Pathways of liquefied petroleum gas pyrolysis in hydrogen plasma: A density functional theory study

能源化学(英文) ›› 2013, Vol. 22 ›› Issue (3): 484-492.

Pathways of liquefied petroleum gas pyrolysis in hydrogen plasma: A density functional theory study

Xiaoyuan Huang^a, Jiaming Gu^a, Dang-Guo Cheng^a, Fengqiu Chen^b, Xiaoli Zhan^a

a. Department of Chemical and Biological Engineering, Zhejiang University Hangzhou 310027, Zhejiang, China;
b. Key Laboratory of Biomass Chemical Engineering of Ministry of Education, Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China

收稿日期:2012-11-30 修回日期:2013-02-18 出版日期:2013-05-20 发布日期:2013-05-31
通讯作者: Dang-Guo Cheng

Pathways of liquefied petroleum gas pyrolysis in hydrogen plasma: A density functional theory study

Xiaoyuan Huang^a, Jiaming Gu^a, Dang-Guo Cheng^a, Fengqiu Chen^b, Xiaoli Zhan^a

a. Department of Chemical and Biological Engineering, Zhejiang University Hangzhou 310027, Zhejiang, China;
b. Key Laboratory of Biomass Chemical Engineering of Ministry of Education, Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China

Received:2012-11-30 Revised:2013-02-18 Online:2013-05-20 Published:2013-05-31

摘要/Abstract

摘要： A density functional theory (DFT) study has been conducted in this work to investigate the pyrolysis pathways of propane and n-butane, which are the main components of liquefied petroleum gas (LPG), for better understanding the pyrolysis behavior of LPG in hydrogen thermal plasma. Over 60 possible reactions are considered. The reaction enthalpies and activation energies of these reactions are calculated and analyzed with a Gaussian method of B3LYP and basic set of 6-31G (d,p). A most possible reaction pathway is brought up. According to this reaction pathway, the main products of LPG pyrolysis are acetylene, ethylene, methane, ethane and extra hydrogen. Acetylene mainly comes from the pyrolysis of propylene and ethylene, and hydrogen abstraction reactions are the main source of extra hydrogen gas. Active H? radicals are found to play a very important role in many reactions, and they can remarkably lower the energies needed for reactions.

关键词: LPG, density functional theory, plasma, pyrolysis, hydrogen

Abstract: A density functional theory (DFT) study has been conducted in this work to investigate the pyrolysis pathways of propane and n-butane, which are the main components of liquefied petroleum gas (LPG), for better understanding the pyrolysis behavior of LPG in hydrogen thermal plasma. Over 60 possible reactions are considered. The reaction enthalpies and activation energies of these reactions are calculated and analyzed with a Gaussian method of B3LYP and basic set of 6-31G (d,p). A most possible reaction pathway is brought up. According to this reaction pathway, the main products of LPG pyrolysis are acetylene, ethylene, methane, ethane and extra hydrogen. Acetylene mainly comes from the pyrolysis of propylene and ethylene, and hydrogen abstraction reactions are the main source of extra hydrogen gas. Active H? radicals are found to play a very important role in many reactions, and they can remarkably lower the energies needed for reactions.

Key words: LPG, density functional theory, plasma, pyrolysis, hydrogen

Xiaoyuan Huang, Jiaming Gu, Dang-Guo Cheng, Fengqiu Chen, Xiaoli Zhan. Pathways of liquefied petroleum gas pyrolysis in hydrogen plasma: A density functional theory study[J]. 能源化学(英文), 2013, 22(3): 484-492.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.jenergychem.com/CN/

https://www.jenergychem.com/CN/Y2013/V22/I3/484

参考文献

[1] Zhang Q W, Li X H, Asami K, Asaoka S, Fujimoto K. Fuel Process Technol, 2004, 85(8-10): 1139

[2] Zou X J, Wang X G, Li L, Shen K, Lu X G, Ding W Z. Int J Hydrog Energy, 2010, 35(22): 12191

