Fe_2O_3对污泥热解特性及部分NO_x前驱物转化规律的影响
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摘要
使用热重-质谱联用(TG-MS)技术研究Fe_2O_3对污泥热解特性以及部分NOx前驱物转化规律的影响,根据TG与DTG曲线,分别求出不同Fe_2O_3含量的污泥在热解过程中的挥发分析出指数Rv.结果表明,Fe_2O_3的加入会抑制污泥热解低温段与中温段挥发分的析出,但是在高温段,由于Fe4N等含Fe化合物的分解,挥发分析出随着Fe_2O_3含量增加而增大;在Fe_2O_3与污泥质量比为0、0.1、0.2和0.3的工况下,随着Fe_2O_3的含量增加,NOx前驱物的释放量先减少后增加,并且在Fe_2O_3与污泥质量比为0.2时,Fe_2O_3对NOx前驱物抑制效果最好.
The influence of Fe_2O_3 on sludge pyrolysis characteristics and partial transformation mechanisms of NO_x precursors was investigated by TG-MS.The devolatilization indexes of sludge for different Fe_2O_3 contents were computed based on TG and DTG curves in the pyrolysis process.Results indicate that devolatilization is generally suppressed by the addition of Fe_2O_3 in the sludge pyrolysis process at low and medium temperatures,while it increases with the increase of Fe_2O_3 content at high temperatures due to the decomposition of Fe_4N and other Fe related compounds.Based on four Fe_2O_3 to sludge mass ratios,i.e.,0,0.1,0.2 and 0.3,the release of NO_x precursors firstly decreases and then increases with the increase of Fe_2O_3.Most effective suppression of Fe_2O_3 on NO_x precursors will be achieved when the mass ratio of Fe_2O_3 to sludge is 0.2.
The influence of Fe_2O_3 on sludge pyrolysis characteristics and partial transformation mechanisms of NO_x precursors was investigated by TG-MS.The devolatilization indexes of sludge for different Fe_2O_3 contents were computed based on TG and DTG curves in the pyrolysis process.Results indicate that devolatilization is generally suppressed by the addition of Fe_2O_3 in the sludge pyrolysis process at low and medium temperatures,while it increases with the increase of Fe_2O_3 content at high temperatures due to the decomposition of Fe_4N and other Fe related compounds.Based on four Fe_2O_3 to sludge mass ratios,i.e.,0,0.1,0.2 and 0.3,the release of NO_x precursors firstly decreases and then increases with the increase of Fe_2O_3.Most effective suppression of Fe_2O_3 on NO_x precursors will be achieved when the mass ratio of Fe_2O_3 to sludge is 0.2.
引文
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[17]Liu Xu.Effects of minerals on the release of nitrogen species from anthracite[J].Energy Sources Part A Recovery Utilization&Environmental Effects,2007,29(4):313-327.
[18]Qiang Z,Liu H,Peng L,et al.Pyrolysis characteristics and kinetic analysis of different dewatered sludge[J].Bioresource Technology,2014,170(5):325-330.
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[21]陈应泉,朱波,王贤华,等.生物质热解过程中焦炭物化结构演变特性[J].太阳能学报,2012,33(8):1267-1272.Chen Yingquan,Zhu Bo,Wang Xianhua,et al.Evolution characteristics of coke in the process of biomass pyrolysis[J].Acta Energiae Solaris Sinica,2012,33(8):1267-1272(in Chinese).
[22]陈建原,孙学信.煤的挥发分释放特性指数及燃烧特性指数的确定[J].动力工程学报,1987(5):13-18.Chen Jianyuan,Sun Xuexin.Determination of the devolatilization index and combustion characteristic index of pulverized coals[J].Journal of Chinese Society of Power Engineering,1987(5):13-18(in Chinese).
[23]张军.微波热解污水污泥过程中氮转化途径及调控策略[D].哈尔滨:哈尔滨工业大学市政环境工程学院,2013.Zhang Jun.Nitrogen Conversion and Control of Nitrogen-Containing Compounds During Microwave Pyrolysis of Sewage Sludge[D].Harbin:School of Municipality&Environment Engineering,Harbin Institute of Technology,2013(in Chinese).
[24]H?m?l?inen Jouni P,Aho Martti J.Effect of fuel composition on the conversion of volatile solid fue I-N to N2Oand NO[J].Fuel,1995,74(12):1922-1924.
[25]徐秀峰,顾永达.铁催化剂对煤热解过程中氮元素迁移的影响[J].燃料化学学报,1998,26(1):18-23.Xu Xiufeng,Gu Yongda.Effect of iron addition on transformation of nitrogen during coal pyrolysis[J].Journal of Fuel Chemistry,1998,26(1):18-23(in Chinese).
