Synthesis and Thermal Decomposition of Tetrahydrotricyclopentadiene as a High Density Hydrocarbon Fuel†

doi:10.7503/cjcu20130749

Abstract

Abstract:

As a high density hydrocarbon fuel, tetrahydrotricyclopentadiene(THTCPD) was synthesized from dicyclopentadiene and indene by D-A reaction and hydrogenation. The density of THTCPD is 1.082 g/cm³, volumetric combustion heat is 47.5 MJ/L, flash point is 120 ℃ and freezing point is 48—49 ℃. Thermal decomposition of THTCPD was studied in a decomposition reactor at atmospheric pressure, in the temperature range of 973—1153 K. Products were detected by gas chromatography-mass spectroscopy. The major products were methane, ethylene, propylene, cyclopentene, cyclopentadiene, benzene and toluene. The conversion of THTCPD at different temperatures and time was investigated. The results indicated that the effect of temperature was superior to other factors in this reaction. A primary mechanism including nine pathways was also presumed according to the main products of the reaction and the monoradical mechanism. Density functional theory calculations(X3LYP) of the potential energy surface was performed to investigate the mechanisms of THTCPD breakdown. Relative energy and ratio of reation routes were computed. The kinetic equation of thermal decomposition was obtained by relation of the conversion and temperature. The pre-exponential factor and activation energy overall reaction order for thermal cracking of THTCPD were determined by linear regression analysis to be 133.75 and 6.67×10⁴ kJ/mol, respectively.

Key words: High density hydrocarbon fuel, Tetrahydrotricyclopentadiene, Thermal decomposition

CLC Number:

O622
O642

TrendMD:

DU Yongmei, LI Chunying, ZHANG Jianwei, WANG Wei, KANG Jianping, LÜ Jian. Synthesis and Thermal Decomposition of Tetrahydrotricyclopentadiene as a High Density Hydrocarbon Fuel^†[J]. Chem. J. Chinese Universities, 2014, 35(4): 755.

Figures/Tables 9

References 22

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Test item	Test result	Test method
Density/(g·cm^-3)(20 ℃)	1.082	GJB770B-2005
Combustionheat/(MJ·L^-1)	47.5	GJB770B-2005 701.2
Flash point/℃	120	GB/T261
Freezing point/℃	48—49	GB/T2430-81

Test item	Test result	Test method
Density/(g·cm^-3)(20 ℃)	1.082	GJB770B-2005
Combustionheat/(MJ·L^-1)	47.5	GJB770B-2005 701.2
Flash point/℃	120	GB/T261
Freezing point/℃	48—49	GB/T2430-81

Temperature/K	973	973	1073	1073	1123	1123
Pyrolysis time/s	4	8	4	7	4	8
Product of methane(%)	0.13	0.17	0.07	0.13	0.02	0.02
Product of ethylene(%)	1.21	2.34	2.15	9.42	5.93	18.32
Product of ethane(%)	0.28	0.42	0.42	1.32	0.78	2.74
Product of propylene(%)	0.30	0.36	0.73	1.41	0.26	1.56
Product of propane(%)	0.05	0.07	0.23	0.32	0.40	0.13
Product of butane(%)	0.52	0.59	0.86	1.62	0.93	1.73
Product of penditene(%)	0.03	0.23	0.13	0.14	0.02	0.02
Product of cyclopentene+cyclopenditene(%)	2.44	4.12	3.81	8.46	3.47	7.08
Product of benzene(%)	1.35	3.56	3.73	10.98	8.03	20.53
Product of toluene(%)	0.53	1.75	1.52	2.59	1.82	6.97
Product of 5-penditenylcyclopenditene(%)	1.85	2.04	0.62	2.48	0.85	3.83
Product of other(%)	1.06	3.32	1.75	1.89	1.10	1.24
Product of conversion(%)	9.32	18.97	16.02	40.76	23.61	64.17

Temperature/K	973	973	1073	1073	1123	1123
Pyrolysis time/s	4	8	4	7	4	8
Product of methane(%)	0.13	0.17	0.07	0.13	0.02	0.02
Product of ethylene(%)	1.21	2.34	2.15	9.42	5.93	18.32
Product of ethane(%)	0.28	0.42	0.42	1.32	0.78	2.74
Product of propylene(%)	0.30	0.36	0.73	1.41	0.26	1.56
Product of propane(%)	0.05	0.07	0.23	0.32	0.40	0.13
Product of butane(%)	0.52	0.59	0.86	1.62	0.93	1.73
Product of penditene(%)	0.03	0.23	0.13	0.14	0.02	0.02
Product of cyclopentene+cyclopenditene(%)	2.44	4.12	3.81	8.46	3.47	7.08
Product of benzene(%)	1.35	3.56	3.73	10.98	8.03	20.53
Product of toluene(%)	0.53	1.75	1.52	2.59	1.82	6.97
Product of 5-penditenylcyclopenditene(%)	1.85	2.04	0.62	2.48	0.85	3.83
Product of other(%)	1.06	3.32	1.75	1.89	1.10	1.24
Product of conversion(%)	9.32	18.97	16.02	40.76	23.61	64.17

T/K	t/s	ln[1/(1-x)]	k	T/K	t/s	ln[1/(1-x)]	k
973	5	0.1823	0.03646	1123	5	0.5376	0.10755
1023	6	0.3098	0.05163	1153	8	1.0381	0.12976
1073	7	0.5036	0.07194