• Korean Chemical Engineering Research
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• v.58 no.2
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• pp.235-247
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• 2020

Simulation study and validation on 50 L/hr pilot-scale Bunsen process was carried out in order to investigate thermodynamics parameters, suitable reactor type, separator configuration, and the optimal conditions of reactors and separation. Sulfur-Iodine is thermochemical process using iodine and sulfur compounds for producing hydrogen from decomposition of water as net reaction. Understanding in phase separation and reaction of Bunsen Process is crucial since Bunsen Process acts as an intermediate process among three reactions. Electrolyte Non-Random Two-Liquid model is implemented in simulation as thermodynamic model. The simulation results are validated with the thermodynamic parameters and the 50 L/hr pilot-scale experimental data. The SO₂ conversions of PFR and CSTR were compared as varying the temperature and reactor volume in order to investigate suitable type of reactor. Impurities in H₂SO₄ phase and HI_X phase were investigated for 3-phase separator (vapor-liquid-liquid) and two 2-phase separators (vapor-liquid & liquid-liquid) in order to select separation configuration with better performance. The process optimization on reactor and phase separator is carried out to find the operating conditions and feed conditions that can reach the maximum SO₂ conversion and the minimum H₂SO₄ impurities in HI_X phase. For reactor optimization, the maximum 98% SO₂ conversion was obtained with fixed iodine and water inlet flow rate when the diameter and length of PFR reactor are 0.20 m and 7.6m. Inlet water and iodine flow rate is reduced by 17% and 22% to reach the maximum 10% SO₂ conversion with fixed temperature and PFR size (diameter: 3/8", length:3 m). When temperature (121℃) and PFR size (diameter: 0.2, length:7.6 m) are applied to the feed composition optimization, inlet water and iodine flow rate is reduced by 17% and 22% to reach the maximum 10% SO₂ conversion.

• Transactions of the Korean hydrogen and new energy society
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• v.22 no.4
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• pp.424-431
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• 2011

The Sulfur-Iodine(SI) thermochemical hydrogen production process consists of three sections, which are so called the Bunsen reaction section, the $H_2SO_4$ decomposition section and the HI decomposition section. In order to identify the phase separation characteristics in the reaction conditions with the high solubility of $SO_2$, we conducted the Bunsen reaction at the low temperatures, ranging from 283 to 298K, with the $I_2/H_2O$ molar ratios of 2.5/16.0 and 3.5/16.0. The molar ratios of HI/$H_2SO_4$ products obtained from low temperature Bunsen reactions were ca. 2, indicating that there were no side reactions. The amount of reacted $SO_2$ was increased with decreasing the temperature, while the amounts of unreacted $I_2$ and $H_2O$ were decreased. In the phase separation of the products, the amount of a $H_2SO_4$ impurity in $HI_x$ phase was increased with decreasing the temperature, though the temperature has little affected on HI and $I_2$ impurities in $H_2SO_4$ phase.

• Transactions of the Korean hydrogen and new energy society
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• v.19 no.1
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• pp.49-55
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• 2008

The feasibility of ionic liquid as a novel absorbent of $SO_2$ for the separation of $SO_2$ from $SO_2/O_2$ mixture in the thermochemical IS(Iodine-Sulfur) cycle was investigated. 1,3-dimethylimidazolium methylsulfate ([DMIm]$MeSO_4$) had shown twenty five times higher solubility of $SO_2$ than that of $O_2$. The dependence of $SO_2$ solubility by [DMIm]$MeSO_4$ on temperature and $SO_2$ partial pressure was examined, which confirmed the possibility of temperature and pressure swing for the separation process. Through cyclic absorption and desorption with temperature swing the stability of [DMIm]$MeSO_4$ in the separation process was also demonstrated. As a result of the experiments carried out, $SO_2$ separation from $SO_2/O_2$ mixture with ionic liquid([DMIm]$MeSO_4$) can be applied to the thermochemical IS cycle.

