Electrochemical investigation of the Bunsen reaction in the sulfur–iodine cycle

The Bunsen reaction, as a part of the sulfur–iodine thermochemical cycle, was studied using an electrochemical cell. The effects of current density, operating temperature, H₂SO₄ concentration in the anolyte, HI concentration and I₂/HI molar ratio in the catholyte were explored. Both the H₂SO₄ in anolyte and the HI in catholyte were concentrated during electrolysis. Increasing current density amplified this H₂SO₄ and HI concentration, while the other operating parameters also varied the anolyte and catholyte concentration. The transport properties of the cation exchange membrane were examined. The electrode current efficiency remained close to 100% for most runs except those at high current density. Both the average cell voltage and the heat equivalent of electric energy were determined at different conditions.     

Equilibrium potential for the electrochemical Bunsen reaction in the sulfur–iodine cycle

The electrochemical Bunsen reaction was carried out in an electrochemical cell, where the anodic and cathodic compartments were separated by a Nafion 117 membrane. The equilibrium potential of the cell was experimentally measured and theoretically modeled. The effect of electrolyte concentration and temperature was explored. An increase in SO₂ or I₂ concentration reduced the equilibrium potential, whereas increasing H₂SO₄ or HI concentration had a contrary effect. The cell equilibrium potential decreased with increasing temperature. The derived theoretical equilibrium potential model was verified by the experimental data. The regression parameters M and Z in the model were independent of electrolyte concentration, but M decreased and Z kept constant with increasing temperature. An empirical equilibrium potential formula was proposed based on the theoretical and experimental results. The good reproducibility of this formula for measured data indicated its feasibility to estimate the equilibrium potential and also its guidance for optimizing the electrochemical Bunsen reaction.     

Study on a lab-scale hydrogen production by closed cycle thermo-chemical iodine–sulfur process

The Iodine–Sulfur (IS) thermo-chemical process for the production of hydrogen is one of the most promising approaches for use of the high temperature process heat supplied by high temperature reactor, which was developed in the Institute of nuclear and new energy technology (INET) of Tsinghua University, China, and INET initiated the fundamental studies on IS cycle since 2005. Based on the experiment results obtained by fundamental researches, a lab-scaled closed cycle loop (IS-10), which featured in electro-electrodialysis (EED) for hydriodic acid (HI) concentration, was designed and built at INET. The loop was composed of three sections, i.e., Bunsen section, HI section and sulfuric acid section. The closed cycle experiment on the loop was successfully carried out recently. In HI section, HI_x produced by Bunsen reaction was continuously purified through reverse Bunsen reaction, concentrated by EED, and then HI solution was obtained by distillation. Finally HI was catalytically decomposed to H₂ and I₂ with the conversion of 20%. In sulfuric acid section, sulfuric acid was continuously purified, concentrated by distillation, and catalytically decomposed to SO₂, O₂ and H₂O with the conversion of 75%. In Bunsen section, water, including recycled water, reacted with I₂ and SO₂ recycled from HI section and sulfuric acid section to form two separated acids phases, thus to form a closed cycle. The closed cycle experiment lasted for 7 h with the hydrogen production rate of 10 NL/h, with Pt loaded on activated carbon and copper chromite used as the catalysts for HI and sulfuric acid decomposition, respectively. This paper summarizes the main features of IS-10 and the main results of the closed cycle experiment. So far IS-10 is the second reported facility on which closed experiment was carried out, and the first one with EED embedded to perform a closed cycle operation.     

Kinetic and thermodynamic studies of the Bunsen reaction in the sulfur–iodine thermochemical process

This work presents the kinetic and thermodynamic studies of the Bunsen reaction in the sulfur–iodine thermochemical cycle for hydrogen production by water splitting. A series of experimental runs have been carried out by feeding the gas mixture SO₂/N₂ in an I₂/H₂O medium in the temperature range of 336–358 K. The effects of the various operating parameters on the SO₂ conversion ratio have been evaluated. The results showed that the efficiency of SO₂ conversion into H₂SO₄ increased with the amount of I₂ or H₂O increase. The increasing reaction temperature impeded SO₂ conversion into H₂SO₄. A kinetic model has been developed to fit to the experimental data obtained in a semi-batch reactor. A good fitting can be observed for each experiment, which discloses the overall kinetic mechanism of the complex Bunsen reaction. The apparent activation energies were found to be 23.513 kJ mol⁻¹ and 9.212 kJ mol⁻¹ for the sequential reactions  and , respectively.     

