燃烧反应机理构建的双参数速率常数方法

doi:10.7503/cjcu20190567

摘要/Abstract

摘要：

采用Arrhenius方程的双参数形式描述反应的速率常数对温度的依赖关系, 解决了三参数(A, n, E)过拟合造成的复杂燃烧机理参数缺乏通用性等问题. 在不改变物种数和基元反应数条件下, 将UCSD核心机理进行双参数处理, 并应用于小分子体系的动力学模拟, 得到的模拟结果与三参数机理基本相符. 双参数机理恢复了Arrhenius活化能的物理意义, 可实现机理的参数比较和迁移, 缩小了机理整体优化的变量空间, 为燃烧机理参数的统一奠定了基础.

关键词: 燃烧反应机理, 速率常数, 双参数, 数值模拟

Abstract:

The Arrhenius equation with two parameters, activation energy(E) and pre-exponential factor(A), was proposed to describe the temperature dependence of reaction rate constant in developing combustion mechanisms. As a test, the UCSD core mechanism has been re-parameterized using the two-parameter Arrhenius equation and applied to the kinetic simulation of some small molecule systems, without changing the numbers of species and elemental reactions. The results showed that although the overall mechanism optimization is not performed, the results are basically comparable with the three-parameter mechanism. The advantage of the two-parameterization is the physics of the activation energy in Arrhenius equation, and in this way one can carry out the comparison and migration of the rate constants between different mechanisms. Furthermore, the number of the variable in the global optimization of mechanism aimed at such as ignition delay time of a fuel, can be reduced considerably.

Key words: Combustion reaction mechanism, Rate constant, Two-parameterization, Numerical simulation

中图分类号:

O641
O643

TrendMD:

李象远,姚晓霞,申屠江涛,孙晓慧,李娟琴,刘明夏,许诗敏. 燃烧反应机理构建的双参数速率常数方法. 高等学校化学学报, 2020, 41(3): 512.

LI Xiangyuan,YAO Xiaoxia,SHENTU Jiangtao,SUN Xiaohui,LI Juanqin,LIU Mingxia,XU Shimin. Combustion Reaction Mechanism Construction by Two-parameter Rate Constant Method ^†. Chem. J. Chinese Universities, 2020, 41(3): 512.

图/表 7

Table 1 Temperature-dependence equations of rate contants

Differential form	Expression for k	Author and publication date^[1]
$dln k d t$ = $B + CT + D T 2 T 2$	k=AT^C $e - (B - D T 2) / T$	Van’t Hoff, 1898; Bodenstein,1899
$dln k d t$ = $B + CT T 2$	k=AT^Ce^-^B/T	Kooij,1893; Trautz, 1909
$dln k d t$ = $B + D T 2 T 2$	k=A $e - (B - D T 2) / T$	Schwab,1883; van’tHoff,1884; Spohr,1888
$dln k d t$ = $CT + D T 2 T 2$	k=AT^Ce^DT	…
$dln k d t$ = $B T 2$	k=Ae^-^B/T	Van’t Hoff,1884; Arrhenius,1889; Kooij, 1893
$dln k d t$ = $C T$	k=AT^C	Harcurt and Esson,1895; Veley, 1908

Table 1 Temperature-dependence equations of rate contants

Differential form	Expression for k	Author and publication date^[1]
$dln k d t$ = $B + CT + D T 2 T 2$	k=AT^C $e - (B - D T 2) / T$	Van’t Hoff, 1898; Bodenstein,1899
$dln k d t$ = $B + CT T 2$	k=AT^Ce^-^B/T	Kooij,1893; Trautz, 1909
$dln k d t$ = $B + D T 2 T 2$	k=A $e - (B - D T 2) / T$	Schwab,1883; van’tHoff,1884; Spohr,1888
$dln k d t$ = $CT + D T 2 T 2$	k=AT^Ce^DT	…
$dln k d t$ = $B T 2$	k=Ae^-^B/T	Van’t Hoff,1884; Arrhenius,1889; Kooij, 1893
$dln k d t$ = $C T$	k=AT^C	Harcurt and Esson,1895; Veley, 1908