[3] Laosiripojana N, Sutthisripok W, Charojrochkul S, Assabumrungrat S. Fuel, 2011, 90(1): 136

[4] Zhou J M, Lin G D, Zhang H B. Catal Commun, 2009, 10(14): 1944

[5] Pfender E. Plasma Chem Plasma Process, 1999, 19(1): 1

[6] Bogaerts A, Neyts E, Gijbels R, van der Mullen J. Spectroc Acta Part B-Atom Spectr, 2002, 57(4): 609

[7] Diercks R, Arndt J D, Freyer S, Geier R, Machhammer O, Schwartze J, Volland M. Chem Eng Technol, 2008, 31(5): 631

[8] Chen H G, Xie K C. Pet Sci Technol, 2003, 21(5-6): 709

[9] Chen H G, Xie K C. J Sichuan Univ (Sichuan Daxue Xuebao) (Eng Sci Ed), 2002, 34(5): 72

[10] Moss? A L, Gorbunov A V, Galinovskii A A, Savchin V V, Lozhechnik A V. J Eng Phys Thermophys, 2008, 81(4): 652

[11] Vogulkin V E, Gorbunov A V, Moss? A L, Galinovsky A A. High Temp Mater Process, 2005, 9(3): 463

[12] Towfighi J, Niaei A, Karimzadeh R, Saedi G. Korean J Chem Eng, 2006, 23(1): 8

[13] Belohlav Z, Zamostny P, Herink T. Chem Eng Process, 2003, 42(6): 461

[14] Nabavi R, Niaei A, Salari D, Towfighi J J. J Anal Appl Pyrolysis, 2007, 80(1): 175

[15] Nabavi S R, Rangaiah G P, Niaei A, Salari D. Ind Eng Chem Res, 2009, 48(21): 9523

[16] Frisch M J, Trucks G W, Schlegel H B, Scuseria G E, Robb M A, Cheeseman J R, et al. Gaussian 09 Revision A.02. Wallingford, CT: Gaussian Inc., 2009

[17] Becke A D. J Chem Phys, 1993, 98(7): 5648

[18] Lee C T, Yang W T, Parr R G. Phys Rev B, 1988, 37(2): 785

[19] Huggins M L. J Am Chem Soc, 1953, 75(17): 4124

[20] Dean A M. J Phys Chem, 1985, 89(21): 4600

[21] Lifshitz A, Frenklach M. J Phys Chem, 1975, 79(7): 686

[22] Schmich P H, Ederer H J, Ebert K H. Ind Eng Chem Res, 1992, 31(1): 29

[23] Laidler K J, Sagert N H, Wojciechowski B W. Proc R Soc A, 1962, 270(1341): 242

[24] Layokun S K, Slater D H. Ind Eng Chem Process Des Dev, 1979, 18(2): 232

[25] Moreau N, Pasquiers S, Blin-Simiand N, Magne L, Jorand F, Postel C, Vacher J R. J Phys D-Appl Phys, 2010, 43(28): 285201

[26] Quah E B H, Li C Z. Int J Chem Kinet, 2003, 35(12): 637

[27] Kim K, Shin K S. Bull Korean Chem Soc, 2001, 22(3): 303

[28] Sivaramakrishnan R, Su M C, Michael J V, Klippenstein S J, Harding L B, Ruscic B. J Phys Chem A, 2011, 115(15): 3366

[29] Al-Alami M Z, Kiefer J H. J Phys Chem, 1983, 87(3): 499

[30] von Horsten H F, Banks S T, Clary D C. J Chem Phys, 2011, 135(9): 094311

[31] Kerkeni B, Clary D C. Mol Phys, 2005, 103(3): 1745

[32] Zheng X, Blowers P. Mol Simul, 2005, 31(14-15): 979

[33] Wang J G, Liu C J, Eliassion B. Energy Fuels, 2004, 18(1): 148

[34] Oehlschlaeger M A, Davidson D F, Hanson R K. J Phys Chem A, 2004, 108(19): 4247