Influence of the initial HI on the multiphase Bunsen reaction in the sulfur–iodine thermochemical cycle

In the sulfur–iodine cycle flowsheet, HI may exist in the feeds of Bunsen reaction. The effects of the initial HI and the operating temperature on the kinetic process and thermodynamic equilibrium of the multiphase Bunsen reaction were investigated. Increasing initial HI concentration (HI/H₂O = 0–1/18) or temperature (303 K–358 K) amplified the reaction kinetic rate, and led to the earlier appearance of liquid–liquid separation and less time to reach the thermodynamic equilibrium. But the separation became difficult for further increase of the initial HI content. The liquid–liquid equilibrium (LLE) phase separation was enhanced with rising temperature. An increase in the initial HI content slightly weakened the LLE phase separation at a lower temperature, while at 345 K and 358 K, the LLE phase separation characteristics showed little variation in the HI/H₂O molar ratio range of 0–1/18. A hyper-azeotropic HI concentration in the HIx phase was obtained with feeding HI. The conversion of SO₂ lowered as the initial HI content and the temperature increased.     

Electrochemical characterization of electrodes in the electrochemical Bunsen reaction of the sulfur–iodine cycle

In the electrochemical Bunsen reaction, SO₂ is oxidized to H₂SO₄ at the anode while I₂ is reduced to HI at the cathode. Both electrodes were electrochemically characterized using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The effects of H₂SO₄ concentration in the anolyte, as well as HI concentration and I₂/HI molar ratio in the catholyte, were explored. The cyclic voltammograms of platinum electrode shift with rising scan rate, indicating the irreversibility of two electrode reactions. The equivalent circuit for the cathode reaction impedance consists of an ohmic resistance of the solution, in series with a parallel combination of a charge transfer resistor and a constant phase element, yet the impedance spectra for the anode reaction can be modeled using a parallel combination of a charge transfer resistor and a constant phase element. The electrode reaction kinetics was also analyzed using the exchange current density (j₀) and the standard reaction rate constant (k⁰). The results indicate that a high electrode reaction rate in the cell can be obtained for a HI concentration of 8 mol/kg_H2O and an I₂/HI molar ratio of 0.5 in the catholyte and a H₂SO₄ concentration of 13 mol/kg_H2O in the anolyte.     

Three-dimensional electrochemical Bunsen reaction characteristics in the sulfur–iodine water splitting cycle for hydrogen production

Hydrogen production from the sulfur–iodine water splitting cycle integrated with solar or nuclear energy has been proposed as a promising technique. Bunsen reaction is one of the three main steps in the cycle and electrochemical method has been applied to this reaction. In present work, a three-dimensional numerical study of the electrochemical Bunsen reaction was conducted. A three-dimensional, steady state, laminar and isothermal mathematical model of electrolytic cell was developed and verified by experiments. The spatial maldistribution of species concentration was found between electrodes and proton exchange membrane (PEM). The electric power drives most H₂SO₄ and I₂ to the anode and cathode surface, respectively, while the proton attraction contributes to HI enrichment on the surface of PEM. At the high inlet H₂SO₄ concentration of 50 wt%, the transformation of flow channel from single serpentine to single entry & double serpentine with the same inlet flow rate cannot solve the insufficient problem of SO₂. But the increase of the overall inlet flow rate in the double entry & double serpentine flow channel make SO₂ sufficient for anode reaction. Further decreasing the inlet H₂SO₄ concentration to 40 wt% and 30 wt% make the initial SO₂ sufficient for overall reactions. The single serpentine channel gives the highest SO₂ conversion rate, followed by the single entry & double serpentine and double entry & double serpentine flow channels. The single serpentine flow channel at the H₂SO₄ inlet concentration of 40 wt% is found optimal for achieving a high electrochemical Bunsen reaction performance.     

