• 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.

• Korean Chemical Engineering Research
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• v.46 no.3
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• pp.633-638
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• 2008

The bunsen reaction, part of IS(Iodine-sulfur) cycle that one of the hydrogen production by the thermochemical water splitting, was investigated. It was observed that $H_2SO_4$ was uniformly generated and generation of $H_2SO_4$ was independent of iodine input. However, generation of HI was decreased with increasing iodine input. It was thought that HI and unreacted iodine were formed complex compound such as $HI_3$ $HI_5$ or $HI_7$. The complex compound accelerated liquid-liquid separation properties in the product. It was also revealed that reaction kinetics was increased with increasing iodine input. Liquid-liquid separation properties were improved with increasing iodine input and reaction temperature. Moreover, no side reaction was occurred at all reaction conditions.

• Applied Chemistry for Engineering
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• v.29 no.1
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• pp.56-61
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• 2018

In Bunsen reaction section for the integrated operation of sulfur-iodine (SI) process, $I_2$ and $H_2O$ reactants are supplied as dissolved species in an $HI_x$ solution. Most of the $H_2SO_4$ product is found in the $HI_x$ phase when Bunsen reaction is performed using the $HI_x$ solution and $SO_2$ feed, so that the volume ratio of the $H_2SO_4$ phase to the $HI_x$ phase is very low. In this study, we investigated the effects of ultrasound irradiation on Bunsen reaction using the $HI_x$ solution to improve its phase separation performance. With ultrasound irradiation, the amount of $H_2SO_4$ moved to the $H_2SO_4$ phase from the $HI_x$ phase increased by up to 58.0 mol% and the volume of $H_2SO_4$ phase also increased by up to 13.1 vol%. In particular, the effect of ultrasound irradiation on the phase separation was improved with decreasing operating temperature, $I_2$ and $H_2O$ feed concentrations. The ultrasound irradiation induces the formation of additional $H_2O$ molecules by shifting microscopically the reaction equilibrium in the $HI_x$ phase. Afterward, the additionally generated $H_2O$ and isolated $H_2SO_4$ molecules form more $H_2SO_4{\cdot}xH_2O$ (x = 5-6) clusters that can be moved to the $H_2SO_4$ phase.

• Transactions of the Korean hydrogen and new energy society
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• v.19 no.6
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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.

• Transactions of the Korean hydrogen and new energy society
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• v.27 no.1
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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.

• Transactions of the Korean hydrogen and new energy society
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• v.19 no.2
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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.

• Transactions of the Korean hydrogen and new energy society
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• v.21 no.4
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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.

• 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.5
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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.

• Transactions of the Korean hydrogen and new energy society
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• v.21 no.3
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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.