Table 2 Kinetic parameters in popular core mechanisms

Reaction	GRI-Mech 3.0^[4]			UCSD^[5]			AramcoMech 2.0^[6]
Reaction	A/(cm³· mol^-1·s^-1)	n	E/ (J·mol^-1)	A/(cm³· mol^-1·s^-1)	n	E/ (J·mol^-1)	A/(cm³· mol^-1·s^-1)	n	E/ (J·mol^-1)
O+C₂H₂=H+HCCO	1.35×10⁷	2.00	7949	4.00×10¹⁴	0	44600	2.96×10⁹	1.28	10342
O+C₂H₂=CO+CH₂	6.94×10⁶	2.00	7949	1.60×10¹⁴	0	41400	7.40×10⁸	1.28	10342
C₂H₃+O₂=HCO+CH₂O	4.58×10¹⁶	-1.39	4246	1.70×10²⁹	-5.31	27209	1.16×10¹⁶	-1.13	15861
CH₂CHO=CH₂CO+H	4.87×10¹¹	0.42	-7342	1.05×10³⁷	-7.19	185519	1.43×10¹⁵	-0.15	190790
CH₂CHO=CH₃+CO				1.17×10⁴³	-9.80	183080	2.93×10¹²	0.29	168454
H+CH₃CHO=CH₂CHO+H₂	2.05×10⁹	1.16	10062	1.85×10¹²	0.40	22425	2.72×10³	3.10	21798
C₂H₅+O₂=HO₂+C₂H₄	8.40×10¹¹	0	16213	7.50×10¹⁴	-1.00	20082	2.09×10⁹	0.49	-1637
CH₃O+O₂=HO₂+CH₂O	4.28×10^-13	7.60	-14769	4.28×10^-13	7.60	-14799	4.38×10^-19	9.50	-23016
CH₃+CH₂O=HCO+CH₄	3.32×10³	2.81	24518				3.83×10¹	3.36	18024
H+CH₄=CH₃+H₂	6.60×10⁸	1.62	45354	1.30×10⁴	3.00	33629	6.14×10⁵	2.50	40112
OH+CH₂O=HCO+H₂O	3.43×10⁹	1.18	-1870	3.90×10¹⁰	0.89	1700	7.82×10⁷	1.63	-4414
OH+C₂H₂=H+CH₂CO	2.18×10^-4	4.50	-4184	1.90×10⁷	1.70	4179	1.58×10³	2.56	-3533
OH+C₂H₆=C₂H₅+H₂O	3.54×10⁶	2.12	3640	2.20×10⁷	1.90	4700	1.48×10⁷	1.90	3974
HO₂+CH₂O=HCO+H₂O₂	5.60×10⁶	2.00	50207	4.11×10⁴	2.50	42720	1.88×10⁴	2.70	48199
2CH₃(+M)=C₂H₆(+M)	6.77×10¹⁶	-1.18	2736	1.81×10¹³	0	0	2.28×10¹⁵	-0.69	731
CH+H₂O=H+CH₂O	5.71×10¹²	0	-3158	1.17×10¹⁵	-0.75	0	1.77×10¹⁶	-1.22	99
CH+CO₂=HCO+CO				4.80×10¹	3.22	-13500	1.70×10¹²	0	2863
H+CH₃OH=CH₂OH+H₂	1.70×10⁷	2.10	20376	1.35×10³	3.20	14605	3.07×10⁵	2.55	22760
H+CH₃OH=CH₃O+H₂	4.20×10⁶	2.10	20376	6.83×10¹	3.40	30291	1.99×10⁵	2.56	43095

Fig.1 Temperature dependence of reaction rate constants for HO2+H=H2+O2(A) and C2H3+O2=CHO+CH2O(B) by three-parameter fitting and two-parameter fitting

Fig.2 Flash photolysis-resonance fluorescence(504—923 K) and flash photolysis-shock tube(880—2495 K) rate constants of O(3P)+H2=OH+H

Fig.3 Ignition delay time by UCSD, UCSD-R, UCSD-SC and the experimental data (A) 100% CH4, p=1.09 MPa; (B) 80%/20% CH4/H2, p=2.14 MPa; (C) 60%/40% CH4/H2, p=2.36 MPa.

Fig.4 Ignition delay time by UCSD, UCSD-R and the experimental data (A) 6.25%C2H4/18.75%O2/75%N2, p=0.6—0.83 MPa; (B) 6.25%C2H4/18.75%O2/75%N2, p=1.12—1.61 MPa; (C) 11.76%C2H4/17.65%O2/70.59%N2, p=0.64—0.82 MPa.

