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Frontiers in Energy

Front. Energy    2020, Vol. 14 Issue (1) : 71-80
Thermodynamic assessment of hydrogen production via solar thermochemical cycle based on MoO2/Mo by methane reduction
Jiahui JIN1, Lei WANG2, Mingkai FU3(), Xin LI2, Yuanwei LU1()
1. College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100022, China
2. Institute of Electrical Engineering, Chinese Academy of Sciences, Beijing 100190, China; University of Chinese Academy of Sciences, Beijing 100049, China
3. Institute of Electrical Engineering, Chinese Academy of Sciences, Beijing 100190, China
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Inspired by the promising hydrogen production in the solar thermochemical (STC) cycle based on non-stoichiometric oxides and the operation temperature decreasing effect of methane reduction, a high-fuel-selectivity and CH4-introduced solar thermochemical cycle based on MoO2/Mo is studied. By performing HSC simulations, the energy upgradation and energy conversion potential under isothermal and non-isothermal operating conditions are compared. In the reduction step, MoO2: CH4 = 2 and 1020 K<Tred<1600 K are found to be most favorable for syngas selectivity and methane conversion. Compared to the STC cycle without CH4, the introduction of methane yields a much higher hydrogen production, especially at the lower temperature range and atmospheric pressure. In the oxidation step, a moderately excessive water is beneficial for energy conversion whether in isothermal or non-isothermal operations, especially at H2O: Mo= 4. In the whole STC cycle, the maximum non-isothermal and isothermal efficiency can reach 0.417 and 0.391 respectively. In addition, the predicted efficiency of the second cycle is also as high as 0.454 at Tred = 1200 K and Toxi = 400 K, indicating that MoO2 could be a new and potential candidate for obtaining solar fuel by methane reduction.

Keywords MoO2/Mo based on solar thermochemical cycle      methanothermal reduction      isothermal and non-isothermal operation      syngas and hydrogen production      thermodynamic analysis     
Corresponding Authors: Mingkai FU,Yuanwei LU   
Online First Date: 19 December 2019    Issue Date: 16 March 2020
 Cite this article:   
Jiahui JIN,Lei WANG,Mingkai FU, et al. Thermodynamic assessment of hydrogen production via solar thermochemical cycle based on MoO2/Mo by methane reduction[J]. Front. Energy, 2020, 14(1): 71-80.
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Jiahui JIN
Mingkai FU
Xin LI
Yuanwei LU
Fig.1  ?G versus temperature with (red) and without (blue) CH4.
Fig.2  Process of solar thermochemical cycle with methane reduction based on MoO2/Mo.
Parameter Definition Unit
C0 Mean flux concentration ratio suns
I Normal beam solar insolation W/m2
σ Stefan- Boltzmann constant, 5.67 × 108 W/(m2·K4)
T0 Ambient temperature K
Tred Reduction step temperature K
Toxi Oxidation step temperature K
Qreactor Received energy of solar reactor kJ
neq Equilibrium amount of substance mol
ni Number of moles of substance mol
hsolar-to-fuel Solar-to-fuel efficiency
ΔfH Standard molar enthalpy of formation kJ/mol
ΔH Enthalpy change kJ/mol
CP Specific heat capacity kJ/(mol·K)
Si Production selectivity of i
HHV Higher heating value kJ/mol
χCH4 Conversion ratio of CH4
Rred CH4:MoO2 ratio at the reduction step
Roxi H2O:Mo ratio at the oxidation step
Tab.1  Nomenclature of main parameters
Fig.3  Equilibrium composition analysis under different Rred and temperature conditions.
Fig.4  Equilibrium composition selectivity of STC system at 600 K<Tred<1600 K.
Fig.5  Equilibrium compositions of oxidation step at 400 K<Toxi<1600 K, and Roxi = 2 (red), 4 (blue), 6 (pink), 8 (black).
Fig.6  Maximum production of H2 with (solid line) and without (dash line) CH4 at 1000 K<Tred<3000 K ( p O2 represents partial oxygen pressure.)
Fig.7  Computational U at temperature ranges of 600 K<Tred<1600 K, 400 K<Toxi<1600 K and Rred = 2.
Fig.8  hsolar-to-fuel of STC system at 1020 K<Tred<1200 K, 400 K<Toxi<1600 K.
Fig.9  Solar to fuel efficiency under isothermal operation at Roxi = 2, 4, 6, and 8.
Fig.10  Solar-to-fuel efficiency in the second STC redox cycle.
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