Minimized Reaction Network Method for Pyrolysis Mechanisms of n-Alkanes

doi:10.7503/cjcu20240531

Abstract

Abstract:

Simultaneously considering both high fidelity and low computational cost presents a significant challenge in modeling the pyrolysis and oxidation of fuels. In this work， a comprehensive kinetic model for the pyrolysis of n-alkanes covering n-heptane， n-decane， and n-dodecane had been developed based on the minimized reaction network（MRN） method. The total mechanism consists of 32 species and 58 reactions， which are validated against pyrolysis experimental data and mechanisms of multi-sizes in numerical simulations. In the pressure range of 0.02—5.00 MPa and the temperature range of 573—1732 K， the ability of this mechanism to predict the pyrolysis conversion and gas production of n-alkanes with temperature， pressure， and time variations is comparable to that of the detailed mechanism. Especially at high pressures， the sub-mechanisms for n-decane and n-dodecane exhibit higher predictive precision regarding both fuel conversion rates and the profiles of alkenes and acetylene， which makes them suitable for engineering numerical simulations of fuel pyrolysis and heat transfer. The pyrolysis mechanism can also be coupled with oxidation reactions to construct combustion mechanisms.

Key words: Minimized reaction network method, Pyrolysis, n-Alkane, Kinetic modeling

CLC Number:

O643.12

TrendMD:

LU Yanrong, SHENTU Jiangtao, LI Yiwei, MAO Yebing, LI Xiangyuan. Minimized Reaction Network Method for Pyrolysis Mechanisms of n-Alkanes[J]. Chem. J. Chinese Universities, 2025, 46(5): 20240531.

Figures/Tables 10

References 34

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Fuel	Type	Mechanism	Species	Reactions	Comment
n⁃Heptane	Detailed	LLNL3.1^［18］	654	2827	Pyrolysis and oxidation
n⁃Heptane	Reduced	Wu et al.^［19］	44	166	Pyrolysis
n⁃Heptane	MRN	This work	27	46	Pyrolysis
n⁃Decane	Detailed	Zeng et al.^［20］	234	1452	Pyrolysis and oxidation
n⁃Decane	Detailed	Gong et al.^［21］	298	1104	Pyrolysis
n⁃Decane	Reduced	Xiao^［22］	96	256	Pyrolysis and oxidation
n⁃Decane	MRN	This work	27	45	Pyrolysis
n⁃Decane and n⁃dodecane	Detailed	rev1stGen^［23］	1942	7849	Pyrolysis and oxidation
n⁃Dodecane	Detailed	Dahm et al.^［24］	154	1175	Pyrolysis
n⁃Dodecane	Detailed	Zhou et al.^［25］	146	842	Pyrolysis
n⁃Dodecane	MRN	This work	27	45	Pyrolysis
n⁃Alkanes up to n⁃dodecane	Detailed	JetSurF2.0^［26］	348	2163	Pyrolysis and oxidation
n⁃Alkanes up to n⁃hexadecane	Semi⁃detailed	Ranzi et al.^［27］	368	14462	Pyrolysis and oxidation
n⁃Heptane， n⁃decane， n⁃dodecane	MRN	This work	32	58	Pyrolysis

Fuel	Type	Mechanism	Species	Reactions	Comment
n⁃Heptane	Detailed	LLNL3.1^［18］	654	2827	Pyrolysis and oxidation
n⁃Heptane	Reduced	Wu et al.^［19］	44	166	Pyrolysis
n⁃Heptane	MRN	This work	27	46	Pyrolysis
n⁃Decane	Detailed	Zeng et al.^［20］	234	1452	Pyrolysis and oxidation
n⁃Decane	Detailed	Gong et al.^［21］	298	1104	Pyrolysis
n⁃Decane	Reduced	Xiao^［22］	96	256	Pyrolysis and oxidation
n⁃Decane	MRN	This work	27	45	Pyrolysis
n⁃Decane and n⁃dodecane	Detailed	rev1stGen^［23］	1942	7849	Pyrolysis and oxidation
n⁃Dodecane	Detailed	Dahm et al.^［24］	154	1175	Pyrolysis
n⁃Dodecane	Detailed	Zhou et al.^［25］	146	842	Pyrolysis
n⁃Dodecane	MRN	This work	27	45	Pyrolysis
n⁃Alkanes up to n⁃dodecane	Detailed	JetSurF2.0^［26］	348	2163	Pyrolysis and oxidation
n⁃Alkanes up to n⁃hexadecane	Semi⁃detailed	Ranzi et al.^［27］	368	14462	Pyrolysis and oxidation
n⁃Heptane， n⁃decane， n⁃dodecane	MRN	This work	32	58	Pyrolysis

