Operation Window of Integrated Methanol Steam Reformer/High-Temperature Proton Exchange Membrane Fuel Cells: A Three-Dimensional Numerical Study

Abstract

Stack-integrated methanol steam reformer (MSR)/high-temperature proton exchange membrane fuel cell (HT-PEMFC) systems enable simultaneous hydrogen production and power generation within monolithic devices, significantly reducing system complexity and costs. However, in situ heat exchange between endothermic reforming layers and exothermic fuel cell layers creates complex thermal interactions under variable loads, posing a critical challenge to stable operation. Here, we systematically evaluate the adiabatic operational limits of a fully coupled stack-integrated MSR/HT-PEMFC using three-dimensional computational fluid dynamics. Although thermoneutral operation can be achieved at 0.4 A/cm² under isothermal conditions, adiabatic operation introduces temperature gradients exceeding 30 °C and elevates reformate carbon monoxide (CO) concentrations beyond 2000 × 10⁻⁶, which can irreversibly degrade fuel cell performance. Parametric analysis reveals a critical trade-off: reducing voltage or increasing methanol feed rates lowers CO levels by 38% but degrades system efficiency by 15%, highlighting an inherent safety–efficiency conflict in adiabatic systems. These findings underscore the necessity of coordinated voltage and methanol feed flow regulation, as well as strategic decoupling of MSR and PEMFC for practical implementation.

Keywords

Methanol steam reforming / High-temperature proton exchange membrane fuel cell / Computational fluid dynamics / Multiphysics modeling / Integration

References

[1] Lotrič A, Sekavčnik M, Hočevar S. Effectiveness of heat-integrated methanol steam reformer and polymer electrolyte membrane fuel cell stack systems for portable applications. J Power Sources, 2014, 270: 166-182.

[2] Wang Y, Wu Q, Mei D, et al. . Development of highly efficient methanol steam reforming system for hydrogen production and supply for a low temperature proton exchange membrane fuel cell. Int J Hydrogen Energ, 2020, 45(46): 25317-25327.

[3] Tang XW, Zhang YJ, Xu SC. Experimental study of PEM fuel cell temperature characteristic and corresponding automated optimal temperature calibration model. Energy, 2023, 283128456

[4] Liu M, Shi Y, Cai N. Modeling of packed bed methanol steam reformer integrated with tubular high temperature proton exchange membrane fuel cell. J Therm Sci, 2023, 32(1): 81-92.

[5] Baak JA, Pozarlik AK, Arentsen MJ, et al. . Techno-economic study of a zero-emission methanol based energy storage system. Energy Convers Manag, 2019, 182: 530-545.

[6] Thomas S, Vang JR, Araya SS, et al. . Experimental study to distinguish the effects of methanol slip and water vapour on a high temperature PEM fuel cell at different operating conditions. Appl Energ, 2017, 192: 422-436.

[7] Sikarwar VS, Pfeifer C, Ronsse F, et al. . Progress in in-situ CO₂-sorption for enhanced hydrogen production. Prog Energy Combust Sci, 2022, 91101008

[8] Avgouropoulos G, Schlicker S, Schelhaas K-P, et al. . Performance evaluation of a proof-of-concept 70 W internal reforming methanol fuel cell system. J Power Sources, 2016, 307: 875-882.

[9] Papavasiliou J, Schütt C, Kolb G, et al. . Technological aspects of an auxiliary power unit with internal reforming methanol fuel cell. Int J Hydrog Energy, 2019, 44(25): 12818-12828.

[10] Ji F, Yang L, Li Y, et al. . Performance enhancement by optimizing the reformer for an internal reforming methanol fuel cell. Energy Sci Eng, 2019, 7(6): 2814-2824.

[11] Lin C, Kerscher F, Herrmann S, et al. . Analysis on temperature uniformity in methane-rich internal reforming solid oxide fuel cells (SOFCs). Int J Hydrogen Energ, 2024, 57: 769-788.

[12] Zhang R, Zheng H, Li C, et al. . Optimization of kW-scale methanol reforming high-temperature proton exchange membrane fuel cells with efficient waste heat utilization. Fuel, 2024, 375132478

[13] Wu Q, Mei D, Qiu X, et al. . Development of multilevel amplified methanol steam reforming microreactor with high hydrogen production rate. Fuel, 2023, 350128800

[14] Ben-Mansour R, Haque MA, Habib MA, et al. . Effect of temperature and heat flux boundary conditions on hydrogen production in membrane-integrated steam-methane reformer. Appl Energ, 2023, 346121407

[15] Wang L, Li X, Wang C, et al. . Enhancing collaborative PHM of complex equipment: a MBSE approach for PEMFC health management systems. Int J Hydrogen Energ, 2024, 94: 1361-1373.

[16] Zhu J, Cui X, Araya SS. Comparison between 1D and 2D numerical models of a multi-tubular packed-bed reactor for methanol steam reforming. Int J Hydrogen Energy, 2022, 47(54): 22704-22719.

[17] Saidi M. Performance assessment and evaluation of catalytic membrane reactor for pure hydrogen production via steam reforming of methanol. Int J Hydrogen Energ, 2017, 42(25): 16170-16185.

[18] Habib MA, Haque MA, Harale A, et al. . Palladium-alloy membrane reactors for fuel reforming and hydrogen production: hydrogen production modeling. Case Stud Therm Eng, 2023, 49103359

[19] Uriz I, Arzamendi G, Diéguez PM. CFD analysis of the effects of the flow distribution and heat losses on the steam reforming of methanol in catalytic (Pd/ZnO) microreactors. Chem Eng J, 2014, 238: 37-44.

