高シリカ型ゼオライト膜の合成と分離プロセスへの応用 [論文要旨及び審査の要旨]

関西大

高シリカ型ゼオライト膜の合成と分離プロセスへの応用

関西大

Synthesis and gas permeation properties of chabazite-type titanosilicate membranes synthesized using nano-sized seed crystals

Chabazite (CHA)-type zeolite membranes have received considerable attention regarding their high permeance and separation performance. A recent report detailing a unique preparation procedure for a CHA-type titanosilicate (Ti-CHA) zeolite—in which titanium heteroatoms were incorporated into the zeolite framework by substitution of aluminum—demonstrates excellent physico-chemical properties when compared with conventional aluminosilicate CHA-type zeolites. In this study, the synthesis of Ti-CHA zeolite membranes (Ti-CHA membrane) was investigated. The Ti-CHA membrane was synthesized on an alumina support via a secondary growth method using Ti-CHA zeolite seed crystals. The Ti-CHA membrane properties were studied as a function of seed crystal size. The average particle diameter was observed to reduce from 2.3 μm to 450 nm by increasing the loading of Ti-CHA into the synthesis gel. Regardless of the seed crystal particle size, the presence of CHA-type zeolites on the alumina support was confirmed by x-ray diffraction. UV-Vis demonstrated the incorporation of titanium heteroatoms into the zeolite framework. The results indicated the successful synthesis of the Ti-CHA membrane regardless of the seed crystal particle size. Additionally, the membrane thickness decreased by using the seed crystal. Single gas permeation tests showed that the thinnest Ti-CHA membrane prepared in this study exhibited a relatively high CO2 permeance of 1.5×10−6 mol m−2 s−1 Pa−1, compared with that of previously reported CHA-type zeolite membranes. The influence of moisture on the separation performance of the Ti-CHA membrane was evaluated in the presence of gas mixtures composed of CO2, methane and H2O ranging from 0.1 to 5 vol.%. In the presence of 1 vol.% H2O, the CO2 permeance and selectivity were only marginally reduced as a result of the highly hydrophobic pore structure.This work was partially supported by Kansai University Fund for Supporting Young Scholars, 2018

