2022/12/04 更新

写真a

マツカタ マサヒコ
松方 正彦
Scopus 論文情報  
論文数: 0  Citation: 0  h-index: 12

Citation Countは当該年に発表した論文の被引用数

所属
理工学術院 先進理工学部
職名
教授
ホームページ

他学部・他研究科等兼任情報

  • 理工学術院   大学院先進理工学研究科

  • 理工学術院   大学院環境・エネルギー研究科

学内研究所・附属機関兼任歴

  • 2020年
    -
    2022年

    理工学術院総合研究所   兼任研究員

  • 2020年
    -
    2022年

    リサーチイノベ オープンイノベーション推進セクション   兼任センター員

学歴

  •  
    -
    1989年

    早稲田大学   理工学研究科   応用化学  

  •  
    -
    1984年

    早稲田大学   理工学部   応用化学  

学位

  • 早稲田大学   工学博士

経歴

  • 2001年
    -
     

    早稲田大学理工学部 教授

  • 1997年
    -
    2001年

    早稲田大学理工学部 助教授

  • 1996年
    -
    1997年

    大阪大学基礎工学部 助教授

  • 1992年
    -
    1996年

    大阪大学基礎工学部 助手

  • 1989年
    -
    1991年

    成蹊大学工学部 助手

所属学協会

  •  
     
     

    日本膜学会

  •  
     
     

    American Institute of Chemical Engineers(アメリカ化学工学会)

  •  
     
     

    Materials Research Society

  •  
     
     

    日本化学会

  •  
     
     

    American Chemical Society(アメリカ化学会)

  •  
     
     

    触媒学会

  •  
     
     

    エネルギー資源学会

  •  
     
     

    ゼオライト学会

  •  
     
     

    石油学会

  •  
     
     

    日本エネルギー学会

  •  
     
     

    化学工学会

▼全件表示

 

研究分野

  • ナノ構造化学

  • 移動現象、単位操作

  • 反応工学、プロセスシステム工学

  • 触媒プロセス、資源化学プロセス

  • 無機物質、無機材料化学

研究キーワード

  • ミクロ・メソ多孔体、触媒、分離膜、水素製造、ゼオライト、プラスチックリサイクル、エネルギー、バイオマス、石炭・廃棄物有効利用、ナノ構造化学、ナノ反応場、化石燃料有効利用技術、触媒調製化学、多孔体、結晶・多結晶材料、反応分離工学、

論文

  • Ultrapermeable 2D-channeled graphene-wrapped zeolite molecular sieving membranes for hydrogen separation

    Radovan Kukobat, Motomu Sakai, Hideki Tanaka, Hayato Otsuka, Fernando Vallejos-Burgos, Christian Lastoskie, Masahiko Matsukata, Yukichi Sasaki, Kaname Yoshida, Takuya Hayashi, Katsumi Kaneko

    Science Advances   8 ( 20 ) abl3521  2022年05月  [査読有り]

    DOI

    Scopus

    2
    被引用数
    (Scopus)
  • Alkaline-treatment with pore-filling agent for defect-healing of zeolite membrane

    Motomu Sakai, Hayata Hori, Masahiko Matsukata

    Microporous and Mesoporous Materials   336  2022年05月

     概要を見る

    Defects in silicalite-1 membrane is readily healed by an alkaline-treatment in aqueous solutions of NaOH and organic additives such as cetyltrimethylammonium bromide (CTAB) and tetramethylammonium bromide (TMABr). In this study, we investigated the role of organic additive in the course of alkaline-treatment. From the evaluation of weight and micropore volume of silicalite-1, it was shown that 3.6 and 3.1 molecules per unit cell of CTA+ and TMA+ entered the micropore of silicalite-1 during the treatment. CTA+ or TMA+ locating in the micropore inhibited the diffusion of NaOH into the micropore of zeolite and suppressed the dissolution from the inside of crystal. In contrast, the defect in silicalite-1 membrane was not healed by using an aqueous solution of NaOH and tetrabutylammonium bromide (TMABr), which was not able to enter the micropore of silicalite-1. We concluded that the use of organic additives, which can enter the micropore, was important for the defect-healing of siliclaite-1 membrane by the alkaline-treatment.

    DOI

    Scopus

    1
    被引用数
    (Scopus)
  • Contribution of Pore-Connectivity to Permeation Performance of Silicalite-1 Membrane; Part II, Diffusivity of C6 Hydrocarbon in Micropore.

    Motomu Sakai, Yukichi Sasaki, Takuya Kaneko, Masahiko Matsukata

    Membranes   11 ( 6 )  2021年05月  [国際誌]

     概要を見る

    This study investigated the permeation behaviors of n-hexane and 2-methylpentane through two-types of silicalite-1 membranes that have different pore-connectivity. The permeation mechanisms of these hydrocarbons were able to be explained by the adsorption-diffusion model. In addition, the fluxes through silicalite-1 membranes could be expressed by the modified Fick's first law. The hydrocarbon fluxes through S-1S with better pore-connectivity were ca. 3-20 times larger than those through S-1M with poor pore-connectivity. For these membranes with different pore-connectivity, the activation energy of diffusion of n-hexane was 17.5 kJ mol-1 for the membrane with better pore-connectivity and 18.0 kJ mol-1 for the membrane with poorer pore-connectivity, whereas for 2-methylpentane it was 17.9 and 33.0 kJ mol-1, respectively. We concluded that the pore-connectivity in silicalite-1 membrane significantly influences the molecular diffusivities.

    DOI PubMed

    Scopus

    3
    被引用数
    (Scopus)
  • Contribution of Pore-Connectivity to Permeation Performance of Silicalite-1 Membrane; Part I, Pore Volume and Effective Pore Size.

    Motomu Sakai, Yukichi Sasaki, Takuya Kaneko, Masahiko Matsukata

    Membranes   11 ( 6 )  2021年05月  [国際誌]

     概要を見る

    The micropore volumes and effective pore sizes of two types of silicalite-1 membranes were compared with those of a typical silicalite-1 powder. The silicalite-1 membrane with fewer grain boundaries in the membrane layer showed similar micropore volume and effective pores size to those of the silicalite-1 powder. In contrast, when the silicalite-1 membrane contained many grain boundaries, relatively small micropore volume and effective pore size were observed, suggesting that narrowing and obstruction of the micropore would occur along grain boundaries due to the disconnection of the zeolite pore. The silicalite-1 membrane with fewer grain boundaries exhibited relatively high permeation properties for C6-C8 hydrocarbons. There was an over 50-fold difference in benzene permeance between these two types of membranes. We concluded that it is important to reduce grain boundaries and improve pore-connectivity to develop an effective preparation method for obtaining a highly permeable membrane.

    DOI PubMed

    Scopus

    6
    被引用数
    (Scopus)
  • Self-defect-healing of silicalite-1 membrane in alkaline aqueous solution with surfactant

    Motomu Sakai, Hayata Hori, Masahiko Matsukata

    MATERIALS ADVANCES    2021年05月

     概要を見る

    Alkaline treatment with surfactant was applied to silicalite-1 membrane for defect healing. By immersion of silicalite-1 membrane into an aqueous solution of sodium hydroxide and cetyltrimethylammonium bromide (CTAB), defects among crystals were sealed, with amorphous silica leached from the membrane itself. During the treatment, the zeolite pores in the membrane were protected by CTAB from excess alkaline etching. As a result, the separation performance of silicalite-1 membrane was successfully improved by this post-treatment without a decrease in permeability due to the collaborative effect of NaOH and CTAB. The separation factor for n-hexane/2,3-dimethylbutane mixture increased from 86.5 to 559 after only a 15 min treatment. In addition, the separation performances of other zeolite membranes (Na-*BEA, Na-ZSM-5, and Na-MOR) were also improved by the treatment. This novel defect-healing technique breaks the trade-off line of permeation and separation performance observed with previous post-treatments.

    DOI

    Scopus

    1
    被引用数
    (Scopus)
  • Synthesis of FAU-Zeolite Membrane by a Secondary Growth Method: Influence of Seeding on Membrane Growth and Its Performance in the Dehydration of Isopropyl Alcohol-Water Mixture

    Masahiko Matsukata, Yasushi Sekine, Eiichi Kikuchi, Motomu Sakai, Bharathi Subramanian, Makoto Toyoda, Taisuke Furuhata

    ACS Omega   6 ( 14 ) 9834 - 9842  2021年04月

     概要を見る

    Y-type zeolite membranes were prepared on a porous tubular α-alumina support by a secondary growth process. Various experimental conditions such as seed size, pH of seed solution, and degassing of support were examined for understanding their influence on the membrane deposition process. The experimental results showed that the potential of alumina support surface and the USY seed slurry plays a significant role in controlling the electrostatic interaction between seed particles and support surface and also the aggregation of USY seed particles in the slurry. In addition, we also noted the significance of the capillary forces working at the three-phase interface on the support surface and is a key factor that governs the seeding behavior onto the tubular support surface. Optimization of these parameters resulted in crack-free compact membranes that were able to effectively separate a mixture of isopropyl alcohol and water in a vapor-phase separation process.

    DOI

    Scopus

    1
    被引用数
    (Scopus)
  • Formation Process of Columnar Grown (101)-Oriented Silicalite-1 Membrane and Its Separation Property for Xylene Isomer

    Motomu Sakai, Takuya Kaneko, Yukichi Sasaki, Miyuki Sekigawa, Masahiko Matsukata

    Crystals   10 ( 10 ) 949 - 949  2020年10月  [査読有り]  [招待有り]

     概要を見る

    Silicalite-1 membrane was prepared on an outer surface of a tubular α-alumina support by a secondary growth method. Changes of defect amount and crystallinity during secondary growth were carefully observed. The defect-less well-crystallized silicalite-1 membrane was obtained after 7-days crystallization at 373 K. The silicalite-1 membrane became (h0l)-orientation with increasing membrane thickness, possibly because the orientation was attributable to “evolutionally selection”. The (h0l)-oriented silicalite-1 membrane showed high p-xylene separation performance for a xylene isomer mixture (o-/m-/p-xylene = 0.4/0.4/0.4 kPa). The p-xylene permeance through the membrane was 6.52 × 10−8 mol m−2 s−1 Pa−1 with separation factors αp/o, αp/m of more than 100 at 373 K. As a result of microscopic analysis, it was suggested that a very thin part in the vicinity of surface played as effective separation layer and could contribute to high permeation performance.

    DOI

    Scopus

    8
    被引用数
    (Scopus)
  • Preferential Adsorption of Propylene over Propane on a Ag-Exchanged X-Type Zeolite Membrane

    Motomu Sakai, Naoyuki Fujimaki, Yasuhito Sasaki, Noriyuki Yasuda, Masahiro Seshimo, Masahiko Matsukata

    ACS applied materials & interfaces   12 ( 21 ) 24086 - 24092  2020年05月  [査読有り]

     概要を見る

    We investigated the adsorption properties of propylene and propane on an olefin-selective Ag-X membrane and discussed the contribution of adsorption selectivity to propylene/propane separation performance through this membrane. The isotherms of propylene and propane on Ag-X membranes were measured in unary systems at 313 K. The amount of propylene adsorbed on the Ag-X membrane at a lower pressure increased remarkably compared with that on the Na-X membrane. Such a change of adsorption property could induce excellent separation property for the Ag-X membrane. We compared the adsorption properties in a binary system calculated based on the Markham-Benton approach with the results of a permeation test. The molar fractions of propylene in the adsorbed phase in the binary system provided good agreement with propylene purity on the permeation side of the Ag-X membrane. These results clearly show that permeation selectivity of the Ag-X membrane for the propylene/propane mixture is mainly governed by adsorption selectivity.

    DOI PubMed

    Scopus

    10
    被引用数
    (Scopus)
  • Higher activity of ni/γ-al<inf>2</inf>o<inf>3</inf> over fe/γ-al<inf>2</inf>o<inf>3</inf> and ru/γ- al<inf>2</inf>o<inf>3</inf> for catalytic ammonia synthesis in nonthermal atmospheric-pressure plasma of n<inf>2</inf> and h<inf>2</inf>

    Masakazu Iwamoto, Masataka Horikoshi, Ryu Hashimoto, Kaori Shimano, Tomiko Sawaguchi, Harunobu Teduka, Masahiko Matsukata

    Catalysts   10 ( 5 )  2020年05月  [査読有り]

     概要を見る

    © 2020 by the authors. Licensee MDPI, Basel, Switzerland. T. Developing a novel ammonia synthesis process from N2 and H2 is of interest to the catalysis and hydrogen research communities. γ-Alumina-supported nickel was determined capable of serving as an efficient catalyst for ammonia synthesis using nonthermal plasma under atmospheric pressure without heating. The catalytic activity was almost unrelated to the crystal structure and the surface area of the alumina carrier. The activity of Ni/Al2O3 was quantitatively compared with that of Fe/Al2O3 and Ru/Al2O3, which contained active metals for the conventional Haber–Bosch process. The activity sequence was Ni/Al2O3 > Al2O3 > Fe/Al2O3 > no additive > Ru/Al2O3, surprisingly indicating that the loading of Fe and Ru decreased the activity of Al2O3. The catalytic activity of Ni/Al2O3 was dependent on the amount of loaded Ni, the calcination temperature, and the reaction time. XRD, visual, and XPS observations of the catalysts before the plasma reaction indicated the generation of NiO and NiAl2O4 on Al2O3, the latter of which was generated upon high-temperature calcination. The NiO species was readily reduced to Ni metal in the plasma reaction, whereas the NiAl2O4 species was difficult to reduce. The catalytic behavior could be attributed to the production of fine Ni metal particles that served as active sites. The PN2/PH2 ratio dependence and rate constants of formation and decomposition of ammonia were finally determined for 5.0 wt % Ni/Al2O3 calcined at 773 K. The ammonia yield was 6.3% at an applied voltage of 6.0 kV, a residence time of reactant gases of 0.12 min, and PH2/PN2 = 1.

    DOI

    Scopus

    9
    被引用数
    (Scopus)
  • Organic structure-directing agent-free synthesis for *Bea-type zeolite membrane

    Motomu Sakai, Noriyuki Yasuda, Yuto Tsuzuki, Masahiko Matsukata

    Journal of Visualized Experiments   2020 ( 156 )  2020年02月  [査読有り]

     概要を見る

    © 2020 Journal of Visualized Experiments. Membrane separation has drawn attention as a novel-energy saving separation process. Zeolite membranes have great potential for hydrocarbon separation in petroleum and petrochemical fields because of their high thermal, chemical, and mechanical strength. A *BEA-type zeolite is an interesting membrane material because of its large pore size and wide Si/Al range. This manuscript presents a protocol for *BEA membrane preparation by a secondary growth method that does not use an organic structure-directing agent (OSDA). The preparation protocol consists of four steps: pretreatment of support, seed preparation, dip-coating, and membrane crystallization. First, the *BEA seed crystal is prepared by conventional hydrothermal synthesis using OSDA. The synthesized seed crystal is loaded on the outer surface of a 3 cm long tubular α-Al2O3 support by a dip-coating method. The loaded seed layer is prepared with the secondary growth method using a hydrothermal treatment at 393 K for 7 days without using OSDA. A *BEA membrane having very few defects is successfully obtained. The seed preparation and dip-coating steps strongly affect the membrane quality.

    DOI PubMed

    Scopus

    1
    被引用数
    (Scopus)
  • Hydrophilic ZSM-5 membrane for forward osmosis operation

    Motomu Sakai, Masahiro Seshimo, Masahiko Matsukata

    Journal of Water Process Engineering   32  2019年12月  [査読有り]

     概要を見る

    © 2019 The Authors A potential of zeolite membrane in forward osmosis operation was investigated for the first time. A hydrophilic zeolite, ZSM-5, membrane was prepared on an α-alumina tubular support by a secondary growth method. NaCl aqueous solution and distilled water were used as draw and feed solutions, respectively. The membrane exhibited a water flux of 2.2 L m−2 h−1 with a salt flux of 0.69 g m−2 h−1 at 313 K by using 9.0 wt% draw solution. ZSM-5 membrane showed a quite small reverse salt flux based on a molecular sieving effect in the relatively wide temperature ranges of 298–333 K. ZSM-5 membrane also kept its performance under acidic conditions. In addition, obvious deterioration of the membrane performance was not observed after intermittent use of our membrane for more than one month.

    DOI

    Scopus

    11
    被引用数
    (Scopus)
  • Formation process of *BEA-type zeolite membrane under OSDA-free conditions and its separation property

    Motomu Sakai, Naoyuki Fujimaki, Genki Kobayashi, Noriyuki Yasuda, Yoshikazu Oshima, Masahiro Seshimo, Masahiko Matsukata

    Microporous and Mesoporous Materials   284   360 - 365  2019年08月  [査読有り]

     概要を見る

    © 2019 The Authors Tubular zeolite *BEA membrane was prepared by a hydrothermal secondary growth method in the absence of an organic structure directing agent (OSDA). Membrane formation process was carefully observed by using FE-SEM, XRD, and N2 adsorption, and the role of seed crystals on the support surface was discussed. Seed crystals loaded on the outer surface of a tubular porous alumina support partially dissolved and a small amount of seeds remained in an amorphous layer formed on the support surface in the early stage of secondary growth step. Subsequently, crystal growth of remaining crystals occurred, and a continuous *BEA layer was obtained following crystallization for 7 days at 393 K. In the secondary growth step, the supported seed layer played an important role in inducing the formation of a high local concentration in the vicinity of the support surface. The prepared OSDA-free *BEA membrane was then applied in the separation of hydrocarbons. We found that this membrane contained very few defects, and exhibited a high ideal selectivity for cyclohexane/1,3,5-trimethylbenzene mixture of 100, with cyclohexane permeance of 1.0 × 10−7 mol m−2 s−1 Pa−1 based on molecular sieving effect at 623 K.

    DOI

    Scopus

    9
    被引用数
    (Scopus)
  • Olefin Selective Ag-Exchanged X-Type Zeolite Membrane for Propylene/Propane and Ethylene/Ethane Separation

    Motomu Sakai, Yasuhito Sasaki, Taisuke Tomono, Masahiro Seshimo, Masahiko Matsukata

    ACS Applied Materials and Interfaces   11 ( 4 ) 4145 - 4151  2019年01月  [査読有り]

     概要を見る

    © 2019 American Chemical Society. Propylene/propane and ethylene/ethane separation was examined with Ag-exchanged X-type zeolite membrane (Ag-X membrane). The Na-X membrane was prepared on a porous tubular α-alumina support by a secondary growth method. The resulting Na-X membrane was ion-exchanged by using AgNO 3 aq. Olefin selectivities in both mixtures were markedly improved after the ion exchange from Na to Ag cation. The Ag-X membrane exhibited a maximum propylene selectivity of 55.4 with a permeance of 4.13 × 10 -8 mol m -2 s -1 Pa -1 at 353 K for a propylene/propane (50:50) mixture. This membrane also exhibited a maximum ethylene selectivity of 15.9 with a permeance of 9.04 × 10 -8 mol m -2 s -1 Pa -1 at 303 K for an ethylene/ethane (50:50) mixture. We consider that the strong interaction between olefin and Ag cation plays an important role for the appearance of such high selectivity of olefin.

    DOI PubMed

    Scopus

    49
    被引用数
    (Scopus)
  • Ammonia decomposition to clean hydrogen using non-thermal atmospheric-pressure plasma

    Mao Akiyama, Keigo Aihara, Tomiko Sawaguchi, Masahiko Matsukata, Masakazu Iwamoto

    International Journal of Hydrogen Energy   43 ( 31 ) 14493 - 14497  2018年08月

     概要を見る

    © 2018 Hydrogen Energy Publications LLC The plasma decomposition of ammonia was studied as a function of applied voltage/power, residence time including length of an inner electrode and flow rate of reactant gases, partial pressure of ammonia, and amount and the metal species of the inner electrodes. The ammonia decomposition rates were in excellent agreement with the hydrogen production rates and no hydrazine production was detected, indicating the clean decomposition of ammonia in the current system. The decomposition rates were dependent on the applied power and the residence time and independent of metal species of the inner electrodes, in contrast to the strong dependence of the ammonia synthesis reaction on the metal species. A hydrogen yield of 100% was achieved with an applied power of approximately 50 W and a residence time of 1.2 s at ambient temperature and atmospheric pressure, with an applied voltage of 5 kV and a frequency of 50 kHz.

    DOI

    Scopus

    22
    被引用数
    (Scopus)
  • Depolymerization of Cellulose with Superheated Steam: Remarkable Obstruction Effects of Sodium and High Reactivity of Crystalline Cellulose

    Masakazu Iwamoto, Asami Shimatai, Masayoshi Honda, Masahiko Matsukata

    ACS Sustainable Chemistry and Engineering   6 ( 5 ) 6570 - 6576  2018年05月

     概要を見る

    © 2018 American Chemical Society. A superheated steam (SHS) treatment was found to be effective for conversion of cellulose to levoglucosan (LG) and other organic compounds. Yields of water-soluble organic compounds (TOC) and LG reached 88% and 41%, respectively, with the SHS treatment at 300 °C for 30 min. The reaction temperature was far lower than temperatures employed in conventional pyrolysis treatments (≥500 °C), and the TOC and LG yields were comparable to values reported for pyrolysis. Product distributions were significantly altered by sodium content in the parent cellulose. Sodium at 0.05 wt % or more in cellulose lowered the LG yield to almost zero, giving approximately constant TOC values other than LG, and increased solid residue, which indicated that sodium greatly reduced the reactivity of cellulose to form LG. In the absence of sodium, the reactivity of the crystalline phase of cellulose was much higher than the amorphous phase, indicating that the widely reported phenomena in which amorphous cellulose has higher reactivity than crystalline cellulose might result from a sodium impurity. In addition, the effect of ball-milling treatment was investigated to reveal the reactivity of crystalline and amorphous phases of cellulose with or without sodium contamination. The crystalline phase was converted to an amorphous phase distinct from the original amorphous phase, which could be distinguished by XRD patterns. The reactivity of the new amorphous phase was higher than that of the original crystalline phase. The obstruction of the LG formation by sodium was suggested to be due to its coordination onto a terminal glucose unit of a cellulose nanocrystal, based on the cellulose structure and amounts of sodium.

    DOI

    Scopus

    6
    被引用数
    (Scopus)
  • A Collective Case Screening of the Zeolites made in Japan for High Performance NH3-SCR of NOx

    Priya Subramaniam Vishnu, Ohnishi Takeshi, Shimada Yumiko, Kubota Yoshihiro, Masuda Takao, Nakasaka Yuta, Matsukata Masahiko, Itabashi Keiji, Okubo Tatsuya, Sano Tsuneji, Tsunoji Nao, Yokoi Toshiyuki, Ogura Masaru

    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN   91 ( 3 ) 355 - 361  2018年03月  [査読有り]

    DOI

    Scopus

    32
    被引用数
    (Scopus)
  • 加圧条件下におけるFAU型ゼオライト膜のプロピレン/プロパン分離特性

    酒井 求, 佐々木 康人, 松方 正彦

    石油学会 年会・秋季大会講演要旨集   2016   9 - 9  2016年

     概要を見る

    加圧条件下におけるFAU型ゼオライト膜のプロピレン/プロパン透過分離特性について検討した。また、得られた透過分離特性から、FAU型ゼオライト膜を用いたプロピレン回収の可能性についても併せて検討した。

    DOI CiNii

  • 吸着を用いたゼオライト膜の非破壊測定手法およびその解析方法

    瀬下 雅博, 酒井 求, 松方 正彦

    膜   41 ( 1 ) 30 - 35  2016年

     概要を見る

    We have successfully investigated nitrogen adsorption measurement using ZSM–5 type zeolite membrane prepared by seed assisted hydrothermal synthesis with various crystallization periods under non–destructive condition. Micro– and meso–pores derived from zeolitic and non–zeolitic structures were analyzed using nitrogen adsorption isotherm with the Saito–Foley model and the Kelvin equation. ZSM–5 membranes synthesized for various crystallization periods were characterized and evaluated by SEM, XRD, nanopermporometry and permeation tests. In this study, it could be considered that ZSM–5 membrane formation process had two–step as follows. First, ZSM–5 seed crystal was grown up in/onα–alumina support, and ZSM–5 micro–crystals generated in pore ofα–alumina support until 6 hours synthesis. After that, ZSM–5 crystals on theα–alumina support surface were predominantly grown up, and these crystals covered the support surface. After synthesis of 12 hours, the membrane had hardly defects.

    DOI CiNii

  • Zeolite Membrane for Dehydration of Isopropylalcohol-Water Mixture by Vapor Permeation

    Ken-ichi Sawamura, Taisuke Furuhata, Yasushi Sekine, Eiichi Kikuchi, Bharathi Subramanian, Masahiko Matsukata

    ACS APPLIED MATERIALS & INTERFACES   7 ( 25 ) 13728 - 13730  2015年07月

     概要を見る

    Highly stable FAU-type zeolite membrane for the separation of isopropanol (IPA)-water mixture by pervaporation is described. FAU membrane showed high water permselectivity and permeance. Comparison of FAU membrane with a conventional LTA-type zeolite membrane revealed superior stability of FAU zeolite membrane in a mixture containing a large water content.

    DOI

    Scopus

    35
    被引用数
    (Scopus)
  • Ag-FAU型ゼオライト膜のプロパン・プロピレン吸着特性

    酒井 求, 佐々木 康人, 飯島 優貴, 松方 正彦

    石油学会 年会・秋季大会講演要旨集   2015   50 - 50  2015年

     概要を見る

    当研究室ではAg-FAU型ゼオライト膜が高いプロピレン/プロパン透過分離特性を有することを報告している。本発表では、FAU型ゼオライト膜に対するプロピレン・プロパンの吸着挙動が分離特性に与える影響について検討した結果を報告する。

    DOI CiNii

  • FAU型ゼオライト膜を用いた1,3-ブタジエン/1-ブテン分離

    酒井 求, 佐々木 康人, 松方 正彦

    石油学会 年会・秋季大会講演要旨集   2015   52 - 52  2015年

     概要を見る

    当研究室ではFAU型ゼオライト膜が高いオレフィン/パラフィン透過分離特性を有することを報告している。本発表では、FAU型ゼオライト膜を用いて1,3-ブタジエン/1-ブテンの透過分離特性について検討した結果を報告する。

    DOI CiNii

  • Physicochemical Characterization of Highly Dispersed Platinum and Chromium on Zeolite Beta

    Yoshiyuki Izutsu, Yuki Oku, Yusuke Hidaka, Naoki Kanaya, Yoshiki Nakajima, Jun Fukuroi, Kaname Yoshida, Yukichi Sasaki, Yasushi Sekine, Masahiko Matsukata

    JOURNAL OF PHYSICAL CHEMISTRY C   118 ( 20 ) 10746 - 10753  2014年05月

     概要を見る

    Structures of platinum and chromium supported on zeolite beta were investigated by XAFS, XPS, UV-vis, NH3-TPD, XRD, CO chemisorption, and molecular dynamics simulation. Both platinum and chromium were uniformly dispersed in the micropore of zeolite beta. Loading of chromium helped platinum to disperse highly and stabilized in the micropore of beta. Major species of platinum on PtCr/beta after calcination at 773 K was Pt2+ forming a Pt-O bond. The Pt-O bond disappeared, and a Pt-Pt bond did not appear by reducing PtCr/beta in hydrogen, accompanying formation of Pt-0. Chromium was loaded as chromate anion in the micropore of zeolite. Results of molecular dynamics simulation showed that Pt2+ associated with CrO42- in the micropore of zeolite beta was more stable than those in the absence of chromium species. We concluded that CrO42- electrostatically stabilizes Pt2+ and inhibits migration and aggregation of platinum.

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    10
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  • silicalite-1膜を用いた長鎖直鎖アルカンの分離

    酒井 求, 金子 拓矢, 松方 正彦

    石油学会 年会・秋季大会講演要旨集   2014 ( 0 ) 13 - 13  2014年

     概要を見る

    MFI型ゼオライトの1種であるsilicalite-1を、種結晶を用いた2次成長法によって管状a-アルミナ支持体上に製膜した。得られたsilicalite-1膜を用いて、炭化水素混合物からの直鎖アルカンの分離を行った。本発表では、炭素数の異なる直鎖アルカンの透過分離特性について報告する。

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  • Synthesis and Characterization of Chromium-Added Pt/Beta Zeolite and its Catalytic Performance for n-Heptane Isomerization

    Yoshiyuki Izutsu, Yuki Oku, Yusuke Hidaka, Kaname Yoshida, Yukichi Sasaki, Yasushi Sekine, Eiichi Kikuchi, Masahiko Matsukata

    CATALYSIS LETTERS   143 ( 5 ) 486 - 494  2013年05月

     概要を見る

    Catalysis of Pt/beta zeolite catalyst modified via the addition of various elements (Ca, Cr, Mn, Fe, Co, Ni or Cu) for n-heptane skeletal isomerization was investigated at 513 K in a conventional flow reactor with a fixed catalyst bed. It was found that, among the catalysts tested, PtCr/beta was the most promising, since its use resulted in relatively high yields of multi-branched alkanes in conjunction with a very low selectivity for cracking products. Ion exchange was found to be an effective method for the addition of chromium to zeolite, compared to the evaporation to dryness process. Platinum particle sizes were observed using STEM. While particles similar to 10-30 nm in size were evident on the surface of Pt/beta, they were rarely observed on the PtCr/beta catalyst. It was concluded that platinum homogeneously dispersed within beta zeolite micropores resulted in the observed decreased cracking activity during n-heptane isomerization and that the addition of chromium had been effective in increasing degree of platinum dispersion.

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    11
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  • 国際無機膜学会報告

    都留 稔了, 金指 正言, 野村 幹弘, 上宮 成之, 田中 俊輔, 佐藤 公則, 荒木 貞夫, 松方 正彦, 吉岡 朋久

    膜   38 ( 1 ) 39 - 49  2013年

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  • 無機規則性多孔体分離膜を用いた有機溶剤脱水技術

    松方 正彦

    膜   38 ( 5 ) 224 - 228  2013年

     概要を見る

    Reduction of energy consumption in the industry sector, especially chemical industry, is strong demand. In chemical industry about 40% of the total energy consumption is for distillation. Thus, reduction of the energy used in distillation by introducing membrane technology would have strong impact. Zeolites, a class of microporous ceramic materials, have superior physicochemical properties, such as molecular sieving and preferential adsorption, in addition to high thermal, chemical, and structural stability. In this report, development of zeolite membranes will be emphasized to be attractive as a strong candidate enabling us to reduce energy consumption in chemical industry. In particular, we have started operation of a bench-scale test plant for the separation of water and isopropyl alcohol (IPA) at the production site of IPA, Kawasaki, Japan. This is the first on-site test plant using ceramic membrane in petrochemical industry. Also, acid-resistant zeolite membrane has been developed for the dehydration of acetic acid.

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  • C10炭化水素に対するsilicalite-1膜の透過分離特性

    酒井 求, 金子 拓矢, 松方 正彦

    石油学会 年会・秋季大会講演要旨集   2013 ( 0 ) 51 - 51  2013年

     概要を見る

    MFI型ゼオライト膜の一種であるsilicalite-1膜を用いて、C10炭化水素の分離可能性について検討した。多孔質&alpha;-アルミナ管上に製膜したsilicalite-1膜に対して、n-デカン、n-ブチルベンゼン、テトラリンの蒸気透過特性を調べた。その結果、n-デカンとn-ブチルベンゼンは膜を透過したがテトラリンの透過は観測されず、n-デカンとテトラリンの分離係数100以上と高選択的な分離が可能であることを見出した。

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  • Plasma-assisted oxidation of carbon particle by lattice oxygen on/in oxide catalyst

    Yasushi Sekine, Hiroshi Koyama, Masahiko Matsukata, Eiichi Kikuchi

    FUEL   103   2 - 6  2013年01月  [査読有り]

     概要を見る

    Oxidation of carbon particles by lattice oxygen on/in catalysts was investigated with and without electrical discharge at 673 K in a fluidized bed reactor. Application of dielectric barrier discharge promoted the evolution of lattice oxygen in the oxide catalyst, and oxidation of carbon by the evolved lattice oxygen was accelerated by application of the discharge. The total amount of consumed lattice oxygen in/on the catalyst was not changed by the application of the discharge due to the low diffusion rate of bulk oxygen at low temperature. Metal-loaded catalysts such as Ni/CeO2 evolved larger amounts of lattice oxygen because of interaction between the supported Ni particle and ceria support. (C) 2011 Elsevier Ltd. All rights reserved.

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  • H-ベータゼオライトを用いたCSTR中でのイソブタンの1-ブテンによるアルキル化 (第2報) : ゼオライト触媒の劣化メカニズムとCSTRの操作最適化

    関根 泰, 田嶋 祐一, 市川 洋介, 松方 正彦, 菊地 英一

    Journal of the Japan Petroleum Institute   55 ( 5 ) 308 - 318  2012年09月

     概要を見る

    これまでに我々は,CSTRを用いた1-ブテンによるイソブタンのアルキレーションにおいて,DGC法で調製したベータ型ゼオライトが他のゼオライトに比べて高い活性・安定性を示すことを見出した。そこでより高い活性安定性を発現させるため,DGC法で調製したベータ型ゼオライトを用いて,活性劣化の原因を探るとともに,最適な操作条件を探索した。その結果,活性劣化の原因となっているのはゼオライト表面に吸着した炭化水素ではなく,細孔内部に蓄積した炭化水素であり,これは多重アルキル化あるいはオレフィンの重合によって生成していることが分かった。よって,これら反応を抑制する条件を探索し最適化することで,高い活性と安定性を両立することができた。

    DOI CiNii

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    5
    被引用数
    (Scopus)
  • Alkylation of Isobutane by 1-Butene over H-beta Zeolite in CSTR (Part 1) Effects of Zeolite-structures and Synthesis Methods on Alkylation Performance

    Yasushi Sekine, Yo-suke Ichikawa, Yu-ichi Tahma, Keita Nakabayashi, Masahiko Matsukata, Eiichi Kikuchi

    JOURNAL OF THE JAPAN PETROLEUM INSTITUTE   55 ( 5 ) 299 - 307  2012年09月

     概要を見る

    The effects of zeolite structures on alkylation of isobutane with 1-butene were investigated in a batch reactor and in a continuously stirred tank reactor (CSTR) using the proton-form zeolites, H-ZSM-5, H-L, H-Y, and H-*BEA (beta). H-ZSM-5 and H-L zeolite catalysts were deactivated rapidly, whereas H-Y and H-*BEA zeolites retained catalytic activity for a long time in the CSTR, implying that zeolites with three-dimensional large pore systems are useful for preventing deactivation of the catalyst during alkylation of isobutane with 1-butene. H-*BEA synthesized using a dried-gel method (DGC-H-*BEA) showed the most stable activity among the various H-*BEA zeolites. The effects of the synthesis methods and zeolite characteristics were investigated using H-*BEA zeolite. Characterization using NH3-TPD and pyridine-sorption monitored by FT-IR showed that high acid density and high Bronsted acid ratio promoted alkylation of isobutane with 1-butene over H-*BEA zeolite.

  • Catalytic Oxidative Coupling of Methane Assisted by Electric Power over a Semiconductor Catalyst

    Keisuke Tanaka, Yasushi Sekine, Kazumasa Oshima, Yoshitaka Tanaka, Masahiko Matsukata, Eiichi Kikuchi

    CHEMISTRY LETTERS   41 ( 4 ) 351 - 353  2012年04月

     概要を見る

    Oxidative coupling of methane (OCM) on La2O3 semiconductor catalysts at 423 K external temperature was investigated. DC power supplied from two electrodes in a catalyst bed enabled stable and selective production of C2H6 and C2H4 over Sr-La2O3 (Sr/La = 1/200 and 1/20), but plasma reactions proceeded over other catalysts. The electrical conductivity of the semiconductor catalyst was important for controlling this reaction. A high yield of C2 (49% selectivity, 51.3% O-2 conversion) was obtained using 2.7 W of electricity at a lower external temperature (423 K).

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  • Pt/LaSrAlOx触媒上でのメタンの反応及びその特異的な構造

    関根 泰, 向井 大揮, 井筒 義行, 田中 啓介, 細村 直美, 井上 純貴, 松方 正彦, 菊地 英一

    石油学会 年会・秋季大会講演要旨集   2012   54 - 54  2012年

     概要を見る

    メタンの反応(水蒸気改質、酸化的改質、部分酸化)について、Pt/LaSrAlOxペロブスカイト型酸化物を用いて検討を行った。Pt/LaSrAlOxペロブスカイト型酸化物触媒は、他の担体に担持した触媒と異なり、酸素共存雰囲気では高温ほど高い分散度を取ることがわかった。構造についてはSPring-8でのEXAFS/XANESスペクトル解析や、XPSスペクトルおよびSTEM/EDXなどから詳細な解析を行った。この触媒は、酸素が存在する酸化的改質及び部分酸化において、高い活性を安定に発現した。

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  • n-heptane骨格異性化に対するPt/WOx/ZrO2の活性点の形成過程

    井筒 義行, 金谷 直樹, 森 みね子, 関根 泰, 菊地 英一, 松方 正彦

    石油学会 年会・秋季大会講演要旨集   2012   115 - 115  2012年

     概要を見る

    クリーンなガソリン基材の製造方法としてn-ヘプタンの骨格異性化に注目した。比較的分岐パラフィンの選択率が高いことで知られる白金担持酸化タングステン-ジルコニアを用い、その活性点の構造と性質を検討した。活性点はブレンステッド酸点であると考えられ、さらに焼成温度および焼成時間が触媒活性に及ぼす影響について検討を行った。

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  • Oxidative Coupling of Methane over Ba-incorporated LalnO(3) Perovskite Catalyst

    Keisuke Tanaka, Yasushi Sekine, Jyunki Inoue, Hiroto Araki, Masahiko Matsukata, Eiichi Kikuchi

    JOURNAL OF THE JAPAN PETROLEUM INSTITUTE   55 ( 1 ) 71 - 72  2012年01月

     概要を見る

    We found that LalnO(3) perovskite catalyst showed high activity for oxidative coupling of methane (OCM). Partial substitution of La3+ site in the LalnO(3) catalyst with Ba2+ increased its catalytic activity and selectivity to C2 hydrocarbons drastically. The partial substitution of La3+ site in LalnO(3) with Ba2+ increased oxygen vacancies in the stable cubic phase, and then contributed to the production of active oxygen species on its surface for selective C2 formation.

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    7
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  • Low temperature steam reforming of methane over metal catalyst supported on CexZr1-xO2 in an electric field

    Yasushi Sekine, Masayuki Haraguchi, Masahiko Matsukata, Eiichi Kikuchi

    CATALYSIS TODAY   171 ( 1 ) 116 - 125  2011年08月  [査読有り]

     概要を見る

    Catalytic steam reforming of methane in an electric field (named "electreforming") was conducted over metal catalysts supported on CeO2 or CexZr1-xO2 at low temperatures such as 423 K where conventional catalytic reactions hardly proceeded. The conversion of methane was greatly increased by weak and effective application of an electric field to the catalyst bed. Use of CexZr1-xO2 as a catalyst support promoted electreforming, the lattice oxygen of CexZr1-xO2 playing an important role. Energy efficiency of electreforming, reaction mechanism, and the role of lattice oxygen were investigated and are discussed in this paper. (C) 2011 Elsevier B. V. All rights reserved.

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    76
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  • Microporous membrane: A key to large-scale energy-saving in fuel and petrochemical industry

    Masahiko Matsukata, Yasushi Sekine, Eiichi Kikuchi

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   242  2011年08月

  • Coke-free dry reforming of model diesel fuel by a pulsed spark plasma at low temperatures using an exhaust gas recirculation (EGR) system

    Yasushi Sekine, Naotsugu Furukawa, Masahiko Matsukata, Eiichi Kikuchi

    JOURNAL OF PHYSICS D-APPLIED PHYSICS   44 ( 27 )  2011年07月

     概要を見る

    Dry reforming of diesel fuel, an endothermic reaction, is an attractive process for on-board hydrogen/syngas production to increase energy efficiency. For operating this dry reforming process in a vehicle, we can use the exhaust gas from an exhaust gas recirculation (EGR) system as a source of carbon dioxide. Catalytic dry reforming of heavy hydrocarbon is a very difficult reaction due to the high accumulation of carbon on the catalyst. Therefore, we attempted to use a non-equilibrium pulsed plasma for the dry reforming of model diesel fuel without a catalyst. We investigated dry reforming of model diesel fuel (n-dodecane) with a low-energy pulsed spark plasma, which is a kind of non-equilibrium plasma at a low temperature of 523 K. Through the reaction, we were able to obtain syngas (hydrogen and carbon monoxide) and a small amount of C(2) hydrocarbon without coke formation at a ratio of CO(2)/C(fuel) = 1.5 or higher. The reaction can be conducted at very low temperatures such as 523 K. Therefore, it is anticipated as a novel and effective process for on-board syngas production from diesel fuel using an EGR system.

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    17
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  • Dehydrogenation of ethylbenzene over highly active and stable perovskite oxide catalyst - Effect of lattice oxygen on/in perovskite oxide and role of A/B site in perovskite oxide

    Ryo Watanabe, Yasushi Sekine, Jung Kojima, Masahiko Matsukata, Eiichi Kikuchi

    APPLIED CATALYSIS A-GENERAL   398 ( 1-2 ) 66 - 72  2011年05月

     概要を見る

    Previously we reported that La(0.8)Ba(0.2)Fe(0.4)Mn(0.6)O(3-delta) (LBFMO) perovskite oxide catalyst showed extremely high activity for dehydrogenation of ethylbenzene to produce styrene. The reaction mechanism of dehydrogenation of ethylbenzene over LBFMO catalyst and the role of A/B site cation in the perovskite were investigated using transient response experiments and thermogravimetric analyses in a H(2)O/H(2) atmosphere. Results showed that the dehydrogenation of ethylbenzene over LBFMO perovskite catalyst proceeded via reduction-oxidation (redox) of the perovskite oxide in this temperature range (800-900 K). Thereby, oxidative dehydrogenation of ethylbenzene consumed lattice oxygen in the perovskite; the consumed lattice oxygen was regenerated by H(2)O. We measured the lattice oxygen release rate and regenerating rate over LBFMO perovskite catalyst. The regeneration rate of lattice oxygen was almost equal to the formation rate of styrene in the steady state of the dehydrogenation reaction. Substituting the B site of perovskite with Fe has a stabilizing effect for the lattice oxygen in the perovskite, and enhanced the regeneration rate of lattice vacancy drastically using steam. We concluded that the better stability of LBFMO than that of other catalysts was derived from enhanced lattice oxygen regeneration in the perovskite. (C) 2011 Elsevier B.V. All rights reserved.

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    25
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  • 酸型ゼオライトを用いた1ブテンによるイソブタンのアルキル化反応

    関根 泰, 藤岡 慎也, 加藤 優基, 松方 正彦, 菊地 英一

    石油学会 年会・秋季大会講演要旨集   2011   42 - 42  2011年

     概要を見る

    硫黄を含まない軽質なガスからオクタン価の高いガソリンを作ることができるアルキレーションプロセスは重要なガソリン製造プロセスの一つである。工業化されているプロセスは、HFとH2SO4が触媒として用いられているが、いずれも毒性、腐食性が強く、多くの問題点を抱えているため、ゼオライトを触媒として用いたプロセスの開発が望まれている。ゼオライトを用いたプロセスは腐食性、毒性がなく比較的安価であるが、急速な活性劣化が原因で工業化には至っていない。そこで、本研究では、重合を抑え、選択的にC8を生成する反応条件および触媒の探索を目的とした。

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  • 低温域で高活性を示す貴金属フリーなメタン部分酸化用触媒の開発

    田中 啓介, 関根 泰, 向井 大揮, 松方 正彦, 菊地 英一

    石油学会 年会・秋季大会講演要旨集   2011   71 - 71  2011年

     概要を見る

    合成ガスの製造法としてメタンの部分酸化があげられる。この反応は発熱反応であるため、低温域で高活性を示す触媒の開発が望まれる。我々は高価な貴金属を用いないNi/La0.8Sr0.2Al0.8Co0.2O3-触媒が前還元処理を行うことで623 Kという低温域で活性を示すことを明らかにした。本研究では活性試験や様々なキャラクタリゼーションを通して、同触媒の低温域での活性発現理由を解明することを目的とした。

    DOI CiNii

  • エタノールの水蒸気改質におけるコバルト系触媒への微量鉄添加効果

    関根 泰, 大山 恒志, 松方 正彦, 菊地 英一

    石油学会 年会・秋季大会講演要旨集   2011   75 - 75  2011年

     概要を見る

    本研究室では、コバルトを担持した触媒に微量の鉄を添加することにより、エタノールの水蒸気改質に対する転化率、水素収率が大きく向上することを見出してきた。そして、担体の違いによるコバルト系触媒への微量の鉄添加効果の違いを検討した結果、コバルトをアルミナに担持した場合の鉄の効果が最大であった。そこで、鉄添加効果について、XANES/EXAFSやIRによりキャラクタリゼーションを行い、プロモーションの効果について検討したので報告する。

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  • Pt/WOx/ZrO2の調製法とn-heptaneの骨格異性化に対する触媒特性の検討

    井筒 義行, 森 みね子, 金谷 直樹, 関根 泰, 菊地 英一, 松方 正彦

    石油学会 年会・秋季大会講演要旨集   2011   41 - 41  2011年

     概要を見る

    白金を担持したタングステン酸ジルコニア(WO3/ZrO2)を用いてn-heptaneの骨格異性化を行った。WO3/ZrO2の調製条件を変えることで触媒活性に与える因子を検討した。その結果タングステン酸の担持量を増加させるとテトラゴナル相のジルコニアが増加し、触媒活性は向上することがわかった。また、タングステン酸の担持量によってWO3/ZrO2の焼成温度の最適値も変化することがわかった。

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  • 芳香族炭化水素の水蒸気改質におけるNi/ペロブスカイト触媒の最適化

    関根 泰, 村井 由季, 栃谷 智, 向井 大揮, 松方 正彦, 菊地 英一

    石油学会 年会・秋季大会講演要旨集   2011   74 - 74  2011年

     概要を見る

    芳香族炭化水素から水素を製造することは重質油やバイオマスタールの有効利用につながると考えられる。芳香族炭化水素のモデル物質としてトルエンを用いた水蒸気改質においてNi/La0.7Sr0.3AlO3-dを用いることで高活性、耐炭素析出性を実現し、また酸化に対する耐性を持つことを見出した。この触媒に第二金属としてPtを担持したところ、更なる析出炭素量の減少、前処理還元なしでの活性発現を実現した。これらの効果について、キャラクタリゼーションを用いて検討した。

    DOI CiNii

  • La系ペロブスカイト型酸化物触媒を用いたメタンの酸化カップリング

    田中 啓介, 関根 泰, 井上 純貴, 荒木 寛人, 松方 正彦, 菊地 英一

    石油学会 年会・秋季大会講演要旨集   2011   159 - 159  2011年

     概要を見る

    天然ガスの有効利用として、メタンの酸化カップリングによるエチレン(C2化合物)の直接合成があるが、工業的に満足する収率が得られる触媒は見つかっていない。そこで、メタンの酸化カップリングにおいて高いC2選択率・収率が得られる触媒の探索を行った。その結果、ペロブスカイト型酸化物であるLaInO3が比較的高いC2選択率を示した。また、LaInO3をベースとして触媒設計を行い、Laの一部をBaで置換したLaBaInO3-dがより高いC2選択率を示した。

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  • ペロブスカイト型酸化物触媒の酸化還元を生かしたプロパン選択脱水素用新規触媒の開発

    渡部 綾, 本道 佳明, 関根 泰, 松方 正彦, 菊地 英一

    石油学会 年会・秋季大会講演要旨集   2011   150 - 150  2011年

     概要を見る

    選択性の高いプロピレン製造技術としてプロパン脱水素がある。この反応に活性を示すCr系触媒は析出炭素による活性劣化が問題となっている。また、Cr系触媒は水蒸気存在下では活性が著しく低下するため、析出炭素の抑制を目的とした水蒸気の同伴が出来ない。そこで我々は、水蒸気存在下のプロパン脱水素において活性・選択性・安定性に優れた触媒の探索を行った。その結果、ペロブスカイト型酸化物触媒が安定な活性を示すことを見出した。

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  • 希土類元素を含まないペロブスカイト型酸化物を触媒に用いたエチルベンゼン脱水素

    関根 泰, 渡部 綾, 生嶋 麻衣子, 中野 慧, 松方 正彦, 菊地 英一

    石油学会 年会・秋季大会講演要旨集   2011   148 - 148  2011年

     概要を見る

    石油化学工業における主要なモノマーであるスチレンはエチルベンゼン脱水素を用いて製造されている。工業的には安価な元素からなり、かつ高活性・高安定性を有する触媒が望まれる。そこで高価な希土類元素を含まないペロブスカイト型酸化物を触媒として用いて検討したところ、Ba0.4Sr0.6Fe0.6Mn0.4O3-δが高い活性と比較的高い安定性を示した。

    DOI CiNii

  • 電場アシスト触媒反応による低温メタン酸化カップリング

    田中 啓介, 関根 泰, 大島 一真, 田中 芳貴, 松方 正彦, 菊地 英一

    石油学会 年会・秋季大会講演要旨集   2011   160 - 160  2011年

     概要を見る

    メタン酸化カップリングは、メタンが構造的に安定であるため、反応には900 K以上の高温を必要とする。そこで我々は反応の低温化を目的として電場中でメタン酸化カップリングを試みた。その結果、外熱供給423 Kという低温で反応が進行した。その際の生成物組成や経時変化から安定な反応場であることが示された。本発表では電場印加による活性向上のメカニズムの解明を目的とし、電場中での活性の挙動について詳細に検討する。

    DOI CiNii

  • Tackling Power Outages in Japan: The Earthquake Compels a Swift Transformation of the Power Supply

    Yasuhiro Fukushima, Yasunori Kikuchi, Yuya Kajikawa, Mitsuhiro Kubota, Takao Nakagaki, Masahiko Matsukata, Yukitaka Kato, Michihisa Koyama

    JOURNAL OF CHEMICAL ENGINEERING OF JAPAN   44 ( 6 ) 365 - 369  2011年

     概要を見る

    This article discusses the directions for energy systems based on an urgent proposal to counter the energy crisis in eastern Japan, published from the Society of Chemical Engineers, Japan. We first illustrate the situation Japan faces, highlighting the urgency and seriousness of the consequences of power outages in industry and daily life. Then, we elaborate on the necessity for policy support to trigger collective actions to temporarily practice countermeasures that would not necessarily save resources or that could disrupt society's established routines. In this way, Japan can choose technologies without regret based on society-wide discussions on the future energy supply. Finally, we warn of the drawbacks induced by shortsighted decisions e. g., avoiding power outages by depending on less-efficient gas turbines. We conclude that Japan should commence a transition of its energy systems rather than compromising resource efficiency and grid robustness over the next decades.

    DOI

    Scopus

    18
    被引用数
    (Scopus)
  • Effect of Loading Potassium and Palladium over Iron-Based Catalyst for Low Temperature Water-Gas Shift Reaction

    Yasushi Sekine, Takahiro Chihara, Ryo Watanabe, Yuji Sakamoto, Masahiko Matsukata, Eiichi Kikuchi

    CATALYSIS LETTERS   140 ( 3-4 ) 184 - 188  2010年12月

     概要を見る

    We investigated the effect of loading potassium over iron-based catalysts for water-gas shift (WGS) reaction at 573 K. The iron-based water-gas shift catalyst has been known as a redox-mechanism catalyst. Therefore, to promote the redox reaction over iron oxide, we impregnated a small amount of Pd on various iron oxides. Results revealed that coexisting potassium and palladium accelerated the WGS reaction over iron-oxide catalyst. We examined the optimum amount of potassium over Pd/iron catalyst, and we found that the optimum molar ratio was about 2 (K/Pd molar ratio). From the viewpoint of reducibility of the catalyst, the addition of small amount of Pd onto iron oxide promotes reduction from Fe(2)O(3) to Fe(3)O(4). However, impregnation of potassium on iron oxide makes the catalyst structure robust. The promotion effect of Pd and potassium was not observed on SiO(2) support. We therefore concluded that the synergetic effect among Pd, K, and iron oxide, was important for the WGS reaction.

    DOI

    Scopus

    12
    被引用数
    (Scopus)
  • Promoting effect of small amount of Fe addition onto Co catalyst supported on alpha-Al2O3 for steam reforming of ethanol

    A. Kazama, Y. Sekine, K. Oyama, M. Matsukata, E. Kikuchi

    APPLIED CATALYSIS A-GENERAL   383 ( 1-2 ) 96 - 101  2010年07月  [査読有り]

     概要を見る

    We examined the promotion effect of loading small amounts of Fe onto various Co catalysts for steam reforming of ethanol. Among these catalysts, catalysts supported on SrTiO3 and alpha-Al2O3 showed remarkable effects of iron loading onto cobalt catalyst. The Fe-loaded Co/alpha-Al2O3 showed higher yield of hydrogen, low coke deposition on the catalysts, and high activity for steam reforming of acetaldehyde, which was an intermediate of the steam reforming of ethanol. Characterization of the catalyst revealed that Fe and Co metal coexisted on the catalyst support. Synergetic effects of these two metals were observed. (C) 2010 Elsevier B.V. All rights reserved.

    DOI

    Scopus

    46
    被引用数
    (Scopus)
  • Pt and/or Pd Supported/Incorporated Catalyst on Perovskite-Type Oxide for Water Gas Shift Reaction

    R. Watanabe, Y. Sekine, H. Takamatsu, Y. Sakamoto, S. Aramaki, M. Matsukata, E. Kikuchi

    TOPICS IN CATALYSIS   53 ( 7-10 ) 621 - 628  2010年06月  [査読有り]

     概要を見る

    Catalytic properties of Pd and/or Pt supported/incorporated on/in perovskite-type oxides for water gas shift (WGS) reaction have been investigated. We found that the dominant reaction mechanism over these catalysts was redox mechanism by CO and steam, and their redox properties were controllable by the bulk structure of perovskite.

    DOI

    Scopus

    18
    被引用数
    (Scopus)
  • Separation and Purification Technology: Preface

    Masahiko Matsukata, Shigeyuki Uemiya, Hidetoshi Kita

    Separation and Purification Technology   73 ( 1 ) 1  2010年05月  [査読有り]  [招待有り]

    DOI

    Scopus

  • Papers presented at the Inorganic Membrane-ICIM10 Preface

    Masahiko Matsukata, Shigeyuki Uemiya, Hidetoshi Kita

    SEPARATION AND PURIFICATION TECHNOLOGY   73 ( 1 ) 1 - 1  2010年05月

    DOI

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  • Low-Temperature Hydrogen Production by Highly Efficient Catalytic System Assisted by an Electric Field

    Yasushi Sekine, Masayuki Haraguchi, Masahiko Tomioka, Masahiko Matsukata, Eiichi Kikuchi

    JOURNAL OF PHYSICAL CHEMISTRY A   114 ( 11 ) 3824 - 3833  2010年03月

     概要を見る

    We investigated four catalytic reactions assisted with in electric field to promote catalytic activity, and we could achieve an effective process for hydrogen production at low temperatures. Such as 423 K. In the presence of the electric field, four reactions of steam reforming of ethanol, decomposition of ethanol, water gas shift, and steam reforming of methane proceeded at very low temperature, Such as 423 K, where a conventional catalytic reaction hardly proceeded. Conversion of reactant was greatly increased by the electric field, Zinc apparent activation energies for these four reactions were lowered by the application of the electric field. This process cart produce hydrogen and syngas by using a considerably small energy demand and has quick response.

    DOI

    Scopus

    74
    被引用数
    (Scopus)
  • Fe doped La2O3 catalyst for oxidative coupling of methane

    Keisuke Tanaka, Yasushi Sekine, Masahiko Matsukata, Eiichi Kikuchi

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   239  2010年03月

  • 産業排水中のホウ素の効率的除去を目的とした材料開発

    松方 正彦, 正田 武則, 関根 泰, 菊地 英一, 山崎 淳司

    化学工学会 研究発表講演要旨集   2010   184 - 184  2010年

    DOI CiNii

  • [招待講演] 2040年のCO2排出量予測 -骨太のエネルギーロードマップ第2版-

    菊池 康紀, 梶川 裕矢, 加藤 之貴, 窪田 光宏, 古山 通久, 鈴木 健雄, 中垣 隆雄, 福島 康裕, 藤岡 恵子, 松方 正彦

    化学工学会 研究発表講演要旨集   2010   97 - 97  2010年

    DOI CiNii

  • Na型ZSM-5膜による炭化水素の高温分離特性の検討

    松方 正彦, 佐藤 圭介, 河崎 圭利, 澤村 健一, 関根 泰, 菊地 英一

    化学工学会 研究発表講演要旨集   2010   932 - 932  2010年

    DOI CiNii

  • NaYゼオライト膜の形成過程に対するseeding条件の影響

    松方 正彦, 古畑 泰介, 関根 泰, 菊地 英一

    化学工学会 研究発表講演要旨集   2010   931 - 931  2010年

    DOI CiNii

  • 酢酸のエステル化に対するモルデナイト膜による脱水の効果

    松方 正彦, 平井 太一朗, 萩野 貴之, 澤村 健一, 関根 泰, 菊地 英一

    化学工学会 研究発表講演要旨集   2010   922 - 922  2010年

    DOI CiNii

  • モルデナイト膜を用いた蒸気透過法による水/酢酸の分離

    松方 正彦, 楢島 雅俊, 大小原 慎太郎, 澤村 健一, 関根 泰, 菊地 英一

    化学工学会 研究発表講演要旨集   2010   925 - 925  2010年

    DOI CiNii

  • 2-4-3 電場触媒反応を用いた低温メタン水蒸気改質による水素製造(2-4 天然ガス転換技術1,Session 2 天然ガス・メタンハイドレート等,研究発表)

    関根 泰, 原口 将征, 松方 正彦, 菊地 英一

    日本エネルギー学会大会講演要旨集   19   60 - 61  2010年

     概要を見る

    We conducted steam reforming of methane at very low temperature like as 423 K in an electric field. Application of the electric field enabled to conduct low temperature steam reforming of methane. The promotion effect of catalytic reaction in the electric field was not derived from plasma activation, electrolysis, and it was not a faradic reaction, but a non-faradic reaction. The distribution of products was 4 to 1 for hydrogen and carbon dioxide. We found that some noble metals, and supports which had redox ability with its lattice oxygen, were effective for the low temperature steam reforming of methane with an aid of the electric field.

    DOI CiNii

  • 担持Ni触媒を用いたトルエンの水蒸気改質

    関根 泰, 細村 直美, 関口 慶, 奥 裕希, 水野 翔太, 井筒 義行, 松方 正彦, 菊地 英一

    石油学会 年会・秋季大会講演要旨集   2010   39 - 39  2010年

     概要を見る

    トルエンの水蒸気改質反応に対して、高い活性、水素選択性、耐炭素析出性を有するNi触媒の担体について検討を行った。中でもNi/La0.7Sr0.3AlOxが高活性であり、参照用Rh触媒を上回る水素収率が得られた。高い水素収率は副生成物であるベンゼンとメタンの生成が少ないことに起因し、Ni触媒はRh触媒で顕著な脱アルキル反応が起こりにくい水素製造に適した触媒であることがわかった。

    DOI CiNii

  • ぺロブスカイト型酸化物を担体に用いた水性ガスシフト反応用触媒の反応機構

    関根 泰, 坂本 裕貴, 渡部 綾, 井上 純貴, 松方 正彦, 菊地 英一

    石油学会 年会・秋季大会講演要旨集   2010   53 - 53  2010年

     概要を見る

    これまでの当研究室の研究より、ペロブスカイト型酸化物であるLaCoO3に、Pt、Pdを担持した触媒が、水性ガスシフト反応において高い活性を示すことがわかっている。ただ、その挙動は異なっており、Pt/LaCoO3については、初期活性は高いが経時的に活性劣化を起こし、Pd/LaCoO3については、Ptを担持した触媒に比べて初期活性は劣るものの、活性は安定していた。この違いは何に起因するものであるのか、また、Pt、Pdの役割を解明するため、反応メカニズムの検討を行っている。

    DOI CiNii

  • 電場中での触媒反応による低温メタン水蒸気改質

    関根 泰, 原口 将征, 大島 一真, 松方 正彦, 菊地 英一

    石油学会 年会・秋季大会講演要旨集   2010   41 - 41  2010年

     概要を見る

    メタンの水蒸気改質を低温にて電場アシスト存在の環境で行った。電場の存在によって、わずか150度という低温でもメタンの水蒸気改質が進行し、その際の生成物選択率は触媒による水性ガスシフト平衡組成に近い値をとった。このことから、メタンの活性化に対して電場がポジティブに活性化をアシストし、その後の逐次的な反応に対しては触媒上での反応制御が支配していると考えられることがわかった。また、ディスク状の触媒を用いた反応の結果から、電子リッチな担持金属が活性点を構成しており、電子プアな担持金属はその活性を失っていることがわかった。

    DOI CiNii

  • Ni/ペロブスカイト触媒を用いたトルエンの水蒸気改質

    関根 泰, 関口 慶, 水野 翔太, 細村 直美, 松方 正彦, 菊地 英一

    石油学会 年会・秋季大会講演要旨集   2010   144 - 144  2010年

     概要を見る

    石油精製やアンモニア合成に利用される水素は、主に炭化水素の水蒸気改質から製造されている。触媒の活性金属として安価なNiが用いられるが、炭素析出による触媒の劣化が問題である。また芳香族炭化水素は水蒸気改質において炭素析出が起きやすい反応である。以上のことから、我々は芳香族炭化水素の水蒸気改質において、炭素析出を抑制し、水素製造に適したNi触媒の開発を目的として研究を行った。

    DOI CiNii

  • イソプロピルアルコールの脱水に対するゼオライト膜と蒸留を組み合わせたHybridプロセス

    味村 健一, 蛙石 健一, 畑山 実, 木村 信啓, 関根 泰, 菊地 英一, 松方 正彦

    石油学会 年会・秋季大会講演要旨集   2010   167 - 167  2010年

     概要を見る

    平成21年度より、NEDO殿のご支援のもと、ゼオライト膜の開発プロジェクトが開始された。このプロジェクトでは、IPA-水系や酢酸-水系の分離に対して、十分な耐久性と高い分離性能を有する分離膜の開発を行う。本発表では、開発される分離膜の特長を十分生かすことができるような膜と蒸留のHybrid分離プロセスの検討を行い、開発される分離膜が、既存のIPA-水の蒸留分離に対して、プロセスの簡素化や省エネルギー化に有効であることを示す。

    DOI CiNii

  • Simultaneous dry reforming and desulfurization of biomethane with non-equilibrium electric discharge at ambient temperature

    Yasushi Sekine, Junya Yamadera, Masahiko Matsukata, Eiichi Kikuchi

    CHEMICAL ENGINEERING SCIENCE   65 ( 1 ) 487 - 491  2010年01月

     概要を見る

    We investigated two types of electrical discharges for converting. biomethane into syngas at ambient temperature and atmospheric pressure. Low energy pulsed discharge (LEP) has a good property for this reaction and it could convert biomethane into syngas and also H(2)S was converted into solid sulfur simultaneously. This is due to the high electron energy of LEP, and the electron has enough energy to dissociate C-C bond and C-S bond. On the other hand, dielectric barrier discharge could convert H(2)S into solid sulfur, but methane and CO(2) in the biomethane were not reacted at lower input power. Our investigation showed that proper choice of electric discharge could bring selective reaction for dry reforming of biomethane and desulfurization, and this was due to the correlation between the bond dissociation energy of each molecule and electron energy level of each discharge. (C) 2009 Elsevier Ltd. All rights reserved.