• Nuclear Engineering and Technology
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• v.46 no.3
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• pp.363-372
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• 2014

In this study, we proposed a newly designed sulfuric acid transfer system for the sulfur-iodine (SI) thermochemical cycle. The proposed sulfuric acid transfer system was evaluated using a computational fluid dynamics (CFD) analysis for investigating thermodynamic/hydrodynamic characteristics and material properties. This analysis was conducted to obtain reliable continuous operation parameters; in particular, a thermal analysis was performed on the bellows box and bellows at amplitudes and various frequencies (0.1, 0.5, and 1.0 Hz). However, the high temperatures and strongly corrosive operating conditions of the current sulfuric acid system present challenges with respect to the structural materials of the transfer system. To resolve this issue, we designed a novel transfer system using polytetrafluoroethylene (PTFE, $Teflon^{(R)}$) as a bellows material for the transfer of sulfuric acid. We also carried out a CFD analysis of the design. The CFD results indicated that the maximum applicable temperature of PTFE is about 533 K ($260^{\circ}C$), even though its melting point is around 600 K. This result implies that the PTFE is a potential material for the sulfuric acid transfer system. The CFD simulations also confirmed that the sulfuric acid transfer system was designed properly for this particular investigation.

• 한국신재생에너지학회:학술대회논문집
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• 2007.06a
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• pp.69-72
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• 2007

The objective of this work was to study the properties of purification of two liquid phase for exclusion of impurities in each phase. The experiments for process variables were carried out in the temperature range($H_{2}SO_{4}$ phase: $413{\sim}513$ K, $HI_{x}$ phase: $353{\sim}453$ K) and in the $N_{2}$ flow rate range($H_{2}SO_{4}$, $HI_{x}$ phase: $50{\sim}200$ mL/min). As the results, it is appeared that the principles of $H_{2}SO_{4}$ phase purification was due to stripping, evaporation and reverse bunsen reaction and $HI_{x}$ phase purification was due to stripping and reverse bunsen reaction. In purification of $H_{2}SO_{4}$ phase, the concentration rate of $H_{2}SO_{4}$ phase was controled by temperature but the temperature had few effects on yield of $H_{2}SO_{4}$. In purification of $HI_{x}$ phase, we observed products of side reactions($H_{2}S$, S) over 433 K. The purity of $HI_{x}$ phase was increased with increasing $N_{2}$ flow rate because impurites were decreased with increasing conversion of reverse reaction.

• Transactions of the Korean hydrogen and new energy society
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• v.19 no.1
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• pp.71-76
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• 2008

CuFeOx/$Al_2O_3$ catalysts are developed for the use in sulfuric acid decomposition which is a subcycle in thermochemical iodine-sulfur cycle to split water into hydrogen and oxygen. Both Cu and Fe components are co-precipitated with Al component to enhance distribution of active components. Developed catalysts are improved in the capability of sulfuric acid decomposition and endurance under highly acidic environment compared to commercial catalysts such as Pt/$Al_2O_3$ and $2CuO{\cdot}Cr_2O_3$. Developed CuFeAlOx catalysts exhibited higher sulfuric acid decomposition ability than $2CuO{\cdot}Cr_2O_3$ and longer endurance trends than Pt/$Al_2O_3$ maintaining comparable performance, respectively.

• Transactions of the Korean hydrogen and new energy society
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• v.23 no.5
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• pp.421-428
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• 2012

The Sulfur-Iodine (SI) thermochemical hydrogen production process is one of the most promising thermochemical water splitting technologies. In the integrated operation of the SI process, the $O_2$ produced from a $H_2SO_4$ decomposition section could be supplied directly to the Bunsen reaction section without preliminary separation. A $HI_x$ ($I_2+HI+H_2O$) solution could be also provided as the reactants in a Bunsen reaction section, since the sole separation of $I_2$ in a $HI_x$ solution recycled from a HI decomposition section was very difficult. Therefore, the Bunsen reaction using $SO_2-O_2$ mixture gases in the presence of the $HI_x$ solution was carried out to identify the effect of $O_2$. The amount of $I_2$ unreacted under the feed of $SO_2-O_2$ mixture gases was little higher than that under the feed of $SO_2$ gas only, and the amount of HI produced was relatively decreased. The $O_2$ in $SO_2-O_2$ mixture gases also played a role to decrease the amount of a impurity in $HI_x$ phase by only striping effect, while that in $H_2SO_4$ phase was hardly affected.

