Current R&D status of thermochemical water splitting iodine-sulfur process in Japan Atomic Energy Agency

Kasahara, Seiji; Iwatsuki, Jin; Takegami, Hiroaki; Tanaka, Nobuyuki; Noguchi, Hiroki; Kamiji, Yu; Onuki, Kaoru; Kubo, Shinji

International Journal of Hydrogen Energy, 42(19), p.13477 - 13485, 2017/05

https://doi.org/10.1016/j.ijhydene.2017.02.163

Current R&D on the thermochemical water splitting iodine-sulfur (IS) process in Japan Atomic Energy Agency is summarized. Reactors were fabricated with industrial materials and verified by test operations: a Bunsen reactor, a HSO decomposer, and a HI decomposer. Reactors of industrial materials showed corrosion stability. Demonstration of the test facility verified integrity of process components and stability of hydrogen production. An 8 hours continuous operation of the total IS process was performed in February 2016 with H production rate of 10 L/h.

Research and development on chemical reactors made of industrial structural materials and hydriodic acid concentration technique for thermochemical hydrogen production IS process

Kubo, Shinji; Iwatsuki, Jin; Takegami, Hiroaki; Kasahara, Seiji; Tanaka, Nobuyuki; Noguchi, Hiroki; Kamiji, Yu; Onuki, Kaoru

JAEA-Technology 2015-028, 32 Pages, 2015/10

JAEA-Technology-2015-028.pdf:23.69MB

JAEA has been conducting a study on IS process for thermochemical hydrogen production in order to develop massive hydrogen production technology for hydrogen society. Integrity of the chemical reactors and concentration technology of hydrogen iodide in HIx solution were studied. In the former study, the chemical reactors were trial-fabricated using industrial materials. A test of 30 times of thermal cycle test under circulating condition of the Bunsen reaction solution showed integrity of the Bunsen reactor made of fluororesin lined steel. Also, 100 hours of reaction tests showed integrity of the sulfuric acid decomposer made of silicon carbide and of the hydrogen iodide decomposer made of Hastelloy C-276. In the latter study, concerning electro-electrodialysis using cation-exchange membrane, sulfuric acid in the anolyte had little influence on the concentration performance. These results suggest the purification system of HIx solution can be simplified. Based on the Nernst-Planck equation and the Smoluchowski equation, proton transport number, water permeance, and IR drop of the cation exchange membrane were formulated. The derived equations enable quantitative estimation for the performance indexes of Nafion membrane and, also, of ETFE-St membranes made by radiation-induced graft polymerization method.

Mizunami Underground Research Laboratory Project, Annual report for fiscal year 2013

Hama, Katsuhiro; Mikake, Shinichiro; Nishio, Kazuhisa; Kawamoto, Koji; Yamada, Nobuto; Ishibashi, Masayuki; Murakami, Hiroaki; Matsuoka, Toshiyuki; Sasao, Eiji; Sanada, Hiroyuki; et al.

JAEA-Review 2014-038, 137 Pages, 2014/12

JAEA-Review-2014-038.pdf:162.61MB

Japan Atomic Energy Agency (JAEA) at Tono Geoscience Center (TGC) is pursuing a geoscientific research and development project namely the Mizunami Underground Research Laboratory (MIU) Project in crystalline rock environment in order to construct scientific and technological basis for geological disposal of High-level Radioactive Waste (HLW). The MIU Project has three overlapping phases: Surface-based Investigation phase (Phase I), Construction phase (Phase II), and Operation phase (Phase III). The MIU Project has been ongoing the Phase II and the Phase III in fiscal year 2013. This report presents the results of the investigations, construction and collaboration studies in fiscal year 2013, as a part of the Phase II and Phase III based on the MIU Master Plan updated in 2010.

Components development for sulfuric acid processing in the IS process

Noguchi, Hiroki; Kubo, Shinji; Iwatsuki, Jin; Kasahara, Seiji; Tanaka, Nobuyuki; Imai, Yoshiyuki; Terada, Atsuhiko; Takegami, Hiroaki; Kamiji, Yu; Onuki, Kaoru; et al.

