Methane cracking in molten tin for hydrogen and carbon production—a comparison with homogeneous gas phase process

Abstract

Methane cracking is considered a bridge technology between gray and green hydrogen production processes. In this work an experimental study of methane cracking in molten tin is performed. The tests were conducted in a quartz reactor (i.d. = 1.5 cm, L = 20 cm) with capillary injection, varying temperature (950–1070 °C), inlet methane flow rate (30–60 mL·min^–1) and tin height (0–20 cm). The influence of the residence time in the tin and in the headspace on methane conversion and on carbon morphology was investigated. The conversions obtained in tin and in the empty reactor were measured and compared with results of detailed kinetic simulations (CRECK). Furthermore, an expression of a global kinetic constant for methane conversion in tin was also derived. The highest conversion (65% at Q₀ = 30 mL·min^–1 and t = 1070 °C) is obtained for homogeneous gas phase reaction due to the long residence time (70 s), the presence of tin leads to a sharp decrease of residence time (1 s), obtaining a conversion of 35% at 1070 °C, thus meaning that tin owns a role in the reaction. Carbon characterization (scanning electron microscopy, Raman) reported a change in carbon toward sheet-like structures and an increase of the carbon structural order in the presence of molten tin media.

Key words： methane cracking; molten media; H₂ production; carbon morphology

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://dx.doi.org/10.1007/s11705-024-2437-x and is accessible for authorized users.

Competing interests

The authors declare that they have no competing interests.

References

1 Ferraren-De Cagalitan D D T , Abundo M L S . A review of biohydrogen production technology for application towards hydrogen fuel cells. Renewable & Sustainable Energy Reviews, 2021, 151: 111413

2 Soltani R , Rosen M A , Dincer I . Assessment of CO₂ capture options from various points in steam methane reforming for hydrogen production. International Journal of Hydrogen Energy, 2014, 39(35): 20266–20275

3 Patlolla S R , Katsu K , Sharafian A , Wei K , Herrera O E , Mérida W . A review of methane pyrolysis technologies for hydrogen production. Renewable & Sustainable Energy Reviews, 2023, 181: 113323

4 Song H , Luo S , Huang H , Deng B , Ye J . Solar-driven hydrogen production: recent advances, challenges, and future perspectives. ACS Energy Letters, 2022, 7(3): 1043–1065

5 Damizia M , Bracciale M P , Anania F , Tai L , De Filippis P , de Caprariis B . Efficient utilization of Al₂O₃ as structural promoter of Fe into 2 and 3 steps chemical looping hydrogen process: pure H₂ production from ethanol. International Journal of Hydrogen Energy, 2023, 48(99): 39112–39123

6 Arutyunov V , Savchenko V , Sedov I , Nikitin A . Non-catalytic gas phase oxidation of hydrocarbons. Eurasian Chemico-Technological Journal, 2022, 24(1): 13

7 De Filippis P , Scarsella M , de Caprariis B , Uccellari R . Biomass gasification plant and syngas clean-up system. Energy Procedia, 2015, 75: 240–245

8 Fabry F , Rehmet C , Rohani V , Fulcheri L . Waste gasification by thermal plasma: a review. Waste and Biomass Valorization, 2013, 4(3): 421–439

9 EuropeanCommission. Directorate-General for Climate Action. Going climate-neutral by 2050—a strategic long-term vision for a prosperous, modern, competitive and climate-neutral EU economy. 2019. Available at the website of Publication Office of the European Union

10 Weger L , Abánades A , Butler T . Methane cracking as a bridge technology to the hydrogen economy. International Journal of Hydrogen Energy, 2017, 42(1): 720–731

11 Serban M , Lewis M A , Marshall C L , Doctor R D . Hydrogen production by direct contact pyrolysis of natural gas. Energy & Fuels, 2003, 17(3): 705–713

12 Muradov N , Vezirolu T . From hydrocarbon to hydrogen? carbon to hydrogen economy. International Journal of Hydrogen Energy, 2005, 30(3): 225–237

13 de Caprariis B , Damizia M , Busillo E , De Filippis P . Advances in molten media technologies for methane pyrolysis. Advances in Chemical Engineering, 2023, 61: 319–356

14 Arutyunov V S , Strekova L N . The interplay of catalytic and gas-phase stages at oxidative conversion of methane: a review. Journal of Molecular Catalysis A Chemical, 2017, 426: 326–342

