• 융복합기술연구소 논문집
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• 제2권2호
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• pp.30-34
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• 2012

The SI thermochemical cycle process accomplishes water splitting through distinctive three chemical reactions. We focused on thermodynamic models applicable to the process. Recently, remarkable models based on the assumed ionic species have been developed to describe highly nonideal behavior on the liquid phase reactions. ElecNRTL models with ionic reactions were proposed in order to provide reliable process simulation results for phase equilibrium calculations in Section II and III. In this study, the current thermodynamic models of SI thermochemical cycle process were briefly described and the calculation results of the applied ElecNRTL models for phase equilibrium calculations were illustrated for binary systems.

• 한국수소및신에너지학회논문집
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• 제22권2호
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• pp.139-151
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• 2011

The sulfur-iodine (SI) thermochemical water splitting cycle is one of promising hydrogen production methods from water using high-temperature heat generated from a high temperature gas-cooled nuclear reactor (HTGR). The SI cycle consists of three main units, such as Bunsen reaction, HI decomposition, and $H_2SO_4$ decomposition. The feasibility of continuous operation of a series of subunits for $H_2SO_4$ decomposition was investigated with a bench-scale facility working at ambient pressure. It showed stable and reproducible $H_2SO_4$ decomposition by steadily producing $SO_2$ and $O_2$ corresponding to a capacity of 1 mol/h $H_2$ for 24 hrs.

• 한국수소및신에너지학회논문집
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• 제19권3호
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• pp.226-231
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• 2008

Cu/Fe/$Al_2O_3$ granules with various sizes have been prepared by a combination of sol-gel and oil drop method for the use in sulfur trioxide decomposition, a subcycle in thermochemical sulfur-iodine cycle to split water in the hydrogen and oxygen. The size of composite granules have been mainly changed by the flow-rate of the gel mixture before dropping in the synthesis. The structural properties of the samples were comparable with granule size. In the reaction, the catalytic activity was enhanced by decreasing size in the entire reaction temperature ranges.

• 한국수소및신에너지학회논문집
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• 제19권5호
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• pp.386-393
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• 2008

The Sulfur-iodine(SI) thermochemical cycle is one of the most promising methods for massive hydrogen production. For the purpose of continuous operation of SI cycle, phase separation characteristics into two liquid phases ($H_2SO_4$-rich phase and $HI_x$-rich phase) were directly investigated via Bunsen reaction. The experiments for Bunsen reaction were carried out in the temperature range, from 298 to 333 K, and in the $I_2/H_2O$ molar ratio of $0.109{\sim}0.297$ under a continuous flow of $SO_2$ gas. As the results, solubility of $SO_2$, decreased with increasing the temperature, had considerable influence on the global composition in the Bunsen reaction system. The amounts of impurity in each phase(HI and $I_2$ in $H_2SO_4$-rich phase and $H_2SO_4$ in $HI_x$-rich phase) were decreased with increasing $H_2SO_4$ molar ratio and temperature. To control the amounts of impurity in $HI_x$-rich phase, temperature is a factor more important than $I_2/H2_O$ molar ratio. On the other hand, the affinity between $HI_x$ and $H_2O$ was increased with increasing $I_2/H2_O$molar ratio.

• Korean Chemical Engineering Research
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• 제52권4호
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• pp.459-466
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• 2014

열화학적인 수소 생산 공정 중 하나인 S-I Cycle은 요오드와 황을 이용한 수소 생산 공정으로써 물 분자로부터 수소 분자를 얻어내는 순환 공정이다. 수소 생산 공정에 열을 공급하고자 하는 초고온 원자로(VHTR; Very High Temperature Reactor)는 원자로에서 수소 생산 공정으로 방사능 없이 안전하게 열을 전달하기 위하여 중간열교환기(IHX; Intermediate Heat Exchanger)가 필요하다. 본 연구에서는 수소 생산공정과 초고온 원자로간의 중간 열교환 공정을 모사하여 운전압력 및 작동 유체의 변화에 따른 중간 열교환기의 효율을 계산하고 가장 경제적인 중간 열교환기를 설계하기 위한 공정 조건을 도출하였다.

