正癸烷与二甲苯在超临界压力下的热裂解

doi:10.3866/PKU.WHXB201302061

Abstract

Abstract:

The pyrolysis of n-decane and dimethylbenzene under supercritical pressure was studied using a continuous flow reactor. Samples were heated to a temperature of 650, 700, or 750 ℃ under a pressure of 4 MPa without oxygen. n-Decane pyrolyzed more easily than dimethylbenzene. We analyzed gaseous products by online gas chromatography, and liquid products by gas chromatography-mass spectrometry, allowing us to calculate the cracking gas yield and cracking conversion of these systems. A quantum chemistry computation was used to evaluate the binding energies of C－C and C－H bonds in n-decane and dimethylbenzene. Both experimental and theoretical results were also used to analyze the cracking reactivity of these species. Analysis of the components in the products indicated that the main products of n-decane were C₁-C₃ hydrocarbons and hydrogen, whereas ethylbenzene, toluene and other aromatic compounds were the main products of dimethylbezene after pyrolysis. Binding energy calculations showed that both C－C and C－H bonds in n-decane possessed lower binding energies than those in dimethylbezene, and a C－C bond was the weakest. In dimethylbenzene, a C－H bond in the methyl groups was the weakest, and its binding energy was much smaller than those of the C－C and CH bonds in the benzene ring. Therefore, the main reactions in the cracking process of n-decane are breakage of a C－C bond and dehydrogenation. However, the cracking process in dimethylbenzene mainly involves the fracture and dehydrogenation of methyl groups. The theoretical calculations reasonably explained the experimental phenomena.

Key words: n-Decane, Dimethylbenzene, Supercritical condition, Pyrolysis, Binding energy

MSC2000:

O643

ZHOU Hao, MAO Jia, WANG Bi-Yao, ZHU Quan, WANG Jian-Li, LI Xiang-Yuan. Pyrolysis of n-Decane and Dimethylbenzene under Supercritical Pressure[J].Acta Phys. -Chim. Sin., 2013, 29(04): 689-694.

References

(1) Dagaut, P.; Bakali, E. A.; Ristori, A. Fuel 2006, 85, 944. doi: 10.1016/j.fuel.2005.10.008
(2) Humer, S.; Frassoldati, A.; Granata, S.; Faravelli, T.; Ranzi, E.;Seiser, R.; Seshadri, K. Proc. Combust. Inst. 2007, 31, 393. doi: 10.1016/j.proci.2006.08.008
(3) Westbrook, C. K.; Pitz,W. J.; Herbinet, O.; Curran, H. J.; Silke,E. J. Combust. Flame 2009, 156, 181. doi: 10.1016/j.combustflame.2008.07.014
(4) Olchanski, E.; Burcat, A. Int. J. Chem. Kinet. 2006, 38, 703.
(5) Bikas, G.; Peters, N. Combust. Flame 2001, 126, 1456. doi: 10.1016/S0010-2180(01)00254-1
(6) Nehse, M.;Warnatz, J.; Chevalier, C. Symposium (International)on Combustion 1996, 26, 773. doi: 10.1016/S0082-0784(96)80286-4
(7) Battin-Leclerc, F.; Fournet, R.; Glaude, P. A.; Judenherc, B.;Warth, V.; Come, G. M.; Scacchi, G. Proc. Combust. Inst. 2000,28, 1597. doi: 10.1016/S0082-0784(00)80557-3
(8) Zeppieri, S. P.; Klotz, S. D.; Dryer, F. L. Proc. Combust. Inst.2000, 28, 1587. doi: 10.1016/S0082-0784(00)80556-1
(9) Yin, K. L.;Wu, G. Y.; Chen, Z. L. Acta Petr. Sin. 2006, 17, 77.[殷开梁, 邬国英, 陈正隆. 石油学报, 2006, 17, 77.]
(10) Wang, Z.W.; Zhang, X.W.; Mi, Z. T.; Hao,W. H. Petrochem.Technol. 2005, 34, 518. [王占卫, 张香文, 米镇涛, 郝伟华.石油化工, 2005, 34, 518.]
(11) Jiao, Y.; Li, J.;Wang, J. B.;Wang, J. L.; Zhu, Q.; Chen, Y. Q.;Li, X. Y. Acta Phys. -Chim. Sin. 2011, 27, 1061. [焦毅,李军, 王静波, 王健礼, 朱权, 陈耀强, 李象远. 物理化学学报, 2011, 27, 1061.] doi: 10.3866/PKU.WHXB20110437
(12) Pitz,W. J.; Cernansky, N. P.; Dryer, F. L.; Egolfopoulos, F. N.;Farrell, J. T.; Friend, D. G.; Pitsch, H. In SAE 2007 TransactionsJournal of Passenger Cars-Mechanical Systems, SEA Paper2007-01-0175, 2007.
(13) Farrell, J. T.; Cernansky, N. P.; Dryer, F. L.; Friend, D. G.;Hergart, C. A.; Law, C. K.; McDavid, R. M.; Mueller, C. J.;Patel, A. K.; Pitsch, H. In 2007 SAE International Congress,SEA Paper 2007-01-0201, Detroit, MI, 2007.
(14) Sivaramakrishnan, R.; Tranter, R. S.; Brezinsky, K. J. Phys.Chem. A 2006, 110, 9388. doi: 10.1021/jp060820j
(15) Zhang, L. D.; Cai, J. H.; Zhang, T. C.; Qi, F. Combust. Flame2010, 157, 1686. doi: 10.1016/j.combustflame.2010.04.002
(16) Lannuzel, F.; Bounaceur, R.; Michels, R.; Scacchi, G.;Marquaire, P. J. Anal. Appl. Pyrolysis 2010, 87, 236. doi: 10.1016/j.jaap.2010.01.001
(17) Richter, H.; Howard, J. B. Prog. Energy Combust. Sci. 2000, 26,565. doi: 10.1016/S0360-1285(00)00009-5
(18) Guo, L. Z. Study on Stability and Endothermic Capability ofHydrocarbon Fuels. MS Dissertation, Tianjin University,Tianjin, 2005. [郭兰珍. 碳氢化合物安定性和吸热性能的研究[D]. 天津: 天津大学, 2005.]
(19) Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996,77, 3865. doi: 10.1103/PhysRevLett.77.3865
(20) Becke, A. D. J. Chem. Phys. 1993, 98, 5648. doi: 10.1063/1.464913
(21) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 03[CP]; Gaussian Inc.: Pittsburgh, PA, 2003.

