Citation: 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 Physico-Chimica Sinica doi: 10.3866/PKU.WHXB201302061 shu

Pyrolysis of n-Decane and Dimethylbenzene under Supercritical Pressure

ZHOU Hao ¹ ,
MAO Jia ¹ ,
WANG Bi-Yao ¹ ,
ZHU Quan ¹ ,
WANG Jian-Li ^2, ,
LI Xiang-Yuan ^1,

1.
1 Colledge of Chemical Engineering, Sichuan University, Chengdu 610065, P.R. China;
2 Colledge of Chemistry, Sichuan University, Chengdu 610064, P.R. China

Received Date: 15 November 2012
Available Online: 6 February 2013
Fund Project: 国家自然科学基金(91116001/A0204)资助项目 (91116001/A0204)

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.
- n-Decane,
- Dimethylbenzene,
- Supercritical condition,
- Pyrolysis,
- Binding energy
1. [1]
  
  (1) Dagaut, P.; Bakali, E. A.; Ristori, A. Fuel 2006, 85, 944. doi: 10.1016/j.fuel.2005.10.008
2. [2]
  (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. [3]
  (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. [4]
  (4) Olchanski, E.; Burcat, A. Int. J. Chem. Kinet. 2006, 38, 703.
5. [5]
  (5) Bikas, G.; Peters, N. Combust. Flame 2001, 126, 1456. doi: 10.1016/S0010-2180(01)00254-1
6. [6]
  (6) Nehse, M.;Warnatz, J.; Chevalier, C. Symposium (International)on Combustion 1996, 26, 773. doi: 10.1016/S0082-0784(96)80286-4
7. [7]
  (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. [8]
  (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. [9]
  (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. [10]
  (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. [11]
  (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. [12]
  (12) Pitz,W. J.; Cernansky, N. P.; Dryer, F. L.; E lfopoulos, 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. [13]
  (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. [14]
  (14) Sivaramakrishnan, R.; Tranter, R. S.; Brezinsky, K. J. Phys.Chem. A 2006, 110, 9388. doi: 10.1021/jp060820j
15. [15]
  (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. [16]
  (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. [17]
  (17) Richter, H.; Howard, J. B. Prog. Energy Combust. Sci. 2000, 26,565. doi: 10.1016/S0360-1285(00)00009-5
18. [18]
  (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. [19]
  (19) Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996,77, 3865. doi: 10.1103/PhysRevLett.77.3865
20. [20]
  (20) Becke, A. D. J. Chem. Phys. 1993, 98, 5648. doi: 10.1063/1.464913
21. [21]
  (21) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 03[CP]; Gaussian Inc.: Pittsburgh, PA, 2003.
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