[26]Hansson K M,Samuelsson J,Tullin C,et al.Formation of HNCO,HCN,and NH3 from the pyrolysis of bark and nitrogen-containing model compounds[J].Combustion&Flame,2004,137(3):265-277.
[27]谭涛.污水污泥含氮模型化合物的构建及热解过程中氮转化途径研究[D].哈尔滨:哈尔滨工业大学市政环境过程学院,2011.Tan Tao.Construction of Nitrogen Model Compounds of the Sewage Sludge and Research of Nitrogen Transformation in the Process of Pyrolysis[D].Harbin:School of Municipal and Environmental Engineering,Harbin Institute of Technology,2011(in Chinese).
[28]周浩生,陆继东.燃煤流化床加入氧化钙的氮转化机理[J].工程热物理学报,2000,21(5):647-651.Zhou Haosheng,Lu Jidong.Nitrogen conversion in fluidized bed combustion of coal with limestone addition[J].Journal of Engineering Thermophysics,2000,21(5):647-651(in Chinese).
[2]Kim Y,Parker W.A technical and economic evaluation of the pyrolysis of sewage sludge for the production of bio-oil[J].Bioresource Technology,2008,99(5):1409-1416.
[3]Ahlberg G,Gustafsson O,Wedel P.Leaching of metals from sewage sludge during one year and their relationship to particle size[J].Environmental Pollution,2006,144(2):545-553.
[4]邹绍文,张树清,王玉军,等.中国城市污泥的性质和处置方式及土地利用前景[J].中国农学通报,2005,21(1):198-201.Zou Shaowen,Zhang Shuqing,Wang Yujun,et al Character and disposal of municipal sludge and its prospect of using on farmland and forestland in China[J]Chinese Agricultural Science Bulletin,2005,21(1):198-201(in Chinese).
[5]陆继东,华玉龙,孙路石,等.污水污泥的燃烧特性[J].燃烧科学与技术,2001,7(3):271-274.Lu Jidong,Hua Yulong,Sun Lushi,et al.Kinetics of sewage sludge combustion[J].Journal of Combustion Science and Technology,2001,7(3):271-274(in Chinese).
[6]李爱民,高宁博,李润东,等.NOx和SO2在污泥气化焚烧处理中的排放特性[J].燃烧科学与技术,2004,10(4):289-294.Li Aimin,Gao Ningbo,Li Rundong,et al.NOx and SO2 emission characteristics of sewage sludge in gasified incineration treatment[J].Journal of Combustion Science and Technology,2004,10(4):289-294(in Chinese).
[7]Gibbs P A,Chambers B J,Chaudri A M,et al.Initial results from a long-term,multi-site field study of the effects on soil fertility and microbial activity of sludge cakes containing heavy metals[J].Soil Use&Management,2006,22(1):11-21.
[8]邓文义,严建华,李晓东,等.造纸污泥干化及焚烧系统污染物排放特性[J].燃烧科学与技术,2009,14(6):545-550.Deng Wenyi,Yan Jianhua,Li Xiaodong,et al.Pollutants emission characteristics of paper mill sludge drying and combustion system[J].Journal of Combustion Science and Technology,2009,14(6):545-550(in Chinese).
[9]曾武勇,金晶,张号,等.两种典型污泥热解特性及动力学机理[J].燃烧科学与技术,2013,19(6):544-548.Zeng Wuyong,Jin Jing,Zhang Hao,et al.Pyrolysis characteristics and kinetics mechanism of two typical sludge[J].Journal of Combustion Science and Technology,2013,19(6):544-548(in Chinese).
[10]李海英,张书廷,赵新华.城市污水污泥热解实验及产物特性[J].天津大学学报,2006,39(6):739-744.Li Haiying,Zhang Shuting,Zhao Xinhua.Pyrolysis experiment of municipal sewage sludge and characteristics of fractions[J].Journal of Tianjin University,2006,39(6):739-744(in Chinese).
[11]贾相如,金保升,肖睿,等.污水污泥热解和燃烧特性的实验研究[J].锅炉技术,2006,36(6):39-42.Jia Xiangru,Jin Baosheng,Xiao Rui,et al.An experimental study on the pyrolysis and combustion properties of sewage sludge[J].Boiler Technology,2006,36(6):39-42(in Chinese).
[12]王宗华,张军营,赵永椿,等.污泥热解和气化过程中NOx前驱物的释放特性[J].华中科技大学学报:自然科学版,2011,39(1):98-101.Wang Zonghua,Zhang Junying,Zhao Yongchun,et al.Release features of NOx precursors during the pyrolysis and gasification of sewadge sludge[J].Journal of Huazhong University of Science and Technology:Natural Science Edition,2011,39(1):98-101(in Chinese).
[13]谢克昌,凌大奇.煤的气化动力学和矿物质的作用[M].太原:山西科学教育出版社,1990.Xie Kechang,Ling Daqi.Gasification Kinetics of Coal and Effects of Minerals[M].Taiyuan:Shanxi Science Education Publisher,1990(in Chinese).
