• Transactions of the Korean hydrogen and new energy society
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• v.13 no.3
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• pp.249-258
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• 2002

Thermochemical water-splitting IS(Iodine-Sulfur) process has been investigating for large-scale hydrogen production. For the construction of an efficient process scheme, two kinds of membrane technologies are under investigating to improve the hydrogen producing HI decomposition step. One is a concentration of HI in quasi-azeotropic HIx ($HI-H_2O-I_2$) solution by elecro-electrodialysis. It was confirmed that HI concentrated from the $HI-H_2O-I_2$ solution with a molar ratio of 1:5:1 at $80^{\circ}C$. The other is a membrane reactor to enhance the one-pass conversion of thermal decomposition reaction of gaseous hydrogen iodide (HI). It was found from the simulation study that the conversion of over 0.9 would be attainable using the membrane reactor using the gas permeation properties of the prepared silica hydrogen permselective membrane by chemical vapor deposition (CVD). Design criterion of the membrane reactor was also discussed.

• Transactions of the Korean hydrogen and new energy society
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• v.12 no.3
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• pp.219-229
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• 2001

Hydrogen production by a 2-step water-splitting thermochemical cycle using metal oxides (ferrites) redox pairs and $CH_4$ have been studied in this experiment. The ferrites were reacted with $CH_4$ at $700{\sim}800^{\circ}C$ to produce CO, $H_2$ and various reduced phases (reduction step); these were then reoxidized with water vapor to generate $H_2$ in water-splitting step (oxidation step) at $600{\sim}700^{\circ}C$. The reduced ferrites, Ni-FeO and Ni-Fe alloy showed respectively different reactivity for $H_2$ formation from $H_2O$. In reduction reaction at $800^{\circ}C$, carbon was deposited on surface of Ni-ferrite due to $CH_4$ decomposition. This reduced phase containing carbon, which was taken quite different feature from other phase, produced $H_2$, CO, $CO_2$ by reacting with $H_2O$ at $600^{\circ}C$. The amount of $H_2$ evolved using reduced phase containing carbon was much higher than that of other phase.

• Transactions of the Korean hydrogen and new energy society
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• v.17 no.4
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• pp.353-361
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• 2006

As one of the thermochemical water splitting hydrogen production cycles, which could be operated at the lower temperature below 1200 K, we investigated the feasibility of the cyclic operation of Ispra Mark 2 cycle with the addition of $ZrO_2$. The cycle is theoretically composed of three reaction steps; (1) 1st step($2MnO_2{\rightarrow}Mn_2O_3+0.5O_2$), (2) 2nd step($Mn_2O_3+4NaOH{\rightarrow}2Na_2O{\cdot}MnO_2+H_2+H_2O$) and (3) 3rd step($2Na_2O{\cdot}MnO_2H_2O{\rightarrow}4NaOH+2MnO_2$). From the TPR tests, the temperature ranges for $O_2$ production in 1st step and $H_2$ production in 2nd step were $550{\sim}750^{\circ}C$ and $650{\sim}750^{\circ}C$, respectively. In $MnO_2/Mn_2O_3/NaOH$ system, the formation of molten products due to the reaction between manganese oxides and NaOH were greatly decreased with the addition of $ZrO_2$. In addition, the results of a cyclic test were discussed with the viewpoint of $H_2$ production amounts and the feasibility of the process improvement.

• Transactions of the Korean hydrogen and new energy society
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• v.19 no.6
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• pp.505-513
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• 2008

The two-step thermochemical cycle was examined on the $CeO_2$, YSZ, and $ZrO_2$-supported $NiFe_2O_4$ to investigate the effects of support material addition. The supported $NiFe_2O_4$ was prepared by the aerial oxidation method. Thermal reduction was conducted at 1573K and 1523K while water-splitting was carried out at 1073K. Supporting $NiFe_2O_4$ on $CeO_2$, YSZ and $ZrO_2$ alleviated the high-temperature sintering of iron-oxide. As a result, the supported $NiFe_2O_4$ exhibited greater reactivity and repeatability in the water-splitting cycle as compared to the unsupported $NiFe_2O_4$. Especially, $ZrO_2$-supported $NiFe_2O_4$ showed better sintering inhibition effect than other supporting materials, but hydrogen production amount was decreased as cycle repeated. In case of $CeO_2$-supported $NiFe_2O_4$, improvement of hydrogen production was found when the thermal reduction was conducted at 1573K. It was deduced that redox reaction of $CeO_2$ activated above 1573K.

