Reaction Mechanism of Methane-Flue Gas Thermochemical Reforming

doi:10.16552/j.cnki.issn1001-1625.2025.0886

Abstract

Abstract:

Studying the mechanism of methane-flue gas thermochemical reforming reaction is crucial for a deeper understanding of the interactions between methane-flue gas reforming reactants， optimizing methane-flue gas reforming reaction conditions and parameters， and improving the reaction yield and purity of methane-flue gas reforming reaction products. Experimental studies were conducted on dry reforming of methane and steam methane reforming reactions under different experimental conditions using an atmospheric pressure tube furnace. The effects of different experimental parameters on the reaction processes， reaction activity， and selectivity of dry reforming of methane and steam methane reforming reactions were analyzed. The results indicate that the methane-flue gas reforming reaction process is accompanied by the occurrence of methane cracking reaction. At temperatures below 1 100 ℃， methane cracking tends to generate carbon black and hydrogen gas. At temperatures above 1 100 ℃， methane cracking tends to generate acetylene ［C₂H₂］ and hydrogen gas. Under the same reaction conditions， the activity of steam methane reforming reaction is greater than that of dry reforming of methane. The increase in reforming reaction temperature is beneficial for the progress of methane-flue gas reforming reaction.

Key words: reaction mechanism, flue gas reforming, thermochemical regeneration, oxy-fuel, glass furnace

CLC Number:

TQ171.62

ZENG Hongjie, ZHOU Wencai, GUAN Min, SHEN Zhongjie, HE Guinan, CHEN Shuyong, CHEN Jiarui, LI Hongqiang, WANG Wei, ZUO Zefang. Reaction Mechanism of Methane-Flue Gas Thermochemical Reforming[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(2): 646-654.

Figures/Tables 10

References 19

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Experimentalparameter group	Volume flow （25 ℃）/（mL·min^-1）			Gas volume ratio			Gas volume flow/（mL·min^-1）
Experimentalparameter group	CH₄（gas）	CO₂ （gas）	H₂O （gas）	CH₄	CO₂	H₂O	Gas volume flow/（mL·min^-1）
1	397.08	397.08	0	1	1	0	794.16
2	264.72	529.44	0	1	2	0	794.16
3	529.44	264.72	0	2	1	0	794.16
4	397.08	0	397.08	1	0	1	794.16
5	264.72	0	529.44	1	0	2	794.16
6	529.44	0	264.72	2	0	1	794.16

Experimentalparameter group	Volume flow （25 ℃）/（mL·min^-1）			Gas volume ratio			Gas volume flow/（mL·min^-1）
Experimentalparameter group	CH₄（gas）	CO₂ （gas）	H₂O （gas）	CH₄	CO₂	H₂O	Gas volume flow/（mL·min^-1）
1	397.08	397.08	0	1	1	0	794.16
2	264.72	529.44	0	1	2	0	794.16
3	529.44	264.72	0	2	1	0	794.16
4	397.08	0	397.08	1	0	1	794.16
5	264.72	0	529.44	1	0	2	794.16
6	529.44	0	264.72	2	0	1	794.16

Reaction No.	Amount needed by reforming	Reaction
1	a	a CH₄→a C+2a H₂
2	b	b CH₄+b CO₂→2b H₂+2b CO
3	c	c CH₄+c H₂O→3c H₂+c CO
4	d	d CO+d H₂O→d CO₂+d H₂
5	e	e CO+2e H₂→e CH₃OH
6	f	f CO₂+3f H₂→f CH₃OH+ f H₂O

Reaction No.	Amount needed by reforming	Reaction
1	a	a CH₄→a C+2a H₂
2	b	b CH₄+b CO₂→2b H₂+2b CO
3	c	c CH₄+c H₂O→3c H₂+c CO
4	d	d CO+d H₂O→d CO₂+d H₂
5	e	e CO+2e H₂→e CH₃OH
6	f	f CO₂+3f H₂→f CH₃OH+ f H₂O