Fig.5 Ignition delay time by UCSD, UCSD-R and the experimental data (A) 30%C2H6/70%H2, p=0.12 MPa; (B) 30%C2H6/70%H2, p=0.41 MPa; (C) 30%C2H6/70%H2, p=1.62 MPa.

参考文献 22

[1]	Laidler K. J ., J. Chem. Educ, 1984, 61( 6), 494— 498
[2]	Tsang W., Hampson R. F ., J. Phys. Chem. Ref. Data, 1986, 15( 3), 1087— 1279
[3]	Wang H., Sheen D. A ., Prog. Energy Combust., 2015, 47, 1— 31
[4]	Smith G. P., Golden D. M., Frenklach M., Moriarty N. W., Eiteneer B., Goldenberg M., Bowman C. T., Hanson R. K., Song S., Gardiner W. C., Lissianski Jr. V. V., Qin Z . 1999. GRI-Mech 3.0. Available at:
[5]	Mechanical and Aerospace Engineering(Combustion Research), University of California at San Diego, San Diego Mechanism, Version 2016-12-14.
[6]	Li Y., Zhou C. W., Somers K. P., Zhang K. W., Curran H. J ., Proc. Combust. Inst., 2017, 36, 403— 411
[7]	Manion J. A., Huie R. E., Levin R. D., Burgess D. R., Orkin V. L., Tsang W., McGivern W. S., Hudgens J. W., Knyazev V. D., Atkinson D. B., Chai E., Tereza A. M., Lin C. Y., Allison T. C., Mallard W. G., Westley F., Herron J. T., Hampson R. F., Frizzell D. H ., NIST Chemical Kinetics Database, National Institute of Standards and Technology, USA,
[8]	Baulch D. L., Bowman C. T., Cobos C. J., Cox R. A., Just T., Kerr J. A., Pilling M. J., Stocker D., Troe J., Tsang W., Walker R. W., Warnatz J ., J. Phys. Chem. Ref. Data, 2005, 34( 3), 757— 1397
[9]	Sutherland J. W., Michael J. V., Pirraglia A. N., Nesbitt F. L., Klemm R. B ., Symposium on Combustion, 1988, 21( 1), 929— 941
[10]	Lindemann F. A., Arrhenius S., Langmuir I., Dhar N. R., Perrin J., McC. Lewis W. C ., Transactions of the Faraday Society, 1922, 17, 598— 606
[11]	Turányi T., Tomlin A. S ., Analysis of Kinetic Reaction Mechanisms, Springer-Verlag, Berlin Heidelberg, 2014
[12]	Curran H. J ., Proc. Combust. Inst., 2019, 37( 1), 57— 81
[13]	Marcus R. A ., J. Chem. Phys., 1952, 20( 3), 359— 364
[14]	Gilbert R. G., Smith S. C ., Theory of Unimolecular and Recombination Reactions, Blackwell, London, 1990
[15]	Jasper A. W., Miller J. A., Klippenstein S. J ., J. Phys. Chem. A, 2013, 117( 47), 12243— 12255
[16]	Miller J. A., Klippenstein S. J ., J. Phys. Chem. A, 2013, 117( 13), 2718— 2727
[17]	Li X. Y., Shentu J. T., Li Y. W., Li J. Q., Wang J. B ., Chem. J. Chinese Universities, 2020, doi: 10.7503/cjcu20190568
	( 李象远, 申屠江涛, 李宜蔚, 李娟琴, 王静波 . 高等学校化学学报, 2020, doi: 10.7503/cjcu20190568)
[18]	Glass I. I., Patterson G. N ., J. Aeronaut. Sci., 1955, 22( 2), 73— 100
[19]	CHEMKIN-PRO 15101, Reaction Design,San Diego, 2010
[20]	Petersen E. L., Hall J. M., Smith S. D., Vries J. D., Amadio A. R., Crofton M. W ., J. Eng. Gas. Turb. Power, 2007, 129( 4), 937— 944
[21]	Penyazkov O. G., Sevrouk K. L., Tangirala V., Joshi N ., Proc. Combust. Inst., 2009, 32( 2), 2421— 2428
[22]	Pan L., Zhang Y. J, Zhang J. X, Tian Z. M, Huang Z. H , Int. J. Hydrogen Energy, 2014, 39( 11), 6024— 6033