[35] Wang Y L, Rinker R G, Corcoran W H. Ind Eng Chem Fundam, 1963, 2(3): 161

[36] Sagert N H, Laidler K J. Can J Chem, 1963, 41(4): 838

[37] Purnell J H, Quinn C P. Proc R Soc London Ser A, 1962, 270(1341): 267

[38] Sun W J, Saeys M. AIChE J, 2011, 57(9): 2458

[39] Roscoe J M, Bossard A R, Back M H. Can J Chem, 2000, 78(1): 16

[40] Kiefer J H, Al-Alami M Z, Budach K A. J Phys Chem, 1982, 86(5): 808

[41] Li Q S, Zhang Y, Zhang S W. J Mol Model, 2005, 11(1): 41

[42] Singh O V, Pant K K. Can J Chem Eng, 2003, 81(5): 981

[43] Knyazev V D, Slagle I R. J Phys Chem, 1996, 100(13): 5318

[44] Towfighi J, Modarres J, Omidkhah M, Niaei A. IJE Trans B: Appl, 2004, 17(4): 319

[45] Tsang W. Ind Eng Chem Res, 1992, 31(1): 3

[46] Roscoe J M, Jayaweera I S, Mackenzie A L, Pacey P D. Int J Chem Kinet, 1996, 28(3): 181

[47] Norinaga K, Deutschmann O. Ind Eng Chem Res, 2007, 46(11): 3547

[48] Deslauriers H, Makulski W, Collin G J. Can J Chem, 1987, 65(7): 1631

[49] Hidaka Y, Higashihara T, Ninomiya N, Oshita H, Kawano H. J Phys Chem, 1993, 97(42): 10977

[50] Davis S G, Law C K, Wang H. J Phys Chem A, 1999, 103(30): 5889

[51] Bentz T, Giri B R, Hippler H, Olzmann M, Striebel F, Szöri M. J Phys Chem A, 2007, 111(19): 3812

[52] Hidaka Y, Higashihara T, Oki T, Kawano H. Int J Chem Kinet, 1995, 27(4): 321

[53] Olson D B, Tanzawa T, Gardiner W C. Int J Chem Kinet, 1979, 11(1): 23

[54] Hidaka Y, Nishimori T, Sato K, Henmi W, Okuda R, Inami K, Higashihara T. Combust Flame, 1999, 117(4): 755

[55] Westbrook C K, Dryer F L, Schug K P. Nineteenth Symposium (International) on Combustion, 1982, 19(1): 153

[56] Khan R U, Bajohr S, Buchholz D, Reimert R, Minh H D, Norinaga K, Janardhanan V M, Tischer S, Deutschmann O. J Anal Appl Pyrolysis, 2008, 81(2): 148

Pathways of liquefied petroleum gas pyrolysis in hydrogen plasma: A density functional theory study

Pathways of liquefied petroleum gas pyrolysis in hydrogen plasma: A density functional theory study

