正癸烷与二甲苯在超临界压力下的热裂解

引用本文: 周灏, 毛佳, 汪必耀, 朱权, 王健礼, 李象远. 正癸烷与二甲苯在超临界压力下的热裂解[J]. 物理化学学报, doi: 10.3866/PKU.WHXB201302061 shu

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

正癸烷与二甲苯在超临界压力下的热裂解

周灏 ^1, ,
毛佳 ^1, ,
汪必耀 ^1, ,
朱权 ^1, ,
王健礼 ^2, ,
李象远 ^1,

基金项目:
国家自然科学基金(91116001/A0204)资助项目 (91116001/A0204)

摘要:

采用连续流动装置对正癸烷和二甲苯在超临界压力下的热裂解对比研究. 用气相色谱和色质联用仪对其气相产物和液相产物进行分析, 计算气相产物产率和裂解转化率, 并运用计算化学方法获得正癸烷和二甲苯不同化学键的键能, 从实验和理论上分析其裂解反应的难易程度和裂解规律. 实验结果表明, 在4 MPa和650、700、750 ℃条件下, 正癸烷比二甲苯更容易裂解, 正癸烷裂解产物以C₁-C₃小分子的烃类和氢气为主, 而二甲苯裂解产物主要为乙苯、甲苯和其它芳香类化合物; 键能计算结果表明, 正癸烷碳链骨架的C－C键能和C－H键能均较小, 裂解反应的诱发步骤应该是C－C键断裂, 而二甲苯苯环上C－C和C－H键能均较大, 裂解诱发步骤应该是侧链甲基脱氢反应. 因此正癸烷裂解反应以C－C键断裂和脱氢反应为主, 二甲苯裂解主要发生侧链甲基C－C键断裂和脱氢反应, 而芳环则比较稳定, 理论计算键能分析与裂解实验结果一致.

关键词:

正癸烷
/ 二甲苯
/ 超临界
/ 热裂解
/ 键能

English

Pyrolysis of n-Decane and Dimethylbenzene under Supercritical Pressure

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: 25 March 2013
Fund Project:
国家自然科学基金(91116001/A0204)资助项目

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:

1. [1]
  
  (1) Dagaut, P.; Bakali, E. A.; Ristori, A. Fuel 2006, 85, 944. doi: 10.1016/j.fuel.2005.10.008
  (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(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(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.(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(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(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(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(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.](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.](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(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.(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.(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(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(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(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(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.](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(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(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.
  (21) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 03[CP]; Gaussian Inc.: Pittsburgh, PA, 2003.

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沈阳化工大学材料科学与工程学院沈阳 110142

正癸烷与二甲苯在超临界压力下的热裂解

English

Pyrolysis of n-Decane and Dimethylbenzene under Supercritical Pressure

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通讯作者: 陈斌, bchen63@163.com

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正癸烷与二甲苯在超临界压力下的热裂解

English

Pyrolysis of n-Decane and Dimethylbenzene under Supercritical Pressure

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

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