15 Horn R , Schlögl R . Methane activation by heterogeneous catalysis. Catalysis Letters, 2015, 145(1): 23–39

16 Parfenov V E , Nikitchenko N V , Pimenov A A , Kuz’min A E , Kulikova M V , Chupichev O B , Maksimov A L . Methane pyrolysis for hydrogen production: specific features of using molten metals. Russian Journal of Applied Chemistry, 2020, 93(5): 625–632

17 Kang D , Palmer C , Mannini D , Rahimi N , Gordon M J , Metiu H , McFarland E W . Catalytic methane pyrolysis in molten alkali chloride salts containing iron. ACS Catalysis, 2020, 10(13): 7032–7042

18 Rahimi N , Kang D , Gelinas J , Menon A , Gordon M J , Metiu H , McFarland E W . Solid carbon production and recovery from high temperature methane pyrolysis in bubble columns containing molten metals and molten salts. Carbon, 2019, 151: 181–191

19 Kudinov I V , Pimenov A A , Kryukov Y A , Mikheeva G V . A theoretical and experimental study on hydrodynamics, heat exchange and diffusion during methane pyrolysis in a layer of molten tin. International Journal of Hydrogen Energy, 2021, 46(17): 10183–10190

20 Plevan M , Geißler T , Abánades A , Mehravaran K , Rathnam R K , Rubbia C , Salmieri D , Stoppel L , Stückrad S , Wetzel T . Thermal cracking of methane in a liquid metal bubble column reactor: experiments and kinetic analysis. International Journal of Hydrogen Energy, 2015, 40(25): 8020–8033

21 Geißler T , Plevan M , Abánades A , Heinzel A , Mehravaran K , Rathnam R K , Rubbia C , Salmieri D , Stoppel L , Stückrad S . . Experimental investigation and thermo-chemical modeling of methane pyrolysis in a liquid metal bubble column reactor with a packed bed. International Journal of Hydrogen Energy, 2015, 40(41): 14134–14146

22 Assael M J , Kalyva A E , Antoniadis K D , Michael Banish R , Egry I , Wu J , Kaschnitz E , Wakeham W A . Reference data for the density and viscosity of liquid copper and liquid tin. Journal of Physical and Chemical Reference Data, 2010, 39(3): 033105

23 Msheik M , Rodat S , Abanades S . Experimental comparison of solar methane pyrolysis in gas-phase and molten-tin bubbling tubular reactors. Energy, 2022, 260: 124943

24 Cuoci A , Frassoldati A , Faravelli T , Ranzi E . OpenSMOKE++: an object-oriented framework for the numerical modeling of reactive systems with detailed kinetic mechanisms. Computer Physics Communications, 2015, 192: 237–264

25 Zeng J , Tarazkar M , Pennebaker T , Gordon M J , Metiu H , McFarland E W . Catalytic methane pyrolysis with liquid and vapor phase tellurium. ACS Catalysis, 2020, 10(15): 8223–8230

26 Leal Pérez B J , Medrano Jiménez J A , Bhardwaj R , Goetheer E , van Sint Annaland M , Gallucci F . Methane pyrolysis in a molten gallium bubble column reactor for sustainable hydrogen production: proof of concept & techno-economic assessment. International Journal of Hydrogen Energy, 2021, 46(7): 4917–4935

27 Alcock C B , Itkin V P , Horrigan M K . Vapour pressure equations for the metallic elements: 298–2500 K. Canadian Metallurgical Quarterly, 1984, 23(3): 309–313

28 Thapliyal V , Alabdulkarim M E , Whelan D R , Mainali B , Maxwell J L . A concise review of the Raman spectra of carbon allotropes. Diamond and Related Materials, 2022, 127: 1–16

29 Kim J , Oh C , Oh H , Lee Y , Seo H , Kim Y K . Catalytic methane pyrolysis for simultaneous production of hydrogen and graphitic carbon using a ceramic sparger in a molten NiSn alloy. Carbon, 2023, 207: 1–12

30 Parkinson B , Patzschke C F , Nikolis D , Raman S , Hellgardt K . Molten salt bubble columns for low-carbon hydrogen from CH₄ pyrolysis: mass transfer and carbon formation mechanisms. Chemical Engineering Journal, 2021, 417: 127407