2017～2019年度 関西大学研究拠点形成支援経費研究成果報告書

目次・研究成果の概要・2-1　工藤 宏人・宮前 翼・上田 正人・村山 憲弘・林 順一 "ノーリア骨格をテンプレートとした空孔内に水酸基を有する架橋化合物の合成とそれらの金属イオン包接性能" ネットワークポリマー論文集 vol.41, No.2, 65 - 71 (2020).・2-2　Mitsuaki Matsuoka, Kaho Yokoyama, Kohei Okura, Norihiro Murayama, Masato Ueda, Makio Naito " Synthesis of Geopolymers from Mechanically Activated Coal Fly Ash and Improvement of Their Mechanical Properties" Minerals 9, 791- 801 (2019).・2-3　Daisuke Shimoyama, Ryo Sekiya, Hiroto Kudo, Takeharu Haino, "Feet-to-Feet Connected Trisresorcinarenes" Organic Letters 22, 352 - 356 (2019).・2-4　Masato Ueda, Masahiko Ikeda, Shigeo Mori, Kenji Doi, Hisashi Kitagaki, Shuntaro Terauchi "Mechanical Properties of Additively Manufactured Porous Titanium with Sub-Millimetre Structural Units" Materials Transactions Vol.60, No.9, 1792 - 1798 (2019).・2-5　五十井 浩平・白杉 文香・松岡 光昭・林 順一・村山 憲弘 "種々のMg-Fe系複合酸化物を用いた希薄水溶液中のホウ素およびヒ素の除去" 環境資源工学 66, 29 - 35 (2019).・2-6　Toru Maruyama, Mitsuyoshi Tamaki, Keisuke Nakamura, Gou Nakamura "EFFECT OF MOLTEN METAL TEMPERATURE ON MOLD FILLING IN EVAPORATIVE PATTERN CASTING" International Journal of Metalcasting 13, 611–617 (2019).・2-7　Ryuta Saito, Toru Maruyama, Toshiki Nakamura, Hitoshi Yanagitani, Takahiro Sakai, Kouji Nakamoto "Influence of Tellurium Addition to Spheroidal Graphite Cast Iron on the Number of Graphite Particles" International Journal of Metalcasting Vol.13, 3, 571-577 (2018).・2-8　Masato Ueda, Rika Yamaguchi, Chika Fujita, Masahiko Ikeda "Control of Cell Adhesion on Titanium Dioxide by Light Irradiation" Materials Science Forum Vol.941, 2507 - 2512 (2018).・2-9　Hiroto Kudo, Mari Fukunaga, Kohei Shiotsuki, Hiroya Takeda, Hiroki Yamamoto, Takahiro Kozawa, Takeo Watanabe "Synthesis of hyperbranched polyacetals containing C-(4-t-butylbenz)calix[4]resorcinarene: Resist properties for extreme ultraviolet (EUV) lithography" Reactive and Functional Polymers 131, 361 - 367 (2018).・2-10　大隈 修・前 一廣・林 順一 "直接液化による豪州ビクトリア褐炭の高度利用 : 改新BCLプロセスによる化学原料の生産" Journal of the Japan Institute of Energy 98, 17 - 26 (2019).・2-11　Issei Suzuki, Ayako Kakinuma, Masato Ueda, Takahisa Omata "Flux growth of β-NaGaO₂ single crystals" Journal of Crystal Growth 504, 26 -30 (2018).・2-12　上田 正人、坂本 貴則、池田 勝彦 "電気抵抗率の精密測定による純チタンの組織評価" 環境資源工学 65, 74 -76 (2018).・2-13　Satoshi Imasaka, Hiroyasu Ishii, Jun\u27ichi Hayashi, Sadao Araki, Hideki Yamamoto "Synthesis of CHA-type titanosilicate zeolites using titanium oxide as Ti source and evaluation of their physicochemical properties" Microporous and Mesoporous Materials 273, 243-248 (2019).・2-14　Hiroto Kudo, Shizuya Ohori, Hiroya Takeda, Hiroki Ogawa, Takeo Watanbe, Hiroki Yamamoto, Takahiro Kozawa "Synthesis and Property of Tannic Acid Derivatives and Their Application for Extreme Ultraviolet Laser Lithography System" Journal of Photopolymer Science and Technology Vol.31, 221 - 225 (2018).・2-15　Hiroto Kudo, Tsubasa Miyamae, Kouta Kitagawa, Kohei Isoi, Norihiro Murayama, Jun\u27ichi Hayashi " Synthesis and Metal-Complexation Ability of Cross-Linking Materials Containing Noria-Templated Cavities with Pendant Carboxylic Acid Groups" Chemistry Select 3, 2223 - 2228 (2018).・2-16　上田 正人、池田 勝彦、土井 研児、 森 重雄、北垣 壽、寺内 俊太郎、関 あずさ "骨部分置換用ポーラスチタン : ポリグリコール酸 : 炭酸カルシウム複合体の開発" 高分子論文集 Vol.75, No.1, 69 - 74 (2018).・2-17　Alexandru C Sonoc, Jacob Jeswiet, Norihiro Murayama, Junji Shibata "A study of the application of Donnan dialysis to the recycling of lithium ion batteries" Hydrometallurgy 175, 133 - 143 (2018).2-3は、著作権の関係により非公開としております。2-8は、著作権の関係により非公開としております。2-9は、著作権の関係により非公開としております。2-10は、著作権の関係により非公開としております。2-11は、著作権の関係により非公開としております。2-16は、著作権の関係により非公開としております

Antenna-enhanced high harmonic generation in a wide-bandgap semiconductor ZnO

We demonstrate high harmonic generation (HHG) into deep-UV range in a ZnO single crystal with resonant nanoantennas. Non-perturbative HHG is successfully induced by optical excitation of as low as 20 GW/cm2. The spectral selection rule is found to reflect crystal symmetry, suggesting the possibility of nano-scaled EUV sources and band-structure reconstruction

Antenna-enhanced high harmonic generation in a wide-bandgap semiconductor ZnO

We demonstrate high harmonic generation (HHG) into deep-UV range in a ZnO single crystal with resonant nanoantennas. Non-perturbative HHG is successfully induced by optical excitation of as low as 20 GW/cm2. The spectral selection rule is found to reflect crystal symmetry, suggesting the possibility of nano-scaled EUV sources and band-structure reconstruction