低阶煤热解及催化解聚动力学Kinetics of pyrolysis and catalytic depolymerization of low rank coal
吕婧,王俊丽,张进,李淑英,李金萍,赵强,郝晓刚,赵建国
LYU Jing,WANG Junli,ZHANG Jin,LI Shuying,LI Jinping,ZHAO Qiang,HAO Xiaogang,ZHAO Jianguo
摘要(Abstract):
低阶煤热解及催化解聚过程的精确描述是反应器多尺度模拟、反应器设计和放大的基础和关键。因此,基于低阶煤非等温热解试验及催化裂解试验,提出了一种简单、精密度高且易与反应器多尺度模拟耦合的低阶煤解聚模型,并将该模型与反应器模拟中采用最多的一步反应动力学模型和分布活化能模型(DAEM)进行对比。最后验证了4种催化剂催化低阶煤的催化裂解试验数据对该模型的适应性。结果表明,提出的新模型能很好地模拟低阶煤热解整个过程,相较一步反应模型和分布活化能模型(DAEM),该模型不仅简单,且模拟精度高很多,可达0.99以上。4种催化剂催化煤样的热解模拟结果表明,本模型能很好模拟催化剂催化解聚过程,证明本模型简单、模拟精度高,且适用范围更广,适用性更高。因此提出的低阶煤解聚模型具有与多尺度反应器模拟相结合的显著优势,丰富了煤热解的动力学体系,也为反应器的模拟与放大提供了更简单、精确的方法。
The accurate description of low-rank coal pyrolysis and catalytic depolymerization process is the basis and key to multi-scale simulation, design and scale-up of reactors. Therefore, a simple, high-precision, and easily coupled low order coal depolymerization model with multi-scale reactor simulation was proposed based on the non-isothermal pyrolysis and catalytic pyrolysis experiments of low rank coal. The proposed model was compared with the one-step kinetic model and the distributed activation energy model(DAEM) which were most commonly used in reactor simulation. Finally, the adaptability of the model was verified by the experimental data of catalytic cracking of coal samples catalyzed by four catalysts. The results show that the new model proposed in this study can effectively simulate the whole process of low-rank coalpyrolysis. Compared with the one-step reaction model and the distribution activation energy model(DAEM), the model is not only simple, but also has a much higher simulation accuracy than those two models, reaching over 0.99. In addition, the pyrolysis simulation results of coal samples catalyzed by four catalysts show that the model can also simulate the catalytic depolymerization process very well, which further proves that the model is not only simple and accuracy, but also with wider range of application and higher applicability. It can be seen that the model proposed in this study has significant advantages in combining with multi-scale reactor simulation. The proposed model not only enrichs the kinetic system of coal pyrolysis, but also provides a simpler and more accurate method for the simulation and amplification of the reactor.
关键词(KeyWords):
煤;热解;热重分析;动力学;模型
coal;pyrolysis;thermogravimetry analysis;kinetic;model
基金项目(Foundation): 国家自然科学基金青年科学基金资助项目(21908135);; 山西省面上基金资助项目(201901D211435,201901D111308);; 山西省留学回国人员科技活动择优资助项目(2019-20);; 山西大同大学博士科研启动基金资助项目(2018-B-01,2020-B-02)
作者(Author):
吕婧,王俊丽,张进,李淑英,李金萍,赵强,郝晓刚,赵建国
LYU Jing,WANG Junli,ZHANG Jin,LI Shuying,LI Jinping,ZHAO Qiang,HAO Xiaogang,ZHAO Jianguo
DOI: 10.13226/j.issn.1006-6772.22083001
参考文献(References):
- [1] 刘壮,田宜水,胡二峰,等.低阶煤热解影响因素及其工艺技术研究进展[J].洁净煤技术,2021,27(1):50-59.LIU Zhuang,TIAN Yishui,HU Erfeng,et al.Research progress on influencing factors and technology of low-rank coal pyrolysis [J].Clean Coal Technology,2021,27(1):50-59.
- [2] 谢强,梁鼎成,刘金昌.高碱低阶煤热解及热解半焦研究进展[J].洁净煤技术,2020,26(1):83-89.XIE Qiang,LIANG Dingcheng,LIU Jinchang.Research progress on pyrolysis and pyrolysis of char of low-rank coal with high alkali [J].Clean Coal Technology,2020,26(1):83-89.
- [3] JIN H,FAN C,WEI W,et al.Evolution of pore structure and produced gases of zhundong coal particle during gasification in supercritical water [J].Journal of Supercritical Fluids,2018,136(6):102-109.
- [4] ZHANG X X,LU X X,XIAO M H,et al.Molecular reaction dynamics simulation of pyrolysis mechanism of typical bituminous coal via ReaxFF [J].Journal of Fuel Chemistry and Technology,2020,48(9):1035-1046.
