addition to the original types. The degree of decomposition of organic sulfur in preheated semi-coke increases with the increase in air equivalent ratio during preheating, among which mercaptans and sulfides are reduced the most due to decomposition, followed by thiophenes and sulfoxides, and the relative content of sulfones increases. The reason of the sulfones increasing is from two aspects, one is due to the discompose of other substance like mercaptans or thiophenes, and the other is due to the conversion from mercaptans to sulfones.

关键词(KeyWords)： 烟煤;预热燃烧;有机硫;析出转化
bituminous coal;preheating combustion;organic sulfur;transformation of precipitation

Abstract:

Keywords:

基金项目(Foundation): 中国科学院战略先导科技专项资助项目(XDA21040100)

作者(Author): 张嘉航,朱建国
ZHANG Jiahang,ZHU Jianguo

DOI: 10.13226/j.issn.1006-6772.CE20102202

参考文献(References)：

• [1] 崔建会.高硫煤中有机硫的赋存结构研究[D].马鞍山：安徽工业大学，2019.CUI Jianhui.Study on theoccurrence structure of organic sulfur in high sulfur coal[D].Maanshan:Anhui University of Technology,2019.
• [2] 李伟，耿瑞光，金大桥.锅炉硫氧化物生成机理及控制技术研究[J].黑龙江工程学院学报，2019,33(6):6-9,19.LI wei,GENG ruiguang,JIN Daqiao.Formation mechanism and control technologies of boiler NOx[J].Journal of Heilongjiang Institute of Technology,2019,33(6):6-9,19.
• [3] 国家发展改革委，环境保护部，国家能源局.煤电节能减排升级与改造行动计划(2014—2020年)[EB/OL].(2014-09-12)[2020-10-22].http://www.gov.cn/gongbao/content/2015/content_2818468.htm.National Development and Reform Commission,Ministry of Environmental Protection of People′s Republic of China,Energy Board.Coal-fired energy-saving emission reduction upgrade and transformation plan of action(2014-2020)[EB/OL].(2014-09-12)[2020-10-22].http://www.gov.cn/gongbao/content/2015/content_2818468.htm.
• [4] MICHAEL Müller,UWE Schnell,GüNTER Scheffknecht.Modelling the fate of sulphur during pulverized coal combustion under conventional and oxy-fuel conditions[J].Energy Procedia,2013,37:1377-1388.
• [5] 魏强，唐跃刚，李薇薇，等.煤中有机硫结构研究进展[J].煤炭学报，2015,40(8):1911-1923.WEI Qiang,TANG Yuegang,LI Weiwei,et al.Research advances on organic sulfur structures in coal[J].Journal of China Coal Society,2015,40(8):1911-1923.
• [6] 邹碧海，石晨飞，谯自强，等.煤的燃前脱硫技术发展趋势研究[J].产业与科技论坛，2018,17(18):48-50.ZOU Bihai,SHI Chenfei,JIAO Ziqiang,et al.Research ondevelopment trend of coal desulfurization technology before combustion[J].Industrial & Science Tribune,2018,17(18):48-50.
• [7] ZHANG Dongke,YANI Setyawati.Sulphur transformation during pyrolysis of an Australian lignite[J].Proceedings of the Combustion Institute,2011,33:1747-1753.
• [8] WANG Xinlong,GUO Huiqing,LIU Fenrong,et al.Effects of CO2 on sulfur removal and its release behavior during coal pyrolysis[J].Fuel,2016,165:484-489.
• [9] LIU Shuai,WEI Mengmeng,QIAO Yu,et al.Release of organic sulfur as sulfur-containing gases during low temperature pyrolysis of sewage sludge[J].Proceedings of the Combustion Institute,2015,35(3):2767-2775.
• [10] 李丽君，姜曙，李丽萍.不同气氛下煤粉燃烧硫氮污染物析出的特性研究[J].电站系统工程，2015,31(5):23-25,28.LI Lijun,JIANG Shu,LI Liping.Study oncharacteristics of sulfur and nitrogen pollutants from coal combustion under different atmosphere[J].Power System Engineering,2015,31(5):23-25,28.
• [11] 王利花，王素珍，赵炜.还原性气氛下煤中硫热解迁移规律(Ⅰ)H2和N2气氛下煤中硫热解释出规律的比较[J].煤炭转化，2009,32(1):10-13.WANG Lihua,WANG Suzhen,ZHAO Wei.Migration of sulfur in coal under the reductive pyrolysis part(Ⅰ)comparison of experimental resultis under H2 and N2 atmosphere[J].Coal Conversion,2009,32(1):10-13.
• [12] 吕清刚，朱建国，牛天钰，等.煤粉高温预热方法：CN101158468[P].2008-04-09.LYU Qinggang,ZHU Jianguo,NIU Tianyu,et al.High-temperature preheating method for pulverized coal:CN101158468[P].2008-04-09.
• [13] 欧阳子区，朱建国，吕清刚，等.无烟煤粉经循环流化床预热后燃烧特性及NOx排放特性实验研究[J].中国电机工程学报，2014,34(11):1748-1754.OUYANG Ziqu,ZHU Jianguo,LYU Qinggang,et al.Experimental study on combustion and NOx emission of pulverized anthracite coal preheated by a circulating fluidized bed[J].Processdings of the CSEE,2014,34(11):1748-1754.
• [14] 张毅，朱建国，吕清刚，等.烟煤循环流化床预热特性实验[J].中国粉体技术，2019,25(6):7-11.ZHANG Yi,ZHU Jianguo,LYU Qinggang,et al.Experiment on preheating characteristics of bituminous coal by circulating fluidized bed[J].China Powder Science and Technology,2019,25(6):7-11.
• [15] 朱书骏.煤/半焦富氧预热燃烧特性及NOx排放特性试验研究[D].北京：中国科学院大学(中国科学院工程热物理研究所),2019.ZHU Shujun.Experimentalstudy on preheating oxy-fuel combustion and NOx emission characteristics of coal/char[D].Beijing:University of Chinese Academy of Sciences(Institute of Engineering Thermophysics Chinese Academy of Sciences),2019.
• [16] 马玲玲，秦志宏，张露，等.煤有机硫分析中XPS分峰拟合方法及参数设置[J].燃料化学学报，2014,42(3):277-283.MA Lingling,QIN Zhihong,ZHANG Lu,et al.Peak fitting methods and parameter settings in XPS analysis for organic sulfur in coal[J].Journal of Fuel Chemistry and Technology,2014,42(3):277-283.
• [17] 陈鹏.鉴定煤中有机硫类型的方法研究[J].煤炭学报，2000,25(S1):174-181.CHEN Peng.Study on determination of the forms of organic sulfur in coals[J].Journal of China Coal Society,2000,25(S1):174-181.
• [18] KOZOWSKI M.XPS study of reductively and non-reductivelymodified coals[J].Fuel,2004,83(3):259-265.
• [19] 朱应军，郑明东.炼焦用精煤中硫形态的XPS分析方法研究[J].选煤技术，2010(3):55-57.ZHU Yingjun,ZHENG Mingdong.Study on the analysis method of using sulfur forms in XPS coking coal[J].Coal Preparation Technology,2010(3):55-57.
• [20] LI Dong,ZHANG Cheng,TAN Peng,et al.Evolution of organic sulfur in the thermal upgrading process of Shengli lignite[J].Energy Fuels,2013,27:3446-3453.
• [21] LIU Fengrong,XIE Lili,GUO Huiqing,et al.Sulfur release and transformation behaviours of sulfur-containing model compounds during pyrolysis under oxidative atmosphere[J].Fuel,2014,115:596-599.