废弃推进剂改善无烟煤燃烧的热重-红外实验研究
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摘要
采用热重?红外(TG?FTIR)联用技术研究废弃推进剂与无烟煤混合试样的燃烧特性,以10 K·min~(-1)的加热速率将不同配比的推进剂?无烟煤混合物从室温加热至1300℃,分析热分析曲线获得热力学参数,采用Satava?Sestak积分法计算氧化反应动力学参数,并进行红外光谱的同步分析。结果表明,将废弃推进剂加入到无烟煤中,随着推进剂含量的上升,热分析曲线向低温区移动,无烟煤固定碳的着火温度由560℃降至383℃,燃尽温度由676℃降至616℃,综合燃烧特性指数由2.36E?8升至1.27E?7,反应表观活化能由165.6 kJ·mol~(-1)降低至91.2 kJ·mol~(-1);红外光谱结果显示,随着推进剂掺混量增加,热氧化标志性气体产物CO_2、CO波峰向低温区移动,表明废弃推进剂对无烟煤的氧化和点火燃烧过程具有促进作用。
Large amount of solid propellants would be discarded each year due to failure,and the recycling/reuse of the waste propellants is important for energy conservation and environmental protection. On the basis of thermogravimetry?differential scanning calorimetry,coupled with Fourier transform infrared spectroscopy(TG?DSC?FTIR)technique,the solid?state reaction properties of the mixtures of propellant and anthracite has been investigated with details. Propellant?anthracite blends at different ratios were heated up to 1300 ℃ at 10 K·min~(-1) heating rate in air,and the FTIR spectra have been obtained synchronously. The results show that as the propellant content increases,the decomposition process moves to the low temperature zone. The ignition temperature of anthracite decreases from 560 ℃ to 383 ℃. The burn out temperature decreases from 676 ℃ to 616 ℃,and the comprehensive combustion characteristic index increases from 2.36 E?8 to 1.27 E?7. Moreover,the apparent activation energy of the fixed carbon combustion part decreases from 165.6 to 91.2 kJ·mol~(-1). The FTIR spectra show that as the propellant content increases,the release of CO_2 and CO as the major gaseous products of anthracite oxidation,move to the low temperature zone. It indicates that the waste propellants can greatly enhance the oxidation process,ignition and combustion of anthracite.
Large amount of solid propellants would be discarded each year due to failure,and the recycling/reuse of the waste propellants is important for energy conservation and environmental protection. On the basis of thermogravimetry?differential scanning calorimetry,coupled with Fourier transform infrared spectroscopy(TG?DSC?FTIR)technique,the solid?state reaction properties of the mixtures of propellant and anthracite has been investigated with details. Propellant?anthracite blends at different ratios were heated up to 1300 ℃ at 10 K·min~(-1) heating rate in air,and the FTIR spectra have been obtained synchronously. The results show that as the propellant content increases,the decomposition process moves to the low temperature zone. The ignition temperature of anthracite decreases from 560 ℃ to 383 ℃. The burn out temperature decreases from 676 ℃ to 616 ℃,and the comprehensive combustion characteristic index increases from 2.36 E?8 to 1.27 E?7. Moreover,the apparent activation energy of the fixed carbon combustion part decreases from 165.6 to 91.2 kJ·mol~(-1). The FTIR spectra show that as the propellant content increases,the release of CO_2 and CO as the major gaseous products of anthracite oxidation,move to the low temperature zone. It indicates that the waste propellants can greatly enhance the oxidation process,ignition and combustion of anthracite.
引文
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[2]于潜.废弃固体推进剂主要组分的分离及回收研究[D].太原:中北大学,2010.YU Qian.Research on separating and recycling main solid components from obsolete propellant[D].Taiyuan:North University of China,2010.
[3]李金龙,袁俊明,刘玉存,等.端羟基聚丁二烯基聚氨酯的溶胀试验研究[J].中国胶黏剂,2015,24(10):14-22.LI Jin?long,YUAN Jun?ming,LIU Yu?cun,et al.Study on swelling experiment of hydroxyl?terminated polybutadiene based polyurethane[J].China Adhesives,2015,24(10):14-22.
[4]李立远,张丽华,王鹏,等.废弃丁羟推进剂的处理与再利用研究进展[J].河南化工,2010,27(12):3-7.LI Li?yuan,ZHANG Li?hua,WANG Peng,et al.Research progress on treatment and reuse of waste butylated?hydroxy propellant[J].Henan Chemical Industry,2010,27(12):3-7.
