高密度烃燃料四氢环戊二烯三聚体的合成及热裂解

doi:10.7503/cjcu20130749

摘要/Abstract

摘要：

以双环戊二烯为原料, 经D-A反应及催化加氢合成了高密度烃燃料四氢环戊二烯三聚体(THTCPD). 该三聚体的密度为1.082 g/cm³, 体积热值为47.5 MJ/L, 闪点为120 ℃, 凝固点为48~49 ℃. 采用裂解器与色谱-质谱联用技术, 对THTCPD的热裂解进行了在线监测, 结果表明温度对裂解反应影响较大. 对裂解产物的结构进行了分析, 产物以甲烷、乙烯、丙烯、环戊烯、环戊二烯、苯和甲苯为主. 依据产物结构及单分子自由基反应模型, 推测得到了9种路径的裂解机理. 采用X3LYP法进行了各自由基的热力学计算, 得到各反应路径的相对能量及路径比. 通过不同温度下的裂解转化率, 计算得到热裂解反应动力学方程, 经线性拟合得到活化能E_a=6.67×10⁴ kJ/mol, 指前因子A=133.75.

关键词: 高密度烃燃料, 四氢环戊二烯三聚体, 热裂解

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

中图分类号:

O622
O642

TrendMD:

杜咏梅, 李春迎, 张建伟, 王伟, 亢建平, 吕剑. 高密度烃燃料四氢环戊二烯三聚体的合成及热裂解. 高等学校化学学报, 2014, 35(4): 755.

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

图/表 9

参考文献 22

[1]	Li C. Y., Du Y. M., He F., Lü J., Chemistry Bulletin,2006, 69(2), w020
	(李春迎, 杜咏梅, 何飞, 吕剑. 化学通报, 2006, 69(2), w020)
[2]	Han K. J., Hwang I. C., Park S. J., Choi M. J., Fluid Phase Equilibria,2006, 249, 187—191
[3]	Edwards T., Journal of Propulsion and Power, 2003, 19(6), 1089—1288
[4]	Roy G. D., Journal of Propulsion and Power, 2000, 16(4), 546—558
[5]	Bernhard H., Michael P., Domenico S., Claudio B., Acta Astronautica,2008, 63, 379—388
[6]	Norton R. V., Howe S. C., Production of High Energy Fuel, US 4270014,1981-03-26
[7]	Maurice L. Q., Landerl H., Edwards T., Harrison W. E., Fuel,2001, 80, 747—756
[8]	He F., Yu T. F., Li Y. Y., Missiles and Space Vehicles,2005, 274(1) , 26—29
	(贺芳, 禹天福, 李亚裕. 导弹与航天运载技术, 2005, 274(1) , 26—29)
[9]	Yu J., Eser S., Ind. Eng. Chem. Res., 1997, 36, 585—591
[10]	Hou L. Y., Dong N., Sun D. P., Fuel,2013, 103, 1132—1137
[11]	McClaineW. J., Ona O. J., Wornat M. J., J. Chromatogr. A,2007, 1138, 175—183
[12]	Rao P. N., Kunzru D., J. Anal. Appl. Pyrolysis,2006, 76, 154—156
[13]	Striebich R. C., Lawrence J., J. Anal. Appl. Pyrolysis,2003, 70, 339—352
[14]	Xing Y., Li D., Xie W. L., Fang W. J., Guo Y. S., Lin R. S., Fuel,2010, 89, 1422—1428
[15]	Qin J., Zhang S. L., Bao W., Yu W. L., Yu B., Zhou W. X., Yu D. R., Fuel,2013, 108, 445—450
[16]	Moses P. L., Rausch V. L., Nguyen L. T., Hill J. R., Acta Astronautica,2004, 55, 619—630
[17]	Balsterc L. M., Corporand E., Dewittc M. J., Edwardsd J. T., Ervinc J. S., Grahamc J. L., Lee S. Y., Pale S., Phelpsd D. K., Rudnicka L. R., Santoroa R. J., Schoberta H. H., Shaferc L. M., Striebichc R. C., Westc Z. J., Wilsonb G. R., Woodwarde R., Zabarnickc S., Fuel Processing Technology,2008, 89, 364—378
[18]	Herbinet O., Sirjean B., Bounaceur R., Fournet R., Scacchi G., Marquaire P., J. Phys. Chem. A,2006, 110, 11298—11314
[19]	Chae K. Y., Violi A., J. Org. Chem., 2007, 72, 3179—3185
[20]	Tsang W., Int. J. Chem. Kinet., 1978, 10, 599—617
[21]	Davidson D. F., Horning D. C., Dehlschlaeger M. A., Proceeding of the 37th AIAA/ASME/SAE/ASEE Joint Propulsion Conference and Exhibit, Paper No.AIAA-2001-3887, Salt Lake City,2001, July 8-11
[22]	Du Y. M., Wang W., Kang J. P., Li C. Y., Yang J. M., Zhang W., Lü J., Chem. J. Chinese Universities,2011, 32(8), 1849—1853
	(杜咏梅, 王伟, 亢建平, 李春迎, 杨建明, 张伟, 吕剑. 高等学校化学学报, 2011, 32(8), 1849—1853)

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