31 Andreini R J , Foster J S , Callen R W . Characterization of gas bubbles injected into molten metals under laminar flow conditions. Metallurgical Transactions. B, Process Metallurgy, 1977, 8(4): 625–631

32 Sun Z , Parkinson B , Agbede O O , Hellgardt K . Noninvasive differential pressure technique for bubble characterization in high-temperature opaque systems. Industrial & Engineering Chemistry Research, 2020, 59(13): 6236–6246

33 von MorgensternI BMersmannA. Bildung fluider Partikeln in ruhenden und strömenden Flüssigkeiten. Chemieingenieurtechnik (Weinheim), 1983, 55(7): 580-581 (in German)

34 Lee J , Shimoda W , Tanaka T . Surface tension and its temperature coefficient of liquid Sn-X (X = Ag, Cu) alloys. Materials Transactions, 2004, 45(9): 2864–2870

35 Davidson L , Amick E H Jr . Formation of gas bubbles at horizontal orifices. AIChE Journal. American Institute of Chemical Engineers, 1956, 2(3): 337–342

36 Cuoci A , Frassoldati A , Faravelli T , Ranzi E . Numerical modeling of laminar flames with detailed kinetics based on the operator-splitting method. Energy & Fuels, 2013, 27(12): 7730–7753

37 Ranzi E , Cavallotti C , Cuoci A , Frassoldati A , Pelucchi M , Faravelli T . New reaction classes in the kinetic modeling of low temperature oxidation of n-alkanes. Combustion and Flame, 2015, 162(5): 1679–1691

38 Ranzi E , Frassoldati A , Grana R , Cuoci A , Faravelli T , Kelley A P , Law C K . Hierarchical and comparative kinetic modeling of laminar flame speeds of hydrocarbon and oxygenated fuels. Progress in Energy and Combustion Science, 2012, 38(4): 468–501

39 Zaghloul N , Kodama S , Sekiguchi H . Hydrogen production by methane pyrolysis in a molten hyphen metal bubble column. Chemical Engineering & Technology, 2021, 44(11): 1986–1993

40 Arutyunov V S , Vedeneev V I . Pyrolysis of methane in the temperature range 1000–1700 K. Russian Chemical Reviews, 1991, 60(12): 1384–1397

41 Kevorkian V , Heath C E , Boudart M . The decomposition of methane in shock waves 1. Journal of Physical Chemistry, 1960, 64(8): 964–968

42 Msheik M , Rodat S , Abanades S . Enhancing molten tin methane pyrolysis performance for hydrogen and carbon production in a hybrid solar/electric bubbling reactor. International Journal of Hydrogen Energy, 2024, 49: 962–980

43 Santangelo S , Messina G , Faggio G , Lanza M , Milone C . Evaluation of crystalline perfection degree of multi-walled carbon nanotubes: correlations between thermal kinetic analysis and micro-Raman spectroscopy. Journal of Raman Spectroscopy: JRS, 2011, 42(4): 593–602

44 Bokobza L , Bruneel J L , Couzi M . Raman spectra of carbon-based materials (from graphite to carbon black) and of some silicone composites. Journal of Carbon Research, C, 2015, 1: 77–94

45 Ferrari A C , Robertson J . Interpretation of Raman spectra of disordered and amorphous carbon. Physical Review B: Condensed Matter, 2000, 61(20): 14095–14107

46 Abánades A , Ruiz E , Ferruelo E M , Hernández F , Cabanillas A , Martínez-Val J M , Rubio J A , López C , Gavela R , Barrera G . . Experimental analysis of direct thermal methane cracking. International Journal of Hydrogen Energy, 2011, 36(20): 12877–12886

47 Qiao C , Che J , Wang J , Wang X , Qiu S , Wu W , Chen Y , Zu X , Tang Y . Cost effective production of high quality multilayer graphene in molten Sn bubble column by using CH₄ as carbon source. Journal of Alloys and Compounds, 2023, 930: 167495

48 Johansson K O , El Gabaly F , Schrader P E , Campbell M F , Michelsen H A . Evolution of maturity levels of the particle surface and bulk during soot growth and oxidation in a flame. 7Aerosol Science and Technology, 2017, 51(12): 1333–1344

49 Msheik M , Rodat S , Abanades S . Methane cracking for hydrogen production: a review of catalytic and molten media pyrolysis. Energies, 2021, 14(11): 3107