    DOI

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    26
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  • Effect of Steam on the Steam-Assisted Crystallization of *BEA-Type Zeolite

    Satoshi Inagaki, Kei Nakatsuyama, Eiichi Kikuchi, Masahiko Matsukata

    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN   83 ( 1 ) 69 - 74  2010年01月

     概要を見る

    We have studied the effect of steam in the steam-assisted crystallization (SAC) of *BEA-type zeolite. It was found that after an aluminosilicate dry gel with SiO2/Al2O3 = 100 was treated with steam in an autoclave at 130 degrees C and autogenous pressure, the thermal treatment of a resulting product at 130 degrees C in an autoclave without the addition of water gave *BEA nanoparticles with a high crystallinity. It was presumed that pseudo-*BEA structures as intermediates were formed during the SAC treatment, and the dehydration of silanols in the pseudo-*BEA solids during the thermal treatment in the presence of a minimum amount of water possibly promoted the transformation of the pseudo-*BEA phase into *BEA crystalline phase with a periodicity in long-range order.

    DOI

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    4
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  • Steam Reforming of Ethanol Over Cobalt Catalyst Modified with Small Amount of Iron

    Yasushi Sekine, Atsushi Kazama, Yoshiyuki Izutsu, Masahiko Matsukata, Eiichi Kikuchi

    CATALYSIS LETTERS   132 ( 3-4 ) 329 - 334  2009年10月  [査読有り]

     概要を見る

    Steam reforming of ethanol was examined over Co/SrTiO(3) with addition of another metal-Pt, Pd, Rh, Cr, Cu, or Fe-for promotion of the catalytic activity. Ethanol conversion and H(2) yield were improved greatly by adding Fe or Rh at 823 K. Although Rh addition promoted CH(4) formation, Fe addition enhanced steam reforming of ethanol selectively. A suitable amount of Fe loading was in the window of 0.33-1.3 mol%. A comparative study of the reaction over a catalyst supported on SiO(2) was conducted, but no additional effect of Fe was observed on the Co/SiO(2) catalyst. High activity of Fe/Co/SrTiO(3) catalyst came from interaction among Fe, Co, and SrTiO(3).

    DOI

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    25
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  • Catalytic degradation of ethanol in an electric field

    Y. Sekine, M. Tomioka, M. Matsukata, E. Kikuchi

    CATALYSIS TODAY   146 ( 1-2 ) 183 - 187  2009年08月  [査読有り]

     概要を見る

    We investigated novel catalytic reaction systems which were activated by an electric field. This is the first report for the synergetic effect of catalyst and electric field. These catalytic systems showed very high activity compared to conventional catalytic reaction systems. Although Pt supported on CeO(2) catalyst without an electric field showed no activity at 473 K, the addition of an electric field to the catalyst promoted the degradation of ethanol. Pt/CeO(2) catalyst was activated by the electric field and synergetic effect of Pt catalyst and electric field was observed. Thermal analyses showed that about 5-10% of input electrical power was wasted as a heat and about 90-95% was consumed for the endothermic reaction. Catalytic reactions in an electric field proceed under mild conditions and show a quick response. (C) 2009 Elsevier B.V. All rights reserved.

    DOI

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    39
    被引用数
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  • Novel Perovskite-Type Oxide Catalysts for Dehydrogenation of Ethylbenzene to Styrene

    Ryo Watanabe, Yasushi Sekine, Masahiko Matsukata, Eiichi Kikuchi

    CATALYSIS LETTERS   131 ( 1-2 ) 54 - 58  2009年08月  [査読有り]

     概要を見る

    We investigated novel LaMnOx perovskite-oxide (ABO(3)) catalysts for effective catalytic dehydrogenation of ethylbenzene to produce styrene monomer. Comparison with industrial Fe-K catalyst, our La(0.8)Ba(0.2)Mn(0.6)Fe(0.4)O(3-delta) catalyst showed higher activity. Results show that the A-site in perovskite-type oxides affected catalytic dehydrogenation activities and that the B-site affected stability of the activities.

    DOI

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    14
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  • Rapid crystallization of mesoporous silica with highly stable 2d-hexagonal structure

    Inagaki, Satoshi, Aratani, Yasuhiro, Nakata, Satoshi, Yashiro, Yuichi, Sekine, Yasushi, Kikuchi, Eiichi, Matsukata, Masahiko

    Bulletin of the Chemical Society of Japan   82 ( 5 ) 606 - 612  2009年05月  [査読有り]

    DOI CiNii J-GLOBAL

    Scopus

    2
    被引用数
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  • No.32 流動層気固固反応によるチャーの触媒格子酸素による酸化(ガス化・燃焼・液化(2))

    関根 泰, 小山 博史, 松方 正彦, 菊地 英一

    石炭科学会議発表論文集   46   62 - 63  2009年

     概要を見る

    Low temperature catalytic oxidation of solid carbon was conducted in a fluidized bed reactor with/without a non-equilibrium discharge. Solid carbons like as soot, PM, and char cause many operational problems and have lower reactivity. We tried to oxidize such carbon particles to carbon oxide and/or carbon dioxide by lattice oxygen in/on the oxide catalysts at lower temperature. To maintain high contact frequency between the catalyst and carbon particles, we applied a fluidized-bed reaction apparatus for this reaction. As a result, we found that carbon particles are oxidized at 673K by the lattice oxygen in/on the catalyst. Among various oxide catalysts, Fe/CeO_2 and some other catalysts showed higher activity for the oxidation of carbon particles.

    DOI CiNii

  • 7-2-3 非平衡放電と酸化物触媒を併用した固体炭素の酸化(7-2 環境対策1,Session 7 環境対策・リサイクル,研究発表)

    関根 泰, 小山 博史, 松方 正彦, 菊地 英一

    日本エネルギー学会大会講演要旨集   18   388 - 389  2009年

     概要を見る

    Low temperature catalytic oxidation of solid carbon was conducted in a fluidized bed reactor with a non-equilibrium discharge. Solid carbons like as soot, PM, and char cause many operational problems and have lower reactivity. We tried to oxidize such carbon particles to carbon dioxide by oxide catalysts with DBD discharge at lower temperature. Also to maintain high contact frequency between the catalyst and carbon particles, we applied a fluidized-bed reaction apparatus for this reaction. As a result, we found that carbon particles are oxidized at 673 K by the plasma-catalytic reaction with some oxide catalysts. Among various oxide catalysts, Pt/BaCeMnOx showed higher activity for the oxidation of carbon particles in the hybrid process of catalyst and plasma.

    DOI CiNii

  • 7-2-4 プラズマアシスト触媒反応によるNOの直接分解(7-2 環境対策1,Session 7 環境対策・リサイクル,研究発表)

    関根 泰, 小菅 健太郎, 松方 正彦, 菊地 英一

    日本エネルギー学会大会講演要旨集   18   390 - 391  2009年

     概要を見る

    Direct decomposition of nitric oxide (NO) was carried out with a plasma-assisted catalytic reaction system. As NO decomposition catalysts for the conversion of NO into N_2 and O_2, Ba/Ce-Mn-Ox and perovskite oxide were used as catalysts in this experiment. The combination of catalytic reaction and non-equilibrium electric discharge allows higher N_2 yield at low temperatures than catalytic reaction without plasma or non-equilibrium electric discharge without catalyst. And it was found that Ba/Ce-Mn-Ox is effective as a catalyst in this plasma-assisted catalytic reaction for direct decomposition of NO. Coexistence of oxygen or steam decreased N_2 yield drastically in this reaction. However, the synergistic effect of catalytic reaction and non-equilibrium electric discharge existed even though coexistence of oxygen or steam.

    DOI CiNii

  • 4-7-3 電場アシスト触媒反応による低温メタン水蒸気改質反応(4-7 メタン・DME,Session 4 新エネルギー,研究発表)

    関根 泰, 原口 将征, 富岡 真彦, 松方 正彦, 菊地 英一

    日本エネルギー学会大会講演要旨集   18   284 - 285  2009年

     概要を見る

    To achieve lower reaction temperature and higher conversion than existing catalytic processes for hydrogen production, catalytic reaction of methane steam reforming in an electric field was conducted. Conversion of methane increased on catalytic reaction in the electric field by the interaction of electric field and catalyst. In the presence of the electric field, reaction proceeded in considerably low temperature where conventional catalytic reaction hardly proceeded. Then, to investigate response of catalytic reaction in the electric field, transient experiment was conducted. As a result, conversion of methane quickly increased with impressing of the electric field.

    DOI CiNii

  • 電場を利用した低温触媒反応

    関根 泰, 原口 将征, 富岡 真彦, 松方 正彦, 菊地 英一

    石油学会 年会・秋季大会講演要旨集   2009   43 - 43  2009年

     概要を見る

    我々は、メタンの水蒸気改質において、電場中の触媒反応によって著しい低温でも触媒活性を発現することを見いだした。電場の存在によって、反応温度は423Kまで低温化することが可能であった。このような温度では、触媒反応のみでは平衡の制約からメタンの水蒸気改質はほとんど起こりえない。電場の存在で大幅な転化率の向上が達成できた。また、このプロセスは水素あるいは合成ガスを非常に低いエネルギー投入で合成可能であり、素早い応答性も有していた。メタン以外に、エタノール、DMEの水蒸気改質なども検討し、電場の影響が大きいことがわかった。

    DOI CiNii

  • 水性ガスシフト反応のための新規レドックス触媒の開発

    関根 泰, 渡部 綾, 千原 崇弘, 坂本 裕貴, 高松 遥, 松方 正彦, 菊地 英一

    石油学会 年会・秋季大会講演要旨集   2009   54 - 54  2009年

     概要を見る

    水性ガスシフト反応は水素製造ならびに合成ガス製造プロセスにおいて重要な反応である。工業的には、高温シフト反応(HTS)は593-723 Kで行われ、Fe-Cr系触媒が用いられる。また、低温シフト反応(LTS)は573 K以下で行われ、Cu-Zn系触媒や貴金属触媒が用いられる。Fe-Cr系触媒は低温域では活性が低く、Cu-Zn系触媒は熱や酸化による活性劣化が問題となっている。これまで本研究室はCu-Zn系触媒を超える活性を示す触媒としてPd/Pt/LaCoO3を報告してきた。貴金属触媒は比較的安定ではあるが、Fe-Cr系触媒やCu-Zn系触媒と比べてコストがかかってしまうことから、貴金属量を削減することは重要である。本研究は、反応温度の低温化を目的とした水性ガスシフト反応における新規触媒の開発を行い、酸化還元特性を活かした活性及び熱に対する耐性の向上を期待して、酸化鉄やペロブスカイト型酸化物(LaCoO3)を用いた触媒の検討を行った。

    DOI CiNii

  • ZSM-5膜による水/酢酸蒸気透過分離の機構

    澤村 健一, 大小原 慎太郎, 古畑 泰介, 関根 泰, 菊地 英一, 松方 正彦

    化学工学会 研究発表講演要旨集   2009   671 - 671  2009年

    DOI CiNii

  • モルデナイト膜を用いた酢酸とエタノールのエステル化

    澤村 健一, 萩野 貴之, 小嶋 淳吾, 関根 泰, 菊地 英一, 松方 正彦

    化学工学会 研究発表講演要旨集   2009   681 - 681  2009年

    DOI CiNii

  • Na型ZSM-5膜によるヘキサン異性体高温透過分離特性

    澤村 健一, 河崎 圭利, 大小原 慎太郎, 佐藤 圭介, 関根 泰, 菊地 英一, 松方 正彦

    化学工学会 研究発表講演要旨集   2009   660 - 660  2009年

    DOI CiNii

  • Reverse-Selective Microporous Membrane for Gas Separation

    Ken-ichi Sawamura, Teruaki Izumi, Kiyotoshi Kawasaki, Shintaro Daikohara, Tetsu Ohsuna, Mitsuko Takada, Yasushi Sekine, Eiichi Kikuchi, Masahiko Matsukata

    CHEMISTRY-AN ASIAN JOURNAL   4 ( 7 ) 1070 - 1077  2009年  [査読有り]

     概要を見る

    Reverse-selective membranes, through which bigger molecules selectively permeate, are attractive for developing chemical processes utilizing hydrogen because they can maintain the high partial pressure of hydrogen required for their further downstream utilization. Although several of these chemical processes are operated above 473 K, membranes with outstanding reverse-selective separation performance at these temperatures are still to be reported. Herein, we propose a new adsorption-based reverse-selective membrane that utilizes a Na cation occluded in a zeolitic framework. The membrane developed in this work, a compact Na(+)-exchanged ZSM-5 (NaZSM-5) type zeolite membrane. enables us to selectively permeate and separate bigger polar molecules, such as methanol and water, from a stream containing hydrogen, above 473 K. On the other hand, a Na(+)-free, H(+)-exchanged ZSM-5 (HZSM-5) type zeolite membrane did not show separation properties at these temperatures. The microporous zeolite membrane developed in this study can be applied to a variety of chemical reaction systems to minimize energy consumption.

    DOI

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    14
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  • Synergistic effect of Pt or Pd and perovskite oxide for water gas shift reaction

    Yasushi Sekine, Haruka Takamatsu, Sho Aramaki, Kazuki Ichishima, Mitsuko Takada, Masahiko Matsukata, Eiichi Kikuchi

    APPLIED CATALYSIS A-GENERAL   352 ( 1-2 ) 214 - 222  2009年01月  [査読有り]

     概要を見る

    The water gas shift (WGS) reaction over Pt and Pd catalysts supported on various perovskite oxides has been investigated at 573 K without catalyst pretreatment. The Pt and Pd catalysts on LaCoO(3) support showed high catalytic activity. Interaction between Pt or Pd and the support is considered to promote the WGS reaction: Pt/LaCoO(3) had high initial activity but deactivated immediately: Pd/LaCoO(3) was less active than Pt/LaCoO(3), but had superior stability. Catalysts were characterized using XRD, STEM, XPS, and H(2)-temperature programmed reduction (TPR). Results of this study showed that reduction of the support decreased the CO conversion on Pt/LaCoO(3). On the other hand, Pd/LaCoO(3) showed stable activity for the WGS reaction. Therefore, Pd was added to Pt/LaCoO(3) for stabilizing the catalyst activity, and 0.5 wt.% Pd/1 wt.% Pt/LaCoO(3) catalyst showed higher activity and stability. (C) 2008 Elsevier B.V. All rights reserved.

    DOI

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    24
    被引用数
    (Scopus)
  • Oxidative Coupling of Methane on Fe-Doped La2O3 Catalyst

    Yasushi Sekine, Keisuke Tanaka, Masahiko Matsukata, Eiichi Kikuchi

    ENERGY & FUELS   23 ( 1-2 ) 613 - 616  2009年01月  [査読有り]

     概要を見る

    Various La2O3-based catalysts are well-known to be useful for the oxidative coupling of methane (OCM reaction). We examined the catalytic activities of various La2O3-based OCM catalysts for the OCM reaction in the kinetic region (i.e., lower O-2 conversion). Our investigation revealed that the Fe-doped La2O3 catalyst is a good candidate for the OCM reaction. The La/Fe ratio of the Fe-doped La2O3 catalyst is an important factor for OCM activity. Especially, the O-2-based C-2 yield of the Fe-doped La2O3 catalyst was higher than that of La2O3 in the case of La/Fe &gt; 5. The Fe-doped La2O3 catalyst modified with Na2O and Na4P2O7 showed high C-2 Selectivity (83%). Moreover, modification with Bi compounds also enhanced C-2 selectivity of the Fe-doped La2O3 catalyst. This catalyst showed higher C-2 yield than the Fe-doped La2O3 catalyst.

    DOI

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    39
    被引用数
    (Scopus)
  • High performance of Fe-K oxide catalysts for dehydrogenation of ethylbenzene to styrene with an aid of ppm-order Pd

    Yasushi Sekine, Ryo Watanabe, Masahiko Matsukata, Eiichi Kikuchi

    CATALYSIS LETTERS   125 ( 3-4 ) 215 - 219  2008年10月  [査読有り]

     概要を見る

    Styrene is manufactured industrially through catalytic dehydrogenation of ethylbenzene on Fe-K oxide-based catalysts. It was invented by Sud-Chemie Group that the activity of the industrial ethylbenzene dehydrogenation catalysts (Styromax) based on the oxides of Fe and K is highly promoted by the addition of small amount (hundreds ppm-order) of precious metals such as Pd. The present work is intended to elucidate the role of Pd on the Fe-K catalyst empirically by use of a periodical pulse technique from a mechanistic point of view. The oxidative dehydrogenation was faster than the simple dehydrogenation, and it proceeded by consuming the surface lattice oxygen in the catalyst. The lattice oxygen was subsequently supplied from steam. Palladium added to the Fe-K oxide catalysts was found to enhance the rate of regeneration (supplying) of the lattice oxygen, although it hardly changed the rate of dehydrogenation of ethylbenzene or consumption of surface lattice O(2-) anions. This study demonstrated that steam works not only as a diluent but also as a reactant to form hydrogen and lattice oxygen.

    DOI

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    19
    被引用数
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  • Separation Behavior of Steam from Hydrogen and Methanol through Mordenite Membrane

    Ken-ichi Sawamura, Tsutomu Shirai, Tetsu Ohsuna, Takayuki Hagino, Mitsuko Takada, Yasushi Sekine, Eiichi Kikuchi, Masahiko Matsukata

    JOURNAL OF CHEMICAL ENGINEERING OF JAPAN   41 ( 9 ) 870 - 877  2008年09月  [査読有り]

     概要を見る

    A mordenite membrane was prepared on the outer surface of a porous a-alumina tubular support by a secondary-growth method. Permeation tests for water/methanol/hydrogen mixtures were performed at 423 and 473 K. A mordenite membrane free from non-zeolitic pores allowed us selective permeation of steam and blocked the permeation of hydrogen and methanol. In order to elucidate the mechanism of such selective permeation behavior, adsorption, permeation, and structural properties of the mordenite membrane were discussed. As a result, it was considered that selective permeation of steam against hydrogen was based on its preferential adsorption of steam, while boundaries between mordenite crystals in the membrane may play a key role for inhibiting the permeation of methanol.

  • Controlled growth for synthesizing a compact mordenite membrane

    Masahiko Matsukata, Ken-ichi Sawamura, Tsutomu Shirai, Mitsuko Takada, Yasushi Sekine, Eiichi Kikuchi

    JOURNAL OF MEMBRANE SCIENCE   316 ( 1-2 ) 18 - 27  2008年05月  [査読有り]

     概要を見る

    Controlling the growth of zeolite crystals on a porous alumina support is essential for preparing a compact zeolite membarne. First, mordenite seed crystals applied on a nonporous a-alumina disk were grown and morphological change of mordenite crystals were observed in the course of growth. Then, mordenite membranes were synthesized on a porous a-alumina tube under the same conditions employed in the study using the alumina disks. We found that seed crystal growth was widely controllable by changing water content in reaction solution, which resulted in better control of the morphology of mordenite crystals for synthesizing a thin compact mordenite membrane. Separation properties for mordenite membranes were studied in water-hydrogen binary system at 473 K with 10 kPa of water partial pressure, where no capillary condensation was expected in non-zeolitic pores. Separation factor for a mordenite membrane with a few defects was poor; however, a defect-free mordenite membrane prepared under a suitable condition highly separated steam from hydrogen. (C) 2007 Elsevier B.V. All rights reserved.

    DOI

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    27
    被引用数
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  • Production of hydrogen by steam reforming of ethanol over cobalt and nickel catalysts supported on perovskite-type oxides

    Kohei Urasaki, Kazuhisa Tokunaga, Yasushi Sekine, Masahiko Matsukata, Eiichi Kikuchi

    CATALYSIS COMMUNICATIONS   9 ( 5 ) 600 - 604  2008年03月  [査読有り]

     概要を見る

    The steam reforming of ethanol was performed over Co and Ni catalysts supported on perovskite-type oxides (LaAlO3, SrTiO3 and BaTiO3). Co and Ni catalysts supported on LaAlO3 and SrTiO3 showed high catalytic activities and long-term stabilities and suppressed coke formation while Co/BaTiO3 showed lower catalytic activities and poorer coking resistance. The average particle size of Co oil BaTiO3 was larger than that on SrTiO3. Lattice oxygen in perovskites may play positive roles in hindering coking and Co/SrTiO3 has more frequent participation of lattice oxygen in the oxidation of intermediates or precursor of coke in comparison with Co/BaTiO3. (c) 2007 Elsevier B.V. All rights reserved.

    DOI

    Scopus

    99
    被引用数
    (Scopus)
  • Steam reforming of ethanol over Co/La1-xSrxBO3 (B=Al, Cr, Mn, Fe) catalysts

    Kohei Urasaki, Yoshic Fukuda, Yasushi Sekine, Masahiko Matsukata, Eiichi Kikuchi

    JOURNAL OF THE JAPAN PETROLEUM INSTITUTE   51 ( 2 ) 83 - 87  2008年03月  [査読有り]

     概要を見る

    The steam reforming of ethanol for producing hydrogen was evaluated over 5 wt% Co catalysts supported on perovskite-type oxides, La1-xSrxBO3 (B = Al, Cr, Mn, Fe, x = 0-0.2) at 823 K with a molar H2O/C2H5OH ratio of 6. Co/LaAlO3 showed higher catalytic activity and stability than Co catalysts supported on LaCrO3, LaFeO3 and LaMnO3. The molar La/Al ratio markedly affected the stability of Co/LaAlO3 catalyst and a molar La/Al ratio of I was the most suitable, suggesting that the properties of the perovskite structure are important in the catalytic activity and stability. Partial substitution of Sr2+ for La 31 in LaAlO3 resulted in further remarkable improvement of catalytic activity and hydrogen yield. We consider that enhanced mobility of lattice oxygen in La1-xSrxAlO3-delta allows more frequent participation in the oxidation of intermediates over metallic cobalt, leading to both high catalytic activity and stability of Co/La1-xSrxAlO3-delta,5 in comparison with Co/LaAlO3.

  • Selective permeation and separation of steam from water-methanol-hydrogen gas mixtures through mordenite membrane

    Ken-Ichi Sawamura, Tsutomu Shirai, Mitsuko Takada, Yasushi Sekine, Eiichi Kikuchi, Masahiko Matsukata

    CATALYSIS TODAY   132 ( 1-4 ) 182 - 187  2008年03月  [査読有り]

     概要を見る

    Separation properties of a mordenite membrane for water-methanol-hydrogen mixtures were studied in the temperature range from 423 to 523 K under pressurized conditions. The mordenite membrane was prepared on the outer surface of a porous alumina tubular support by a secondary-growth method. It was found that water was selectively permeated through the membrane. The separation factor of water/hydrogen and water/methanol were 49-156 and 73-101, respectively. Even when only hydrogen was fed at 0.5 MPa, its permeance was as low as 10(-9) mol m(-2) s(-1) Pa-1 up to 493 K, possibly suggesting that water pre-adsorbed in the micropores of mordenite hindered the permeation of hydrogen. The hydrogen permeance dramatically increased to 6.5 x 10(-7) mol m(-2) s(-1) Pa-1 at 503 K and reached to 1.4 x 10(-6) mol m(-2) s(-1) Pa-1 at 523 K because of the formation of cracks in the membrane. However, the membrane was thermally stabilized in the presence of steam and/or methanol. (C) 2007 Elsevier B.V. All rights reserved.

    DOI

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    39
    被引用数
    (Scopus)
  • 52 セルロースの熱分解・ガス化で放出されるタール分の分解に有効な触媒の開発(重質油・バイオマス・コプロセッシング(1))

    関根 泰, 田村 博文, 松方 正彦, 菊地 英一

    石炭科学会議発表論文集   45   104 - 105  2008年

     概要を見る

    We investigated effective catalysts for converting biomass-tar derived from the gasification/combustion of cellulose. Experiments were conducted with a sequential combined reactor with a fluidized bed gasifier/combustor and a fixed bed reactor for removing tar. Several kinds of Co or Ni supported catalysts were investigated. As a result, we found that Ni/CeO_2 and Ni/CaO catalysts showed higher activities for removing biomass-tar.

    DOI CiNii

  • ZSM-5膜のパームポロメトリーによるキャラクタリゼーション

    澤村 健一, 河崎 圭利, 大小原 慎太郎, 関根 泰, 菊地 英一, 松方 正彦

    化学工学会 研究発表講演要旨集   2008   153 - 153  2008年

    DOI CiNii

  • Release behavior of trace elements from coal during high-temperature processing

    Yasushi Sekine, Kunihisa Sakajin, Eiichi Kikuchi, Masahiko Matsukata

    POWDER TECHNOLOGY   180 ( 1-2 ) 210 - 215  2008年01月  [査読有り]

     概要を見る

    High-temperature coal utilization processes (combustion, gasification and pyrolysis) emit toxic trace elements into the atmosphere, where they affect the environment and human health. We carried out coal combustion and gasification experiments using several kinds of coals at various temperatures and atmospheric conditions to examine the release behavior of trace elements. Results showed that Group 1 and 2 metals such as Fig, Se, Sb, and Zn were partly released from coal during combustion, gasification and pyrolysis. Oxygen or steam in the operating atmosphere affected the behavior of Fig, Se, Sb, and Zn release from coal. (C) 2007 Elsevier B.V. All rights reserved.

    DOI

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    51
    被引用数
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  • High-efficiency dry reforming of biomethane directly using pulsed electric discharge at ambient condition

    Yasushi Sekine, Junya Yamadera, Shigeru Kado, Masahiko Matsukata, Eiichi Kikuchi

    ENERGY & FUELS   22 ( 1 ) 693 - 694  2008年01月  [査読有り]

    DOI

    Scopus

    14
    被引用数
    (Scopus)
  • Application of FAU-type zeolite membranes to vapor/gas separation under high pressure and high temperature up to 5 MPa and 180 degrees C

    Kiminori Sato, Kazunori Sugimoto, Yasushi Sekine, Mitsuko Takada, Masahiko Matsukata, Takashi Nakane

    MICROPOROUS AND MESOPOROUS MATERIALS   101 ( 1-2 ) 312 - 318  2007年04月  [査読有り]

     概要を見る

    Tubular FAU-type zeolite membrane was synthesized on porous alumina substrate with 80 cm long by a seeded growth method. Pervaporation experiments using a mixture of water (10 wt%)/ethanol (90 wt%) at 75 degrees C demonstrated superior permeation properties of this type of membrane showing the total flux of 4-10 (kg m(-2) h(-1)) with the separation factor of 110-300. A part of the synthesized membrane with 10 cm long was applied to gas separation at high pressures of 1-5 MPa and high temperatures of 130 and 180 degrees C. Ternary mixtures of water, methanol and hydrogen were used for evaluating the permselectivities of FAU-type membrane. It was found that hydrogen permeation was strongly depressed in the presence of water and methanol. Preferential adsorption of water and methanol in the micropores of FAU-type zeolite possibly played an important role for the appearance of permselectivity. (c) 2006 Elsevier Inc. All rights reserved.

    DOI

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    66
    被引用数
    (Scopus)
  • Shape selectivity of MWW-type aluminosilicate zeolites in the alkylation of toluene with methanol

    Satoshi Inagaki, Kohei Kamino, Eiichi Kikuchi, Masahiko Matsukata

    APPLIED CATALYSIS A-GENERAL   318   22 - 27  2007年02月

     概要を見る

    We investigated the alkylation of toluene with methanol at 250 degrees C over MCM-22 and ITQ-2 zeolites possessing an MWW structure. Whereas ITQ-2, produced by the delamination of MCM-22 precursor, showed a poor p-xylene selectivity of 23% at 1.7% of the level of toluene conversion, a high p-xylene selectivity of 80% at 0.6% of the level of toluene conversion was obtained by poisoning the external surface of ITQ-2 with collidine. Similarly, MCM-22 treated with collidine showed a high p-xylene selectivity of 74% at 3.8% of the level of toluene conversion. We concluded that both interlayer and intralayer 10-membered ring (10MR) micropores in the MWW structure caused the shape-selective formation of p-xylene in the alkylation of toluene with methanol. (c) 2006 Elsevier B.V. All rights reserved.

    DOI

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    59
    被引用数
    (Scopus)
  • Shape selectivity of MWW-type aluminosilicate zeolites in the alkylation of toluene with methanol

    Satoshi Inagaki, Kohei Kamino, Eiichi Kikuchi, Masahiko Matsukata

    APPLIED CATALYSIS A-GENERAL   318   22 - 27  2007年02月

     概要を見る

    We investigated the alkylation of toluene with methanol at 250 degrees C over MCM-22 and ITQ-2 zeolites possessing an MWW structure. Whereas ITQ-2, produced by the delamination of MCM-22 precursor, showed a poor p-xylene selectivity of 23% at 1.7% of the level of toluene conversion, a high p-xylene selectivity of 80% at 0.6% of the level of toluene conversion was obtained by poisoning the external surface of ITQ-2 with collidine. Similarly, MCM-22 treated with collidine showed a high p-xylene selectivity of 74% at 3.8% of the level of toluene conversion. We concluded that both interlayer and intralayer 10-membered ring (10MR) micropores in the MWW structure caused the shape-selective formation of p-xylene in the alkylation of toluene with methanol. (c) 2006 Elsevier B.V. All rights reserved.

    DOI

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    59
    被引用数
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  • モルデナイト膜の吸着特性と水蒸気選択的透過機構

    澤村 健一, 白井 努, 高田 光子, 関根 泰, 菊地 英一, 松方 正彦

    化学工学会 研究発表講演要旨集   2007   610 - 610  2007年

    DOI CiNii

  • ZSM-5膜への水・メタノールの吸着が水素の透過に及ぼす影響

    澤村 健一, 泉 輝明, 小澤 和貴, 高田 光子, 関根 泰, 菊地 英一, 松方 正彦

    化学工学会 研究発表講演要旨集   2007   609 - 609  2007年

    DOI CiNii

  • 7-1 放電を用いた常温常圧でのバイオメタンの脱硫と改質((3)改質および燃料化,Session 7 環境対策・リサイクル,研究発表(口頭発表))

    関根 泰, 山寺 順哉, 菊地 英一, 松方 正彦

    日本エネルギー学会大会講演要旨集   16   310 - 311  2007年

    DOI CiNii

  • 電場印加を併用した低温での触媒反応によるエタノールの分解

    関根 泰, 富岡 真彦, 松方 正彦, 菊地 英一

    石油学会 年会・秋季大会講演要旨集   2007   91 - 91  2007年

     概要を見る

    電場中での触媒反応を、エタノールの分解などをモデル反応として検討した。触媒には白金など活性金属を担持した触媒を用い、電場を印加して反応を行った。白金を担持したセリア触媒などがとりわけ高い活性を示し、300度以下の低温で高い転化率を示した。従来の触媒反応に比べ、低温で高い活性を発現することができ、また投入する電力も小さいことから、小型装置においてはとりわけ、飛躍的に効率の高いプロセスとすることが可能である。

    DOI CiNii

  • 固溶体触媒を用いたカーボンナノチューブの合成

    関根 泰, 児玉 慎平, 田中 啓介, 菊地 英一, 松方 正彦

    石油学会 年会・秋季大会講演要旨集   2007   40 - 40  2007年

     概要を見る

    現在、シングルウォールカーボンナノチューブ(SWNT)はその特異的性質から注目され、様々な分野での応用が期待されている。工業化のためにはCCVD法(Catalytic Chemical Vapor Deposition)による合成が期待されている。これまで本研究室ではコバルトマグネシア固溶体触媒を用いたCCVD法によってSWNTを合成してきた。触媒の調製法、焼成法が触媒と生成するSWNTへ与える影響について検討を行ったので報告する。

    DOI CiNii

  • ペロブスカイト型酸化物を担体としたNi触媒を用いたメタン水蒸気改質反応

    関根 泰, 土井 あずさ, 西澤 龍彦, 松方 正彦, 菊地 英一

    石油学会 年会・秋季大会講演要旨集   2007   2 - 2  2007年

     概要を見る

    水素製造法である水蒸気改質反応では触媒上に析出する炭素による活性劣化が問題となっており、炭素析出を抑制することで小型燃料電池へ早期導入が期待されている。これまでに本研究室では、易動性の酸素を有するペロブスカイト型酸化物を担体に適用し、担体の格子酸素を反応に利用するサイクルを提案している。そこでこれらNi/perovskite触媒について、担体が触媒性能に与える影響について検討を行った。

    DOI CiNii

  • 常圧での低エネルギー放電を用いたバイオメタンの二酸化炭素改質と同時脱硫

    関根 泰, 山寺 順哉, 菊地 英一, 松方 正彦

    石油学会 年会・秋季大会講演要旨集   2007   23 - 23  2007年

     概要を見る

    最近のエネルギー資源の一つとして用いられているバイオガスは動植物など有機性資源の嫌気発酵により得られるが、バイオガスは高濃度のH2Sを含有しているため、現状での触媒を用いた改質には様々な問題点が生じる。そこで本研究では常温、常圧、無触媒条件下において非平衡放電(特にDBD放電及びLEP放電)を用いたバイオガスの直接改質について検討を行い、更に放電形態の違いが化学反応に及ぼす影響についても検討する。

    DOI CiNii

  • 酸型ゼオライトを用いた1-ブテンによるイソブタンのアルキル化

    関根 泰, 大森 悠哉, 田嶋 祐一, 市川 洋介, 松方 正彦, 菊地 英一

    石油学会 年会・秋季大会講演要旨集   2007   178 - 178  2007年

     概要を見る

    近年、環境問題の関心が高まる中、硫黄、芳香族を含まないガソリン基材を製造することのできるアルキレーションプロセスが注目されている。現行のプロセスでは触媒として液体酸が用いられているが、様々な問題点があるため固体酸触媒によるプロセスの開発が望まれている。本研究において、固体酸であるゼオライトを触媒とし、連続式完全混合層型反応器を用いることで良い反応成績が得られたので、これを報告する。

    DOI CiNii

  • Elucidation of medium-range structure in a dry gel forming *BEA-type zeolite

    Inagaki, Satoshi, Nakatsuyama, Kei, Saka, Yuji, Kikuchi, Eiichi, Kohara, Shinji, Matsukata, Masahiko

    Journal of Physical Chemistry C   111 ( 28 ) 10285 - 10293  2007年01月  [査読有り]

    DOI J-GLOBAL

    Scopus

    39
    被引用数
    (Scopus)
  • Changes of intermediate-range structure in the course of crystallization of zeolite beta

    Inagaki, Satoshi, Nakatsuyama, Kei, Saka, Yuji, Kikuchi, Eiichi, Kohara, Shinji, Matsukata, Masahiko

    Microporous and Mesoporous Materials   101 ( 1-2 ) 50 - 56  2007年01月  [査読有り]

    DOI J-GLOBAL

    Scopus

    12
    被引用数
    (Scopus)
  • Indication of successful crystallization of dry gel into *BEA-type zeolite

    Satoshi Inagaki, Kei Nakatsuyama, Yuji Saka, Eiichi Kikuchi, Shinji Kohara, Masahiko Matsukata

    CHEMISTRY LETTERS   35 ( 12 ) 1370 - 1371  2006年12月

     概要を見る

    Tetraethylammonium (TEA(+))-containing silicate dry gels exhibiting a maximum in the reflection peak at 2 theta = 28 degrees in an XRD pattern using Cu K alpha radiation are always transformed into *BEA-type zeolite with steam-assisted crystallization.

    DOI

    Scopus

    5
    被引用数
    (Scopus)
  • Indication of successful crystallization of dry gel into *BEA-type zeolite

    Satoshi Inagaki, Kei Nakatsuyama, Yuji Saka, Eiichi Kikuchi, Shinji Kohara, Masahiko Matsukata

    CHEMISTRY LETTERS   35 ( 12 ) 1370 - 1371  2006年12月

     概要を見る

    Tetraethylammonium (TEA(+))-containing silicate dry gels exhibiting a maximum in the reflection peak at 2 theta = 28 degrees in an XRD pattern using Cu K alpha radiation are always transformed into *BEA-type zeolite with steam-assisted crystallization.

    DOI

    Scopus

    5
    被引用数
    (Scopus)
  • Syntheses of mesoporous hybrid iron oxophenyl phosphate, iron oxophosphate, and sulfonated oxophenyl phosphate

    Nawal Kishor Mal, Asim Bhaumik, Masahiko Matsukata, Masahiro Fujiwara

    INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH   45 ( 23 ) 7748 - 7751  2006年11月

     概要を見る

    A novel organic-inorganic hybrid mesoporous iron oxophenyl phosphate has been synthesized by using supramolecular assembly of sodium dodecyl sulfate molecules. X-ray diffraction, transmission electron microscopic studies, and N-2 adsorption data indicated the wormhole-like disordered mesostructure in this sample. The C-13 and P-31 MAS NMR, FT IR, UV-visible spectroscopic data, and chemical analysis results indicated that all P atoms are attached to phenyl groups directly and combined with Fe atoms through O atoms. Calcination of this hybrid material produced organic-free mesoporous iron oxophosphate material, whereas sulfonation of the mesoporous iron oxophenyl phosphate resulted in sulfonated oxophenyl phosphate. The latter showed outstanding proton conductivity, which could be utilized in membrane or supports of anode and cathode materials in fuel cells.

    DOI

    Scopus

    35
    被引用数
    (Scopus)
  • Syntheses of mesoporous hybrid iron oxophenyl phosphate, iron oxophosphate, and sulfonated oxophenyl phosphate

    Nawal Kishor Mal, Asim Bhaumik, Masahiko Matsukata, Masahiro Fujiwara

    INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH   45 ( 23 ) 7748 - 7751  2006年11月

     概要を見る

    A novel organic-inorganic hybrid mesoporous iron oxophenyl phosphate has been synthesized by using supramolecular assembly of sodium dodecyl sulfate molecules. X-ray diffraction, transmission electron microscopic studies, and N-2 adsorption data indicated the wormhole-like disordered mesostructure in this sample. The C-13 and P-31 MAS NMR, FT IR, UV-visible spectroscopic data, and chemical analysis results indicated that all P atoms are attached to phenyl groups directly and combined with Fe atoms through O atoms. Calcination of this hybrid material produced organic-free mesoporous iron oxophosphate material, whereas sulfonation of the mesoporous iron oxophenyl phosphate resulted in sulfonated oxophenyl phosphate. The latter showed outstanding proton conductivity, which could be utilized in membrane or supports of anode and cathode materials in fuel cells.

    DOI

    Scopus

    35
    被引用数
    (Scopus)
  • C1化学における分離膜技術展開の可能性

    松方正彦

    膜   31 ( 5 ) 271 - 274  2006年09月

    DOI CiNii

  • Preparation of ferrierite zeolite membranes in the absence of organic structure-directing agents

    Xiao Hui Su, Gang Li, Rui Sen Lin, Eiichi Kikuchi, Masahiko Matsukata

    CHINESE CHEMICAL LETTERS   17 ( 7 ) 977 - 980  2006年07月  [査読有り]

     概要を見る

    Ferrierite zeolite membranes were prepared for the first time in the absence of organic structure-directing agents (SDA) on the surface of a porous a-alumina support. These membranes were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and pervaporation tests.

  • Novel organic-inorganic hybrid and organic-free mesoporous niobium oxophosphate synthesized in the presence of an anionic surfactant

    Nawal Kishor Mal, Asim Bhaumik, Masahiro Fujiwara, Masahiko Matsukata

    MICROPOROUS AND MESOPOROUS MATERIALS   93 ( 1-3 ) 40 - 45  2006年07月

     概要を見る

    A novel organic-inorganic hybrid mesoporous niobium oxophenylphosphate was synthesized by using supramolecular assembly of sodium dodecylsulfate molecules. X-ray diffraction, transmission electron microscopic image and NZ adsorption data indicated the formation of a wormhole-like disordered mesostructure in the sample. The C-13 and P-31 MAS NMR, FTIR, UV-visible spectroscopic data and chemical analysis results indicated that all P atoms are attached to phenyl groups directly and these are combined with Nb atoms through O atoms. Calcination of this hybrid material yielded an organic-free mesoporous niobium oxophosphate material. (c) 2006 Elsevier Inc. All rights reserved.

    DOI

    Scopus

    22
    被引用数
    (Scopus)
  • Novel organic-inorganic hybrid and organic-free mesoporous niobium oxophosphate synthesized in the presence of an anionic surfactant

    Nawal Kishor Mal, Asim Bhaumik, Masahiro Fujiwara, Masahiko Matsukata

    MICROPOROUS AND MESOPOROUS MATERIALS   93 ( 1-3 ) 40 - 45  2006年07月

     概要を見る

    A novel organic-inorganic hybrid mesoporous niobium oxophenylphosphate was synthesized by using supramolecular assembly of sodium dodecylsulfate molecules. X-ray diffraction, transmission electron microscopic image and NZ adsorption data indicated the formation of a wormhole-like disordered mesostructure in the sample. The C-13 and P-31 MAS NMR, FTIR, UV-visible spectroscopic data and chemical analysis results indicated that all P atoms are attached to phenyl groups directly and these are combined with Nb atoms through O atoms. Calcination of this hybrid material yielded an organic-free mesoporous niobium oxophosphate material. (c) 2006 Elsevier Inc. All rights reserved.

    DOI

    Scopus

    22
    被引用数
    (Scopus)
  • 炭化水素分離

    松方正彦

    膜   31 ( 1 ) 18 - 19  2006年06月

    DOI CiNii

  • 3-22.バイオガスの常温常圧での同時改質・脱硫((5)ガス化5,Session 3 バイオマス等)

    関根 泰, 山寺 順哉, 菊地 英一, 松方 正彦

    日本エネルギー学会大会講演要旨集   15   149 - 150  2006年

    DOI CiNii

  • ZSM-5膜による高温における極性分子/無機ガス分離

    澤村 健一, 泉 輝明, 高田 光子, 関根 泰, 菊地 英一, 松方 正彦

    化学工学会 研究発表講演要旨集   2006   341 - 341  2006年

    DOI CiNii

  • 形状の違うゼオライトの土壌改良材としての比較

    金親 暁, 鈴木 絵里, 浜野 裕之, 里川 重夫, 小島 紀徳, 松方 正彦

    化学工学会 研究発表講演要旨集   2006   558 - 558  2006年

    DOI CiNii

  • Reactivity and structural change of coal char during steam gasification

    Y Sekine, K Ishikawa, E Kikuchi, M Matsukata, A Akimoto

    FUEL   85 ( 2 ) 122 - 126  2006年01月  [査読有り]

     概要を見る

    This study is intended to clarify the relationship among the reactivity of coal char with steam, structural change in residual carbon, and ash behavior. Steam gasification of various coal chars and demineralized chars was carried out in a fixed-bed reactor. After gasification, the reacted char was analyzed using laser raman spectroscope (LRS), and scanning electron microscope, energy dispersive X-ray spectroscope (SEM/EDX) mapping. Results of SEM images and EDX-mappings revealed that novel parallel analysis of cross correlation between EDX-mapping and LRS-mapping was found to be very effective for the comprehensive evaluation of ash behavior and carbonaceous structure. As the gasification reaction proceeds, the reactivity of the char was varied; existence of Si and Al seemed to suffocate the char reactivity. (c) 2005 Elsevier Ltd. All rights reserved.

    DOI

    Scopus

    119
    被引用数
    (Scopus)
  • Release behavior of trace metals from coal during high temperature processing

    Y. Sekine, K. Sakajiri, R. Inoue, E. Kikuchi, M. Matsukata

    NEW DEVELOPMENT AND APPLICATION IN CHEMICAL REACTION ENGINEERING, 4TH ASIA-PACIFIC CHEMICAL REACTION ENGINEERING SYMPOSIUM (APCRE 05)   159   573 - 576  2006年

  • Preparation of mordenite composite membranes with seeding

    X. Su, G. Li, R. Lin, E. Kikuchi, M. Matsukata

    Chinese Chem. Lett.   17 ( 7 ) 977 - 980  2006年

  • Hydrogen production from biomass-ethanol at ambient temperature with novel diaphragm reactor

    Y. Sekine, S. Asai, E. Kikuchi, M. Matsukata, F. Haga

    NEW DEVELOPMENT AND APPLICATION IN CHEMICAL REACTION ENGINEERING, 4TH ASIA-PACIFIC CHEMICAL REACTION ENGINEERING SYMPOSIUM (APCRE 05)   159   813 - 816  2006年

  • Hydrogen production from biomass-ethanol at ambient temperature with novel diaphragm reactor

    Y. Sekine, S. Asai, E. Kikuchi, M. Matsukata, F. Haga

    NEW DEVELOPMENT AND APPLICATION IN CHEMICAL REACTION ENGINEERING, 4TH ASIA-PACIFIC CHEMICAL REACTION ENGINEERING SYMPOSIUM (APCRE 05)   159   813 - 816  2006年

  • Release behavior of trace metals from coal during high temperature processing

    Y. Sekine, K. Sakajiri, R. Inoue, E. Kikuchi, M. Matsukata

    NEW DEVELOPMENT AND APPLICATION IN CHEMICAL REACTION ENGINEERING, 4TH ASIA-PACIFIC CHEMICAL REACTION ENGINEERING SYMPOSIUM (APCRE 05)   159   573 - 576  2006年

  • Preparation of mordenite composite membranes with seeding

    X. Su, G. Li, R. Lin, E. Kikuchi, M. Matsukata

    Chinese Chem. Lett.   17 ( 7 ) 977 - 980  2006年

  • Hydrogen production from biomass-ethanol at ambient temperature with novel diaphragm reactor

    Y. Sekine, S. Asai, E. Kikuchi, M. Matsukata, F. Haga

    NEW DEVELOPMENT AND APPLICATION IN CHEMICAL REACTION ENGINEERING, 4TH ASIA-PACIFIC CHEMICAL REACTION ENGINEERING SYMPOSIUM (APCRE 05)   159   813 - 816  2006年

  • Reaction and oxygen permeation studies in Sm0.4Ba0.6Fe0.8Co0.2O3-delta membrane reactor for partial oxidation of methane to syngas

    M Ikeguchi, T Mimura, Y Sekine, E Kikuchi, M Matsukata

    APPLIED CATALYSIS A-GENERAL   290 ( 1-2 ) 212 - 220  2005年08月  [査読有り]

     概要を見る

    A disk-type SM0.4Ba0.6Co0.2Fe0.8O3 (- delta) perovskite-type mixed-conducting membrane was applied to a membrane reactor for the partial oxidation of methane to syngas (CO + H-2). The reaction was carried out using Rh (1 wt%)/MgO catalyst by feeding CH4 diluted with Ar. While CH4 conversion increased and CO selectivity slightly decreased with increasing temperature, a high level of CH4 conversion (90 %) and a high selectivity to CO (98 %) were observed at 1173 K. The oxygen flux was increased under the conditions for the catalytic partial oxidation of CH4 compared with that measured when Ar was fed to the permeation side. We investigated the reaction pathways in the membrane reactor using different membrane reactor configurations and different kinds of gas. In the membrane reactor without the catalyst, the oxygen flux was not improved even when CH4 was fed to the permeation side, whereas the oxygen flux was enhanced when CO or H-2 was fed. It is implied that the oxidation of CO and H-2 with the surface oxygen on the permeation side improves the oxygen flux through the membrane, and that CO2 and H2O react with CH4 by reforming reactions to form syngas. (c) 2005 Elsevier B.V. All rights reserved.

    DOI

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    73
    被引用数
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  • Solid State Synthesis of SrFeCo_<0.5>O_x Asymmetric Membranes for Oxygen Separation

    Ikeguchi Masayuki, Uchida Yasukazu, Sekine Yasushi, KIKUCHI Eiichi, MATSUKATA Masahiko

    Journal of chemical engineering of Japan   38 ( 7 ) 502 - 508  2005年07月

     概要を見る

    SrFeCo0.5Ox asymmetric membranes for oxygen permeation consisting of a thin dense layer and a porous support layer were prepared using a simple method. A given amount of SrFeCo0.5Ox powder was placed in a die, and then a mixture of SrFeCo0.5Ox powder and ethyl cellulose powder was added on top of the SrFeCo0.5Ox powder. The layered powders were pressed into a 13 mm-diameter disk, and calcined at 1423 K. This produced a membrane with a thin dense layer and, through the elimination of the ethyl cellulose, a porous support layer. Oxygen flux through membranes thus produced increased with decreasing dense-layer thickness. The maximum oxygen flux through an asymmetric membrane at 1173 K observed was 0.23 cm3 (STP) cm–2 min–1, which was 2.8 times larger than that through a 0.95 mm-thick symmetric membrane. Oxygen permeation was primarily limited by bulk diffusion in the thin dense layer, although the porous support layer acted to resist oxygen permeation.

    DOI CiNii

    Scopus

    1
    被引用数
    (Scopus)
  • Hydrogen production by steam reforming of ethanol using cobalt and nickel catalysts supported on strontium titanate

    Kohei Urasaki, Kazuhisa Tokunaga, Yasushi Sekine, Eiichi Kikuchi, Masahiko Matsukata

    Chemistry Letters   34 ( 5 ) 668 - 669  2005年05月

     概要を見る

    The steam reforming of ethanol over Co and Ni catalysts supported on SrTiO3 was carried out at 823 K and atmospheric pressure. It was found that Co/SrTiO3 showed a high catalytic activity and long-term stability and remarkably inhibited carbon deposition. Copyright © 2005 The Chemical Society of Japan.

    DOI

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    17
    被引用数
    (Scopus)
  • Hydrogen production by steam reforming of ethanol using cobalt and nickel catalysts supported on strontium titanate

    Kohei Urasaki, Kazuhisa Tokunaga, Yasushi Sekine, Eiichi Kikuchi, Masahiko Matsukata

    Chemistry Letters   34 ( 5 ) 668 - 669  2005年05月

     概要を見る

    The steam reforming of ethanol over Co and Ni catalysts supported on SrTiO3 was carried out at 823 K and atmospheric pressure. It was found that Co/SrTiO3 showed a high catalytic activity and long-term stability and remarkably inhibited carbon deposition. Copyright © 2005 The Chemical Society of Japan.

    DOI

    Scopus

    17
    被引用数
    (Scopus)
  • Improving oxygen permeability in SrFeCo0.5Ox asymmetric membranes by modifying support-layer porous structure

    M Ikeguchi, K Ishii, Y Sekine, E Kikuchi, M Matsukata

    MATERIALS LETTERS   59 ( 11 ) 1356 - 1360  2005年05月

     概要を見る

    Disk-type SrFeCo0.50Ox, asymmetric membranes were prepared for high-temperature oxygen separation using both a previously reported solid state technique in which ethyl cellulose is introduced and then removed by calcination to produce a porous support layer and a modified technique in which carbon fiber is added to the ethyl cellulose. The oxygen permeabilities of the resulting SrFeCo0.50Ox asymmetric membranes were measured at 973-1173 K. The addition of carbon fiber to ethyl cellulose resulted in the improvement of gas diffusivity in the porous support layer, which increased the flux of oxygen through the modified asymmetric membrane. (c) 2005 Elsevier B.V. All rights reserved.

    DOI

    Scopus

    40
    被引用数
    (Scopus)
  • Catalytic activities and coking resistance of Ni/perovskites in steam reforming of methane

    K Urasaki, Y Sekine, S Kawabe, E Kikuchi, M Matsukata

    APPLIED CATALYSIS A-GENERAL   286 ( 1 ) 23 - 29  2005年05月

     概要を見る

    Steam reforming of methane for the purpose of hydrogen production was performed using nickel catalysts supported on a variety of perovskites, including LaAlO3, LaFeO3, SrTiO3, BaTiO3, La0.4Ba0.6Co0.2Fe0.8O3-delta, to compare the catalytic activity and resistance to coking of these catalysts to those of the conventional Ni/alpha-Al2O3 catalyst. Ni/LaAlO3 and Ni/SrTiO3 showed high catalytic activities among the Ni/perovskites and longer-term stabilities than the conventional catalyst. Temperature programmed oxidation of carbon deposited on used catalysts revealed that inactive carbon species detected on Ni/alpha-Al2O3 were not formed in the case of Ni/LaAlO3. The results of temperature programmed reduction confirmed that consumption and recovery of the lattice oxygen in perovskites occurred during the reaction, and that the reducibility of perovskites had a great impact on the steam reforming activity. The lattice oxygen in perovskites is considered to play important roles in promoting the oxidation of CH, fragments adsorbed on metallic nickel. (c) 2005 Published by Elsevier B.V.

    DOI

    Scopus

    149
    被引用数
    (Scopus)
  • Improving oxygen permeability in SrFeCo0.5Ox asymmetric membranes by modifying support-layer porous structure

    M Ikeguchi, K Ishii, Y Sekine, E Kikuchi, M Matsukata

    MATERIALS LETTERS   59 ( 11 ) 1356 - 1360  2005年05月

     概要を見る

    Disk-type SrFeCo0.50Ox, asymmetric membranes were prepared for high-temperature oxygen separation using both a previously reported solid state technique in which ethyl cellulose is introduced and then removed by calcination to produce a porous support layer and a modified technique in which carbon fiber is added to the ethyl cellulose. The oxygen permeabilities of the resulting SrFeCo0.50Ox asymmetric membranes were measured at 973-1173 K. The addition of carbon fiber to ethyl cellulose resulted in the improvement of gas diffusivity in the porous support layer, which increased the flux of oxygen through the modified asymmetric membrane. (c) 2005 Elsevier B.V. All rights reserved.

    DOI

    Scopus

    40
    被引用数
    (Scopus)
  • Catalytic activities and coking resistance of Ni/perovskites in steam reforming of methane

    K Urasaki, Y Sekine, S Kawabe, E Kikuchi, M Matsukata

    APPLIED CATALYSIS A-GENERAL   286 ( 1 ) 23 - 29  2005年05月

     概要を見る

    Steam reforming of methane for the purpose of hydrogen production was performed using nickel catalysts supported on a variety of perovskites, including LaAlO3, LaFeO3, SrTiO3, BaTiO3, La0.4Ba0.6Co0.2Fe0.8O3-delta, to compare the catalytic activity and resistance to coking of these catalysts to those of the conventional Ni/alpha-Al2O3 catalyst. Ni/LaAlO3 and Ni/SrTiO3 showed high catalytic activities among the Ni/perovskites and longer-term stabilities than the conventional catalyst. Temperature programmed oxidation of carbon deposited on used catalysts revealed that inactive carbon species detected on Ni/alpha-Al2O3 were not formed in the case of Ni/LaAlO3. The results of temperature programmed reduction confirmed that consumption and recovery of the lattice oxygen in perovskites occurred during the reaction, and that the reducibility of perovskites had a great impact on the steam reforming activity. The lattice oxygen in perovskites is considered to play important roles in promoting the oxidation of CH, fragments adsorbed on metallic nickel. (c) 2005 Published by Elsevier B.V.

    DOI

    Scopus

    149
    被引用数
    (Scopus)
  • Standardization of catalyst preparation using reference catalyst: ion exchange of mordenite type zeolite - 2. Origin of dealumination and recommended standard conditions

    N Katada, T Takeguchi, T Suzuki, T Fukushima, K Inagaki, S Tokunaga, H Shimada, K Sato, Y Oumi, T Sano, K Segawa, K Nakai, H Shoji, P Wu, T Tatsumi, T Komatsu, T Masuda, K Domen, E Yoda, JN Kondo, T Okuhara, T Kanai, M Niwa, M Ogura, M Matsukata, E Kikuchi, N Okazaki, M Takahashi, A Tada, S Tawada, Y Kubota, Y Sugi, Y Higashio, M Kamada, Y Kioka, K Yamamoto, T Shouji, S Satokawa, Y Arima, Y Okamoto, H Matsumoto

    APPLIED CATALYSIS A-GENERAL   283 ( 1-2 ) 75 - 84  2005年04月

     概要を見る

    The undesired structural change of mordenite with Si/Al-2 = 15 during the ion exchange and during calcination from the sodium form into proton form, especially the dealumination after the calcination, was studied. The Si-29 NMR results clarified that calcination of the NH4-form mordenite with Si/Al-2 = 15 at &gt; ca. 800 K, followed by the contact of proton-form sample with the atmosphere containing humidity, induced the dealumination. However, the samples carefully kept free from humidity after the heat treatment showed no dealumination or only a low degree of it. The Al-27 NMR and ammonia TPD results agreed with these findings. The origin of dealumination is thus considered to be the contact of the proton-form sample with humidity after the calcination. On the other hand, the dealumination was not observed after calcination at &lt; 673 K. The H-1 NMR indicated that the ca. 1/3 of the ion-exchange sites were blocked by the ammonium cations after calcination at 673 K, suggesting that the dealumination was prevented by the ammonium cations. On the basis of these findings, a standard set of conditions in which one can safely prepare the proton-form zeolite with high quality is proposed. The recommended temperature for the ion exchange is room temperature, because it is high enough to exchange the ions in this case. The most important variable is the calcination temperature; it should be lower than 673 K in order to avoid the dealumination. These conditions were confirmed to yield zeolites with a high framework aluminum content and ordinary catalytic performance. (c) 2005 Elsevier B.V. All rights reserved.

    DOI

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    14
    被引用数
    (Scopus)
  • Standardization of catalyst preparation using reference catalyst: ion exchange of mordenite type zeolite - 1. Remarkable dealumination accompanying ion exchange

    N Katada, T Takeguchi, T Suzuki, T Fukushima, K Inagaki, S Tokunaga, H Shimada, K Sato, Y Oumi, T Sano, K Segawa, K Nakai, H Shoji, P Wu, T Tatsumi, T Komatsu, T Masuda, K Domen, E Yoda, JN Kondo, T Okuhara, Y Kageyama, M Niwa, M Ogura, M Matsukata, E Kikuchi, N Okazaki, M Takahashi, A Tada, S Tawada, Y Kubota, Y Sugi, Y Higashio, M Kamada, Y Kioka, K Yamamoto, T Shouji, Y Arima, Y Okamoto, H Matsumoto

    APPLIED CATALYSIS A-GENERAL   283 ( 1-2 ) 63 - 74  2005年04月

     概要を見る

    A joint study was organized to establish a standard set of conditions for the ion exchange of zeolite from sodium into proton-form. The sodium-form mordenite with Si/Al-2 = ca. 15 was ion exchanged into an NH4-form, followed by calcination according to various recipes. Then various advanced techniques for characterization (ICP, TG, XPS, SEM, XRD, N-2 adsorption Si-29 and Al-27 NMR, benzene diffusion, IR of OH and adsorbed pyridine and CO, ammonia TPD) were applied. and some test reactions (cracking of cumene, isopropylation of biphenyl, oligomerization of propene and chichibabin condensation of acetaldehyde and ammonia into picoline) were conducted. The ion exchange (removal of sodium) proceeded as expected, but remarkable differences were observed in physicochemical and catalytic properties of the thus-prepared proton-form samples. Exceptionally high temperature (383 K) for the ion exchange resulted in the structural degradation, while most samples exchanged at 333-353 K maintained the crystallinity and pore volume. The use of NH4Cl slightly changed the crystal morphology. Extra-framework aluminum species was formed on most samples after calcination above 773 K. In contrast, calcination at 673 K maintained the framework aluminum. Therefore, the dealumination is considered to proceed after complete removal of ammonia from the ammonium-form zeolite. However, the proton-form zeolite was stable under dry conditions, so it is speculated that the dealumination was induced by the contact of the proton-form zeolite to atmosphere with humidity. The total and Bronsted acidity decreased with the dealumination, while Lewis acidity increased. On the other hand, rapid heating of the ammonium type zeolite caused narrowing of the micropores. These structural changes seriously affected the catalytic activities for various reactions. (c) 2005 Elsevier B.V. All rights reserved.

    DOI

    Scopus

    17
    被引用数
    (Scopus)
  • Standardization of catalyst preparation using reference catalyst: ion exchange of mordenite type zeolite - 2. Origin of dealumination and recommended standard conditions

    N Katada, T Takeguchi, T Suzuki, T Fukushima, K Inagaki, S Tokunaga, H Shimada, K Sato, Y Oumi, T Sano, K Segawa, K Nakai, H Shoji, P Wu, T Tatsumi, T Komatsu, T Masuda, K Domen, E Yoda, JN Kondo, T Okuhara, T Kanai, M Niwa, M Ogura, M Matsukata, E Kikuchi, N Okazaki, M Takahashi, A Tada, S Tawada, Y Kubota, Y Sugi, Y Higashio, M Kamada, Y Kioka, K Yamamoto, T Shouji, S Satokawa, Y Arima, Y Okamoto, H Matsumoto

    APPLIED CATALYSIS A-GENERAL   283 ( 1-2 ) 75 - 84  2005年04月

     概要を見る

    The undesired structural change of mordenite with Si/Al-2 = 15 during the ion exchange and during calcination from the sodium form into proton form, especially the dealumination after the calcination, was studied. The Si-29 NMR results clarified that calcination of the NH4-form mordenite with Si/Al-2 = 15 at &gt; ca. 800 K, followed by the contact of proton-form sample with the atmosphere containing humidity, induced the dealumination. However, the samples carefully kept free from humidity after the heat treatment showed no dealumination or only a low degree of it. The Al-27 NMR and ammonia TPD results agreed with these findings. The origin of dealumination is thus considered to be the contact of the proton-form sample with humidity after the calcination. On the other hand, the dealumination was not observed after calcination at &lt; 673 K. The H-1 NMR indicated that the ca. 1/3 of the ion-exchange sites were blocked by the ammonium cations after calcination at 673 K, suggesting that the dealumination was prevented by the ammonium cations. On the basis of these findings, a standard set of conditions in which one can safely prepare the proton-form zeolite with high quality is proposed. The recommended temperature for the ion exchange is room temperature, because it is high enough to exchange the ions in this case. The most important variable is the calcination temperature; it should be lower than 673 K in order to avoid the dealumination. These conditions were confirmed to yield zeolites with a high framework aluminum content and ordinary catalytic performance. (c) 2005 Elsevier B.V. All rights reserved.