Experimental investigation of reaction kinetics of gas–liquid–solid Bunsen reaction in iodine–sulfur process

Iodine–sulfur (IS) cycle is the most promising thermochemical water-splitting process for nuclear hydrogen production. The Bunsen reaction, which produces sulfuric and hydriodic acid for the two decomposition reactions, plays a crucial role for the continuous stable operation of the IS cycle. Insufficient kinetics studies on Bunsen reaction, particularly under the gas–liquid–solid heterogeneous conditions, have caused difficulties for the design of Bunsen reactor, as well as the optimization and improvement of the efficiency of the process. In this work, the reaction kinetics of gas–liquid–solid Bunsen reaction denoted in the pressure drop of SO₂ was experimentally investigated, and the effluences of the main factors, including the initial SO₂ pressure, molar ratio of I₂ to H₂O, temperature, and stirring rate, were studied. In addition, a kinetics model for simulating the heterogeneous reaction was proposed and verified by the experimental data obtained under the three-phase Bunsen reaction conditions.     

Survey of Bunsen reaction routes to improve the sulfur–iodine thermochemical water-splitting cycle

A large excess of water and iodine is typically employed in the Bunsen reaction step of the sulfur–iodine thermochemical cycle in order to induce liquid–liquid phase separation of the two acid products. This paper presents an overview of some alternative routes for carrying out the Bunsen reaction. The use of a reaction solvent other than water is first discussed, and experimental results obtained with tributylphosphate are presented. Another approach is separation of the product acids by selective precipitation of insoluble salts, and the addition of lead sulfate as the precipitating agent is discussed in detail. Finally, the electrochemical Bunsen reaction route is investigated. All of these methods have the potential to reduce the iodine and/or water requirement of the sulfur–iodine cycle.     

Continuous Bunsen reaction and simultaneous separation using a counter-current flow reactor for the sulfur–iodine hydrogen production process

The sulfur–iodine (SI) process, which consists of three chemical reactions of the Bunsen reaction, a H₂SO₄ decomposition and a HI decomposition, is an important potential method for hydrogen production among thermochemical water splitting methods. For steady-state operation of the SI process, it is very important to provide information on the composition of each phase that passes from the Bunsen reaction section to the following H₂SO₄ and HI decomposition sections. In this study, the Bunsen reaction was carried out using a counter-current flow reactor, the Bunsen reaction and product separation steps were shown capable of being performed simultaneously, and the composition variation of each phase discharged at the top and bottom of reactor was investigated. The process variables were the SO₂ feed rate, temperature, I₂/H₂O molar ratio. As a result of constant reactant feed and continuous product discharge operation, it was found that the composition remained constant after 120 min of reaction time, indicating steady-state operation. The phase separation characteristics of the Bunsen reaction were minimally affected by the SO₂ feed rate. As the amount of I₂ introduced increased with increasing temperature, the volume of the H₂SO₄ phase discharged from the upper phase was unchanged, while that of the HI_x phase discharged from the lower phase increased proportionally. The average molar composition of the H₂SO₄ phase (H₂SO₄/H₂O/HI) obtained at a typical operation condition (353 K, I₂/H₂O molar ratio of 0.406) was 1/5.30–5.39/0.02–0.04, and the composition of the HI_x phase (HI/I₂/H₂O/H₂SO₄) was 1/2.81–3.09/5.67–6.40/0.04–0.06. These results could be used for the design and operation of H₂SO₄ and HI decomposition sections of the SI process.     

Numerical analysis of the electrochemical Bunsen reaction for hydrogen production from sulfur–iodine cycle

The sulfur–iodine (S-I) water-splitting cycle is one of the most promising hydrogen production methods. The Bunsen reaction in the cycle affects the flowsheet complexity and thermal efficiency, but an electrochemical technique has recently been applied to make the S-I cycle more simplified and energy efficient. However, the performance of the electrochemical Bunsen reaction, especially the electrode reactions inside the electrolytic cell (EC) are not clear at present. In this work, a two-dimensional numerical model of EC was developed. The detailed reaction process was numerically calculated with considering the coupling of mass transfer and electrochemical reactions, and was verified using experimental data. The effects of various operating parameters on the reactions were investigated. The results showed that the increase of current density significantly improves the conversion rates of reactants. A higher temperature is unfavorable for concentrating H₂SO₄ and HI. Increase in the inlet flow rate reduces the conversion rates of reactants, but the impact declines with further rising flow rate. An optimal operating condition is also proposed. The theoretical simulation study will provide guidance for the improvement of experimental work.     

