• 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.

• Korean Chemical Engineering Research
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• 제46권3호
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• pp.633-638
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• 2008

열화학적 물분해에 의한 수소 생산 공정 중의 하나인 IS(Iodine-sulfur) 사이클에서 요오드와 이산화황, 그리고 물을 반응물로 하여 요오드화수소와 황산을 제조하는 분젠 반응에 대한 연구를 수행하였다. 요오드의 투입 몰수에 관계없이 황산의 생성량은 일정하였으나 요오드화수소의 생성량은 요오드의 투입 몰수가 증가함에 따라 감소하는 경향을 나타내었다. 이는 생성된 요오드화수소와 미 반응된 요오드가 $HI_3$ $HI_5$ or $HI_7$와 같은 착화합물인 polyiodide를 형성하기 때문인 것으로 생각된다. 이들 착화합물의 형성은 생성물의 2액상 분리 특성의 향상을 가져온다. 또한 요오드 투입 몰수의 증가함에 따라 반응 속도는 향상되었다. 반응물인 요오드의 투입 몰수 및 반응 온도가 증가함에 따라 생성 용액의 2액상 분리 특성이 향상되었으며 모든 실험의 조건 하에서 부반응은 발생 되지 않는 것으로 나타났다.

• 공업화학
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• 제29권1호
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• pp.56-61
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• 2018

황-요오드(SI) 공정의 통합 운전을 위한 분젠 반응 단계에서, $I_2$ 및 $H_2O$ 반응물들은 $HI_x$ 용액 내 용해된 성분들로써 공급된다. $HI_x$ 용액과 $SO_2$ 공급을 이용하여 분젠 반응이 수행될 때 $HI_x$ 상 내 대부분의 $H_2SO_4$ 생성물이 존재하며, 이에 따라 $HI_x$ 상에 대한 $H_2SO_4$ 상의 부피 비가 매우 낮다. 본 연구에서 우리는 상 분리 성능을 향상시키기 위해 $HI_x$ 용액을 이용한 분젠 반응에 대한 초음파 조사의 효과들을 연구하였다. 분젠 반응과 함께 초음파가 조사될 때 $HI_x$ 상으로부터 $H_2SO_4$ 상으로 이동된 $H_2SO_4$의 양은 최대 58.0 mol%까지 증가하였으며, $H_2SO_4$ 상의 부피 또한 최대 13.1 vol%까지 증가하였다. 특히, 상 분리에 대한 초음파 조사의 효과는 온도, $I_2$ 및 $H_2O$ 공급 농도가 감소함에 따라 향상되었다. 초음파 조사는 $HI_x$ 상 내 반응 평형을 미시적으로 이동시킴으로써 추가적인 $H_2O$ 분자들의 형성을 유도하였다. 이로부터 추가적으로 생성된 $H_2O$ 및 분리된 $H_2SO_4$ 분자들이 $H_2SO_4$ 상으로 이동할 수 있는 더 많은 $H_2SO_4{\cdot}xH_2O$ (x = 5-6) 착물들을 형성하였다.

• 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.

• 한국수소및신에너지학회논문집
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• 제27권1호
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• pp.13-21
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• 2016

The Sulfur-Iodine thermochemical hydrogen production process (SI process) consists of the Bunsen reaction section, the $H_2SO_4$ decomposition section, and the HI decomposition section. The $HI_x$ solution ($I_2-HI-H_2O$) could be recycled to Bunsen reaction section from the HI decomposition section in the operation of the integrated SI process. The phase separation characteristic of the Bunsen reaction using the $HI_x$ solution was similar to that of $I_2-H_2O-SO_2$ system. On the other hands, the amount of produced $H_2SO_4$ phase was small. To investigate the effects of $SO_2$ solubility on Bunsen reaction, the continuous Bunsen reaction was performed at variation of the amounts of $SO_2$ gas. Also, it was carried out to make sure of the effects of partial pressure of $SO_2$ in the condition of 3bar of $SO_2-O_2$ atmosphere. As the results, the characteristic of Bunsen reaction was improved with increasing the amounts and solubility of $SO_2$ gas. The concentration of Bunsen products was changed by reverse Bunsen reaction and evaporation of HI after 12 h.

• 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.

• 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.

• 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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• 제21권3호
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• pp.158-166
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• 2010

The purification of two liquid phases ($H_2SO_4$ phase and HIx phase) formed from a Bunsen reaction in Sulfur-Iodine (SI) hydrogen production process was investigated in order to operate SI process efficiently. The each synthetic solution for two liquid phases contained impurities was prepared on the basis of a proper composition obtained from Bunsen reaction. The purification of each solution was performed by counter-current flow using a packed column at different temperatures and $N_2$ flow rates. As the results of purification, impurities existed in each phase were decreased with increasing the temperature and the $N_2$ flow rate. In particular, the increase of the $N_2$ flow rate at the lower temperatures was effective to remove impurities by a reverse Bunsen reaction without side reactions. On the whole, it may be concluded that the purification of each phase is accomplished by mixing effects of the stripping, the evaporation, and the reverse Bunsen reaction.