    DOI

    Scopus

    14
    被引用数
    (Scopus)
  • Standardization of catalyst preparation using reference catalyst: ion exchange of mordenite type zeolite - 1. Remarkable dealumination accompanying ion exchange

    N Katada, T Takeguchi, T Suzuki, T Fukushima, K Inagaki, S Tokunaga, H Shimada, K Sato, Y Oumi, T Sano, K Segawa, K Nakai, H Shoji, P Wu, T Tatsumi, T Komatsu, T Masuda, K Domen, E Yoda, JN Kondo, T Okuhara, Y Kageyama, M Niwa, M Ogura, M Matsukata, E Kikuchi, N Okazaki, M Takahashi, A Tada, S Tawada, Y Kubota, Y Sugi, Y Higashio, M Kamada, Y Kioka, K Yamamoto, T Shouji, Y Arima, Y Okamoto, H Matsumoto

    APPLIED CATALYSIS A-GENERAL   283 ( 1-2 ) 63 - 74  2005年04月

     概要を見る

    A joint study was organized to establish a standard set of conditions for the ion exchange of zeolite from sodium into proton-form. The sodium-form mordenite with Si/Al-2 = ca. 15 was ion exchanged into an NH4-form, followed by calcination according to various recipes. Then various advanced techniques for characterization (ICP, TG, XPS, SEM, XRD, N-2 adsorption Si-29 and Al-27 NMR, benzene diffusion, IR of OH and adsorbed pyridine and CO, ammonia TPD) were applied. and some test reactions (cracking of cumene, isopropylation of biphenyl, oligomerization of propene and chichibabin condensation of acetaldehyde and ammonia into picoline) were conducted. The ion exchange (removal of sodium) proceeded as expected, but remarkable differences were observed in physicochemical and catalytic properties of the thus-prepared proton-form samples. Exceptionally high temperature (383 K) for the ion exchange resulted in the structural degradation, while most samples exchanged at 333-353 K maintained the crystallinity and pore volume. The use of NH4Cl slightly changed the crystal morphology. Extra-framework aluminum species was formed on most samples after calcination above 773 K. In contrast, calcination at 673 K maintained the framework aluminum. Therefore, the dealumination is considered to proceed after complete removal of ammonia from the ammonium-form zeolite. However, the proton-form zeolite was stable under dry conditions, so it is speculated that the dealumination was induced by the contact of the proton-form zeolite to atmosphere with humidity. The total and Bronsted acidity decreased with the dealumination, while Lewis acidity increased. On the other hand, rapid heating of the ammonium type zeolite caused narrowing of the micropores. These structural changes seriously affected the catalytic activities for various reactions. (c) 2005 Elsevier B.V. All rights reserved.

    DOI

    Scopus

    17
    被引用数
    (Scopus)
  • Effect of a small amount of zirconia additive on the activity and stability of iron oxide during repeated redox cycles

    K Urasaki, Y Sekine, N Tanimoto, E Tamura, E Kikuchi, M Matsukata

    CHEMISTRY LETTERS   34 ( 2 ) 230 - 231  2005年02月  [査読有り]

     概要を見る

    Addition of an exceedingly small amount of zirconia onto iron oxide enhanced the activity for hydrogen production by the oxidation of partially reduced iron oxide. Sintering of iron oxide was also suppressed.

  • Influence of zirconia additive on the property of iron oxide during repeated redox cycles

    K. Urasaki, Y. Sekine, N. Tanimoto, E. Tamura, E. Kikuchi, M. Matsukata

    Chem. Lett.   34 ( 2 ) 230 - 231  2005年02月

    DOI

    Scopus

    8
    被引用数
    (Scopus)
  • Influence of zirconia additive on the property of iron oxide during repeated redox cycles

    K. Urasaki, Y. Sekine, N. Tanimoto, E. Tamura, E. Kikuchi, M. Matsukata

    Chem. Lett.   34 ( 2 ) 230 - 231  2005年02月

    DOI

    Scopus

    8
    被引用数
    (Scopus)
  • 7-2.廃棄物ガス化・燃焼における石灰石による塩素分の捕捉挙動((1)環境対策1,Session 7 環境対策・リサイクル)

    関根 泰, 宮井 裕一, 松澤 雅登, 菊地 英一, 松方 正彦

    日本エネルギー学会大会講演要旨集   14   326 - 327  2005年

    DOI CiNii

  • 5.石炭チャーの水蒸気ガス化における構造変化と反応性

    関根 泰, 石川 清宏, 菊地 英一, 松方 正彦, 秋本 明光

    石炭科学会議発表論文集   42   13 - 14  2005年

     概要を見る

    We examined the influence of carbonaceous structural change and ash behavior affecting reactivity. We developed a novel analysis method using LRS (Laser Raman Spectroscopy) and EDX (Energy Dispersive X-ray diffraction) for this examination. From these observations, Si and Al existence accorded with the rate of non-graphitic carbon at higher conversion of carbonaceous material. On the other hand, our previous results have shown that the ratio of graphitic carbon increases regardless of ash as gasification reactions proceed. Based on these results we inferred that Si and Al existence suppressed char conversion, so the reaction gas was unable to contact with the carbon. The effect of Fe for catalyst was also investigated and it showed catalytic activity for gasification in some cases.

    DOI CiNii

  • Rh/MgO触媒を用いたSm0.4Ba0.6Fe0.8Co0.2O3-δ膜反応器によるメタンの部分酸化

    池口 真之, 三村 知弘, 関根 泰, 菊地 英一, 松方 正彦

    化学工学会 研究発表講演要旨集   2005   355 - 355  2005年

    DOI CiNii

  • モルデナイト膜による高温・高圧下における水の選択的透過

    松方 正彦, 澤村 健一, 泉 輝明, 関根 泰, 菊地 英一, 佐藤 公則, 中根 尭, 渡邊 朋子

    化学工学会 研究発表講演要旨集   2005   362 - 362  2005年

    DOI CiNii

  • ZSM-5膜を用いた高温における水/メタノール/水素分離

    松方 正彦, 澤村 健一, 泉 輝明, 関根 泰, 菊地 英一, 佐藤 公則, 中根 尭, 渡邊 朋子

    化学工学会 研究発表講演要旨集   2005   363 - 363  2005年

    DOI CiNii

  • Synthesis of organic-inorganic hybrid mesoporous tin oxophosphate in the presence of anionic surfactant

    NK Mal, M Fujiwara, M Matsukata

    CHEMICAL COMMUNICATIONS   ( 41 ) 5199 - 5201  2005年

     概要を見る

    Synthesis of novel mesoporous hybrid tin oxophosphate is reported from phenylphosphonic acid as the only precursor of phosphorus in the presence of anionic surfactant (SDS), which possesses a wormhole mesoporous structure and is stable even after calcination at 550 degrees C.

    DOI

    Scopus

    21
    被引用数
    (Scopus)
  • Rapid crystallization of Si-MCM-41 under Na-free conditions

    S Inagaki, Y Aratani, Y Sekine, E Kikuchi, M Matsukata

    MOLECULAR SIEVES: FROM BASIC RESEARCH TO INDUSTRIAL APPLICATIONS, PTS A AND B   158   533 - 540  2005年

     概要を見る

    Rapid synthesis of Si-MCM-41 was accomplished in successive two steps; (1) aging of a Mixture of silica, hexadecylammonium bromide and water with ail aqueous ammonia solution for a short period of 30 min, and (2) successive evaporation-to-dryness of the resultant mixture at 80 degrees C in about 2 h. The yield of Si-MCM-41 reached 99% after calcination at 550 degrees C. The product obtained by this method gave a well-ordered 2d-hexagonal structure with high thermal stability and water-resistance. It was noteworthy that the d(100) value of calcined Si-MCM-41 was almost the same as that of as-made Si-MCM-41, suggesting that pore wall of as-made product was dense and rigid.

  • Progress of crystallization into zeolite beta in the absence of steam

    S Inagaki, K Nakatsuyama, E Kikuchi, M Matsukata

    MOLECULAR SIEVES: FROM BASIC RESEARCH TO INDUSTRIAL APPLICATIONS, PTS A AND B   158   343 - 350  2005年

     概要を見る

    The role of steam oil the crystallization of zeolite beta by the steam-assisted crystallization (SAC) method was studied. It was found that after an aluminosilicate dry gel with SiO2/Al2O3 molar ratio = 100 was treated with steam in an autoclave at 130 degrees C and autogenous pressure, thermal treatment of a resultant product at 130 degrees C without the addition of water in an autoclave gave zeolite beta with a high crystallinity. Zeolite beta obtained by this method consisted of nano-particles with a diameter of ca. 30 nm. It was presumed that intermediates of zeolite beta was formed during steam treatment, and the dehydration between silanols in the intermediates during the thermal treatment in the absence of steam possibly caused the transformation from ill-ordered structures to zeolite beta crystals with a periodicity in long-range order.

  • New evaluation method of carbonaceous structure on coal steam gasification

    Y Sekine, K Ishikawa, E Kikuchi, M Matsukata

    ENERGY & FUELS   19 ( 1 ) 326 - 327  2005年01月

    DOI

    Scopus

    24
    被引用数
    (Scopus)
  • Growth mechanism of a preferentially oriented mordenite membrane

    Gang Li, Rui-Sen Lin, Eiichi Kikuchi, Masahiko Matsukata

    Journal of Zhejiang University: Science   6 ( 5 ) 369 - 372  2005年

     概要を見る

    A preferentially oriented mordenite membrane was successfully prepared on a seeded porous α-alumina support. Characterization results of XRD (X-ray diffractometer) and FE-SEM (field emission scanning electron microscope) revealed that evolutionary selection might predominantly contribute to the formation of the sharply oriented mordenite membrane. The necessary conditions under which evolutionary selection occurs are: (a) the number density of nuclei on the support surface should be high enough at the early stage
    (b) the crystals should grow fastest along one direction
    and (c) the zeolite layer should proceed via the successive growth of the crystals nucleated on the support surface instead of the accumulation of the crystals formed in the bulk solution.

    DOI

    Scopus

    3
    被引用数
    (Scopus)
  • A novel method for hydrogen production from liquid ethanol/water at room temperature

    Y Sekine, K Urasaki, S Asai, M Matsukata, E Kikuchi, S Kado

    CHEMICAL COMMUNICATIONS   ( 1 ) 78 - 79  2005年

     概要を見る

    We demonstrated that non-catalytic ethanol steam reforming proceeds efficiently and selectively without coking at the conditions of room temperature and atmospheric pressure using low-energy pulsed (LEP) discharge in combination with carbon fiber electrodes.

    DOI

    Scopus

    35
    被引用数
    (Scopus)
  • Synthesis of organic-inorganic hybrid mesoporous tin oxophosphate in the presence of anionic surfactant

    NK Mal, M Fujiwara, M Matsukata

    CHEMICAL COMMUNICATIONS   ( 41 ) 5199 - 5201  2005年

     概要を見る

    Synthesis of novel mesoporous hybrid tin oxophosphate is reported from phenylphosphonic acid as the only precursor of phosphorus in the presence of anionic surfactant (SDS), which possesses a wormhole mesoporous structure and is stable even after calcination at 550 degrees C.

    DOI

    Scopus

    21
    被引用数
    (Scopus)
  • Rapid crystallization of Si-MCM-41 under Na-free conditions

    S Inagaki, Y Aratani, Y Sekine, E Kikuchi, M Matsukata

    MOLECULAR SIEVES: FROM BASIC RESEARCH TO INDUSTRIAL APPLICATIONS, PTS A AND B   158   533 - 540  2005年

     概要を見る

    Rapid synthesis of Si-MCM-41 was accomplished in successive two steps; (1) aging of a Mixture of silica, hexadecylammonium bromide and water with ail aqueous ammonia solution for a short period of 30 min, and (2) successive evaporation-to-dryness of the resultant mixture at 80 degrees C in about 2 h. The yield of Si-MCM-41 reached 99% after calcination at 550 degrees C. The product obtained by this method gave a well-ordered 2d-hexagonal structure with high thermal stability and water-resistance. It was noteworthy that the d(100) value of calcined Si-MCM-41 was almost the same as that of as-made Si-MCM-41, suggesting that pore wall of as-made product was dense and rigid.

  • Progress of crystallization into zeolite beta in the absence of steam

    S Inagaki, K Nakatsuyama, E Kikuchi, M Matsukata

    MOLECULAR SIEVES: FROM BASIC RESEARCH TO INDUSTRIAL APPLICATIONS, PTS A AND B   158   343 - 350  2005年

     概要を見る

    The role of steam oil the crystallization of zeolite beta by the steam-assisted crystallization (SAC) method was studied. It was found that after an aluminosilicate dry gel with SiO2/Al2O3 molar ratio = 100 was treated with steam in an autoclave at 130 degrees C and autogenous pressure, thermal treatment of a resultant product at 130 degrees C without the addition of water in an autoclave gave zeolite beta with a high crystallinity. Zeolite beta obtained by this method consisted of nano-particles with a diameter of ca. 30 nm. It was presumed that intermediates of zeolite beta was formed during steam treatment, and the dehydration between silanols in the intermediates during the thermal treatment in the absence of steam possibly caused the transformation from ill-ordered structures to zeolite beta crystals with a periodicity in long-range order.

  • New evaluation method of carbonaceous structure on coal steam gasification

    Y Sekine, K Ishikawa, E Kikuchi, M Matsukata

    ENERGY & FUELS   19 ( 1 ) 326 - 327  2005年01月

    DOI

    Scopus

    24
    被引用数
    (Scopus)
  • Growth mechanism of a preferentially oriented mordenite membrane

    Gang Li, Rui-Sen Lin, Eiichi Kikuchi, Masahiko Matsukata

    Journal of Zhejiang University: Science   6 ( 5 ) 369 - 372  2005年

     概要を見る

    A preferentially oriented mordenite membrane was successfully prepared on a seeded porous α-alumina support. Characterization results of XRD (X-ray diffractometer) and FE-SEM (field emission scanning electron microscope) revealed that evolutionary selection might predominantly contribute to the formation of the sharply oriented mordenite membrane. The necessary conditions under which evolutionary selection occurs are: (a) the number density of nuclei on the support surface should be high enough at the early stage
    (b) the crystals should grow fastest along one direction
    and (c) the zeolite layer should proceed via the successive growth of the crystals nucleated on the support surface instead of the accumulation of the crystals formed in the bulk solution.

    DOI

    Scopus

    3
    被引用数
    (Scopus)
  • A novel method for hydrogen production from liquid ethanol/water at room temperature

    Y Sekine, K Urasaki, S Asai, M Matsukata, E Kikuchi, S Kado

    CHEMICAL COMMUNICATIONS   ( 1 ) 78 - 79  2005年

     概要を見る

    We demonstrated that non-catalytic ethanol steam reforming proceeds efficiently and selectively without coking at the conditions of room temperature and atmospheric pressure using low-energy pulsed (LEP) discharge in combination with carbon fiber electrodes.

    DOI

    Scopus

    35
    被引用数
    (Scopus)
  • A compact ZSM-5 membrane prepared without structure-directing agent

    G. Li, E. Kikuchi, M. Matsukata

    Stud. Surf. Sci. Catal.   154   620 - 625  2005年

  • Hydrogen production from ethanol using low energy pulse discharge at ambient temperature

    Y. Sekine, M. Matsukata, E. Kikuchi, S. Kado, F. Haga

    ACS Division of Fuel Chemistry, Preprints   49 ( 2 ) 914 - 915  2004年09月  [査読有り]

     概要を見る

    Fuel cell is attracting attention, especially polymer electrolyte membrane fuel cell. However, hydrogen production and transportation processes have many problems with the present technology so innovative technological methods to produce hydrogen are needed. Low energy pulse discharge was used for this goal. The energy efficiency was improved because the liquid phase reactor did not require a heater which is needed to vaporize the mixture of water and ethanol. Any pump supplying the liquid into the reactor was not required. So the liquid phase reactor made the process scale reduced, and also made the device size compact without spoiling its function. This process would be very useful for room temperature hydrogen formation system.

  • Synthesis of MCM-41-type mesoporous materials using filtrate of alkaline dissolution of ZSM-5 zeolite

    S. Inagaki, M. Ogura, T. Inami, Y. Sasaki, E. Kikuchi, M. Matsukata

    Micropor. Mesopor. Mater.   74 ( 1月3日 ) 163 - 170  2004年09月

    DOI

  • Structure and Reactivity of Coal Char on Steam Gasification

    Twenty-First Annual International Pittsburgh Coal Conference   Osaka, Japan  2004年09月

  • Hydrogen Production from Biomass-Ethanol at Ambient Temperature with Novel Diaphragm Reactor

    Twenty-First Annual International Pittsburgh Coal Conference   Osaka, Japan  2004年09月

  • Behavior of Trace Element on Steam Gasification of Coal Char

    Twenty-First Annual International Pittsburgh Coal Conference   Osaka, Japan  2004年09月

  • Synthesis of MCM-41-type mesoporous materials using filtrate of alkaline dissolution of ZSM-5 zeolite

    S Inagaki, M Ogura, T Inami, Y Sasaki, E Kikuchi, M Matsukata

    MICROPOROUS AND MESOPOROUS MATERIALS   74 ( 1-3 ) 163 - 170  2004年09月

     概要を見る

    MCM-41-type mesoporous materials possessing strong Bronsted acidity originated from ZSM-5 zeolite were synthesized by using soluble aluminosilicate species containing the fragments of the structure of ZSM-5 zeolite. The thermal stability of the mesoporous structure of the obtained mesoporous material was enhanced by the post-treatment with an ammonium aqueous solution. These results suggest an important role of alkalinity of slurries on the following two processes; (1) alkaline dissolution of ZSM-5 zeolite and (2) formation of mesoporous structure. These successive processes were efficiently improved by use of a continuous-flow reactor. The mesoporous material synthesized in the continuous-flow reactor catalyzed the cracking of cumene at 523 K, while a conventional Al-MCM-41 hardly catalyzed. The mesoporous material synthesized by using the filtrate of alkaline dissolution of ZSM-5 possessed a stronger Bronsted acidity than a conventional Al-MCM-41. (C) 2004 Elsevier Inc. All rights reserved.

    DOI

  • Synthesis of MCM-41-type mesoporous materials using filtrate of alkaline dissolution of ZSM-5 zeolite

    S Inagaki, M Ogura, T Inami, Y Sasaki, E Kikuchi, M Matsukata

    MICROPOROUS AND MESOPOROUS MATERIALS   74 ( 1-3 ) 163 - 170  2004年09月

     概要を見る

    MCM-41-type mesoporous materials possessing strong Bronsted acidity originated from ZSM-5 zeolite were synthesized by using soluble aluminosilicate species containing the fragments of the structure of ZSM-5 zeolite. The thermal stability of the mesoporous structure of the obtained mesoporous material was enhanced by the post-treatment with an ammonium aqueous solution. These results suggest an important role of alkalinity of slurries on the following two processes; (1) alkaline dissolution of ZSM-5 zeolite and (2) formation of mesoporous structure. These successive processes were efficiently improved by use of a continuous-flow reactor. The mesoporous material synthesized in the continuous-flow reactor catalyzed the cracking of cumene at 523 K, while a conventional Al-MCM-41 hardly catalyzed. The mesoporous material synthesized by using the filtrate of alkaline dissolution of ZSM-5 possessed a stronger Bronsted acidity than a conventional Al-MCM-41. (C) 2004 Elsevier Inc. All rights reserved.

    DOI

  • Structure and Reactivity of Coal Char on Steam Gasification

    Twenty-First Annual International Pittsburgh Coal Conference   Osaka, Japan  2004年09月

  • Behavior of Trace Element on Steam Gasification of Coal Char

    Twenty-First Annual International Pittsburgh Coal Conference   Osaka, Japan  2004年09月

  • Synthesis of MCM-41-type mesoporous materials using filtrate of alkaline dissolution of ZSM-5 zeolite

    S Inagaki, M Ogura, T Inami, Y Sasaki, E Kikuchi, M Matsukata

    MICROPOROUS AND MESOPOROUS MATERIALS   74 ( 1-3 ) 163 - 170  2004年09月

     概要を見る

    MCM-41-type mesoporous materials possessing strong Bronsted acidity originated from ZSM-5 zeolite were synthesized by using soluble aluminosilicate species containing the fragments of the structure of ZSM-5 zeolite. The thermal stability of the mesoporous structure of the obtained mesoporous material was enhanced by the post-treatment with an ammonium aqueous solution. These results suggest an important role of alkalinity of slurries on the following two processes; (1) alkaline dissolution of ZSM-5 zeolite and (2) formation of mesoporous structure. These successive processes were efficiently improved by use of a continuous-flow reactor. The mesoporous material synthesized in the continuous-flow reactor catalyzed the cracking of cumene at 523 K, while a conventional Al-MCM-41 hardly catalyzed. The mesoporous material synthesized by using the filtrate of alkaline dissolution of ZSM-5 possessed a stronger Bronsted acidity than a conventional Al-MCM-41. (C) 2004 Elsevier Inc. All rights reserved.

    DOI

  • Hydrogen production from ethanol using low energy pulse discharge at ambient temperature.

    S Yasushi, M Masahiko, E Kikuchi, S Kado, F Haga

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   228   U683 - U683  2004年08月

  • Hydrogen production from ethanol using low energy pulse discharge at ambient temperature.

    S Yasushi, M Masahiko, E Kikuchi, S Kado, F Haga

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   228   U683 - U683  2004年08月

  • Recent Advances of Zeolite Membrane Technologies for Dehydration

    3rd International Zeolite Membrane Meeting   Breckenridge、Co  2004年07月

  • Influence of Microstructure on Gas Separation Properties of High-Silica MFI Zeolite Membrane

    8th International Conference on Inorganic Membranes (ICIM8)   Cincinatti, USA  2004年07月

  • Recent Advances of Zeolite Membrane Technologies for Dehydration

    3rd International Zeolite Membrane Meeting   Breckenridge、Co  2004年07月

  • Influence of Microstructure on Gas Separation Properties of High-Silica MFI Zeolite Membrane

    8th International Conference on Inorganic Membranes (ICIM8)   Cincinatti, USA  2004年07月

  • Textural and catalytic properties of MCM-22 zeolite crystallized by the vapor-phase transport method

    S Inagaki, K Kamino, M Hoshino, E Kikuchi, M Matsukata

    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN   77 ( 6 ) 1249 - 1254  2004年06月

     概要を見る

    MCM-22 zeolite crystallized by the vapor-phase transport (VPT) method showed a higher shape-selectivity to p-xylene in the alkylation of toluene with methanol, compared with MCM-22 crystallized by the hydrothermally synthetic (HTS) method, because VPT-MCM-22 has a smaller external surface area and a smaller number of acid sites thereon than HTS-MCM-22. Such textural properties of VPT-MCM-22 are caused by the fact that the spherical particles of VPT-MCM-22 are composed of hexagonal plates as thin as 55 nm; they are larger than those of HTS-MCM-22, which are 30 nm thick. The acidic properties, characterized by NH3-TPD and FT-IR using a pyridine adsorption technique, showed no significant difference between VPT- and HTS-MCM-22, except for the acidity on the external surface.

    DOI

    Scopus

    13
    被引用数
    (Scopus)
  • Textural and catalytic properties of MCM-22 zeolite crystallized by the vapor-phase transport method

    S Inagaki, K Kamino, M Hoshino, E Kikuchi, M Matsukata

    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN   77 ( 6 ) 1249 - 1254  2004年06月

     概要を見る

    MCM-22 zeolite crystallized by the vapor-phase transport (VPT) method showed a higher shape-selectivity to p-xylene in the alkylation of toluene with methanol, compared with MCM-22 crystallized by the hydrothermally synthetic (HTS) method, because VPT-MCM-22 has a smaller external surface area and a smaller number of acid sites thereon than HTS-MCM-22. Such textural properties of VPT-MCM-22 are caused by the fact that the spherical particles of VPT-MCM-22 are composed of hexagonal plates as thin as 55 nm; they are larger than those of HTS-MCM-22, which are 30 nm thick. The acidic properties, characterized by NH3-TPD and FT-IR using a pyridine adsorption technique, showed no significant difference between VPT- and HTS-MCM-22, except for the acidity on the external surface.

    DOI

    Scopus

    13
    被引用数
    (Scopus)
  • Zeolite Membrane for High Temperature Gas Separation

    2nd Conference of Aseanian Membrane Society   Seoul, Korea  2004年05月

  • Zeolite Membrane for High Temperature Gas Separation

    2nd Conference of Aseanian Membrane Society   Seoul, Korea  2004年05月

  • Rapid synthesis of MCM-41

    14th International Zeolite Conference   Cape Town, South Africa  2004年04月

  • Hydrovapothermal conversion of tetraethoxysilane vapor to polycrystalline zeolite layer by in situ gelation

    A Mitra, S Ichikawa, E Kikuchi, M Matsukata

    CHEMICAL COMMUNICATIONS   2004 ( 7 ) 900 - 901  2004年04月

     概要を見る

    Zeolite membrane has been fabricated on porous alumina substrate in a single continuous process of gelation and subsequent crystallization while suppressing nucleation of zeolite powder in the bulk.

    DOI

    Scopus

    6
    被引用数
    (Scopus)
  • Rapid synthesis of MCM-41

    14th International Zeolite Conference   Cape Town, South Africa  2004年04月

  • Hydrovapothermal conversion of tetraethoxysilane vapor to polycrystalline zeolite layer by in situ gelation

    A Mitra, S Ichikawa, E Kikuchi, M Matsukata

    CHEMICAL COMMUNICATIONS   2004 ( 7 ) 900 - 901  2004年04月

     概要を見る

    Zeolite membrane has been fabricated on porous alumina substrate in a single continuous process of gelation and subsequent crystallization while suppressing nucleation of zeolite powder in the bulk.

    DOI

    Scopus

    6
    被引用数
    (Scopus)
  • Nonequilibrium pulsed discharge: A novel method for steam reforming of hydrocarbons or alcohols

    Y Sekine, K Urasaki, S Kado, M Matsukata, E Kikuchi

    ENERGY & FUELS   18 ( 2 ) 455 - 459  2004年03月  [査読有り]

     概要を見る

    Steam reforming of methane, propane, hexane, cyclohexane, methanol, and ethanol using a nonequilibrium pulsed discharge was investigated under the conditions of atmospheric pressure and low temperature (393 K) without the use of catalyst. In each case, steam reforming proceeded efficiently and selectively and hydrogen was formed as a main product. Although the steam/ carbon ratio was 1, there were trace amounts of carbon deposition or wax formation. The energy injection for the discharge region calculated by current and voltage waveforms measured by a digital signal oscilloscope was very small. As compared with the conventional catalytic steam reforming process, this method has some advantages such as fast start-up, quick response, and miniaturization and simplification of a hydrogen production system. Therefore we consider that the hydrogen production system employing a nonequilibrium pulsed discharge has a potential for being an effective way for supplying hydrogen or syngas.

    DOI

    Scopus

    47
    被引用数
    (Scopus)
  • Separation of C6 Isomers through a High Silica MFI-type Zeolite Membrane

    Kaneshiro Jun, Matsukata Masahiko, Sekine Yasushi, Kikuchi Eiichi

    アジア・太平洋化学工学会議発表論文要旨集   2004   740 - 740  2004年

     概要を見る

    In this study, a compact MFI-type zeolite membrane was prepared by a secondary growth method. Seed crystals of MFI-type zeolite were hydrothermally synthesized at 135°C and recovered by centrifugation. A porous alumina tube was used as a support and seeded by dip coating using a slurry of the seeds. Hydrothermal treatment was carried out at 125°C for 24 h to grow a thin layer of MFI-type zeolite on the support. The separation of an equimolar mixtures of C6 hydrocarbon isomers, n-hexane, 2-methylpentane and 2,2-dimethylbutane, was carried out by a vapor permeation method. As a result of separation tests, the membrane showed a high n-Hex selectivity at 100°C. The permeation tests using the binary mixtures of n-Hex/2,2-DMB and n-Hex/2-MP and using the unary systems of these three kinds of molecules were carried out to explain that the appearance of the permselectivity to n-Hex. Molecular sieving effect caused the appearance of the permselectivity to n-Hex against 2,2-DMB and preferential adsorption of n-Hex enhanced its permselectivity. In the case of the selectivity of n-Hex against 2-MP, both differences in the amounts of adsorption and diffusion coefficients of C6 isomers may contribute to determining the permeances of C6 isomers.

    DOI CiNii

  • Synthesis of Faujasite-Type Zeolite from Coal Fly Ash

    Kawamoto Hideto, Matsukata Masahiko, Ito Mitsuhiro, Kikuchi Eiichi

    アジア・太平洋化学工学会議発表論文要旨集   2004   852 - 852  2004年

     概要を見る

    Hydrothermal synthesis of faujasite-type (FAU) zeolite using a coal fly ash was investigated while rotating. We discussed that the formation of FAU from coal fly ash was influenced by four synthetic factors as follows; 1) the addition of FAU seeds, 2) the addition of an aluminum source, 3) alkalinity of synthetic mixture and 4) crystallization temperature in the temperature range of 90 to 120°C. The addition of FAU seeds in the synthetic mixture was essential for the formation of FAU, otherwise GIS-type zeolite (GIS), an undesired by-product, was simultaneously formed. Higher alkaline conditions using aqueous NaOH solution (3 N) gave a higher yield of FAU (45.4 wt%). The highest yield of FAU (56.7 wt%) was obtained with the addition of 1.4 mmol (g-coal)-1 of aluminum in 3N-aqueous NaOH solution. A further increasing amount of the addition of aluminum resulted in increasing yields of sodalite (SOD) and LTA-type zeolite (LTA). The induction period of the formation of GIS was longer at the lower crystallization temperature of 90°C.

    DOI CiNii

  • High Temperature Separation of Water/Hydrogen Mixtures through Mordenite Membrane

    Sawamura Kenichi, Matsukata Masahiko, Sekine Yasusi, Kikuchi Eiichi, Sato Kiminori, Nakane Takashi, Ichikawa Shinichi, Suzuki Shinichi

    アジア・太平洋化学工学会議発表論文要旨集   2004   208 - 208  2004年

     概要を見る

    Separation properties of mordenite membrane for water-methanol-hydrogen mixtures were studied in the temperature range from 150 to 250°C under pressurized conditions. Mordenite is a kind of large pore zeolites with a pore diameter of 0.65 x 0.70 nm. Mordenite membrane was prepared on the outer surface of a porous alumina tubular support by a secondary-growth method. We found that water was selectively permeated through the membrane. The separation factors of water/hydrogen and water/methanol were 49 and 73, respectively, at 250°C. When only hydrogen was fed at 5 atm, its permeance was as low as 10-9 mol m-2 s-1 Pa-1 up to about 220°C, possibly suggesting that water pre-adsorbed in the micropores of mordenite hindered the permeation of hydrogen. The hydrogen permeance, however, dramatically increased to 6.5 x 10-7 mol m-2 s-1 Pa-1 at 230°C and reached to 1.4 x 10-6 mol m-2 s-1 Pa-1 at 250°C owing to the formation of cracks in the membrane. It was, however, found that the membrane was thermally stabilized in the presence of steam and/or methanol.

    DOI CiNii

  • Development of Liquid Fuel Reformer using Low Energy Pulse (LEP) Discharge at Room Temperature

    Asai Shinjiro, Sekine Yasushi, Urasaki Kouhei, Kikuchi Eiichi, Matsukata Masahiko, Kado Shigeru

    アジア・太平洋化学工学会議発表論文要旨集   2004   255 - 255  2004年

     概要を見る

    We studied steam reforming of ethanol at room temperature and atmospheric pressure using low energy pulse (LEP) discharge. In this study, we employed characteristic novel reformer, one electrode was made of carbon fibers (o.d. 7.0µm) bundle. So fuel was supplied to discharge region by capillary action of the fibers and reformed directly by LEP plasma without any pump or heater. When using this reformer, at first, the fuel was evaporated by heat emission from electrode, and then the vaporized reactants were reacted. Produced gaseous compounds were collected from upper part of the reactor, and analyzed by gas chromatography. H2 and other compounds: CO, CH4, CO2, C2H4, and C2H6 were produced, and the formation rates were increased in proportion to the increase of the gap distance and input power. And compared to the former conventional reformer, the results were equivalent to the rates of gas phase reactor. The effects of ethanol concentration and of energy efficiency were studied, and the efficiency has reached 41.7 % at the ethanol concentration of 50 %, the discharge gap of 3.0 mm.

    DOI CiNii

  • Effect of Limestone on Cl Compounds Emission during Model-RDF Pyrolysis

    Miyai Yuichi, Sekine Yasushi, Matsuzawa M., Okutsu H., Kikuchi Eiichi, Matsukata Masahiko

    アジア・太平洋化学工学会議発表論文要旨集   2004   598 - 598  2004年

     概要を見る

    In this study, the reaction mechanism of limestone and Cl compounds was investigated by using fixed bed plug flow reactor. Trichloroethane(TCE) was identified as one of the Cl compounds emitting during the pyrolysis of model-RDF at 500°C 1), so TCE was chosen as the model compound of organic Cl compounds, and HCl was used as that of inorganic Cl compounds. Under any the partial pressure of steam, TCE and HCl were reacted with both CaO and Ca(OH)2. Products of each reaction were identified by X-ray diffraction. Moreover by changing the injection volume of Cl compounds, the Cl absorption mechanisms of CaO and Ca(OH)2 were investigated. The reaction of TCE with CaO was not observed. On the other hand, the product of TCE with Ca(OH)2 was identified as CaClOH. And when the volume of TCE injection was increased, only CaClOH was identified. So, no further dechlorination was occurred. The products of HCl reaction with CaO were identified as CaCl2 and CaCl2·2H2O. When the steam was added, the HCl reaction with Ca(OH)2 was occurred, the product was identified as CaClOH and when the injection volume of HCl was increased, identified as CaCl2, CaCl2·2H2O. That is to say, more dechlorination was occurred differently from TCE reactions with both CaO and Ca(OH)2. CaClOH was also proposed as a product of HCl reaction with CaO, because the reaction of CaO with H2O resulting from HCl reaction with CaO was occurred and the same time, HCl reaction with Ca(OH)2 was also occurred. At high temperature(800°C), the reaction of TCE with limestone was considered as the reaction of HCl generated from decomposition of TCE with limestone, and it was considered that both the reaction of TCE with Ca(OH)2 and that of HCl with CaO or Ca(OH)2 were occurred at 650°C.

    DOI CiNii

  • 2-22.Sm_<0.4>Ba_<0.6>Fe_<0.8>Co_<0.2>O_3膜反応器を用いたメタンの部分酸化((5)天然ガス転換利用I,Session 2 天然ガス・メタンハイドレート等)

    池口 真之, 蟹江 小五郎, 関根 泰, 菊地 英一, 松方 正彦

    日本エネルギー学会大会講演要旨集   13   96 - 97  2004年

    DOI CiNii

  • 4-2.常温で作動する液体燃料改質による水素製造プロセスの開発((1)水素,Session 4 新エネルギー)

    関根 泰, 浅井 慎二郎, 浦崎 浩平, 菊地 英一, 松方 正彦, 角 茂, 羽賀 史浩

    日本エネルギー学会大会講演要旨集   13   228 - 229  2004年

    DOI CiNii

  • 36.石炭チャー水蒸気ガス化における炭素構造の変化と反応性の相関

    関根 泰, 石川 清宏, 菊地 英一, 松方 正彦

    石炭科学会議発表論文集   41   77 - 78  2004年

     概要を見る

    In order to clarify the influence among ash behavior, carbonaceous structural change and char reactivity, the analysis method from a microscopic viewpoint was proposed. This novel method utilized overlaying both the distribution mapping of carbonaceous structure by LRS and the distribution mapping of elements by SEM/EDX. Consequently, the function of ash content on carbonaceous structure was clarified by this novel method.

    DOI CiNii

  • 16.石炭高温利用プロセスにおける微量金属の放出挙動

    関根 泰, 坂尻 邦尚, 井上 涼太, 菊地 英一, 松方 正彦

    石炭科学会議発表論文集   41   37 - 38  2004年

     概要を見る

    Four kinds of coal samples whose Cl-contents vary from 30ppm to 300ppm were pyrolyzed and burned, and the release behavior of Zn was examined. In the coal pyrolysis step, as the increase of Cl contents in coal, the release amounts of Zn also increased. It was considered that the generation of ZnCl2 was one reason for Zn emission. In the coal combustion, a part of Zn was released as ZnCl2 and the other part was remained in the ash as non-volatile ZnO, because some of Zn in the coal was reacted with Cl and others were oxidized during volatilization.

    DOI CiNii

  • Synthesis and characterization of microporous layered zirconium phenylphosphonate

    NK Mal, M Sasidharan, M Fujiwara, Y Yamada, M Matsukata

    RECENT ADVANCES IN THE SCIENCE AND TECHNOLOGY OF ZEOLITES AND RELATED MATERIALS, PTS A - C   154   1153 - 1159  2004年

     概要を見る

    Microporous layered zirconium phenylphosphonate, Zr(O3P-C6H5)(2) was prepared in presence of sodium dodecylsulfate (SDS), for the first time. Interplanar spacing (d(001)) and surface area of microporous zirconium phenylphosphonate are 1.47 nm and 198 m(2)g(-1), respectively. FT-IR spectrum indicates absence or negligible amount of hydroxyls groups ill zirconium phenylphosphonate sample. P-31 solid MAS NMR also confirms the presence of trace amount of hydroxyl groups in zirconium phenylphosphonate. The presence of tetra-coordinated phosphorous ions and hexa-coordinated zirconium ions were realized by the P-31 solid MAS NMR and UV-visible, respectively. Sulfonated derivative of zirconium phenylphosphonate, Zr(O3PC6H4SO3H)(1.9) (O3PC6H5)(0.1)center dot 3.7H(2)O were also prepared.

  • Reforming of n-hexane over Pt-tin silicalite-1

    NK Mal, M Sasidharan, M Matsukata, S Sivasanker, AV Ramaswamy

    RECENT ADVANCES IN THE SCIENCE AND TECHNOLOGY OF ZEOLITES AND RELATED MATERIALS, PTS A - C   154   2403 - 2410  2004年

     概要を見る

    The catalytic behavior of Pt supported on non-acidic silicalite-1 (MFI structure) and on the stannosilicate, Sn-sil-1 molecular sieves in the aromatization of n-hexane is investigated. The influence of Pt content, temperature, space velocity, H-2/n-hexane ratio and time on stream (TOS) on the n-hexane conversion, aromatic selectivity and aromatic yield are presented. Aromatics are the main products and this suggests that the aromatization proceeds via dehydrocyclization and/or hydrogenolysis, dehydrogenation to C-2-C-4 olefins followed by oligomerization inside the pores of the molecular sieve into cyclic intermediates in presence of hydrogen. The incorporation of Pt during the synthesis of the stannosilicate (Sn-sil-1) yields a more active catalyst (42 wt% aromatic selectivity) without any deactivation than when Pt is loaded by impregnation on Sn-sil-1 because catalyst deactivation associate with platinum outside the zeolite pores. A formation mechanism is proposed.

  • Modified TS-1 for shape selective phenol hydroxylation to hydroquinone

    NK Mal, P Kumar, M Sasidharan, M Matsukata

    RECENT ADVANCES IN THE SCIENCE AND TECHNOLOGY OF ZEOLITES AND RELATED MATERIALS, PTS A - C   154   2618 - 2625  2004年

     概要を見る

    A new method of modification of TS-1 by weak base (aqueous NH3) treatment leads to formation of bigger crystals and generation of internal hydroxyl groups as evident by SEM and IR (hydroxyl region). All the catalysts were characterized using, XRD, N-2-sorption, UV-VIS, FT-IR and SEM. Activity of the modified and unmodified TS-1 were compare in the hydroxylation of phenol to hydroquinone and catechol in presence of aqueous H2O2. A ratio of hydroquinone to catechol over modified,(TS-1 (33)/OH1 and unmodified, TS-1(33) catalysts were 1.40 and 1.15, respectively, using H2O as solvent, and 2.01 and 1.68, respectively, using MeOH as solvent. Modification of TS-1 with strong base (e.g. NaOH) causes decrease in crystallinity, and hence decreases the conversion of phenol and selectivity of hydroquinone. A new mechanism controlling the product selectivity is proposed.

  • A compact ZSM-5 membrane prepared without structure-directing agent

    G Li, E Kikuchi, M Matsukata

    RECENT ADVANCES IN THE SCIENCE AND TECHNOLOGY OF ZEOLITES AND RELATED MATERIALS, PTS A - C   154   620 - 625  2004年

     概要を見る

    Compact ZSM-5 zeolite membranes have been prepared on the outer surface of a porous alpha-alumina tub without structure-directing agents (SDAs) by the seed-assisted crystallization method. An SDA-free gel and an SDA-free clear solution were used for the membrane preparation, respectively. ZSM-5 membrane prepared from the SDA-free gel showed the H-2/i-C4H10 ideal selectivity of 13.8 at 200 degrees C, but it decreased to be 2.1 after the pretreatment at 300 degrees C, indicating the limited thermal stability of this kind of ZSM-5 membrane. On the other hand, ZSM-5 membranes prepared from the SDA-free clear solution showed high thermal stability and good separation properties. After the pretreatment at 400 degrees C, the H-2/i-C4H10 idea selectivity was as high as 61 at 270 degrees C. The maximum of the n/i-C4H10 ideal selectivity was 36 at 300 degrees C and the separation factor was as high as 12.7 at 400 degrees C for a 50/50 n/i-C4H10 mixture.

  • Synthesis and characterization of microporous layered zirconium phenylphosphonate

    NK Mal, M Sasidharan, M Fujiwara, Y Yamada, M Matsukata

    RECENT ADVANCES IN THE SCIENCE AND TECHNOLOGY OF ZEOLITES AND RELATED MATERIALS, PTS A - C   154   1153 - 1159  2004年

     概要を見る

    Microporous layered zirconium phenylphosphonate, Zr(O3P-C6H5)(2) was prepared in presence of sodium dodecylsulfate (SDS), for the first time. Interplanar spacing (d(001)) and surface area of microporous zirconium phenylphosphonate are 1.47 nm and 198 m(2)g(-1), respectively. FT-IR spectrum indicates absence or negligible amount of hydroxyls groups ill zirconium phenylphosphonate sample. P-31 solid MAS NMR also confirms the presence of trace amount of hydroxyl groups in zirconium phenylphosphonate. The presence of tetra-coordinated phosphorous ions and hexa-coordinated zirconium ions were realized by the P-31 solid MAS NMR and UV-visible, respectively. Sulfonated derivative of zirconium phenylphosphonate, Zr(O3PC6H4SO3H)(1.9) (O3PC6H5)(0.1)center dot 3.7H(2)O were also prepared.

  • Reforming of n-hexane over Pt-tin silicalite-1

    NK Mal, M Sasidharan, M Matsukata, S Sivasanker, AV Ramaswamy

    RECENT ADVANCES IN THE SCIENCE AND TECHNOLOGY OF ZEOLITES AND RELATED MATERIALS, PTS A - C   154   2403 - 2410  2004年

     概要を見る

    The catalytic behavior of Pt supported on non-acidic silicalite-1 (MFI structure) and on the stannosilicate, Sn-sil-1 molecular sieves in the aromatization of n-hexane is investigated. The influence of Pt content, temperature, space velocity, H-2/n-hexane ratio and time on stream (TOS) on the n-hexane conversion, aromatic selectivity and aromatic yield are presented. Aromatics are the main products and this suggests that the aromatization proceeds via dehydrocyclization and/or hydrogenolysis, dehydrogenation to C-2-C-4 olefins followed by oligomerization inside the pores of the molecular sieve into cyclic intermediates in presence of hydrogen. The incorporation of Pt during the synthesis of the stannosilicate (Sn-sil-1) yields a more active catalyst (42 wt% aromatic selectivity) without any deactivation than when Pt is loaded by impregnation on Sn-sil-1 because catalyst deactivation associate with platinum outside the zeolite pores. A formation mechanism is proposed.

  • Modified TS-1 for shape selective phenol hydroxylation to hydroquinone

    NK Mal, P Kumar, M Sasidharan, M Matsukata

    RECENT ADVANCES IN THE SCIENCE AND TECHNOLOGY OF ZEOLITES AND RELATED MATERIALS, PTS A - C   154   2618 - 2625  2004年

     概要を見る

    A new method of modification of TS-1 by weak base (aqueous NH3) treatment leads to formation of bigger crystals and generation of internal hydroxyl groups as evident by SEM and IR (hydroxyl region). All the catalysts were characterized using, XRD, N-2-sorption, UV-VIS, FT-IR and SEM. Activity of the modified and unmodified TS-1 were compare in the hydroxylation of phenol to hydroquinone and catechol in presence of aqueous H2O2. A ratio of hydroquinone to catechol over modified,(TS-1 (33)/OH1 and unmodified, TS-1(33) catalysts were 1.40 and 1.15, respectively, using H2O as solvent, and 2.01 and 1.68, respectively, using MeOH as solvent. Modification of TS-1 with strong base (e.g. NaOH) causes decrease in crystallinity, and hence decreases the conversion of phenol and selectivity of hydroquinone. A new mechanism controlling the product selectivity is proposed.

  • A compact ZSM-5 membrane prepared without structure-directing agent

    G Li, E Kikuchi, M Matsukata

    RECENT ADVANCES IN THE SCIENCE AND TECHNOLOGY OF ZEOLITES AND RELATED MATERIALS, PTS A - C   154   620 - 625  2004年

     概要を見る

    Compact ZSM-5 zeolite membranes have been prepared on the outer surface of a porous alpha-alumina tub without structure-directing agents (SDAs) by the seed-assisted crystallization method. An SDA-free gel and an SDA-free clear solution were used for the membrane preparation, respectively. ZSM-5 membrane prepared from the SDA-free gel showed the H-2/i-C4H10 ideal selectivity of 13.8 at 200 degrees C, but it decreased to be 2.1 after the pretreatment at 300 degrees C, indicating the limited thermal stability of this kind of ZSM-5 membrane. On the other hand, ZSM-5 membranes prepared from the SDA-free clear solution showed high thermal stability and good separation properties. After the pretreatment at 400 degrees C, the H-2/i-C4H10 idea selectivity was as high as 61 at 270 degrees C. The maximum of the n/i-C4H10 ideal selectivity was 36 at 300 degrees C and the separation factor was as high as 12.7 at 400 degrees C for a 50/50 n/i-C4H10 mixture.

  • Synthesis and characterization of microporous layered zirconium phenylphosphonate

    NK Mal, M Sasidharan, M Fujiwara, Y Yamada, M Matsukata

    RECENT ADVANCES IN THE SCIENCE AND TECHNOLOGY OF ZEOLITES AND RELATED MATERIALS, PTS A - C   154   1153 - 1159  2004年

     概要を見る

    Microporous layered zirconium phenylphosphonate, Zr(O3P-C6H5)(2) was prepared in presence of sodium dodecylsulfate (SDS), for the first time. Interplanar spacing (d(001)) and surface area of microporous zirconium phenylphosphonate are 1.47 nm and 198 m(2)g(-1), respectively. FT-IR spectrum indicates absence or negligible amount of hydroxyls groups ill zirconium phenylphosphonate sample. P-31 solid MAS NMR also confirms the presence of trace amount of hydroxyl groups in zirconium phenylphosphonate. The presence of tetra-coordinated phosphorous ions and hexa-coordinated zirconium ions were realized by the P-31 solid MAS NMR and UV-visible, respectively. Sulfonated derivative of zirconium phenylphosphonate, Zr(O3PC6H4SO3H)(1.9) (O3PC6H5)(0.1)center dot 3.7H(2)O were also prepared.

  • Reforming of n-hexane over Pt-tin silicalite-1

    NK Mal, M Sasidharan, M Matsukata, S Sivasanker, AV Ramaswamy

    RECENT ADVANCES IN THE SCIENCE AND TECHNOLOGY OF ZEOLITES AND RELATED MATERIALS, PTS A - C   154   2403 - 2410  2004年

     概要を見る

    The catalytic behavior of Pt supported on non-acidic silicalite-1 (MFI structure) and on the stannosilicate, Sn-sil-1 molecular sieves in the aromatization of n-hexane is investigated. The influence of Pt content, temperature, space velocity, H-2/n-hexane ratio and time on stream (TOS) on the n-hexane conversion, aromatic selectivity and aromatic yield are presented. Aromatics are the main products and this suggests that the aromatization proceeds via dehydrocyclization and/or hydrogenolysis, dehydrogenation to C-2-C-4 olefins followed by oligomerization inside the pores of the molecular sieve into cyclic intermediates in presence of hydrogen. The incorporation of Pt during the synthesis of the stannosilicate (Sn-sil-1) yields a more active catalyst (42 wt% aromatic selectivity) without any deactivation than when Pt is loaded by impregnation on Sn-sil-1 because catalyst deactivation associate with platinum outside the zeolite pores. A formation mechanism is proposed.

  • Modified TS-1 for shape selective phenol hydroxylation to hydroquinone

    NK Mal, P Kumar, M Sasidharan, M Matsukata

    RECENT ADVANCES IN THE SCIENCE AND TECHNOLOGY OF ZEOLITES AND RELATED MATERIALS, PTS A - C   154   2618 - 2625  2004年

     概要を見る

    A new method of modification of TS-1 by weak base (aqueous NH3) treatment leads to formation of bigger crystals and generation of internal hydroxyl groups as evident by SEM and IR (hydroxyl region). All the catalysts were characterized using, XRD, N-2-sorption, UV-VIS, FT-IR and SEM. Activity of the modified and unmodified TS-1 were compare in the hydroxylation of phenol to hydroquinone and catechol in presence of aqueous H2O2. A ratio of hydroquinone to catechol over modified,(TS-1 (33)/OH1 and unmodified, TS-1(33) catalysts were 1.40 and 1.15, respectively, using H2O as solvent, and 2.01 and 1.68, respectively, using MeOH as solvent. Modification of TS-1 with strong base (e.g. NaOH) causes decrease in crystallinity, and hence decreases the conversion of phenol and selectivity of hydroquinone. A new mechanism controlling the product selectivity is proposed.

  • A compact ZSM-5 membrane prepared without structure-directing agent

    G Li, E Kikuchi, M Matsukata

    RECENT ADVANCES IN THE SCIENCE AND TECHNOLOGY OF ZEOLITES AND RELATED MATERIALS, PTS A - C   154   620 - 625  2004年

     概要を見る

    Compact ZSM-5 zeolite membranes have been prepared on the outer surface of a porous alpha-alumina tub without structure-directing agents (SDAs) by the seed-assisted crystallization method. An SDA-free gel and an SDA-free clear solution were used for the membrane preparation, respectively. ZSM-5 membrane prepared from the SDA-free gel showed the H-2/i-C4H10 ideal selectivity of 13.8 at 200 degrees C, but it decreased to be 2.1 after the pretreatment at 300 degrees C, indicating the limited thermal stability of this kind of ZSM-5 membrane. On the other hand, ZSM-5 membranes prepared from the SDA-free clear solution showed high thermal stability and good separation properties. After the pretreatment at 400 degrees C, the H-2/i-C4H10 idea selectivity was as high as 61 at 270 degrees C. The maximum of the n/i-C4H10 ideal selectivity was 36 at 300 degrees C and the separation factor was as high as 12.7 at 400 degrees C for a 50/50 n/i-C4H10 mixture.

  • Synthesis and characterization of microporous layered zirconium phenylphosphonate

    NK Mal, M Sasidharan, M Fujiwara, Y Yamada, M Matsukata

    RECENT ADVANCES IN THE SCIENCE AND TECHNOLOGY OF ZEOLITES AND RELATED MATERIALS, PTS A - C   154   1153 - 1159  2004年

     概要を見る

    Microporous layered zirconium phenylphosphonate, Zr(O3P-C6H5)(2) was prepared in presence of sodium dodecylsulfate (SDS), for the first time. Interplanar spacing (d(001)) and surface area of microporous zirconium phenylphosphonate are 1.47 nm and 198 m(2)g(-1), respectively. FT-IR spectrum indicates absence or negligible amount of hydroxyls groups ill zirconium phenylphosphonate sample. P-31 solid MAS NMR also confirms the presence of trace amount of hydroxyl groups in zirconium phenylphosphonate. The presence of tetra-coordinated phosphorous ions and hexa-coordinated zirconium ions were realized by the P-31 solid MAS NMR and UV-visible, respectively. Sulfonated derivative of zirconium phenylphosphonate, Zr(O3PC6H4SO3H)(1.9) (O3PC6H5)(0.1)center dot 3.7H(2)O were also prepared.

  • Reforming of n-hexane over Pt-tin silicalite-1

    NK Mal, M Sasidharan, M Matsukata, S Sivasanker, AV Ramaswamy

    RECENT ADVANCES IN THE SCIENCE AND TECHNOLOGY OF ZEOLITES AND RELATED MATERIALS, PTS A - C   154   2403 - 2410  2004年

     概要を見る

    The catalytic behavior of Pt supported on non-acidic silicalite-1 (MFI structure) and on the stannosilicate, Sn-sil-1 molecular sieves in the aromatization of n-hexane is investigated. The influence of Pt content, temperature, space velocity, H-2/n-hexane ratio and time on stream (TOS) on the n-hexane conversion, aromatic selectivity and aromatic yield are presented. Aromatics are the main products and this suggests that the aromatization proceeds via dehydrocyclization and/or hydrogenolysis, dehydrogenation to C-2-C-4 olefins followed by oligomerization inside the pores of the molecular sieve into cyclic intermediates in presence of hydrogen. The incorporation of Pt during the synthesis of the stannosilicate (Sn-sil-1) yields a more active catalyst (42 wt% aromatic selectivity) without any deactivation than when Pt is loaded by impregnation on Sn-sil-1 because catalyst deactivation associate with platinum outside the zeolite pores. A formation mechanism is proposed.

  • Modified TS-1 for shape selective phenol hydroxylation to hydroquinone

    NK Mal, P Kumar, M Sasidharan, M Matsukata

    RECENT ADVANCES IN THE SCIENCE AND TECHNOLOGY OF ZEOLITES AND RELATED MATERIALS, PTS A - C   154   2618 - 2625  2004年

     概要を見る

    A new method of modification of TS-1 by weak base (aqueous NH3) treatment leads to formation of bigger crystals and generation of internal hydroxyl groups as evident by SEM and IR (hydroxyl region). All the catalysts were characterized using, XRD, N-2-sorption, UV-VIS, FT-IR and SEM. Activity of the modified and unmodified TS-1 were compare in the hydroxylation of phenol to hydroquinone and catechol in presence of aqueous H2O2. A ratio of hydroquinone to catechol over modified,(TS-1 (33)/OH1 and unmodified, TS-1(33) catalysts were 1.40 and 1.15, respectively, using H2O as solvent, and 2.01 and 1.68, respectively, using MeOH as solvent. Modification of TS-1 with strong base (e.g. NaOH) causes decrease in crystallinity, and hence decreases the conversion of phenol and selectivity of hydroquinone. A new mechanism controlling the product selectivity is proposed.

  • Gas separation through MFI-type zeolite membrane

    International Conference on Materials for Advanced Technologies (ICMAT 2003)   Sinpapore  2003年12月

  • Gas separation through MFI-type zeolite membrane

    International Conference on Materials for Advanced Technologies (ICMAT 2003)   Sinpapore  2003年12月

  • 無機膜よもやま話

    松方正彦

    化学工学会分離プロセス部会膜工学分科会,第4回無機膜勉強会「無機膜研究の基礎から最先端まで」    2003年11月

  • DGC法によるゼオライトの結晶化機構について

    松方正彦

    触媒学会規則性多孔体研究会,ナノ細孔体の合成と機能に関する講演会「規則性ナノ空間化学はどこまで進んだか」    2003年11月

  • Perspectives of Zeolite Membrane Technologies for Greener Production

    10th Asican Chemical Congress, 8th Eurasia Conference on Chemical Sciences   Hanoi, Vietnum  2003年10月

  • Perspectives of Zeolite Membrane Technologies for Greener Production

    10th Asican Chemical Congress, 8th Eurasia Conference on Chemical Sciences   Hanoi, Vietnum  2003年10月

  • Treatment of LCO fractions on zeolite beta

    M. Matsukata, P. Sharma, Y. Iguchi, Y. Sekine, E. Kikuchi

    ACS Division of Petroleum Chemistry, Inc. Preprints   48 ( 3 ) 172 - 173  2003年09月  [査読有り]

     概要を見る

    Beta zeolite catalysts with different crystal sizes and similar acid strengths were synthesized in a "Steam-Assisted conversion (SAC)" technique. Pt loaded H-beta with an optimized crystal size of 600 nm showed high activity for hydrotreatment of tetralin by producing alkylbenzenes through area and low coke deposition. Isomerization reaction, which was expected to occur on the zeolite surface, was reduced considerably since tetralin interacted with strong Brönsted acid sites as soon as it penetrated the pore of the zeolite and underwent cracking to form linear hydrocarbons, C6 and C7 aromatics products. The method of supporting platinum on the zeolite had a significant effect on the activity of catalyst. For loading platinum of beta zeolite, ion exchange was a suitable method as it helped in well dispersion of platinum on the zeolite surface and inside the micropore.

  • 産学官連携の新しいモデルを目指してーゼオライトの連続製造プロセスの開発—

    松方正彦

    触媒   1.878472222  2003年09月

  • The control of phase and orientation in zeolite membranes by the secondary growth method

    Gang Li, Eiichi Kikuchi, Masahiko Matsukata

    Microporous and Mesoporous Materials   62 ( 3 ) 211 - 220  2003年08月

     概要を見る

    Mordenite and ZSM-5 seeds could grow on the surface of an asymmetric α-Al2O3 support using an identical organic-free aluminosilicate solution under the same hydrothermal conditions. It suggests that the phase of zeolite can be controlled by varying the type of seed. Continuous mordenite and ZSM-5 membranes were prepared by the secondary growth method using corresponding seeds under appropriate conditions. The water content in the secondary growth mixture strongly influenced the growth of zeolite crystals. ZSM-5 seeds grew at a smaller rate and showed a habit of thin hexagonal plate in a concentrated mixture, while the crystals with a habit of rectangular parallelepiped were formed from a diluted secondary growth mixture. ZSM-5 crystals had poor intergrowth in the former case, whereas the crystals were highly intergrown in the latter case. ZSM-5 crystals in either membrane have a random orientation. In contrast to ZSM-5 zeolite, the crystal orientation in the secondary grown mordenite membranes strongly depended on the water content in the secondary growth mixture. The crystals in the mordenite membrane developed in a diluted secondary growth mixture were oriented with the (1 5 0) face parallel to the support surface, whereas the crystals in the membrane grown in a concentrated mixture were oriented with the (0 0 2) face parallel to the support surface. These results suggest that the crystal orientation in mordenite membranes can be manipulated only by changing the water content in a secondary growth mixture. The formation of the preferred crystal orientation in the secondary grown mordenite membrane is discussed in terms of an "evolutionary selection" process. © 2003 Elsevier Inc. All rights reserved.

    DOI

    Scopus

    77
    被引用数
    (Scopus)
  • ZSM-5 zeolite membranes prepared from a clear template-free solution

    Micropor. Mesopor. Mater.   60  2003年08月

    DOI

    Scopus

    52
    被引用数
    (Scopus)
  • Photo-switched storage and release of guest molecules in the pore void of coumarin-modified MCM-41

    NK Mal, M Fujiwara, Y Tanaka, T Taguchi, M Matsukata

    CHEMISTRY OF MATERIALS   15 ( 17 ) 3385 - 3394  2003年08月

     概要を見る

    A photoresponsive coumarin derivative was grafted on the pore outlet of Si-MCM-41. Irradiation of UV light longer than 310-nm wavelength to this coumarin-modified MCM-41 induced the photodimerization of coumarin to close the pore outlet with cyclobutane dimer. Guest molecules such as phenanthrene neither can enter nor escape from the one-dimensional, isolated, individual pores of MCM-41. On the other hand, the irradiation to the dimerized-coumarin-modified MCM-41 with shorter wavelength UV light around 250 nm regenerates the coumarin monomer derivative by the photocleavage of cyclobutane dimer, and guest molecules included inside are released from the pore void. For the first time, this intermolecular reversible photodimerization-cleavage cycle realized photo-switched storage and release of guest molecules from coumarin-modified MCM-41. Coumarin-modified MCM-41 prepared using tetradecyltrimethylammonium bromide as surfactant was able to store 21.6 wt % of phenanthrene as guest molecule after photodimerization and washing with n-hexane. Among the four different methods studied for the modification by the coumarin derivative, a grafting procedure with as-synthesized MCM-41 for short reaction time was found to be the most effective for the dense attachment of coumarin-derived monomer at the pore outlets of MCM-41, which is essential for effective storage-release controlled release.

    DOI

    Scopus

    263
    被引用数
    (Scopus)
  • The control of phase and orientation in zeolite membranes by the secondary growth method

    G Li, E Kikuchi, M Matsukata

    MICROPOROUS AND MESOPOROUS MATERIALS   62 ( 3 ) 211 - 220  2003年08月

     概要を見る

    Mordenite and ZSM-5 seeds could grow on the surface of an asymmetric alpha-Al2O3 support using an identical organic-free aluminosilicate solution under the same hydrothermal conditions. It suggests that the phase of zeolite can be controlled by varying the type of seed. Continuous mordenite and ZSM-5 membranes were prepared by the secondary growth method using corresponding seeds under appropriate conditions. The water content in the secondary growth mixture strongly influenced the growth of zeolite crystals. ZSM-5 seeds grew at a smaller rate and showed a habit of thin hexagonal plate in a concentrated mixture, while the crystals with a habit of rectangular parallelepiped were formed from a diluted secondary growth mixture. ZSM-5 crystals had poor intergrowth in the former case, whereas the crystals were highly intergrown in the latter case. ZSM-5 crystals in either membrane have a random orientation. In contrast to ZSM-5 zeolite, the crystal orientation in the secondary grown mordenite membranes strongly depended on the water content in the secondary growth mixture. The crystals in the mordenite membrane developed in a diluted secondary growth mixture were oriented with the (1 5 0) face parallel to the support surface, whereas the crystals in the membrane grown in a concentrated mixture were oriented with the (0 0 2) face parallel to the support surface. These results suggest that the crystal orientation in mordenite membranes can be manipulated only by changing the water content in a secondary growth mixture. The formation of the preferred crystal orientation in the secondary grown mordenite membrane is discussed in terms of an "evolutionary selection" process. (C) 2003 Elsevier Inc. All rights reserved.

    DOI

    Scopus

    77
    被引用数
    (Scopus)
  • Photo-switched storage and release of guest molecules in the pore void of coumarin-modified MCM-41

    NK Mal, M Fujiwara, Y Tanaka, T Taguchi, M Matsukata

    CHEMISTRY OF MATERIALS   15 ( 17 ) 3385 - 3394  2003年08月

     概要を見る

    A photoresponsive coumarin derivative was grafted on the pore outlet of Si-MCM-41. Irradiation of UV light longer than 310-nm wavelength to this coumarin-modified MCM-41 induced the photodimerization of coumarin to close the pore outlet with cyclobutane dimer. Guest molecules such as phenanthrene neither can enter nor escape from the one-dimensional, isolated, individual pores of MCM-41. On the other hand, the irradiation to the dimerized-coumarin-modified MCM-41 with shorter wavelength UV light around 250 nm regenerates the coumarin monomer derivative by the photocleavage of cyclobutane dimer, and guest molecules included inside are released from the pore void. For the first time, this intermolecular reversible photodimerization-cleavage cycle realized photo-switched storage and release of guest molecules from coumarin-modified MCM-41. Coumarin-modified MCM-41 prepared using tetradecyltrimethylammonium bromide as surfactant was able to store 21.6 wt % of phenanthrene as guest molecule after photodimerization and washing with n-hexane. Among the four different methods studied for the modification by the coumarin derivative, a grafting procedure with as-synthesized MCM-41 for short reaction time was found to be the most effective for the dense attachment of coumarin-derived monomer at the pore outlets of MCM-41, which is essential for effective storage-release controlled release.

