Stepwise production of syngas and hydrogen through methane reforming and water splitting by using a cerium oxide redox system

Jeong, Hye Heun; Kwak, Jung Hun; Han, Gui Young; Yoon, Ki June

doi:10.1016/j.ijhydene.2011.08.079

Cited by 52 publications

(13 citation statements)

References 21 publications

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“…A4). Similar amount of methane cracking and carbon deposit have also been reported for the benchmark cerium dioxide in thermochemical CO 2 and H 2 O splitting cycles with MPO reduction [6,52,53]. While carbon formation by methane cracking decreases the amount of CO produced in the reduction step, the CO deficit can be recovered in the oxidation step during CO 2 splitting by the reverse Boudouard reaction.…”

Section: Resultssupporting

confidence: 72%

Earth-abundant transition metal oxides with extraordinary reversible oxygen exchange capacity for efficient thermochemical synthesis of solar fuels

et al. 2018

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Efficient storage of solar and wind power is one of the most challenging tasks still limiting the utilization of the prime but intermittent renewable energy sources. The direct storage of concentrated solar power in renewable fuels via thermochemical splitting of water and carbon dioxide on a redox material is a scalable approach with up to 54% solar-to-fuel conversion efficiency. Despite progress, the search for earth-abundant materials that can provide and maintain high H 2 and CO production rates over long period of high-temperature cycles continues. Here, we report a strategy to unlock the use of manganese, the 12th most abundant element in the Earth's crust, for thermochemical synthesis of solar fuels, achieving superior thermochemical stability, oxygen exchange capacity, and up to seven times higher mass-specific H 2 and CO yield than cerium dioxide. We observe that incorporation of a small fraction of cerium ions in the manganese (II,III) oxide crystal lattice drastically increases its oxygen ion mobility, allowing its reduction from oxide to carbide during methane partial oxidation with simultaneous Ce exsolution. High CO 2 and H 2 O splitting rates are achieved by re-oxidation of the carbide to manganese (II) oxide with simultaneous reincorporation of the cerium ions. We demonstrate that the oxide to carbide reaction is highly reversible achieving remarkable CO 2 splitting rates over 100 thermochemical cycles of methane partial oxidation and CO 2 splitting, and preserving the initial oxygen exchange capacity of 0.65 mol O − mol Mn 1 and 89% of the fuel production rates. Due to this extraordinarily high reversible oxygen exchange capacity, the 3% Ce-doped manganese oxide achieves an average mass-specific CO yield for CO 2 splitting of 17.72 mmol CO g −1 , which is significantly higher than that previously achieved in thermochemical redox cycles. More generally, these findings suggest that incorporation of small soluble amounts of cerium in earth-abundant transition metal oxides like manganese oxide is a powerful approach to enable solar thermochemical fuel synthesis.

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Section: Resultssupporting

confidence: 72%

Earth-abundant transition metal oxides with extraordinary reversible oxygen exchange capacity for efficient thermochemical synthesis of solar fuels

et al. 2018

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“…Steam and methane are singly entered to the reactor; hence, the problem of purification in the SMR process is avoided in the current method. Different metal oxides including Fe-based oxides [17][18][19][20][21], WO 3 [22,23], ferrites [24][25][26][27][28], and Ce-based oxides [29][30][31][32][33] were investigated as oxygen carriers for hydrogen production using chemical looping technology. CeO 2 has high capacity for oxygen storage and cerium-based oxides also exhibit a desirable reactivity in the methane partial oxidation to synthesis gas [29][30][31]34].…”

Section: Introductionmentioning

confidence: 99%

Kinetic Study of the Reduction Step for Chemical Looping Steam Methane Reforming by CeO₂‐Fe₂O₃ Oxygen Carriers

2020

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The reduction stage of chemical looping steam methane reforming was investigated to determine the kinetics of the reduction reaction for CeO2‐Fe2O3 mixed oxides. CeO2, Fe2O3, and CeO2‐Fe2O3 mixed oxides with different molar ratios were prepared by chemical precipitation. Characterization tests indicated the lowest Brunauer‐Emmett‐Teller surface area for samples with higher Fe content. The largest area under reduction peaks during hydrogen temperature‐programmed reduction measurements was also related to the samples with highest Fe content. Reduction of the oxygen carriers with lower Fe content was well represented by a phase boundary‐controlled model.

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“…carriers from the first to the second cycle which can be attributed to the growing and sticking of particles in the water splitting step [27]. Also, it can be stated that after repeated cycles a very small amount of carbon deposits on the oxygen carriers and may cause a slight deactivation of these oxygen carriers.…”

Section: Ni039fe261o4-ceo2mentioning

confidence: 99%

“…Also, it can be stated that after repeated cycles a very small amount of carbon deposits on the oxygen carriers and may cause a slight deactivation of these oxygen carriers. But in the water splitting step, by increasing the temperature, the oxygen carriers were regenerated by steam and from the second cycle to the fifth cycle the conversion rates become nearly constant [17,27]. In order to evaluate the obtained results, they were compared with the investigation of Kodama et al on Ni 0.39 Fe 2.61 O 4 /ZrO 2 [13].…”

Section: Ni039fe261o4-ceo2mentioning

confidence: 99%

Chemical Looping Steam Methane Reforming via Ni‐ferrite Supported on Cerium and Zirconium Oxides

2020

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Pure hydrogen was produced by means of chemical looping steam methane reforming with novel oxygen carriers. Ni‐ferrite, Ni‐ferrite‐ZrO2, and Ni‐ferrite‐CeO2 were synthesized as oxygen carriers and characterized by X‐ray diffraction (XRD), Brunauer‐Emmett‐Teller (BET) method, scanning electron microscopy (SEM), dynamic light scattering (DLS), and hydrogen temperature‐programmed reduction (H2‐TPR). The performances of the as‐synthesized oxygen carriers in the cyclic oxidation‐reduction were investigated in the packed‐bed microreactor at a defined temperature range and under atmospheric pressure. Ni0.39Fe2.61O4‐ZrO2 exhibited the best performance and maximum methane conversion among the other oxygen carriers. In addition, high selectivities for H2 and CO were reached.

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Stepwise production of syngas and hydrogen through methane reforming and water splitting by using a cerium oxide redox system

Cited by 52 publications

References 21 publications

Earth-abundant transition metal oxides with extraordinary reversible oxygen exchange capacity for efficient thermochemical synthesis of solar fuels

Earth-abundant transition metal oxides with extraordinary reversible oxygen exchange capacity for efficient thermochemical synthesis of solar fuels

Kinetic Study of the Reduction Step for Chemical Looping Steam Methane Reforming by CeO₂‐Fe₂O₃ Oxygen Carriers

Chemical Looping Steam Methane Reforming via Ni‐ferrite Supported on Cerium and Zirconium Oxides

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Stepwise production of syngas and hydrogen through methane reforming and water splitting by using a cerium oxide redox system

Cited by 52 publications

References 21 publications

Earth-abundant transition metal oxides with extraordinary reversible oxygen exchange capacity for efficient thermochemical synthesis of solar fuels

Earth-abundant transition metal oxides with extraordinary reversible oxygen exchange capacity for efficient thermochemical synthesis of solar fuels

Kinetic Study of the Reduction Step for Chemical Looping Steam Methane Reforming by CeO2‐Fe2O3 Oxygen Carriers

Chemical Looping Steam Methane Reforming via Ni‐ferrite Supported on Cerium and Zirconium Oxides

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Kinetic Study of the Reduction Step for Chemical Looping Steam Methane Reforming by CeO₂‐Fe₂O₃ Oxygen Carriers