C2H3与C2H5OH和CH3HCO间的脱氢反应对乙醇-碳氢混合燃料燃烧过程的影响

doi:10.7503/cjcu20140603

摘要/Abstract

摘要：

在QCISD(T)/6-311++G(d,p)//B3LYP/6-311G(d,p) 的水平下计算了乙醇及乙醇燃烧裂解产物与C₂H₃之间的脱氢反应机理, 利用正则变分过渡态理论(CVT)结合小曲率隧道效应模型(SCT)计算400~2000 K范围内的速率, 对比OH, H及CH₃等自由基相似脱氢反应速率, 选择2条具有较快反应速率的通道(C₂H₃+C₂H₅OH→TS1→C₂H₄+C₂H₅O和C₂H₃+CH₃HCO→TS4→C₂H₄+CH₃CO). 将这2个反应耦合到正庚烷/乙醇混合燃料及异辛烷/乙醇混合燃料的机理中, 利用CHEMKIN程序中预混火焰模型模拟混合燃料的燃烧过程并进行路径分析. 对比相应的实验数据发现, 改进的动力学模型对燃烧过程中C₂H₃路径上相近组分的预测精度有较大改善, 而对C₂H₃路径上较远的组分丙炔(C₃H₄)和乙烯基乙炔(C₄H₄)等影响不大.

Abstract The mechanism of C₂H₃ new reactions on the combustion of ethanol/hydrocarbon blends was investigated at QCISD(T)/6-311++G(d, p)//B3LYP/6-311G(d,p) level. The results indicated 2H-abstraction channels with fast reaction rate: C₂H₃+C₂H₅OH→TS1→C₂H₄+C₂H₅O和C₂H₃+CH₃HCO→TS4→C₂H₄+CH₃CO. The rate constants of these two reactions were calculated via the canonical variational transition state theory(CVT) among a temperature range of 400—2000 K and a small curvature tunneling correction was also considered. Path analyses about the n-heptane/ethanol and iso-octane/ethanol premixed flames were carried out with CHEMKIN. Compared with the experimental data, the prediction was apparently improved for the species adjacent to the reaction paths of C₂H₃, after the addition of the new reactions of C₂H₃ to each mechanism. However, few influences were observed on other large species(e.g. C₃H₄, C₄H₄), which are far from the pathways of C₂H₃.

关键词: 脱氢反应, 速率常数, 正庚烷/乙醇燃烧, 异辛烷/乙醇燃烧, 动力学模拟

Key words: H-Atom abstraction reaction, Rate constant, n-Heptane/ethanol, iso-Octane/ethanol, Kinetics simulation

中图分类号:

O643

TrendMD:

马鹏, 宋金瓯, 宋崇林, 吕刚, 陈朝旭, 杨传旺. C₂H₃与C₂H₅OH和CH₃HCO间的脱氢反应对乙醇-碳氢混合燃料燃烧过程的影响. 高等学校化学学报, 2015, 36(1): 149.

MA Peng, SONG Jinou, SONG Chonglin, LÜ Gang, CHEN Chaoxu, YANG Chuanwang. Effect of H-atom Abstraction Reactions Among C₂H₃, C₂H₅OH and CH₃HCO on the Combustion of Ethanol-Hydrocarbon Fuels^†. Chem. J. Chinese Universities, 2015, 36(1): 149.

图/表 12

Fig.1 Optimized geometries of transition states of these 5 paths at the B3LYP/6-311++G(d,p) level Bond lengths are in nm.

Fig.2 Potential energy profile of reactions between C2H3 and C2H5OH/CH3HCO

Fig.3 Rate comparison between this work and Literature of following reaction(CH3+C2H5OHCH4+CH3CHOH)

Table 1 Rate coefficient of the new reactions[k=ATnexp(-E/RT)]

Path	Reaction	A	n	E/(J·mol^-1)
1	C₂H₃+C₂H₅OH=C₂H₄+C₂H₅O	2.61×10^-1	3.93	5410
2	C₂H₃+C₂H₅OH=C₂H₄+CH₃CHOH	3.99×10^-1	3.82	19960
3	C₂H₃+C₂H₅OH=C₂H₄+C₂H₄OH	1.18×10^-1	4.13	37150
4	C₂H₃+CH₃HCO=C₂H₄+CH₃CO	9.32×10^-1	3.74	5060
5	C₂H₃+CH₃CO =C₂H₄+CH₂HCO	4.12×10^-1	3.83	16800

Table 2 Reaction rate constants comparison with other intermediates in similar reactions at 1000 K*

Pathway	k/s^-1
Pathway	C₂H₃	CH₃	OH	H
a	6.81×10¹⁰	5.39×10¹⁰	2.60×10¹²	2.04×10¹¹
b	1.03×10¹⁰	2.61×10¹¹	1.31×10¹²	1.64×10¹²
c	3.09×10⁹	2.39×10¹¹	1.05×10¹²	1.67×10¹²
d	8.42×10¹⁰	7.52×10¹⁰	4.75×10¹¹	9.18×10¹¹
e	1.50×10¹⁰	3.47×10¹⁰	2.47×10¹²	1.54×10¹³

Table 3 Experimental parameters

Mixture	Equivalence ratio	Flow rate/(L·min^-1)	Inlet temperature/K	Pressure/Pa
n-C₇H₁₆/O₂/Ar	1.0	0.0914/1/0.8	498	4000
n-C₇H₁₆/C₂H₅OH/O₂/Ar	1.0	0.065/0.14/1/0.8	473	4000
i-C₈H₁₈/O₂/Ar	1.0	0.127/1.574/0.8	498	4000
i-C₈H₁₈/C₂H₅OH/O₂/Ar	1.0	0.089/0.154/1.574/0.8	473	4000

Fig.4 C2H4 molar fraction in the flames compared with experimental data (A) Octane flame and octane/ethanol flame; (B) heptane flame and heptane/ethanol flame.

Fig.5 C2H2 molar fraction in the flames compared with experimental data(A) Octane flame and octane/ethanol flame; (B) heptane flame and heptane/ethanol flame.

Fig.6 C3H4 molar fraction in the flames compared with experimental data(A) Octane flame and octane/ethanol flame; (B) heptane flame and heptane/ethanol flame.

Fig.7 C4H4 molar fraction in the flames compared with experimental data (A) Octane flame and octane/ethanol flame; (B) heptane flame and heptane/ethanol flame.

Table 4 Peak concentration ratio(r) on these species in different flames*

Species	r(C₂H₂)		r(C₂H₄)		r(C₃H₄)		r(C₄H₄)
Species	Heptane	Octane	Heptane	Octane	Heptane	Octane	Heptane	Octane
Mech-3(path 3)	1.34	1.12	0.92	0.56	0.91	0.84	0.93	0.90
Mech-2(path 2)	1.16	1.04	1.11	0.71	0.86	0.86	0.91	0.87
Mech-1(path 1)	1.10	0.93	1.22	0.84	0.90	0.93	0.88	0.91
Expt.	1.10^[13]	0.76^[13]	1.00^[13]	0.78^[13]	0.80^[25]	0.97^[16]	1.10^[25]	0.86^[16]

Fig.8 Pathways in n-heptane/O2/Ar(A) and iso-octane/O2/Ar(B) flames Numerical values correspond to the percent contribution to the fuel carbon conversion.

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C₂H₃与C₂H₅OH和CH₃HCO间的脱氢反应对乙醇-碳氢混合燃料燃烧过程的影响

Effect of H-atom Abstraction Reactions Among C₂H₃, C₂H₅OH and CH₃HCO on the Combustion of Ethanol-Hydrocarbon Fuels^†

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