    DOI

    Scopus

    263
    被引用数
    (Scopus)
  • Solid State Synthesis of SrFeCo0.5Ox Asymmetric Membranes for Oxygen Separation

    M. Ikeguchi, Y. Uchida, Y. Sekine, E. Kikuchi, M. Matsukata

    Sep. Purif. Technol.   32 ( 1月3日 ) 313 - 318  2003年07月

  • Effects of preparation method on oxygen permeation properties of SrFeCo0.5Ox membrane

    M Ikeguchi, Y Yoshino, K Kanie, M Nomura, E Kikuchi, M Matsukata

    SEPARATION AND PURIFICATION TECHNOLOGY   32 ( 1-3 ) 313 - 318  2003年07月

     概要を見る

    It was investigated that the effects of preparation methods and conditions for SrFeCo0.5Ox dense membrane on their oxygen permeability. Three different methods, a solid-state reaction method, an evaporation-to-dryness method, and a combined citrate and EDTA complexing method, were applied for the preparation of parent powder. The oxygen flux through membrane at 900 degreesC was increased in the order listed above. The oxygen flux could be greatly improved by repeated calcination and grinding of parent powder. The membrane sintered at a temperature as high as 1200 degreesC showed a higher oxygen flux (0.22 cm(3) (STP)/cm(2) min). (C) 2003 Elsevier Science B.V. All rights reserved.

    DOI

    Scopus

    22
    被引用数
    (Scopus)
  • A study on the pervaporation of water-acetic acid mixtures through ZSM-5 zeolite membranes

    G Li, E Kikuchi, M Matsukata

    JOURNAL OF MEMBRANE SCIENCE   218 ( 1-2 ) 185 - 194  2003年07月

     概要を見る

    A study was carried out on the pervaporation of water from water-acetic acid mixtures through tubular ZSM-5 zeolite membranes. ZSM-5 zeolite membranes were prepared on the outer surface of a porous a-alumina tube by the seed-assisted crystallization method in the absence of organic templates. It was observed that water preferentially permeated with selectivities higher than the selectivity based on the vapor-liquid equilibrium in the entire range of acetic acid concentration. The separation mechanism of water through ZSM-5 zeolite membranes was discussed and compared with that through mordenite membranes. It was found that the permeability coefficients of both water and acetic acid decreased with increasing temperature, although the pervaporation fluxes of both water and acetic acid increased. As a result, it was concluded that the increase in the pervaporation flux with temperature was due to the increase in the driving force in terms of transmembrane partial vapor pressure difference with temperature. According to the mechanism proposed herein, a study was also directed to modify as-synthesized membranes for the improvement in their pervaporation performance. It was observed that both the water flux and the separation factor were increased through a membrane treated in alkaline solution under appropriate conditions. (C) 2003 Elsevier Science B.V. All rights reserved.

    DOI

    Scopus

    77
    被引用数
    (Scopus)
  • Solid State Synthesis of SrFeCo0.5Ox Asymmetric Membranes for Oxygen Separation

    M. Ikeguchi, Y. Uchida, Y. Sekine, E. Kikuchi, M. Matsukata

    Sep. Purif. Technol.   32 ( 1月3日 ) 313 - 318  2003年07月

  • Separation of water-acetic acid mixtures by pervaporation using a thin mordenite membrane

    G Li, E Kikuchi, M Matsukata

    SEPARATION AND PURIFICATION TECHNOLOGY   32 ( 1-3 ) 199 - 206  2003年07月

     概要を見る

    Mordenite membranes have been prepared on the outer surface of a porous a-alumina tube by seed-assisted crystallization. The kind of silica source was found to have significant influence on the microstructure of the membrane grown on the seeded support. Highly water-selective mordenite membranes were prepared with crystallization time as short as 2-4 h at 180 degreesC. The dehydration of acetic acid by pervaporation was investigated using these thin membranes as functions of temperature and feed concentration. The separation mechanism is discussed. (C) 2003 Published by Elsevier Science B.V.

    DOI

    Scopus

    102
    被引用数
    (Scopus)
  • Effects of preparation method on oxygen permeation properties of SrFeCo0.5Ox membrane

    M Ikeguchi, Y Yoshino, K Kanie, M Nomura, E Kikuchi, M Matsukata

    SEPARATION AND PURIFICATION TECHNOLOGY   32 ( 1-3 ) 313 - 318  2003年07月

     概要を見る

    It was investigated that the effects of preparation methods and conditions for SrFeCo0.5Ox dense membrane on their oxygen permeability. Three different methods, a solid-state reaction method, an evaporation-to-dryness method, and a combined citrate and EDTA complexing method, were applied for the preparation of parent powder. The oxygen flux through membrane at 900 degreesC was increased in the order listed above. The oxygen flux could be greatly improved by repeated calcination and grinding of parent powder. The membrane sintered at a temperature as high as 1200 degreesC showed a higher oxygen flux (0.22 cm(3) (STP)/cm(2) min). (C) 2003 Elsevier Science B.V. All rights reserved.

    DOI

    Scopus

    22
    被引用数
    (Scopus)
  • A study on the pervaporation of water-acetic acid mixtures through ZSM-5 zeolite membranes

    G Li, E Kikuchi, M Matsukata

    JOURNAL OF MEMBRANE SCIENCE   218 ( 1-2 ) 185 - 194  2003年07月

     概要を見る

    A study was carried out on the pervaporation of water from water-acetic acid mixtures through tubular ZSM-5 zeolite membranes. ZSM-5 zeolite membranes were prepared on the outer surface of a porous a-alumina tube by the seed-assisted crystallization method in the absence of organic templates. It was observed that water preferentially permeated with selectivities higher than the selectivity based on the vapor-liquid equilibrium in the entire range of acetic acid concentration. The separation mechanism of water through ZSM-5 zeolite membranes was discussed and compared with that through mordenite membranes. It was found that the permeability coefficients of both water and acetic acid decreased with increasing temperature, although the pervaporation fluxes of both water and acetic acid increased. As a result, it was concluded that the increase in the pervaporation flux with temperature was due to the increase in the driving force in terms of transmembrane partial vapor pressure difference with temperature. According to the mechanism proposed herein, a study was also directed to modify as-synthesized membranes for the improvement in their pervaporation performance. It was observed that both the water flux and the separation factor were increased through a membrane treated in alkaline solution under appropriate conditions. (C) 2003 Elsevier Science B.V. All rights reserved.

    DOI

    Scopus

    77
    被引用数
    (Scopus)
  • ZSM-5 zeolite membranes prepared from a clear template-free solution

    G Li, E Kikuchi, M Matsukata

    MICROPOROUS AND MESOPOROUS MATERIALS   60 ( 1-3 ) 225 - 235  2003年06月

     概要を見る

    Template-free nanosized ZSM-5 seeds were prepared from commercially available ZSM-5 powder. By use of these seeds, thin and hydrophilic ZSM-5 zeolite membranes were prepared on the outer surface of a porous a-alumina tube in a clear solution free from organic template. The membranes showed high thermal stability to withstand pretreatment at 400 degreesC, At 270 degreesC, the ideal selectivities for H-2/i-butane and N-2/SF6 were 61 and 20, respectively. The membrane was effective to separate butane isomers at high temperatures. The maximum of the n/i-butane ideal selectivity was 36 at 300 degreesC. The separation factors for a 50/50 n/i-butane mixture were as high as 13 in the temperature range from 300 to 400 degreesC. (C) 2003 Elsevier Science Inc. All rights reserved.

    DOI

    Scopus

    52
    被引用数
    (Scopus)
  • Synthesis of a microporous layered titanium phenylphosphonate in presence of sodium dodecylsulfate

    NK Mal, M Fujiwara, Y Yamada, K Kuraoka, M Matsukata

    JOURNAL OF THE CERAMIC SOCIETY OF JAPAN   111 ( 4 ) 219 - 221  2003年04月

     概要を見る

    Microporous layered titanium phenylphosphonate, Ti(O3PC6H5)(2) and sulfonated titanium phenylphosphonate, Ti(O3PC6H4SO3H)(0.89) (O3PC6H5)(1.1).1.8H(2)O were prepared in the presence of sodium dodecylsulfate (SDS). Interplanar spacing (d(001)) of titanium phenylphosphonate is 1.43 nm and after sulfonation it increased to 1.64 nm. The surface area of titanium phenylphosphonate is 264 m(2) g(-1).

  • Synthesis of a microporous layered titanium phenylphosphonate in presence of sodium dodecylsulfate

    NK Mal, M Fujiwara, Y Yamada, K Kuraoka, M Matsukata

    JOURNAL OF THE CERAMIC SOCIETY OF JAPAN   111 ( 4 ) 219 - 221  2003年04月

     概要を見る

    Microporous layered titanium phenylphosphonate, Ti(O3PC6H5)(2) and sulfonated titanium phenylphosphonate, Ti(O3PC6H4SO3H)(0.89) (O3PC6H5)(1.1).1.8H(2)O were prepared in the presence of sodium dodecylsulfate (SDS). Interplanar spacing (d(001)) of titanium phenylphosphonate is 1.43 nm and after sulfonation it increased to 1.64 nm. The surface area of titanium phenylphosphonate is 264 m(2) g(-1).

  • MFI-alumina composite membrane: Influence of the support porous structure on separative performance.

    Landrivon E, Miachon S, Kumakiri I, Matsukata M, Dalmon JA

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   225   U872  2003年03月  [査読有り]

  • パラジウムメンブレンリアクターにおけるNi/Al2O3触媒上でのメタノール水蒸気改質

    菊地 英一, 河部 正, 松方 正彦

    Journal of the Japan Petroleum Institute   46 ( 2 ) 93 - 98  2003年03月

    CiNii

  • Separation of water-acetic acid mixtures by pervaporation using a thin mordenite membrane

    Sep. Purif. Technol.   32:1-3  2003年03月

    DOI

    Scopus

    102
    被引用数
    (Scopus)
  • Steam reforming of methanol on Ni/Al2O3 catalyst in a Pd-membrane reactor

    E Kikuchi, S Kawabe, M Matsukata

    JOURNAL OF THE JAPAN PETROLEUM INSTITUTE   46 ( 2 ) 93 - 98  2003年03月

     概要を見る

    The application of the membrane reactor to steam reforming of methanol was studied as a hydrogen producing reaction. The activities, stabilities and selectivities of Cu/ZnO, Ni/Al2O3 and Ru/Al2O3 catalysts were tested using a conventional fixed-bed flow reactor. Ni/Al2O3 catalyst showed the most stable activity at 723 K but relatively low hydrogen yield because of methanation. However, the hydrogen-permeable membrane reactor suppressed methanation and hydrogen yield was enhanced compared with the conventional reactor. The membrane reactor was more effective at higher temperatures and higher W/F.

  • Synthesis of Surfactant-assisted Microporous Layered Tin Phenylphosphonate

    Chem. Lett.   1.335416667  2003年02月

  • Synthesis of Surfactant-assisted Microporous Layered Tin Phenylphosphonate

    Chem. Lett.   1.335416667  2003年02月

  • 8-20.超臨界二酸化炭素を溶媒として用いるクリーンなポリウレタンのリサイクルプロセス((5)廃棄物転換素材の利用,Session 8 環境対策・リサイクル)

    関根 泰, 松方 正彦, 菊地 英一, 滝野 寛志

    日本エネルギー学会大会講演要旨集   12   396 - 397  2003年

    DOI CiNii

  • ドデシル硫酸ナトリウム存在下でのミクロポーラスな層状フェニルリン酸チタンの合成

    Mal Nawal Kishor, 藤原 正浩, 山田 裕介, 藏岡 孝治, 松方 正彦

    公益社団法人日本セラミックス協会 日本セラミックス協会学術論文誌   111 ( 1292 ) 219 - 221  2003年  [査読有り]

     概要を見る

    Microporous layered titanium phenylphosphonate, Ti(O3PC6H5)2 and sulfonated titanium phenylphosphonate, Ti(O3PC6H4SO3H)0.89 (O3PC6H5)1.1&middot;1.8H2O were prepared in the presence of sodium dodecylsulfate (SDS). Interplanar spacing (d001) of titanium phenylphosphonate is 1.43 nm and after sulfonation it increased to 1.64 nm. The surface area of titanium phenylphosphonate is 264m2g-1.

    DOI

    Scopus

    17
    被引用数
    (Scopus)
  • 石炭灰からのA型ゼオライト合成時の無機元素の挙動

    松方 正彦, 伊藤 光宏, 菊地 英一

    化学工学会 研究発表講演要旨集   2003   336 - 336  2003年

    DOI CiNii

  • in situ結晶化法で合成したMFI型ゼオライト膜のガス分離特性

    松方 正彦, 奈良 智之, 関根 泰, 菊地 英一, Jean A. Jalmon, Sylvain Miachon

    化学工学会 研究発表講演要旨集   2003   529 - 529  2003年

    DOI CiNii

  • 湿式法による酸素透過性非対称膜の合成

    金子 正幸, 池口 真之, 関根 泰, 菊地 英一, 松方 正彦

    化学工学会 研究発表講演要旨集   2003   537 - 537  2003年

    DOI CiNii

  • 2次成長法で合成したハイシリカMFI型膜のガス分離特性

    松方 正彦, 秋本 彦和, Li Gang, 関根 泰, 菊地 英一

    化学工学会 研究発表講演要旨集   2003   528 - 528  2003年

    DOI CiNii

  • Selective deposition of Pd on porous alumina support using supercritical CO2

    M Matsukata, T Nishizuka, Y Sekine, E Kikuchi

    MEMBRANES-PREPARATION, PROPERTIES AND APPLICATIONS   752   265 - 270  2003年

     概要を見る

    A Pd/alpha-Al2O3 composite membrane was prepared on a porous alpha-Al2O3 disk via the thermal decomposition of bis(hexafluoroacetylacetonato)Pd(II), Pd(hfac)(2). Pd(hfac)(2) was dissolved in supercritical CO2 at 303 K, supplied to the substrate, and thermally decomposed at 403 and 443 K. The decomposition of Pd(hfac)(2) at 443 K resulted in a sufficient pore filling of substrate with Pd as well as the formation of a thin Pd top layer. The hydrogen flux through this membrane was about 1.7 times than that of a electro-less plating Pd membrane with about 20 mum thick. Hydrogen permeation was governed by the solution-diffusion mechanism which gave a high separation selectivity.

  • Hydroisomerization of tetralin on zeolite beta: Influence of crystal size

    P Sharma, Y Iguchi, Y Sekine, E Kikuchi, M Matsukata

    SCIENCE AND TECHNOLOGY IN CATALYSIS 2002   145   219 - 222  2003年

     概要を見る

    Though light cycle oils (LCO) obtained in the fluid catalytic cracking (FCC) are rich in aromatics and sulphur but are insufficient to diesel fuels due to the low cetane number. It is worthwhile to produce alkylbenzenes from LCO without producing small olefinic hydrocarbons through hydrotreating polyaromatic compounds present in the LCO. In the present study tetralin was used as a model compound. Reactions such as ring opening, dealkylation, transalkylation, hydrogen transfer and coke formation were studied using Platinum-supported beta as catalyst. The objective of this study was to investigate the relationship between the crystal size of beta zeolite and catalytic properties for hydrotreatment of tetralin.

  • Current status and perspectives of porous ceramic membranes & membrane reactors

    Gordon Research Conference, Hydrocarbon Resources    2003年01月

  • Hydroisomerization of tetralin on zeolite beta: Influence of crystal size

    P Sharma, Y Iguchi, Y Sekine, E Kikuchi, M Matsukata

    SCIENCE AND TECHNOLOGY IN CATALYSIS 2002   145   219 - 222  2003年

     概要を見る

    Though light cycle oils (LCO) obtained in the fluid catalytic cracking (FCC) are rich in aromatics and sulphur but are insufficient to diesel fuels due to the low cetane number. It is worthwhile to produce alkylbenzenes from LCO without producing small olefinic hydrocarbons through hydrotreating polyaromatic compounds present in the LCO. In the present study tetralin was used as a model compound. Reactions such as ring opening, dealkylation, transalkylation, hydrogen transfer and coke formation were studied using Platinum-supported beta as catalyst. The objective of this study was to investigate the relationship between the crystal size of beta zeolite and catalytic properties for hydrotreatment of tetralin.

  • Selective deposition of Pd on porous alumina support using supercritical CO2

    M Matsukata, T Nishizuka, Y Sekine, E Kikuchi

    MEMBRANES-PREPARATION, PROPERTIES AND APPLICATIONS   752   265 - 270  2003年

     概要を見る

    A Pd/alpha-Al2O3 composite membrane was prepared on a porous alpha-Al2O3 disk via the thermal decomposition of bis(hexafluoroacetylacetonato)Pd(II), Pd(hfac)(2). Pd(hfac)(2) was dissolved in supercritical CO2 at 303 K, supplied to the substrate, and thermally decomposed at 403 and 443 K. The decomposition of Pd(hfac)(2) at 443 K resulted in a sufficient pore filling of substrate with Pd as well as the formation of a thin Pd top layer. The hydrogen flux through this membrane was about 1.7 times than that of a electro-less plating Pd membrane with about 20 mum thick. Hydrogen permeation was governed by the solution-diffusion mechanism which gave a high separation selectivity.

  • Hydroisomerization of tetralin on zeolite beta: Influence of crystal size

    P Sharma, Y Iguchi, Y Sekine, E Kikuchi, M Matsukata

    SCIENCE AND TECHNOLOGY IN CATALYSIS 2002   145   219 - 222  2003年

     概要を見る

    Though light cycle oils (LCO) obtained in the fluid catalytic cracking (FCC) are rich in aromatics and sulphur but are insufficient to diesel fuels due to the low cetane number. It is worthwhile to produce alkylbenzenes from LCO without producing small olefinic hydrocarbons through hydrotreating polyaromatic compounds present in the LCO. In the present study tetralin was used as a model compound. Reactions such as ring opening, dealkylation, transalkylation, hydrogen transfer and coke formation were studied using Platinum-supported beta as catalyst. The objective of this study was to investigate the relationship between the crystal size of beta zeolite and catalytic properties for hydrotreatment of tetralin.

  • Current status and perspectives of porous ceramic membranes & membrane reactors

    Gordon Research Conference, Hydrocarbon Resources    2003年01月

  • Selective Deposition of Pd on Porous Alumina Support Using Supercritical CO2

    Materials Research Society 2002MRS Fall Meeting    2002年12月

  • 産学連携の新しいモデル構築の試み

    松方正彦

    鳥取大学産学連携フェアー    2002年12月

  • Selective Deposition of Pd on Porous Alumina Support Using Supercritical CO2

    Materials Research Society 2002MRS Fall Meeting    2002年12月

  • Solid State Synthesis of Asynnetric Membrane for Oxygen Permeation

    第6回日韓合同分離技術シンポジウム THE SIXTH INTERNATIONAL SYMPOSIUM ON SEPARATION TECHNOLOGY -BETWEEN JAPAN AND KOREA-    2002年11月

  • One-step Synthesis of Template-free MFI-type Zeolite Membranes

    第6回日韓合同分離技術シンポジウム THE SIXTH INTERNATIONAL SYMPOSIUM ON SEPARATION TECHNOLOGY -BETWEEN JAPAN AND KOREA-    2002年11月

  • Solid State Synthesis of Asynnetric Membrane for Oxygen Permeation

    第6回日韓合同分離技術シンポジウム THE SIXTH INTERNATIONAL SYMPOSIUM ON SEPARATION TECHNOLOGY -BETWEEN JAPAN AND KOREA-    2002年11月

  • One-step Synthesis of Template-free MFI-type Zeolite Membranes

    第6回日韓合同分離技術シンポジウム THE SIXTH INTERNATIONAL SYMPOSIUM ON SEPARATION TECHNOLOGY -BETWEEN JAPAN AND KOREA-    2002年11月

  • Crystallization behavior of zeolite beta during steam-assisted crystallization of dry gel

    M Matsukata, T Osaki, M Ogura, E Kikuchi

    MICROPOROUS AND MESOPOROUS MATERIALS   56 ( 1 ) 1 - 10  2002年10月

     概要を見る

    Zeolite beta with SiO2/Al2O3 ratios from 30 to 730 was synthesized by a steam-assisted crystallization method, and the crystallized products obtained within 24 h were characterized by means of chemical analyses, XRD, FE-SEM, Si-29- MAS NMR, N-2 adsorption, and temperature-programmed decomposition of tetraethylammonium cation occluded in the micropores of zeolite beta. Based on these results, the crystallization mechanism is discussed herein. It was found that agglomerates of nano-particles were formed from a dry gel before the development of a periodical structure in a long-range order, which can be detected by XRD. After several hours of crystallization, morphological changes in nano-particle agglomerates proceeded to give highly crystalline zeolite beta. (C) 2002 Elsevier Science Inc. All rights reserved.

    DOI

    Scopus

    101
    被引用数
    (Scopus)
  • Co cation effects on activity and stability of isolated Pd(II) cations in zeolite matrices for selective catalytic reduction of nitric oxide with methane

    M Ogura, S Kage, T Shimojo, J Oba, M Hayashi, M Matsukata, E Kikuchi

    JOURNAL OF CATALYSIS   211 ( 1 ) 75 - 84  2002年10月

     概要を見る

    Palladium ion-exchanged zeolites (ZSM-5, mordenite, ferrierite, Y, beta) were tested to evaluate catalytic activity for selective reduction of nitric oxide with methane (CH4-SCR) and stability in the presence of 10% water vapor at a relatively high temperature of 500degreesC. Deactivation of the catalytic activity was inevitable on Pd/HZSM-5 with a Si/Al ratio of 19.8 under the reaction conditions. When the Si/Al ratio decreased, the durability was slightly enhanced. Among the zeolites tested, palladium supported on mordenite showed stable NO conversions. The addition of cobalt effectively stabilized the activity of Pd-H-zeolites, particularly with the addition of 3.3 wt% cobalt onto Pd/HZSM-5, of which no deactivation was noticeable for at least 50 h. Isolated Pd2+ cations on HZSM-5 were the active and selective sites for CH4-SCR. The isolated Pd2+ cations could not be exchanged by Na+ cations in NaCl titration test after the addition of 3.3 wt% cobalt, while NH4NO3 titration revealed that the isolated Pd2+ existed in the sample. This means that Co2+ changes the ion-exchange property of the isolated Pd2+, leading to a much higher stability than Pd/HZSM-5 with regard to durability. The effect of Co2+ on the stability of the isolated Pd2+ cations and their sitings in zeolite cavities is discussed. (C) 2002 Elsevier Science (USA).

    DOI

    Scopus

    1
    被引用数
    (Scopus)
  • メソポーラスマテリアルの展開

    松方正彦

    触媒学会東北地区講演会「材料化学の新展開ー新しい触媒調製に向けて」    2002年10月

  • Crystallization behavior of zeolite beta during steam-assisted crystallization of dry gel

    M Matsukata, T Osaki, M Ogura, E Kikuchi

    MICROPOROUS AND MESOPOROUS MATERIALS   56 ( 1 ) 1 - 10  2002年10月

     概要を見る

    Zeolite beta with SiO2/Al2O3 ratios from 30 to 730 was synthesized by a steam-assisted crystallization method, and the crystallized products obtained within 24 h were characterized by means of chemical analyses, XRD, FE-SEM, Si-29- MAS NMR, N-2 adsorption, and temperature-programmed decomposition of tetraethylammonium cation occluded in the micropores of zeolite beta. Based on these results, the crystallization mechanism is discussed herein. It was found that agglomerates of nano-particles were formed from a dry gel before the development of a periodical structure in a long-range order, which can be detected by XRD. After several hours of crystallization, morphological changes in nano-particle agglomerates proceeded to give highly crystalline zeolite beta. (C) 2002 Elsevier Science Inc. All rights reserved.

    DOI

    Scopus

    101
    被引用数
    (Scopus)
  • Co cation effects on activity and stability of isolated Pd(II) cations in zeolite matrices for selective catalytic reduction of nitric oxide with methane

    M Ogura, S Kage, T Shimojo, J Oba, M Hayashi, M Matsukata, E Kikuchi

    JOURNAL OF CATALYSIS   211 ( 1 ) 75 - 84  2002年10月

     概要を見る

    Palladium ion-exchanged zeolites (ZSM-5, mordenite, ferrierite, Y, beta) were tested to evaluate catalytic activity for selective reduction of nitric oxide with methane (CH4-SCR) and stability in the presence of 10% water vapor at a relatively high temperature of 500degreesC. Deactivation of the catalytic activity was inevitable on Pd/HZSM-5 with a Si/Al ratio of 19.8 under the reaction conditions. When the Si/Al ratio decreased, the durability was slightly enhanced. Among the zeolites tested, palladium supported on mordenite showed stable NO conversions. The addition of cobalt effectively stabilized the activity of Pd-H-zeolites, particularly with the addition of 3.3 wt% cobalt onto Pd/HZSM-5, of which no deactivation was noticeable for at least 50 h. Isolated Pd2+ cations on HZSM-5 were the active and selective sites for CH4-SCR. The isolated Pd2+ cations could not be exchanged by Na+ cations in NaCl titration test after the addition of 3.3 wt% cobalt, while NH4NO3 titration revealed that the isolated Pd2+ existed in the sample. This means that Co2+ changes the ion-exchange property of the isolated Pd2+, leading to a much higher stability than Pd/HZSM-5 with regard to durability. The effect of Co2+ on the stability of the isolated Pd2+ cations and their sitings in zeolite cavities is discussed. (C) 2002 Elsevier Science (USA).

    DOI

    Scopus

    1
    被引用数
    (Scopus)
  • Flow synthesis of mesoporous materials using filtrate of the alkaline dissolution of ZSM-5 zeolite

    British Zeolite Association 25th Annual Meeting    2002年08月

  • Flow synthesis of mesoporous materials using filtrate of the alkaline dissolution of ZSM-5 zeolite

    British Zeolite Association 25th Annual Meeting    2002年08月

  • The Oxidation State of VPO Catalyst for Selective Oxidation of n-Butane in an in situ Redox Fluidized-Bed Reactor

    TOCAT4    2002年07月

  • The Catalytic Property of ZSM-5 Possessing Mesopores

    TOCAT4    2002年07月

  • Hydroisomerization of Tetralin on Zeolite Beta: Influence of Crystallite Size

    TOCAT4    2002年07月

  • Effect of Alkaline Treatment of USY Zeolite on Acidity, Mesopore-Structure and Catalytic Property

    TOCAT4    2002年07月

  • The Oxidation State of VPO Catalyst for Selective Oxidation of n-Butane in an in situ Redox Fluidized-Bed Reactor

    TOCAT4    2002年07月

  • The Catalytic Property of ZSM-5 Possessing Mesopores

    TOCAT4    2002年07月

  • Effect of Alkaline Treatment of USY Zeolite on Acidity, Mesopore-Structure and Catalytic Property

    TOCAT4    2002年07月

  • ドライゲル・コンバージョン法によるさまざまなゼオライトの合成とその特性

    松方正彦

    化学工学   66;6  2002年06月

  • Mesoporous material from zeolite

    Y Goto, Y Fukushima, P Ratu, Y Imada, Y Kubota, Y Sugi, M Ogura, M Matsukata

    JOURNAL OF POROUS MATERIALS   9 ( 1 ) 43 - 48  2002年03月

     概要を見る

    Zeolite/mesoporous molecular sieve composites (ZMC) are made using zeolites as silica-alumina source. XRD patterns of the ZMC show the peaks for both zeolite and mesoporous molecular sieve with hexagonal symmetry. Morphology of the ZMC is different from that of a physical mixture of the two components. Unlike Al-containing mesoporous molecular sieves, the ZMC shows a strong acidity like zeolites. The activity of cracking of n-hexane for ZMC was higher than that of the zeolite. These products are expected to be useful for catalysts and adsorbents for their acidity and pore size.

    DOI

  • Mesoporous material from zeolite

    Y Goto, Y Fukushima, P Ratu, Y Imada, Y Kubota, Y Sugi, M Ogura, M Matsukata

    JOURNAL OF POROUS MATERIALS   9 ( 1 ) 43 - 48  2002年03月

     概要を見る

    Zeolite/mesoporous molecular sieve composites (ZMC) are made using zeolites as silica-alumina source. XRD patterns of the ZMC show the peaks for both zeolite and mesoporous molecular sieve with hexagonal symmetry. Morphology of the ZMC is different from that of a physical mixture of the two components. Unlike Al-containing mesoporous molecular sieves, the ZMC shows a strong acidity like zeolites. The activity of cracking of n-hexane for ZMC was higher than that of the zeolite. These products are expected to be useful for catalysts and adsorbents for their acidity and pore size.

    DOI

  • 3-3.バイオマス熱分解に伴うタール発生の挙動解明及びその分解触媒の開発((1)ガス化・合成I,Session 3 バイオマス等)

    関根 泰, 松永 武久, 菊地 英一, 松方 正彦

    日本エネルギー学会大会講演要旨集   80   148 - 149  2002年

    DOI CiNii

  • 50 高温燃焼時及びガス化条件下における石炭からの無機成分の放出挙動

    関根 泰, 川端 友寛, 坂尻 邦尚, 松方 正彦, 菊地 英一

    石炭科学会議発表論文集   39   117 - 118  2002年

     概要を見る

    The release of trace elements from coal combustion at high temperature was investigated in this study. About 0.1g of Wallarah coal smaller than 150μm was held in a platinum basket, inserted into an electronic furnace predetermined 573〜1573K and burned for 10min to release trace elements. The quantities of trace elements in the coal or ash in the platinum basket after coal combustion were determined by ICP-AES. It was found that initially, trace elements such as Zn and Pb released from a coal above 1173K in the absence of additional steam. Se, Sb and Hg released during 573〜773K and steam influenced the releasing behavior of these elements. Whereas Se and Sb enhanced, that of Hg depressed in the presence of steam.

    DOI CiNii

  • 48.石炭の外表面鉱物とその親水性がカラム浮選に及ぼす影響

    関根 泰, 山口 大輔, 石川 清宏, 菊地 英一, 松方 正彦

    石炭科学会議発表論文集   39   113 - 114  2002年

     概要を見る

    Whereas the optimization of apparatus and the development of flotation results have been extensively reported in the research of column flotation of coal, there have been few studies on the relation of flotation results with the characteristics of coal. The changes in the distributions of particle size and inorganic elements involved in cleaned coal and tail refuse were studied in the course of column flotation. Demineralization mechanisms in a column flotation system were investigated.

    DOI CiNii

  • 78.石炭チャーの水蒸気ガス化における灰分とガス化速度の相関

    関根 泰, 中谷 浩之, 千葉 美沙, 菊地 英一, 松方 正彦

    石炭科学会議発表論文集   39   173 - 174  2002年

     概要を見る

    We conducted steam gasification of various coal char under atomospheric pressure on pressurized conditions. Raw lank coal showed high hydrogen producibility at low temperature. And also alkaline metals catalyzed water gas shift reaction. From these results, we optimized the conditions for production of syngas from coal char and steam.

    DOI CiNii

  • Synthesis of MCM-22 zeolite by the vapor-phase transport method

    S Inagaki, M Hoshino, E Kikuchi, M Matsukata

    IMPACT OF ZEOLITES AND OTHER POROUS MATERIALS ON THE NEW TECHNOLOGIES AT THE BEGINNING OF THE NEW MILLENNIUM, PTS A AND B   142   53 - 60  2002年

     概要を見る

    It is reported that the first synthesis of MCM-22 zeolite by the vapor-phase transport (VPT) method and the comparison in the morphologies of MCM-22 synthesized by the VPT and hydrothermal synthetic (HTS) methods. In the VPT method, pure MCM-22 zeolite was crystallized at 150degreesC for 5 days and at 175degreesC for 3 days. The morphology of MCM-22 zeolite crystallized by the VPT method was sphere which is an agglomerate of hexagonal thin plates having about 3similar to5 mum in width with less than 100 nm thick. Such morphology was similar to MCM-22 zeolite synthesized by the HTS method under static condition. The crystallization by the VPT method with the addition of HMI onto dry gel gave smaller MCM-22 crystals consisting of thin plates with 1similar to2 mum in width.

  • Synthesis of MCM-22 zeolite by the vapor-phase transport method

    S Inagaki, M Hoshino, E Kikuchi, M Matsukata

    IMPACT OF ZEOLITES AND OTHER POROUS MATERIALS ON THE NEW TECHNOLOGIES AT THE BEGINNING OF THE NEW MILLENNIUM, PTS A AND B   142   53 - 60  2002年

     概要を見る

    It is reported that the first synthesis of MCM-22 zeolite by the vapor-phase transport (VPT) method and the comparison in the morphologies of MCM-22 synthesized by the VPT and hydrothermal synthetic (HTS) methods. In the VPT method, pure MCM-22 zeolite was crystallized at 150degreesC for 5 days and at 175degreesC for 3 days. The morphology of MCM-22 zeolite crystallized by the VPT method was sphere which is an agglomerate of hexagonal thin plates having about 3similar to5 mum in width with less than 100 nm thick. Such morphology was similar to MCM-22 zeolite synthesized by the HTS method under static condition. The crystallization by the VPT method with the addition of HMI onto dry gel gave smaller MCM-22 crystals consisting of thin plates with 1similar to2 mum in width.

  • Synthesis of MCM-22 zeolite by the vapor-phase transport method

    S Inagaki, M Hoshino, E Kikuchi, M Matsukata

    IMPACT OF ZEOLITES AND OTHER POROUS MATERIALS ON THE NEW TECHNOLOGIES AT THE BEGINNING OF THE NEW MILLENNIUM, PTS A AND B   142   53 - 60  2002年

     概要を見る

    It is reported that the first synthesis of MCM-22 zeolite by the vapor-phase transport (VPT) method and the comparison in the morphologies of MCM-22 synthesized by the VPT and hydrothermal synthetic (HTS) methods. In the VPT method, pure MCM-22 zeolite was crystallized at 150degreesC for 5 days and at 175degreesC for 3 days. The morphology of MCM-22 zeolite crystallized by the VPT method was sphere which is an agglomerate of hexagonal thin plates having about 3similar to5 mum in width with less than 100 nm thick. Such morphology was similar to MCM-22 zeolite synthesized by the HTS method under static condition. The crystallization by the VPT method with the addition of HMI onto dry gel gave smaller MCM-22 crystals consisting of thin plates with 1similar to2 mum in width.

  • Synthesis of MCM-22 zeolite by the vapor-phase transport method

    S Inagaki, M Hoshino, E Kikuchi, M Matsukata

    IMPACT OF ZEOLITES AND OTHER POROUS MATERIALS ON THE NEW TECHNOLOGIES AT THE BEGINNING OF THE NEW MILLENNIUM, PTS A AND B   142   53 - 60  2002年

     概要を見る

    It is reported that the first synthesis of MCM-22 zeolite by the vapor-phase transport (VPT) method and the comparison in the morphologies of MCM-22 synthesized by the VPT and hydrothermal synthetic (HTS) methods. In the VPT method, pure MCM-22 zeolite was crystallized at 150degreesC for 5 days and at 175degreesC for 3 days. The morphology of MCM-22 zeolite crystallized by the VPT method was sphere which is an agglomerate of hexagonal thin plates having about 3similar to5 mum in width with less than 100 nm thick. Such morphology was similar to MCM-22 zeolite synthesized by the HTS method under static condition. The crystallization by the VPT method with the addition of HMI onto dry gel gave smaller MCM-22 crystals consisting of thin plates with 1similar to2 mum in width.

  • Synthesis of EMT zeolite by a steam-assisted crystallization method using crown ether as a structure-directing agent

    M Matsukata, K Kizu, M Ogura, E Kikuchi

    CRYSTAL GROWTH & DESIGN   1 ( 6 ) 509 - 516  2001年11月

     概要を見る

    A high-silica hexagonal faujasite EMT was crystallized by a steam-assisted crystallization (SAC) method using a crown ether of 1,4,7,10,13,16-hexaoxacyclooctadecane, 18-crown-6, as a structure-directing agent. The growth mechanism of EMT by SAC is quite different from that of EMT by the conventional hydrothermal synthetic method, in which layer-by-layer growth occurs. Another characteristic of SAC is that nanoparticles fuse and the surface of the dry gel is rearranged, resulting in a distinct hexagonal shape for the EMT crystals. Sodium content must be strictly defined when the SAC method is used, and the crystallization temperature must be kept below 408 K to keep the crown ether in the dry gel to obtain a pure phase of EMT.

    DOI

    Scopus

    19
    被引用数
    (Scopus)
  • Quantitative analyses for TEA(+) and Na+ contents in zeolite beta with a wide range of Si/2Al ratio

    M Matsukata, M Ogura, T Osaki, E Kikuchi, A Mitra

    MICROPOROUS AND MESOPOROUS MATERIALS   48 ( 1-3 ) 23 - 29  2001年11月

     概要を見る

    Beta zeolites with a wide range of Si/2Al ratios from 7 to infinity were synthesized by steam-assisted crystallization method. X-ray diffraction, FE-SEM, and MASNMR studies confirmed the formation of highly crystalline zeolite beta and Al incorporation in the framework under various conditions by the SAC method at temperatures ranging from 373 to 438 K. Na+ and TEA(+) contents occluded in micropores of beta zeolite were determined. Quantitative knowledge on such occluded cations gave great insight on understanding crystallization mechanism of beta. (C) 2001 Published by Elsevier Science B.V.

    DOI

    Scopus

    27
    被引用数
    (Scopus)
  • Synthesis of EMT zeolite by a steam-assisted crystallization method using crown ether as a structure-directing agent

    M Matsukata, K Kizu, M Ogura, E Kikuchi

    CRYSTAL GROWTH & DESIGN   1 ( 6 ) 509 - 516  2001年11月

     概要を見る

    A high-silica hexagonal faujasite EMT was crystallized by a steam-assisted crystallization (SAC) method using a crown ether of 1,4,7,10,13,16-hexaoxacyclooctadecane, 18-crown-6, as a structure-directing agent. The growth mechanism of EMT by SAC is quite different from that of EMT by the conventional hydrothermal synthetic method, in which layer-by-layer growth occurs. Another characteristic of SAC is that nanoparticles fuse and the surface of the dry gel is rearranged, resulting in a distinct hexagonal shape for the EMT crystals. Sodium content must be strictly defined when the SAC method is used, and the crystallization temperature must be kept below 408 K to keep the crown ether in the dry gel to obtain a pure phase of EMT.

    DOI

    Scopus

    19
    被引用数
    (Scopus)
  • Quantitative analyses for TEA(+) and Na+ contents in zeolite beta with a wide range of Si/2Al ratio

    M Matsukata, M Ogura, T Osaki, E Kikuchi, A Mitra

    MICROPOROUS AND MESOPOROUS MATERIALS   48 ( 1-3 ) 23 - 29  2001年11月

     概要を見る

    Beta zeolites with a wide range of Si/2Al ratios from 7 to infinity were synthesized by steam-assisted crystallization method. X-ray diffraction, FE-SEM, and MASNMR studies confirmed the formation of highly crystalline zeolite beta and Al incorporation in the framework under various conditions by the SAC method at temperatures ranging from 373 to 438 K. Na+ and TEA(+) contents occluded in micropores of beta zeolite were determined. Quantitative knowledge on such occluded cations gave great insight on understanding crystallization mechanism of beta. (C) 2001 Published by Elsevier Science B.V.

    DOI

    Scopus

    27
    被引用数
    (Scopus)
  • Alkali-treatment technique - New method for modification of structural and acid-catalytic properties of ZSM-5 zeolites

    M Ogura, SY Shinomiya, J Tateno, Y Nara, M Nomura, E Kikuchi, M Matsukata

    APPLIED CATALYSIS A-GENERAL   219 ( 1-2 ) 33 - 43  2001年10月

     概要を見る

    ZSM-5 zeolite having a SiO2/Al2O3 molar ratio of 39.4 was treated in a NaOH alkali solution and the changes in structural and acidic properties were investigated. A siliceous species was selectively dissolved from the framework of zeolite, although a lower amount of Al was also eluted. In this procedure, mesopores with a uniform size were formed on the zeolite, while the microporous structure remained. The acidic property was changed very little quantitatively or qualitatively, even though the catalytic activity for cracking of cumene was enhanced by the alkali-treatment. This can be explained by the facts that adsorptive and diffusive properties of cumene through micropores of the ZSM-5 are increased by the creation of mesopores. (C) 2001 Elsevier Science B.V. All rights reserved.

    DOI

    Scopus

    453
    被引用数
    (Scopus)
  • Alkali-treatment technique - New method for modification of structural and acid-catalytic properties of ZSM-5 zeolites

    M Ogura, SY Shinomiya, J Tateno, Y Nara, M Nomura, E Kikuchi, M Matsukata

    APPLIED CATALYSIS A-GENERAL   219 ( 1-2 ) 33 - 43  2001年10月

     概要を見る

    ZSM-5 zeolite having a SiO2/Al2O3 molar ratio of 39.4 was treated in a NaOH alkali solution and the changes in structural and acidic properties were investigated. A siliceous species was selectively dissolved from the framework of zeolite, although a lower amount of Al was also eluted. In this procedure, mesopores with a uniform size were formed on the zeolite, while the microporous structure remained. The acidic property was changed very little quantitatively or qualitatively, even though the catalytic activity for cracking of cumene was enhanced by the alkali-treatment. This can be explained by the facts that adsorptive and diffusive properties of cumene through micropores of the ZSM-5 are increased by the creation of mesopores. (C) 2001 Elsevier Science B.V. All rights reserved.

    DOI

    Scopus

    453
    被引用数
    (Scopus)
  • Fabrication of an asymmetric SRFECO0.5OX membrane for oxygen permeation.

    M Matsukata, M Ikeguchi, G Nakayama, E Kikuchi

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   222   U316 - U316  2001年08月

  • Fabrication of an asymmetric SRFECO0.5OX membrane for oxygen permeation.

    M Matsukata, M Ikeguchi, G Nakayama, E Kikuchi

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   222   U316 - U316  2001年08月

  • The Impact of Preparation Method on the Membrane Structure and Separation Properties

    Book of Abstracts, Intern. Workshop on Zeolitic and Microporous Membranes, Pumerend, The Netherlands    2001年07月

  • Synthesis of Mesoporous Materials Using Filtrate of Alkali Treatment of MFI Zeolite

    Stud. Surf. Sci. Catal.,   135(1290-1297)  2001年07月

  • MFI Zeolite with Uniform Mesopores Created by Alkali Treatment

    Stud. Surf. Sci. Catal.   135(1820-1827)  2001年07月

  • The Impact of Preparation Method on the Membrane Structure and Separation Properties

    Book of Abstracts, Intern. Workshop on Zeolitic and Microporous Membranes, Pumerend, The Netherlands    2001年07月

  • Synthesis of Mesoporous Materials Using Filtrate of Alkali Treatment of MFI Zeolite

    Stud. Surf. Sci. Catal.,   135(1290-1297)  2001年07月

  • MFI Zeolite with Uniform Mesopores Created by Alkali Treatment

    Stud. Surf. Sci. Catal.   135(1820-1827)  2001年07月

  • Novel organic-vycor glass composite membrane having Si-C bonds

    M Nomura, Y Mineta, N Yamaguchi, E Kikuchi, K Fukunaga, N Nishiyama, K Ueyama, M Matsukata

    JOURNAL OF CHEMICAL ENGINEERING OF JAPAN   34 ( 6 ) 731 - 736  2001年06月

     概要を見る

    A novel organic-ceramic membrane having stable Si-C bonds was developed for separation of high temperature organic solutions. Porous vycor glass was employed for a substrate which was modified by a series of chemical vapor deposition (CVD) and hydrosilylation. 1,3,5,7-Tetramethylcyclotetrasiloxane (1-14) was used as a CVD source in order to introduce Si-H bonds on the surface of porous vycor glass. The Si-H bonds were then catalytically hydrosilylated with olefins. As a result, organic functional groups were introduced via Si-C bonds. A compact membrane was obtained when CVD treatment was carried out at 343 K. The membrane that was modified by the hydrosilylation of styrene showed benzene permselectivity in benzene/cyclohexane vapor permeation test at 373 K. The separation factor of benzene over cyclohexane was 2.9 and benzene flux was 1.2 x 10(-8) mol m(-2)s(-1)Pa(-1), and the permeation properties are stable for more than 1000 min at 373 K.

    DOI

    Scopus

    1
    被引用数
    (Scopus)
  • Novel organic-vycor glass composite membrane having Si-C bonds

    M Nomura, Y Mineta, N Yamaguchi, E Kikuchi, K Fukunaga, N Nishiyama, K Ueyama, M Matsukata

    JOURNAL OF CHEMICAL ENGINEERING OF JAPAN   34 ( 6 ) 731 - 736  2001年06月

     概要を見る

    A novel organic-ceramic membrane having stable Si-C bonds was developed for separation of high temperature organic solutions. Porous vycor glass was employed for a substrate which was modified by a series of chemical vapor deposition (CVD) and hydrosilylation. 1,3,5,7-Tetramethylcyclotetrasiloxane (1-14) was used as a CVD source in order to introduce Si-H bonds on the surface of porous vycor glass. The Si-H bonds were then catalytically hydrosilylated with olefins. As a result, organic functional groups were introduced via Si-C bonds. A compact membrane was obtained when CVD treatment was carried out at 343 K. The membrane that was modified by the hydrosilylation of styrene showed benzene permselectivity in benzene/cyclohexane vapor permeation test at 373 K. The separation factor of benzene over cyclohexane was 2.9 and benzene flux was 1.2 x 10(-8) mol m(-2)s(-1)Pa(-1), and the permeation properties are stable for more than 1000 min at 373 K.

    DOI

    Scopus

    1
    被引用数
    (Scopus)
  • Influence of Mesopore on Cumene Cracking on MFI Zeolite

    Proc. of The 8th Japan-Korea Symp. on Catal., Osaka    2001年05月

  • Effect of Post-synthesis Treatments on the Acidity and Catalytic Activity of Zeolite Beta

    Proc. Intern. Symp. on Acid-Base Catal. IV    2001年05月

  • Influence of Mesopore on Cumene Cracking on MFI Zeolite

    Proc. of The 8th Japan-Korea Symp. on Catal., Osaka    2001年05月

  • Effect of Post-synthesis Treatments on the Acidity and Catalytic Activity of Zeolite Beta

    Proc. Intern. Symp. on Acid-Base Catal. IV    2001年05月

  • Effect of NH4+ exchange on hydrophobicity and catalytic properties of Al-free Ti-Si-beta zeolite

    J. Catal.   199;1(41-47)  2001年04月

    DOI

    Scopus

    35
    被引用数
    (Scopus)
  • Effect of NH4+ exchange on hydrophobicity and catalytic properties of Al-free Ti-Si-beta zeolite

    M Ogura, S Nakata, E Kikuchi, M Matsukata

    JOURNAL OF CATALYSIS   199 ( 1 ) 41 - 47  2001年04月

     概要を見る

    Al-free Ti-Si-beta was synthesized by a steam-assisted crystallization (SAC) method using tetraethylammonium hydroxide as a structure-directing agent. It was noted that Na in a parent gel was essential for synthesizing highly crystalline Ti-Si-beta by means of the SAC method. An absorption band at 225 nm, assigned to isolated Ti species, and another band at around 270 nm appeared in the UV spectra of the Ti-Si-beta. The latter absorption band decreased upon ion exchange of as-synthesized materials with 1 M aqueous NH4NO3 solution, and this treatment did not change the SiO2/TiO2 molar ratio in Ti-Si-beta. The Q(3) signal in the Si-29-NMR spectrum almost disappeared and the amount of H2O adsorbed decreased due to the NH4+ exchange of Ti-Si-beta. The NH4+ exchange resulted in a higher catalytic activity of the zeolite far cyclohexene epoxidation with H2O2 and a high selectivity toward epoxide compared with the H2SO4-treated Ti-Si-beta and AI-containing Ti-beta samples prepared in this study. Summarizing these results, the NH4+ exchange of Ti-Si-beta zeolite is found to induce a hydrophobic environment around Ti sites without detitanation from the zeolite framework. (C) 2001 Academic Press.

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  • 1-31.CO存在下における石灰石と二酸化硫黄の高温反応挙動(Session 1 石炭・重質油)

    松方 正彦, 玉理 裕介, 菊地 英一, 豊田 誠一郎, 両角 文明

    日本エネルギー学会大会講演要旨集   10   140 - 143  2001年

    DOI CiNii

  • 75.石炭表面の親疎水性分布がカラム浮選成績に及ぼす影響

    関根 泰, 佐藤 大介, 山口 大輔, 菊地 英一, 松方 正彦

    石炭科学会議発表論文集   38   307 - 310  2001年

     概要を見る

    It is important to estimate the distribution of hydrophilic/hydrophobic sites on coal in a coal-cleaning process. The relationship between the distribution of hydrophilic/hydrophobic sites on coal and the carbonaceous materials recovery in a continuous column flotation was investigated. The amount of adsorbed methylene blue was determined to estimate the fraction of hydrophilic surface on coal surface. As a result, it turned out that the hydrophilic nature estimated by using methylene blue adsorption was closely related to the carbonaceous materials recovery.

    DOI CiNii

  • 95.石炭チャーの水蒸気ガス化による水素製造

    関根 泰, 千葉 美沙, 菊地 英一, 松方 正彦

    石炭科学会議発表論文集   38   387 - 390  2001年

     概要を見る

    We conducted steam gasification of various coal char under atomospheric pressure or pressurized conditions. Raw coal such as Adaro (SS-013) showed high hydrogen producibility at low temperature. And also alkaline metals catalyzed water gas shift reaction. From these results, we optimized the conditions for production of syngas from coal char and steam.

    DOI CiNii

  • 69.石炭からの水溶性無機成分の溶出挙動

    関根 泰, 草場 健太郎, 竹内 大輔, 菊地 英一, 松方 正彦

    石炭科学会議発表論文集   38   283 - 286  2001年

     概要を見る

    The elution behavior of inorganic matters from SS013, SS015, SS020, SS027, SS029 and SS045 was investigated. In particular, the amount of elution and time course were estimated by using ion chromatography. The time course of elution indicates that soluble minerals on the surface of coal was rapidly eluted within 5 minutes. The elution rate from SS027 was higher than those from SS020 or SS029. The amount of soluble minerals determines elution rate. We concluded that there was little relation between the amount of elution and ash content.

    DOI CiNii

  • 74.石炭表面の親疎水性分布に関する検討

    関根 泰, 佐藤 大介, 山口 大輔, 菊地 英一, 松方 正彦

    石炭科学会議発表論文集   38   303 - 306  2001年

     概要を見る

    The distribution of hydrophilic/hydrophobic sites on coal is one of the essential factors in a column flotation process. In this study, methylene blue adsorption on coal was conducted to estimate the area of hydrophilic surface. The experimental results successfully suggested that methylene blue was adsorbed on the hydrophilic surface sites on minerals and oxygen-containing functional groups.

    DOI CiNii

  • Influence of nano-particle agglomeration on the catalytic properties of MFI zeolite

    S. Inagaki, I. Matsunaga, E. Kikuchi, M. Matsukata

    Studies in Surface Science and Catalysis   135   332  2001年

     概要を見る

    Microstructures of spherical and coffin-shaped MFI zeolite and its effect on the catalytic activity for cumene cracking were studied. While spherical MFI was composed of nanoparticles, coffin-shaped one has a layered structure where nanoparticles with ~ 30 nm in size were accumulated on the dense core. Both the thickness of nano-particles layer and mesopore volume linearly correlated with the activity for cumene cracking, suggesting that the mesopores in MFI particles formed during nanoparticles agglomeration, and that the reaction rate of cumene cracking was significantly affected by the diffusion of cumene molecule in the nanoparticles agglomerating layer. This is an abstract of a paper presented at the 13th International Zeolite Conference (Montpellier, France 7/8-13/2001).

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  • Growth of oriented mordenite membranes on porous α-Al2O3 supports

    G. Li, X. Lin, E. Kikuchi, M. Matsukata

    Studies in Surface Science and Catalysis   135   162  2001年

     概要を見る

    A highly oriented mordenite membrane with c-axis of crystals perpendicular to the support surface was successfully prepared on a porous α-alumina support. Seeding was necessary to form a compact layer of mordenite. The "evolutionary selection" mechanism significantly contributed to the formation of a sharply oriented mordenite layer. Pervaporation results for separation of a water/iso-propanol mixture exhibited highly preferential permeation of water through the oriented mordenite membrane. This is an abstract of a paper presented at the 13th International Zeolite Conference (Montpellier, France 7/8-13/2001).

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    17
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  • Influence of nano-particle agglomeration on the catalytic properties of MFI zeolite

    S. Inagaki, I. Matsunaga, E. Kikuchi, M. Matsukata

    Studies in Surface Science and Catalysis   135   332  2001年

     概要を見る

    Microstructures of spherical and coffin-shaped MFI zeolite and its effect on the catalytic activity for cumene cracking were studied. While spherical MFI was composed of nanoparticles, coffin-shaped one has a layered structure where nanoparticles with ~ 30 nm in size were accumulated on the dense core. Both the thickness of nano-particles layer and mesopore volume linearly correlated with the activity for cumene cracking, suggesting that the mesopores in MFI particles formed during nanoparticles agglomeration, and that the reaction rate of cumene cracking was significantly affected by the diffusion of cumene molecule in the nanoparticles agglomerating layer. This is an abstract of a paper presented at the 13th International Zeolite Conference (Montpellier, France 7/8-13/2001).

    DOI

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    2
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  • Growth of oriented mordenite membranes on porous α-Al2O3 supports

    G. Li, X. Lin, E. Kikuchi, M. Matsukata

    Studies in Surface Science and Catalysis   135   162  2001年

     概要を見る

    A highly oriented mordenite membrane with c-axis of crystals perpendicular to the support surface was successfully prepared on a porous α-alumina support. Seeding was necessary to form a compact layer of mordenite. The "evolutionary selection" mechanism significantly contributed to the formation of a sharply oriented mordenite layer. Pervaporation results for separation of a water/iso-propanol mixture exhibited highly preferential permeation of water through the oriented mordenite membrane. This is an abstract of a paper presented at the 13th International Zeolite Conference (Montpellier, France 7/8-13/2001).

    DOI

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    17
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  • Crystallization Behavior of High Silica Zeolite Beta

    Proc. Ind. Appl. of Zeolites, Brugge, Belgium    2000年10月

  • Crystallization Behavior of High Silica Zeolite Beta

    Proc. Ind. Appl. of Zeolites, Brugge, Belgium    2000年10月

  • Separation of butane and xylene isomers with MFI-type zeolitic membrane synthesized by a vapor-phase transport method

    T Matsufuji, N Nishiyama, M Matsukata, K Uyama

    JOURNAL OF MEMBRANE SCIENCE   178 ( 1-2 ) 25 - 34  2000年09月

     概要を見る

    MFI-type zeolitic membranes were prepared by a vapor-phase transport (VPT) method on porous alpha-alumina flat disks. Single- and mixed-gas permeation measurements of butane isomers were performed in the temperature range of 300-375 K. The separation factor was always greater than the ideal selectivity. This result is explained by the preferential adsorption of n-butane on MFI in the binary system.
    The pervaporation tests for xylene isomers were performed at 303 K. p-Xylene was the most permeable component in the unary system. In the permeation measurements of a binary mixture of p-xylene/m-xylene and a ternary mixture of p-xylene/m-xylene/o-xylene, p-xylene predominantly permeated in the early stage, and then, the Aux of p-xylene decreased gradually and finally became lower than that of the other xylene isomers. The adsorption of m-xylene in the pores of MFI seemed to block the permeation of p-xylene. (C) 2000 Elsevier Science B.V. All rights reserved.

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    106
    被引用数
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  • ドライゲルコンバージョン法によるゼオライト合成

    機能材料   20;10  2000年09月

  • Separation of butane and xylene isomers with MFI-type zeolitic membrane synthesized by a vapor-phase transport method

    T Matsufuji, N Nishiyama, M Matsukata, K Uyama

    JOURNAL OF MEMBRANE SCIENCE   178 ( 1-2 ) 25 - 34  2000年09月

     概要を見る

    MFI-type zeolitic membranes were prepared by a vapor-phase transport (VPT) method on porous alpha-alumina flat disks. Single- and mixed-gas permeation measurements of butane isomers were performed in the temperature range of 300-375 K. The separation factor was always greater than the ideal selectivity. This result is explained by the preferential adsorption of n-butane on MFI in the binary system.
    The pervaporation tests for xylene isomers were performed at 303 K. p-Xylene was the most permeable component in the unary system. In the permeation measurements of a binary mixture of p-xylene/m-xylene and a ternary mixture of p-xylene/m-xylene/o-xylene, p-xylene predominantly permeated in the early stage, and then, the Aux of p-xylene decreased gradually and finally became lower than that of the other xylene isomers. The adsorption of m-xylene in the pores of MFI seemed to block the permeation of p-xylene. (C) 2000 Elsevier Science B.V. All rights reserved.

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    106
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  • Formation of Uniform Mesopores in ZSM-5 Zeolite through Treatment in Alkaline Solution

    OGURA Masaru, SHINOMIYA Shin-ya, TATENO Junko, NARA Yasuto, KIKUCHI Eiichi, MATSUKATA Masahiko

    Chemistry letters   2000 ( 8 ) 882 - 883  2000年08月

     概要を見る

    Treatment of ZSM-5 in alkaline solution dramatically changes morphology of the ZSM-5, leading to the formation of mesopores whose size is almost uniform without destruction of microporous structure.

    DOI CiNii

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  • Synthesis and permeation studies of ferrierite/alumina composite membranes

    T Matsufuji, S Nakagawa, N Nishiyama, M Matsukata, K Ueyama

    MICROPOROUS AND MESOPOROUS MATERIALS   38 ( 1 ) 43 - 50  2000年07月

     概要を見る

    Polycrystalline ferrierite/alumina composite membranes were prepared by a vapor-phase transport method. Pervaporation of m-xylene and 1,3,5-triisopropylbenzene was then used to evaluate the compactness of the membranes.
    Permeation measurements were carried out for hydrogen, helium, methane, n-butane, i-butane and sulfur hexafluoride at 300-375 K. Ideal selectivities and the mixed gas separation factors were compared. The separation factor of butane isomers depended on the compactness of the membrane. The separation factor of n-butane/i-butane was as high as 40-70 at 375 K, and no detectable permeation flux of m-xylene was observed at 303 K.
    Separation of a 25/75 p-xylene/m-xylene mixture was also performed at 303 K using pervaporation. The permeation of p-xylene was detectable, whereas that of m-xylene was below the detection limit of the experiment. The separation factor of p-xylene to m-xylene was greater than 16, which is much higher than the value of 1.0 expected from the vapor-liquid equilibrium. (C) 2000 Elsevier Science B.V. All rights reserved.

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    30
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  • Synthesis and permeation studies of ferrierite/alumina composite membranes

    T Matsufuji, S Nakagawa, N Nishiyama, M Matsukata, K Ueyama

    MICROPOROUS AND MESOPOROUS MATERIALS   38 ( 1 ) 43 - 50  2000年07月

     概要を見る

    Polycrystalline ferrierite/alumina composite membranes were prepared by a vapor-phase transport method. Pervaporation of m-xylene and 1,3,5-triisopropylbenzene was then used to evaluate the compactness of the membranes.
    Permeation measurements were carried out for hydrogen, helium, methane, n-butane, i-butane and sulfur hexafluoride at 300-375 K. Ideal selectivities and the mixed gas separation factors were compared. The separation factor of butane isomers depended on the compactness of the membrane. The separation factor of n-butane/i-butane was as high as 40-70 at 375 K, and no detectable permeation flux of m-xylene was observed at 303 K.
    Separation of a 25/75 p-xylene/m-xylene mixture was also performed at 303 K using pervaporation. The permeation of p-xylene was detectable, whereas that of m-xylene was below the detection limit of the experiment. The separation factor of p-xylene to m-xylene was greater than 16, which is much higher than the value of 1.0 expected from the vapor-liquid equilibrium. (C) 2000 Elsevier Science B.V. All rights reserved.

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    30
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  • 石炭—水サスペンジョンの脱水技術

    石炭利用技術情報   232; 21-3, pp.7-8  2000年03月

  • ゼオライトの構造・物性に制御に関するいくつかの話題

    新化学発展協会先端化学技術部会    2000年03月

  • Permeation characteristics of butane isomers through MFI-type zeolitic membranes

    T Matsufuji, N Nishiyama, K Ueyama, M Matsukata

    CATALYSIS TODAY   56 ( 1-3 ) 265 - 273  2000年02月

     概要を見る

    MFI-type lozenge zeolitic membranes were prepared by a vapor-phase transport method on porous or-alumina flat disks. Pure or mixed gas permeation measurements of butane isomers were performed at 375 K using two methods: pressure gradient (PG) and concentration gradient (CG) methods. Pure gas permeation measurements of H-2, He, CH4, N-2, O-2, CO2 and SF6 were also carried out using PG method. Counter-diffusion of helium as a sweep gas was evaluated by determining the gas composition at the outlet of the feed side. It was confirmed that the counter-diffusion of helium occurs only when the total pressure of the feed side was &lt;80 kPa.
    In the mixed gas permeation measurements, the value of separation factor depended on the method of gas permeation. The separation factors of n-butane to i-butane were ca. 10 in the PG method and 30-60 in the CG method. (C) 2000 Elsevier Science B.V. All rights reserved.

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    30
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  • Catalytic activity of Ir for NO-CO reaction in the presence of SO2 and excess oxygen

    M Ogura, A Kawamura, M Matsukata, E Kikuchi

    CHEMISTRY LETTERS   pp.146-147 ( 2 ) 146 - 147  2000年02月

     概要を見る

    Catalytic performance of Ir catalysts for reduction of nitric oxide with carbon monoxide in the presence of SO, and excess oxygen was investigated. NO was selectively reduced with CO on Ir/silicalite in an oxidizing atmosphere containing 1% to 10% O-2 in the temperature range of 300-500 degrees C. The catalytic activity was scarcely influenced by 150 ppm SO2.

    DOI

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    77
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  • Permeation characteristics of butane isomers through MFI-type zeolitic membranes

    T Matsufuji, N Nishiyama, K Ueyama, M Matsukata

    CATALYSIS TODAY   56 ( 1-3 ) 265 - 273  2000年02月

     概要を見る

    MFI-type lozenge zeolitic membranes were prepared by a vapor-phase transport method on porous or-alumina flat disks. Pure or mixed gas permeation measurements of butane isomers were performed at 375 K using two methods: pressure gradient (PG) and concentration gradient (CG) methods. Pure gas permeation measurements of H-2, He, CH4, N-2, O-2, CO2 and SF6 were also carried out using PG method. Counter-diffusion of helium as a sweep gas was evaluated by determining the gas composition at the outlet of the feed side. It was confirmed that the counter-diffusion of helium occurs only when the total pressure of the feed side was &lt;80 kPa.
    In the mixed gas permeation measurements, the value of separation factor depended on the method of gas permeation. The separation factors of n-butane to i-butane were ca. 10 in the PG method and 30-60 in the CG method. (C) 2000 Elsevier Science B.V. All rights reserved.

    DOI

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    30
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  • Catalytic activity of Ir for NO-CO reaction in the presence of SO2 and excess oxygen

    M Ogura, A Kawamura, M Matsukata, E Kikuchi

    CHEMISTRY LETTERS   pp.146-147 ( 2 ) 146 - 147  2000年02月

     概要を見る

    Catalytic performance of Ir catalysts for reduction of nitric oxide with carbon monoxide in the presence of SO, and excess oxygen was investigated. NO was selectively reduced with CO on Ir/silicalite in an oxidizing atmosphere containing 1% to 10% O-2 in the temperature range of 300-500 degrees C. The catalytic activity was scarcely influenced by 150 ppm SO2.