Fuel	Type of reaction	Reaction
n⁃Heptane	Radical chain reaction initiation	C₇H₁₆⇌C₃H₇+C₄H₉
		C₇H₁₆⇌C₇H₁₅+H
	Radical chain propagation reaction	C₇H₁₆+H⇌C₇H₁₅+H₂
		C₇H₁₆+CH₃⇌C₇H₁₅+CH₄
		C₇H₁₅⇌C₅H₁₁+C₂H₄
		C₇H₁₅⇌CH₃+C₆H₁₂
n⁃Decane	Radical chain reaction initiation	C₁₀H₂₂⇌C₆H₁₃+C₄H₉
		C₁₀H₂₂⇌C₁₀H₂₁+H
	Radical chain propagation reaction	C₁₀H₂₂+H⇌C₁₀H₂₁+H₂
		C₁₀H₂₂+CH₃⇌C₁₀H₂₁+CH₄
		C₁₀H₂₁⇌C₄H₉+C₆H₁₂
n⁃Dodecane	Radical chain reaction initiation	C₁₂H₂₆⇌C₆H₁₃+ C₆H₁₃
		C₁₂H₂₆⇌C₁₂H₂₅+H
	Radical chain propagation reaction	C₁₂H₂₆+H⇌C₁₂H₂₅+H₂
		C₁₂H₂₆+CH₃⇌C₁₂H₂₅+CH₄
		C₁₂H₂₅⇌C₆H₁₃+C₆H₁₂
	Fundamental mechanism for C₀—C₆
H₂⇌H+H	C₃H₈⇌C₃H₇+H	C₄H₉⇌C₃H₆+CH₃
CH₄⇌CH₃+H	C₃H₈+H⇌C₃H₇+H₂	C₄H₉⇌C₄H₈+H
CH₄+H⇌CH₃+H₂	C₃H₇⇌CH₃+C₂H₄	C₄H₈⇌C₃H₅+CH₃
CH₃⇌CH₂+H	C₃H₇⇌C₃H₆+H	C₄H₈⇌C₄H₇+H
C₂H₆⇌CH₃+CH₃	C₃H₆⇌C₂H₃+CH₃	C₄H₈+H⇌C₄H₇+H₂
C₂H₆⇌C₂H₅+H	C₃H₆⇌C₃H₅+H	C₄H₇⇌C₂H₄+C₂H₃
C₂H₆+H⇌C₂H₅+H₂	C₃H₆+H⇌C₃H₅+H₂	C₄H₇⇌C₄H₆+H
C₂H₅⇌C₂H₄+H	C₃H₆+CH₃⇌C₃H₅+CH₄	C₄H₆⇌C₂H₃+C₂H₃
C₂H₄⇌C₂H₃+H	C₃H₅⇌C₂H₂+CH₃	C₄H₆⇌C₄H₅+H
C₂H₄+H⇌C₂H₃+H₂	C₃H₅⇌C₃H₄+H	C₄H₅⇌C₂H₂+C₂H₃
C₂H₄+CH₃⇌C₂H₃+CH₄	C₄H₁₀⇌2C₂H₅	C₄H₆+H⇌C₄H₅+H₂
C₂H₃⇌C₂H₂+H	C₄H₁₀⇌C₄H₉+H	C₅H₁₁⇌C₂H₅+C₃H₆
C₂H₂⇌C₂H+H	C₄H₁₀+H⇌C₄H₉+H₂	C₆H₁₂⇌C₄H₉+C₂H₃
C₃H₈⇌CH₃+C₂H₅	C₄H₉⇌C₂H₄+C₂H₅	C₆H₁₃⇌C₄H₉+C₂H₄