Experimental parameter group	Temperature/℃	a	b	c	d	Accompanying reactions
1	1 000	0.38	0.62	0	0	0.38 CH₄→0.38 C+0.76H₂； 0.62 CH₄+0.62 CO₂→1.24 H₂+1.24 CO
	1 100	0.15	0.85	0	0	0.15 CH₄→0.15 C+0.30 H₂； 0.85 CH₄+0.85 CO₂→1.70 H₂+1.70 CO
	1 200	0.20	0.80	0	0	0.20 CH₄→0.20 C+0.40 H₂； 0.80 CH₄+0.80 CO₂→1.60 H₂+1.60 CO
	1 300	0.17	0.83	0	0	0.17 CH₄→0.17 C+0.34 H₂； 0.83 CH₄+0.83 CO₂→1.66 H₂+1.66 CO
	1 400	0.13	0.87	0	0	0.13 CH₄→0.13 C+0.26 H₂； 0.87 CH₄+0.87 CO₂→1.74 H₂+1.74 CO
2	1 000	0.17	0.83	0	0	0.17 CH₄→0.17 C+0.34 H₂； 0.83 CH₄+0.83 CO₂→1.66 H₂+1.66 CO
	1 100	0	1.00	0	0	CH₄+CO₂→2 H₂+2 CO
	1 200	0	1.00	0	0	CH₄+CO₂→2 H₂+2 CO
	1 300	0	1.00	0	0	CH₄+CO₂→2 H₂+2 CO
	1 400	0	1.00	0	0	CH₄+CO₂→2 H₂+2 CO
3	1 000	0.73	0.27	0	0	0.73 CH₄→0.73 C+1.46 H₂； 0.27 CH₄+0.27 CO₂→0.54 H₂+0.54 CO
	1 100	0.63	0.37	0	0	0.63 CH₄→0.63 C+1.26 H₂； 0.37 CH₄+0.37 CO₂→0.74 H₂+0.74 CO
	1 200	0.57	0.43	0	0	0.57 CH₄→0.57 C+1.14 H₂； 0.43 CH₄+0.43 CO₂→0.86 H₂+0.86 CO
	1 300	0.53	0.47	0	0	0.53 CH₄→0.53 C+1.06 H₂； 0.47 CH₄+0.47 CO₂→0.94 H₂+0.94 CO
	1 400	0.50	0.50	0	0	0.50 CH₄→0.50 C+H₂； 0.50 CH₄+0.50 CO₂→H₂+CO
4	1 000	0.57	0	0.43	0.03	0.57 CH₄→0.57 C+1.14 H₂； 0.43 CH₄+0.43 H₂O→1.29 H₂+0.43 CO
	1 100	0.09	0	0.91	0.03	0.09 CH₄→0.09 C+0.18 H₂； 0.91 CH₄+0.91 H₂O→2.73 H₂+0.91 CO
	1 200	0.10	0	0.90	0.02	0.10 CH₄→0.10 C+0.20 H₂； 0.90 CH₄+0.90 H₂O→2.70 H₂+0.90 CO
	1 300	0	0	1.00	0.02	CH₄+H₂O→3 H₂+CO
	1 400	0	0	1.00	0	CH₄+H₂O→3 H₂+CO
5	1 000	0.14	0	0.86	0.01	0.14 CH₄→0.14 C+0.28 H₂； 0.86 CH₄+0.86 H₂O→2.58 H₂+0.86 CO
	1 100	0	0	1.00	0.02	CH₄+H₂O→3 H₂+CO
	1 200	0	0	1.00	0	CH₄+H₂O→3 H₂+CO
	1 300	0.06	0	0.94	0	0.06 CH₄→0.06 C+0.12 H₂； 0.94 CH₄+0.94 H₂O→2.82 H₂+0.94 CO
	1 400	0.08	0	0.92	0	0.08 CH₄→0.08 C+0.16 H₂； 0.92 CH₄+0.92 H₂O→2.76 H₂+0.92 CO
6	1 000	0.59	0	0.41	0	0.59 CH₄→0.59 C+1.18 H₂； 0.41 CH₄+0.41 H₂O→1.23 H₂+0.41 CO
	1 100	0.30	0	0.70	0	0.30 CH₄→0.30 C+0.60 H₂； 0.70 CH₄+0.70 H₂O→2.10 H₂+0.70 CO
	1 200	0.29	0	0.71	0	0.29 CH₄→0.29 C+0.58 H₂； 0.71 CH₄+0.71 H₂O→2.13 H₂+0.71 CO
	1 300	0.27	0	0.73	0	0.27 CH₄→0.27 C+0.54 H₂； 0.73 CH₄+0.73 H₂O→2.19 H₂+0.73 CO
	1 400	0.26	0	0.74	0	0.26 CH₄→0.26 C+0.52 H₂； 0.74 CH₄+0.74 H₂O→2.22 H₂+0.74 CO