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.
1. [1]
  Zunxiang Zeng , Yuling Hu , Yufei Hu , Hua Xiao . Analysis of Plant Essential Oils by Supercritical CO₂Extraction with Gas Chromatography-Mass Spectrometry: An Instrumental Analysis Comprehensive Experiment Teaching Reform. University Chemistry, doi: 10.3866/PKU.DXHX202309069
2. [2]
  Zhuo WANG , Junshan ZHANG , Shaoyan YANG , Lingyan ZHOU , Yedi LI , Yuanpei LAN . Preparation and photocatalytic performance of CeO₂-reduced graphene oxide by thermal decomposition. Chinese Journal of Inorganic Chemistry, doi: 10.11862/CJIC.20240067
3. [3]
  Yang Lv , Yingping Jia , Yanhua Li , Hexiang Zhong , Xinping Wang . Integrating the Ideological Elements with the “Chemical Reaction Heat” Teaching. University Chemistry, doi: 10.12461/PKU.DXHX202402059
4. [4]
  Rui Li , Jiayu Zhang , Anyang Li . Two Levels of Understanding of Chemical Bonds: a Case of the Bonding Model of Hypervalent Molecules. University Chemistry, doi: 10.3866/PKU.DXHX202308051
5. [5]
  Danqing Wu , Jiajun Liu , Tianyu Li , Dazhen Xu , Zhiwei Miao . Research Progress on the Simultaneous Construction of C—O and C—X Bonds via 1,2-Difunctionalization of Olefins through Radical Pathways. University Chemistry, doi: 10.12461/PKU.DXHX202403087
6. [6]
  Yunxin Xu , Wenbo Zhang , Jing Yan , Wangchang Geng , Yi Yan . A Fascinating Saga of “Energetic Materials”. University Chemistry, doi: 10.3866/PKU.DXHX202307008
7. [7]
  Linhan Tian , Changsheng Lu . Discussion on Sextuple Bonding in Diatomic Motifs of Chromium Family Elements. University Chemistry, doi: 10.3866/PKU.DXHX202401056
8. [8]
  Ruming Yuan , Pingping Wu , Laiying Zhang , Xiaoming Xu , Gang Fu . Patriotic Devotion, Upholding Integrity and Innovation, Wholeheartedly Nurturing the New: The Ideological and Political Design of the Experiment on Determining the Thermodynamic Functions of Chemical Reactions by Electromotive Force Method. University Chemistry, doi: 10.3866/PKU.DXHX202311057
9. [9]
  Limei CHEN , Mengfei ZHAO , Lin CHEN , Ding LI , Wei LI , Weiye HAN , Hongbin WANG . Preparation and performance of paraffin/alkali modified diatomite/expanded graphite composite phase change thermal storage material. Chinese Journal of Inorganic Chemistry, doi: 10.11862/CJIC.20230312
10. [10]
  Jiaqi AN , Yunle LIU , Jianxuan SHANG , Yan GUO , Ce LIU , Fanlong ZENG , Anyang LI , Wenyuan WANG . Reactivity of extremely bulky silylaminogermylene chloride and bonding analysis of a cubic tetragermylene. Chinese Journal of Inorganic Chemistry, doi: 10.11862/CJIC.20240072
11. [11]
  Xiao Liu , Guangzhong Cao , Mingli Gao , Hong Wu , Hongyan Feng , Chenxiao Jiang , Tongwen Xu . Seawater Salinity Gradient Energy’s Job Application in the Field of Membranes. University Chemistry, doi: 10.3866/PKU.DXHX202306043
12. [12]
  Xinxin JING , Weiduo WANG , Hesu MO , Peng TAN , Zhigang CHEN , Zhengying WU , Linbing SUN . Research progress on photothermal materials and their application in solar desalination. Chinese Journal of Inorganic Chemistry, doi: 10.11862/CJIC.20230371
13. [13]
  Yuanyin Cui , Jinfeng Zhang , Hailiang Chu , Lixian Sun , Kai Dai . Rational Design of Bismuth Based Photocatalysts for Solar Energy Conversion. Acta Physico-Chimica Sinica, doi: 10.3866/PKU.WHXB202405016
14. [14]
  Yixuan Gao , Lingxing Zan , Wenlin Zhang , Qingbo Wei . Comprehensive Innovation Experiment: Preparation and Characterization of Carbon-based Perovskite Solar Cells. University Chemistry, doi: 10.3866/PKU.DXHX202311091
15. [15]
  Wenqi Gao , Xiaoyan Fan , Feixiang Wang , Zhuojun Fu , Jing Zhang , Enlai Hu , Peijun Gong . Exploring Nernst Equation Factors and Applications of Solid Zinc-Air Battery. University Chemistry, doi: 10.3866/PKU.DXHX202310026
16. [16]
  Simin Fang , Hong Wu , Wei Liu , Wei Wei , Hongyan Feng , Wan Li . Construction and Application of Teaching Resources for Inorganic and Analytical Chemistry Experimental Course in the Context of Digital Empowerment. University Chemistry, doi: 10.3866/PKU.DXHX202402053
17. [17]
  Zeyuan WANG , Songzhi ZHENG , Hao LI , Jingbo WENG , Wei WANG , Yang WANG , Weihai SUN . Effect of I₂ interface modification engineering on the performance of all-inorganic CsPbBr₃ perovskite solar cells. Chinese Journal of Inorganic Chemistry, doi: 10.11862/CJIC.20240021
18. [18]
  Jizhou Liu , Chenbin Ai , Chenrui Hu , Bei Cheng , Jianjun Zhang . 六氯锡酸铵促进钙钛矿太阳能电池界面电子转移及其飞秒瞬态吸收光谱研究. Acta Physico-Chimica Sinica, doi: 10.3866/PKU.WHXB202402006
19. [19]
  Yipeng Zhou , Chenxin Ran , Zhongbin Wu . Metacognitive Enhancement in Diversifying Ideological and Political Education within Graduate Course: A Case Study on “Solar Cell Performance Enhancement Technology”. University Chemistry, doi: 10.3866/PKU.DXHX202312096
20. [20]
  Yongming Zhu , Huili Hu , Yuanchun Yu , Xudong Li , Peng Gao . Construction and Practice on New Form Stereoscopic Textbook of Electrochemistry for Energy Storage Science and Engineering: Taking Basic Course of Electrochemistry as an Example. University Chemistry, doi: 10.3866/PKU.DXHX202312086

Get Citation

PDF

XML

Metrics

PDF Downloads(873)
Abstract views(902)
HTML views(23)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142