Nuclear Engineering and Design, 271, p.201 - 205, 2014/05

https://doi.org/10.1016/j.nucengdes.2013.11.032

The Japan Atomic Energy Agency has been conducting research and development on a thermochemical iodine-sulfur (IS) process. An examination is planned to verify the integrity of the components in the sulfuric acid decomposition section. A bayonet-type sulfuric acid decomposer made of SiC ceramics, a key component in the section, was test-fabricated. In parallel, a direct-contact heat exchanger (DCHX) is contemplated for use in the sulfuric acid decomposition section to simplify the process. Although the concept is very attractive, little is known about the heat and mass transfer behavior in the DCHX. Therefore, a test apparatus was constructed to measure the gas-phase mass transfer coefficients required for the optimal design of the DCHX. These coefficients of water were acquired and compared with an empirical correlation. The experimental data were in good agreement with those obtained from empirical correlation, and thus, the apparatus was confirmed to be reasonable.

Effect of sulfuric acid on electro-electrodialysis of HIx solution

Tanaka, Nobuyuki; Onuki, Kaoru; Kubo, Shinji

International Journal of Hydrogen Energy, 39(1), p.86 - 89, 2014/01

https://doi.org/10.1016/j.ijhydene.2013.10.103

The effect of sulfuric acid on the concentration of HIx solution by electro-electrodialysis (EED) was examined for the thermochemical water-splitting iodine-sulfur process. Presence of sulfuric acid in the anolyte HIx solution did not affect the concentration behavior. However, sulfuric acid in the catholyte solution caused side reaction(s) producing whitish precipitates, which indicates that the sulfur compound should be removed prior to the EED operation.

Corrosion resistance of structural materials in high-temperature aqueous sulfuric acids in thermochemical water-splitting iodine-sulfur process

Kubo, Shinji; Futakawa, Masatoshi; Ioka, Ikuo; Onuki, Kaoru; Yamaguchi, Akihisa*

International Journal of Hydrogen Energy, 38(16), p.6577 - 6585, 2013/05

https://doi.org/10.1016/j.ijhydene.2013.01.106

Very harsh environments exist in the iodine-sulfur process for hydrogen production. Structural materials for sulfuric acid vaporizers and concentrators are exposed to high-temperature corrosive environments. Immersion tests were carried out to evaluate the corrosion resistance of ceramics and to evaluate corrosion-resistant metals exposed to environments of aqueous sulfuric acids at temperatures of 320, 380, and 460C, and pressure of 2 MPa. The aqueous sulfuric acid concentrations for the temperatures were 75, 85, and 95 wt%, respectively. Ceramic specimens of silicon carbides (SiC), silicon impregnated silicon carbides (Si-SiC), and silicon nitrides (SiN) showed excellent corrosion resistance from weight loss measurements after exposure to 75, 85, and 95 wt% sulfuric acid. High-silicon irons with silicon content of 20 wt% showed a fair measure of corrosion resistance. However, evidence of crack formation was detected via microscopy. Silicon enriched steels severely suffered from uniform corrosion with a corrosion rate in 95 wt% sulfuric acid of approximately 1 gmh. Among the tested materials, the ceramics SiC, Si-SiC, and SiN were found to be suitable candidates for structural materials in direct contact with the considered environments.

Adaptability of Metallic Structural Materials to gaseous HI decomposition environment in thermochemical water-splitting iodine-sulfur process

Kubo, Shinji; Futakawa, Masatoshi; Onuki, Kaoru; Yamaguchi, Akihisa*

Corrosion Engineering, 62(3), p.104 - 111, 2013/03

The iodine-sulfur thermochemical cycle for hydrogen production takes place in very harsh environments. Structural metallic materials for the hydrogen iodide decomposition are exposed in a high temperature halogen corrosion and hydrogen embrittlement environment. To evaluate adaptability of the materials, the corrosion rates and mechanical properties (the yield strength, the tensile strength, and the elongation) were measured. Prepared test specimens were exposed to ambient gas consisting of HI, I, HO, and H (molar fraction of 1:1:6:0.16) at 450C for 1000 h at atmospheric pressure. After the exposure, the corrosion rates were obtained by the weight loss of each specimen. Nickel-based alloys (Hastelloy C-276, MAT21, Inconel 625) exhibited appropriate corrosion resistance ( 0.03 g m h. In addition, no degradations of the mechanical properties for the MAT21 and the Inconel 625 were observed. The specimens of tantalum and titanium showed hydrogen embrittlement; the specimens of zirconium and niobium exhibited poor corrosion resistance. The specimens of molybdenum (Mo) exhibited good corrosion resistance; however, the strength degradation of Mo is cause for concern. As the results show, the nickel-based alloys are well suited for the structural materials within this environment from the viewpoint of the corrosion resistance. MAT21 among them is an outstanding material with an eye to its corrosion resistance and mechanical properties.