[20] Ribeirinha P, Abdollahzadeh M, Pereira A, et al. . High temperature PEM fuel cell integrated with a cellular membrane methanol steam reformer: experimental and modelling. Appl Energ, 2018, 215: 659-669.

[21] Avgouropoulos G, Papavasiliou J, Daletou MK, et al. . Reforming methanol to electricity in a high temperature PEM fuel cell. Appl Catal B, 2009, 90(3/4): 628-632.

[22] Iulianelli A, Ribeirinha P, Mendes A, et al. . Methanol steam reforming for hydrogen generation via conventional and membrane reactors: a review. Renew Sustain Energy Rev, 2014, 29: 355-368.

[23] Jiao K, Xuan J, Du Q, et al. . Designing the next generation of proton-exchange membrane fuel cells. Nature, 2021, 595(7867): 361-369.

[24] Li N, Cui X, Zhu J, et al. . A review of reformed methanol-high temperature proton exchange membrane fuel cell systems. Renew Sustain Energy Rev, 2023, 182113395

[25] Ghodba A, Sharifzadeh M, Rashtchian D. Integrated and inherently safe design and operation of a mobile power generation: process intensification through microreactor reformer and HT-PEMFC. Int J Hydrogen Energ, 2021, 46(46): 23839-23854.

[26] Garcia G, Arriola E, Chen W-H, et al. . A comprehensive review of hydrogen production from methanol thermochemical conversion for sustainability. Energy, 2021, 217119384

[27] Hu Y, Han C, Li W, et al. . Investigation of methanol steam reforming reformer heated by catalyst combustion for kW-scale fuel cell. Therm Sci Eng Prog, 2023, 45102114

[28] Ribeirinha P, Abdollahzadeh M, Sousa JM, et al. . Modelling of a high-temperature polymer electrolyte membrane fuel cell integrated with a methanol steam reformer cell. Appl Energy, 2017, 202: 6-19.

[29] Haghighat Mamaghani A, Najafi B, Casalegno A, et al. . Predictive modelling and adaptive long-term performance optimization of an HT-PEM fuel cell based micro combined heat and power (CHP) plant. Appl Energ, 2017, 192: 519-529.

[30] Perng S-W, Wu H-W. Influence of inlet-nozzle and outlet-diffuser mounted in the plate-shape reactor on PEMFC net power output and methanol steam reforming performance. Appl Energ, 2022, 323119510

[31] Ghasemzadeh K, Harasi JN, Amiri TY, et al. . Methanol steam reforming for hydrogen generation: a comparative modeling study between silica and Pd-based membrane reactors by CFD method. Fuel Process Technol, 2020, 199106273

[32] Shao Q, Yang Y, Liang H, et al. . Progresses in treatment processes and quantification strategies of micro-and nanoplastics. Prog Nat Sci-Mater, 2025, 35: 666-682.

[33] Pei H, Liu Z, Sun L, et al. . Visualisation study on water management of cathode dead-ended PEMFC under pressure-swing operation. Prog Nat Sci-Mater, 2024, 34(4): 814-823.

[34] Pei H, Liu Z, Chen J, et al. . Dynamic response study of air-cooled proton exchange membrane fuel cell stack. Prog Nat Sci-Mater, 2024, 34(6): 1318-1326.

[35] He X, Zhu Z, Liao X, et al. . In-situ construction of epitaxial phase for boosting zinc nucleation on three-dimensional interface. Prog Nat Sci-Mater, 2024, 34(3): 578-584.

[36] Chippar P, Ju H. Three-dimensional non-isothermal modeling of a phosphoric acid-doped polybenzimidazole (PBI) membrane fuel cell. Solid State Ion, 2012, 225: 30-39.

[37] Oh K, Jeong G, Cho E, et al. . A CO poisoning model for high-temperature proton exchange membrane fuel cells comprising phosphoric acid-doped polybenzimidazole membranes. Int J Hydrogen Energ, 2014, 39(36): 21915-21926.

[38] Abdul Rasheed RK, Chan SH. Transient carbon monoxide poisoning kinetics during warm-up period of a high-temperature PEMFC: physical model and parametric study. Appl Energ, 2015, 140: 44-51.

[39] Jiao K, Alaefour IE, Li X, et al. . Three-dimensional non-isothermal modeling of carbon monoxide poisoning in high temperature proton exchange membrane fuel cells with phosphoric acid doped polybenzimidazole membranes. Fuel, 2011, 90(2): 568-582.

[40] Ribeirinha P, Abdollahzadeh M, Boaventura M, et al. . H₂ production with low carbon content via MSR in packed bed membrane reactors for high-temperature polymeric electrolyte membrane fuel cell. Appl Energ, 2017, 188: 409-419.

[41] Peppley BA, Amphlett JC, Kearns LM, et al. . Methanol–steam reforming on Cu/ZnO/Al₂O₃ catalysts. Part 2. A comprehensive kinetic model. Appl Catal A Gen, 1999, 179(1/2): 31-49.

[42] Ribeirinha P, Schuller G, Boaventura M. Synergetic integration of a methanol steam reforming cell with a high temperature polymer electrolyte fuel cell. Int J Hydrogen Energ, 2017, 42(19): 13902-13912.

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