Thermodynamic Equilibrium Analysis of Hydrogen Production Via Dry Reforming of Methane Process Using Gibbs Free Energy Minimization Method

Document Type : Research Article


1 Department of Chemical Engineering, Tarbiat Modares University, Tehran, I.R.IRAN

2 Department of Chemical, Polymer and Materials Engineering, Boyin Zahra Technical and Engineering Higher Education Center, Imam Khomeini International University (RA), Qazvin, I.R.IRAN


In this paper, the thermodynamic equilibrium analysis of dry reforming of methane was performed by Aspen Plus software in order to increase the selectivity of hydrogen, elimination of carbon and adjust the H2/CO ratio. Equilibrium calculations were performed using Gibbs free energy minimization method. The effect of CO2/CH4 molar ratio (0-6), pressure (0.5-20 bar) and reaction temperature (300-1100 K) on equilibrium conversion rate, products selectivity and carbon formation were evaluated. The results showed that increasing the temperature and decreasing the molar ratio of CO2 / CH4 has positive effect on the rate of hydrogen selectivity, so that at the molar ratio of less than one CO2 / CH4 and temperature range above 1000 K, the rate of hydrogen selectivity reaches 100%. In contrast, with increasing pressure at constant temperature, the rate of hydrogen selectivity decreases, indicating the negative effect of the pressure on the rate of hydrogen selectivity. Carbon is the main by-product of dry reforming of methane, which must be removed in order to optimize operating conditions. At the ratio of CO2 / CH4 =1-6, with increasing the temperature and especially in the temperature range of 300-1000K, the amount of carbon formation decreases, but with increasing pressure, the amount of carbon production has an upward trend. On the other hand, with increasing the temperature, the conversion rate of carbon dioxide first decreases and then, with further increase in temperature, increases. In addition, the adjustment of H2/CO ratio of the syngas was performed for using in various processes, which can be achieved to the desired value by changing the CO2/CH4 ratio and pressure.


Main Subjects

[1] Aramouni N.A.K., Zeaiter J., Kwapinski W., Ahmad M.N., Thermodynamic Analysis of Methane Dry Reforming: Effect of the Catalyst Particle Size on Carbon Formation, Energy Convers. Manag., 150: 614–622 (2017).
[2] Turap Y., Wang I., Fu T., Wu Y., Wang Y., Wang W., Co–Ni Alloy Supported on CeO2 as a Bimetallic Catalyst for Dry Reforming of Methane, Int. J. Hydro. Ener., 45(11): 6538–6548 (2020).
[3] He X., Liu L., "Thermodynamic Analysis on the CO2 Conversion Processes of Methane Dry Reforming for Hydrogen Production and CO2 Hydrogenation to Dimethyl Ether", IOP Conference Series: Earth and Environmental Science, 1st International Global on Renewable Energy and Development (IGRED 2017) 22–25 December, Singapore, (2017).
[4] Bach V.R., de Camargo A.C., de Souza T.L., Cardozo-Filho L., Alves H.J., Dry Reforming of Methane over Ni/MgO–Al2O3 Catalysts: Thermodynamic Equilibrium Analysis and Experimental Application, Int. J. Hydrogen Energy, 45(8): 5252–5263 (2020).
[5] Lu, C., Xu, R., khan Muhammad, I., Zhu, X., Wei, Y., Qi, X., & Li, K., Thermodynamic Evolution of Magnetite Oxygen Carrier via Chemical Looping Reforming of Methane, J. Nat. Gas Sci. Eng., 85: 103704 (2021).
[6] Pham, T.P., Ro, K.S., Chen, L., Mahajan, D., Siang, T.J., Ashik, U.P.M., Hayashi, J.I., Pham Minh, D. and Vo, D.V.N., Microwave-Assisted Dry Reforming of Methane for Syngas Production: a Review, Environ. Chem. Lett., 18: 1987-2019 (2020).
[7] Chein R.-Y., Hsu W.-H., Thermodynamic Analysis of Syngas Production via Chemical Looping Dry Reforming of Methane, Energy, 180: 535–547 (2019).
[9] Cao P., Adegbite S., Zhao H., Lester E., Wu T., Tuning Dry Reforming of Methane for FT Syntheses: A Thermodynamic Approach, Appl. Energy, 227: 190–197 (2018).
[10] Chein R.Y., Hsu W.H., Yu C.T., Parametric Study of Catalytic Dry Reforming of Methane for Syngas Production at Elevated Pressures, Int. J. Hydrogen Energy, 42(21): 14485–14500 (2017).
[11] Bhattar S., Abedin M.A., Kanitkar S., Spivey J.J., A Review on Dry Reforming of Methane over Perovskite Derived Catalysts, Catal. Today, 365: 2–23 (2021).
[12] Marinho A.L.A., Rabelo-Neto R.C., Epron F., Bion N., Toniolo F.S.,  Noronha F.B., Embedded Ni Nanoparticles in CeZrO2 as Stable Catalyst for Dry Reforming of Methane, Appl. Catal. B Environ., 268: 118387 (2020).
[13] Bian Z., Zhong W., Yu Y., Wang Z., Jiang B., Kawi S., Dry Reforming of Methane on Ni/Mesoporous-Al2O3 Catalysts: Effect of Calcination Temperature, Int. J. Hydrogen Energy, 46(60): 31041-31053 (2021).
[14] Nikoo M.K., Amin N.A.S., Thermodynamic Analysis of Carbon Dioxide Reforming of Methane in View of Solid Carbon Formation, Fuel Process. Technol., 92(3): 678–691 (2011).
[15] Swapnesh A., Srivastava V.C., Mall I.D., Comparative Study on Thermodynamic Analysis of CO2 Utilization Reactions, Chem. Eng. Technol., 37(10): 1765–1777 (2014).
[16] Jafarbegloo M., Tarlani A., Mesbah A.W., Sahebdelfar S., Thermodynamic Analysis of Carbon Dioxide Reforming of Methane and its Practical Relevance, Int. J. Hydro. Ener., 40(6): 2445–2451 (2015).
[17] Aramouni  N.A.K., Touma J.G., Tarboush B.A., Zeaiter J., Ahmad M.N., Catalyst Design for Dry Reforming of Methane: Analysis Review, Renew. Sustain. Energy Rev., 82: 2570–2585 (2018).
[18] Chein R.Y., Chen Y.C., Yu C.T., Chung J.N., Thermodynamic Analysis of Dry Reforming of CH4 with CO2 at High Pressures, J. Nat. Gas Sci. Eng., 26: 617–629 (2015).