• Korean Chemical Engineering Research
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• v.52 no.4
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• pp.459-466
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• 2014

SI Cyclic process is one of the thermochemical hydrogen production processes using iodine and sulfur for producing hydrogen molecules from water. VHTR (Very High Temperature Reactor) can be used to supply heat to hydrogen production process, which is a high temperature nuclear reactor. IHX (Intermediate Heat Exchanger) is necessary to transfer heat to hydrogen production process safely without radioactivity. In this study, the strategy for the optimum design of IHX between SI hydrogen process and VHTR is proposed for various operating pressures of the reactor, and the different cooling fluids. Most economical efficiency of IHX is also proposed along with process conditions.

• Korean Chemical Engineering Research
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• v.44 no.4
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• pp.410-416
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• 2006

For highly efficient operation of a Bunsen process section in an iodine-sulfur thermochemical hydrogen production cycle using nuclear heat, the process characteristics of $H_2SO_4-HI-H_2-O-I_2$ mixture system for separating into two liquid phases ($H_2SO_4$-rich phase and $HI_x$-rich phase) and the distribution of $H_2O$ to each phase were investigated.The experiments for process variables were carried out in the temperature range, from 298 to 353 K, and in the $H_2SO_4/HI/H_2O/I_2$ molar ratio of 1/2/14~20/0.5~8.0. As the results, for the $SO_2-I_2-H_2O$ Bunsen reaction system, the ranges between the starting point and the saturation point for two liquid phases separation were determined by calculation. The best result for the minimization of impurities (HI and $I_2$ in $H_2SO_4$ phase and $H_2SO_4$ in $HI_x$ phase) in each phase was obtained in an optimum condition with the highest temperature of 353 K and the highest $I_2$ molar composition. In this condition, the $HI/H_2SO_4$ molar ratio in the $H_2SO_4$-rich phase and the $H_2SO_4/HI_x$ molar ratio in the $HI_x$-rich phase were 0.024 and 0.028, respectively. For the distribution of $H_2O$ to each phase, it is appeared that the affinity between $HI_x$ and $H_2O$ was more superior to that between $H_2SO_4$ and $H_2O$. The affinity between $HI_x$ and $H_2O$ was decreased with increasing temperature but increased with increasing $I_2$ molar composition.

• Transactions of the Korean hydrogen and new energy society
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• v.22 no.1
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• pp.51-59
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• 2011

Sulfur-Iodine (SI) cycle, which thermochemically splits water to hydrogen and oxygen through three stages of Bunsen reaction, HI decomposition, and $H_2SO_4$ decomposition, seems a promising process to produce hydrogen massively. Among them, the decomposition of $H_2SO_4$ ($H_2SO_4=H_2O+SO_2+1/2O_2$) requires high temperature heat over $800^{\circ}C$ such as the heat from concentrated solar energy or a very high temperature gas-cooled nuclear reactor. Because of harsh reaction conditions of high temperature and pressure with extremely corrosive reactants and products, there have been scarce and limited number of data reported on the pressurized $H_2SO_4$ decomposition. This work focuses whether the $H_2SO_4$ decomposition can occur at high pressure in a noble-metal reactor, which possibly resists corrosive acidic chemicals and possesses catalytic activity for the reaction. Decomposition reactions were conducted in a Pt-lined tubular reactor without any other catalytic species at conditions of $800^{\circ}C$ to $900^{\circ}C$ and 0 bar (ambient pressure) to 10 bar with 95 wt% $H_2SO_4$. The Pt-lined reactor was found to endure the corrosive pressurized condition, and its inner surface successfully carried out a catalytic role in decomposing $H_2SO_4$ to $SO_2$ and $O_2$. This preliminary result has proposed the availability of noble metal-lined reactors for the high temperature, high pressure sulfuric acid decomposition.