Safety measures for integrity test apparatus for IS process (Bunsen section)

Kubo, Shinji; Tanaka, Nobuyuki; Noguchi, Hiroki; Iwatsuki, Jin; Onuki, Kaoru; Inagaki, Yoshiyuki

JAEA-Technology 2012-043, 41 Pages, 2013/02

JAEA-Technology-2012-043.pdf:7.74MB

Providing safety measures for workers and external environments are indispensable in R&D activities of the iodine sulfur water-splitting hydrogen production process, since this process uses toxic chemicals as sulfur dioxide, sulfuric acid, iodine and hydriodic acid. One of the R&D subjects is proof of manufacturability of chemical reactors made of practical structural materials and confirmation of the reactors' sound performance in the harsh process conditions. In order to examine the task, test apparatuses of the process are being constructed; the apparatus for a Bunsen reactor has been built and assembled. Capacities of vessels of the apparatus are about 50-150 liter; normal operating pressure will be 0.5 MPa [abs], and that of temperature will be 90 degrees centigrade. Safety measures for the test apparatus, operations, and in abnormal situations were considered prior to the start of the operation. This report summarizes the results of the considerations.

Energy requirement of HI separation from HI-I-HO mixture using electro-electrodialysis and distillation

Guo, H.*; Kasahara, Seiji; Tanaka, Nobuyuki; Onuki, Kaoru

International Journal of Hydrogen Energy, 37(19), p.13971 - 13982, 2012/10

https://doi.org/10.1016/j.ijhydene.2012.07.078

Separation of HI from HI-I-HO mixture determines the efficiency of the IS process for thermochemical hydrogen production. Energy requirement of HI separation from HI-I-HO mixture using electro-electrodialysis (EED) and distillation was evaluated by a process simulation. For EED, ideal membrane properties and properties of the reported EED experiments using Nafion membrane were evaluated. Effects of the operating parameters on heat duty were estimated, which comprised column pressure, HI molality in the column feed, and the flow rate ratio of the input from the Bunsen section to distillate rate. Low column pressure and high HI molality in the column feed were preferable for the ideal-membrane case; column pressure of 1.0 MPa and optimized HI molality in the column feed were desired for the Nafion-membrane case. The flow rate ratio had little effect on the minimum heat duty in the ideal-membrane case; a value in the vicinity of the lower limit of the flow rate ratio was optimal for the Nafion-membrane case. Optimization of these parameters was also carried out. The minimum heat duty of the Nafion-membrane case was 3.0710 J/mol-HI, and that of the ideal-membrane case was 12.5% of the value.

Components for sulfuric acid processing in the IS process

Noguchi, Hiroki; Kubo, Shinji; Iwatsuki, Jin; Kasahara, Seiji; Tanaka, Nobuyuki; Imai, Yoshiyuki; Terada, Atsuhiko; Takegami, Hiroaki; Kamiji, Yu; Onuki, Kaoru; et al.

Proceedings of 6th International Topical Meeting on High Temperature Reactor Technology (HTR 2012) (USB Flash Drive), 6 Pages, 2012/10

The Japan Atomic Energy Agency (JAEA) has been conducting research and development on a thermochemical iodine-sulfur (IS) process. An examination is planned to verify the integrity of the components in the sulfuric acid decomposition section. A bayonet-type sulfuric acid decomposer made of SiC ceramics, a key component in the section, was test-fabricated. In parallel, a direct-contact heat exchanger (DCHX) is contemplated for use in the sulfuric acid decomposition section to simplify the process. Although the concept is very attractive, little is known about the heat and mass transfer behavior in the DCHX. Therefore, a test apparatus was constructed to measure the gas-phase mass transfer coefficients required for the optimal design of the DCHX. These coefficients of water were acquired and compared with an empirical correlation. The experimental data were in good agreement with those obtained from empirical correlation, and thus, the apparatus was confirmed to be reasonable.