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

参考文献

相关文章 15

编辑推荐

Metrics

[1]	Sasan Ghashghaie, Samson Ho-Sum Cheng, Jie Fang, Hafiz Khurram Shahzad, Robin Lok-Wang Ma, chi-Yuen Chung. Electrophoretically deposited binder-free 3-D carbon/sulfur nanocomposite cathode for high-performance Li-S batteries[J]. 能源化学(英文版), 2020, 48(9): 92-101.
[2]	Ziqun Wang, Longfeng Li, Mingzhu Liu, Tifang Miao, Xiangju Ye, Sugang Meng, Shifu Chen, Xianliang Fu. A new phosphidation route for the synthesis of NiP_x and their cocatalytic performances for photocatalytic hydrogen evolution over g-C₃N₄[J]. 能源化学(英文版), 2020, 48(9): 241-249.
[3]	Wenjing Dong, di Wang, Xiaoyun Li, Yuan Yao, Xu Zhao, Zhao Wang, Hong-En Wang, Yu Li, Lihua Chen, dong Qian, bao-Lian Su. Bronze TiO₂ as a cathode host for lithium-sulfur batteries[J]. 能源化学(英文版), 2020, 48(9): 259-266.
[4]	Jing-Qi Chi, Min Yang, Yong-Ming Chai, Zhi Yang, Lei Wang, bin Dong. Design and modulation principles of molybdenum carbide-based materials for green hydrogen evolution[J]. 能源化学(英文版), 2020, 48(9): 398-423.
[5]	Weiwei Wang, Zhenping Qu, Lixin Song, Qiang Fu. An investigation of Zr/Ce ratio influencing the catalytic performance of CuO/Ce_1-xZr_xO₂ catalyst for CO₂ hydrogenation to CH₃OH[J]. 能源化学(英文版), 2020, 47(8): 18-28.
[6]	Jae Hyeon Nam, Myeong Je Jang, Hye Yeon Jang, Woojin Park, Xiaolei Wang, Sung Mook Choi,byungjin Cho. Room-temperature sputtered electrocatalyst WSe₂ nanomaterials for hydrogen evolution reaction[J]. 能源化学(英文版), 2020, 47(8): 107-111.
[7]	Zhong-Pan Hu, Yansu Wang,dandan Yang, Zhong-Yong Yuan. CrO_x supported on high-silica HZSM-5 for propane dehydrogenation[J]. 能源化学(英文版), 2020, 47(8): 225-233.
[8]	Hui-Ying Sun, Guang-Rui Xu,fu-Min Li, Qing-Ling Hong, Pu-Jun Jin, Pei Chen, Yu Chen. Hydrogen generation from ammonia electrolysis on bifunctional platinum nanocubes electrocatalysts[J]. 能源化学(英文版), 2020, 47(8): 234-240.
[9]	Lishun Meng, Yuan Yao, Jing Liu, Zhao Wang,dong Qian, Liuchun Zheng,bao-Lian Su, Hong-En Wang. MoSe₂ nanosheets as a functional host for lithium-sulfur batteries[J]. 能源化学(英文版), 2020, 47(8): 241-247.
[10]	Danyang He, Liyun Cao, Jianfeng Huang, Koji Kajiyoshi, Jianpeng Wu,changcong Wang, Qianqian Liu,dan Yang, Liangliang Feng. In-situ optimizing the valence configuration of vanadium sites in NiV-LDH nanosheet arrays for enhanced hydrogen evolution reaction[J]. 能源化学(英文版), 2020, 47(8): 263-271.
[11]	Zhao Liu, Jing Li, Shiji Xue, Shunfa Zhou, Konggang Qu, Ying Li, Weiwei Cai. Pt/Mo₂C heteronanosheets for superior hydrogen evolution reaction[J]. 能源化学(英文版), 2020, 47(8): 317-323.
[12]	Hongyan Li, Le Yang, Zhongxu Wang, Peng Jin, Jingxiang Zhao, Zhongfang Chen. N-heterocyclic carbene as a promising metal-free electrocatalyst with high efficiency for nitrogen reduction to ammonia[J]. 能源化学(英文版), 2020, 46(7): 78-86.
[13]	Jintao Sun, Qi Chen, Yuanwei Guo, Zili Zhou, Yang Song. Quantitative behavior of vibrational excitation in AC plasma assisted dry reforming of methane[J]. 能源化学(英文版), 2020, 46(7): 133-143.
[14]	Meng Zhang, Xuezhang Xiao, Bosang Luo, Meijia Liu, Man Chen, Lixin Chen. Superior de/hydrogenation performances of MgH₂ catalyzed by 3D flower-like TiO₂@C nanostructures[J]. 能源化学(英文版), 2020, 46(7): 191-198.
[15]	Zhikai Li, Tao Yang, Shaojun Yuan, Yongxiang Yin, Edwin J. Devid, Qiang Huang, Daniel Auerbach, Aart W. Kleyn. Boudouard reaction driven by thermal plasma for efficient CO₂ conversion and energy storage[J]. 能源化学(英文版), 2020, 45(6): 128-134.