Fuel	Type of reaction	Reaction
n⁃Heptane	Radical chain reaction initiation	C₇H₁₆⇌C₃H₇+C₄H₉
		C₇H₁₆⇌C₇H₁₅+H
	Radical chain propagation reaction	C₇H₁₆+H⇌C₇H₁₅+H₂
		C₇H₁₆+CH₃⇌C₇H₁₅+CH₄
		C₇H₁₅⇌C₅H₁₁+C₂H₄
		C₇H₁₅⇌CH₃+C₆H₁₂
n⁃Decane	Radical chain reaction initiation	C₁₀H₂₂⇌C₆H₁₃+C₄H₉
		C₁₀H₂₂⇌C₁₀H₂₁+H
	Radical chain propagation reaction	C₁₀H₂₂+H⇌C₁₀H₂₁+H₂
		C₁₀H₂₂+CH₃⇌C₁₀H₂₁+CH₄
		C₁₀H₂₁⇌C₄H₉+C₆H₁₂
n⁃Dodecane	Radical chain reaction initiation	C₁₂H₂₆⇌C₆H₁₃+ C₆H₁₃
		C₁₂H₂₆⇌C₁₂H₂₅+H
	Radical chain propagation reaction	C₁₂H₂₆+H⇌C₁₂H₂₅+H₂
		C₁₂H₂₆+CH₃⇌C₁₂H₂₅+CH₄
		C₁₂H₂₅⇌C₆H₁₃+C₆H₁₂
	Fundamental mechanism for C₀—C₆
H₂⇌H+H	C₃H₈⇌C₃H₇+H	C₄H₉⇌C₃H₆+CH₃
CH₄⇌CH₃+H	C₃H₈+H⇌C₃H₇+H₂	C₄H₉⇌C₄H₈+H
CH₄+H⇌CH₃+H₂	C₃H₇⇌CH₃+C₂H₄	C₄H₈⇌C₃H₅+CH₃
CH₃⇌CH₂+H	C₃H₇⇌C₃H₆+H	C₄H₈⇌C₄H₇+H
C₂H₆⇌CH₃+CH₃	C₃H₆⇌C₂H₃+CH₃	C₄H₈+H⇌C₄H₇+H₂
C₂H₆⇌C₂H₅+H	C₃H₆⇌C₃H₅+H	C₄H₇⇌C₂H₄+C₂H₃
C₂H₆+H⇌C₂H₅+H₂	C₃H₆+H⇌C₃H₅+H₂	C₄H₇⇌C₄H₆+H
C₂H₅⇌C₂H₄+H	C₃H₆+CH₃⇌C₃H₅+CH₄	C₄H₆⇌C₂H₃+C₂H₃
C₂H₄⇌C₂H₃+H	C₃H₅⇌C₂H₂+CH₃	C₄H₆⇌C₄H₅+H
C₂H₄+H⇌C₂H₃+H₂	C₃H₅⇌C₃H₄+H	C₄H₅⇌C₂H₂+C₂H₃
C₂H₄+CH₃⇌C₂H₃+CH₄	C₄H₁₀⇌2C₂H₅	C₄H₆+H⇌C₄H₅+H₂
C₂H₃⇌C₂H₂+H	C₄H₁₀⇌C₄H₉+H	C₅H₁₁⇌C₂H₅+C₃H₆
C₂H₂⇌C₂H+H	C₄H₁₀+H⇌C₄H₉+H₂	C₆H₁₂⇌C₄H₉+C₂H₃
C₃H₈⇌CH₃+C₂H₅	C₄H₉⇌C₂H₄+C₂H₅	C₆H₁₃⇌C₄H₉+C₂H₄

Case	Dimension	Inlet mass flow rate/ （g·s^-1）	Inlet temperature， T_in/K	Operating pressure，p/MPa	Wall temperature， T_wall/K	Wall heat flux， q_w/（kW·m^-2）	Fuel
1	2D	0.05	573	0.1	973	—	n⁃Heptane
2	2D	1.00	573	0.1	973	—	n⁃Heptane
3	2D	1.00	573	2.0	973	—	n⁃Heptane
4	2D	0.05	573	2.0	973	—	n⁃Heptane
5	3D	1.00	753	4.0	—	640	n⁃Decane