• Transactions of the Korean hydrogen and new energy society
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• v.15 no.3
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• pp.201-207
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• 2004

Redox characteristics of metal oxide for hydrogen production by thermochemical water-splitting were investigated. $CuFe_2O_4$ as a redox pair that had a different molar ratio of Cu and Fe were prepared by co-precipitation method. Hydrogen production consisted of water-splitting step and thermal reduction step was performed below 1200K. Redox characteristics of Cu-ferrites were studied using the thermal gravimetric analysis technique. Also, structure change of Cu-ferrite during thermal reduction was investigated using the high temperature controlled XRD. In results, oxygen release of Cu-ferrite during the thermal reduction was initiated at oxygen site combined with Cu. Consequently, oxygen release amount of Cu-ferrite was increased with increase of Cu molar ratio of Cu-ferrite. It was found that thermal reduction of Cu-ferrite was begun at $875^\circ{C}$. It was confirmed that structure of Cu-ferrite was changed to metal and cation excess metal oxide during the thermal reduction step.

• Journal of the Korean Solar Energy Society
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• v.33 no.2
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• pp.93-100
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• 2013

Two-step thermochemical cycle using ferrite-oxide($Fe_2O_4$) device was investigated. The $H_2O$(g) was converted into $H_2$ in the first experiment which was performed using a dish type solar thermal system. However the experiment was lasted only for 2 cycles because the metal oxide device was sintered and broken down. Another problem was that the reaction was taken place mainly on a side of the metal oxide device. The m-$ZrO_2$, which was widely known as a material preventing sintering, was applied on the metal oxide device. The ferrite loading rate and the thickness of the metal oxide device were increased from 10.67wt% to 20wt% and from 10mm to 15mm, respectively. The chemical reactor having two inlets was designed in order to supply the reactants uniformly to the metal oxide device. The second-experiment was lasted for 5 cycles, which was for 6 hours. The total amount of the $H_2$ production was 861.30ml. And cerium oxide($CeO_2$) device was used for increasing $H_2$ production rate. $CeO_2$ device had low thermal resistance, however, more $H_2$ production rate than $Fe_2O_4$ device.

• Journal of Energy Engineering
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• v.15 no.2 s.46
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• pp.107-117
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• 2006

The status of water splitting thermochemical cycle for hydrogen production was reviewed in this article. Mass production of hydrogen could be possible using the thermochemical process which is similar to the concept of conventional chemical reaction system if the high temperature heat source is available. The mediators (chemicals and reagents) should be used to split chemically stable water, and should be recycled in a closed cycle in order to be environmentally acceptable. Though there is no process to reach commercial stage, IS cycle, two-step cycles based on metallic oxide such as ZnO/Zn, $Fe_3O_4/FeO$ and the associated cycles are attracted due to their possibilities of application. Development of materials for high temperature and/or corrosive conditions during thermochemical process is still important topic in some thermochemical processes.

• Applied Chemistry for Engineering
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• v.18 no.6
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• pp.618-624
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• 2007

thermochemical methane reforming consisting of two steps on Cu/Fe/Zr mixed oxide media was carried out using a fixed bed infrared reactor. In the first step, the metal oxide was reduced with methane to produce CO, $H_2$ and the reduced metal oxide in the temperature of 1173 K. In the second step, the reduced metal oxide was re-oxidized with steam to produce $H_2$ and the metal oxide in the temperature of 973 K. The reaction characteristics on the added amounts of Cu in Cu/Fe/Zr mixed oxide media and the cyclic tests were evaluated. With the increase of the added amount of Cu in Cu/Fe/Zr mixed oxide media, the conversion of $CH_4$, the selectivity of $CO_2$ and the $H_2/CO$ molar ratio were increased, while the selectivity of CO was decreased in the first step. On the other hand, the evolved amount of $H_2$ was decreased with increasing the added amount of Cu in the second step. The $Cu_xFe_{3-x}O_4/ZrO_2$ medium added with Cu of x = 0.7 showed good regeneration properties in the 10th cyclic tests indicating that the medium had high durability. In addition, the gasification of the deposited carbon in the water splitting step was promoted with the addition of Cu in the media.

• Journal of the Korean Solar Energy Society
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• v.31 no.1
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• pp.107-114
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• 2011

Two-step thermochemical cycle using ferrite-oxide($Fe_3O_4$) device was investigated. The $H_2O$(g) was converted into $H_2$ in the first experiment which was performed using a dish type solar thermal system. However the experiment was lasted only for 2 cycles because the metal oxide device was sintered and broken down. Another problem was that the reaction was taken place mainly on a side of the metal oxide device. The $m-ZrO_2$, which was widely known as a material preventing sintering, was applied on the metal oxide device. The ferrite loading rate and the thickness of the metal oxide device were increased from 10.67wt% to 20wt% and from 10mm to 15mm, respectively. The chemical reactor having two inlets was designed in order to supply the reactants uniformly to the metal oxide device. The second-experiment was lasted for 5 cycles, which was for 6 hours. The total amount of the $H_2$ production was 861.30mL.