• 한국수소및신에너지학회논문집
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• 제22권1호
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• pp.13-20
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• 2011

$SO_2$ has been absorbed and separated selectively by an ionic liquid from $SO_2/O_2$ mixture decomposed from sulfuric acid during the thermochemical SI cycle for the water splitting. In order to design and operate high pressure $SO_2/O_2$ separation system, the solubility of $SO_2$ in [EMIm]$EtSO_4$ (1-ethyl-3-methylimidazolium ethylsulfate) has been measured by Magnetic Suspension Balance at high pressure and temperature. Based on the measured solubility, a pressurized separation system was set up and operated. 194 L/h of $SO_2$($SO_2:O_2$=0.65:1) has been separated with 99.85% of $O_2$ at the vent of absorption tower, which is 22.7% of the theoretically ideal capacity of the system. This discrepancy results from the reduced contact between the gaseous $SO_2$ and the ionic liquid. Increased $SO_2$ supply, scale-up of the absorption column, and a faster ionic liquid circulation speed were suggested to improve the separation capacity.

• Nuclear Engineering and Technology
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• 제52권2호
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• pp.279-286
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• 2020

In this article, we develop a reactive distillation (RD) column configuration for the production of hydrogen. This RD column is in the HI decomposition section of the sulphur - iodine (SI) thermochemical cycle, in which HI decomposition and H₂ separation take place simultaneously. The section plays a major role in high hydrogen production efficiency (that depends on reaction conversion and separation efficiency) of the SI cycle. In the column simulation, the rigorous thermodynamic phase equilibrium and reaction kinetic model are used. The tuning parameters involved in phase equilibrium model are dependent on interactive components and system temperature. For kinetic model, parameter values are adopted from the Aspen flowsheet simulator. Interestingly, there is no side reaction (e.g., solvation reaction, electrolyte decomposition and polyiodide formation) considered aiming to make the proposed model simple that leads to a challenging prediction. The process parameters are determined on the basis of optimal hydrogen production as reflux ratio = 0.87, total number of stages = 19 and feeding point at 8th stage. With this, the column operates at a reasonably low pressure (i.e., 8 bar) and produces hydrogen in the distillate with a desired composition (H₂ = 9.18 mol%, H₂O = 88.27 mol% and HI = 2.54 mol%). Finally, the results are compared with other model simulations. It is observed that the proposed scheme leads to consume a reasonably low energy requirement of 327 MJ/kmol of H₂.

• 한국수소및신에너지학회논문집
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• 제22권1호
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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.

• 한국수소및신에너지학회논문집
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• 제19권2호
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• pp.111-117
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• 2008

A Bunsen reaction section is a primary stage of Sulfur-iodine thermochemical hydrogen production cycle. This section is important, because it decides the efficiency of next stages. In order to produce hydrogen very efficiently, the characteristics of Bunsen reaction were investigated via two experimental methods. The one is a phase separation of $H_2SO_4-HI-H_2O-I_2$ mixture system, and the other is a direct Bunsen reaction. The characteristics of each method were investigated and compared. As the result of this study, the amount of HI and $I_2$ in $H_2SO_4$ phase via Bunsen reaction was more decreased than that via $H_2SO_4-HI-H_2O-I_2$ mixture system with increasing $I_2$ concentration. However, the amount of $H_2SO_4$ in $HI_x$ phase via Bunsen reaction was remarkably increased with increasing $I_2$ concentration, while that via $H_2SO_4-HI-H_2O-I_2$ mixture system was decreased. On the other hand, the range of initial composition which is able to separate into two liquid phases without $I_2$ solidification was almost alike.

• 한국수소및신에너지학회논문집
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• 제21권4호
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• pp.278-285
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• 2010

The Sulfur-Iodine (SI) thermochemical hydrogen production process of a closed cycle consists of three sections, which are so called the Bunsen reaction section, the $H_2SO_4$ decomposition section and the HI decomposition section. To identify the role of oxygen that can be supplied to the Bunsen reaction section via the $H_2SO_4$ decomposition section, Bunsen reactions with a $SO_2,\;SO_2-O_2$ mixture and $SO_2-N_2$ mixture as feed gases were carried out using a stirred reactor in the presence of $I_2/H_2O$ mixture. As the results, the amounts of $I_2$ unreacted under the feed of mixture gases were higher than those under the feed of $SO_2$ gas only, and the amount of HI produced was relatively decreased. The results of Bunsen reaction using $SO_2-O_2$ mixture were similar to those using $SO_2-N_2$ mixture. It may be concluded that an oxygen in $SO_2-O_2$ mixture has a role as a carrier gas like a nitrogen in $SO_2-N_2$ mixture. The effects of oxygen were decreased with increasing temperature and decreasing oxygen content in $SO_2-O_2$ mixture.