Thermodynamic assessment of hydrogen production via solar thermochemical cycle based on MoO<sub>2</sub>/Mo by methane reduction

doi:10.1007/s11708-019-0652-9

Front. Energy

2020, Vol. 14

Issue (1) : 71-80 https://doi.org/10.1007/s11708-019-0652-9

RESEARCH ARTICLE

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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Abstract

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<T_red<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 T_red = 1200 K and T_oxi = 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 Author(s): 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.

URL:

https://academic.hep.com.cn/fie/EN/10.1007/s11708-019-0652-9
https://academic.hep.com.cn/fie/EN/Y2020/V14/I1/71

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
$C 0$	Mean flux concentration ratio	suns
I	Normal beam solar insolation	W/m²
σ	Stefan- Boltzmann constant, 5.67 × 10⁻⁸	W/(m²·K⁴)
T₀	Ambient temperature	K
T_red	Reduction step temperature	K
T_oxi	Oxidation step temperature	K
Q_reactor	Received energy of solar reactor	kJ
n_eq	Equilibrium amount of substance	mol
n_i	Number of moles of substance	mol
h_{solar-to-fuel}	Solar-to-fuel efficiency
$Δ f H$	Standard molar enthalpy of formation	kJ/mol
$Δ H$	Enthalpy change	kJ/mol
C_P	Specific heat capacity	kJ/(mol·K)
S_i	Production selectivity of i
HHV	Higher heating value	kJ/mol
$χ CH 4$	Conversion ratio of CH₄
R_red	CH₄:MoO₂ ratio at the reduction step
R_oxi	H₂O:Mo ratio at the oxidation step

Tab.1 Nomenclature of main parameters

Fig.3 Equilibrium composition analysis under different R_red and temperature conditions.

Fig.4 Equilibrium composition selectivity of STC system at 600 K<T_red<1600 K.

Fig.5 Equilibrium compositions of oxidation step at 400 K<T_oxi<1600 K, and R_oxi = 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<T_red<3000 K (

p O 2

represents partial oxygen pressure.)

Fig.7 Computational U at temperature ranges of 600 K<T_red<1600 K, 400 K<T_oxi<1600 K and R_red = 2.

Fig.8 h_{solar-to-fuel} of STC system at 1020 K<T_red<1200 K, 400 K<T_oxi<1600 K.

Fig.9 Solar to fuel efficiency under isothermal operation at R_oxi = 2, 4, 6, and 8.

Fig.10 Solar-to-fuel efficiency in the second STC redox cycle.

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