- [5] 谢克昌.煤的结构与反应性[D].北京:科学出版社,2002.
- [6] 李勇,闫伦靖,李晓荣,等.酸/碱催化剂对低阶煤热解挥发分转化行为的作用机制研究[J].化工学报,2022,73(3):1173-1183.LI Yong,YAN Lunjing,LI Xiaorong,et al.Study on the mechanism of acid/base catalyst on the release behavior of volatiles during low rank coal pyrolysis [J].CIESC Journal,2022,73(3):1173-1183.
- [7] WANG C,HOU Y,BAI Z,et al.Exploring thermokinetic beha-viour of Jurassic coal during pyrolysis and oxidation[J].Journal of Thermal Analysis and Calorimetry,2022,147(2):1439-1453.
- [8] 魏利平,江国栋,古玉宽,等.五彩湾煤和吐鲁番煤热解动力学模型评估与应用[J].化工学报,2019,70(S2):275-286.WEI Liping,JIANG Guodong,GU Yukuan,et al.Evaluation and application of pyrolysis kinetic model of Wucaiwan coal and Tulufan coal [J].CIESC Journal,2019,70(S2):275-286.
- [9] SAU D C,BANERJEE A,CHAKRAVARTY S,et al.Thermal decomposition behavior and kinetic study of Jamadoba coal and its density separated macerals:A non-isothermal approach [J].Advances in Chemical Engineering and Science,2021,11(3):203-227.
- [10] 白佳杰,梁丽彤,张忠林,等.基于CPD模型的低阶煤催化解聚过程模拟分析[J].化工学报,2019,70(S2):265-274.BAI Jiajie,LIANG Litong,ZHANG Zhonglin,et al.Simulation and analysis of catalytic depolymerization of low-rank coal by chemical percolation devolatilization model[J].CIESC Journal,2019,70(S2):265-274.
- [11] SHARMA R,MAY J,ALOBAID F,et al.Euler-Euler CFD simulation of the fuel reactor of a 1 MWth chemical-looping pilot plant:Influence of the drag models and specularity coefficient [J].Fuel,2017,200(15):435-446.
- [12] KLIMANEK A,ADAMCZYK W,KATELBACH-WOZNIAK A,et al.Towards a hybrid Eulerian-Lagrangian CFD modeling of coal gasification in a circulating fluidized bed reactor[J].Fuel,2015,152 (15):131-137.
- [13] LI S Y,SHU Z,WANG J W.Multifluid modeling of coal pyrolysis in a coupled downer reactor[J].Journal of Analytical and Applied Pyrolysis,2021,159:105335-105338.
- [14] 杨景标,张彦文,蔡宁生.煤热解动力学的单一反应模型和分布活化能模型比较[J].热能动力工程,2010,25(3):301-305.YANG Jingbiao,ZHANG Yanwen,CAI Ningsheng.A comparison of a single reaction model with a distributed activation energy model based on coal pyrolysis kinetics[J].Journal of Engineering for Thermal Energy and Power,2010,25(3):301-305.
- [15] PITT G J.The kinetics of the evolution of volatile products fr-om coal[J].Fuel,1962,41:267-274.
- [16] CAPRARII S B,FILIPPIS P D,HERCE C,et al.Double-gaussian distributed activation energy model for coal devolatilization[J].Energy & Fuels,2012,26 (10):6153-6159.
- [17] JAIN A A,MEHRA A,RANADE V V.Processing of TGA data:Analysis of isoconversional and model fitting methods[J].Fuel,2016,165 (1):490-498.
- [18] SERIO M A,HAMBLEN D G,MARKHAM J R,et al.Kinetics of volatile product evolution in coal pyrolysis:Experiment and theory[J].Energy & Fuels,1987,1 (2):138-152.
- [19] WANG J L,LI P,LIANG L T,et al.Kinetics modeling of low-rank coal pyrolysis based on a three-gaussian distributed activation energy model (DAEM) reaction model[J].Energy & Fuels,2016,30(11):9693-9702.
- [20] PAN X,LIAN W H,YANG J X,et al.Downer reactor simulation and itsapplication on coal pyrolysis:A review[J].Carbon Resources Conversion,2022,5(1):35-51.
- [21] ZHANG Z,ZHOU H,WANG X,et al.Influence mechanism of water-soluble sodium on Zhundong coal pyrolysis[J].ACS Omega,2022,7(14):11862-11870.
- [22] FU Y,GUO Y H,ZHANG K X.Effect of three different catalysts (KCl,CaO,and Fe2O3) on the reactivity and mechanism of low-rank coal pyrolysis[J].Energy & Fuels,2016,30(3):2428-2433.