吉化油泥热解燃烧特性及动力学研究  

Thermal and kinetic study into pyrolysis and combustion of Jihua oil sludge

作　　者：王斌[1] 马跃[1] 岳长涛[1] 李术元[1] 唐勋[2] 常少英[2] WANG Bin;MA Yue;YUE Changtao;LI Shuyuan;TANG Xun;CHANG Shaoying(College of Science,China University of Petroleum-Beijing,Beijing 102249,China;Beijing GuodianLongyuan Environmental Protection Engineering Co.,Ltd.,Beijing 100039,China)

机构地区：[1]中国石油大学(北京)理学院,北京102249 [2]北京国电龙源环保工程有限公司,北京100039

出　　处：《石油科学通报》2021年第2期292-301,共10页Petroleum Science Bulletin

基　　金：大型燃煤锅炉处置污泥废弃物关键技术研究项目(KH-2018-06);大型燃煤锅炉资源化处置多种污泥固废关键技术研究及工程示范(GJNY2030XDXM-19-10.2)联合资助。

摘　　要：本文对吉化集团炼厂油泥进行基本性质分析、热重实验、热解和燃烧特性分析及动力学研究。结果表明,吉化油泥含油率为14.74%,含水率为72.82%。通过设置5、10、15、20、30℃/min共5组升温速率,得到热解和燃烧特性及动力学参数。油泥热解过程由挥发阶段及热解阶段组成,主要分为有机物的挥发以及少量易反应杂原子的热解、少量有机物挥发以及重组分热解两个过程。燃烧过程由挥发燃烧阶段与固定碳燃烧阶段构成,第一阶段为小分子有机物挥发燃烧,第二阶段为大分子有机物挥发热解进而燃烧,以及氧气扩散至坩埚内部发生固定碳燃烧。燃烧受升温速率影响较小,活化能不会因有机物消耗而明显增长。而且在燃烧过程中,挥发燃烧比热解挥发难发生,固定碳燃烧比热解容易发生。本文将油泥热解过程中存在相互影响的挥发和热解阶段拆解,利用Coats-Redfern、DAEM两种模型计算动力学参数,并与正常处理方法结果对比,优化动力学计算过程。DAEM模型挥发阶段活化能为61.82~81.05 kJ/mol,热解阶段活化能初始值为121.60 kJ/mol,随着转化率增大升高至237.07 kJ/mol。采用DAEM模型对油泥燃烧过程进行计算,燃烧活化能为73.95~110.93 kJ/mol,并与CoatsRedfern模型及热解过程相对比。Coats-Redfern模型假设反应单一,所得为某一区间的活化能均值,局限性较大;DAEM活化能模型的假设更加贴合油泥复杂的组成,方法更优。热解计算中分峰方法将热解阶段与挥发段分离,所得动力学数据更接近真实数据。研究表明DAEM模型准确性更好,可靠性更高。最后通过热重实验,研究吉化油泥热解及燃烧特性,并计算动力学参数,本文研究成果可以为油泥热解处理技术提供基出实验数据支撑。The basic properties,thermogravimetry,pyrolysis characteristics and combustion characteristics of Jihua oil sludge were determined in this manuscript.The results show that the oil content of Jihua sludge is 14.74%and the water content is 72.82%.The characteristics and kinetic parameters of pyrolysis and combustion were obtained by using thermogravimetric analysis with heating rates of 5,10,15,20 and 30℃/min.The pyrolysis process includes volatilization and pyrolysis stages.One is the volatilization of organic matter at 150~380℃,and a small proportion of reactive heteroatoms is pyrolyzed.The other is the pyrolysis process of a small amount of volatile heavy components at 380~550℃.The combustion process includes the volatilization combustion stage and the fixed carbon combustion stage.The combustion of Jihua sludge in the first stage is the volatile combustion of small molecular organics.The second stage is the volatile combustion of large molecular organics and pyrolysis combustion,and the diffusion of oxygen into the crucible to produce fixed carbon combustion.The effect of heating rate on combustion is small,and the activation energy will not increase significantly due to the consumption of organic matter.In addition,the volatilization combustion stage occurs with more difficulty than pyrolysis volatilization,and the fixed carbon combustion stage occurs more easily than pyrolysis.Two models,Coats-Redfern and the Distributed Activation Energy Model(DAEM),are used to calculate the kinetic parameters and the results are compared with those of normal treatment methods to optimize the calculation process.In the DAEM model,the activation energy of the volatilization stage is 61.82 to 81.05 kJ/mol,while the activation energy in the pyrolysis stage increased from 121.60 kJ/mol to 237.11 kJ/mol with the increase of conversion.When the DAEM model is applied to the calculation of the combustion process of oil sludge,the combustion activation energy ranges from 73.95 to 110.93 kJ/mol,which is then compared with Coats-

关 键 词：含油污泥 热解特性 热解动力学 燃烧特性 燃烧动力学 

分 类 号：X742[环境科学与工程—环境工程]