Use of PSA for design of emergency systems in a sulfur–iodine cycle

A methodology is proposed to design emergency systems using Probabilistic Safety Assessment (PSA). It was used to design mitigation systems in the case of the formation of a toxic cloud due to an uncontrolled leakage of concentrated sulfuric acid in the second section of the General Atomics S–I cycle of a hydrogen production plant. Mitigation systems based on the isolation of a possible leak, the neutralization of a puddle of sulfuric acid and finally the flushing of that puddle were proposed and later analyzed with PSA. Many scenarios were taken into account to determine design changes and their impact on the probability of failure of the systems. Finally, the information produced in the PSA was used to provide feedback to optimize the design of the toxic cloud mitigation systems. The specific recommendations from the study suggest several design changes based on the PSA sensitivity runs. The results include optimized isolation and neutralization systems that will maintain the frequency of toxic cloud formation below 1.0E − 09 per year, which is only 16% of the frequency calculated for the original design based only on process engineering.     

Optimization of liquid–liquid phase separation characteristics in the Bunsen section of the sulfur–iodine hydrogen production process

In order to optimize the sulfur–iodine thermochemical cycle, a series of experiments were conducted to investigate the separation characteristics of the liquid–liquid phase in the H₂SO₄/HI/I₂/H₂O quaternary solution produced by Bunsen reaction. The effects of the solution composition in the feed and the operating temperature on the separation characteristics were analyzed to determine the preferable operating conditions in the Bunsen section. The increases in both the iodine content and the operating temperature improved the separation characteristics of the liquid–liquid phase when the occurrence of secondary reactions was neglected. The amount of impurities in both phases obviously decreased as the iodine content increased. The effect of the iodine content was more significant relative to that of the operating temperature. The optimal operating conditions were proposed to achieve the concentrations of HI in the HIx phase in excess of the azeotropic composition.     

Process simulations of HI decomposition via reactive distillation in the sulfur–iodine cycle for hydrogen manufacture

Process simulations of HI decomposition via reactive distillation in the Sulfur–Iodine (S–I) cycle have been performed using heat pumps for energy recovery and a recently developed thermodynamic properties model. Several differences from previous flow sheets have been found through manual optimization of reflux ratio, number of stripping and rectifying stages, and pressure of the distillation column for typical inlet conditions to the HIx Section III. In particular, the RD column should have a minimal stripping section, can have as few as 10 total stages, an operating pressure of 12 bar, and a reflux ratio of 0.75, while achieving the production requirements. Though this design has limited improvement in energy requirements because the General Atomics energy recovery system is extremely effective, these results mean there should be a significant reduction in capital costs from prior estimates. In addition, as the inlet flow rate is increased, the input energy requirements decrease because of an increased ratio of H₂O to I₂ in the reboiler, lowering its temperature, and reducing the temperature differences for heat pump operations. The optimal inlet flow is between 126 and 140 mol/mol H₂, with a Section energy requirement of 367 kJ/mol H₂, and an overall process thermal efficiency estimated to be 41.5% relative to the higher heating value of hydrogen. These findings suggest there may be greater flexibility in conditions for the Bunsen reaction section as well as other possibilities for further energy efficiency improvement.     

Preliminary process analysis for the closed cycle operation of the iodine–sulfur thermochemical hydrogen production process

In the iodine–sulfur thermochemical hydrogen production process, a separation characteristic of 2-liquid phase (H₂SO₄ phase and HI_x phase) in the separator at 0°C was measured. Two-phase separation began to occur at about 0.32 of I₂ molar fraction and over. The separation characteristic became better with the increase in iodine concentration in the solution. The effect of flow rate variations of HI solution and I₂ solution from the HI_x distillation column on the process was evaluated. The flow rate increase in HI solution from the distillation column did not have a large effect on the flow rate of HI solution fed to the distillation column from the separator. The decreasing flow rate of I₂ solution from the distillation column decreased the flow rate of I₂ solution fed to the distillation column from the separator. The variation of I₂ molar fraction in the H₂SO₄ phase in the separator was sensitive to the variation in flow rate of both solutions from the distillation column. The tolerance level of the variation was investigated by considering I₂ solubility, 2-liquid phase disappearance and SO₂ reaction amount.     