    DOI

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    77
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  • 72.カラム浮選法における無機成分挙動に関する基礎的検討(石炭利用における科学と工学の融合)

    松方 正彦, 佐藤 大介, 小野 洋一郎, 菊地 英一

    石炭科学会議発表論文集   37   293 - 296  2000年

     概要を見る

    Inorganic matters behavior during column flotation which is a good candidate for preparing clean coal, was fundamentally studied. A column with 180cm high was continuously operated for 5 kinds of coal. The samples obtained from the top and bottom of column and aqueous phase were analyzed for the contents of inorganic elements. Inorganic elements were classified into three groups: (1) Those included in clean coal, (2) those rejected from the bottom of column, and (3) those soluble in aqueous phase. Alkali and alkaline elements were suggested to be extracted partly into aqueous phase. Predominant distribution of other elements like Al and Fe in clean coal or drain were observed in some types of coal, implying possible control of ash composition.

    DOI CiNii

  • 101.石炭燃焼時の無機成分の放出に関する基礎的検討

    松方 正彦, 林 桃子, 川端 友寛, 菊地 英一

    石炭科学会議発表論文集   37   409 - 412  2000年

     概要を見る

    The release of inorganic matters from coal combustion as volatile matters and aerosols at high temperatures and their deposition on lower temperature surfaces were investigated fundamentally. About 100mg of coal (SS027) smaller than 100μm held in a platinum basket was inserted into an electronic furnace and burned at 1080℃ to release vapor and aerosols of inorganic matters. A packed bed of ZrO_2 beads of 2mm was placed in the downstream of the reactor. The temperature of the bed was controlled at about 100℃ so that inorganic matters would be cauyht on the ZrO_2 beads. The quantities of inorganic matters ccaught on the ZrO_2 beads after 1, 10, 30, 60 and 180min of coal combustion were determined by use of inductively coupled plasma (ICP). It was found that initially, inorganic matters such as alkali, alkaline earth metals and iron release during volatilization followed by the release from char burning process. Inorganic matters further continued to be released from ash.

    DOI CiNii

  • 73.ガラスビーズの表面改質を用いた石炭モデル粒子の作製と粒子・気泡間付着現象の検討(石炭利用における科学と工学の融合)

    松方 正彦, 高橋 誠人, 菊地 英一

    石炭科学会議発表論文集   37   297 - 300  2000年

     概要を見る

    The preparation of model particles having controlled hydrophobic/hydrophilic surfaces was attempted to investigate flotation behavior of coal in a column flotation process quantitatively. The surface properties of glass beads with ca. 50μm diameter were modified by chemical vapor deposition of 1, 3, 5, 7, -tetrametyltetracyclosiloxane (H-4), followed by catalytic hydrosilylation with vinylacetic acid. The CVD of H-4 was performed for making the surface of glass beads hydrophobic and the successive hydrosilylation allowed us to prepare particles with moderate hydrophilic surfaces. The CVD conditions to adjust hydrophobicity of glass beads were explored. The surface properties of these particles and their distribution were evaluated by means of a film flotation technique. The bubble-particle attachment probability was preliminary studied using these model particles.

    DOI CiNii

  • 80.石炭中水溶性無機成分のイオンクロマトグラフィーによる分析

    松方 正彦, 草場 健太郎, 菊地 英一

    石炭科学会議発表論文集   37   325 - 328  2000年

     概要を見る

    A coal-water slurry was prepared by mixing 250ml of distilled water and a given amount of Datong Coal. The concentrations of slurry prepared was 0.596, 5.66 and 23.1wt%. The slurry was stirred for 3h. One ml of the slurry was taken by a syringe every 20min to investigate the elution rate of inorganic ions. Water-soluble inorganic matters in coal was attempted to quantitatively analyzed using ion chromatography. In comparison with ICP-AES, ion chromatography could be a method much easier to operate and cost effective. Three types of columns, YK-421 (HITACHI) for cations analysis, #2740 for anions analysis, and #2617 (HITACHI) for trace elements analysis, were used. It was found that cations were mostly eluted within 20min, while the elution of SO_4^<2-> continued up to 80min, leading to a decrease of pH from 5.3 to 2.6.

    DOI CiNii

  • Remarkable enhancement in durability of Pd/H-ZSM-5 zeolite catalysts for CH4-SCR

    Ogura M, Kage S, Hayashi M, Matsukata M, Kikuchi E

    Applied Catalysis B-Environmental   27 ( 4 ) L213 - L216  2000年  [査読有り]

    DOI

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    34
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  • Preparation of mordenite membranes on alpha-alumina tubular supports for pervaporation of water-isopropyl alcohol mixtures

    Lin, X, E Kikuchi, M Matsukata

    CHEMICAL COMMUNICATIONS   (957-958) ( 11 ) 957 - 958  2000年

     概要を見る

    Mordenite membranes prepared on alpha-alumina tubular supports by in situ hydrothermal synthesis using organic template-free media showed high water permselectivity for pervaporation of water-isopropyl alcohol mixtures.

    DOI

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    96
    被引用数
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  • Preparation of mordenite membranes on alpha-alumina tubular supports for pervaporation of water-isopropyl alcohol mixtures

    Lin, X, E Kikuchi, M Matsukata

    CHEMICAL COMMUNICATIONS   (957-958) ( 11 ) 957 - 958  2000年

     概要を見る

    Mordenite membranes prepared on alpha-alumina tubular supports by in situ hydrothermal synthesis using organic template-free media showed high water permselectivity for pervaporation of water-isopropyl alcohol mixtures.

    DOI

    Scopus

    96
    被引用数
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  • Determination of active palladium species in ZSM-5 zeolite for selective reduction of nitric oxide with methane

    M Ogura, M Hayashi, S Kage, M Matsukata, E Kikuchi

    APPLIED CATALYSIS B-ENVIRONMENTAL   23 ( 4 ) 247 - 257  1999年12月

     概要を見る

    The active site in ZSM-5 zeolite-supported palladium, which shows the catalytic activity for NO reduction with methane as a reducing agent, has been investigated qualitatively and quantitatively by means of NO chemisorption and NaCl titration, comparing with PdO supported on silica. Palladium species in 0.4 wt.% Pd loaded H-ZSM-5 can adsorb NO equimolarly after calcination at 773 K, and almost all the NO was desorbed at around 673 K; while the palladium species on PdO/SiO2 hardly adsorbed NO. The palladium species in Pd(0.4)/H-ZSM-5 are ion-exchangeable with Na+ in NaCl solution, indicating that they exist in a cationic state of an isolated Pd2+. This method for quantitative analysis of the isolated Pd2+ cations is named as 'NaCl titration'. The amount of the isolated Pd2+ cationic species increased with increasing palladium content on Pd/H-ZSM-5, and PdO co-existed above 1 wt.%. The amount of the isolated Pd2+ cation was unchanged after the reaction of NO2-CH4, NO2-CH4-O-2, or CH4-O-2 at 673 K, while the adsorbed amount of NO per the Pd2+ as determined by NO-TPD decreased after the NO2-CH4-O-2 reaction. It was found by NaCl titration that the catalytic activity of Pd/H-ZSM-5 for NO2-CH4-O-2 reaction increased with increasing amount of the isolated Pd2+ cationic species up to 0.7 wt.%, while the increase in the amount of PdO led to decrease in selectivity towards NO2 reduction. The palladium species that are active and selective for NO reduction with CH4 will be proposed. (C) 1999 Elsevier Science B.V. All rights reserved.

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  • Determination of active palladium species in ZSM-5 zeolite for selective reduction of nitric oxide with methane

    M Ogura, M Hayashi, S Kage, M Matsukata, E Kikuchi

    APPLIED CATALYSIS B-ENVIRONMENTAL   23 ( 4 ) 247 - 257  1999年12月

     概要を見る

    The active site in ZSM-5 zeolite-supported palladium, which shows the catalytic activity for NO reduction with methane as a reducing agent, has been investigated qualitatively and quantitatively by means of NO chemisorption and NaCl titration, comparing with PdO supported on silica. Palladium species in 0.4 wt.% Pd loaded H-ZSM-5 can adsorb NO equimolarly after calcination at 773 K, and almost all the NO was desorbed at around 673 K; while the palladium species on PdO/SiO2 hardly adsorbed NO. The palladium species in Pd(0.4)/H-ZSM-5 are ion-exchangeable with Na+ in NaCl solution, indicating that they exist in a cationic state of an isolated Pd2+. This method for quantitative analysis of the isolated Pd2+ cations is named as 'NaCl titration'. The amount of the isolated Pd2+ cationic species increased with increasing palladium content on Pd/H-ZSM-5, and PdO co-existed above 1 wt.%. The amount of the isolated Pd2+ cation was unchanged after the reaction of NO2-CH4, NO2-CH4-O-2, or CH4-O-2 at 673 K, while the adsorbed amount of NO per the Pd2+ as determined by NO-TPD decreased after the NO2-CH4-O-2 reaction. It was found by NaCl titration that the catalytic activity of Pd/H-ZSM-5 for NO2-CH4-O-2 reaction increased with increasing amount of the isolated Pd2+ cationic species up to 0.7 wt.%, while the increase in the amount of PdO led to decrease in selectivity towards NO2 reduction. The palladium species that are active and selective for NO reduction with CH4 will be proposed. (C) 1999 Elsevier Science B.V. All rights reserved.

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  • Development of Stable Organic-Vycor Glass Composite Membrane

    Proc. AIChE Fall Meeting, Dallas, U.S.A.   in CD-ROM  1999年11月

  • Crystallization of ferrierite (FER) on a porous alumina support by a vapor-phase transport method

    T Matsufuji, N Nishiyama, K Ueyama, M Matsukata

    MICROPOROUS AND MESOPOROUS MATERIALS   32 ( 1-2 ) 159 - 168  1999年11月

     概要を見る

    The formation of a ferrierite (FER) membrane by a vapor-phase transport method is discussed. The formation process was studied using X-ray diffraction, scanning electron microscopy (SEM), field emission-SEM and energy dispersive X-ray analysis. The same location on the top surface was repeatedly observed at different crystallization times using SEM. It was found that an aluminosilicate species formed from a dry gel layer was mobile over the surface of support during crystallization. This intermediate aluminosilicate species penetrated into the pores of the alumina support to fill them, generating a compact FER-alumina composite layer. (C) 1999 Elsevier Science B.V. All rights reserved.

    DOI

    Scopus

    24
    被引用数
    (Scopus)
  • Development of Stable Organic-Vycor Glass Composite Membrane

    Proc. AIChE Fall Meeting, Dallas, U.S.A.   in CD-ROM  1999年11月

  • Crystallization of ferrierite (FER) on a porous alumina support by a vapor-phase transport method

    T Matsufuji, N Nishiyama, K Ueyama, M Matsukata

    MICROPOROUS AND MESOPOROUS MATERIALS   32 ( 1-2 ) 159 - 168  1999年11月

     概要を見る

    The formation of a ferrierite (FER) membrane by a vapor-phase transport method is discussed. The formation process was studied using X-ray diffraction, scanning electron microscopy (SEM), field emission-SEM and energy dispersive X-ray analysis. The same location on the top surface was repeatedly observed at different crystallization times using SEM. It was found that an aluminosilicate species formed from a dry gel layer was mobile over the surface of support during crystallization. This intermediate aluminosilicate species penetrated into the pores of the alumina support to fill them, generating a compact FER-alumina composite layer. (C) 1999 Elsevier Science B.V. All rights reserved.

    DOI

    Scopus

    24
    被引用数
    (Scopus)
  • Ash Deposition Behavior on a Gasifier Wall of 2000t/D PDU of IGCC

    Proc. on Sixteenth Annual Intern. Pittsburgh Coal Conf.,   in CD-ROM  1999年10月

  • ドライゲルを用いたゼオライト合成

    第84回触媒学会秋季大会触媒討論会B    1999年10月

  • Ash Deposition Behavior on a Gasifier Wall of 2000t/D PDU of IGCC

    Proc. on Sixteenth Annual Intern. Pittsburgh Coal Conf.,   in CD-ROM  1999年10月

  • Synthesis of Zn-BEA Using a Dry Gel Conversion Technique

    Proc. 4th Europe Congress on Catal.    1999年09月

  • ドライゲルコンバージョン法によるメタロシリケートの合成

    日本化学会秋季大会    1999年09月

  • Synthesis of Zn-BEA Using a Dry Gel Conversion Technique

    Proc. 4th Europe Congress on Catal.    1999年09月

  • 新しいゼオライト合成法とその展開

    化学工学   63; 8, pp.462-463  1999年08月

  • ドライゲルを用いたゼオライト合成

    触媒   41; 8, pp.427-428  1999年08月

  • 無機膜技術の最近の動向

    工業材料   47; 7, pp.22-25  1999年07月

  • Pore modification of anodic alumina membrane by position-controlled CVD using catalytic reaction

    N Mori, Y Funakoshi, T Minami, Y Egashira, M Matsukata, K Ueyama

    JOURNAL OF CHEMICAL ENGINEERING OF JAPAN   32 ( 3 ) 307 - 313  1999年06月

     概要を見る

    We propose a new technique, "position-controlled CVD using catalytic reaction," to modify pore structure. By loading the catalyst for the reverse water gas shift reaction on a support that is to be modified, He can confine the hydrolysis reaction zone to a narrow region surrounding the catalyst where H2O is generated, An anodic alumina membrane with pore size of 26 nm was used as the support. Reactant gases, H-2, CO2 and TiCl4, were led into the same side of the membrane. The effects of reaction conditions on pore modification are investigated on the basis of FE-SEM observations and permeation tests, The pore size and permeance through the membrane gradually decrease with reaction time. Deposition morphology changes with reaction conditions, such as temperature, and H-2, CO2 and TiCl4 feed rates. In some cases, particles with 0.1-1 mu m diameter are formed on the outer surface of membrane.

    DOI

    Scopus

  • Evaluation of flotation results using metanil yellow adsorption

    H Fujimoto, M Matsukata, K Ueyama

    JOURNAL OF CHEMICAL ENGINEERING OF JAPAN   32 ( 3 ) 362 - 365  1999年06月

     概要を見る

    A new method was proposed to assess the surface properties of coal hy adsorption of metanil yellow using a continuous feed sg stem. The area fraction of the hydrophobic site on the exterior surface, alpha(m), was measured for Datong, Tyanfu, Shanxi No. 1, Illinois No. 6 and Blair Athol. Except for Tyanfu coal, the order of the values of alpha(m) is consistent with that of carbonaceous materials recovery. The,metanil yellow adsorption experiment requires no specific preparation, and can be applied to powder samples.

    DOI

    Scopus

    1
    被引用数
    (Scopus)
  • Behavior of coal particles in column flotation

    H Fujimoto, M Matsukata, K Ueyama

    JOURNAL OF CHEMICAL ENGINEERING OF JAPAN   32 ( 3 ) 322 - 327  1999年06月

     概要を見る

    The behavior of Datong coal particles in a flotation column was investigated in a batchwise operation using a gas distributor evolving uniform bubbles by varying the superficial gas velocity and column height. The value of superficial gas velocity was controlled at 0.66 or 1.99 cm s(-1)
    The time course of ash content in floats was measured when column height was 1.85 In, The ash content in clean coal was larger for higher superficial gas velocity. The hydrophobicity of coal particles recovered from the top of the column was evaluated by means of a film flotation method. Hydrophilic particles having the critical wetting surface tension of particles, gamma(c), greater than 60 mN m(-1) floated well for higher superficial gas velocity, The weight percent of fractions having gamma(c) above 60 mN m(-1) was 29.5, 31.9 and 40.5% for 0.25, 2.00 and 4.25 min. respectively. These values increased with sampling time, and were much greater than those for the lower superficial gas velocity. At lower superficial gas velocity, the hydrophobic coal particles seem to be selectively floated by colliding and attaching to the bubble surfaces. On the other hand, at higher superficial gas velocity, hydrophilic particles that are difficult to attach to bubbles seem to be entrained in the turbulent wake of bubble swamis and float.
    The grade of clean coal was better for the lower superficial gas velocity, however, carbonaceous materials recovery was lower than that for higher superficial gas velocity. Carbonaceous materials recovery was improved by increasing the recovery zone height.

    DOI

    Scopus

    2
    被引用数
    (Scopus)
  • Pore modification of anodic alumina membrane by position-controlled CVD using catalytic reaction

    N Mori, Y Funakoshi, T Minami, Y Egashira, M Matsukata, K Ueyama

    JOURNAL OF CHEMICAL ENGINEERING OF JAPAN   32 ( 3 ) 307 - 313  1999年06月

     概要を見る

    We propose a new technique, "position-controlled CVD using catalytic reaction," to modify pore structure. By loading the catalyst for the reverse water gas shift reaction on a support that is to be modified, He can confine the hydrolysis reaction zone to a narrow region surrounding the catalyst where H2O is generated, An anodic alumina membrane with pore size of 26 nm was used as the support. Reactant gases, H-2, CO2 and TiCl4, were led into the same side of the membrane. The effects of reaction conditions on pore modification are investigated on the basis of FE-SEM observations and permeation tests, The pore size and permeance through the membrane gradually decrease with reaction time. Deposition morphology changes with reaction conditions, such as temperature, and H-2, CO2 and TiCl4 feed rates. In some cases, particles with 0.1-1 mu m diameter are formed on the outer surface of membrane.

    DOI

    Scopus

  • Evaluation of flotation results using metanil yellow adsorption

    H Fujimoto, M Matsukata, K Ueyama

    JOURNAL OF CHEMICAL ENGINEERING OF JAPAN   32 ( 3 ) 362 - 365  1999年06月

     概要を見る

    A new method was proposed to assess the surface properties of coal hy adsorption of metanil yellow using a continuous feed sg stem. The area fraction of the hydrophobic site on the exterior surface, alpha(m), was measured for Datong, Tyanfu, Shanxi No. 1, Illinois No. 6 and Blair Athol. Except for Tyanfu coal, the order of the values of alpha(m) is consistent with that of carbonaceous materials recovery. The,metanil yellow adsorption experiment requires no specific preparation, and can be applied to powder samples.

    DOI

    Scopus

    1
    被引用数
    (Scopus)
  • Behavior of coal particles in column flotation

    H Fujimoto, M Matsukata, K Ueyama

    JOURNAL OF CHEMICAL ENGINEERING OF JAPAN   32 ( 3 ) 322 - 327  1999年06月

     概要を見る

    The behavior of Datong coal particles in a flotation column was investigated in a batchwise operation using a gas distributor evolving uniform bubbles by varying the superficial gas velocity and column height. The value of superficial gas velocity was controlled at 0.66 or 1.99 cm s(-1)
    The time course of ash content in floats was measured when column height was 1.85 In, The ash content in clean coal was larger for higher superficial gas velocity. The hydrophobicity of coal particles recovered from the top of the column was evaluated by means of a film flotation method. Hydrophilic particles having the critical wetting surface tension of particles, gamma(c), greater than 60 mN m(-1) floated well for higher superficial gas velocity, The weight percent of fractions having gamma(c) above 60 mN m(-1) was 29.5, 31.9 and 40.5% for 0.25, 2.00 and 4.25 min. respectively. These values increased with sampling time, and were much greater than those for the lower superficial gas velocity. At lower superficial gas velocity, the hydrophobic coal particles seem to be selectively floated by colliding and attaching to the bubble surfaces. On the other hand, at higher superficial gas velocity, hydrophilic particles that are difficult to attach to bubbles seem to be entrained in the turbulent wake of bubble swamis and float.
    The grade of clean coal was better for the lower superficial gas velocity, however, carbonaceous materials recovery was lower than that for higher superficial gas velocity. Carbonaceous materials recovery was improved by increasing the recovery zone height.

    DOI

    Scopus

    2
    被引用数
    (Scopus)
  • Kinetics of CaO-H2S Reaction at High Temperature under Pressurized Conditions

    Proc. 15th Intern. ASME Conf. on Fluidized Bed Combustion, Georgia, U.S.A.   Paper no. 99-0009  1999年05月

  • Kinetics of CaO-H2S Reaction at High Temperature under Pressurized Conditions

    Proc. 15th Intern. ASME Conf. on Fluidized Bed Combustion, Georgia, U.S.A.   Paper no. 99-0009  1999年05月

  • Synthesis of Pure Silica BEA and Al-free Ti-BEA Using TEAOH and Their Characterization

    Proc. the 12th Intern. Zeolite Conf., Baltimore, 1998, Ed. by M.M.J. Treacy, B. Marcus, J.B. Higgins, M.E. Bisher, Mater. Res. Soc.   (1515-1522)  1999年04月

  • Synthesis of OU-1, a Large-Pore, High Silica Zeolite, by Dry Gel Conversion

    Proc. the 12th Intern. Zeolite Conf., Baltimore, 1998, Ed. by M.M.J. Treacy, B. Marcus, J.B. Higgins, M.E. Bisher, Mater. Res. Soc.   (2009-2014)  1999年04月

  • Evaluation of flotation results using rubidium ion exchange

    H Fujimoto, M Matsukata, K Ueyama

    JOURNAL OF CHEMICAL ENGINEERING OF JAPAN   32 ( 2 ) 204 - 210  1999年04月

     概要を見る

    Coal particles contain oxygen functional groups such as hydroxyl, carbonyl, and carboxyl, and mineral matters that contribute surface hydrophilicity, The occurrence of them varies considerably from coal to coal, hence the characteristics of column flotation changes from coal to coal. We expected that the characteristics of column flotation could be simply evaluated by using the area fraction of oxygen functional group sites on the exterior surface of the coal particles.
    In this work, we conducted column flotation for Shanxi (anthracite), Tyanfu (bituminous), Blair Athol (bituminous), Datong (bituminous), and Illinois (brown coal). The order of carbonaceous materials recovery was found to be Tyanfu &gt; Shanxi &gt; Blair Athol &gt; Datong &gt; Illinois, We also evaluated the area fraction of hydroxyl group on the exterior surface of the coal particles, alpha(ex-OH), and that in the coal particles, alpha i(n-OH). For Datong coal, the value of alpha(ex-OH) was larger than that of alpha(in-OH). It means that Datong coal was slightly oxidized. The order of carbonaceous materials recovery was inconsistent with that of alpha(ex-OH) for the three kinds of bituminous coal. For Shanxi anthracite coal, the flotability is evaluated by considering the wettability of the hydrophobic sites as well as the hydrophilic sites.

    DOI

    Scopus

    1
    被引用数
    (Scopus)
  • Effect of Pinholes on Permselectivities of MFI Membranes

    Proc. the 12th Intern. Zeolite Conf., Baltimore, 1998, Ed. by M.M.J. Treacy, B. Marcus, J.B. Higgins, M.E. Bisher, Mater. Res. Soc.   (613-620)  1999年04月

  • Synthesis of Pure Silica BEA and Al-free Ti-BEA Using TEAOH and Their Characterization

    Proc. the 12th Intern. Zeolite Conf., Baltimore, 1998, Ed. by M.M.J. Treacy, B. Marcus, J.B. Higgins, M.E. Bisher, Mater. Res. Soc.   (1515-1522)  1999年04月

  • Synthesis of OU-1, a Large-Pore, High Silica Zeolite, by Dry Gel Conversion

    Proc. the 12th Intern. Zeolite Conf., Baltimore, 1998, Ed. by M.M.J. Treacy, B. Marcus, J.B. Higgins, M.E. Bisher, Mater. Res. Soc.   (2009-2014)  1999年04月

  • Evaluation of flotation results using rubidium ion exchange

    H Fujimoto, M Matsukata, K Ueyama

    JOURNAL OF CHEMICAL ENGINEERING OF JAPAN   32 ( 2 ) 204 - 210  1999年04月

     概要を見る

    Coal particles contain oxygen functional groups such as hydroxyl, carbonyl, and carboxyl, and mineral matters that contribute surface hydrophilicity, The occurrence of them varies considerably from coal to coal, hence the characteristics of column flotation changes from coal to coal. We expected that the characteristics of column flotation could be simply evaluated by using the area fraction of oxygen functional group sites on the exterior surface of the coal particles.
    In this work, we conducted column flotation for Shanxi (anthracite), Tyanfu (bituminous), Blair Athol (bituminous), Datong (bituminous), and Illinois (brown coal). The order of carbonaceous materials recovery was found to be Tyanfu &gt; Shanxi &gt; Blair Athol &gt; Datong &gt; Illinois, We also evaluated the area fraction of hydroxyl group on the exterior surface of the coal particles, alpha(ex-OH), and that in the coal particles, alpha i(n-OH). For Datong coal, the value of alpha(ex-OH) was larger than that of alpha(in-OH). It means that Datong coal was slightly oxidized. The order of carbonaceous materials recovery was inconsistent with that of alpha(ex-OH) for the three kinds of bituminous coal. For Shanxi anthracite coal, the flotability is evaluated by considering the wettability of the hydrophobic sites as well as the hydrophilic sites.

    DOI

    Scopus

    1
    被引用数
    (Scopus)
  • Effect of Pinholes on Permselectivities of MFI Membranes

    Proc. the 12th Intern. Zeolite Conf., Baltimore, 1998, Ed. by M.M.J. Treacy, B. Marcus, J.B. Higgins, M.E. Bisher, Mater. Res. Soc.   (613-620)  1999年04月

  • 1-21.ガス化炉内付着灰およびチャーのキャラクタリゼーション(Session(1)石炭・重質油)

    松方 正彦, 林 桃子, 菊地 英一, 藤田 直一, 上山 惟一

    日本エネルギー学会大会講演要旨集   8   91 - 94  1999年

    DOI CiNii

  • Conversion of dry gels to zeolites

    M Matsukata, PRHP Rao, T Osaki, M Ogura, E Kikuchi

    JAPAN INSTITUTE OF METALS, PROCEEDINGS, VOL 12, (JIMIC-3), PTS 1 AND 2   (1421-1424)   1421 - 1424  1999年

     概要を見る

    Crystallization of zeolite using an organic compound as a structure-directing agent (SDA) and phase transformation of zeolite into another phase were investigated by means of a new crystallization method of dry gel conversion (DGC). Different types of zeolite were crystallized by DGC with SDAs having different sizes in alkyl chains of organics. Not the size of SDAs but the type of them determines the phase crystallized. Phase transformation of zeolite beta occurred into a new phase of zeolite OU-1, which has the same topology as zeolites SSZ-31 and NCL-1. From XRD and SEM observations, it can be concluded that the phase transformation occurs via surface-mediated nucleation and growth without significant dissolution nor destruction of zeolite structure.

  • Conversion of dry gel to microporous crystals in gas phase

    M Matsukata, M Ogura, T Osaki, PRHP Rao, M Nomura, E Kikuchi

    TOPICS IN CATALYSIS   9 ( 1-2 ) 77 - 92  1999年

     概要を見る

    Recently the dry gel conversion (DGC) technique, where a hydrogel is dried and the resultant dry gel is converted into microporous crystals in steam or in a mixed vapor of steam and organic structure-directing agents (SDAs), has been developed. It has been shown that a wide variety of microporous crystals, pure silica microporous crystals, aluminosilicates, metallosilicates, and aluminophosphates, can be synthesized using the DGC method. Remarkable results have been reported in the synthesis of BEA types zeolites, namely aluminosilicate, titaniumsilicate, zincosilicate, and borosilicate with BEA topology, using tetraethylammonium hydroxide, a commercially available SDA. It has also been found that zeolite OU-1, probably analogous to SSZ-31 and NCL-1, is formed via phase transformation from BEA. Dense zeolite coatings like membranes are possible using this method. Characteristics of the DGC method are discussed in detail.

  • Conversion of dry gels to zeolites

    M Matsukata, PRHP Rao, T Osaki, M Ogura, E Kikuchi

    JAPAN INSTITUTE OF METALS, PROCEEDINGS, VOL 12, (JIMIC-3), PTS 1 AND 2   (1421-1424)   1421 - 1424  1999年

     概要を見る

    Crystallization of zeolite using an organic compound as a structure-directing agent (SDA) and phase transformation of zeolite into another phase were investigated by means of a new crystallization method of dry gel conversion (DGC). Different types of zeolite were crystallized by DGC with SDAs having different sizes in alkyl chains of organics. Not the size of SDAs but the type of them determines the phase crystallized. Phase transformation of zeolite beta occurred into a new phase of zeolite OU-1, which has the same topology as zeolites SSZ-31 and NCL-1. From XRD and SEM observations, it can be concluded that the phase transformation occurs via surface-mediated nucleation and growth without significant dissolution nor destruction of zeolite structure.

  • Conversion of dry gel to microporous crystals in gas phase

    M Matsukata, M Ogura, T Osaki, PRHP Rao, M Nomura, E Kikuchi

    TOPICS IN CATALYSIS   9 ( 1-2 ) 77 - 92  1999年

     概要を見る

    Recently the dry gel conversion (DGC) technique, where a hydrogel is dried and the resultant dry gel is converted into microporous crystals in steam or in a mixed vapor of steam and organic structure-directing agents (SDAs), has been developed. It has been shown that a wide variety of microporous crystals, pure silica microporous crystals, aluminosilicates, metallosilicates, and aluminophosphates, can be synthesized using the DGC method. Remarkable results have been reported in the synthesis of BEA types zeolites, namely aluminosilicate, titaniumsilicate, zincosilicate, and borosilicate with BEA topology, using tetraethylammonium hydroxide, a commercially available SDA. It has also been found that zeolite OU-1, probably analogous to SSZ-31 and NCL-1, is formed via phase transformation from BEA. Dense zeolite coatings like membranes are possible using this method. Characteristics of the DGC method are discussed in detail.

  • ゼオライトOU-1合成の経緯と構造

    ゼオライト   15;4,PP152-156  1998年12月

  • Novel Organic-inorganic Composite Membrane having Si-C Bonds

    Proc. AIChE Fall Meeting, Miami, U.S.A.    1998年11月

  • 新しい酸化技術—非エアロビック酸化への挑戦

    第3回次世代化学プロセス技術開発シンポジウム、主催 日本化学工業協会/霞ヶ関ビル1Fプラザホール    1998年11月

  • Novel Organic-inorganic Composite Membrane having Si-C Bonds

    Proc. AIChE Fall Meeting, Miami, U.S.A.    1998年11月

  • A Study of The Release of Inorganic Matters from Coal during Combustion/Gasification

    Proc. 6th Japan-China Symp. on Coal and C1 Chemistry, Zao, Miyagi   480-483  1998年10月

  • A Study of The Release of Inorganic Matters from Coal during Combustion/Gasification

    Proc. 6th Japan-China Symp. on Coal and C1 Chemistry, Zao, Miyagi   480-483  1998年10月

  • Permeation Characteristics of Butane Isomers through MFI-type Zeolitic Membranes

    Proc. III International Conference on Catalysis in Membrane Reactors, Copenhagen, Denmark   PP17  1998年09月

  • Molecular Size Recognition with Zeolitic Membranes

    Proc. III International Conference on Catalysis in Membrane Reactors, Copenhagen, Denmark   PPO16  1998年09月

  • 実験と分子シミュレーションの接点を求めて

    化学工学会第31回秋季大会シンポジウム「分子シミュレーション工学:コンピュータ化学への工学ツールへの展開を目指して」/山形大学工学部(米沢)    1998年09月

  • Permeation Characteristics of Butane Isomers through MFI-type Zeolitic Membranes

    Proc. III International Conference on Catalysis in Membrane Reactors, Copenhagen, Denmark   PP17  1998年09月

  • Molecular Size Recognition with Zeolitic Membranes

    Proc. III International Conference on Catalysis in Membrane Reactors, Copenhagen, Denmark   PPO16  1998年09月

  • Selective Permeation of Hydrocarbons through A Zeolitic Membrane

    Proc. Fifth International Conference on Inorganic Membranes (ICIM5 '98), Nagoya   PP184-187  1998年06月

  • Permeation Studies of Butane Isomers through MFI-type Zeolitic Membranes

    Proc. Fifth International Conference on Inorganic Membranes (ICIM5 '98), Nagoya   PP568-571  1998年06月

  • Dry Gel Conversion Synthesis of Zeolitic Membranes

    International Workshop of Zeolitic Membranes and Films, Nagaragawa, Gifu, Japan    1998年06月

  • Selective Permeation of Hydrocarbons through A Zeolitic Membrane

    Proc. Fifth International Conference on Inorganic Membranes (ICIM5 '98), Nagoya   PP184-187  1998年06月

  • Permeation Studies of Butane Isomers through MFI-type Zeolitic Membranes

    Proc. Fifth International Conference on Inorganic Membranes (ICIM5 '98), Nagoya   PP568-571  1998年06月

  • Dry Gel Conversion Synthesis of Zeolitic Membranes

    International Workshop of Zeolitic Membranes and Films, Nagaragawa, Gifu, Japan    1998年06月

  • Dry-Gel Converted Zeolite Membranes: A Comprehensive Review and Application in Membrane Reactors

    The 10th Annual Meeting of the North American Membrane Society, Cleveland, Ohio, U.S.A.    1998年05月

  • 酸素透過型メンブレンリアクターによるメタンからの合成ガスの(トピックス)

    化学と工業   51;5,PP787  1998年05月

  • Dry-Gel Converted Zeolite Membranes: A Comprehensive Review and Application in Membrane Reactors

    The 10th Annual Meeting of the North American Membrane Society, Cleveland, Ohio, U.S.A.    1998年05月

  • Phase Transformation of BEA Zeolite by Dry Gel Conversion

    Chem. Letters.   PP311-312  1998年04月

  • 無機膜による炭化水素分離

    松方 正彦

    膜   23;2,PP55-61 ( 2 ) 55 - 61  1998年04月

     概要を見る

    State-of-the art of hydrocarbon separation technology by inorganic membranes is reviewed. Targets for hydrocarbon separation are classified into five groups : H2/Lower hydrocarbons, alkane/alkene, straight chain hydrocarbons/branched hydrocarbons, aliphatic hydrocarbons/aromatic hydrocarbons, and aromatic hydrocarbon mixtures. Various types of microporous inorganic membranes, amorphous silica, zeolites and carbon membranes, have been under development. Some of them show very high permselectivities, indicating the promising prospects of inorganic membrane technology. While molecular sieving property has long been anticipated to appear on the basis of size recognition by micropores smaller than 1 nm, there have been a few reports with conclusive evidence on the separation by molecular sieving. On the other hand, the difference in adsorption properties into a membrane can lead to the appearance of permselectivity particularly at lower temperatures.

    DOI CiNii

  • Phase Transformation of BEA Zeolite by Dry Gel Conversion

    Chem. Letters.   PP311-312  1998年04月

  • Fundamental Study on Emission of Inorganic Matters from Coal and Their Deposition

    Proc. International Conference on Ash Behavior Control in Energy Conversion Systems   PP75-85  1998年03月

  • Fundamental Study on Emission of Inorganic Matters from Coal and Their Deposition

    Proc. International Conference on Ash Behavior Control in Energy Conversion Systems   PP75-85  1998年03月

  • Synthesis of Pure Silica BEA and Al-free Ti-BEA Using TEAOH and Their Characterization

    Proc. the 12th Intern. Zeolite Conf., Baltimore, 1998/Mater. Res. Soc.    1998年

  • Synthesis of OU-1, a Large-Pore, High Silica Zeolite, by Dry Gel Conversion

    Proc. the 12th Intern. Zeolite Conf., Baltimore, 1998/Mater. Res. Soc.    1998年

  • Synthesis of borosilicate zeolites by dry gel conversion (DGC) method

    Rajib Bandyopadhyay, Yoshihiro Kubota, Yoshihiro Sugi

    Chemistry Letters   PP20 ( 8 ) 813 - 814  1998年

     概要を見る

    Synthesis of borosilicate zeolites, namely [B]-BEA, [B]-MFI and [B]-MTW by dry gel conversion (DGC) method was described for the first time. Phase selection and thereby the outcome of the product was dependent upon the gel composition, mainly on the SiO2/B2O3 ratio and the TEAOH content.

    DOI

  • Synthesis of BEA by dry gel conversion and its characterization

    P. R. Hari Prasad Rao, C. A. Leon Y Leon, K. Ueyama, M. Matsukata

    Microporous and Mesoporous Materials   21 ( 4-6 ) 305 - 313  1998年

     概要を見る

    Zeolite BEA with SiO2/Al2O3 ratios ranging from 30 to 740 were crystallized at 413 and 453 K by the dry gel conversion technique. The particle size of the products increased with increasing SiO2/Al2O3 ratio as well as with increasing crystallization temperature. In as-synthesized BEA, the TEA+ ions interacting with Si-O- decomposed between 473 and 673 K and those interacting with Al-O- were cleaved between 673 and 798 K. During their elimination, the TEA+ ions interacting with Al-O- underwent higher degradation than those interacting with Si-O-. Chemical compositions showed the least influence on the fractions of decomposition product during the elimination between 473 and 673 K. The framework of H-BEA and NH4-BEA zeolites with SiO2/Al2O3 ratios ranging from 400 to 740 were stable even at 1373 K, whereas H-BEA with SiO2/Al2O3 = 30 was stable only up to 1173 K and became amorphous when calcined at 1373 K. After calcination at 1373 K, Na-BEA with SiO2/Al2O3 = 400 and 730 were transformed to tridymite (dense phase) whereas that with SiO2/Al2O3 = 30 became amorphous. The elimination of Na+ ions is necessary to have a BEA remain stable above 1173 K. © 1998 Elsevier Science B.V. All rights reserved.

    DOI

    Scopus

    71
    被引用数
    (Scopus)
  • Effect of Pinholes on Permselectivities of MFI Membranes

    Proc. the 12th Intern. Zeolite Conf., Baltimore, 1998/Mater. Res. Soc.    1998年

  • Crystallization of high silica BEA by dry gel conversion

    PRHP Rao, K Ueyama, M Matsukata

    APPLIED CATALYSIS A-GENERAL   166 ( 1 ) 97 - 103  1998年01月

     概要を見る

    Zeolite with BEA structure was prepared using a new crystallization method called 'Dry Gel Conversion Technique'. This dry gel conversion technique is a convenient method to prepare zeolites and enables one to synthesize zeolite BEA with SiO2/Al2O3 ratios from 30 to infinity using tetraethylammonium hydroxide (TEAOH) as a structure directing agent. Zeolite BEA with SiO2/Al2O3 ratios from 30 to 730 were rapidly crystallized in 3 and 12 h, respectively. The Al-27 NMR spectrum for BEA with SiO2/Al2O3 ratio of 30 confirmed the absence of octahedrally coordinated aluminum. The crystallization rates were higher for BEA with low SiO2/Al2O3 ratios than for those with high SiO2/Al2O3 ratios. BEA crystallized by this method had uniform particles of about 60 nm. Higher Na+ ion concentrations in the gel promoted the formation of high silica BEA. Elimination of occluded TEA cations took place at lower temperatures (around 623 K) in high silica BEA than that in BEA with low SiO2/Al2O3 ratios (around 900 K). This method also allowed to synthesize BEA in the form of self-bonded pellets. (C) 1998 Elsevier Science B.V.

    DOI

    Scopus

    88
    被引用数
    (Scopus)
  • Synthesis of Pure Silica BEA and Al-free Ti-BEA Using TEAOH and Their Characterization

    Proc. the 12th Intern. Zeolite Conf., Baltimore, 1998/Mater. Res. Soc.    1998年

  • Synthesis of OU-1, a Large-Pore, High Silica Zeolite, by Dry Gel Conversion

    Proc. the 12th Intern. Zeolite Conf., Baltimore, 1998/Mater. Res. Soc.    1998年

  • Synthesis of borosilicate zeolites by dry gel conversion (DGC) method

    Rajib Bandyopadhyay, Yoshihiro Kubota, Yoshihiro Sugi

    Chemistry Letters   PP20 ( 8 ) 813 - 814  1998年

     概要を見る

    Synthesis of borosilicate zeolites, namely [B]-BEA, [B]-MFI and [B]-MTW by dry gel conversion (DGC) method was described for the first time. Phase selection and thereby the outcome of the product was dependent upon the gel composition, mainly on the SiO2/B2O3 ratio and the TEAOH content.

    DOI

  • Synthesis of BEA by dry gel conversion and its characterization

    P. R. Hari Prasad Rao, C. A. Leon Y Leon, K. Ueyama, M. Matsukata

    Microporous and Mesoporous Materials   21 ( 4-6 ) 305 - 313  1998年

     概要を見る

    Zeolite BEA with SiO2/Al2O3 ratios ranging from 30 to 740 were crystallized at 413 and 453 K by the dry gel conversion technique. The particle size of the products increased with increasing SiO2/Al2O3 ratio as well as with increasing crystallization temperature. In as-synthesized BEA, the TEA+ ions interacting with Si-O- decomposed between 473 and 673 K and those interacting with Al-O- were cleaved between 673 and 798 K. During their elimination, the TEA+ ions interacting with Al-O- underwent higher degradation than those interacting with Si-O-. Chemical compositions showed the least influence on the fractions of decomposition product during the elimination between 473 and 673 K. The framework of H-BEA and NH4-BEA zeolites with SiO2/Al2O3 ratios ranging from 400 to 740 were stable even at 1373 K, whereas H-BEA with SiO2/Al2O3 = 30 was stable only up to 1173 K and became amorphous when calcined at 1373 K. After calcination at 1373 K, Na-BEA with SiO2/Al2O3 = 400 and 730 were transformed to tridymite (dense phase) whereas that with SiO2/Al2O3 = 30 became amorphous. The elimination of Na+ ions is necessary to have a BEA remain stable above 1173 K. © 1998 Elsevier Science B.V. All rights reserved.

    DOI

    Scopus

    71
    被引用数
    (Scopus)
  • Effect of Pinholes on Permselectivities of MFI Membranes

    Proc. the 12th Intern. Zeolite Conf., Baltimore, 1998/Mater. Res. Soc.    1998年

  • Crystallization of high silica BEA by dry gel conversion

    PRHP Rao, K Ueyama, M Matsukata

    APPLIED CATALYSIS A-GENERAL   166 ( 1 ) 97 - 103  1998年01月

     概要を見る

    Zeolite with BEA structure was prepared using a new crystallization method called 'Dry Gel Conversion Technique'. This dry gel conversion technique is a convenient method to prepare zeolites and enables one to synthesize zeolite BEA with SiO2/Al2O3 ratios from 30 to infinity using tetraethylammonium hydroxide (TEAOH) as a structure directing agent. Zeolite BEA with SiO2/Al2O3 ratios from 30 to 730 were rapidly crystallized in 3 and 12 h, respectively. The Al-27 NMR spectrum for BEA with SiO2/Al2O3 ratio of 30 confirmed the absence of octahedrally coordinated aluminum. The crystallization rates were higher for BEA with low SiO2/Al2O3 ratios than for those with high SiO2/Al2O3 ratios. BEA crystallized by this method had uniform particles of about 60 nm. Higher Na+ ion concentrations in the gel promoted the formation of high silica BEA. Elimination of occluded TEA cations took place at lower temperatures (around 623 K) in high silica BEA than that in BEA with low SiO2/Al2O3 ratios (around 900 K). This method also allowed to synthesize BEA in the form of self-bonded pellets. (C) 1998 Elsevier Science B.V.

    DOI

    Scopus

    88
    被引用数
    (Scopus)
  • FER membrane synthesized by a vapor-phase transport method: its structure and separation characteristics

    N Nishiyama, T Matsufuji, K Ueyama, M Matsukata

    MICROPOROUS MATERIALS   12 ( 4-6 ) 293 - 303  1997年12月  [査読有り]

     概要を見る

    The mechanism of formation of ferrierite (FER) membrane on an alumina support by a vapor-phase transport (VPT) method was studied using XRD, SEM, FE-SEM and EDX. The XRD measurement for a FER membrane after the removal of FER particles formed on the support showed that FER was formed in the pores of the alumina support, namely, a FER-alumina composite layer was formed. The FE-SEM image for the cross-sectional view of the FER-alumina composite layer showed that FER nanocrystals of about 50 nm diameter grew in the pores of the alumina support. Pervaporation tests for benzene/p-xylene mixtures were performed at 303 K. Even when the concentration of benzene in the feed solution was extremely small (0.5 mol%), the flux of benzene through the FER membrane was still greater than that of p-xylene. Therefore, a separation factor as high as 600 was obtained in the low feed concentration of benzene. Such a high selectivity for the benzene/p-xylene mixture suggested that the selectivity for the benzene/p-xylene mixture appears at the pore mouths of FER on the feed side of the FER-alumina composite layer. (C) 1997 Elsevier Science B.V.

  • 新規なゼオライト合成法とナノ構造制御の可能性

    「ALE法による表面処理および触媒合成」KRI ICC'97 Workshop    1997年12月

  • 無機ガス分離膜の開発動向

    化学工学会    1997年11月

  • Zeolitic membranes: Synthesis, properties, and prospects

    M Matsukata, E Kikuchi

    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN   70 ( 10 ) 2341 - 2356  1997年10月

     概要を見る

    This article is intended to describe recent progress in the synthesis of zeolitic membranes and their permeation properties. While hydrothermal synthesis has been widely employed for zeolitic-membrane synthesis, the development of a new technique for zeolite synthesis, vapor-phase transport (VPT), has enabled us to prepare pinhole-free, zeolite-porous support composite membranes. This article consists of three sections that describe: a survey of the hydrothermal synthesis of zeolitic membranes, our synthesis results and the formation mechanism of zeolitic membranes by the VPT method as well as some permeation results to show the prospects of zeolitic membranes.

    DOI

    Scopus

    113
    被引用数
    (Scopus)
  • Zeolitic membranes: Synthesis, properties, and prospects

    M Matsukata, E Kikuchi

    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN   70 ( 10 ) 2341 - 2356  1997年10月

     概要を見る

    This article is intended to describe recent progress in the synthesis of zeolitic membranes and their permeation properties. While hydrothermal synthesis has been widely employed for zeolitic-membrane synthesis, the development of a new technique for zeolite synthesis, vapor-phase transport (VPT), has enabled us to prepare pinhole-free, zeolite-porous support composite membranes. This article consists of three sections that describe: a survey of the hydrothermal synthesis of zeolitic membranes, our synthesis results and the formation mechanism of zeolitic membranes by the VPT method as well as some permeation results to show the prospects of zeolitic membranes.

    DOI

    Scopus

    113
    被引用数
    (Scopus)
  • Reduction of Boron Concentration in Water Produced by a Reverse Osmosis Sea Water Desalination Unit

    Membrane(Maku)   22;4, PP211-216  1997年09月

    DOI

  • ゼオライト単結晶膜による分子の分離

    化学/東京化学同人   52:9, PP66-67  1997年09月

  • Reduction of Boron Concentration in Water Produced by a Reverse Osmosis Sea Water Desalination Unit

    Membrane(Maku)   22;4, PP211-216  1997年09月

    DOI

  • Dry Gel Conversion Synthesis of Zeolites

    Post Symp. ZMPC '97, Synthesis and Characterization of Zeolite-Related Materials    1997年08月

  • Dry Gel Conversion Synthesis of Zeolites

    Post Symp. ZMPC '97, Synthesis and Characterization of Zeolite-Related Materials    1997年08月

  • Phase Transformation of High Silica BEA

    Proc. Intern. Symp. on Zeolites and Microporous Crystals   PP133  1997年07月

  • Formation Mechanism of FER Membranes by Vapor-phase Transport Method

    Proc. Intern. Symp. on Zeolites and Microporous Crystals   PP34  1997年07月

  • ゼオライトの新しい合成法:ドライゲルコンバージョン

    化学工学会    1997年07月

  • Phase Transformation of High Silica BEA

    Proc. Intern. Symp. on Zeolites and Microporous Crystals   PP133  1997年07月

  • Formation Mechanism of FER Membranes by Vapor-phase Transport Method

    Proc. Intern. Symp. on Zeolites and Microporous Crystals   PP34  1997年07月

  • Microscopic Structure of a Ferrierite Membrane Synthesized by a Vapor-phase Transport Technique

    Proc. 15th North American Catalysis Society Meeting    1997年05月

  • HCl and SO2 Absorption at 1023 K with Calcined Limestone

    Proc. 14th Intern. ASME Conf. on Fluidized Bed Combustion   PP397-404  1997年05月

  • Dry Gel Conversion Synthesis of beta and EMT Zeolites

    Proc. 15th North American Catalysis Society Meeting    1997年05月

  • ゼオライトの合成および膜作成技術の最近の進歩

    セラミックス   32:5, PP351-355  1997年05月

  • Microscopic Structure of a Ferrierite Membrane Synthesized by a Vapor-phase Transport Technique

    Proc. 15th North American Catalysis Society Meeting    1997年05月

  • HCl and SO2 Absorption at 1023 K with Calcined Limestone

    Proc. 14th Intern. ASME Conf. on Fluidized Bed Combustion   PP397-404  1997年05月

  • Dry Gel Conversion Synthesis of beta and EMT Zeolites

    Proc. 15th North American Catalysis Society Meeting    1997年05月

  • ゼオライトの薄膜化とその機能

    触媒   39;2  1997年03月

  • Synthesis of a zeolitic thin layer by a vapor-phase transport method: Appearance of a preferential orientation of MFI zeolite

    Eiichi Kikuchi, Kazuhiko Yamashita, Sachioko Hiromoto, Korekazu Ueyama, Masahiko Matsukata

    Microporous Materials   11 ( 3-4 ) 107 - 116  1997年

     概要を見る

    Zeolitic membranes were synthesized on a porous alumina support by the vapor-phase transport method using one of two alumina sources: aluminum sulfate and sodium aluminate. By choosing the appropriate period and temperature for drying the aluminosilicate gel on the alumina support, MOR, FER and MFI could be synthesized. MOR was formed when the water content in the dry gel was high. As the water content decreased, FER and MFI were formed sequentially. Preferential formation of MFI was achieved by treating the dry gel at 373 K. The temperature at which the support was dipped in the parent gel also influenced the type of zeolite formed, although the effect of drying conditions was more pronounced. A similar trend was found for both aluminum sulfate and sodium aluminate. When the alumina source was sodium aluminate and the aluminosilicate gel was treated at 373 K, a preferentially oriented MFI membrane could be synthesized, as the (a00) and (0b0) crystal faces were oriented in parallel to the surface of porous alumina support. The uniform and dense morphology of the dry gel seems to account for the appearance of the orientation. © 1997 Elsevier Science B.V.

    DOI

    Scopus

    40
    被引用数
    (Scopus)
  • Gas permeation through zeolite-alumina composite membranes

    N Nishiyama, K Ueyama, M Matsukata

    AICHE JOURNAL   43 ( 11 ) 2724 - 2730  1997年

     概要を見る

    Mordenite (MOR) and ferrierite (FER) membranes without any pinhole and crack were synthesized by a vapor-phase transport method. The permeance of H-2, He, CH4, N-2, O-2 and CO2 was determined at 290-400 K; which showed minimum with increasing temperatures for most cases. In the parallel diffusion model was proposed, molecules adsorbed in a micropore are assumed to diffuse in parallel through the central region of the pore and along the wall region of the pore. This parallel diffusion model accounts for the effect of pore Size of MOR and FER on the permeation and expresses the experimental data well. The interaction between gas molecules and pore walls are evaluated for each gas.

    DOI

    Scopus

    43
    被引用数
    (Scopus)
  • FER membrane synthesized by a vapor-phase transport method: Its structure and separation characteristics

    Norikazu Nishiyama, Takaaki Matsufuji, Korekazu Ueyama, Masahiko Matsukata

    Microporous Materials   12 ( 4-6 ) 293 - 303  1997年

     概要を見る

    The mechanism of formation of ferrierite (FER) membrane on an alumina support by a vapor-phase transport (VPT) method was studied using XRD, SEM, FE-SEM and EDX. The XRD measurement for a FER membrane after the removal of FER particles formed on the support showed that FER was formed in the pores of the alumina support, namely, a FER-alumina composite layer was formed. The FE-SEM image for the cross-sectional view of the FER-alumina composite layer showed that FER nanocrystals of about 50 nm diameter grew in the pores of the alumina support. Pervaporation tests for benzene/p-xylene mixtures were performed at 303 K. Even when the concentration of benzene in the feed solution was extremely small (0.5 mol%), the flux of benzene through the FER membrane was still greater than that of p-xylene. Therefore, a separation factor as high as 600 was obtained in the low feed concentration of benzene. Such a high selectivity for the benzene/p-xylene mixture suggested that the selectivity for the benzene/p-xylene mixture appears at the pore mouths of FER on the feed side of the FER-alumina composite layer. © 1997 Elsevier Science B.V.

    DOI

    Scopus

    61
    被引用数
    (Scopus)
  • Synthesis of a zeolitic thin layer by a vapor-phase transport method: Appearance of a preferential orientation of MFI zeolite

    Eiichi Kikuchi, Kazuhiko Yamashita, Sachioko Hiromoto, Korekazu Ueyama, Masahiko Matsukata

    Microporous Materials   11 ( 3-4 ) 107 - 116  1997年

     概要を見る

    Zeolitic membranes were synthesized on a porous alumina support by the vapor-phase transport method using one of two alumina sources: aluminum sulfate and sodium aluminate. By choosing the appropriate period and temperature for drying the aluminosilicate gel on the alumina support, MOR, FER and MFI could be synthesized. MOR was formed when the water content in the dry gel was high. As the water content decreased, FER and MFI were formed sequentially. Preferential formation of MFI was achieved by treating the dry gel at 373 K. The temperature at which the support was dipped in the parent gel also influenced the type of zeolite formed, although the effect of drying conditions was more pronounced. A similar trend was found for both aluminum sulfate and sodium aluminate. When the alumina source was sodium aluminate and the aluminosilicate gel was treated at 373 K, a preferentially oriented MFI membrane could be synthesized, as the (a00) and (0b0) crystal faces were oriented in parallel to the surface of porous alumina support. The uniform and dense morphology of the dry gel seems to account for the appearance of the orientation. © 1997 Elsevier Science B.V.

    DOI

    Scopus

    40
    被引用数
    (Scopus)
  • Gas permeation through zeolite-alumina composite membranes

    N Nishiyama, K Ueyama, M Matsukata

    AICHE JOURNAL   43 ( 11 ) 2724 - 2730  1997年

     概要を見る

    Mordenite (MOR) and ferrierite (FER) membranes without any pinhole and crack were synthesized by a vapor-phase transport method. The permeance of H-2, He, CH4, N-2, O-2 and CO2 was determined at 290-400 K; which showed minimum with increasing temperatures for most cases. In the parallel diffusion model was proposed, molecules adsorbed in a micropore are assumed to diffuse in parallel through the central region of the pore and along the wall region of the pore. This parallel diffusion model accounts for the effect of pore Size of MOR and FER on the permeation and expresses the experimental data well. The interaction between gas molecules and pore walls are evaluated for each gas.

    DOI

    Scopus

    43
    被引用数
    (Scopus)
  • FER membrane synthesized by a vapor-phase transport method: Its structure and separation characteristics

    Norikazu Nishiyama, Takaaki Matsufuji, Korekazu Ueyama, Masahiko Matsukata

    Microporous Materials   12 ( 4-6 ) 293 - 303  1997年

     概要を見る

    The mechanism of formation of ferrierite (FER) membrane on an alumina support by a vapor-phase transport (VPT) method was studied using XRD, SEM, FE-SEM and EDX. The XRD measurement for a FER membrane after the removal of FER particles formed on the support showed that FER was formed in the pores of the alumina support, namely, a FER-alumina composite layer was formed. The FE-SEM image for the cross-sectional view of the FER-alumina composite layer showed that FER nanocrystals of about 50 nm diameter grew in the pores of the alumina support. Pervaporation tests for benzene/p-xylene mixtures were performed at 303 K. Even when the concentration of benzene in the feed solution was extremely small (0.5 mol%), the flux of benzene through the FER membrane was still greater than that of p-xylene. Therefore, a separation factor as high as 600 was obtained in the low feed concentration of benzene. Such a high selectivity for the benzene/p-xylene mixture suggested that the selectivity for the benzene/p-xylene mixture appears at the pore mouths of FER on the feed side of the FER-alumina composite layer. © 1997 Elsevier Science B.V.

    DOI

    Scopus

    61
    被引用数
    (Scopus)
  • Synthesis of Zeolitic Membranes by a Vapor-phase Transport Method

    Microporous Materials   7;6  1996年12月

  • Synthesis of FER Membrane on an Alumina Support and Its Separation Properties

    Stud. Surf. Sci. Catal.   105(2195-2202)  1996年12月

  • Synthesis of defect-free zeolite-alumina composite membranes by a vapor-phase transport method

    N Nishiyama, K Ueyama, M Matsukata

    MICROPOROUS MATERIALS   7 ( 6 ) 299 - 308  1996年12月

     概要を見る

    The value of pH for gel preparation has a significant influence on the compactness of a dry gel. A compact gel was prepared at high pH of ca. 12. An amorphous dry gel on a porous alumina support was crystallized by a vapor-phase transport (VPT) method. Membranes of low silica zeolites, analcime (ANA) and mordenite (MOR), were formed because alumina was partly dissolved and incorporated into the framework of zeolite. Coating of the alumina support with colloidal silica depressed the dissolution of alumina. On the alumina support coated with colloidal silica, ferrierite (FER) and ZSM-5 (MFI) membranes were obtained. Compactness of the MOR membrane was examined by a permeation test of 1,3,5-triisopropylbenzene (TIPB) at room temperature. Since no permeation of TIPB was detected, it was concluded that there existed no pinholes and cracks in the MOR membrane. The pervaporation test of a benzene/p-xylene mixture of which the molar ratio was 0.860, was carried out. The separation factor ((benzene/p-xylene)permeate/(benzene/p-xylene)feed) exceeded 160. Thus some shape selectivity appeared at the pore mouths of MOR. The formation process of the MOR membrane was studied by using SEM and XRD. The gel which penetrated in the alumina pores crystallized to MOR and formed a defect-free MOR-alumina composite layer.

    DOI

    Scopus

    132
    被引用数
    (Scopus)
  • Synthesis of defect-free zeolite-alumina composite membranes by a vapor-phase transport method

    N Nishiyama, K Ueyama, M Matsukata

    MICROPOROUS MATERIALS   7 ( 6 ) 299 - 308  1996年12月

     概要を見る

    The value of pH for gel preparation has a significant influence on the compactness of a dry gel. A compact gel was prepared at high pH of ca. 12. An amorphous dry gel on a porous alumina support was crystallized by a vapor-phase transport (VPT) method. Membranes of low silica zeolites, analcime (ANA) and mordenite (MOR), were formed because alumina was partly dissolved and incorporated into the framework of zeolite. Coating of the alumina support with colloidal silica depressed the dissolution of alumina. On the alumina support coated with colloidal silica, ferrierite (FER) and ZSM-5 (MFI) membranes were obtained. Compactness of the MOR membrane was examined by a permeation test of 1,3,5-triisopropylbenzene (TIPB) at room temperature. Since no permeation of TIPB was detected, it was concluded that there existed no pinholes and cracks in the MOR membrane. The pervaporation test of a benzene/p-xylene mixture of which the molar ratio was 0.860, was carried out. The separation factor ((benzene/p-xylene)permeate/(benzene/p-xylene)feed) exceeded 160. Thus some shape selectivity appeared at the pore mouths of MOR. The formation process of the MOR membrane was studied by using SEM and XRD. The gel which penetrated in the alumina pores crystallized to MOR and formed a defect-free MOR-alumina composite layer.

  • Synthesis of FER Membrane on an Alumina Support and Its Separation Properties

    Stud. Surf. Sci. Catal.   105(2195-2202)  1996年12月

  • Synthesis of defect-free zeolite-alumina composite membranes by a vapor-phase transport method

    N Nishiyama, K Ueyama, M Matsukata

    MICROPOROUS MATERIALS   7 ( 6 ) 299 - 308  1996年12月

     概要を見る

    The value of pH for gel preparation has a significant influence on the compactness of a dry gel. A compact gel was prepared at high pH of ca. 12. An amorphous dry gel on a porous alumina support was crystallized by a vapor-phase transport (VPT) method. Membranes of low silica zeolites, analcime (ANA) and mordenite (MOR), were formed because alumina was partly dissolved and incorporated into the framework of zeolite. Coating of the alumina support with colloidal silica depressed the dissolution of alumina. On the alumina support coated with colloidal silica, ferrierite (FER) and ZSM-5 (MFI) membranes were obtained. Compactness of the MOR membrane was examined by a permeation test of 1,3,5-triisopropylbenzene (TIPB) at room temperature. Since no permeation of TIPB was detected, it was concluded that there existed no pinholes and cracks in the MOR membrane. The pervaporation test of a benzene/p-xylene mixture of which the molar ratio was 0.860, was carried out. The separation factor ((benzene/p-xylene)permeate/(benzene/p-xylene)feed) exceeded 160. Thus some shape selectivity appeared at the pore mouths of MOR. The formation process of the MOR membrane was studied by using SEM and XRD. The gel which penetrated in the alumina pores crystallized to MOR and formed a defect-free MOR-alumina composite layer.

    DOI

    Scopus

    132
    被引用数
    (Scopus)
  • ゼオライト膜の現状と可能性

    触媒   38;7  1996年11月

  • 担持Pd触媒によるp-キシレンの酸化的アセトキシル化:Auの添加効果

    触媒   38;6  1996年10月

  • Crystallization of FER and MFI zeolites by a vapor-phase transport method

    M Matsukata, N Nishiyama, K Ueyama

    MICROPOROUS MATERIALS   7 ( 2-3 ) 109 - 117  1996年09月

     概要を見る

    Dry aluminosilicate gels were crystallized to MFI and FER by a vapor-phase transport (VPT) method using ethylenediamine (EDA), triethylamine (Et(3)N) and water as vapor sources. The roles of water and amines in this crystallization were investigated. While Et(3)N and water encouraged crystallization, EDA acted as a structure-directing agent. A dry gel was crystallized to FER when no water was added. The Al-27- and the Si-29-NMR spectra indicated that all Al atoms were incorporated into the zeolitic framework in the early stage of crystallization and that the rest of the Si-rich phase gradually crystallized. Full crystallization of Si and Al atoms in dry gel was possible by selecting optimum synthetic conditions. FER was transformed to MFI with prolonged crystallization. The structure and crystallinity of zeolite significantly depended on the sort of support on which the dry gel was placed.

    DOI

    Scopus

    69
    被引用数
    (Scopus)
  • Crystallization of FER and MFI zeolites by a vapor-phase transport method

    M Matsukata, N Nishiyama, K Ueyama

    MICROPOROUS MATERIALS   7 ( 2-3 ) 109 - 117  1996年09月

     概要を見る

    Dry aluminosilicate gels were crystallized to MFI and FER by a vapor-phase transport (VPT) method using ethylenediamine (EDA), triethylamine (Et(3)N) and water as vapor sources. The roles of water and amines in this crystallization were investigated. While Et(3)N and water encouraged crystallization, EDA acted as a structure-directing agent. A dry gel was crystallized to FER when no water was added. The Al-27- and the Si-29-NMR spectra indicated that all Al atoms were incorporated into the zeolitic framework in the early stage of crystallization and that the rest of the Si-rich phase gradually crystallized. Full crystallization of Si and Al atoms in dry gel was possible by selecting optimum synthetic conditions. FER was transformed to MFI with prolonged crystallization. The structure and crystallinity of zeolite significantly depended on the sort of support on which the dry gel was placed.

