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Improvement of HI concentration performance for hydrogen production iodine-sulfur process using crosslinked cation-exchange membrane

架橋イオン交換膜を用いた水素製造法ISプロセスにおけるHI濃縮性能の改良

田中 伸幸; 澤田 真一*; 八巻 徹也*; 小平 岳秀*; 木村 壮宏*; 野村 幹弘*

Tanaka, Nobuyuki; Sawada, Shinichi*; Yamaki, Tetsuya*; Kodaira, Takahide*; Kimura, Takehiro*; Nomura, Mikihiro*

熱化学水素製造法ISプロセスでは、HI-I$$_{2}$$-H$$_{2}$$O (HIx)溶液のHI濃縮のため、イオン交換膜を用いた電解電気透析法(EED)が適用されている。本報では、放射線グラフト膜に対して架橋構造を導入することで、HI濃縮性能の改良を試み、導電率($$sigma$$),輸率(t$$_{+}$$),水透過係数($$beta$$)の性能指標を用いて、実験的及び理論的に性能評価を行った。架橋導入により、H$$^{+}$$及び水の透過選択性が改善されることが示された。また、EEDの数理モデルに基づく理論解析から、架橋導入による影響はHI吸収量及びH$$^{+}$$拡散係数にはほとんど影響を与えず、I$$^{-}$$の拡散係数に影響することが明らかとなり、$$sigma$$, t$$_{+}$$に対しては、その結果が反映されることで、H$$^{+}$$の選択性が改善された。また、架橋の効果により、HI溶液の吸収に伴う膨潤が抑制され、その効果により、水の透過が抑制され、HI濃縮効果が高まることが示された。

We have been developing the ion exchange membranes by a radiation grafted polymerization method to improve HI concentration performance for Electro-electrodialysis (EED) in the thermochemical water-splitting hydrogen production iodine-sulfur process. In this work, the crosslinking structures were introduced to the ion exchange membranes. The proton conductivity ($$sigma$$), transport number (t$$_{+}$$), and water permeation factor ($$beta$$) of these crosslinked ion exchange membranes were measured and the effect of crosslinks to these performance indexes were investigated. The introduction of crosslinks was found to improve the selectivity of H$$^{+}$$ and water transport (increase of t$$_{+}$$ and decrease of $$beta$$), although the $$sigma$$ somewhat decreased. The EED model that we established to discuss the permeation mechanism of EED system was used to theoretically analyze the effect of crosslink on the performance indexes. Based on this analysis of measurement results, the introduction of the crosslink was found to little affect the absorbed amount of HIx solution and H$$^{+}$$ diffusion coefficient in the tested membranes, whereas it could lead to decrease I$$^{-}$$ diffusion coefficient. The results of $$sigma$$ and t$$_{+}$$ could reflect these effects. In addition, we found the fact that crosslink can inhibit the swelling due to the absorption of the HIx solution. As a result, the $$beta$$ value decreased owing to the introduction of crosslink.

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