Apparent kinetics of the Bunsen reaction in I2/HI solution for the iodine–sulfur hydrogen production process

Massive hydrogen production featuring high efficiency, CO₂ free, and cost effectiveness is a crucial challenge for the hydrogen economy. Nuclear hydrogen production through thermochemical iodine–sulfur (IS) process is a potential candidate for this purpose. Chemical reaction kinetics data are indispensable for developing a high-performance reactor as well as the scaling up of the process. The apparent kinetics of the reaction under simulated recycling conditions of IS closed cycle operation was studied by initial rate method. The effects of key parameters, including agitation speed, SO₂ partial pressure, I₂ concentration, and reaction temperature, on reaction rate, were systematically investigated by measuring the variation in SO₂ pressure with reaction time. Initial rate analysis method indicated that the Bunsen reaction rates were 0.23 ± 0.01 and 0.77 ± 0.01 order with respect to SO₂ pressure and I₂ concentration. The apparent activation energy was 5.86 ± 0.21 kJ/mol. Based on these results, an exponential rate expression of the Bunsen reaction was established. In addition, a simplified method for calculation of kinetics parameters was proposed and compared with conventional techniques. Experimental results provide theoretical basis for design and development of Bunsen reactors and for elucidating the reaction process.     

Ceria as a catalyst for hydrogen iodide decomposition in sulfur–iodine cycle for hydrogen production

In this work, ceria (CeO₂) prepared with different methods and at various calcination temperatures have been tested to evaluate their effect on hydrogen iodide (HI) decomposition in sulfur–iodine (SI) cycle at various temperatures. The CeO₂ catalysts' strongly enhance the HI decomposition by comparison with blank test, especially gel CeO₂ 300. TG–FTIR, BET, XRD, TEM and TPR were performed for catalysts' characterization. The results show that the CeO₂ catalyst synthesized by citric-aided sol–gel method and calcined at low temperature (<500 °C) shows more lattice defects, smaller crystallites, larger surface area and better reducibility. Oxygen can promote the significantly rapid surface reaction, but simultaneously consume hydrogen species (H) contained in HI. Lattice defects, especially the reduced surface sites, i.e., Ce³⁺ and oxygen vacancy, play the dominant role in surface reactions of HI decomposition. A new reaction mechanism for HI catalytic decomposition over CeO₂ catalyst is proposed.     

Membrane electrolysis of Bunsen reaction in the iodine–sulphur process for hydrogen production

In traditional IS process for production of hydrogen by water decomposition, the Bunsen reaction (SO₂ + I₂ + 2H₂O → H₂SO₄ + 2HI) was carried out by direct contact of SO₂ with aqueous solution of I₂ where a large excess of I₂ (8 mol) and H₂O (16 mol) were required. Excess amounts of these chemicals severely affected the overall thermal efficiency of the process and new ways including membrane electrolysis was reported in literature for carrying out Bunsen reaction where the amount of excess chemicals can be greatly reduced. We have carried out Bunsen reaction in a two-compartment membrane electrolysis cell containing graphite electrodes and Nafion 117 membrane as a separator between the two-compartments. Electrolysis was carried out at room temperature with continuous recirculation of anolyte and catholyte. Electrolysis was done in constant-current mode with current density in the range of 1.6 A/dm² to 4.8 A/dm². Initial concentrations of H₂SO₄ and HI were about 10 and 5 N, respectively and I₂/HI molar ratio in the catholyte was varied in the range of 0.25–1.5. Current efficiency was found to be close to 100% indicating absence of any side reaction at the electrodes. Cell voltage was found to vary linearly with current densities up to 80 A/dm² and for I₂/HI molar ratio in the range of 0.25–1.5 the cell voltage was found to be lowest for the value of 0.5.     

Construction materials development in sulfur–iodine thermochemical water-splitting process for hydrogen production

The sulfur iodine (SI) water splitting cycle for hydrogen production consists of three coupled chemical reactions, which includes the generation and decomposition of HI. The _HIx${\mathrm{HI}}_x$ environment is extremely corrosive and the severity increases with temperature. Immersion coupon corrosion screening tests were performed on materials selected from four classes of corrosion resistant materials: refractory metal, reactive metal, superalloys and ceramics. Of the materials tested, only Ta and Nb-based refractory metals and ceramic mullite can tolerate the extreme _HIx${\mathrm{HI}}_x$ environment. Severe pitting and dissolution was observed in two different reactive metal zirconium. A nickel based superalloy, C-276, also showed severe dissolution in _HIx${\mathrm{HI}}_x$ solution. The materials which showed good corrosion behavior will undergo further long-term immersion testing to assess performance. In addition, C-ring, U-bend and DCB test samples fabricated from qualified materials will be tested under stress corrosion conditions to investigate their crack initiation and growth properties.