    DOI

    Scopus

    69
    被引用数
    (Scopus)
  • Dry Gel Conversion Technique for Synthesis of Zeolite Beta

    Chem. Commun.   (1441-1442)  1996年08月

    DOI

  • Appearance of Molecular Sieving Properties by Zeolitic Membrane

    Proc. 1996 Intern. Congress on Membranes and Membrane Processes    1996年08月

  • 懸濁気泡塔による親疎水性粒子の分離

    化学工学   60;8  1996年08月

  • 気相を介するゼオライト合成と薄膜化

    触媒   38;5  1996年08月

  • ゼオライト分離膜の新展開

    表面   34;7  1996年08月

  • Dry Gel Conversion Technique for Synthesis of Zeolite Beta

    Chem. Commun.   (1441-1442)  1996年08月

    DOI

  • Appearance of Molecular Sieving Properties by Zeolitic Membrane

    Proc. 1996 Intern. Congress on Membranes and Membrane Processes    1996年08月

  • Gas Permeation of Zeolite-alumina Composite Membranes

    Proc. 5th World Congr. Chem. Eng.   4  1996年07月

  • Development of Production Technique of Multi-composite Ultrafine Particles by CVD

    Proc. 5th World Congr. Chem. Eng.   4  1996年07月

  • Gas Permeation of Zeolite-alumina Composite Membranes

    Proc. 5th World Congr. Chem. Eng.   4  1996年07月

  • Development of Production Technique of Multi-composite Ultrafine Particles by CVD

    Proc. 5th World Congr. Chem. Eng.   4  1996年07月

  • A novel hydrogen/syngas production process: Catalytic activity and stability of Ni/SiO2

    M Matsukata, T Matsushita, K Ueyama

    CHEMICAL ENGINEERING SCIENCE   51 ( 11 ) 2769 - 2774  1996年06月  [査読有り]

     概要を見る

    A reformer using a circulating fluidized bed has been proposed for the production of hydrogen and syngas. A catalyst is circulated between two reactors for the catalytic decomposition of methane to hydrogen and carbon, and for the gasification of carbon deposited on the catalyst. Catalytic activities of Ni/SiO2 for both CH4 decomposition and CO2 gasification of deposited carbon were investigated at 873-1023 K in a periodically-operated fixed bed reactor. Carbon which had a moss-like morphology was hardly gasified and caused deactivation of the catalyst. Such a type of carbon became dominant with raising reaction temperature and with increasing amount of Ni loaded on SiO2. In contrast, filamentous carbon which had a graphitic structure could be gasified with CO2 and became dominant with decreasing amount of Ni loaded and with lowering reaction temperature. It was found that Ni(5 wt%)/SiO2 had a stable activity against the cycles of decomposition/gasification because Ni on Ni(5)/SiO2 was difficult to sinter at 873 K and as a result, the filamentous carbon was exclusively formed.

  • カラム浮選によるコールクリーニング

    上山 惟一, 松方 正彦

    混相流学会誌   10;1 ( 1 ) 83 - 93  1996年04月

     概要を見る

    In under-developing countries as China, coal is mainly used as an energy source, considerable amount of which is for daily living use. However it is very difficult to equip a desulphurizer to each personal furnace. The air pollution problem there is now serious and is becoming an environmental problem on earth. If clean coal can be obtained at a coal field, the air pollution problem can be cleared. Recently, column floatation has been paid much attention as a prospective technique to remove minerals including inorganic sulphur from coal at a coal field. In this article, the prospective aspects of the column floatation as a coal cleaning process at a coal field is described putting special emphasis on the possible application in under developing countries. The floatation mechanisms are also illustrated on the basis of recent data of column floatation. It was shown that the coal recovery and ash rejection strongly depend on hydrophobicity of coal particles and that a surrounding flow of each bubble plays a roll in catching particles regardless of its hydrophobicity for the case of high gas feed.

    DOI CiNii

  • Simultaneous chlorination and sulphation of calcined limestone

    M. Matsukata, K. Takeda, T. Miyatani, K. Ueyama

    Chemical Engineering Science   51 ( 11 ) 2529 - 2534  1996年

     概要を見る

    In order to analyze HCl and SO2 retention in fluidized bed combustors of coal and wastes, chlorination and sulphation of calcined limestone were investigated at 1023 K and atmospheric pressure using thermogravimetry. The rate of chlorination of calcined limestone slightly depended on its particle size and was kept almost constant against the progress of chlorination. In contrast, the rate of sulphation increased with decreasing particle size and steeply decreased with the progress of sulphation as commonly reported. It was found that the sulphation was markedly accelerated in the presence of HCl. Such acceleration of sulphation was remarkable for larger limestone. The level of conversion of CaO to (CaSO4 + CaCl2) always approached 100% in the simultaneous absorption of HCl and SO2. It was observed by SEM that in the chlorination a number of spherical aggregates and large voids were formed on the surface of limestone and that large aggregates with very flat surface and large voids have been formed in the course of the simultaneous chlorination and sulphation. These chlorination behavior and the acceleration of SO2 absorption in the presence of HCl can be due both to the formation of a mobile Cl- ion-containing phase and to the formation of voids playing a role of the diffusion paths for HCl and SO2 toward the interior of a limestone particle. Melting of a eutectic mixture of CaCl2 and CaSO4 might largely contribute to the promotion of SO2 absorption in the case of simultaneous absorption of HCl and SO2.

    DOI

    Scopus

    63
    被引用数
    (Scopus)
  • A novel hydrogen/syngas production process: Catalytic activity and stability of Ni/SiO2

    M. Matsukata, T. Matsushita, K. Ueyama

    Chemical Engineering Science   51 ( 11 ) 2769 - 2774  1996年

     概要を見る

    A reformer using a circulating fluidized bed has been proposed for the production of hydrogen and syngas. A catalyst is circulated between two reactors for the catalytic decomposition of methane to hydrogen and carbon, and for the gasification of carbon deposited on the catalyst. Catalytic activities of Ni/SiO2 for both CH4 decomposition and CO2 gasification of deposited carbon were investigated at 873-1023 K in a periodically-operated fixed bed reactor. Carbon which had a moss-like morphology was hardly gasified and caused deactivation of the catalyst. Such a type of carbon became dominant with raising reaction temperature and with increasing amount of Ni loaded on SiO2. In contrast, filamentous carbon which had a graphitic structure could be gasified with CO2 and became dominant with decreasing amount of Ni loaded and with lowering reaction temperature. It was found that Ni(5 wt%)/SiO2 had a stable activity against the cycles of decomposition/gasification because Ni on Ni(5)/SiO2 was difficult to sinter at 873 K and as a result, the filamentous carbon was exclusively formed.

    DOI

    Scopus

    41
    被引用数
    (Scopus)
  • Characterization and modification of Indonesian natural zeolites and their properties for hydrocracking of a paraffin

    Wega Trisunaryanti, Ryuhei Shiba, Masahiro Miura, Masakatsu Nomura, Norikazu Nishiyama, Masahiko Matsukata

    Sekiyu Gakkaishi (Journal of the Japan Petroleum Institute)   39 ( 1 ) 20 - 25  1996年

     概要を見る

    Attempting to utilize natural zeolites as catalysts, characterization and modification of two kinds of those produced in Indonesia (Z1 and Z2) were carried out and their properties for hydrocracking of paraffins were evaluated using n-hexadecane as a petroleum model compound. The Z1 and Z2 samples were first treated with 6 N HCl at 90°C for 0.5 h or 20 h. X-Ray diffraction analysis of the HCl-treated samples (Z1-0.5 h, Z2-0.5 h, Z1-20 h, and Z2-20 h), as well as Z1 and Z2, indicated that both original samples mainly consist of mordenite type crystalline matter and the acid treatment removes some of crystalline impurities X-Ray fluorescence data revealed that Z1 and Z2 have Si/Al ratios of 4.3 and 3.1, respectively, and the treatment increases the ratio by dealumination as expected. The examination of hydrocracking properties showed that Z1 and Z2 have similar catalytic properties and the acid treatment considerably improves their activities. On the other hand, Z1- and Z2-20 h were less active than were Z1- and Z2-0.5 h, respectively. NH3-TPD and 29Si MAS NMR suggested that this may be due to the significant decrease of active acid sites by the prolonged treatment. It was also found that the loading of a small amount of nickel (0.8 wt%) onto Z1-0.5 h by ion exchange, significantly improves the catalytic property
    the conversion of the paraffin was comparable with that using a synthetic H-mordenite.

    DOI

    Scopus

    9
    被引用数
    (Scopus)
  • Simultaneous chlorination and sulphation of calcined limestone

    M. Matsukata, K. Takeda, T. Miyatani, K. Ueyama

    Chemical Engineering Science   51 ( 11 ) 2529 - 2534  1996年

     概要を見る

    In order to analyze HCl and SO2 retention in fluidized bed combustors of coal and wastes, chlorination and sulphation of calcined limestone were investigated at 1023 K and atmospheric pressure using thermogravimetry. The rate of chlorination of calcined limestone slightly depended on its particle size and was kept almost constant against the progress of chlorination. In contrast, the rate of sulphation increased with decreasing particle size and steeply decreased with the progress of sulphation as commonly reported. It was found that the sulphation was markedly accelerated in the presence of HCl. Such acceleration of sulphation was remarkable for larger limestone. The level of conversion of CaO to (CaSO4 + CaCl2) always approached 100% in the simultaneous absorption of HCl and SO2. It was observed by SEM that in the chlorination a number of spherical aggregates and large voids were formed on the surface of limestone and that large aggregates with very flat surface and large voids have been formed in the course of the simultaneous chlorination and sulphation. These chlorination behavior and the acceleration of SO2 absorption in the presence of HCl can be due both to the formation of a mobile Cl- ion-containing phase and to the formation of voids playing a role of the diffusion paths for HCl and SO2 toward the interior of a limestone particle. Melting of a eutectic mixture of CaCl2 and CaSO4 might largely contribute to the promotion of SO2 absorption in the case of simultaneous absorption of HCl and SO2.

    DOI

    Scopus

    63
    被引用数
    (Scopus)
  • A novel hydrogen/syngas production process: Catalytic activity and stability of Ni/SiO2

    M. Matsukata, T. Matsushita, K. Ueyama

    Chemical Engineering Science   51 ( 11 ) 2769 - 2774  1996年

     概要を見る

    A reformer using a circulating fluidized bed has been proposed for the production of hydrogen and syngas. A catalyst is circulated between two reactors for the catalytic decomposition of methane to hydrogen and carbon, and for the gasification of carbon deposited on the catalyst. Catalytic activities of Ni/SiO2 for both CH4 decomposition and CO2 gasification of deposited carbon were investigated at 873-1023 K in a periodically-operated fixed bed reactor. Carbon which had a moss-like morphology was hardly gasified and caused deactivation of the catalyst. Such a type of carbon became dominant with raising reaction temperature and with increasing amount of Ni loaded on SiO2. In contrast, filamentous carbon which had a graphitic structure could be gasified with CO2 and became dominant with decreasing amount of Ni loaded and with lowering reaction temperature. It was found that Ni(5 wt%)/SiO2 had a stable activity against the cycles of decomposition/gasification because Ni on Ni(5)/SiO2 was difficult to sinter at 873 K and as a result, the filamentous carbon was exclusively formed.

    DOI

    Scopus

    41
    被引用数
    (Scopus)
  • Characterization and modification of Indonesian natural zeolites and their properties for hydrocracking of a paraffin

    Wega Trisunaryanti, Ryuhei Shiba, Masahiro Miura, Masakatsu Nomura, Norikazu Nishiyama, Masahiko Matsukata

    Sekiyu Gakkaishi (Journal of the Japan Petroleum Institute)   39 ( 1 ) 20 - 25  1996年

     概要を見る

    Attempting to utilize natural zeolites as catalysts, characterization and modification of two kinds of those produced in Indonesia (Z1 and Z2) were carried out and their properties for hydrocracking of paraffins were evaluated using n-hexadecane as a petroleum model compound. The Z1 and Z2 samples were first treated with 6 N HCl at 90°C for 0.5 h or 20 h. X-Ray diffraction analysis of the HCl-treated samples (Z1-0.5 h, Z2-0.5 h, Z1-20 h, and Z2-20 h), as well as Z1 and Z2, indicated that both original samples mainly consist of mordenite type crystalline matter and the acid treatment removes some of crystalline impurities X-Ray fluorescence data revealed that Z1 and Z2 have Si/Al ratios of 4.3 and 3.1, respectively, and the treatment increases the ratio by dealumination as expected. The examination of hydrocracking properties showed that Z1 and Z2 have similar catalytic properties and the acid treatment considerably improves their activities. On the other hand, Z1- and Z2-20 h were less active than were Z1- and Z2-0.5 h, respectively. NH3-TPD and 29Si MAS NMR suggested that this may be due to the significant decrease of active acid sites by the prolonged treatment. It was also found that the loading of a small amount of nickel (0.8 wt%) onto Z1-0.5 h by ion exchange, significantly improves the catalytic property
    the conversion of the paraffin was comparable with that using a synthetic H-mordenite.

    DOI

    Scopus

    9
    被引用数
    (Scopus)
  • A CIRCULATING FLUIDIZED-BED CH4 REFORMER - PERFORMANCE OF SUPPORTED NI CATALYSTS

    M MATSUKATA, T MATSUSHITA, K UEYAMA

    ENERGY & FUELS   9 ( 5 ) 822 - 828  1995年09月

     概要を見る

    A methane reformer using a circulating fluidized bed is proposed for the production of hydrogen and synthesis gas (syngas). A catalyst is circulated between two reactors for the catalytic decomposition of methane to hydrogen and carbon and for the gasification of the carbon deposited on the catalyst. Of the metals Cu, Fe, Ni, and W, only Ni showed catalytic activity for the decomposition of methane at 873-1023 K. While studying the structure of the catalyst, it was found that the form of nickel was circulated between oxide and metal through reduction with methane and oxidation with carbon dioxide. X-ray diffraction (XRD) and scanning electron microscopy (SEM) suggested that filamentous carbon having a graphitic structure was gasified with carbon dioxide and that carbon having a mosslike morphology was hardly gasified and caused deactivation of the catalyst. The reactivity of the carbon which was able to be gasified was not altered with cycles of methane decomposition and carbon dioxide gasification.

    DOI

    Scopus

    30
    被引用数
    (Scopus)
  • A CIRCULATING FLUIDIZED-BED CH4 REFORMER - PERFORMANCE OF SUPPORTED NI CATALYSTS

    M MATSUKATA, T MATSUSHITA, K UEYAMA

    ENERGY & FUELS   9 ( 5 ) 822 - 828  1995年09月

     概要を見る

    A methane reformer using a circulating fluidized bed is proposed for the production of hydrogen and synthesis gas (syngas). A catalyst is circulated between two reactors for the catalytic decomposition of methane to hydrogen and carbon and for the gasification of the carbon deposited on the catalyst. Of the metals Cu, Fe, Ni, and W, only Ni showed catalytic activity for the decomposition of methane at 873-1023 K. While studying the structure of the catalyst, it was found that the form of nickel was circulated between oxide and metal through reduction with methane and oxidation with carbon dioxide. X-ray diffraction (XRD) and scanning electron microscopy (SEM) suggested that filamentous carbon having a graphitic structure was gasified with carbon dioxide and that carbon having a mosslike morphology was hardly gasified and caused deactivation of the catalyst. The reactivity of the carbon which was able to be gasified was not altered with cycles of methane decomposition and carbon dioxide gasification.

    DOI

    Scopus

    30
    被引用数
    (Scopus)
  • Removal and recovery of phenol from FCC effluent

    T. Kojima, K. Nishijima, M. Matsukata

    Journal of Membrane Science   102 ( C ) 43 - 47  1995年06月

     概要を見る

    Effluent from the FCC process contains considerable concentrations of phenol, sulfide and ammonium ions. The pH of the effluent is around 9. In the present study, the possibility of the application of anion exchange membranes for its removal and recovery, was investigated. The equilibrium constant between phenol and hydroxide ions and the ion exchange capacity of a commercial anion exchange membrane were determined. The membrane was sandwiched between two glass cells filled with a phenol solution at pH 9, fed and withdrawn continuously to keep the phenol concentration constant, and a sodium hydroxide solution at various pH, respectively. The permeation rate increased with pH and reached a plateau at above pH 13. The permeation rate was measured for various concentrations of phenol in the feed side, keeping the pH of the strip side at 13. The rate linearly increased with the phenol concentration and reached a plateau at concentration greater than 1 mol/m3. The apparent diffusion coefficient of phenol in the membrane was determined from the plateau value. At a concentration of less than 1 mol/m3, the rate was found to be controlled by boundary film resistance. It was also found that the permeation rate of phenol was suppressed by the sulfide ion at a concentration comparable to or larger than that of phenol. © 1995.

    DOI

    Scopus

    31
    被引用数
    (Scopus)
  • Removal and recovery of phenol from FCC effluent

    T. Kojima, K. Nishijima, M. Matsukata

    Journal of Membrane Science   102 ( C ) 43 - 47  1995年06月

     概要を見る

    Effluent from the FCC process contains considerable concentrations of phenol, sulfide and ammonium ions. The pH of the effluent is around 9. In the present study, the possibility of the application of anion exchange membranes for its removal and recovery, was investigated. The equilibrium constant between phenol and hydroxide ions and the ion exchange capacity of a commercial anion exchange membrane were determined. The membrane was sandwiched between two glass cells filled with a phenol solution at pH 9, fed and withdrawn continuously to keep the phenol concentration constant, and a sodium hydroxide solution at various pH, respectively. The permeation rate increased with pH and reached a plateau at above pH 13. The permeation rate was measured for various concentrations of phenol in the feed side, keeping the pH of the strip side at 13. The rate linearly increased with the phenol concentration and reached a plateau at concentration greater than 1 mol/m3. The apparent diffusion coefficient of phenol in the membrane was determined from the plateau value. At a concentration of less than 1 mol/m3, the rate was found to be controlled by boundary film resistance. It was also found that the permeation rate of phenol was suppressed by the sulfide ion at a concentration comparable to or larger than that of phenol. © 1995.

    DOI

    Scopus

    31
    被引用数
    (Scopus)
  • CONTRIBUTION OF LOCAL REACTIONS IN THE GRID ZONE TO THE PERFORMANCE OF A JETTING FLUIDIZED-BED GASIFIER OF COAL CHAR

    T KOJIMA, H YOSHITAKE, T KIMURA, M MATSUKATA, S UEMIYA

    ENERGY & FUELS   9 ( 2 ) 379 - 383  1995年03月

     概要を見る

    The effects of gasification conditions, namely bed temperature, static bed height, and nozzle diameter, on the concentrations of H-2, CO, and CO2 were investigated using a batchwise fluidized bed gasifier of coal char. Gas concentration profiles in the bed could be explained by the production of gases chiefly via combustion, steam gasification, CO2 gasification, and the diffusion of produced gases. The temperature dependence of gas concentrations indicates that steam gasification occurred in the lower part of the grid zone at a higher bed temperature and the selectivity of CO production via combustion in the boundary region of the jet and annulus also increased. The results of the effect of static bed height suggest that CO2 gasification mainly proceeded in the bubbling zone and the local reactions in the grid zone were hardly influenced by gas and solid behavior or reactions in the upper part of the bed. Though the diameter and height of the jet would be dependent on nozzle diameter, the effect of nozzle diameter on the local progress of gasification in the grid zone was hardly observed. It can be concluded that gasification proceeded in both the bubbling zone and annulus region, especially near the distributor, while combustion mainly occurred in the jet and boundary of the jet and annulus.

    DOI

    Scopus

  • CONTRIBUTION OF LOCAL REACTIONS IN THE GRID ZONE TO THE PERFORMANCE OF A JETTING FLUIDIZED-BED GASIFIER OF COAL CHAR

    T KOJIMA, H YOSHITAKE, T KIMURA, M MATSUKATA, S UEMIYA

    ENERGY & FUELS   9 ( 2 ) 379 - 383  1995年03月

     概要を見る

    The effects of gasification conditions, namely bed temperature, static bed height, and nozzle diameter, on the concentrations of H-2, CO, and CO2 were investigated using a batchwise fluidized bed gasifier of coal char. Gas concentration profiles in the bed could be explained by the production of gases chiefly via combustion, steam gasification, CO2 gasification, and the diffusion of produced gases. The temperature dependence of gas concentrations indicates that steam gasification occurred in the lower part of the grid zone at a higher bed temperature and the selectivity of CO production via combustion in the boundary region of the jet and annulus also increased. The results of the effect of static bed height suggest that CO2 gasification mainly proceeded in the bubbling zone and the local reactions in the grid zone were hardly influenced by gas and solid behavior or reactions in the upper part of the bed. Though the diameter and height of the jet would be dependent on nozzle diameter, the effect of nozzle diameter on the local progress of gasification in the grid zone was hardly observed. It can be concluded that gasification proceeded in both the bubbling zone and annulus region, especially near the distributor, while combustion mainly occurred in the jet and boundary of the jet and annulus.

    DOI

    Scopus

  • Experimental study of gas and particle behavior in the grid zone of a jetting fluidized bed cold model

    T. Kimura, K. Horiuchi, T. Watanabe, M. Matsukata, T. Kojima

    Powder Technology   82 ( 2 ) 135 - 143  1995年

     概要を見る

    The local behavior of gas and solids in a grid zone was investigated using a jetting fluidized bed cold model. Spherical alumina particles (440 μm, 1500 kg/m3) were used as bed material. A pair of optical fiber sensors, an A D converter and a personal computer were used to measure particle velocity in the jet, jet diameter and jet height. Tracer gas introduced from a center nozzle was sampled from various points in the grid zone and its concentration was measured by gas chromatography to investigate gas interchange between the jet and the annulus, and the gas dispersion in the annulus region. The effects of operational conditions, i.e., the shape of the gas distributor, nozzle diameter and gas flow rates, on the gas and particle behavior are discussed. It was considered that many more particles entered into the jet when a cone-shaped distributor rather than a flat distributor was employed. Employment of a narrower nozzle caused an increase in particle velocity at the bottom of the bed. © 1995.

    DOI

    Scopus

    27
    被引用数
    (Scopus)
  • A defect-free mordenite membrane synthesized by vapour-phase transport method

    Norikazu Nishiyama, Korekazu Ueyama, Masahiko Matsukata

    Journal of the Chemical Society, Chemical Communications   (1967-1968) ( 19 ) 1967 - 1968  1995年

     概要を見る

    A defect-free MOR membrane is synthesized on a porous alumina plate by a vapour phase transport method: shape selectivity is apparent in the pervaporation of a benzene-p-xylene mixture (the separation factor exceeded 160).

    DOI

    Scopus

    108
    被引用数
    (Scopus)
  • Selective Permeation of Vanadium(V) and Chromium(VI) through Anion Exchange and Supported Liquid Membranes

    T. Kojima, S. Yagi, K. Nishijima, M. Matsukata

    Developments in Chemical Engineering and Mineral Processing   3 ( 3-4 ) 151 - 159  1995年

     概要を見る

    Selective permeation of vanadium(V) and chromium(VI) using three types of membrane systems was studied. The first was an anion exchange membrane, the second and third were supported liquid membranes containing either a tertiary amine or a quaternary ammonium salt. The membrane was sandwiched between two glass cells. One cell was filled with a solution of identical concentrations of vanadium(V) and chromium(VI), and the other cell contained sodium hydroxide solution. The permeation rates of vanadium(V) and chromium(VI) were measured from the concentration change in the solution on the recovery side of the membrane. The selectivity of vanadium(V) over chromium(VI) was defined as the ratio of their rates. The selectivity of vanadium(V) over chromium(VI) was as high as 10 for pH of feed phase between 8 and 10 when using the quaternary ammonium salt and much better than these for the other membranes with an alkaline feed phase, which was used to simulate of the effluent from leaching of the heavy oil combustion ash and other wastes containing vanadium. Copyright © 1995 Publisher John Wiley &amp
    Sons, Ltd.

    DOI

    Scopus

    3
    被引用数
    (Scopus)
  • Experimental study of gas and particle behavior in the grid zone of a jetting fluidized bed cold model

    T. Kimura, K. Horiuchi, T. Watanabe, M. Matsukata, T. Kojima

    Powder Technology   82 ( 2 ) 135 - 143  1995年

     概要を見る

    The local behavior of gas and solids in a grid zone was investigated using a jetting fluidized bed cold model. Spherical alumina particles (440 μm, 1500 kg/m3) were used as bed material. A pair of optical fiber sensors, an A D converter and a personal computer were used to measure particle velocity in the jet, jet diameter and jet height. Tracer gas introduced from a center nozzle was sampled from various points in the grid zone and its concentration was measured by gas chromatography to investigate gas interchange between the jet and the annulus, and the gas dispersion in the annulus region. The effects of operational conditions, i.e., the shape of the gas distributor, nozzle diameter and gas flow rates, on the gas and particle behavior are discussed. It was considered that many more particles entered into the jet when a cone-shaped distributor rather than a flat distributor was employed. Employment of a narrower nozzle caused an increase in particle velocity at the bottom of the bed. © 1995.

    DOI

    Scopus

    27
    被引用数
    (Scopus)
  • A defect-free mordenite membrane synthesized by vapour-phase transport method

    Norikazu Nishiyama, Korekazu Ueyama, Masahiko Matsukata

    Journal of the Chemical Society, Chemical Communications   (1967-1968) ( 19 ) 1967 - 1968  1995年

     概要を見る

    A defect-free MOR membrane is synthesized on a porous alumina plate by a vapour phase transport method: shape selectivity is apparent in the pervaporation of a benzene-p-xylene mixture (the separation factor exceeded 160).

    DOI

    Scopus

    108
    被引用数
    (Scopus)
  • Selective Permeation of Vanadium(V) and Chromium(VI) through Anion Exchange and Supported Liquid Membranes

    T. Kojima, S. Yagi, K. Nishijima, M. Matsukata

    Developments in Chemical Engineering and Mineral Processing   3 ( 3-4 ) 151 - 159  1995年

     概要を見る

    Selective permeation of vanadium(V) and chromium(VI) using three types of membrane systems was studied. The first was an anion exchange membrane, the second and third were supported liquid membranes containing either a tertiary amine or a quaternary ammonium salt. The membrane was sandwiched between two glass cells. One cell was filled with a solution of identical concentrations of vanadium(V) and chromium(VI), and the other cell contained sodium hydroxide solution. The permeation rates of vanadium(V) and chromium(VI) were measured from the concentration change in the solution on the recovery side of the membrane. The selectivity of vanadium(V) over chromium(VI) was defined as the ratio of their rates. The selectivity of vanadium(V) over chromium(VI) was as high as 10 for pH of feed phase between 8 and 10 when using the quaternary ammonium salt and much better than these for the other membranes with an alkaline feed phase, which was used to simulate of the effluent from leaching of the heavy oil combustion ash and other wastes containing vanadium. Copyright © 1995 Publisher John Wiley &amp
    Sons, Ltd.

    DOI

    Scopus

    3
    被引用数
    (Scopus)
  • 3-4.開発途上国のエネルギーと環境(次世代人が考える次世代のエネルギー・環境問題,Session(3)若手会シンポジウム)

    松方 正彦

    日本エネルギー学会大会講演要旨集   3   74 - 77  1994年

     概要を見る

    Environmental issues in deleloping countires is significantly linked to energy issues. Partiuculraly, energy supply in Pacific Rim including Asian countries will become a main issue in the 21st century. Coal will still be one of main enegy source in the mid-21st century. What we must do is to develop technologies to supply and utilize coal at higher efficiency. For this porpose, strategy to utilize coal incuding all process from coal mining to enery production process is required.

    DOI CiNii

  • Zeolitic membrane synthesized on a porous alumina support

    Masahiko Matsukata, Norikazu Nishiyama, Korekazu Ueyama

    Journal of the Chemical Society, Chemical Communications   (339-340) ( 3 ) 339 - 340  1994年

     概要を見る

    A thin zeolitic membrane on porous alumina support has been synthesized
    the permeability of the film to N2 and O2 indicated that the membrane was formed in a compact form.

    DOI

    Scopus

    89
    被引用数
    (Scopus)
  • Vapor-phase Oxidative Acetoxylation of Toluene on Palladium-based Bimetallic Catalysts

    Masahiko Matsukata, Kimikazu Kitakado, Shigeyuki Uemiya, Toshinori Kojima, Masahiko Matsukata, Korekazu Ueyama

    Journal of The Japan Petroleum Institute   37 ( 4 ) 428 - 434  1994年

     概要を見る

    Vapor-phase oxidative acetoxylation of toluene on Pd-based bimetallic catalysts was investigated. The main products were benzylacetate, produced via side-chain acetoxylation, and CO and CO2 resulted from combustion. Nuclear acetoxylation hardly occurred. A K-doped Pd-Au/SiO2 gave the highest activity and selectivity for synthesis of benzylacetate among the catalysts tested
    the yield of benzylacetate on the K-doped Pd-Au/SiO2 was about 150 times greater than that on a Pd/SiO2. It was found that the addition of an adequate amount of Au to Pd/SiO2 inhibited the formation of CO2, and that potassium species worked as sites for adsorption and activation of acetic acid. © 1994, The Japan Petroleum Institute. All rights reserved.

    DOI

    Scopus

    6
    被引用数
    (Scopus)
  • PREPARATION OF A THIN ZEOLITIC MEMBRANE

    M MATSUKATA, N NISHIYAMA, K UEYAMA

    ZEOLITES AND RELATED MICROPOROUS MATERIALS: STATE OF THE ART 1994   84   1183 - 1190  1994年

     概要を見る

    The synthesis method to obtain a tight and thin zeolitic membrane was investigated. It was found that the most important factor to prepare a zeolitic membrane in a compact form was the pH to prepare the parent aluminosilicate gel. The aluminosilicate gel was supported on a porous alumina plate and treated in the vapor of templating reagents. It was found that a thin layer of ferrierite was formed on the surface of the plate. The rates of permeation of H-2, He, CH4, O-2, N-2 and CO2 through the ferrierite membrane were measured. Permeation results indicated that the ferrierite membrane is formed in a compact form.

  • Development of a microwave plasma-fluidized bed reactor for novel particle processing

    M. Matsukata, K. Suzuki, K. Ueyama, T. Kojima

    International Journal of Multiphase Flow   20 ( 4 ) 763 - 773  1994年

     概要を見る

    We developed a fluidized bed-chemical vapor deposition (CVD) reactor for a novel method of particle processing, such as particle coating and surface treatment. Microwave plasma was applied as an excitation source of reactive gases, and alumina and silicon were used as bed materials. The hydrodynamic behavior of the plasma-bubbling fluidized bed was studied and the field of plasma generation was investigated optically. Only minor plasma generation was noted in the dense phase. Plasma emission was observed in most of the bubbles in the alumina-fluidized bed, while plasma generated at the surface of the silicon-fluidized bed where bubbles splashed. Methane conversion was carried out in the alumina-fluidized bed as a model reaction. Although excitation of methane occurred in bubbles, excited species entered into the dense phase from bubbles and were effectively converted to carbon on the surface of the particles. Thus, heterogenous CVD on the surface of particles may occur in this reactor. © 1994.

    DOI

    Scopus

    16
    被引用数
    (Scopus)
  • Zeolitic membrane synthesized on a porous alumina support

    Masahiko Matsukata, Norikazu Nishiyama, Korekazu Ueyama

    Journal of the Chemical Society, Chemical Communications   (339-340) ( 3 ) 339 - 340  1994年

     概要を見る

    A thin zeolitic membrane on porous alumina support has been synthesized
    the permeability of the film to N2 and O2 indicated that the membrane was formed in a compact form.

    DOI

    Scopus

    89
    被引用数
    (Scopus)
  • Vapor-phase Oxidative Acetoxylation of Toluene on Palladium-based Bimetallic Catalysts

    Masahiko Matsukata, Kimikazu Kitakado, Shigeyuki Uemiya, Toshinori Kojima, Masahiko Matsukata, Korekazu Ueyama

    Journal of The Japan Petroleum Institute   37 ( 4 ) 428 - 434  1994年

     概要を見る

    Vapor-phase oxidative acetoxylation of toluene on Pd-based bimetallic catalysts was investigated. The main products were benzylacetate, produced via side-chain acetoxylation, and CO and CO2 resulted from combustion. Nuclear acetoxylation hardly occurred. A K-doped Pd-Au/SiO2 gave the highest activity and selectivity for synthesis of benzylacetate among the catalysts tested
    the yield of benzylacetate on the K-doped Pd-Au/SiO2 was about 150 times greater than that on a Pd/SiO2. It was found that the addition of an adequate amount of Au to Pd/SiO2 inhibited the formation of CO2, and that potassium species worked as sites for adsorption and activation of acetic acid. © 1994, The Japan Petroleum Institute. All rights reserved.

    DOI

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    6
    被引用数
    (Scopus)
  • PREPARATION OF A THIN ZEOLITIC MEMBRANE

    M MATSUKATA, N NISHIYAMA, K UEYAMA

    ZEOLITES AND RELATED MICROPOROUS MATERIALS: STATE OF THE ART 1994   84   1183 - 1190  1994年

     概要を見る

    The synthesis method to obtain a tight and thin zeolitic membrane was investigated. It was found that the most important factor to prepare a zeolitic membrane in a compact form was the pH to prepare the parent aluminosilicate gel. The aluminosilicate gel was supported on a porous alumina plate and treated in the vapor of templating reagents. It was found that a thin layer of ferrierite was formed on the surface of the plate. The rates of permeation of H-2, He, CH4, O-2, N-2 and CO2 through the ferrierite membrane were measured. Permeation results indicated that the ferrierite membrane is formed in a compact form.

  • Development of a microwave plasma-fluidized bed reactor for novel particle processing

    M. Matsukata, K. Suzuki, K. Ueyama, T. Kojima

    International Journal of Multiphase Flow   20 ( 4 ) 763 - 773  1994年

     概要を見る

    We developed a fluidized bed-chemical vapor deposition (CVD) reactor for a novel method of particle processing, such as particle coating and surface treatment. Microwave plasma was applied as an excitation source of reactive gases, and alumina and silicon were used as bed materials. The hydrodynamic behavior of the plasma-bubbling fluidized bed was studied and the field of plasma generation was investigated optically. Only minor plasma generation was noted in the dense phase. Plasma emission was observed in most of the bubbles in the alumina-fluidized bed, while plasma generated at the surface of the silicon-fluidized bed where bubbles splashed. Methane conversion was carried out in the alumina-fluidized bed as a model reaction. Although excitation of methane occurred in bubbles, excited species entered into the dense phase from bubbles and were effectively converted to carbon on the surface of the particles. Thus, heterogenous CVD on the surface of particles may occur in this reactor. © 1994.

    DOI

    Scopus

    16
    被引用数
    (Scopus)
  • Nucleation and Growth of Ultrafine Particles in a Flame

    J. Chemical Vapor Deposition   1;3(280-299)  1993年11月

  • Nucleation and Growth of Ultrafine Particles in a Flame

    J. Chemical Vapor Deposition   1;3(280-299)  1993年11月

  • DEVELOPMENT OF SYSTEM FOR MEASURING BUBBLE COALESCENCE TIME BY USING A LASER

    K UEYAMA, M SAEKI, M MATSUKATA

    JOURNAL OF CHEMICAL ENGINEERING OF JAPAN   26 ( 3 ) 308 - 314  1993年06月

     概要を見る

    A new system to measure very short bubble coalescence time was developed using a laser. The system's reliability was confirmed by comparing the system output with photographic observation by high-speed video camera. The result for aqueous solutions of n-alcohol was in good agreement with the previous data. The system was applied to various kinds of aqueous solutions more dilute than those in previous work where the value of bubble coalescence time was expected to be less than 2 ms. It was revealed that the bubble coalescence time reported in previous work was composed of two parts. The first part was the time length of the contacting period of two bubbles and the second was the time length of the initial stage of a film rupture between the bubbles. The former decreased considerably, even to an undetectably small value, with decrease in concentration, but the latter was constantly at about 0.3 ms regardless of concentration. Effects of bubble age and bubble approach velocity were examined. It was also found that the bubble coalescence time in surfactant solution was significantly influenced in a narrow concentration region as low as ppb order and that the bubbles did not coalesce in solution of higher concentration.

    DOI

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    19
    被引用数
    (Scopus)
  • DEVELOPMENT OF SYSTEM FOR MEASURING BUBBLE COALESCENCE TIME BY USING A LASER

    K UEYAMA, M SAEKI, M MATSUKATA

    JOURNAL OF CHEMICAL ENGINEERING OF JAPAN   26 ( 3 ) 308 - 314  1993年06月

     概要を見る

    A new system to measure very short bubble coalescence time was developed using a laser. The system's reliability was confirmed by comparing the system output with photographic observation by high-speed video camera. The result for aqueous solutions of n-alcohol was in good agreement with the previous data. The system was applied to various kinds of aqueous solutions more dilute than those in previous work where the value of bubble coalescence time was expected to be less than 2 ms. It was revealed that the bubble coalescence time reported in previous work was composed of two parts. The first part was the time length of the contacting period of two bubbles and the second was the time length of the initial stage of a film rupture between the bubbles. The former decreased considerably, even to an undetectably small value, with decrease in concentration, but the latter was constantly at about 0.3 ms regardless of concentration. Effects of bubble age and bubble approach velocity were examined. It was also found that the bubble coalescence time in surfactant solution was significantly influenced in a narrow concentration region as low as ppb order and that the bubbles did not coalesce in solution of higher concentration.

    DOI

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    19
    被引用数
    (Scopus)
  • 逆抽出側水相にキレート剤を添加した含浸型液体膜系における希土類の透過機構

    小島 紀徳, 中山 智香子, 上宮 成之, 松方 正彦

    日本化学会誌 : 化学と工業化学 = Journal of the Chemical Society of Japan : chemistry and industrial chemistry   1993 ( 5 ) 574 - 579  1993年05月  [査読有り]

    DOI CiNii

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    1
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  • Kinetic Role of Diethylenetriaminepentaacetic Acid Added to Stripping Phase in Permeation of Rare Earth Metal Ions Through a Supported Liquid Membrane

    J. Alloys and Compounds   192;2(121-123)  1993年03月

  • Acceleration of Permeation of Pr and Nd Ions Through a Supported Liquid Membrane by the Addition of Complexing Agents to Stripping Phase

    J. Alloys and Compounds   192;2(124-125)  1993年03月

  • Kinetic Role of Diethylenetriaminepentaacetic Acid Added to Stripping Phase in Permeation of Rare Earth Metal Ions Through a Supported Liquid Membrane

    J. Alloys and Compounds   192;2(121-123)  1993年03月

  • Acceleration of Permeation of Pr and Nd Ions Through a Supported Liquid Membrane by the Addition of Complexing Agents to Stripping Phase

    J. Alloys and Compounds   192;2(124-125)  1993年03月

  • Synthesis of zeolites under vapor atmosphere. Effect of synthetic conditions on zeolite structure

    Masahiko Matsukata, Norikazu Nishiyama, Korekazu Ueyama

    Microporous Materials   1 ( 3 ) 219 - 222  1993年

     概要を見る

    The present study found that aluminosilicate gels were crystallized to ZSM-5, ferrierite, KZ-2 or analcime under a vapor atmosphere. The structure and crystallinity of the resultant zeolite significantly depended on the composition of the organic vapor as well as that of the parent gel. © 1993.

    DOI

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    92
    被引用数
    (Scopus)
  • Performance of a fluidized bed coal gasifier with various ways of gas introduction

    M. Matsukata, Y. Honda, H. Yoshitake, T. Kojima

    Fuel Processing Technology   36 ( 1-3 ) 227 - 233  1993年

     概要を見る

    Local concentrations of gases in the jetting fluidized bed coal gasifier, particularly in the grid zone of the bed were measured to discuss gas exchange between the jet and annulus and local progress of chemical reactions. Air was introduced from the gas injection nozzle and steam was introduced from the coneshaped distributor plate. Gas exchange between the annulus and the jet rapidly occurred. Compared with the case that only steam was introduced, it was found that air introduced from the nozzle produced carbon oxides at around the boundary of the jet and as a result decreased the rate of steam gasification in the annulus. Both for physical and chemical phenomena the grid zone cannot be regarded as uniform. The grid structure strongly influenced the performance of the gasifier. © 1993.

    DOI

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    4
    被引用数
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  • Oxidative Acetoxylation of Toluene and Benzene over Supported-Palladium Catalysts

    Masahiko Matsukata, Korekazu Ueyama, Kimikazu Kitakado, Toshinori Kojima

    Journal of The Japan Petroleum Institute   36 ( 3 ) 235 - 238  1993年

     概要を見る

    Oxidative acetoxylation of toluene and benzene using molecular oxygen was carried out over supported palladium catalysts in the temperature range of 453-493 K at atmospheric pressure. It was found that the addition of gold on silica-supported palladium promoted acetoxylation of toluene and benzene. © 1993, The Japan Petroleum Institute. All rights reserved.

    DOI

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    2
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  • Application of Dynamic Light Scattering Based on a Monodisperse Model as an In-Situ Method of Measuring Ultrafine particles Growing and Aggregating in a Flame

    Korekazu Ueyama, Takuya Ono, Masahiko Matsukata, Ryuichiro Osima

    JOURNAL OF CHEMICAL ENGINEERING OF JAPAN   26 ( 6 ) 686 - 691  1993年

     概要を見る

    Dynamic light scattering (DLS) based on a monodisperse model was applied to ultrafine particle formation in a flame where particles grow and deform within several ms, with occasional high number density and broad size distribution. DLS was experimentally evaluated as an in-situ technique of measuring mean particle size by comparing with TEM (transmission electron microscope) photographs. The following results were obtained. 1. For particles formed in a flame, a mean particle size of several tens of nanometers by DLS with monodisperse assumption was in good agreement with the volume mean diameter obtained from TEM photographs, except for particles strongly deviated to small size. 2. For particles with a size distribution strongly deviated to the fine side, DLS with monodisperse assumption gives a considerably large value, around twice the volume mean diameter. This value still reflects a plausible mean size of large particles contained in the measuring volume. © 1993, The Society of Chemical Engineers, Japan. All rights reserved.

    DOI

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    3
    被引用数
    (Scopus)
  • Synthesis of zeolites under vapor atmosphere. Effect of synthetic conditions on zeolite structure

    Masahiko Matsukata, Norikazu Nishiyama, Korekazu Ueyama

    Microporous Materials   1 ( 3 ) 219 - 222  1993年

     概要を見る

    The present study found that aluminosilicate gels were crystallized to ZSM-5, ferrierite, KZ-2 or analcime under a vapor atmosphere. The structure and crystallinity of the resultant zeolite significantly depended on the composition of the organic vapor as well as that of the parent gel. © 1993.

    DOI

    Scopus

    92
    被引用数
    (Scopus)
  • Performance of a fluidized bed coal gasifier with various ways of gas introduction

    M. Matsukata, Y. Honda, H. Yoshitake, T. Kojima

    Fuel Processing Technology   36 ( 1-3 ) 227 - 233  1993年

     概要を見る

    Local concentrations of gases in the jetting fluidized bed coal gasifier, particularly in the grid zone of the bed were measured to discuss gas exchange between the jet and annulus and local progress of chemical reactions. Air was introduced from the gas injection nozzle and steam was introduced from the coneshaped distributor plate. Gas exchange between the annulus and the jet rapidly occurred. Compared with the case that only steam was introduced, it was found that air introduced from the nozzle produced carbon oxides at around the boundary of the jet and as a result decreased the rate of steam gasification in the annulus. Both for physical and chemical phenomena the grid zone cannot be regarded as uniform. The grid structure strongly influenced the performance of the gasifier. © 1993.

    DOI

    Scopus

    4
    被引用数
    (Scopus)
  • Oxidative Acetoxylation of Toluene and Benzene over Supported-Palladium Catalysts

    Masahiko Matsukata, Korekazu Ueyama, Kimikazu Kitakado, Toshinori Kojima

    Journal of The Japan Petroleum Institute   36 ( 3 ) 235 - 238  1993年

     概要を見る

    Oxidative acetoxylation of toluene and benzene using molecular oxygen was carried out over supported palladium catalysts in the temperature range of 453-493 K at atmospheric pressure. It was found that the addition of gold on silica-supported palladium promoted acetoxylation of toluene and benzene. © 1993, The Japan Petroleum Institute. All rights reserved.

    DOI

    Scopus

    2
    被引用数
    (Scopus)
  • Application of Dynamic Light Scattering Based on a Monodisperse Model as an In-Situ Method of Measuring Ultrafine particles Growing and Aggregating in a Flame

    Korekazu Ueyama, Takuya Ono, Masahiko Matsukata, Ryuichiro Osima

    JOURNAL OF CHEMICAL ENGINEERING OF JAPAN   26 ( 6 ) 686 - 691  1993年

     概要を見る

    Dynamic light scattering (DLS) based on a monodisperse model was applied to ultrafine particle formation in a flame where particles grow and deform within several ms, with occasional high number density and broad size distribution. DLS was experimentally evaluated as an in-situ technique of measuring mean particle size by comparing with TEM (transmission electron microscope) photographs. The following results were obtained. 1. For particles formed in a flame, a mean particle size of several tens of nanometers by DLS with monodisperse assumption was in good agreement with the volume mean diameter obtained from TEM photographs, except for particles strongly deviated to small size. 2. For particles with a size distribution strongly deviated to the fine side, DLS with monodisperse assumption gives a considerably large value, around twice the volume mean diameter. This value still reflects a plausible mean size of large particles contained in the measuring volume. © 1993, The Society of Chemical Engineers, Japan. All rights reserved.

    DOI

    Scopus

    3
    被引用数
    (Scopus)
  • Vertical Progress of Methane Conversion in a D.C. Plasma Jetting Fluidized Bed Reactor

    Chem. Eng. Sci.   47;9-11(2963-2968)  1992年07月

  • A NEW CLASSIFICATION OF ALKALI AND ALKALINE-EARTH CATALYSTS FOR GASIFICATION OF CARBON

    M MATSUKATA, E KIKUCHI, Y MORITA

    FUEL   71 ( 7 ) 819 - 823  1992年07月

     概要を見る

    The variations in the amounts of alkali and alkaline earth species actually existing on the surface of carbon black in the courses of heat treatment up to 1123 K and steam gasification at 1073 K were investigated, in order to understand the actual amount of catalyst existing on the surface of carbon in the working state. These gasification catalysts were classified into three groups based on the fact that some of them sunk into the bulk of carbon in the course of heat treatment and some of them vaporized from the surface of carbon. It was found that the migration of species into the bulk of carbon was profoundly associated with the reducibility of their oxide state.

    DOI

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    21
    被引用数
    (Scopus)
  • Vertical Progress of Methane Conversion in a D.C. Plasma Jetting Fluidized Bed Reactor

    Chem. Eng. Sci.   47;9-11(2963-2968)  1992年07月

  • A NEW CLASSIFICATION OF ALKALI AND ALKALINE-EARTH CATALYSTS FOR GASIFICATION OF CARBON

    M MATSUKATA, E KIKUCHI, Y MORITA

    FUEL   71 ( 7 ) 819 - 823  1992年07月

     概要を見る

    The variations in the amounts of alkali and alkaline earth species actually existing on the surface of carbon black in the courses of heat treatment up to 1123 K and steam gasification at 1073 K were investigated, in order to understand the actual amount of catalyst existing on the surface of carbon in the working state. These gasification catalysts were classified into three groups based on the fact that some of them sunk into the bulk of carbon in the course of heat treatment and some of them vaporized from the surface of carbon. It was found that the migration of species into the bulk of carbon was profoundly associated with the reducibility of their oxide state.

    DOI

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    21
    被引用数
    (Scopus)
  • MIGRATION OF ALKALI AND ALKALINE-EARTH ELEMENTS INTO CARBON-BLACK

    M MATSUKATA, E KIKUCHI, Y MORITA

    FUEL   71 ( 6 ) 705 - 707  1992年06月

     概要を見る

    The mobility of alkali and alkaline earth elements loaded on carbon black during heat treatment up to 1123 K in an inert atmosphere was investigated by different spectroscopic methods. The objective was to improve our understanding of gasification by catalysts containing these elements. It was found that Na, Rb, Cs, Sr and Li species migrated into the bulk of carbon on heating up to 1123 K in a flowing inert atmosphere.

    DOI

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    5
    被引用数
    (Scopus)
  • MIGRATION OF ALKALI AND ALKALINE-EARTH ELEMENTS INTO CARBON-BLACK

    M MATSUKATA, E KIKUCHI, Y MORITA

    FUEL   71 ( 6 ) 705 - 707  1992年06月

     概要を見る

    The mobility of alkali and alkaline earth elements loaded on carbon black during heat treatment up to 1123 K in an inert atmosphere was investigated by different spectroscopic methods. The objective was to improve our understanding of gasification by catalysts containing these elements. It was found that Na, Rb, Cs, Sr and Li species migrated into the bulk of carbon on heating up to 1123 K in a flowing inert atmosphere.

    DOI

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    5
    被引用数
    (Scopus)
  • 流動層CVD法によりモノシランから製造した多結晶シリコン粒子中の残留水素

    小島 紀徳, 小田桐 誉, 松方 正彦, 山田 繁

    化学工学論文集   18 ( 5 ) 701 - 707  1992年  [査読有り]

     概要を見る

    流動層CVD法によりモノシランから製造した多結晶シリコン粒子には残留水素が含まれ, CZ引き上げ工程においてるつぼ内の流動を乱し, 問題となることが知られている.本研究では熱処理による多結晶シリコン粒子からの残留水素の脱離を行った.水素脱離の活性化エネルギーを昇温脱離 (TPD) 法により求めた.FTIRによる測定から, 多結晶シリコン粒子中には種々のSi-H結合が存在することが明らかになった.吸収ピーク面積は, TPDによる水素の脱離量の増大とともに小さくなった.この関係から, 残留水素量は反応したモノシランの中に存在していた水素の約0.05%に相当することがわかった.また加熱処理によるFTIRの吸収ピーク面積の減少とともに, シリコン粒子の粒子密度は直線的に増大し, ほほ真密度にまで至ることがわかった.

    DOI CiNii

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  • 炭化室内ガス流れ挙動の解析 第2報

    荒牧寿弘, 枝国利隆, 関根秀人, 小島紀徳, 松方正彦, 上夷孝

    コークス・サーキュラー   40 ( 4 ) 240 - 243  1991年12月  [査読有り]

  • DEVELOPMENT OF A PLASMA JETTING FLUIDIZED-BED REACTOR

    T KOJIMA, M MATSUKATA, M ARAO, M NAKAMURA, Y MITSUYOSHI

    JOURNAL DE PHYSIQUE IV   1 ( C2 ) 429 - 436  1991年09月

     概要を見る

    A plasma jetting fluidized bed reactor was developed for coating particles via PCVD. Conversion of methane was carried out to investigate characteristics of this type of reactor. It was found that introduction of reactive gases from the side of a d.c. plasma jet resulted in no deterioration of the stability of plasma and that the reactive gases were effectively activated even in the presence of particles. Particles packed in the reactor promoted reactions to give carbon in the presence of hydrogen in a large excess, strongly suggesting that PCVD on fluidized particles can be realized.

  • CHARACTERIZATION OF POLYCRYSTALLINE SILICON PARTICLES PRODUCED VIA CVD FROM MONOSILANE IN A FLUIDIZED-BED REACTOR

    M MATSUKATA, T ODAGIRI, T KOJIMA

    JOURNAL DE PHYSIQUE IV   1 ( C2 ) 483 - 490  1991年09月

     概要を見る

    Characterization of polycrystalline silicon particles produced in a fluidized bed reactor via CVD from monosilane was carried out. It was observed that part of the hydrogen from monosilane remained in the particles. Most of hydrogen was bonded to silicon and temperatures as high as 1300 K were required to dehydrogenate the silicon particles. Particles were contaminated with metal elements which were diffused from the reactor wall, suggesting that the material used in constructing the fluidized bed reactor wall also needed to be controlled to improve the purity of product.

  • DEVELOPMENT OF A PLASMA JETTING FLUIDIZED-BED REACTOR

    T KOJIMA, M MATSUKATA, M ARAO, M NAKAMURA, Y MITSUYOSHI

    JOURNAL DE PHYSIQUE IV   1 ( C2 ) 429 - 436  1991年09月

     概要を見る

    A plasma jetting fluidized bed reactor was developed for coating particles via PCVD. Conversion of methane was carried out to investigate characteristics of this type of reactor. It was found that introduction of reactive gases from the side of a d.c. plasma jet resulted in no deterioration of the stability of plasma and that the reactive gases were effectively activated even in the presence of particles. Particles packed in the reactor promoted reactions to give carbon in the presence of hydrogen in a large excess, strongly suggesting that PCVD on fluidized particles can be realized.

  • CHARACTERIZATION OF POLYCRYSTALLINE SILICON PARTICLES PRODUCED VIA CVD FROM MONOSILANE IN A FLUIDIZED-BED REACTOR

    M MATSUKATA, T ODAGIRI, T KOJIMA

    JOURNAL DE PHYSIQUE IV   1 ( C2 ) 483 - 490  1991年09月

     概要を見る

    Characterization of polycrystalline silicon particles produced in a fluidized bed reactor via CVD from monosilane was carried out. It was observed that part of the hydrogen from monosilane remained in the particles. Most of hydrogen was bonded to silicon and temperatures as high as 1300 K were required to dehydrogenate the silicon particles. Particles were contaminated with metal elements which were diffused from the reactor wall, suggesting that the material used in constructing the fluidized bed reactor wall also needed to be controlled to improve the purity of product.

  • Steam Gasification of Benzene Catalyzed by MgO Doped with Alkaline Earth and Alkali Compounds.

    Masahiko Matsukata, Ken-Ichiro Kobayashi, Eiichi Kikuchi, Yoshiro Morita

    Journal of The Japan Petroleum Institute   34 ( 1 ) 44 - 52  1991年

     概要を見る

    The benzene-steam reaction on MgO doped with Ca, Sr, Ba, and K was investigated at 1,173K and at atmospheric pressure to understand the action of steam as gasifying reagent in hydrocarbon gasification. The results were discussed by comparing with those of the benzene-CO2reaction. The benzene-steam reaction was proposed to proceed via the decomposition of benzene to give an intermediate carbon and subsequent gasification of the carbon. The steam adsorbed on the catalyst was found to hinder the decomposition of benzene to give the intermediate. Catalytic activity for the benzene-steam reaction could be interpreted mainly by a combination of catalytic activity for gasification of deposited carbon and the degree of hindrance to the decomposition of benzene by adsorbed steam. The mobility of catalytic species in the layers of the deposited carbon was found to be an important factor governing the rate of gasification of the deposited carbon. © 1991, The Japanese Association of Educational Psychology. All rights reserved.

    DOI

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  • Benzene-Oxygen Reaction Over Alkaline Earth Metal Oxide Catalysts.

    Masahiko Matsukata, Eiji Okanari, Eiichi Kikuchi, Yoshiro Morita

    Journal of The Japan Petroleum Institute   34 ( 1 ) 36 - 43  1991年

     概要を見る

    The benzene-oxygen reaction catalyzed by alkaline earth metal oxides was investigated in the temperature range 773-1,073K to understand the catalytic function of these oxides for hydrocarbon gasification. In the initial stage of reaction, CO, CO2, H2O, and biphenyl were concurrently produced. The consumption of CO and H2O by the water-gas shift reaction subsequently occurred to give CO2and H2. CO oxidation with O2hardly occurred in the course of the benzene-oxygen reaction because benzene was preferentially adsorbed on the MgO catalyst. These reaction sequences were compared with those in the benzene-oxygen reaction catalyzed by metallic nickel. © 1991, The Japanese Association of Educational Psychology. All rights reserved.

    DOI

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  • Steam Gasification of Benzene Catalyzed by MgO Doped with Alkaline Earth and Alkali Compounds.

    Masahiko Matsukata, Ken-Ichiro Kobayashi, Eiichi Kikuchi, Yoshiro Morita

    Journal of The Japan Petroleum Institute   34 ( 1 ) 44 - 52  1991年

     概要を見る

    The benzene-steam reaction on MgO doped with Ca, Sr, Ba, and K was investigated at 1,173K and at atmospheric pressure to understand the action of steam as gasifying reagent in hydrocarbon gasification. The results were discussed by comparing with those of the benzene-CO2reaction. The benzene-steam reaction was proposed to proceed via the decomposition of benzene to give an intermediate carbon and subsequent gasification of the carbon. The steam adsorbed on the catalyst was found to hinder the decomposition of benzene to give the intermediate. Catalytic activity for the benzene-steam reaction could be interpreted mainly by a combination of catalytic activity for gasification of deposited carbon and the degree of hindrance to the decomposition of benzene by adsorbed steam. The mobility of catalytic species in the layers of the deposited carbon was found to be an important factor governing the rate of gasification of the deposited carbon. © 1991, The Japanese Association of Educational Psychology. All rights reserved.

    DOI

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  • Benzene-Oxygen Reaction Over Alkaline Earth Metal Oxide Catalysts.

    Masahiko Matsukata, Eiji Okanari, Eiichi Kikuchi, Yoshiro Morita

    Journal of The Japan Petroleum Institute   34 ( 1 ) 36 - 43  1991年

     概要を見る

    The benzene-oxygen reaction catalyzed by alkaline earth metal oxides was investigated in the temperature range 773-1,073K to understand the catalytic function of these oxides for hydrocarbon gasification. In the initial stage of reaction, CO, CO2, H2O, and biphenyl were concurrently produced. The consumption of CO and H2O by the water-gas shift reaction subsequently occurred to give CO2and H2. CO oxidation with O2hardly occurred in the course of the benzene-oxygen reaction because benzene was preferentially adsorbed on the MgO catalyst. These reaction sequences were compared with those in the benzene-oxygen reaction catalyzed by metallic nickel. © 1991, The Japanese Association of Educational Psychology. All rights reserved.

    DOI

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  • 炭化室内ガス流れ挙動の解明

    荒牧寿弘, 枝国利隆, 関根秀人, 小島紀徳, 松方正彦, 上夷 孝

    コークス・サーキュラー   39 ( 4 ) 251 - 255  1990年12月  [査読有り]

  • AUGER-ELECTRON SPECTROSCOPY AND ELECTRON-PROBE MICROANALYSIS OBSERVATIONS OF BARIUM AND CALCIUM LOADED ON AMORPHOUS-CARBON UNDER GASIFICATION CONDITIONS

    M MATSUKATA, T FUJIKAWA, E KIKUCHI, Y MORITA

    ENERGY & FUELS   4 ( 4 ) 365 - 371  1990年07月  [査読有り]

  • Auger Electron Spectroscopy and Electron Probe Microanalysis Observations of Barium and Calcium Loaded on Amorphous Carbon under Gasification Conditions

    M. Matsukata, T. Fujikawa, E. Kikuchi, Y. Morita

    Energy and Fuels   4 ( 4 ) 365 - 371  1990年07月

     概要を見る

    In order to investigate the mobility and structural change of barium and calcium compounds loaded on carbon substrate in the courses of heat treatment and of gasification, AES and EPMA were employed to observe the surface structure of amorphous carbon black impregnated by barium or calcium nitrate. We found that barium species migrated into the bulk of carbon in the course of heat treatment up to 1123 K, while calcium species did not. The difference in mobility between barium and calcium species is due to the difference in the reducibility of these cations by the action of carbon in the course of heat treatment. Mineral matter was concentrated at the surface of carbon during gasification and reacted with BaCO3 to disperse in the interior of BaCO3 particles on the carbon surface. On the other hand, sulfur was found on the BaCO3 surface under gasification conditions. © 1990, American Chemical Society. All rights reserved.

    DOI

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    9
    被引用数
    (Scopus)
  • Auger Electron Spectroscopy and Electron Probe Microanalysis Observations of Barium and Calcium Loaded on Amorphous Carbon under Gasification Conditions

    M. Matsukata, T. Fujikawa, E. Kikuchi, Y. Morita

    Energy and Fuels   4 ( 4 ) 365 - 371  1990年07月

     概要を見る

    In order to investigate the mobility and structural change of barium and calcium compounds loaded on carbon substrate in the courses of heat treatment and of gasification, AES and EPMA were employed to observe the surface structure of amorphous carbon black impregnated by barium or calcium nitrate. We found that barium species migrated into the bulk of carbon in the course of heat treatment up to 1123 K, while calcium species did not. The difference in mobility between barium and calcium species is due to the difference in the reducibility of these cations by the action of carbon in the course of heat treatment. Mineral matter was concentrated at the surface of carbon during gasification and reacted with BaCO3 to disperse in the interior of BaCO3 particles on the carbon surface. On the other hand, sulfur was found on the BaCO3 surface under gasification conditions. © 1990, American Chemical Society. All rights reserved.

    DOI

    Scopus

    9
    被引用数
    (Scopus)
  • DEVELOPMENT OF NUMERICAL-MODEL FOR REACTIONS IN FLUIDIZED-BED GRID ZONE - APPLICATION TO CHEMICAL VAPOR-DEPOSITION OF POLYCRYSTALLINE SILICON BY MONOSILANE PYROLYSIS

    T KOJIMA, T KIMURA, M MATSUKATA

    CHEMICAL ENGINEERING SCIENCE   45 ( 8 ) 2527 - 2534  1990年

    DOI

    Scopus

    13
    被引用数
    (Scopus)
  • DEVELOPMENT OF NUMERICAL-MODEL FOR REACTIONS IN FLUIDIZED-BED GRID ZONE - APPLICATION TO CHEMICAL VAPOR-DEPOSITION OF POLYCRYSTALLINE SILICON BY MONOSILANE PYROLYSIS

    T KOJIMA, T KIMURA, M MATSUKATA

    CHEMICAL ENGINEERING SCIENCE   45 ( 8 ) 2527 - 2534  1990年

    DOI

    Scopus

    13
    被引用数
    (Scopus)
  • QUANTITATIVE BEHAVIOR OF POTASSIUM SPECIES ON AN AMORPHOUS-CARBON UNDER STEAM GASIFICATION CONDITIONS

    M MATSUKATA, T FUJIKAWA, E KIKUCHI, Y MORITA

    ENERGY & FUELS   3 ( 3 ) 336 - 341  1989年05月

    DOI

    Scopus

    15
    被引用数
    (Scopus)
  • QUANTITATIVE BEHAVIOR OF POTASSIUM SPECIES ON AN AMORPHOUS-CARBON UNDER STEAM GASIFICATION CONDITIONS

    M MATSUKATA, T FUJIKAWA, E KIKUCHI, Y MORITA

    ENERGY & FUELS   3 ( 3 ) 336 - 341  1989年05月

    DOI

    Scopus

    15
    被引用数
    (Scopus)
  • Ca2+添加MgOの触媒特性および物理化学的性質〔英文〕

    松方 正彦

    石油学会誌   32 ( 2 ) p97 - 109  1989年03月

    DOI CiNii

    Scopus

    4
    被引用数
    (Scopus)
  • Benzene-Carbon Dioxide Reaction over Alkaline Earth Metal Oxide Catalysts

    Masahiko Matsukata, Shin-Ya Sekine, Ken-Ichiro Kobayashi, Eiji Okanari, Eiichi Kikuchi, Yoshiro Morita

    Journal of The Japan Petroleum Institute   32 ( 4 ) 206 - 215  1989年

     概要を見る

    The benzene-carbon dioxide reaction was performed over alkaline earth metal oxide catalysts at temperatures in the range 973-1173K to investigate the reaction sequence in hydrocarbon gasification and the catalytic role of these oxides. To discuss the difference in the reactivities of benzene and hexane, we propose a reaction scheme as follows: the reaction proceeds via the intermediate carbon deposited by direct decomposition of benzene on the surface of the catalyst producing hydrogen simultaneously, and the rapid reverse water gas shift reaction concurrently occurs to give carbon monoxide and steam in equilibrium composition. The catalytic activity was determined on the balance between the rate of formation of intermediate carbon and the rate of its gasification. Characterization of catalysts by means of 1-butene isomerization leads to a confirmation that carbon accumulates on an inactive part of the catalyst surface. © 1989, The Japan Petroleum Institute. All rights reserved.