[1]	Haixia Li,Jiwei Wang,Lifang Jiao,Zhanliang Tao,Jing Liang. Spherical Nano-SnSb/C Composite as a High-Performance Anode Material for Sodium Ion Batteries [J]. Acta Physico-Chimica Sinica, 2020, 36(5): 1904017-0.
[2]	Yan-Shuang MENG,Chen WANG,Lei WANG,Gong-Rui WANG,Jun XIA,Fu-Liang ZHU,Yue ZHANG. Efficient Synthesis of Sulfur and Nitrogen Co-Doped Porous Carbon by Microwave-Assisted Pyrolysis of Ionic Liquid [J]. Acta Phys. -Chim. Sin., 2017, 33(9): 1915-1922.
[3]	Zhen YANG,Yuan-Hang HE. Pyrolysis of Octanitrocubane via Molecular Dynamics Simulations [J]. Acta Phys. -Chim. Sin., 2016, 32(4): 921-928.
[4]	Niao-Feng DU,Hong-Bo NING,Ze-Rong LI,Qi-Yi ZHANG,Xiang-Yuan LI. Kinetic Calculation and Modeling Study of 1, 3-Butadiene Pyrolysis [J]. Acta Phys. -Chim. Sin., 2016, 32(2): 453-464.
[5]	ZHOU Xiao-Ying, XI Wen-Hui, WEI Guang-Hong. Molecular Dynamics Simulations on the Binding of Fullerene to Amyloid-β Oligomers [J]. Acta Phys. -Chim. Sin., 2014, 30(8): 1587-1596.
[6]	JIN Hao, SUN Xiao-Dan, DONG Shu, WU Yi-Zhi, SUN Su-Hua, LIU Jie, ZHU Hui-Hong, YANG Guang, YI Xiao-Dong, FANG Wei-Ping. Influence of Cs Substitution on the Structural Properties and Catalytic Performance of Ni-H₃PW₁₂O₄₀/SiO₂ Catalysts [J]. Acta Phys. -Chim. Sin., 2014, 30(3): 527-534.
[7]	LIU Hai, DONG Xiao, HE Yuan-Hang. Reactive Molecular Dynamics Simulations of Carbon-Containing Clusters Formation during Pyrolysis of TNT [J]. Acta Phys. -Chim. Sin., 2014, 30(2): 232-240.
[8]	ZHONG Bei-Jing, YAO Tong, WEN Fei. Skeletal and Reduced Mechanisms of n-Decane Simplified with Eigenvalue Analysis [J]. Acta Phys. -Chim. Sin., 2014, 30(2): 210-216.
[9]	LIU Shuai, LI Shu-Shi, LIU Dong-Jia, WANG Chang-Sheng. Site Preferences of Adenine Hydrogen Bonding to Peptide Amides [J]. Acta Phys. -Chim. Sin., 2013, 29(12): 2551-2557.
[10]	YAO Tong, ZHONG Bei-Jing. Small-Scale Chemical Kinetic Mechanism Models for Pyrolysis of n-Decane [J]. Acta Phys. -Chim. Sin., 2013, 29(07): 1385-1395.
[11]	WANG Chang-Sheng, LIU Peng, YU Nan. Site-Preference of Uracil and Thymine Hydrogen Bonding to Quercetin [J]. Acta Phys. -Chim. Sin., 2013, 29(06): 1173-1182.
[12]	YAO Tong, ZHONG Bei-Jing. Chemical Kinetic Model for Auto-Ignition and Combustion of n-Decane [J]. Acta Phys. -Chim. Sin., 2013, 29(02): 237-244.
[13]	WANG Bi-Yao, TAN Ning-Xin, YAO Qian, LI Ze-Rong, LI Xiang-Yuan. Accurate Calculation of the Reaction Barriers and Rate Constants of the Pyrolysis of Alkyl Radicals in the β Position Using the Isodesmic Reaction Method [J]. Acta Phys. -Chim. Sin., 2012, 28(12): 2824-2830.
[14]	ZHANG Jin-Li, HE Zheng-Hua, HAN You, LI Wei, WU Jiang-Jie-Xing, GAN Zhong-Xue, GU Jun-Jie. Nucleation and Growth of Na₂CO₃ Clusters in Supercritical Water Using Molecular Dynamics Simulation [J]. Acta Phys. -Chim. Sin., 2012, 28(07): 1691-1700.
[15]	WANG Chuan-Ge, ZENG Fan-Gui, PENG Zhi-Long, LI Xia, ZHANG Li. Kinetic Analysis of a Pyrolysis Process and Hydrogen Generation of Humic Acids of Yimin Lignite Fusain Using the Distributed Activation Energy Model [J]. Acta Phys. -Chim. Sin., 2012, 28(01): 25-36.

Pyrolysis of n-Decane and Dimethylbenzene under Supercritical Pressure

PDF (PC)

Like

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Metrics

Comments

Recommended 0