[5]李彦丽,左国平,白兴德,等.报废固体发动机的绿色销毁技术研究[C]//全国危险物质与安全应急技术研讨会论文集,重庆,2011:799-807.LI Yan?li,ZUO Guo?ping,BAI Xing?de,et al.Study on Green Destruction Technology of Obsolete Solid Motor[C]//Proceedings of National Symposium on Hazardous Substances and Safety Emergency Technology,Chongqing,2011:799-807.
[6]顾建良.废弃含能材料的资源化利用[J].江苏大学学报(自然科学版),2004,52(2):180-184.GU Jian?liang.Resource utilization of waste energetic materials[J].Journal of Jiangsu University(Natural Science Edition),2004,52(2):180-184.
[7]李本强,李东升,岳慧娟,等.废弃丁羟推进剂的处理与回收利用方法研究[J].飞航导弹,2018,49(10):90-94.LI Ben?qiang,LI Dong?sheng,YUE Hui?juan,et al.Study on treatment and recycling methods of abandoned butyl hydroxyl propellant[J].Aerodynamic Missile Journal,2018,49(10):90-94.
[8]王军,蔺向阳,潘仁明,等.废弃复合推进剂组分回收与资源化利用[J].材料导报,2011,25(12):69-72.WANG Jun,LIN Xiang?yang,PAN Ren?ming,et al.Recycling component and utilization of abandoned composite propellant[J].Materials Review,2011,25(12):69-72.
[9]叶大钧.能源概论[M].北京:清华大学出版社,1990:54-55.YE Da?jun.Introduction to Energy[M].Beijing:Tsinghua University Press,1990:54-55.
[10]BUCKLEY S G,ROBINSON A L,BAXTER L L.Energetics to energy:combustion and environmental considerations surrounding the reapplication of energetic materials as boiler fuels[J].Symposium on Combustion,1998,27(1):1317-1325.
[11]Materazzi S.Thermogravimetry?Infrared spectroscopy(TG?FT?IR)coupled analysis[J].Applied Spectroscopy Review,1997,32(4):385-404.
[12]李龙津,邹建新,曾小勤.纳米镁基储氢材料对AP热分解性能的影响[J].稀有金属材料与工程,2013,42(7):1445-1449.LI Long?Jin,ZOU Jian?xin,ZENG Xiao?qin.Effect of nano?magnesium based hydrogen storage materials on thermal decomposition of ammonium perchlorate[J].Rare Metal Materials And Engineering,2013,42(7):1445-1449.
[13]张德元,杜廷发,童乙青.端羟基聚丁二烯(H T P B)的热分解研究[J].推进技术,1987,10(5):52-57.ZHANG De?yuan,DU Ting?fa,TONG Yi?qing.The study of thermal decomposition of hydroxy terminated polybutadiene(HTPB)[J].Journal of Propulsion Technology,1987,10(5):52-57.
[14]王架皓,刘建忠,周禹男.微米级铝颗粒热氧化特性[J].含能材料,2017,25(8):667-674.WANG Jia?hao,LIU Jian?zhong,ZHOU Yu?nan.Thermal Reaction characterization of micron?sized aluminum powders in air[J].Chinese Journal of Enengetic Materials(Hanneng Cailiao),2017,25(8):667-674.
[15]何翔,刘建忠,杨雨濛.基于热重红外联用技术的不同煤种燃烧特性研究[J].热力发电,2016,45(11):29-35.HE Xiang,LIU Jian?zhong,YANG Yu?meng.Combustion characterisitcs of different coals based on TG?DSC?FTIR coupled technology[J].Thermal Power Generation,2016,45(11):29-35.
[16]LIQ Z,ZHAO CS,CHEN XP,et al.Comparison of pulverized coal combustion in air and in O2/CO2mixtures by thermo?gravimerric analysis[J].Journal of Analytical and Applied Pyrolysis,2009,85(1/2):521-528.
[17]煤混生物质的富氧燃烧特性及污染物排放特性研究[D].重庆:重庆大学,2015.Study on oxy?fuel combustion characteristic and pollutant emission of coal blent with biomass[D].Chongqing:Chongq?ing University,2015.
[18]胡荣祖,史启祯.热分析动力学[M].北京:科学出版社,2001:127-131.HU Rong?zu,SHI Qi?zhen.Thermal analysis kinetics[M].Bei?jing:Science Press,2001:127-131.
[19]Kissinger D E.Reaction kinetic in differential thermal analysis[J].Analytical Chemistry,1957,29(11):1702-1706.
[20]周俊虎,平传娟,杨卫娟,等.用热重红外光谱联用技术研究混煤热解特性[J].燃料化学学报,2005,32(6):658-662.ZHOU Jun?hu,PING Chuan?juan,YANG Wei?juan.Experimental study on the pyrolysis characteristic of coal blends us?ing TGA?FTIR[J].Journal Of Fuel Chemistry And Technology,2005,32(6):658-662.