    DOI

    Scopus

    1
    被引用数
    (Scopus)
  • Catalytic and Physical Properties of Ca2+-doped MgO

    Masahiko Matsukata, Eiji Okanari, Ken-Ichiro Kobayashi, Eiichi Kikuchi, Yoshiro Morita

    Journal of The Japan Petroleum Institute   32 ( 2 ) 97 - 109  1989年

     概要を見る

    Ca2+ ions loaded on MgO surface markedly promoted catalytic activities of MgO for isomerization of 1-butene, hydrocarbon gasification with CO2 or O2, and the reverse water-gas shift reaction, although MgO itself was almost inactive after treatment at 1273K in air. Ca2+ ions also increased the basicity and basic strength of MgO. Strong basic sites catalyzed isomerization of 1-butene. In the course of impregnation with Ca(NO3)2, MgO (periclase) was completely transformed into hydrate (brucite) by the action of nitrate ions. It is considered that Ca2+ ions interfere with the transformation of surface arrangements accompanied with structural transformation from brucite (hcp) to periclase (fcc). It wasm found that most of Ca2+ ions aggregated to form particles of CaO on the surface of MgO while Ca2+ ions were highly dispersed on the surface of MgO when the MgO was prepared from basic carbonate salt involving calcium as an impurity. © 1989, The Japan Petroleum Institute. All rights reserved.

    DOI

    Scopus

    4
    被引用数
    (Scopus)
  • Benzene-Carbon Dioxide Reaction over Alkaline Earth Metal Oxide Catalysts

    Masahiko Matsukata, Shin-Ya Sekine, Ken-Ichiro Kobayashi, Eiji Okanari, Eiichi Kikuchi, Yoshiro Morita

    Journal of The Japan Petroleum Institute   32 ( 4 ) 206 - 215  1989年

     概要を見る

    The benzene-carbon dioxide reaction was performed over alkaline earth metal oxide catalysts at temperatures in the range 973-1173K to investigate the reaction sequence in hydrocarbon gasification and the catalytic role of these oxides. To discuss the difference in the reactivities of benzene and hexane, we propose a reaction scheme as follows: the reaction proceeds via the intermediate carbon deposited by direct decomposition of benzene on the surface of the catalyst producing hydrogen simultaneously, and the rapid reverse water gas shift reaction concurrently occurs to give carbon monoxide and steam in equilibrium composition. The catalytic activity was determined on the balance between the rate of formation of intermediate carbon and the rate of its gasification. Characterization of catalysts by means of 1-butene isomerization leads to a confirmation that carbon accumulates on an inactive part of the catalyst surface. © 1989, The Japan Petroleum Institute. All rights reserved.

    DOI

    Scopus

    1
    被引用数
    (Scopus)
  • INTERACTION BETWEEN POTASSIUM CARBONATE AND CARBON SUBSTRATE AT SUBGASIFICATION TEMPERATURES - MIGRATION OF POTASSIUM INTO THE CARBON MATRIX

    M MATSUKATA, T FUJIKAWA, E KIKUCHI, Y MORITA

    ENERGY & FUELS   2 ( 6 ) 750 - 756  1988年11月

    DOI

    Scopus

    42
    被引用数
    (Scopus)
  • INTERACTION BETWEEN POTASSIUM CARBONATE AND CARBON SUBSTRATE AT SUBGASIFICATION TEMPERATURES - MIGRATION OF POTASSIUM INTO THE CARBON MATRIX

    M MATSUKATA, T FUJIKAWA, E KIKUCHI, Y MORITA

    ENERGY & FUELS   2 ( 6 ) 750 - 756  1988年11月

    DOI

    Scopus

    42
    被引用数
    (Scopus)
  • Copper-Alumina Spinel Catalysts for Steam Reforming of Methanol

    Chem. Lett.    1988年05月

    DOI

  • COPPER-ALUMINA SPINEL CATALYSTS FOR STEAM REFORMING OF METHANOL

    M MATSUKATA, S UEMIYA, E KIKUCHI

    CHEMISTRY LETTERS   ( 5 ) 761 - 764  1988年05月

    DOI

  • HEXANE CARBON-DIOXIDE REACTION CATALYZED BY ALKALINE-EARTH OXIDES .1. CATALYTIC BEHAVIOR AND INTERMEDIATE

    M MATSUKATA, S SEKINE, K KOBAYASHI, E KIKUCHI, Y MORITA

    APPLIED CATALYSIS   37 ( 1-2 ) 217 - 227  1988年02月

    DOI

    Scopus

    5
    被引用数
    (Scopus)
  • HEXANE CARBON-DIOXIDE REACTION CATALYZED BY ALKALINE-EARTH OXIDES .1. CATALYTIC BEHAVIOR AND INTERMEDIATE

    M MATSUKATA, S SEKINE, K KOBAYASHI, E KIKUCHI, Y MORITA

    APPLIED CATALYSIS   37 ( 1-2 ) 217 - 227  1988年02月

    DOI

    Scopus

    5
    被引用数
    (Scopus)
  • Hexane-carbon dioxide reaction catalyzed by alkaline earth metal oxides. II. Reaction network

    Masahiko Matsukata, Shinya Sekine, Kenichiro Kobayashi, Eiichi Kikuchi, Yoshiro Morita

    Applied Catalysis   41 ( C ) 199 - 211  1988年

     概要を見る

    The catalytic properties of alkaline earth metal oxides and the reaction sequences in the hexane-carbon dioxide reaction were investigated at 1173 K and atmospheric pressure. The catalytic activity for the decomposition of hexane to give deposited carbon increased with increase in the surface area of the catalyst, but the order of the activity for gasification of the deposited carbon was not parallel with either that for the decomposition of hexane or that for the hexane-carbon dioxide reaction. The catalytic activity for the hexane-carbon dioxide reaction was determined from the balance between the activity for the decomposition of hexane to produce the intermediate and that for the gasification of the deposited intermediate carbon. An oxygen transfer mechanism was applied to explain the gasification of carbon deposited on the catalyst surface. It was also confirmed that alkaline earth metal oxides catalyze the water-gas shift reaction under the gasification conditions. Based on these results, a network for the hexane-carbon dioxide reaction is proposed in order to understand comprehensively the catalysis of these oxides. © 1988.

    DOI

    Scopus

    4
    被引用数
    (Scopus)
  • Hexane-carbon dioxide reaction catalyzed by alkaline earth metal oxides. II. Reaction network

    Masahiko Matsukata, Shinya Sekine, Kenichiro Kobayashi, Eiichi Kikuchi, Yoshiro Morita

    Applied Catalysis   41 ( C ) 199 - 211  1988年

     概要を見る

    The catalytic properties of alkaline earth metal oxides and the reaction sequences in the hexane-carbon dioxide reaction were investigated at 1173 K and atmospheric pressure. The catalytic activity for the decomposition of hexane to give deposited carbon increased with increase in the surface area of the catalyst, but the order of the activity for gasification of the deposited carbon was not parallel with either that for the decomposition of hexane or that for the hexane-carbon dioxide reaction. The catalytic activity for the hexane-carbon dioxide reaction was determined from the balance between the activity for the decomposition of hexane to produce the intermediate and that for the gasification of the deposited intermediate carbon. An oxygen transfer mechanism was applied to explain the gasification of carbon deposited on the catalyst surface. It was also confirmed that alkaline earth metal oxides catalyze the water-gas shift reaction under the gasification conditions. Based on these results, a network for the hexane-carbon dioxide reaction is proposed in order to understand comprehensively the catalysis of these oxides. © 1988.

    DOI

    Scopus

    4
    被引用数
    (Scopus)
  • Reaction of 1,2,4-Trimethylbenzene and Methanol on Montmorillonite Catalysts Pillared by Aluminum Complexes

    Appl. Catal.   66;3  1987年03月

  • Reaction of 1,2,4-Trimethylbenzene and Methanol on Montmorillonite Catalysts Pillared by Aluminum Complexes

    Appl. Catal.   66;3  1987年03月

  • Catalytic Methanation of Methanol

    Masahiko Matsukata, Tatsuya Hayashi, Masashi Nishiyama, Eiichi Kikuchi, Yoshiro Morita

    Journal of The Japan Petroleum Institute   30 ( 4 ) 265 - 272  1987年

     概要を見る

    To produce town gas catalytic methanation of methanol was investigated in the temperature range of 300—350°C. Nickel and alumina were excellent components of the catalyst. The catalysts containing 80wt% of nickel prepared by coprecipitation methods showed especially high activities at 300°C. The methanol conversion over the coprecipitated catalysts was dependent upon the size of the nickel crystallite, while the methane selectivities were not. The activity and selectivity of coprecipitated catalysts were steady during a 20hr-run and on addition of water to methanol. © 1987, The Japan Petroleum Institute. All rights reserved.

    DOI

    Scopus

    2
    被引用数
    (Scopus)
  • Catalytic Methanation of Methanol

    Masahiko Matsukata, Tatsuya Hayashi, Masashi Nishiyama, Eiichi Kikuchi, Yoshiro Morita

    Journal of The Japan Petroleum Institute   30 ( 4 ) 265 - 272  1987年

     概要を見る

    To produce town gas catalytic methanation of methanol was investigated in the temperature range of 300—350°C. Nickel and alumina were excellent components of the catalyst. The catalysts containing 80wt% of nickel prepared by coprecipitation methods showed especially high activities at 300°C. The methanol conversion over the coprecipitated catalysts was dependent upon the size of the nickel crystallite, while the methane selectivities were not. The activity and selectivity of coprecipitated catalysts were steady during a 20hr-run and on addition of water to methanol. © 1987, The Japan Petroleum Institute. All rights reserved.

    DOI

    Scopus

    2
    被引用数
    (Scopus)
  • Steam Gasification of Residues Catalyzed by Alumina-supported Potassium Carbonate and Calcium Oxide

    Eiichi Kikuchi, Toru Sekiba, Ken Harasawa, Masahiko Matsukata, Yoshiro Morita

    Journal of The Japan Petroleum Institute   28 ( 6 ) 470 - 476  1985年

     概要を見る

    Steam reforming of atmospheric, vacuum and solvent-deasphalting residues was investigated using a fluidized bed reactor, where alumina-supported potassium and calcium oxide catalysts were packed. Atmospheric residues were gasified with high efficiency on GaO above 850°C. The catalytic activity, however, decreased markedly with increasing Conradson carbon residue (CGR) of the feed residues. On the other hand, high activity of potassium catalyst was attained even in the gasification of very heavy residues from solvent deasphalting. The decrease in catalytic activity of CaO was not due to sulfur-poisoning of active sites, but was attributed to increasing carbon deposition or to decreasing reactivity of the deposited carbon. Carbon deposited on CaO, especially from residues having large CCR, was less reactive than carbon on the potassium catalyst. The mobility of catalytically active species in deposited carbon layers is a possible explanation for the superior catalytic activity of potassium to CaO. © 1985, The Japan Petroleum Institute. All rights reserved.

    DOI

    Scopus

    7
    被引用数
    (Scopus)
  • Steam Gasification of Residues Catalyzed by Alumina-supported Potassium Carbonate and Calcium Oxide

    Eiichi Kikuchi, Toru Sekiba, Ken Harasawa, Masahiko Matsukata, Yoshiro Morita

    Journal of The Japan Petroleum Institute   28 ( 6 ) 470 - 476  1985年

     概要を見る

    Steam reforming of atmospheric, vacuum and solvent-deasphalting residues was investigated using a fluidized bed reactor, where alumina-supported potassium and calcium oxide catalysts were packed. Atmospheric residues were gasified with high efficiency on GaO above 850°C. The catalytic activity, however, decreased markedly with increasing Conradson carbon residue (CGR) of the feed residues. On the other hand, high activity of potassium catalyst was attained even in the gasification of very heavy residues from solvent deasphalting. The decrease in catalytic activity of CaO was not due to sulfur-poisoning of active sites, but was attributed to increasing carbon deposition or to decreasing reactivity of the deposited carbon. Carbon deposited on CaO, especially from residues having large CCR, was less reactive than carbon on the potassium catalyst. The mobility of catalytically active species in deposited carbon layers is a possible explanation for the superior catalytic activity of potassium to CaO. © 1985, The Japan Petroleum Institute. All rights reserved.

    DOI

    Scopus

    7
    被引用数
    (Scopus)

▼全件表示

書籍等出版物

  • ゼロから見直すエネルギー : 節電、創エネからスマートグリッドまで

    化学工学会緊急提言委員会, 化学工学会, 松方, 正彦, 古山, 通久

    丸善出版  2012年02月 ISBN: 9784621085134

  • High Temperature Separation of Water/Methanol/Hydrogen Mixtures through ZSM-5 zeolite Membranes

    K. Sawamura, T. Izumi, T. Shirai, M. Takada, Y. Sekine, E. Kikuchi, M. Matsukata

    Proc. 9th Int. Conf. on Inorganic Membranes, Ed. By R. Bredesen and H. Raeder (ISBN 13:978082-14-04026-5, ISBN 10: 82-14-04026-5)  2006年06月

  • Effect of Ultra Stable Y Seed Crystals on the Separation Performanceof Y-type Zeolite Membrane for Ethanol Dehydration

    T. Mizuno, Y. Katakura, J. Saito, S. Ikeda, M. Matsukata

    Proc. 9th Int. Conf. on Inorganic Membranes, Ed. By R. Bredesen and H. Raeder (ISBN 13:978082-14-04026-5, ISBN 10: 82-14-04026-5)  2006年06月

  • Development of 1000 mm Long LTA Zeolite Membrane for Alcohols Dehydration with High Performance

    S. Inoue, T. Mizuno, J. Saito, S. Ikeda, M. Matsukata

    Proc. 9th Int. Conf. on Inorganic Membranes, Ed. By R. Bredesen and H. Raeder (ISBN 13:978082-14-04026-5, ISBN 10: 82-14-04026-5)  2006年06月

  • Dehydration Behavior of MFI Zeolite Membranes for Various Kinds of Solvents

    K. Sato, K. Sugimoto, T. Nakane, M. Matsukata

    Proc. 9th Int. Conf. on Inorganic Membranes, Ed. By R. Bredesen and H. Raeder (ISBN 13:978082-14-04026-5, ISBN 10: 82-14-04026-5)  2006年06月

  • High Temperature Separation of Water/Methanol/Hydrogen Mixtures through ZSM-5 zeolite Membranes

    K. Sawamura, T. Izumi, T. Shirai, M. Takada, Y. Sekine, E. Kikuchi, M. Matsukata

    Proc. 9th Int. Conf. on Inorganic Membranes, Ed. By R. Bredesen and H. Raeder (ISBN 13:978082-14-04026-5, ISBN 10: 82-14-04026-5)  2006年06月

  • Effect of Ultra Stable Y Seed Crystals on the Separation Performanceof Y-type Zeolite Membrane for Ethanol Dehydration

    T. Mizuno, Y. Katakura, J. Saito, S. Ikeda, M. Matsukata

    Proc. 9th Int. Conf. on Inorganic Membranes, Ed. By R. Bredesen and H. Raeder (ISBN 13:978082-14-04026-5, ISBN 10: 82-14-04026-5)  2006年06月

  • Development of 1000 mm Long LTA Zeolite Membrane for Alcohols Dehydration with High Performance

    S. Inoue, T. Mizuno, J. Saito, S. Ikeda, M. Matsukata

    Proc. 9th Int. Conf. on Inorganic Membranes, Ed. By R. Bredesen and H. Raeder (ISBN 13:978082-14-04026-5, ISBN 10: 82-14-04026-5)  2006年06月

  • Dehydration Behavior of MFI Zeolite Membranes for Various Kinds of Solvents

    K. Sato, K. Sugimoto, T. Nakane, M. Matsukata

    Proc. 9th Int. Conf. on Inorganic Membranes, Ed. By R. Bredesen and H. Raeder (ISBN 13:978082-14-04026-5, ISBN 10: 82-14-04026-5)  2006年06月

  • ゼオライト膜の応用

    松方正彦

    「新時代の多孔性材料とその応用−ナノサイエンスが作る新材料」北川進編、シーエムシー出版  2005年06月

  • Charaterization of Zeolite Membrane Quality by Using Permporosimetry

    K. Nakai, K. Nakamura, J. Kaneshiro, M. Matsukata

    Proc. 7th International Symposium on the Characterisation of Porous Solids (COPS VII), 25th - 28th May 2005, Aix-en-Provence, France  2005年05月

  • Charaterization of Zeolite Membrane Quality by Using Permporosimetry

    K. Nakai, K. Nakamura, J. Kaneshiro, M. Matsukata

    Proc. 7th International Symposium on the Characterisation of Porous Solids (COPS VII), 25th - 28th May 2005, Aix-en-Provence, France  2005年05月

  • ゼオライト膜

    松方正彦

    セラミックデータブック、セラミックデータブック編集委員会、工業製品技術協会  2005年

  • 高圧

    関根 泰, 松方正彦

    第5版 実験化学講座6/丸善(印刷中)  2004年

  • メンブレンリアクター

    松方正彦

    触媒活用大辞典/工業調査会  2004年

  • ゼオライト微細膜触媒

    松方正彦

    微粒子工学体系 第Ⅱ巻応用技術フジテクノシステム  2002年01月

  • 境膜抵抗他5項目

    触媒の事典朝倉書店  2000年09月

  • ゼオライト膜の調製

    ゼオライトの科学と工学講談社サイエンティフィック  2000年07月

  • 4.3 不均一反応系と装置技術者のための化学工学の基礎と実践、第4章反応工学の基礎

    アグネ承風社  1998年10月

  • ドライゲルコンバージョン法による新しいゼオライトの合成とその特性

    触媒技術の動向と展望1998/触媒学会編  1998年04月

▼全件表示

Misc

  • 超空間による新素材開発 ホージャサイト型ゼオライト膜によるオレフィンの分離精製

    酒井求, 松方正彦

    化学工業   71 ( 3 )  2020年

    J-GLOBAL

  • Co内包型ゼオライト触媒によるFT合成における選択的オレフィン合成

    松方正彦, 粕谷壮史

    触媒討論会講演予稿集(CD-ROM)   125th  2020年

    J-GLOBAL

  • ベータ型ゼオライト結晶粒子の自己相似構造発現の由来解明

    佐々木優吉, FISHER Craig, 吉田陽子, 池田卓史, 板橋慶治, 大久保達也, 松方正彦

    JFCC研究成果集   2020  2020年

    J-GLOBAL

  • 脱アルミニウム*BEAに吸着した重質HCの吸着・脱離挙動の検討

    鈴木豪太, 松方正彦

    触媒討論会講演予稿集(CD-ROM)   125th  2020年

    J-GLOBAL

  • Na-MOR膜を用いた酢酸エステル合成用フローメンブレンリアクターの開発

    野中雄貴, 酒井求, 松方正彦, 松方正彦, 松方正彦

    化学工学会年会研究発表講演要旨集(CD-ROM)   85th  2020年

    J-GLOBAL

  • 高圧洗浄技術を応用した新規放射能汚染土減容化技術の開発

    正田武則, 正田武則, 正田武則, 松方正彦, 松方正彦, 山崎淳司, 山崎淳司, 志方洋介, 志方洋介, 水戸洋彦, 相川光明, 上林俊明, 森山克彦

    化学工学会年会研究発表講演要旨集(CD-ROM)   85th  2020年

    J-GLOBAL

  • AEI型ゼオライト膜の合成方法とその透過分離特性の検討

    橋爪優祐, 酒井求, 松方正彦, 松方正彦

    化学工学会年会研究発表講演要旨集(CD-ROM)   85th  2020年

    J-GLOBAL

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    堀隼太, 酒井求, 松方正彦, 松方正彦

    化学工学会年会研究発表講演要旨集(CD-ROM)   85th  2020年

    J-GLOBAL

  • ポアフィリングエージェントを用いたアルカリ処理法:silicalite-1膜の透過分離特性に及ぼす影響

    堀隼太, 酒井求, 松方正彦, 松方正彦, 松方正彦

    日本膜学会年会講演要旨集   42nd  2020年

    J-GLOBAL

  • 銀イオン交換方法がAg-X膜のオレフィン/パラフィン分離特性に及ぼす影響

    野村裕太, 酒井求, 松方正彦, 松方正彦, 松方正彦

    日本膜学会年会講演要旨集   42nd  2020年

    J-GLOBAL

  • ZSM-5膜のAl位置と透過選択性の関連性

    森屋早紀, 酒井求, 松方正彦, 松方正彦, 松方正彦

    日本膜学会年会講演要旨集   42nd  2020年

    J-GLOBAL

  • Y型ゼオライト触媒膜を用いた直鎖アルカンの水素化分解

    橋本湧輝, 酒井求, 松方正彦, 松方正彦, 松方正彦

    日本膜学会年会講演要旨集   42nd  2020年

    J-GLOBAL

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    野村裕太, 酒井求, 松方正彦, 松方正彦, 松方正彦

    膜シンポジウム   ( 32 (CD-ROM) )  2020年

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  • 原子スケール直接観察による細孔内カチオン構造解析

    吉田要, 酒井求, 倉田博基, 中平敦, 松方正彦, 佐々木優吉

    ゼオライト研究発表会講演予稿集   36th  2020年

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  • ゼオライト触媒膜の開発と炭化水素分解能の検討

    橋本湧輝, 酒井求, 松方正彦, 松方正彦

    化学工学会秋季大会研究発表講演要旨集(CD-ROM)   51st  2020年

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    J-GLOBAL

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    日本膜学会年会講演要旨集   41st  2019年

    J-GLOBAL

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    J-GLOBAL

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    J-GLOBAL

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    J-GLOBAL

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    J-GLOBAL

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    化学工学会秋季大会研究発表講演要旨集(CD-ROM)   50th  2018年

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    J-GLOBAL

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    J-GLOBAL

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    J-GLOBAL

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    J-GLOBAL

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    J-GLOBAL

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    J-GLOBAL

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    日本膜学会年会講演要旨集   40th  2018年

    J-GLOBAL

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    J-GLOBAL

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    J-GLOBAL

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    J-GLOBAL

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    J-GLOBAL

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    膜   37 ( 5 ) 211 - 211  2012年09月

    CiNii

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    觸媒 = Catalyst   54 ( 2 ) 141 - 143  2012年03月

    CiNii

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    菊池 康紀, 梶川 裕矢, 加藤 之貴, 窪田 光宏, 中垣 隆雄, 福島 康裕, 松方 正彦, 古山 通久

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    CiNii

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    觸媒 = Catalyst   54 ( 1 ) 34 - 38  2012年01月

    CiNii

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    觸媒 = Catalyst   53 ( 2 ) 95 - 97  2011年03月

    CiNii

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    觸媒 = Catalyst   53 ( 2 ) 98 - 100  2011年03月

    CiNii

  • 骨太エネルギー技術ロードマップ技術の紹介(3) : ものづくりとエネルギー

    加藤 之貴, 松方 正彦

    化学工学 = Chemical engineering   75 ( 3 ) 134 - 136  2011年03月

    CiNii

  • 実装可能な技術による将来エネルギーシステムの設計

    菊池 康紀, 梶川 裕矢, 窪田 光宏, 古山 通久, 松方 正彦, 中垣 隆雄, 福島 康裕, 藤岡 恵子, 加藤 之貴

    日本LCA学会研究発表会講演要旨集   2011 ( 0 ) 10 - 10  2011年

     概要を見る

    震災に端を発したエネルギー問題により将来の日本におけるシナリオ解析に基づくシステム設計の必要性を認識することとなった。本研究では、個別のエネルギー技術のモデル化を通し、将来日本において実装可能な技術によるエネルギー需給構造を分析した。エネルギー技術の専門家へのヒアリングなども通し、将来の技術導入を予測し、現実的な解析に基づくエネルギーシステムの将来シナリオを提案する。

    DOI CiNii

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    渡部 綾, 関根 泰, 会田 知章, 小嶋 淳吾, 生嶋 麻衣子, 松方 正彦, 菊地 英一

    觸媒 = Catalyst   52 ( 2 ) 140 - 142  2010年03月

    CiNii

  • 石炭灰・焼却灰からの微量元素溶出防止剤の開発

    松方正彦, 正田武則, 関根泰, 菊地英一, 山崎淳司

    化学工学会秋季大会研究発表講演要旨集(CD-ROM)   42nd  2010年

    J-GLOBAL

  • Steam reforming of ethanol over supported iron-cobalt catalyst

    Yasushi Sekine, Atsushi Kazama, Yoshiyuki Izutsu, Masahiko Matsukata, Eiichi Kikuchi

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   238  2009年08月

    研究発表ペーパー・要旨(国際会議)  

  • Ultralow temperature steam reforming of methane with novel catalytic system in an electric field

    Yasushi Sekine, Masahiko Tomioka, Masayuki Haraguchi, Masahiko Matsukata, Eiichi Kikuchi

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   238  2009年08月

    研究発表ペーパー・要旨(国際会議)  

  • 第10回無機膜国際会議を終えてセッション報告

    松方 正彦

    膜   34 ( 2 ) 72 - 79  2009年03月

    CiNii

  • 無機系分離膜の最新動向 (特集 分離技術の最新動向)

    松方 正彦

    分離技術   39 ( 6 ) 407 - 409  2009年

    CiNii

  • PETR 112-Catalyst preparation for vapor phase Beckmann rearrangement via deboronation/desilication of B-ZSM-5

    Masahiko Matsukata, Kohsuke Nakagawa, Yasushi Sekine, Eiichi Kikuchi

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   235  2008年04月

    研究発表ペーパー・要旨(国際会議)  

  • FUEL 56-Effective utilization of electrical discharges for hydrogen production

    Yasushi Sekine, Masahiko Matsukata, Elichi Kikuchi

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   235  2008年04月

    研究発表ペーパー・要旨(国際会議)  

  • エタノール分解をモデル反応とした電場印加反応場における触媒の効果

    関根 泰, 富岡 真彦, 岩崎 弘幸, 松方 正彦, 菊地 英一

    触媒 = Catalysts & Catalysis   49 ( 6 ) 450 - 452  2007年09月

    CiNii

  • FUEL 177-Mechanistic study of methnol/water/hydrogen separation through ZSM-5 membrane

    Masahiko Matsukata, Kenichi Sawamura, Teruaki Izumi, Mitsuko Takada, Yasushi Sekine, Tetsu Osuna, Eiichi Kikuchi

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   234  2007年08月

    研究発表ペーパー・要旨(国際会議)  

  • ナノサイズ-ハイドロタルサイト様物質を用いた排水中の低濃度ホウ素・フッ素の除去技術

    大野睦浩, 梶本崇, 松方正彦, 山崎淳司

    粘土科学討論会講演要旨集   51st  2007年

    J-GLOBAL

  • ドライゲルコンバージョン法によるゼオライト合成と結晶化機構―ベータ型ゼオライトを中心に-

    松方正彦, 稲垣怜史, 関根泰, 菊地英一

    触媒   49 ( 7 ) 579 - 584  2007年

    記事・総説・解説・論説等(その他)  

    CiNii

  • FUEL 18-Simultaneous dry reforming and desulfurization of biomethane with nonequilibrium discharge at ambient temperature

    Yasushi Sekine, Junya Yamadera, Eiichi Kikuchi, Masahiko Matsukata

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   232  2006年09月

    研究発表ペーパー・要旨(国際会議)  

  • エタノール水蒸気改質反応用CoおよびNi触媒担体へのペロブスカイト型酸化物の適用

    浦崎 浩平, 石川 清宏, 関根 泰, 菊地 英一, 松方 正彦

    触媒 = Catalysts & Catalysis   48 ( 2 ) 65 - 67  2006年03月

    CiNii

  • 常温常圧非平衡放電による電子励起と酸化物触媒のシナジー

    関根 泰, 菊地 英一, 松方 正彦, 岡崎 健

    触媒 = Catalysts & Catalysis   48 ( 2 ) 80 - 82  2006年03月

    CiNii

  • 石炭表面の親水・疎水度がカラム浮選成績に及ぼす影響

    関根 泰, 佐藤 大介, 山口 大輔, 菊地 英一, 松方 正彦

    日本エネルギー学会誌 = Journal of the Japan Institute of Energy   84 ( 11 ) 917 - 922  2005年11月

     概要を見る

    Continuous column flotation is one of an economical coal cleaning processes. In this study, we examined the effect of hydrophilicity and hydrophobicitiy of coal surface on the continuous column flotation processes. We found that Wallarah coal was most suitable coal for the coal cleaning by the column flotation. From a static separation of film flotation, we found that the floatability of coal particle strongly depended on the hydrophilicity and hydrophobicity of coal surface. On the other hand, the trend of demineralization and the ratio of carbonaceous recovery could be predicted by the observation of methylene-blue adsorption test.

    CiNii

  • Hydrogen production via steam-iron reaction using iron oxide modified with very small amounts of palladium and zirconia

    K Urasaki, N Tanimoto, T Hayashi, Y Sekine, E Kikuchi, M Matsukata

    APPLIED CATALYSIS A-GENERAL   288 ( 1-2 ) 143 - 148  2005年07月

     概要を見る

    We investigated hydrogen production by the steam-iron reaction using iron oxide modified with very small amounts of palladium and/or zirconia at a temperature of 723 K and under atmospheric pressure. Reduction of iron oxide with hydrogen and oxidation of partially reduced iron oxide with steam (Fe3O4 + 4H(2) &lt;-&gt; 3Fe + 4H(2)O) were repeated in the range of reduction degree of 30-50 mol%. Changes in the weight of the samples were monitored using a tapered element oscillating microbalance (TEOM) to control the degree of reduction. Unmodified iron oxide caused significant deactivation due to sintering with increasing number of redox cycles. The addition of a very small amount (0.23 mol%) of palladium or zirconia onto the surface of the iron oxide enhanced the reduction and/or oxidation of the partially reduced iron oxide, which suppressed sintering. Palladium accelerated both the reduction and oxidation rates of partially reduced iron oxide, while zirconia increased only the oxidation rate. Addition of both palladium and zirconia together to the iron oxide resulted in marked enhancement of both reduction and oxidation. (c) 2005 Elsevier B.V. All rights reserved.

    DOI CiNii

  • High-energy x-ray diffraction study on the change of intermediate-range structure in the course of crystallization of high silica zeolite beta

    M Matsukata, S Inagaki, K Nakatsuyama, Y Saka, E Kikuchi, G Sankar, T Okubo, S Kohara

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   229   U736 - U736  2005年03月

    研究発表ペーパー・要旨(国際会議)  

  • 私立大学とベンチャーの連携による共同研究の試み

    松方 正彦

    化学工学 = CHEMICAL ENGINEERING OF JAPAN   69 ( 1 ) 46 - 47  2005年01月

    CiNii

  • 内部循環流動床ガス化炉におけるタール及び塩素の乾式除去技術の開発

    両角 文明, 岩楯 由貴, 松方 正彦

    廃棄物学会研究発表会講演論文集   15   630 - 632  2004年11月

    CiNii

  • トルエンのメタノールによるアルキル化におけるMWW構造をもつゼオライトの反応場の検討

    稲垣 怜史, 神野 耕平, 澁谷 弘樹, 菊地 英一, 松方 正彦

    触媒 = Catalysts & Catalysis   46 ( 2 ) 72 - 74  2004年03月

    CiNii

  • 低エネルギー(LEP)放電を用いた水素製造プロセス (特集 未来を拓く水素エネルギー)

    関根 泰, 松方 正彦, 菊池 英一

    ケミカルエンジニヤリング   48 ( 12 ) 921 - 929  2003年12月

    CiNii

  • 32.石炭のカラム浮選における鉱物挙動と浮選成績

    関根 泰, 山口 大輔, 中田 聡史, 菊地 英一, 松方 正彦

    石炭科学会議発表論文集   ( 40 ) 66 - 67  2003年10月

     概要を見る

    There were few studies on the relation of column flotation results with the characteristic features of coal. We investigated the liberalization of minerals in coal with wet-grinding on by mineral analysis of CCSEM. Then the relation between the liberalization of minerals in coal and the ash rejection was studied, and the effect of the composition and distribution form of coal minerals on flotation results was reported.

    CiNii

  • 53.石炭水蒸気ガス化における炭素構造変化・灰分挙動とガス化速度との相関(2) : 水蒸気ガス化はどのように進行しているか

    関根 泰, 石川 清宏, 菊地 英一, 松方 正彦

    石炭科学会議発表論文集   ( 40 ) 108 - 109  2003年10月

     概要を見る

    We investigated steam gasification of coal char and examined the structural change of carbon and ash. From LRS (Laser Raman Spectra)-mapping, BET surface area, XRD, SEM/EDX elemental mapping, we found that the gasification of coal char was strongly affected by the ash behavior and coal structural change. So we clarify the mechanism of the gasification of coal char from these viewpoints.

    CiNii

  • 52.石炭水蒸気ガス化における炭素構造変化・灰分挙動とガス化速度との相関(1) : 炭素と灰分の構造は反応と共にどう変化するか

    関根 泰, 石川 清宏, 菊地 英一, 松方 正彦

    石炭科学会議発表論文集   ( 40 ) 106 - 107  2003年10月

     概要を見る

    In order to clarify the structural change of carbon and ash, steam gasification of coal char was examined. Relation between D/V ratio that is one of the Raman parameters, and the conversion was acquired. The graphitization of coal char was independent from the ash contents, and was only relative to gasification ratio. On the other hand, the condensed ash of reacted char was observed by SEM/EDX.

    CiNii

  • Treatment of LCO fractions on zeolite beta.

    M Matsukata, Y Sekine, P Sharma, E Kikuchi

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   226   U254 - U254  2003年09月

    研究発表ペーパー・要旨(国際会議)  

  • Behavior of trace elements from high-temperature coal combustion process.

    Y Sekine, T Kawabata, K Sakajiri, E Kikuchi, M Matsukata

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   225   U869 - U869  2003年03月

    研究発表ペーパー・要旨(国際会議)  

  • Hydrogen-butane separation through MFI-type zeolite membrane grown by a secondary growth method.

    M Matsukata, H Akimoto, Y Sekine, E Kikuchi

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   225   U871 - U871  2003年03月

    研究発表ペーパー・要旨(国際会議)  

  • Effect of water adsorption on permeation properties of MFI-type zeolite membrane produced by in situ crystallization.

    M Matsukata, T Nara, Y Sekine, E Kikuchi, JA Dalmon, S Miachon

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   225   U879 - U879  2003年03月

    研究発表ペーパー・要旨(国際会議)  

  • Ash rejection behavior on continuous column flotation process.

    Y Sekine, D Yamaguchi, K Ishikawa, E Kikuchi, M Matsukata

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   225   U876 - U876  2003年03月

    研究発表ペーパー・要旨(国際会議)  

  • デカリン・ナフタレン・テトラリンの水素異性化とそのための触媒開発

    関根泰, 藤咲祐介, 金井慎之介, 井口靖敏, 菊地英一, 松方正彦

    石油・石油化学討論会講演要旨   33rd  2003年

    J-GLOBAL

  • CH_4-SCRに活性なPdゼオライトの活性Pd種とCoによる活性安定化向上効果

    小倉 賢, 鹿毛 晋, 下條 智子, 大場 淳子, 林 正義, 松方 正彦, 菊地 英一

    触媒   43 ( 2 ) 78 - 80  2001年03月

    CiNii

  • 材料プロセッシングにおける形体・構造制御のためのエキスパートシステムの開発

    野田優, 辻佳子, 大沢利男, 小宮山宏, 奥山喜久夫, 島田学, 江頭靖幸, 松方正彦, 野村幹弘, 舟窪浩 KimHeeJoon, 井原学, 高見誠一

    化学工学会第65回年会    2001年

  • アルカリ溶解した ZSM-5 ゼオライトの構造と酸触媒特性

    小倉 賢, 篠宮 信哉, 舘野 潤子, 松方 正彦, 菊地 英一

    触媒   42 ( 6 ) 375 - 377  2000年09月

    CiNii

  • 7-3.石灰石からの塩化物の揮発挙動(Session 4.7.8 燃焼・環境対策技術・エネルギー評価/経済)

    松方 正彦, 中谷 圭吾, 菊地 英一

    日本エネルギー学会大会講演要旨集   ( 9 ) 281 - 284  2000年08月

    CiNii

  • CVD法による水素透過白金膜の調製

    清水隆史, 野村幹弘, 松方正彦, 菊地英一, 上宮成之, 小島紀徳

    日本膜学会年会講演要旨集   22nd   96  2000年04月

  • Pt担持ゼオライト触媒を用いたナフタレン接触改質の反応経路に関する検討

    松方正彦, 渋谷宏之, 井口靖敏, 菊地英一

    石油・石油化学討論会講演要旨   30th  2000年

    J-GLOBAL

  • ゼオライトベータ,Yを用いたナフタレンの接触改質反応

    松方正彦, 渋谷宏之, 小倉賢, 菊地英一

    石油学会年会講演要旨   43rd  2000年

    J-GLOBAL

  • 材料プロセッシングにおける形体・構造制御のためのソフトウエアツール開発

    野田優, 辻佳子, 大沢利男, 小宮山宏, 奥山喜久夫, 島田学, 江頭靖幸, 松方正彦, 野村幹弘, 舟窪浩 KimHeeJoon, 井原学, 高見誠一

    化学工学会第65回年会    2000年

  • Permeation of hexane isomers through an MFI membrane

    Takaaki Matsufuji, Kensuke Watanabe, Norikazu Nishiyama, Yasuyuki Egashira, Masahiko Matsukata, Korekazu Ueyama

    Ind. Eng. Chem. Res.   39, 2434-2438/, ( 7 ) 2434 - 2438  2000年01月

     概要を見る

    The pervaporation tests for n-hexane, 2-methylpentane (2-MP), and 2,3- dimethylbutane (2,3-DMB) were performed using an MFI-type zeolitic membrane at 303 K. In the unary systems, those fluxes followed the order n-hexane &gt;&gt; monobranched hexane (2-MP), &gt; dibranched hexane (2,3-DMB). The ideal selectivities of n-hexane/2-MP and n-hexane/2,3-DMB were 37 and 50, respectively, n-Hexane preferentially permeated in the measurements of a binary mixture of n-hexane/2-MP and n-hexane/2,3-DMB. The feed composition dependence in separating n-hexane/2,3-DMB binary mixtures was studied. The separation factor for the 50/50 n-hexane/2,3-DMB mixture exceeded 120, which was much greater than 54 in the 50/50 n-hexane/2-MP system. When the feed concentration of n-hexane was 10 mol %, the separation factor α(n- hexane/2,3-DMB) at the steady state was as high as 270. n-Hexane effectively inhibited the permeation of 2,3-DMB, even when the concentration of n-hexane was very small.

    DOI CiNii

  • ゼオライトベータの結晶化過程

    松方 正彦, 大崎 貴之, 菊地 英一

    触媒   41 ( 2 ) 134 - 136  1999年03月

    CiNii

  • Oral and Poster Session報告

    上宮 成之, 草壁 克己, 中尾 真一, 山口 猛央, 原谷 賢治, 都留 稔了, 浅枝 正司, 喜多 英敏, 諸岡 成治, 増田 隆夫, 須藤 雅夫, 佐野 庸治, 矢澤 哲夫, 松方 正彦, 伊藤 直次, 田川 智彦

    膜   24 ( 1 ) 46 - 61  1999年01月

    DOI CiNii

  • 気相輸送法によるゼオライト合成法の開発と薄膜化に関する研究

    松方 正彦

    化学工学   59 ( 6 ) 388 - 389  1995年06月

    CiNii

  • ゼオライト分離膜の開発 (最近の膜分離技術の応用と進展<特集>)

    松方 正彦, 西山 憲和, 上山 惟一

    ケミカルエンジニヤリング   38 ( 11 ) p917 - 920,951  1993年11月

    CiNii

  • パラジウム系触媒を用いたトルエンの気相アセトキシル化反応

    上宮成之, 北角公一, 小島紀徳, 松方正彦, 上山惟一

    化学工学会年会研究発表講演要旨集   58th ( Pt 1 ) 123  1993年03月

  • 各種プロセスから排出される有害微量元素の環境影響の評価を目的としたICP-MSによる定量分析法の開発

    松方正彦

    日産科学振興財団研究報告書   15(1992)  1993年

    J-GLOBAL

  • ドナン透析を用いたL‐メチオニンの選択的回収

    小島 紀徳, 八木 重和, 本島 一枝, 西嶋 一裕, 松方 正彦

    膜   18 ( 4 ) 237 - 247  1993年

     概要を見る

    Permeation rates of L-methionine and acethyl-DL-methionine were measured through ion exchange membranes into sodium chloride solution, assuming that the former was produced from the latter using a immobilized enzyme reactor. Both were permeated through an anion exchange membrane. L-methionine was selectively recovered from a L-methionine and acethyl-DL-methionine mixture by Donnan dialysis using a cation exchange membrane under the various pH conditions, however its rate was smaller than that through anion exchange membrane.<BR>At low pH, the permeation of hydrogen ion was dominant while that of L-methionine was suppressed. The flux of L-methionine attained to a maximum at pH 2 and decreased with increasing pH. Its mechanism was discussed based on ion exchange equilibrium at the interface and mass transfer in the boundary layer and membrane.

    DOI CiNii

  • Pd系バイメタル触媒によるトルエンの酸化的アセトキシル化反応

    松方正彦, 北角公一, 上宮成之, 小島紀徳, 上山惟一

    石油・石油化学討論会講演要旨   22nd   264 - 267  1992年11月

  • アルカリ塩添加Pd‐Au/SiO2触媒を用いたトルエンの気相酸化的アセトキシル化反応

    松方正彦, 北角公一, 上宮成之, 上山惟一, 小島紀徳

    触媒討論会討論会A予稿集   70th   582 - 583  1992年09月

  • 逆抽出側に錯化剤を添加した含浸型液体膜による希土類の透過

    中山智香子, 豊永佳弘, 松方正彦, 上宮成之, 小島紀徳

    化学工学会秋季大会研究発表講演要旨集   25th ( Pt 3 ) 231  1992年08月

  • 含浸型液体膜によるバナジウム・クロムの選択的透過

    小島紀徳, 西嶋一裕, 松方正彦

    化学工学シンポジウムシリーズ   31   126 - 135  1992年06月

  • モノシランの気相熱分解による,微粒子へのシリコン超微粉コーティング

    小島 紀徳, 若月 亮太, 松方 正彦, 小沢 英一, Friedt Jean M.

    化学工学論文集   18 ( 3 ) 274 - 280  1992年

     概要を見る

    5~20μm程度の窒化珪素微粒子を核として, この上にサブミクロンシリコン微粉をコーティングすることを試みた.主たる目的は反応焼結時の焼結性改善である.<BR>アルゴンで希釈したモノシラン気流中に窒化珪素の核粒子を均一にかつ希薄に浮遊させ, 核粒子よりなる流動層からCVD反応器に送入した.さらに附加ガスとしてアルゴンを反応器底部周囲から反応器に送入した.生成粒子の流通抵抗は生成粒子中のシリコン微粉量に比例した.SEM, TEMの結果から, 核粒子は, 一次粒子径約0.01μmのシリコン超微粉により覆われていることがわかった.XRDのチャートにはシリコン微粉の弱いパターンが窒化珪素のパターン上に現われていることが観測された.一方附加ガスを流入しない場合には核粒子は密な析出物で覆われ, またXRDチャートはブロードとなり, シリコンのパターンも見られなかった.附加ガスの送入により核粒子上へのシリコンの異相析出が抑えられた.これは附加ガスを装置内で加熱し反応ガスと混合することにより均相反応が生じる一方その導入により反応器内の滞留時間が短くなり異相析出反応が抑えられたからと思われる.

    DOI CiNii

  • 6-7.コークス連続製造プロセスにおける予備加熱(Session(6)コークス製造と利用)

    南雲 篤郎, 松方 正彦, 小島 紀徳

    日本エネルギー学会大会講演要旨集   1 ( 0 ) 193 - 196  1992年

    DOI CiNii

  • Au添加Pd/SiO2を触媒とするベンゼン,トルエンの気相酸化的アセトキシル化反応

    松方正彦, 川村義昭, 石本直正, 北角公一, 小島紀徳

    石油・石油化学討論会講演要旨   21st   138 - 139  1991年10月

  • Pd系触媒を用いたトルエンの気相酸化的アセトキシル化

    松方正彦, 北角公一, 小島紀徳

    触媒討論会討論会A予稿集   68th   504 - 505  1991年09月

  • アルカリ土類金属酸化物触媒を用いたベンゼン-酸素反応〔英文〕

    松方 正彦

    石油学会誌   34 ( 1 ) p36 - 43  1991年01月

    CiNii

  • Pd系触媒を用いたベンゼンの気相酸化的アセトキシル化反応

    松方正彦, 川村義昭, 小島紀徳

    触媒討論会討論会A予稿集   66th   282 - 283  1990年09月

  • 逆抽出側水相へ添加した錯化剤によるPr,Ndイオンの液体膜透過速度の向上

    霜越篤男, 空谷実登里, 松方正彦, 小島紀徳

    化学工学会年会研究発表講演要旨集   55th  1990年

    J-GLOBAL

  • アルカリ土類金属酸化物を触媒とするベンゼン-2酸化炭素反応〔英文〕

    松方 正彦

    石油学会誌   32 ( 4 ) p206 - 215  1989年07月

    CiNii

  • メタノ-ルの接触メタン化〔英文〕

    松方 正彦

    石油学会誌   30 ( 4 ) p265 - 272  1987年07月

    CiNii

▼全件表示

受賞

  • 日本エネルギー学会進歩賞

    2001年  

  • 触媒学会(平成10年度獎励賞)

    1999年  

  • 石油学会(平成7年度奨励賞)

    1996年  

  • 化学工学会(平成7年度)奨励賞

    1995年  

共同研究・競争的資金等の研究課題

  • チャネル型正浸透膜の創製と究極的ゼロエネルギー水処理プロセスの構築

    日本学術振興会  科学研究費助成事業 基盤研究(A)

    研究期間:

    2018年04月
    -
    2022年03月
     

    松山 秀人, 松方 正彦, 小野 努, 吉岡 朋久, 中川 敬三, 神尾 英治, 佐伯 大輔, 高橋 智輝, 稲田 飛鳥, 彌田 智一

     概要を見る

    1. 新規水チャネル型FO膜の創製
    1-1.環状ペプチド分子集合体チャネル膜の創製(松山、吉岡、佐伯):環状ペプチド分子集合体を導入した平面脂質二分子膜について、FO膜としての性能を確認するとともに、環状ペプチド内の官能基が水分子の拡散性や透過性に影響を及ぼすことを明らかにした。1-2.高分子液晶垂直配向チャネル膜の創製(彌田、稲田):液晶性ブロックコポリマー(BCP)をFO膜として使うための複合膜化を検討した。新規購入の超音波ホモジナイザーで乳化したアルギン酸ナトリウム層(犠牲層)をガラス基板上に作製し、その上にBCP薄膜を製膜し、水中でBCP薄膜を犠牲層から剥離させ支持膜に重ねることで複合膜を作製する手法を開発した。1-3.革新的ロバスト無機ゼオライトFO膜の創製(松方):ZSM-5膜を用いて、無機FO膜の正浸透膜特性を説明する透過モデルの検討を進めた。また、高い透過性と塩阻止率を両立する無機FO膜の設計指針を得る検討を継続した。1-4.計算機科学による高機能FO膜開発支援 (吉岡):MD計算によりチャネル内表面特性が水および塩の拡散性に及ぼす影響を評価した。親水的なチャネル入り口が高透水性に寄与するが、疎水化されたチャネル内では塩の拡散性が大きくなることが明らかとなった。
    2. 新規刺激応答性駆動溶液(DS)の創製(小野、高橋)
    熱応答性イオン液体の温度依存的浸透圧発現機構の解析を基に、相図、粘度、浸透圧、相分離性をより最適化したイオン液体DSを設計した。また、イオン液体を利用した膜の調製と膜骨格にイオン液体構造を導入する技術についても開発した。
    3.FO膜透過とDS再生を含む連続システムによるFS評価とFO膜システムの実証(松山、神尾、中川)
    FO膜分離、DS連続再生、RO膜によるDS回収を一体化した小型連続FOシステムを構築し、海水淡水化を想定した連続運転条件検討を行った。

  • ミクロ多孔体薄膜の特異な分離機能を利用した膜分離に関する基盤的研究

    日本学術振興会  科学研究費助成事業 基盤研究(B)

    研究期間:

    2010年
    -
    2012年
     

    松方 正彦

     概要を見る

    新規な膜分離技術を創生し、次世代のエネルギー・化学産業におけるプロセスの一層のグリーン化に貢献することを目指し、結晶性ミクロ多孔体を材料とする無機分離膜の開発のための基盤研究を行った。水、有機物等の混合物の分離の実現を目指し、膜の生成機構と製膜の過程を詳しく明らかにするとともに、透過分離性能の支配因子を抽出し透過分離機構の解明を試みた。 Y 型ゼオライト膜については、膜の生成機構を詳細に解析し、イソプロピルアルコールの脱水用膜として高い性能を発揮する膜の合成に成功した。Silicalite-1 膜については、高い分子ふるい性能を発揮する膜の開発に成功し、その透過挙動の定式化に成功した。また、新規にアルミノリン酸系の膜についても検討し、水/酢酸系の蒸気透過分離に高い性能を示す膜の開発に成功した。

  • 電気化学デバイス工学の確立と深化

    日本学術振興会  科学研究費助成事業 特別推進研究

    研究期間:

    2008年
    -
    2012年
     

    逢坂 哲彌, 門間 聰之, 庄子 習一, 杉山 敦史, 中西 卓也, 本間 敬之, 松方 正彦, 水野 潤, 関口 哲志, 吉野 正洋, 冨中 悟史

     概要を見る

    電気化学ナノテクノロジーに基づく「固液界面制御による新機能発現のための材料開発研究」と「界面構造や界面現象の実践的な活用によるデバイス開発研究」に総合的に取り組むことで、電気化学に立脚した材料およびデバイスの実用化研究の根源にあるものを事象ごとの経験論から抽出し、アウトプットとしてのデバイス(具体的にはエネルギーデバイス、センサデバイス、電子デバイス・磁気記録デバイス)を縦糸に、機能発現および界面設計の次元(3次元、2次元、0次元)を横糸に、「電気化学デバイス工学」という学理の構築を図った。

  • 固体酸化物の格子酸素と金属の協奏機能をもつ水素製造用触媒に関する研究

    日本学術振興会  科学研究費助成事業 特定領域研究

    研究期間:

    2008年
    -
    2009年
     

    松方 正彦

     概要を見る

    再生可能な資源であるバイオマスのエネルギー転換方法は様々あるが、ガス化に伴い生成し装置閉塞を引き起こすタール(主要構造のうち芳香族炭化水素)と蒸留濃縮によるエネルギーロスが問題となっている発酵エタノールに注目した。一方で水素はアンモニア合成、石油精製での大需要に加え燃料電池のエネルギー源として期待される重要な分子であり、その水素は芳香族炭化水素(トルエン)やエタノールの水蒸気改質反応によって得ることができるが、活性・選択性・安定性が十分といえる触媒は現状開発されていない。そこで我々はこの反応の触媒の開発を目的とし、研究を行ってきた。
    トルエン水蒸気改質は高選択性かつ安価なニッケル触媒が有望であるが、炭素析出の抑制が課題となる。そこで触媒担体にペロブスカイト型酸化物を適用することで格子酸素の反応への寄与を期待し、調製・改良を進めてきた。その結果見出したNi/La0.7Sr0.3Al0x触媒は参照用触媒のNi/g-Al203に比べトルエン転化率約2倍、炭素析出量およそ1/4という優れた性能を示した。
    エタノール水蒸気改質では反応中間体であるアセトアルデヒドを分解することなく改質する選択性が求められることを明らかにし、更にCo/SrTi03やCo/a-Al203触媒への様々な金属添加を試みた結果、鉄の微量添加が改質の促進および分解の抑制に非常に有効であることを見出した。Fe/Co触媒のSTEMおよびEDX分析により、FeはCo粒子内あるいは粒子表面に選択的に存在することを確認し、Fe/Coが同一担体上に担持されたときにのみ選択性に変化を及ぼすことも示され、FeとCoはシナジー効果を発現していることを明らかにした。

  • ミクロ多孔膜を用いたメンブレンリアクターの開発

    日本学術振興会  科学研究費助成事業 基盤研究(B)

    研究期間:

    2007年
    -
    2009年
     

    松方 正彦, 菊地 英一, 関根 泰, 高田 光子, 澤村 健一

     概要を見る

    従来型の省エネ手法はすでに成熟域にあり、より一層の効率化には全く新しい原理によるプロセスの開発が必要である。本研究では固体触媒と分離膜を組み合わせた革新的反応分離システム(メンブレンリアクター)の開発を行った。特に、課題となった分離膜の耐性および透過分離性能を向上させるため、耐性に富むミクロ多孔膜(ゼオライト膜)の基盤技術開発に注力し、従来の分離膜の耐性および透過分離性能を大幅に上回る新規ミクロ多孔膜の開発に成功した。

  • 電子励起された酸化物等の固体表面を用いた常温常圧触媒反応の研究

    日本学術振興会  科学研究費助成事業 基盤研究(B)

    研究期間:

    2006年
    -
    2009年
     

    関根 泰, 菊地 英一, 松方 正彦

     概要を見る

    電場を生かした低温での反応について精力的に検討を行い、放電と触媒の複合化が常温での反応性を制御しうること、電場と触媒の複合化が低温での選択的な反応を促進し活性化エネルギーを大幅に下げうることなどを見いだした。とりわけ、金属を担持した酸化物触媒を電極間に設置し、弱い電場を印加することで、150程度の非常に低い温度でメタンの水蒸気改質が十分に進行しうることを見いだした。

  • 固体酸化物の格子酸素と金属の協奏機能をもつ水素製造用触媒に関する研究

    日本学術振興会  科学研究費助成事業 特定領域研究

    研究期間:

    2007年
     
     
     

    松方 正彦, 菊地 英一, 関根 泰

     概要を見る

    炭化水素の水蒸気改質にはNi/Al203系触媒が用いられているが、この触媒の問題点は炭素析出による活性劣化である。本研究では,PtおよびPdといった貴金属を活性成分として用い、活性と安定性の向上を目的として触媒の担体にペロブスカイト型酸化物を適用して触媒特性を検討した。また、過渡応答法を用いて反応機構について、格子酸素の役割について検討を行った。担体にはLaAl03, La0.8Sr0.2Al02.9を用いた。比較用に&#61537;-Al203,を用いた。活性金属のPd, Ptは含浸法にて1wt%になるよう担持した。活性試験は固定床常圧流通式反応器で、1073Kにて反応を行った。過渡応答測定では供給ガスの切り替え直後の生成ガス濃度の推移を追跡、解析した。
    Pd/α-Al203、Pt/α-Al203両触媒を用いて固定流通式反応器によって定常条件下での反応を行ったところ、Pd触媒、Pt触媒ともにα-Al203では劣化が起きた。これは炭素析出または活性成分である貴金属のシンタリングによる活性劣化と考えられる。一方LaAl03を担体とした場合には、α-Al203担体を用いた場合と比較して、著しく活性と安定性が向上した。特に、Ptはα-Al203担体ではほとんど活性を示さないのに対して、LaAl03を担体とするとPdよりも高い活性を示した。
    種々の過渡応答測定の結果により、Pt/LaAl03ではLangmuir-Hinshelwood機構に加え、酸素が格子酸素として担体中に取りこまれてから消費されるMars-van Krevelen機構も同時に起こっていることが示唆された。L-H機構とMVR機構のCO, CO2生成に対する寄与の割合は、L-H機構約40%、MVR機構約60%となり、担体中の格子酸素の反応への寄与が大きいことがわかった。

  • ゼオライト骨格と交換カチオンの協奏による分離場の創生

    日本学術振興会  科学研究費助成事業 特定領域研究

    研究期間:

    2005年
     
     
     

    松方 正彦

     概要を見る

    本研究では、ゼオライトの一種であるモルデナイトを薄膜化し、ゼオライト骨格のイオン交換サイトに固定されたNaカチオンと水分子と相互作用による、高温下での水の選択的分離を目指した。
    配位空間場として用いるゼオライト薄膜を合成するにあたっては、種結晶を用いた緻密な薄膜の調製法の開発を中心に行った。まず、平板型の非多孔質支持体上に塗布した種結晶からの結晶成長の様子を観察して,水熱条件下における結晶成長条件の検討を行った。最適化された結晶成長条件を以って,多孔質支持体アルミナ支持体上に塗布した種結晶を成長させることで,支持体表面付近の空隙をゼオライト結晶で埋めることにより,緻密なゼオライト薄膜の調製を合理的に展開することを試みた。
    上記の手法により、モルデナイトの薄膜化に成功し、当初のもくろみ通り、250℃までの高温において水選択性を示した。こうした高温における水膜選択性分離の実現は、世界的に初めての例となった。しかしいっぼう、この膜は水素を全く透過させず、極めて特異な選択性をもつことがわかった。また、当初の予定以外にもZSM-5型のゼオライトの薄膜化も試みたところ、高温水選択性のある分離膜を合成することができた。モルデナイト膜と異なり、ZSM-5膜は、水が存在しないと水素、あるいはメタノールが透過したため、透過選択性の発現機構が、モルデナイト膜とZSM-5膜では異なることが示唆された。以上、本研究において、当初の予定を上回る成果が得られたと評価している。いっぼう、水透過選択性の発現機構については、上記のように極めて「不思議」な結果が得られており、アルカリイオン交換型ゼオライト内への高温における各種分子の吸着、拡散挙動の特異性について、今後大きく発展が期待できる研究テーマを見いだすことができたのはないかと考えている。

  • 新規非対称酸素過膜の開発とメタン酸化反応への応用

    日本学術振興会  科学研究費助成事業 基盤研究(A)

    研究期間:

    2002年
    -
    2005年
     

    菊地 英一, 松方 正彦, 関根 泰, 池口 真之

     概要を見る

    ABO_3型の酸化物はペロブスカイト型酸化物といわれ、酸素イオン伝導性を有する。これを用いて緻密な薄膜に成形し、酸素の選択的分離透過、ならびにメタンの選択的部分酸化について、反応を行い詳細な検討を行った。非対称膜における酸素透過特性の検討では、材料としてSrFeCO_<0.5>O_xを中心に用いた。対称膜と同じ緻密層膜厚をもつ非対称膜について酸素透過能を比較した結果、空隙率の大きい非対称膜は対称膜を大幅に上回る酸素透過能を示した。そのメカニズムとして、酸素透過は対称膜においては高温ではバルク拡散、低温では表面交換反応が律速となっていることが判明した。一方で、非対称膜については低温でもバルク拡散が支配的であった。緻密層に多孔質層を付与することにより膜表面積が増大し、表面交換反応の影響が減少したためと考えられる。さらに、新規膜材料としてSm_<0.4>Ba_<0.6>Co_<0.2>Fe_<0.8>O_<3-δ>を用いて、緻密膜を合成し、酸素透過と反応に適用した。Rh(1wt%)/MgO触媒を部分酸化のための触媒として用い、酸素透過流束の変化および反応経路にっいて考察した。その結果、まず合成ガスを膜供給側に流すことで酸素透過能が大幅に向上した。このことから、反応器中で生成したCOおよびH_2と膜表面の酸素種とが反応してCO_2とH_2Oを与える反応が酸素透過能の向上に寄与する可能性が示された。また、反応器中で生成したCOおよびH_2が膜表面で酸化され、生成したCO_2とH_2Oが触媒層中でCH_4とドライリフォーミング、水蒸気改質を起こしCO、H_2を生成するという反応経路が存在することが示唆された。これら知見を生かして、Sm_<0.4>Ba_<0.6>Co_<0.2>Fe_<0.8>O_<3-δ>非対称膜および対称膜と前述のRh触媒を組み合わせて用い、本研究の最終目標系であるメンブレンリアクターによるメタンの部分酸化を行った。その結果、SBCF型非対称膜を用いた膜反応器は幅広い反応条件下で高いCH_4転化率および酸素透過流束を示し、さらに高い合成ガス選択率と、低い炭素析出量により、安定した反応成績を示すことができた。

  • ディーゼルエンジン排ガスからの窒素酸化物除去触媒の開発

    日本学術振興会  科学研究費助成事業 基盤研究(B)

    研究期間:

    2000年
    -
    2003年
     

    菊地 英一, 松方 正彦, 小倉 賢, 野村 幹弘

     概要を見る

    Pd/ZSM-5触媒はCH_4によるNO還元反応(NO-CH_4-SCR)に対して酸素過剰、水蒸気存在下においても高い活性を示し、CH_4を主成分とする天然ガス希薄燃焼用触媒として期待されているが、水熱条件下における耐久性に課題を残す。その弱点を克服する可能性の一つとして、第二成分の添加があり、既往の研究においてPd/ZSM-5にCoなどの遷移金属を第二成分として添加することで耐久性が向上することが報告されている。本研究は第二成分としてFeを添加し、それによるNO還元活性や耐久性の変化について検討することを目的とした。
    Pd/ZSM-5、PdFe/ZSM-5、Fe/ZSM-5を調製し、NO還元活性試験を行った。イオン交換法を用いてFeとPdを担持した。NO還元活性試験には常圧固定床流通式反応装置を用いた。
    まず、Pd/ZSM-5とPdFe/ZSM-5のNO還元活性、CH_4酸化活性の経時変化を検討した。PdFe/ZSM-5は初期NO転化率55.2%を示し、Pd/ZSM-5での42.2%よりも優れていた。触媒の耐久性やCH_4酸化活性に大きな変化は見られなかった。また、NO還元活性とCH_4酸化活性の経時変化が一致しないことから、NO還元とCH_4酸化は異なった活性点で起こっていることが示唆された。次に、Fe/ZSM-5のNO還元活性、CH_4酸化活性の経時変化について検討した結果、NO還元活性、CH_4酸化活性ともにみられなかった。これらの結果からFeがNO-CH_4-SCRにおいて、Fe自体はNO-CH_4-SCR活性を有さないが、反応の一部において活性点となっている可能性、あるいは、Fe自体は何の効果ももたずFeイオン交換時のpHなどによってPdの担持状態が変化している可能性が考えられる。
    そこでFeを添加せず、酸処理を行ったPd/ZSM-5のNO還元活性試験を行った。その結果、酸処理を行った触媒は行わなかったものと比較すると、初期NO還元活性は約40%と変わらず、耐久性が低下するという結果となった。また、pH1.8にて酸処理を行ったものはpH0.49、pH3.1で行ったものと比べ耐久性が低かった。以上の結果からPdFe/ZSM-5にみられるNO還元活性の向上は触媒調製時のpHによる影響ではなく、Feの添加効果のためであると考えられる。HC種がCH_4である時はNO還元能を示さなかったFe/ZSM-5だが、iso-C_4H_<10>を還元剤としたNO選択還元に対して活性を有することが報告されている。このことから、Fe/ZSM-5は活性化されたC種が存在すればNOを還元する能力があるのではないかと考えられる。

  • カラム浮選によるクリーンコールの製造

    日本学術振興会  科学研究費助成事業 特定領域研究

    研究期間:

    1999年
    -
    2002年
     

    松方 正彦, 関根 泰

     概要を見る

    カラム浮選法はシンプルな選炭プロセスの一つであり、安価な石炭燃焼前処理技術として注目されている。これまで、主に浮選装置の最適化および浮選成績の向上(高回収率、高脱灰率)に関する研究が多く報告されてきたが、浮選成績と石炭物性をつなげた研究例は、未だ少ないのが現状である。そこで、我々はカラム浮選法の脱灰特性に着目し、カラム塔頂部、塔底部より得られる粒子中の無機成分、および水溶性無機成分を定性・定量を行なうことで、元素レベルでの浮選挙動を把握した。実験は150μmに整粒した4つの炭種を用いて、連続式カラム浮選試験を用いて行なった。その結果、上部から回収される浮遊粒子には炭素質が多く、沈降粒子には鉱物質が多く含まれている。具体的には、浮選試験開始後、まず粒径の大きな鉱物質を比較的多く含んだ浮遊粒子が塔頂部から回収され、時間の経過と共に鉱物質は除去され、粒径は序々に小さくなっており、カラム浮選試験による鉱物質の分離効果が確認された。一方、沈降粒子挙動については、時間の経過と共に沈降粒子径は小さくなった。この原因としては石炭中の鉱物質の存在形態に依存していた。すなわち、比較的粒径の大きいExcludedな鉱物質がTailとして回収され、その後、Includedな鉱物質は単体分離しExcludedな状態となって沈降した。
    あらゆる炭種の中で、最も浮選成績が良好(高回収率、高脱灰率)であったのはワララ炭であった。この場合含有される大半の無機成分が、カラム内で溶出、もしくは塔底部からTailとして回収された、つまり鉱物の単体分離度が大きい。特にNa、Al、Si、Mnの大部分はTailより除去回収されていた。これらのことから、特定の石炭にはカラム浮選プロセスは非常に有効な脱灰プロセスとなりうることがわかった。

  • ゼオライトの結晶化過程の解明と制御に関する研究

    日本学術振興会  科学研究費助成事業 基盤研究(B)

    研究期間:

    1999年
    -
    2002年
     

    松方 正彦, 菊地 英一, 小倉 賢, 野村 幹弘

     概要を見る

    ゼオライトは一般に水熱合成法により調製されるが,近年乾燥ゲルを水蒸気雰囲気下でゼオライトへと結晶化する手法,ドライゲルコンバージョン法が開発された。本研究では,水熱法でのゼオライトの結晶化過程の解明を行うとともに,新規合成法であるドライゲルコンバージョン法での結晶化過程についても研究を行った。ゼオライトの結晶成長過程では原料各種の原子分子サイズでの挙動はもちろんのこと,ナノスケールレベルの原料種にとくに焦点をあてて研究を進めた。
    まず水熱法ではMFI型ゼオライトに注目し,とくに水和ゲル存在下での結晶成長過程では,アルミノケイ酸塩の溶解度が低い条件下では数十nmの大きさのMFI結晶が凝集して1つの粒子を形成していることを明らかにした。またシリカのみで構成されるMFI,シリカライト-1では原料液中の数十nmのアモルファス粒子が固相転移して結晶となる可能性を見出した。
    いっぽうドライゲルコンバージョン法では,EMT型ゼオライトの結晶化に注目したところ,数μm原料の乾燥ゲルが結晶化初期段階で一旦数nmの微粒子へと転化してから平板構造のEMTゼオライトへ結晶化が進行することを見出した。
    このように合成法によらず,本報告でのゼオライトの結晶化過程ではナノスケールレベルの粒子が重要な役割を果たしている。いっぽうでMFI型ゼオライトからアルカリ処理によってサブナノサイズの構造を取り出し,これを用いてゼオライトの強い酸性質をもつメソポーラス物質の調製にも成功した。
    以上,ゼオライトのナノスケールレベルの構造体に注目して結晶化成長過程を明らかにし,またこの構造体を用いて新たな触媒材料の調製への展開までが研究報告である。

  • ミクロ・メソ多孔性結晶内における新反応場の構築

    日本学術振興会  科学研究費助成事業 基盤研究(C)

    研究期間:

    2001年
     
     
     

    丹羽 幹, 山下 弘巳, 岩本 正和, 寺崎 治, 松方 正彦, 黒田 一幸

     概要を見る

    最近のこの分野における研究動向を調査した.
    固体酸性質に関して,(1)ゼオライトとメソポーラス物質内の強い固体酸点の発現,(2)メソポーラス物質内の固体酸点の発現,(3)アルカリ処理によるメソ細孔の発生と触媒活性,およびゼオライト種からのメソポーラス物質の合成,(4)固体酸ゼオライトのノンハロゲン化プロセスヘの応用,(5)ミクロおよびマクロ細孔の触媒反応活性におよぽす影響,の以上5件を調査研究した.
    新物質の合成に関して,(1)酸性条件におけるメソポーラス物質の合成,(2)あたらしいメソポーラス物質の合成,(3)最近のゼオライト合成における進歩,(4)電子顕微鏡による構造決定,(5)リン酸ジルコニア層状化合物め化学,の以上5件を調査研究した.
    有機化学反応への応用に関して,(1)ナノ空間化学の新展開,Asの除去,不整有機反応など,(2)モンモリロナイトとMS4Aの共用による有機反応,(3)金属ナノ細線の生成と触媒活性,(4)メソポーラス物質による重合触媒MAOの精製,の以上4件を調査研究した.
    光触媒反応への応用に関して,(1)Taメソポーラス物質の合成と水の光分解,(2)メソポーラス物質塩基サイトの精製とプロペン分解触媒反応,(3)Crメソポーラス物質の光触媒活性,の以上3件を調査研究した.
    さらに,ミクロおよびメソポーラス物質における計算機化学の進歩も調査した.
    これらを総合して,今後のこの分野の研究遂行における指針とした.なお,まとめた冊子を印刷し,全国の研究者に配布した.

