Kinetics of Methane Decomposition in the Catalytic Liquid Metal Reactor for Hydrogen Production

doi:10.7503/cjcu20230421

Abstract

Abstract:

Liquid metal catalytic pyrolysis of methane is an emerging technology for the efficient production of hydrogen without CO₂ emissions. In this paper， a numerical model for catalytic methane pyrolysis within a liquid metal cracking reactor was introduced. Experimental data from our in-house liquid metal hydrogen production platform align closely with the model's predictions， which demonstrated a strong correlation between experimental findings and model outcomes. The model was constructed by integrating the catalytic thermal decomposition of methane at the gas-liquid interface， the non-catalytic pyrolysis processes within bubbles， and the fluid dynamics during bubble ascent. This framework harmoniously combines the kinetics of catalytic and non-catalytic reactions with fluid dynamics. Our approach utilizes parameters such as gas volumetric， flow rate， pressure， gas composition temperature and the inherent properties of the liquid metal（density， viscosity， and surface tension） to forecast both bubble dimensions and gas content within the melt. The model accurately predicted the methane conversion under different temperatures， methane flow rates， and liquid metal heights during the catalytic methane pyrolysis experiment using liquid copper-bismuth alloy（Cu_0.45Bi_0.55）. In addition， the gas holdup， superficial gas velocity， and pressure distribution along the height of the liquid metal during the catalytic methane pyrolysis process were obtained. Closely matching experimental data with model predictions provides compelling evidence of the model's robustness and reliability. The proposed model would be useful for reactor optimization and high hydrogen scale-up.

Key words: Liquid metal, Kinetics, Hydrodynamics, Catalytic methane pyrolysis

CLC Number:

O643

TrendMD:

LIAO Jiashu, LIU Jianxing, WANG Sishu, CHEN Bo, CHEN Jianjun, WEI Jianjun, YE Zongbiao, GOU Fujun. Kinetics of Methane Decomposition in the Catalytic Liquid Metal Reactor for Hydrogen Production[J]. Chem. J. Chinese Universities, 2024, 45(2): 20230421.

Figures/Tables 6

References 30

1	Midilli A.， Ay M.， Dincer I.， Rosen M. A.， Renew. Sust. Energ. Rev.， 2005， 9（3）， 255—271
2	Midilli A.， Ay M.， Dincer I.， Rosen M. A.， Renew. Sust. Energ. Rev.， 2005， 9（3）， 273—287
3	Muradov N. A.， Veziroglu T. N.， Int. J. Hydrog. Energy， 2008， 33（23）， 6804—6839
4	Muradov N.， Int. J. Hydrog. Energy， 2017， 42（20）， 14058—14088
5	Chen C. J.， Back M. H.， Back R. A.， Can. J. Chem.， 1976， 54（20）， 3117—3124
6	Muradov N.， Smith F.， Huang C.， T⁃Raissi A.， Catal. Today， 2006， 116（3）， 281—288
7	Ashik U. P. M.， Daud W. M. A. W.， Abbas H. F.， Renew. Sust. Energ. Rev.， 2015， 44， 221—256
8	Manoj P.， Zahira Y.， Qingming J.， Takriff M. S.， New J. Chem.， 2018， 42， 14843—14856
9	Kopp M.， Coleman D.， Stiller C.， Scheffer K.， Aichinger J.， Scheppat B.， Int. J. Hydrog. Energy， 2017， 42（19）， 13311—13320
10	Ayillath Kutteri D.， Wang I. W.， Samanta A.， Li L. L.， Hu J. L.， Catal. Sci. Technol.， 2019， 8（3）， 858—869
11	Dunker A. M.， Kumar S.， Mulawa P. A.， Int. J. Hydrog. Energy， 2006， 31（4）， 473—484
12	Patel S.， Kundu S.， Halder P.， Marzbali M. H.， Chiang K.， Surapaneni A.， Shah K.， Int. J. Hydrog. Energy， 2020， 45（55）， 29978—29992
13	Abbas H. F.， Daud W. M. A. W.， Appl. Catal. A： Gen.， 2010， 388（1/2）， 232—239
14	Botas J. A.， Serrano D. P.， Guil⁃López R.， Pizarro P.， Gómez G.， Int. J. Hydrog. Energy， 2010， 35（18）， 9788—9794
15	Bai Z. Q.， Chen H. K.， Li W.， Li B. Q.， Int. J. Hydrog. Energy， 2006， 31（7）， 899—905
16	Lázaro M. J.， Pinilla J. L.， Suelves I.， Moliner R.， Int. J. Hydrog. Energy， 2008， 33（15）， 4104—4111
17	Abánades A.， Rubbia C.， Salmieri D.， Energy， 2012， 46（1）， 359—363
18	Upham D. C.， Agarwal V.， Khechfe A.， Snodgrass Z. R.， Gordon M. J.， Metiu H.， McFarland E. W.， Science， 2017， 358（6365）， 917—921
19	Geißler T.， Abánades A.， Heinzel A.， Mehravaran K.， Müller G.， Rathnam R. K.， Rubbia C.， Salmieri D.， Stoppel L.， Stückrad S.， Weisenburger A.， Wenninger H.， Wetzel T.， Chem. Eng. J.， 2016， 299， 192—200
20	Plevan M.， Geißler T.， Abánades A.， Mehravaran K.， Rathnam R. K.， Rubbia C.， Salmieri D.， Stoppel L.， Stückrad S.， Wetzel T.， Int. J. Hydrog. Energy， 2015， 40（25）， 8020—8033
21	Scheiblehner D.， Neuschitzer D.， Wibner S.， Int. J. Hydrog. Energy， 2023， 48（16）， 6233—6243
22	Catalan L. J. J.， Rezaei E.， Int. J. Hydrog. Energy， 2020， 45（4）， 2486—2503
23	Catalan L. J. J.， Rezaei E.， Int. J. Hydrog. Energy， 2022， 47（12）， 7547—7568
24	Parkinson B.， Patzschke C. F.， Nikolis D.， Raman S.， Dankworth D. C.， Heligardt K.， Int. J. Hydrog. Energy， 2020， 46（9）， 6225—62388
25	Sun Z. T.， Parkinson B.， Agbede O. O.， Hellgardt K.， Ind. Eng. Chem. Res.， 2020， 59， 6236—6246
26	Akita K.， Yoshida F.， Ind. Eng. Chem. Process Des. Dev.， 1974， 13， 84—91
27	Stoppel L.， Fehling T.， Geissler T.， Baake E.， Wetzel T.， Mater. Sci. Engineer.， 2017 ， 228， 012—016
28	Kang D.， Rahimi N.， Gordon M. J.， Metiu H.， McFarland E. W.， Appl. Catal. B， 2019， 254， 659—666
29	Holmen A.， Olsvik O.， Rokstad O. A.， Fuel Process. Technol.， 1995， 42（2/3）， 249—267
30	Khan M. S.， Crynes B. L.， Ind. Eng. Chem.， 1970， 62（10）， 54—59

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