• 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.

• 한국수소및신에너지학회논문집
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• 제19권6호
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• pp.490-497
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• 2008

For continuous operation of the sulfur-iodine(SI) thermochemical cycle, which is expected practical method for massive hydrogen production, suggesting operation conditions at steady state is very important. Especially, in the Bunsen reaction section, the Bunsen reaction as well as side reactions is occurring simultaneously. Therefore, we studied on the relation between the variation of compositions in product solution and side reactions. The experiments for Bunsen reaction were carried out in the temperature range, from 268 to 353 K, and in the $I_2/H_2O$ molar ratio of $0.094{\sim}0.297$ under a continuous flow of $SO_2$ gas. As the result, sulfur formed predominantly with increasing temperature and decreasing $I_2/H_2O$ molar ratios. The molar ratios of $H_2O/H_2SO_4$ and $HI/H_2SO_4$ in global system were decreased as the more side reaction occurred. A side reactions did not appear at $I_2/H_2O$ molar ratios, saturated with $I_2$, irrespective of the temperature change. We concluded that it caused by the increasing stability of an $I_{2x}H^+$ complex and a steric hindrance with increasing $I_2/HI$ molar ratios.

• Korean Chemical Engineering Research
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• 제58권2호
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• pp.235-247
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• 2020

Sulfur-Iodine cycle (SI cycle)은 요오드와 황을 첨가하여 최종적으로 물을 열화학적으로 분해하여 산소와 수소를 생산하는 공정으로 황산분해, 요오드화 수소 분해, 분젠반응 등 세가지 반응들로 이루어져 있다. 분젠 반응은 두가지 공정 중간에 존재하므로 두 반응에 필요한 화학물을 조달하는 역할로 이에 대한 상분리 및 반응기에 대한 분석이 중요하다. 본 연구에서는 50 L/hr 수소를 생산하는 pilot scale의 Sulfur-Iodine Cycle 중 분젠 공정에 대한 모사, 민감도 분석, 민감도 분석을 토대로한 각각 상분리기와 분젠 반응기에 대한 최적 조건을 제시하였다. 열역학 물성치의 계산을 위해 Electrolyte Non-Random Two Liquid (ELECNRTL) model 사용하였다. 모델에 대한 신뢰도 확보를 위해서 실제 pilot scale의 공정 데이터와 검증을 수행하였다. 반응기의 종류를 선정하기 위해 Continuous Stirred Tank Reactor (CSTR)과 Plug Flow Reactor (PFR) 동일한 온도 및 부피 변화에서 SO₂ 전환율을 비교하였다. 상분리기 선정을 위해 3상 분리 시스템(기체-액체-액체)과 액체-기체 분리 후 액체-액체 구조에서 H₂SO₄ 상과 HI_X 상에서의 불순물들을 비교하였다. PFR에서 온도, 지름, 길이를 결정 변수로 SO₂ 전환율을 최대화 하기 위한 최적화를 수행하였는데, 온도 121 ℃와 PFR의 지름이 0.20 m 및 길이 7.6 m 일 때 SO₂ 전환율이 98% 최적 결과임을 확인하였다. 기존 pilot scale과 동일한 운전 조건 하에 PFR의 지름 3/8 inch, 길이 3.0 m, 120 ℃ 일 때 인입 몰량인 I₂ 및 H₂O를 결정 변수로 SO₂ 전환율에 대한 최적화를 수행하였을 때, SO₂ 전환율이 10% 일때 H₂O 및 I₂ 의 인입 몰량은 각각 17%와 22%로 감소하였다. 앞선 조업 조건 최적화 조건 (121 ℃, 지름 0.20 m, 길이: 7.6 m) 경우에는 SO₂ 전환율이 98% 일 때 H₂O가 1% 그리고 I₂가 7% 감소하였다. 상분리기에서 HI_X 상내 H₂SO₄ 최소화하는 목적함수에서 그에 상응하는 온도, I₂와 H₂O를 결정 변수로 설정하였을 때, H₂O 몰량이 기존공정보다 17% 감소하고 I₂ 몰량이 24% 감소하였을 때 최소 불순물이 생성하였다.

• 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.

• 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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• 제22권4호
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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.

• Nuclear Engineering and Technology
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• 제46권3호
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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.

• 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.

• 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.