  • ゼオライトを原料とするメソポーラスマテリアルの新規な合成法の開発とその触媒特性

    日本学術振興会  科学研究費助成事業 萌芽的研究

    研究期間:

    2000年
    -
    2001年
     

    松方 正彦, 小倉 賢

     概要を見る

    ゼオライト構造を有したメソポーラス物質は,ゼオライトの強い酸性質と規則的なメソ孔をあわせもつことから,これまでにない新規触媒材料として期待されている.本研究では,ゼオライトのアルカリ溶解から生成したユニットを原料としたメソ多孔体の合成を,流通式反応器を用いて検討した。特に2段式の流通合成反応器を用い,高いpHでアルカリ溶解を行った後に,引き続き低いpHでメソ多孔体を連続的に合成することを試みた。ZSM-5ゼオライトを充填し80℃に保ったカラムに,NaOH水溶液を流通させて,ゼオライトのアルカリ溶解を行った。続いて,ゼオライトのアルカリ溶解液と界面活性剤が混合するように流路を設け,界面活性剤水溶液をテフロンチューブ内を室温で流通させながら,ゼオライトから溶解したアルミノシリケート種を凝集させた。流路の出口から得られた懸濁液に,塩酸を適宜加えてpH調整をした。得られた生成物は550℃で焼成後でも,壊れることなくメソ孔構造が残っており,この試料の窒素吸着等温線では,メソ孔構造の存在を示すと考えられる相対圧0.4付近で緩やかな立ち上がりを示した。またクメンのクラッキングを行ったところ,回分法で合成したM41Sよりもさらに高いクラッキング活性をもつことがわかった。このようにゼオライトのアルカリ溶解過程とメソ多孔体合成過程を分けることは,強い酸性質をもつメソ多孔体の合成に重要であることが示唆された。

  • メンブレンリアクターを用いたメタン部分酸化による合成ガス製造

    日本学術振興会  科学研究費助成事業 基盤研究(A)

    研究期間:

    1998年
    -
    2001年
     

    菊地 英一, 松方 正彦, 上宮 成之, 野村 幹弘, 小倉 賢

     概要を見る

    本研究では(1)酸素透過膜の非対称膜化、(2)製膜法の最適化、(3)新規物質の探索により酸素透過能の向上を図った。(1)について、含浸法などにより多孔質アルミナ支持体上にSrFeCo_<0.5>O_x(SFC2)膜を製膜することを試みた。合成を繰り返すことにより緻密な膜は得られたが、膜材料が支持体と固相反応し、また、組成が目的酸化物と異なったため、高い酸素透過流束は得られなかった。そこで、これらの問題を回避する方法として、緻密層としてSFC2粉末を成型器中で平らにし、その上に多孔質層として燃焼して細孔を形成する添加剤(エチルセルロース粉末)とSFC2粉末の混合物を入れ、2つの層を同時に加圧成型、焼結することにより一段で非対称平膜を合成する新たな手法を確立した。得られた膜で、最も小さい緻密層の膜厚は約100μmであった。この方法により合成した非対称膜の酸素透過能は対称膜のものを上回り、また、緻密層の膜厚が小さくなるほど酸素透過能は増大した。(2)について、(a)固相反応法、(b)蒸発乾固法、(c)EDTA-クエン酸混合法により合成したSFC2粉末を用いて製膜した。その結果、酸素透過能は(a)<(b)<(c)であった。また、蒸発乾固法による粉末を用いた製膜について、合成条件の検討を行った。原料粉末について焼成および粉砕を繰り返し、膜の焼結を高温で行うことにより酸素透過能が向上した。組成の均一性が重要と考えられる。(3)について、La_<0.4>Ba_<0.6>Fe_<0.8>Co_<0.2>O_<3-δ>のLaサイトを別の希土類(Pr、Nd、Sm等)により置換を行った。しかし、置換してもLaを超える酸素透過能は得られなかった。現在、合成した膜を膜反応器に適用し、評価を行っている。

  • 気相を介する新規合成法によるゼオライト膜の調製とその機能の評価

    日本学術振興会  科学研究費助成事業 基盤研究(B)

    研究期間:

    1997年
    -
    1999年
     

    松方 正彦, 板橋 慶治, 野村 幹弘, 小倉 賢

     概要を見る

    MFIゼオライトメンブレンのαアルミナ多孔質体薄版ディスク上への製膜を、VPT法を用いて検討した。また、これらを用いて、単成分ガスおよび多成分混合ガスの透過試験を行った。多成分混合ガス分離においては、nブタンとiブタンの分離について300-375Kにて検討した。その結果、分離係数は非常に高いものとなり、製膜条件の検討の結果、ブタンの異性体分離が可能なMFI膜を確実に製膜可能な条件を見出した。
    また、o-/m-/p-キシレンの分離についても303Kにて検討を行った。これらのうち、単一成分においては、p-キシレンは最も透過性の高いものである。p-キシレン/m-キシレン混合物、およびp-/m-/o-キシレン混合物の分離においては、いずれの場合も初期段階ではp-キシレン透過選択性が高い値を示した。一方で経時とともに、p-キシレンの透過は低下し、試験後期においてはついに他のキシレンよりも透過性が低下した。これは、m-キシレンのMFIゼオライト中への吸着が起こることで、p-キシレンの透過を阻害したものと考えられる。

  • ゼオライトの相変態過程に関する研究

    日本学術振興会  科学研究費助成事業 特定領域研究(A)

    研究期間:

    1998年
     
     
     

    松方 正彦, 野村 幹弘, 菊地 英一

     概要を見る

    ゼオライトの合成には通常Structure Directing Agent(SDA)として有機アミン分子の共存が必要である場合が多く,これら有機アミンのゼオライト結晶化に果たす役割を明らかにすることはゼオライトの結晶化のメカニズムを明らかにする上で重要となる。本研究では我々の開発したドライゲルコンバージョン(DGC)法によりゼオライト合成を行い,生成物に与えるSDAの効果の検討およびドライゲルの相変態途中における生成物のキャラクタリゼーションをおこなった。
    分子内のアルキル鎖長を変化させた有機アミンをSDAとして用いた場合,結晶構造の異なるゼオライトが合成された。SDAは,アルキル鎖長が得られるゼオライトの細孔径やintersectionの大きさを限定するものではなく,生成するゼオライトの構造を決定づける役割を果たしている。特にBEAにおいて,テトラエチルアンモニウム(TEA)カチオンがゼオライト骨格と相互作用し結合種を形成していること等を見出した。これらのことは,TEAがBEAゼオライト結晶化過程において重要な役割を担っていることを意味している。
    ドライゲルからBEAへの相変態過程を追跡した。結晶化時間の異なるサンプルをSEMにて観察した結果,XRDでは回折線が得られなかったサンプルにおいても,BEAの前駆体と思われる微粒子の生成が見られた。回折線が現れる前にも分子・原子レベルでのBEA前駆体の生成は進行していると推察される。これらの^<29>Si-NMRおよび^<13>C-NMRの結果から,ドライゲル内の親水基であるSi-O-Hが徐々に脱水縮合して疎水基であるSi-O-Siが形成され,TEA周りから徐々にゼオライト骨格が形成されて相変態されてゆくことがわかった。要するに,ドライゲルからBEAゼオライトへの相変態は分子・原子レベルでは経時的に徐々に進行するものの,XRDで観察されるような長周期的規則構造の発達はある程度結晶化が進行した後に急速に起きるものと結論した。

  • ゼオライト分離膜の開発

    日本学術振興会  科学研究費助成事業 奨励研究(A)

    研究期間:

    1997年
    -
    1998年
     

    松方 正彦

     概要を見る

    ゼオライト膜の合成条件を確立し、透過、分離、反応試験に境するアイテムを揃えることを目標とした。合成方法は、乾燥ゲルを有機結晶化剤蒸気や水蒸気中で結晶化させる方法(ドライゲルコンバージョン法)を用いた。検討したゼオライトは、SiO_2/Al_2O_3=50とローシリカなMFI型ゼオライトであり、平均細孔径0.1μmの多孔質アルミナ平板上に製膜した。原料ゲルの調製条件、ゲルの製膜条件、結晶化条件などを詳細に検討し、緻密な膜の調製条件を検討した。特に、緻密な膜の合成条件はアルカリ濃度であった。Na_2O/SiO_2=0.19〜1.14、H_2O/SiO_2=40〜120の範囲で結晶化を検討した。Na_2O/SiO_2=0.32-0.41、H_2O/SiO_2=80にて緻密なMFI膜が得られた。l,3,5-トリイソプロピルベンゼン-(TIPB)の透過流束は測定限界(1×10^<-10>mol m^<-2>s^<-1>Pa^<-1>)以下であった。TIPBはMFI型ゼオライトの細孔より大きく、TIPBの透過は膜が緻密でないことを表している。断面SEM観察より、膜の緻密な部分はアルミナ支持体とゼオライトのコンポジット層であり、コンポジット層の厚みが膜の緻密さに影響を与えていることが示された。また、単成分ガス透過試験では、二酸化炭素の透過速度が窒素やメタンより大きかったため、Knudsen拡散以外の透過機構の寄与があることが示された。原料ゲルのSiO_2/Al_2O_3=50とローシリカなMFI型ゼオライト膜の開発に成功し、TWBの透過試験より緻密な膜であることを示した。

  • 火炎CVDによる非酸化物機能性材料の合成

    日本学術振興会  科学研究費助成事業 基盤研究(B)

    研究期間:

    1995年
    -
    1997年
     

    上山 惟一, 西山 憲和, 松方 正彦

     概要を見る

    火炎CVDによる非酸化物機能性材料の合成を目指して平成7年度から9年度にかけて総合的研究を行った。まず火炎中での固相析出過程を調べるために、酸素-水素拡散層流火炎中にTetraethylorthogermaniumu(TEOG)を送入してゲルマニア超微粒子を合成し、既に行っていたシリカ超微粒子の生成機構との比較検討を行った。ゲルマニア超微粒子生成の場合、火炎下部の酸素不足領域でまずGeOの核発生がおきるが、原料濃度が低いと出来たGeO粒子が火炎上部に至るまでの温度上昇に伴って一度完全に昇華し、火炎上部の酸素過剰領域でGeO_2粒子として再び核発生・成長・ブラウン凝集を起こしていることが分かった。減量濃度が高いと火炎下部での発生GeO粒子が昇華しきらずに火炎上部にいたり、酸化されつつ更にGeO_2の析出が生じていることが分かった。シリカ生成の場合には、昇華過程が無く超微粒子生成機構が全く異なっていた。すなわち、火炎中での固相析出機構に対する減量の種類、原料濃度、火炎温度分布の影響を明らかにした。
    次に同じ酸素-水素拡散層流火炎に1,1,1,3,3,3-Hexamethyldisilazane(HMDS)を送入し、窒化ケイ素粒子合成を試みた。火炎上方で粒子を補集すると完全に酸化されたシリカ粒子のみであったが、火炎中にマグネシア管を挿入して還元炎上方から粒子を補集するとSiN粒子が採取された。火炎は高温場であるが、酸素過剰領域に触れさせない工夫をすれば非酸化物を得る事が可能であることが分かった。
    拡散層流火炎では適当な反応領域の大きさが制限されるため、予混合火炎による非酸化物合成を試みた。まず、アセチレン-酸素予混合炎によるダイヤモンド薄膜合成実験を行い、既往の報告と同程度の好成績を得た。更に、火炎中にHMDSを挿入し、ダイヤモンドライクのSiC薄膜生成を確認した。
    最終年度はアセチレンをプロパンに変えて実験的研究を行い、SiCウィスカ-を得たが、その生成機構などについて結論を得るに至っていない。

  • モレキュラーシービング膜反応器の開発

    日本学術振興会  科学研究費助成事業 重点領域研究

    研究期間:

    1996年
     
     
     

    上山 惟一, 松方 正彦

     概要を見る

    アルミナ支持体上に塗布したゲルを結晶化させる気相輸送法により、クラックのない緻密なゼオライト膜が得られることは既に報告したが,今年度は緻密なゼオライト膜の生成機構について詳細な検討を行い,以下のような知見を得た。
    1.フェリエライト膜合成過程をFESEM観察することによりアルミナ支持体の細孔内にフェリエライト結晶の超微粒子がぎっしりつまっているのがわかった。すなわちアルミナ支持体の細孔はフェリエライト多結晶により埋めつくされているものと思われる。
    2.フェリエライト膜合成過程の膜断面におけるSi原子およびAl原子の分布の経時変化をEDX分析により観察した結果,Siがアルミナ支持体上のゲルからアルミナ支持体内へ移動し,Al原子はアルミナ支持体から支持体の上方へ移動していることがわかった。
    3.支持体上のゲルの結晶化過程のSEM観察から,ゲルはダイナミックに移動しながら結晶化していることがわかった。
    4.支持体上にフェリエライト結晶を置いて同様し操作を行うと,結晶は支持体内へ,その配向性を維持しながら沈み込んでいくように見えた。
    5.ゲルを泌みこませた支持体上のゲルを取り去ってから同様の結晶化操作を行うと支持体上へゼオライト結晶が生えてくるのが観察された。
    以上のことから,緻密なゼオライト膜は固相のダイナミックな結晶化,融解,再結晶化過程によりアルミナゼオライト複合相が形成される結果として出来ると結論した。

  • 開発途上国向け石炭の同時脱硫脱灰プロセスの開発

    日本学術振興会  科学研究費助成事業 重点領域研究

    研究期間:

    1996年
     
     
     

    上山 惟一, 松方 正彦

     概要を見る

    山元で行える安価で簡便なコールクリーニングプロセスとしてカラム浮選方に注目し、カラム浮選成績と石炭の表面物性評価法であるフィルム浮選成績との相関関係を検討している。フィルム浮選成績に応じたカラム浮選プロセスの装置設計や操作指針が与えられれば、炭種に応じたカラム浮選プロセスの構築が可能となる。
    前年度までに瀝青炭である大同炭、エンシャム炭およびイリノイ炭についてフィルム浮選成績とカラム浮選成績との比較を行い、疎水性強化剤であるケロシンの添加効果が炭種により大きく異り、フィルム浮選成績だけでカラム浮選成績を予測し得ないことを見出した。
    今年度は無煙炭であるホンゲイ炭および山西炭について同様の実験的検討を行ったところ、炭種によりケロシン添加効果が大きく異るものの、フィルム浮選成績とカラム浮選成績は良好な一致をみた。これは無煙炭においては炭素質と鉱物質との単体分離性が良いこと、および無煙炭の炭素質は芳香族炭素を多く含んでいることによると思われるが、詳しい機構については今後の課題と考えている。

  • ゼオライト分離膜の開発

    日本学術振興会  科学研究費助成事業 奨励研究(A)

    研究期間:

    1996年
     
     
     

    松方 正彦

     概要を見る

    我々が新規に開発した固体ゲル転換法によるゼオライト合成法を用いて、ゼオライト薄膜の合成を行った。本年度は第1に薄膜生成機構を明らかにすることを目的として検討を行った。さらに得られた膜を用いて液混合物および、ガス混合物の透過分離試験を行い、ゼオライト膜の分子レベルにおける分離への適用性を検討した。1)ゼオライト膜合成法の確立 原料の調整条件、ゲルの乾燥温度、乾燥時間などをパラメーターとして、固体ゲル転換法による多孔質アルミナ支持体上へのゼオライトの製膜を行った。XRDおよびFE-SEMにより結晶化過程の詳細な検討を行い、結晶化条件下ではゲルはMobileであり、適当な条件を選択することによりアルミナ多孔質支持体内に浸透、結晶化し、緻密なアルミナーゼオライトコンポジット膜となることを見いだした。2)透過分離試験 得られたFER膜について、ピンホールの生成の有無を1,3,5-トリイソプロピルベンゼン(TIPB)の浸透気化試験により検討したところ、FER膜にはピンホールが無いことがわかった。この膜はベンゼン/パラキシレン混合物の浸透気化分離に対して100-600と極めて高い選択性を発揮した。また、パラキシレン/オルトキシレン混合物に対しても、3とまだ小さいが選択性が発現することがわかった。これは、供給側のゼオライト細孔入口において選択性がためと考察した。また、高温(200℃以上)における分離特性の評価を行うため、ポリイミド樹脂とグラファイト製Oーリングを用いた膜のシール法を開発した。ガス透過能は膜内に吸着した水蒸気量に著しく影響されることを見いだした。

  • モレキュラーシービング膜反応器の開発

    日本学術振興会  科学研究費助成事業 重点領域研究

    研究期間:

    1995年
     
     
     

    上山 惟一, 松方 正彦

     概要を見る

    気相輸送法によって緻密なゼオライト膜の得られる条件を探索し、その分離特性を検討した。SiO_2/Al_2O_3=25、所定のpH(=11〜13)のアルミノシリケートゲルを調製した。得られたゲルを、アルミナ支持体の上に製膜し、乾燥した。これを、トリエチルアミン、エチレンジアミン、水の混合蒸気雰囲気下0-4日間、453Kに保った。
    ガラス基板上に製膜して363Kで乾燥後、クラックあるいは剥離の有無によりゲルの緻密さを評価した。ゲルの緻密さは溶液のpHに依存した。高pHほど乾燥ゲルの比表面積は小さくなり、ケイ酸ナトリウムを用いた場合pHが11.6以上で、コロイダルシリカを用いた場合12.0以上で、クラックのない薄膜状乾燥ゲル膜が得られた。
    上記により決定した最適な条件にて、アルミナ支持体上に製膜し、気相輸送法により結晶化した。ケイ酸ナトリウムからはANAが、コロイダルシリカからはMORが得られた。コロイダルシリカで表面処理すると、ケイ酸ナトリウムからはFER、コロイダルシリカからはMFIが得られた。
    ゼオライト膜表面をSEMにより観察したところ、表面のゼオライト粒子層には大きな空隙が存在することがわかった。1日目ですでにアルミナ支持体の細孔の中にもMORが生成しているようにみえる。2日目になるとアルミナ細孔内の結晶数が増え、4日目にはアルミナとMORの界面付近の細孔内は完全に埋まり、約10μm程度の緻密層が形成された。
    ベンゼン、p-キシレン0.86:1混合物の浸透気化分離を行った。分離係数は160以上となり、、気液平衡の値11.3を大きく上回った。MOR膜のピンホールの有無を検討する目的で、TIPBの浸透気化分離を行ったが、TIPBは透過しなかったことから、膜内にピンホールは存在しないと結論した。MORの細孔入口で形状選択性が発現したものと考えられる。

  • 開発途上国向け石炭の同時脱硫脱灰プロセスの開発

    日本学術振興会  科学研究費助成事業 重点領域研究

    研究期間:

    1995年
     
     
     

    上山 惟一, 松方 正彦

     概要を見る

    内径27mmの小型カラム浮選器および内径80mm、高さ1850mmの大型カラム浮選器を用いた浮選結果、および石炭粒子の表面疎水性の評価手法であるフィルム浮選法による測定結果を比較検討した。いずれのカラム浮選装置において、特に工夫した気泡発生装置を用いて直径2mmの一定した大きさの気泡を塔底で均一に分散して発生させた。石炭粒子としては75μm以下の、イリノイ炭、エンシャム炭および大同炭を用い、気泡安定化剤としてメチルイソブチルカルビノール、石炭の疎水性強化剤としてケロシンを用いた。
    小型カラム浮選器による実験結果によると精炭回収率、脱灰率の序列は共に大同炭>エンシャム炭>イリノイ炭であり、脱パイライト率はエンシャム炭>大同炭>イリノイ炭であった。フィルム浮選結果から、石炭粒子の疎水性の強さは大同炭>エンシャム炭>イリノイ炭であり、これは精炭回収率および脱灰率の序列と一致した。
    大型カラム浮選装置による実験では、空塔速度0.66,1.99x10-2ms-1および塔高1.25、1.85、2.15mについて検討した。塔頂から精炭を所定の時間に一定時間採取後、その重量、灰分を測定し、炭素質、灰の浮選速度の経時変化を求めた。ガス空塔速度が小さい場合、精炭中の灰の含有率の経時変化は小さいが、高空塔速度の場合、時間の経過に従い精炭中の灰の含有率は増加した。ガス空塔速度が大きいと、気泡下部のウェークと共に上昇した固形分が、そのままフロス層に取り込まれるものと考えられる。

  • ゼオライト分離膜の開発

    日本学術振興会  科学研究費助成事業 奨励研究(A)

    研究期間:

    1995年
     
     
     

    松方 正彦

     概要を見る

    ゼオライト薄膜を用いた分子レベルでの高度連続分離プロセスの実現を目指し、緻密な薄膜状各種ゼオライト膜の合成法を確立することを目的とした。本研究では無機多孔質支持体上に緻密に製膜した乾燥ゲルを我々が開発した気相輸送法により結晶化し,ゼオライト薄膜を合成した。無機多孔質支持体としては平均孔径0.1μmのアルミナ多孔質板を用いた。
    特に、モルデナイト(MOR)、フェリエライト(FER)膜についてその分離透過特性を検討した。XRDより両者とも多結晶膜であった。両膜を用いて、1,3,5-トリイソプロピルベンゼン(TIPB)の透過試験を室温で行った。TIPBはいずれの膜も透過しなかった。TIPBはMOR,FERの細孔より大きい分子であり、したがって、MOR膜、FER膜にはTIPBの透過できるような結晶粒界の空隙は存在しないと結論できる。以上より、ピンホールのない緻密なゼオライト膜の合成に成功したと結論した。
    浸透気化法により芳香族炭化水素の分離特性を室温で検討した。FER,MOR膜ともベンゼン/パラキシレン混合物からベンゼンが選択的に透過することがわかった。分離係数は気液平衡より予測される値(10.1)より著しく大きく、MOR膜では160程度、FER膜では100程度の値が得られた。FER,MORの細孔内ではパラキシレン、ベンゼン分子のすれ違いは起きにくいと考えられるので、上記の高い選択性は細孔入口において形状選択性が発現した結果と結論した。
    以上、気相輸送法によるピンホールのない緻密なゼオライト膜の合成に、世界で始めて成功した。これらの膜は、ゼオライトの特徴である形状選択性を発揮することを実験的に確認した。

  • ゼオライト分離膜の開発

    日本学術振興会  科学研究費助成事業 奨励研究(A)

    研究期間:

    1994年
     
     
     

    松方 正彦

     概要を見る

    ゼオライト薄膜を用いた分子レベルでの高度連続分離プロセスの実現を目指し、緻密な薄膜状各種ゼオライト膜の合成法を確立することを目的とした。本研究では無機多孔質支持体上に緻密に製膜した乾燥ゲルを我々が開発した気相輸送法により結晶化し、ゼオライト薄膜を合成した。無機多孔質支持体としては平均孔径0.1μmのアルミナ多孔質板を用いた。
    緻密な膜の生成条件は多くの因子が関係するが、最も重要なポイントは(1)ゲル調製時のpH、および(2)支持体とゲルの濡れであることを見いだした。特にゲル調整時のpHはシリカ源にもよるがpH=11.6-12.0の範囲で厳密に調製する必要があることがわかった。MORおよびANA膜では支持体のアルミナが一部溶出し、ゼオライト骨格内に取り込まれたものと考えられた。一方、支持体を予め表面処理によって安定化すると、アルミナの溶出を抑制しハイシリカのMFI,FER膜を合成することができた。以上のように原料試薬、ゲル組成、支持体の前処理法等を変え、MFI,FER,MOR,ANA各膜の最適な合成条件を決定した。
    ガス透過試験装置を試作した。得られた膜を用いて室温から373Kの範囲においてヘリウム、メタン、窒素、酸素、水素、二酸化炭素などの無機ガスのガス透過特性を評価した。各ガスの透過流束の温度依存性はクヌッセン拡散から外れ、活性化拡散を示した。こうしたガス透過実験の結果からピンホールのほとんど存在しない緻密な膜が得られたものと考えられた。
    以上、ゼオライト膜の合成に当たっての基礎的な検討を終え、緻密な膜を得るために必要な因子を抽出することができた。ガス透過実験からゼオライト薄膜を用いた分子レベルの超精密分離プロセスの実現の可能性を指摘することができた。

  • 新規な流動層反応装置を利用したシリコン系粉体製造プロセスの開発

    日本学術振興会  科学研究費助成事業 試験研究(B)

    研究期間:

    1991年
    -
    1993年
     

    小島 紀徳, 上山 惟一, 上宮 成之, 松方 正彦

     概要を見る

    均一な高温反応場の形成及び粒子循環が可能な流動層プラズマCVD反応装置を用いて、粒子上への機能性薄膜のコーティングを試みた。プラズマ源として直流プラズマジェットを用いたCVD反応装置を用い、アルミナ粒子上への炭化珪素のコーティングを対象として実験を行った。反応ガス(CH_4・SiH_4)は装置側面よりプラズマジェット底部に旋回流として送入したが、原料ガスを別々に送入し反応場中で混合する拡散混合方式が、原料ガスを予め混合し反応場へ送る予混合方式に比較して、高い反応率を得ることがわかった。析出後のアルミナ粒子内部には、Siが析出したことが断面のEPMAによる元素分析から明らかであり、プラズマ中で特異な反応が起こっていることを示唆している。また、マイクロ波プラズマを用いたCVD反応装置を用い、メタンを反応源とするダイヤモンドのコーティングについて研究を行った。基礎的知見を得るため、装置の流動特性およびメタンの転化反応について検討した。メタンを装置下部から水素で希釈し送入した。層粒子としてアルミナを用いた場合とシリコン粒子を用いた場合では、プラズマの発光場所に顕著な差が見られ、層粒子の違いによる操作条件の変更が示された。反応後のそれぞれの層粒子表面(アルミナ・シリコン)には、ダイヤモンドとは確認されなかったものの、炭素と思われるサブミクロンオーダーの析出物が観察された。

  • 新規な分離膜用膜状ゼオライト合成法の開発と分離特性の評価

    日本学術振興会  科学研究費助成事業 一般研究(C)

    研究期間:

    1992年
     
     
     

    松方 正彦

     概要を見る

    その特異な細孔構造により分子レベルでの選択性を有するゼオライトを高度分離膜として製膜する手法の開発を目的として、ゼオライトの新しい合成法の開発を行った。すなわち従来法の水熱合成ではゼオライトの多結晶粉末が合成されるので製膜は困難と考え、一旦成型した乾燥シリカアルミノゲルを有機蒸気に気相中で接触せしめゼオライト化する手法の開発を行った。合成実験には試作のオートクレーブを用いた。
    結晶化温度は253Kとし、生成物の構造に及ぼすシリカアルミノゲルのpH、ナトリウムイオン濃度、有機テンプレートの種類の影響を主として検討した。トリエチルアミンとジエチルアミン共存下、pH=7-11の広い範囲でフェリエライトが得られることを見いだした。結晶化には両有機テンプレートの共存が必須であった。ナトリウム濃度を下げるとZSM-5が得られた。1-プロパノールを用いてもZSM-5を合成することができた。pH>11ではアナルサイムとなった。また、条件によってはKZ-1,KZ-2が得られることを見いだした。
    固体高分解能NMRスペクトルよりゲル中のアルミニウムはすべて結晶格子中に取り込まれており、またアナルサイムを除いてシリコンも良好に結晶化していることがわかった。従って、本方法を用いると仕込どおりのシリカアルミナ比を有するゼオライトが合成できると考えられる。
    本年度の研究結果より、我々が提案する方法で良好に結晶化した各種ゼオライトが合成できることが明かとなり、ゼオライト薄膜を無機支持体上などへの製膜の可能性が示された。次年度以降は多孔質ガラス、多孔質アルミナ膜などを支持体として製膜実験を行いたいと考えている。

  • 流動層石炭ガス化炉内の局所的反応の解析と制御

    日本学術振興会  科学研究費助成事業 重点領域研究

    研究期間:

    1991年
     
     
     

    小島 紀徳, 松方 正彦

     概要を見る

    ジェッテイング流動層石炭ガス化炉は、ガス化助剤(酸素または空気)をノズルからジェット状で局所的に高温に達せしめ、装置全体のガス化効率を高めるとともに、灰の凝集を器壁から離れた場所で行なうことを特徴とする。このようなガス化炉ではガス送入部(グリッド部)の構造が層全体のガス化性能に大きく影響するため、グリッド部におけるガスと粒子の挙動や化学反応の局所的な進行を解析することが肝要である。そこで、小型バッチ式流動層を用いて局所的温度分布とガス濃度分布を実測し反応の進行を検討するとともに、グリッド部内のガスおよび粒子の挙動モデル解析するための基礎的検討を行なった。
    太平洋炭の乾留チャ-のガス化において、生成ガス組成およびグリッド部近傍における反応の進行に対するノズルから送入した酸素とコ-ン型分散板から送入した水蒸気の寄与を、それぞれ単独に送入した結果と比較することにより検討した。1173Kではジェット周辺部に(アニュラス部)で生成した水素の一部はノズルから送入された酸素により酸化され再び水蒸気となること、水性ガス化反応あるいはシフト反応により二酸化炭素は生成するが発生炉ガス化反応により消費されるため二酸化炭素の層内での濃度変化は比較的小さいことが明らかとなった。また、層温度の影響を1073ー1273Kで検討した結果、層温度が低いときにはジェット近傍では完全酸化反応が主として起こるが、層温度が高くなるにつれ部分酸化が支配的に起こるようになり、アニュラス部の下部における水性ガス化反応が速やかに進行することが確められた。
    さらに、コ-ルドモデル実験により得られたガスおよび粒子の挙動に関する知見をもとに、グリッドゾ-ンモデルを構築した。流動層のアニュラス部におけるガス混合速度は、固定層のそれと比較してかなり大きいと推測した。

  • 流動層石炭ガス化炉内の局所的反応の解析と制御

    日本学術振興会  科学研究費助成事業 重点領域研究

    研究期間:

    1990年
     
     
     

    小島 紀徳, 松方 正彦

     概要を見る

    本研究の目的はノズルからジェット状で送入し局所的に高温に達せしめ、装置全体のガス化効率を高めるとともに、凝集灰を生じさせるタイプの流動層ガス化炉を想定したうえで,装置全体のガス化反応の進行を把握するため酸素(空気)吹き込み口近傍の局所的現象を実験的に解明し,反応・熱効率上昇に必要な因子の抽出と制御法を確立することにある。本年度は種々の形状のガス送入口を用いて,層内の温度分布、生成ガス組成およびそれらの経時変化を測定し,生成ガス組成に及ぼすガス吹き込み法の影響を検討した。さらに、層内の局所的な反応の進行を解析するための基礎的検討を行なった。
    内径43mmの小型流動層に石炭チャ-を充填し、バッチ式反応器内におけるガス生成量,酸素送入部における局所的温度分布およびその時間的変化を測定した。平板型のガス送入口形状を用いた場合と比べ、コ-ン型分散板から水蒸気を送入し,分散板中央に設けたノズルより酸素を送入した場合には一酸化炭素に富む良好な組成が得られることがわかった。
    定常状態における炉内の局所的ガス化剤,生成ガス濃度を実測するため、石炭をアルミナで、ガス化剤を不活性ガスで希釈し,トレ-サ-としてヘリウムを炉内に送入することにより,ガス化剤,生成ガスの移動現象を解析した。その結果ジェット-アニュラス間のガス交換の様子が明らかとなった。ジェット、アニュラスにおけるガス濃度の違いは顕著であり、層内の局所的な反応の進行の解析が可能であることが示された。またアニュラス部における層高方向のガス化反応の進行も明らかであった。特にノズルより送入された酸素は主にジェット-アニュラスの境界付近にて石炭し,一酸化炭素を生成することが明らかとなった。

  • ベンゼンの酸化的接触アセトキシル化を経由するフェノールの気相合成

    日本学術振興会  科学研究費助成事業 奨励研究(A)

    研究期間:

    1990年
     
     
     

    松方 正彦

  • 流動層石炭ガス化炉内の局所的反応の解析と制御

    科学研究費助成事業(成蹊大学)  科学研究費助成事業(重点領域研究)

  • 新規な流動層反応装置を利用したシリコン系粉体製造プロセスの開発

    科学研究費助成事業(成蹊大学)  科学研究費助成事業(試験研究(B))

  • 流動層石炭ガス化炉内の局所的反応の解析と制御

    科学研究費助成事業(成蹊大学)  科学研究費助成事業(重点領域研究)

  • 新規な分離膜用膜状ゼオライト合成法の開発と分離特性の評価

    科学研究費助成事業(大阪大学)  科学研究費助成事業(一般研究(C))

  • ゼオライト分離膜の開発

    科学研究費助成事業(大阪大学)  科学研究費助成事業(奨励研究(A))

  • ゼオライト分離膜の開発

    科学研究費助成事業(大阪大学)  科学研究費助成事業(奨励研究(A))

  • 開発途上国向け石炭の同時脱硫脱灰プロセスの開発

    科学研究費助成事業(大阪大学)  科学研究費助成事業(重点領域研究)

  • モレキュラーシービング膜反応器の開発

    科学研究費助成事業(大阪大学)  科学研究費助成事業(重点領域研究)

  • 火炎CVDによる非酸化物機能性材料の合成

    科学研究費助成事業(大阪大学)  科学研究費助成事業(一般研究(B))

  • モレキュラーシービング膜反応器の開発

    科学研究費助成事業(大阪大学)  科学研究費助成事業(重点領域研究)

  • ゼオライト分離膜の開発

    科学研究費助成事業(大阪大学)  科学研究費助成事業(奨励研究(A))

  • 開発途上国向け石炭の同時脱硫脱灰プロセスの開発

    科学研究費助成事業(大阪大学)  科学研究費助成事業(重点領域研究)

  • ゼオライト分離膜の開発

    科学研究費助成事業(大阪大学)  科学研究費助成事業(奨励研究(A))

  • 気相を介する新規合成法によるゼオライト膜の調製とその機能の評価

    科学研究費助成事業(大阪大学)  科学研究費助成事業(基盤研究(B))

  • ゼオライトの相変態過程に関する研究

    科学研究費助成事業(早稲田大学)  科学研究費助成事業(特定領域研究(A))

  • メンブレンリアクターを用いたメタン部分酸化による合成ガス製造

    科学研究費助成事業(早稲田大学)  科学研究費助成事業(基盤研究(A))

  • カラム浮選によるクリーンコールの製造

    科学研究費助成事業(早稲田大学)  科学研究費助成事業(特定領域研究(B))

  • ゼオライトの結晶化過程の解明と制御に関する研究

    科学研究費助成事業(早稲田大学)  科学研究費助成事業(基盤研究(B))

  • ディーゼルエンジン排ガスからの窒素酸化物除去触媒の開発

    科学研究費助成事業(早稲田大学)  科学研究費助成事業(基盤研究(B))

  • ゼオライトを原料とするメソポーラスマテリアルの新規な合成法の開発とその触媒特性

    科学研究費助成事業(早稲田大学)  科学研究費助成事業(萌芽的研究)

  • ミクロ・メソ多孔性結晶内における新反応場の構築

    科学研究費助成事業(鳥取大学)  科学研究費助成事業(基盤研究(C))

  • 新規非対称酸素過膜の開発とメタン酸化反応への応用

    科学研究費助成事業(早稲田大学)  科学研究費助成事業(基盤研究(A))

  • ゼオライト骨格と交換カチオンの協奏による分離場の創生

    科学研究費助成事業(早稲田大学)  科学研究費助成事業(特定領域研究)

  • 電子励起された酸化物等の固体表面を用いた常温常圧触媒反応の研究

    科学研究費助成事業(早稲田大学)  科学研究費助成事業(基盤研究(B))

  • 固体酸化物の格子酸素と金属の協奏機能をもつ水素製造用触媒に関する研究

    科学研究費助成事業(早稲田大学)  科学研究費助成事業(特定領域研究)

  • ミクロ多孔膜を用いたメンブレンリアクターの開発

    科学研究費助成事業(早稲田大学)  科学研究費助成事業(基盤研究(B))

  • 固体酸化物の格子酸素と金属の協奏機能をもつ水素製造用触媒に関する研究

    科学研究費助成事業(早稲田大学)  科学研究費助成事業(特定領域研究)

  • 電気化学デバイス工学の確立と深化

    科学研究費助成事業(早稲田大学)  科学研究費助成事業(特別推進研究)

  • ミクロ多孔体薄膜の特異な分離機能を利用した膜分離に関する基盤的研究

    科学研究費助成事業(早稲田大学)  科学研究費助成事業(基盤研究(B))

  • 無機分離膜の開発

  • 無機分離膜の開発

  • 無機分離膜の開発

  • 廃棄物燃焼ガス化に関する研究

  • 石炭灰のゼオライト化に関する研究

  • 高温下における微量金属の揮発挙動

  • ハイシリカゼオライトの合成と触媒作用

  • 超精密化学を用いた新規物質変換プロセスの創出プロジェクト

    文部科学省 

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学内研究費(特定課題)

  • ブタジエン分離用ゼオライト膜の創製

    2015年   酒井 求

     概要を見る

    1,3-ブタジエンはブタジエンゴムの原料に用いられる重要な基礎化学品である。本研究ではブタジエン分離用FAU型ゼオライト膜の開発を行った。FAU型ゼオライト膜中の交換カチオンを種々に変化させることで、1,3-ブタジエン分離に適したカチオン種の探索を行った。アルカリ金属元素や、アルカリ土類金属元素、その他の金属(Cr, Mn, Fe, Co, Cu, Zn, Ag, In, Sn)について検討を行った。アルカリ金属土類元素やその他の金属に交換したFAU膜は、いずれも分離係数がほぼ1であり、選択性を示さなかった。一方、NaからCsに交換したFAU膜は探索したカチオン種の内、最も高い選択性= 2.63を示した。

  • リン酸アルミニウム系ミクロ多孔体分離膜の開発

    2014年  

     概要を見る

    本研究では新規膜素材の開発と透過分離特性の解明を主たる目的として、アルミノリン酸塩系ミクロ多孔体(AlPO4-18)を用いて高透過分離性能を発揮することのできる無機系多孔質分離膜の開発を行った。AlPO4-18膜の合成条件を検討することにより、比較的に緻密な膜の合成を可能とした。また水/酢酸二成分混合蒸気透過分離試験においては、水を選択的に分離することに成功した。単成分を透過させた場合と比較して、二成分共存下ではそれぞれの透過度が低下することから、他成分による透過阻害を受けていると考えられる。また膜温度の上昇に伴い水および酢酸の透過度が減少することから、表面拡散的な透過挙動であると考えられる。

  • 重質炭化水素分離用ゼオライト分子ふるい膜の創製

    2014年  

     概要を見る

    本研究では、石油精製・石油化学分野における膜分離の可能性を拡げるため、ゼオライトを素材として炭化水素分離に適した薄膜の開発を行った。MFI型ゼオライトと*BEA型に注目し、それぞれを多孔質アルミナ支持体上に薄膜化し、C6-C16炭化水素の透過分離特性を評価した。検討の結果、1) MFI型ゼオライト膜を用いてC10, C16炭化水素混合物からノルマルアルカンを高選択的に分離可能であることを見出した、 2)*BEA型ゼオライトを支持体上に薄膜化する手法を開発した、 3)*BEA型ゼオライト膜が従来のゼオライト膜に比べ大きな分子分画領域を有し、炭化水素混合物分離に適応可能である事を明らかにした。

  • 新規メソ多孔体固体超強酸の開発

    2008年  

     概要を見る

    Friedel-Crafts 反応は石油化学,ファインケミカルズ合成において重要な反応であり,一般にはAlCl3 やBF3 等のハロゲン化物が触媒に用いられている。グリーンケミストリーの観点からはこの反応にハロゲンを含まない固体酸触媒を用いることが望ましい。シリカメソ多孔体は,高比表面積を有し,均一で精緻な化学修飾が可能なため,触媒担体として注目されている。本研究では,トルエンとベンジルアルコール(BzOH)を原料に用いたFriedel-Crafts ベンジル化をとりあげ,高比表面積化を図ることで活性の向上を期待してシリカメソ多孔体であるSBA-15に,硫酸化ジルコニアを担持し,触媒活性を検討した。 実験に当たってはまずSBA-15を調製した。Zr 源にZrOCl2・8H2O を用い,含浸法にてSBA-15にZrO2 を担持し,その後硫酸処理をして硫酸化ジルコニアSBA15 I ( S/ xZr SBA-15 I ) を調製した。また,SBA-15 のシリカ骨格形成時にZrO2 を直接組み込む直接合成法も併せて検討した。こちらは,Si源のTEOSとZr源のZr 源にZrOCl2・8H2Oを混合し,乾燥,焼成を行い,その後硫酸処理をして硫酸化ジルコニアSBA-15 D ( S/ xZr SBA-15 D ) を調製した。ただし,x = nZr/ (nSi + nZr) = 0.03,0.06,0.09とし,nZr,nSiはそれぞれのモル数を表す。触媒のキャラクタリゼーションは,XRD,窒素吸着測定,ICP測定,Ar吸着熱測定により行った。トルエンのベンジル化は,110℃で4 h行った。なお,触媒の前処理は300℃,3 h焼成し,グローブボックス内で秤量した。調製した触媒は硫酸処理後も細孔径や細孔容積の急激な減少は観察されず,550~800 m2 g-1 程度と比表面積も大きいままであった。特に,直接合成法で調製した触媒は,含浸法で調製した触媒よりも比表面積が大きい値を示した。また,反応は全て一次として整理できたので,それぞれの単位触媒重量当たりの一次反応速度定数を求めたところ,S/0.09Zr SBA-15 Dは市販の硫酸化ジルコニアの反応速度定数よりも大きい値を示した。これらのことから,直接合成法では,シリカ骨格中にジルコニアが高分散したため,高い活性が発現したと推察した。

  • 新規な有機無機ハイブリッド酸塩基触媒に関する研究

    2007年  

     概要を見る

     シリカメソ多孔体であるMCM-41を合成し,次にカルボン酸を末端に有するシランカップリング剤(Triethoxysilylpropylmaleamic acid, Gelest社)のエトキシ基(-OC2H5)とメソ多孔体細孔表面のシラノール基(Si-OH)とで脱水縮合を行い表面修飾し,さらに表面修飾したカップリング剤の末端のカルボキシル基(-COOH)とスルファミン酸(H2NSO3H)でアミド結合(-CONH-)を形成させ,スルファミド酸を固定することを試みた.合成した物質のキャラクタリゼーションを行ったところ,XRDと窒素吸着により, 2d-hexagonal構造をもつMCM-41が合成されていることが確認され,さらに表面修飾・スルファミド化してもメソ孔構造が保たれていることが示された.また, 29Si CPMAS NMRよりT1,T2,T3サイトのピークが確認でき,メソ多孔体表面のSi-OH基とカップリング剤が持つエトキシ基による脱水縮合を経て,カップリング剤が細孔表面シに固定化されていることが確認された.13C MAS NMRより,表面修飾されたシランカップリング剤は, その構造が壊れることなくメソ多孔体表面に修飾されていることが示唆された.さらにIRスペクトルの結果より,スルホン酸基由来のスペクトルの吸収を示した為,スルファミド酸の生成を確認した. 問題となったのは第一に,用いたシランカップリング剤が非常に特殊で高価な為,合成の一般化が困難な点,第二に,スルファミド化前後でMCM-41の比表面積が1000m2 g-1から300m2 g-1まで減少してしまった点であった.これは,弱塩基性の脱水縮合剤と,固定化されたスルファミド酸とで塩が形成されたためであると考えられた.これらの問題点を解決するために,安価で入手しやすく,末端にアミノ基を有するシランカップリング剤である3-aminopropyltriethoxysilaneを用いてメソ多孔体の表面修飾を行い,コハク酸のようなジカルボン酸を介して,スルファミン酸を脱水縮合させることでスルファミド酸合成を検討したところ,スルファミド酸を定量的に導入することができることを見出した。

  • ペンタシル型ゼオライト膜の合理的製膜手法とメンブレンリアクターの開発に関する研究

    2005年  

     概要を見る

    膜分離は省エネルギー技術であり、新規な分離膜、および分離膜と反応器を組み合わせた反応分離場の創生は、エネルギー・環境問題の解決に寄与することが期待できる。本研究では、分子と同程度のミクロ細孔をもつ無機材料であるゼオライトを薄膜化することによって、分子レベルの分離が可能で耐熱性、耐酸性に富む新しい分離膜を開発し、さらにゼオライト膜と固体触媒反応器を用いた新規な反応分離を実現することを目的とした。 モルデナイト膜、ZSM-5膜の二種のゼオライト膜について、その生成過程を検討し、結晶の育成条件と生成する構造の相関を明らかにし、膜の緻密化を合理的に進めるための指針を得た。また、得られた緻密なゼオライト薄膜について、高温(150-300℃)、高圧下(0.-3.0 MPa)における水-メタノール-水素のガス透過試験を実施し、ゼオライト薄膜の分離特性の検討を行った。その結果、モルデナイト膜は水素,メタノールの透過を阻止し,水が選択的に透過した。いっぽう, ZSM-5は水存在下で水,メタノールが透過し,水素の透過を阻止した。このような高温でも機能を発揮する分離膜はこれまで例がなく、本研究による大きな成果である。また、とくに、モルデナイト膜の水選択性の発現機構を検討するために、Na交換型モルデナイト結晶を用いて水蒸気、メタノールの吸着実験を行った。その結果、本実験のような高温下では、ゼオライトのアルミノシリケート骨格ではなく、交換カチオンであるNaと極性分子である水の強い相互作用によって水の吸着が起こり、水が細孔内に選択的に吸着するものと考えられた。しかし、いっぽうでメタノールもモルデナイト細孔に若干吸着することがわかった。モルデナイト膜によって、水素のみならずメタノールの透過も阻止される理由については、吸着特性のみでは完全には説明できず、ゼオライト膜の構造に踏みこんだ議論を進める必要があると推察した。

  • 高温高圧下で分離機能を発揮するゼオライト膜とそれを用いた膜反応器の開発研究

    2004年  

     概要を見る

    1.緒言 ゼオライト膜の研究開発はこれまで,多くのtry and errorによる実験の積み重ねによって合成条件を最適化し,透過分離特性の最適化を図ることが行われてきた。BNRIにおいてはA型ゼオライト膜の脱水膜としての工業化が急がれているが,ゼオライトには多くの種類の骨格構造が存在し,また化学組成(主にはシリカアルミナ比)も変化に富むことから,ゼオライトの膜材料としてのポテンシャルについては,いまだに研究開発の端緒についたばかりといえよう。 ゼオライト膜の透過分離性能を支配するのは,膜厚,結晶の配向,緻密さ,粒界の大きさといった膜構造,および分子ふるい作用,吸着特性といったゼオライト固有の物理化学的特性である。しかしいっぽうで,これら構造,物理化学的特性と分離透過特性の関係,両者の制御方法についてはほとんど明らかになっていないと言ってよい。 したがって,本研究の大きな目的は,合成条件と生成する構造の相関,膜構造と透過分離性能の相関を明らかにし,透過分離性能の合理的な制御方法を明らかにすることにある。本年度は,ZSM-5,モルデナイトを用いた薄膜に関して,高温高圧下における新規な透過分離性能を見出したので報告する.2.実験 母体の種結晶を粉砕して得たスラリーを用いて種結晶を多孔質アルミナ支持体上に担持し,これを水熱合成法により成長させることにより緻密で透過分離性能の高い膜を合成する手法を確立した。水、メタノール,水素の3成分系混合ガスから,水素を供給(高圧)側に残し,水および/あるいはメタノールを選択的に透過せしめることを目的に透過実験を行った.本年度は,モルデナイト膜については全圧30気圧までの高圧下における透過分離性能を評価した.いっぽう,ZSM-5膜に関しては全圧は1気圧に固定して透過実験を行った.3.結果・考察3.1. 合成実験結果 多孔質アルミナ上にZSM-5あるいはモルデナイトの種結晶を塗布し,合成溶液組成および結晶化条件をそろえて結晶化を行ったところ,ZSM-5種結晶を塗布した支持体上にはZSM-5膜が,モルデナイト種結晶を塗布した支持体上にはモルデナイト膜が生成することを見出した.すなわち,種結晶の種類によって異なる構造のゼオライトを製膜することが可能となった.3.2. モルデナイト膜の透過分離性能 30気圧、250℃までの範囲で透過実験を行った。水素の透過量は膜のシール部分からのリーク程度であり,水選択性を発現したことがわかった。モルデナイト膜は高温高圧系において高い水選択性を発揮する膜であると結論できる。選択性は条件にもよるが,水素に対する水の選択性は10000を超えた.水素/メタノール混合ガス,水/メタノール混合ガスの透過試験結果より,水以外の水素,メタノールは膜をほとんど透過しないものと考えられた。 水蒸気濃度20%,常圧,150-250℃において,Na型モルデナイト結晶粉末を用いて,水,メタノールの吸着実験を行った。その結果,水の吸着はモルデナイトの高温安定性に寄与することがわかった。いっぽう,メタノールは吸着するものの透過が起きないことが明らかとなった.このことは,水選択性がミクロ細孔内への吸着性の違いにより発現したことを否定しており,今のところ,モルデナイト結晶の積層欠陥によって細孔が著しく狭まり,結果としてメタノールが透過できなかったものと推察している.3.3. ZSM-5膜の透過分離性能 モルデナイト膜を用いた場合の結果とは異なり,メタノール/水素混合系では,両者とも透過し,ほとんど分離しなかった.これに対し,水/水素系では水が選択的に透過し水素の透過が阻止された.また,水/メタノール/水素3成分系では,水とメタノールが膜を透過し,水素の透過が著しく阻止された.こうした,水の共存による選択性の発現は,水の細孔内への強い吸着によるpore-fillingが原因と考えられるが,詳細は今後検討する予定である.

  • ミクロ多孔性無機膜による分離場の構築と新規な反応分離装置の開発研究

    2004年  

     概要を見る

    1. 緒言細孔径0.74 nm、Si / Al = 1.5~3.0で親水性をもつY型ゼオライトを膜とすることで、水 / 有機物からの脱水や有機混合物分離への適用が期待されている。透過分離性能の高い膜を調製するためには膜構造を制御することが重要になる。しかし、Y型ゼオライト膜構造の制御について報告した例は少ない。そこで、本研究では、Y型ゼオライト層の形成過程、および種々の調製条件が膜構造に及ぼす影響を確認することを目的とした。膜構造に影響する因子には、支持体上の種結晶、ゲル組成、エージング条件、結晶化条件などがある。そこで種々の結晶化条件が膜構造に及ぼす影響を検討した。また、多孔質支持体上では、ゼオライト層の形成過程を観察することは困難であるため、無多孔平板上における種結晶を用いたY型ゼオライト層の形成過程を検討した。2. 実験方法NaYを粉砕し、蒸留水を加えて調製したスラリーに、アルミナ支持体を3 min浸漬した後、ディップコート法によって支持体上に種結晶を塗布した。種結晶を塗布した支持体および塗布していない支持体上に静置あるいはかく拌条件下で結晶化した。結晶化後の支持体は、蒸留水によって流水洗浄、もしくは流水洗浄した後浸漬洗浄した。膜の透過分離性能は10wt%水 / エタノールを用いたPV試験によって評価した。スピンコート法によりアルミナ平板上に種結晶を塗布した後、かく拌条件下、373 Kで結晶化(1~13 h)した。結晶化後の平板は流水、浸漬洗浄した。結晶化後の平板上でのY型ゼオライト層の形成過程をFE-SEMにより観察した。3. 結果・考察3-1. 製膜条件の検討種結晶を塗布してない支持体を用いて結晶化したところ、Y型ゼオライト層は形成しなかった。このことから、Y型ゼオライト膜の調製においては、種結晶を塗布することによりゲル層中で核発生し、Y型ゼオライト層が形成すると考えられる。静置あるいはかく拌条件下いずれで結晶化した場合にも、長時間結晶化すると膜中のFAUの結晶化度が減少し、GISが生成し始めた。膜におけるFAUの結晶化度の減少は、結晶の溶出および熱力学的に安定なGISへの相転移によるものだと考えられる。結晶化した後、流水洗浄した膜のPV試験を行った結果、結晶化後蒸留水に浸漬すると、フラックスが大幅に向上することを見いだした。結晶化後の膜はアモルファスで覆われており、浸漬洗浄することでアモルファスが溶出したと考えられる。3-2. 平板上でのY型ゼオライト層の形成種結晶を用いたY型ゼオライト層の形成においては、ゲル層中での核発生と結晶成長が同時に進行していることが示唆された。そしてさらに結晶化時間を長くすると、Y型ゼオライトが溶出し、GISが生成していくことを確認した。

  • チタノシリケートETS-4支持膜の開発と窒素/酸素分離特性の検討

    2004年   稲垣 怜史

     概要を見る

     ETS-4は結晶性チタノシリケートであり,結晶構造に由来する均一で剛直なミクロ孔を有する。また,Ti原子はETS-4骨格中で4配位と6配位の2種類の配位構造を形成するが,4配位Tiサイトは陽イオン交換サイトとなりうる。ここにNa+,K+,Sr+などのアルカリ金属イオンが交換することで,ETS-4のミクロ孔径を狭めることができ,チッ素・酸素を分子ふるい作用により,分離することが可能となる。本研究では,このような特長をもつETS-4を多孔質支持体上に薄膜化し,チッ素・酸素を膜分離する手法を開発することが目的である。その中で本年度は,粉末のETS-4の調製条件の検討を行った。 ETS-4はSi源としてケイ酸ナトリウム,Ti源として塩化チタンまたはTiアルコキシドを用いる。ただし,用いるTiの種類により,結晶化後に得られる生成物が変わることが知られている。Ti源としてTiブトキシド・モノマーを用いて,SiO2: TiO2: Na2O: H2O: H2O2=1.0: 0.10: 0.65: 67.5: 0.60の組成で原料混合物を調製し,190℃,静置条件下で48時間結晶化を行ったところ,生成物はETS-4であった。ここで原料にH2O2を加えるのは,Tiブトキシドの加水分解を緩やかに進めるためであり,このようにして得られた水酸化チタンモノマーがシリカ源と重合し,結果,ETS-4への結晶化が進行したと考えられる。いっぽう,Ti源に塩化チタンを用いて,SiO2: TiO2: Na2O: H2O: HCl=1.0: 0.30: 1.25: 9.88: 0.32の組成で原料混合物を調製し,190℃で24時間結晶化を行った場合には,結晶性の低いdenseなチタノシリケート相とquartzが生成した。塩酸を用いて塩化チタンを激しく加水分解した場合には,チタネートとシリケートとの重合があまり起こらなかったために,ETS-4が得られなかったと考えられる。 これまでにTi源の加水分解速度を制御することで,再現よくETS-4が得られることが明らかなった。今後はこの手法を用いて,ETS-4を多孔質支持体上への薄膜化を行い,また,得られた薄膜のチッ素・酸素分離試験を行い,高い分離性能を示すETS-4薄膜の開発を進めていく。

  • ドライゲルコンバージョン法を用いたゼオライト分離膜の合成

    1997年  

     概要を見る

    乾燥状態のゲルを有機結晶化剤蒸気雰囲気下で結晶化させる方法(ドライゲルコンバージョン法)により、SiO2/Al2O3比=1000のMFI型ゼオライトの平均細孔径0.1μmの多孔質アルミナ平板への製膜を試みた。ゲル調製から熟成、支持体へのゲルのコーティング、結晶化に至るまで、多くの合成条件が生成物の物性に影響するため、それぞれの最適化を試みた。特に緻密な膜の合成に重要な条件は原料中のアルカリ濃度であった。アルカリ濃度Na2O/SiO2比=0.13-0.23の範囲で緻密な膜が得られた。アルカリ濃度が充分でない場合には、原料ゲルの加水分解が充分に起こらず、また高すぎる場合には加水分解が優先して起きるため、ゼオライト骨格の形成が起きないことがわかった。ベンゼン/n-ヘキサンの浸透気化分離試験を行なった。ピンホールがわずかでも存在すると全く選択性を示さなかったが、ピンホールフリーの膜では等モル混合物で5程度の分離係数を示した。無機ガス(ヘリウム、窒素、二酸化炭素、メタン)透過試験では、ピンホール濃度が減少するほど、無機ガス透過流束は大きな正の温度依存性を示した。また、各ガスの透過流束の差も大きくなる傾向にあった。以上の結果は、分離機能の発現にはピンポールの制御、すなわちゼオライト結晶粒界の制御が本質的に重要であることを示している。 ゼオライト膜を工業的に用いるにはモジュール化が必須であり、それにはチューブ状支持体への製膜法の開発が必要である。そこで、上記で確立した合成条件を用いて、外径7㎜のチューブ状アルミナ多孔質支持体への製膜を試みた。チューブ表面への均一な製膜には、ゲルを支持体細孔中へ吸引・製膜することが必要であった。また、乾燥途中でゲルが重力あるいは毛管凝縮によって片寄らないよう、工夫した。こうして得られた膜を用いて、窒素/二酸化炭素混合物の透過試験を行なったところ、表面拡散の効果による選択性の発現を認めた。研究成果の発表投稿予定Synthesis of MFI Zeolite Membrane and Its Separation Properties. Microporous and Mesoporous Materials, Elsevier.

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