[14]王美君,杨会民,何秀风,等.铁基矿物质对西部煤热解特性的影响[J].中国矿业大学学报,2010,39(3):426-430.Wang Meijun,Yang Huimin,He Xiufeng,et al.Effect of Fe-based minerals on pyrolysis characteristics of coal from western China[J].Journal of China University of Mining&Technology,2010,39(3):426-430(in Chinese).
[15]Xu C,Tsubouchi N,Hashimoto H,et al.Catalytic decomposition of ammonia gas with metal cations present naturally in low rank coals[J].Fuel,2005,84(S14/15):1957-1967.
[16]Xu C,Donald J,Byambajav E,et al.Recent advances in catalysts for hot-gas removal of tar and NH3 from biomass gasification[J].Fuel,2010,89(8):1784-1795.
[17]Liu Xu.Effects of minerals on the release of nitrogen species from anthracite[J].Energy Sources Part A Recovery Utilization&Environmental Effects,2007,29(4):313-327.
[18]Qiang Z,Liu H,Peng L,et al.Pyrolysis characteristics and kinetic analysis of different dewatered sludge[J].Bioresource Technology,2014,170(5):325-330.
[19]崔燕妮,张军,田禹.矿物质对污水污泥微波热解过程中NOx前驱物的影响研究[J].环境工程,2012(S2):481-485.Cui Yanni,Zhang Jun,Tian Yu.The effect of mineral matter on the formation of NOx precursors during microwave-induced pyrolysis of sewage sludge[J].Environmental Engineering,2012(S2):481-485(in Chinese).
[20]何品晶,邵立明,陈正夫,等.污水厂污泥低温热化学转化过程机理研究[J].中国环境科学,1998,18(1):39-42.He Pinjing,Shao Liming,Chen Zhengfu,et al.Study on the mechanism of a low-temperature thermo-chemical conversion process for sewage sludge[J].China Environmental Science,1998,18(1):39-42(in Chinese).
[21]陈应泉,朱波,王贤华,等.生物质热解过程中焦炭物化结构演变特性[J].太阳能学报,2012,33(8):1267-1272.Chen Yingquan,Zhu Bo,Wang Xianhua,et al.Evolution characteristics of coke in the process of biomass pyrolysis[J].Acta Energiae Solaris Sinica,2012,33(8):1267-1272(in Chinese).
[22]陈建原,孙学信.煤的挥发分释放特性指数及燃烧特性指数的确定[J].动力工程学报,1987(5):13-18.Chen Jianyuan,Sun Xuexin.Determination of the devolatilization index and combustion characteristic index of pulverized coals[J].Journal of Chinese Society of Power Engineering,1987(5):13-18(in Chinese).
[23]张军.微波热解污水污泥过程中氮转化途径及调控策略[D].哈尔滨:哈尔滨工业大学市政环境工程学院,2013.Zhang Jun.Nitrogen Conversion and Control of Nitrogen-Containing Compounds During Microwave Pyrolysis of Sewage Sludge[D].Harbin:School of Municipality&Environment Engineering,Harbin Institute of Technology,2013(in Chinese).
[24]H?m?l?inen Jouni P,Aho Martti J.Effect of fuel composition on the conversion of volatile solid fue I-N to N2Oand NO[J].Fuel,1995,74(12):1922-1924.
[25]徐秀峰,顾永达.铁催化剂对煤热解过程中氮元素迁移的影响[J].燃料化学学报,1998,26(1):18-23.Xu Xiufeng,Gu Yongda.Effect of iron addition on transformation of nitrogen during coal pyrolysis[J].Journal of Fuel Chemistry,1998,26(1):18-23(in Chinese).
[26]Hansson K M,Samuelsson J,Tullin C,et al.Formation of HNCO,HCN,and NH3 from the pyrolysis of bark and nitrogen-containing model compounds[J].Combustion&Flame,2004,137(3):265-277.
[27]谭涛.污水污泥含氮模型化合物的构建及热解过程中氮转化途径研究[D].哈尔滨:哈尔滨工业大学市政环境过程学院,2011.Tan Tao.Construction of Nitrogen Model Compounds of the Sewage Sludge and Research of Nitrogen Transformation in the Process of Pyrolysis[D].Harbin:School of Municipal and Environmental Engineering,Harbin Institute of Technology,2011(in Chinese).
[28]周浩生,陆继东.燃煤流化床加入氧化钙的氮转化机理[J].工程热物理学报,2000,21(5):647-651.Zhou Haosheng,Lu Jidong.Nitrogen conversion in fluidized bed combustion of coal with limestone addition[J].Journal of Engineering Thermophysics,2000,21(5):647-651(in Chinese).