研究者データベース

増田 隆夫(マスダ タカオ)
総長、理事・副学長
理事・副学長

基本情報

所属

  • 総長、理事・副学長

職名

  • 理事・副学長

学位

  • 工学博士(京都大学)

ホームページURL

J-Global ID

研究キーワード

  • ゼオライト膜   反応・分離   触媒膜   ゼオライト   高度分離   構造体触媒   オレフィン   廃プラスチック   MTO反応   熱分解   ZSM-5ゼオライト   芳香族アルキル化   ナノクリスタル   ゼオライトナノクリスタル   パーベパレーション   水蒸気   界面活性剤   ナノ結晶ゼオライト   メタノールの反応   燃料電池型反応器   分子篩   鉄触媒   メタノール反応   水素分離   ゼオライト触媒膜   触媒・化学プロセス   メタノール   細孔径制御   PET   PVC   化学工学一般   反応・分離工学   Chemical Engineering in General   Reaction and Separation Engineering   

研究分野

  • ものづくり技術(機械・電気電子・化学工学) / 反応工学、プロセスシステム工学
  • ものづくり技術(機械・電気電子・化学工学) / 移動現象、単位操作
  • ものづくり技術(機械・電気電子・化学工学) / 触媒プロセス、資源化学プロセス
  • ものづくり技術(機械・電気電子・化学工学) / 触媒プロセス、資源化学プロセス
  • ものづくり技術(機械・電気電子・化学工学) / 反応工学、プロセスシステム工学
  • ものづくり技術(機械・電気電子・化学工学) / 移動現象、単位操作

職歴

  • 2020年10月 - 現在 北海道大学 理事・副学長
  • 2001年 - 現在 北海道大学 大学院工学研究院 教授
  • 2017年04月 - 2019年03月 北海道大学 大学院工学研究院長 工学部長
  • 2014年 - 2017年03月 北海道大学 大学院工学研究院 副工学研究院長
  • 1994年 - 2001年 京都大学工学部化学工学科 助教授
  • 1989年 - 1994年 京都大学工学部化学工学科 講師
  • 1982年 - 1989年 京都大学工学部化学工学科 助手

学歴

  •         - 1982年10月   京都大学   大学院工学研究科化学工学専攻博士後期課程   化学工学専攻博士後期課程
  •         - 1981年   京都大学   大学院工学研究科   化学工学専攻修士課程 修了
  •         - 1979年   京都大学   工学部   化学工学科 卒業

所属学協会

  • 日本化学会   石油学会   ゼオライト学会   触媒学会   化学工学会   

研究活動情報

論文

  • Hiroki Konno, Yuta Nakasaka, Kousuke Yasuda, Miho Omata, Takao Masuda
    Catalysis Today in press 2020年 [査読有り][通常論文]
     
    © 2020 Elsevier B.V. Nanocrystalline zeolitic imidazolate frameworks 8 and 67 (ZIF-8 and ZIF-67) were prepared via surfactant-assisted synthesis in aqueous solution at room temperature. The synthesis without surfactant yielded crystal sizes for ZIF-8 and ZIF-67 of 1.19 and 2.95 μm, respectively. However, their crystal sizes obtained via surfactant-assisted synthesis were 81 and 150 nm, respectively. The Brunauer–Emmett–Teller (BET) surface area and micropore volume remained almost constant regardless of the crystal size. TGA analysis confirmed that ZIF-8 and ZIF-67 have sufficient thermal resistance for water treatment. Highly crystalline ZIF-8 and ZIF-67 with different crystal sizes could be obtained, and these ZIF crystals were used as adsorbents for adsorptive removal of perfluorooctane sulfonate (PFOS) from aqueous solution. The amount of PFOS adsorbed by ZIF-67 (734.7 mg-PFOS/g-ZIF-67) was considerably higher than that absorbed by zeolite, activated carbon, and ZIF-8. Additionally, the crystal downsizing was effective in improving the adsorption rate, and adsorption equilibrium was reached faster by nanocrystalline ZIF-67 than by macrocrystalline ZIF-67. This feature makes nanocrystalline ZIF-67 one of the most effective and promising adsorbents for removing PFOS from aqueous solution.
  • Yasuchika Hasegawa, Takafumi Matsui, Yuichi Kitagawa, Takayuki Nakanishi, Tomohiro Seki, Hajime Ito, Yuta Nakasaka, Takao Masuda, Koji Fushimi
    Chemistry - A European Journal 25 53 12308 - 12315 2019年09月20日 [査読有り][通常論文]
     
    © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Oxygen-sensitive and near-infrared (NIR) luminescent YbIII coordination polymers incorporating ligands based on pyrene derivatives were synthesized: YbIII–TBAPy and YbIII–TIAPy (TBAPy: 1,3,6,8-tetrakis(p-benzoate)pyrene; TIAPy: 1,3,6,8-tetrakis(3,5-isophthalic acid)pyrene). The coordination structures of these materials have been characterized by means of electrospray ionization mass spectrometry, X-ray diffraction analysis, and thermogravimetric analysis. Moreover, the porous structure of YbIII–TIAPy has been evaluated by measuring its N2 adsorption isotherm. The NIR luminescence properties of YbIII–TBAPy and YbIII–TIAPy have been examined by acquiring emission spectra and determining emission lifetimes under air or argon and in vacuo. YbIII–TIAPy exhibited high thermal stability (with a decomposition temperature of 400 °C), intense luminescence (with an emission quantum yield under argon of 6.6 %), and effective oxygen-sensing characteristics. These results suggest that NIR luminescent YbIII coordination polymers prepared using pyrene derivatives could have applications in novel thermo-stable oxygen sensors.
  • Kawamata Yuki, Yoshikawa Takuya, Aoki Hiromi, Koyama Yoshihito, Nakasaka Yuta, Yoshida Masayuki, Masuda Takao
    CHEMICAL ENGINEERING JOURNAL 368 71 - 78 2019年07月15日 [査読有り][通常論文]
  • Nakasaka Yuta, Kanda Takumi, Shimizu Ken-ichi, Kon Kenichi, Shibata Gen, Masuda Takao
    CATALYSIS TODAY 332 64 - 68 2019年07月15日 [査読有り][通常論文]
  • Matsagar Babasaheb M, Kang Ting-Cih, Wang Zheng-Yen, Yoshikawa Takuya, Nakasaka Yuta, Masuda Takao, Chuang Li-Ching, Wu Kevin C. -W
    REACTION CHEMISTRY & ENGINEERING 4 3 618 - 626 2019年03月01日 [査読有り][通常論文]
  • Fujitsuka, Hiroyasu, Terai, Kazuhiro, Hayashi, Masanori, Yoshikawa, Takuya, Nakasaka, Yuta, Masuda, Takao, Tago, Teruoki
    JOURNAL OF THE JAPAN PETROLEUM INSTITUTE 62 6 319 - 328 2019年 [査読有り][通常論文]
     
    Glycerol is a major by-product of biodiesel production and has attracted great interest as a precursor for the preparation of various valuable chemicals. Conversion of glycerol over alpha-Fe2O3 catalyst in a fixed-bed flow reactor was investigated to understand the catalytic activity of iron oxide for the selective production of allyl alcohol. Addition of formic acid to the glycerol feed was effective in improving allyl alcohol production because decomposition on the catalyst formed hydrogen atoms, which were consumed in dehydroxylation of glycerol and reduction of alpha-Fe2O3 to Fe3O4 during glycerol conversion. Moreover, the allyl alcohol yield was further increased using potassium-loaded alpha-Fe2O3 catalyst, which was attributed to change in the acid sites. The original acid sites of alpha-Fe2O3, mainly Lewis acid sites, were occupied by potassium, and Bronsted acid sites formed during glycerol conversion. To further enhance the allyl alcohol yield, we attempted to minimize the polymerization reaction by optimizing the potassium loading, W-cat/F-glycerol value (i.e., contact time), and reaction temperature. The highest allyl alcohol yield of 39.8 C-mol% was achieved over 1 mol% potassium-loaded alpha-Fe2O3 at 623 K and with W-cat /F-glycerol of 1 h.
  • Oluwole O. Ajumobi, Oki Muraza, Hisaki Kondoh, Natsumi Hasegawa, Yuta Nakasaka, Takuya Yoshikawa, Adnan M. Al Amer, Takao Masuda
    Applied Energy 218 1 - 9 2018年05月15日 [査読有り][通常論文]
     
    Upgrading of oil sand bitumen by catalytic cracking of its heavy oil fraction via ceria-based catalysts was investigated in a fixed-bed flow-type reactor, in the presence of superheated steam and addition of water. The reaction was carried out over CeZr, FeCoCeZr1 and FeCoCeZr2 catalysts at 470 °C, Wcat/FFeed of 0.4 h and FH2O/Ffeed = 2. The oxygen species in the crystal lattice of the catalysts and the surface Lewis acid sites are responsible for the oxidative decomposition and catalytic cracking of the heavy oil, respectively. Higher light oil yield of approximately 60 mol%-C (gas oil and vacuum gas oil) and lowest coke yield (20.45 mol%-C) was obtained over CeZr catalyst. FeCoCeZr1 and FeCoCeZr2 gave lower residue and higher gas yield, with higher H2 and lower CO2 composition when compared to CeZr. The spent catalysts showed structural stability which is supported by the X-ray diffraction analysis, and thermal stability which agrees to the minimal weight loss from thermogravimetric analysis. The catalysts also exhibited good potential for reusability based on the analysis of the spent samples.
  • Dieni Mansur, Teruoki Tago, Takao Masuda
    Biofuels 9 3 325 - 330 2018年05月04日 [査読有り][通常論文]
     
    Production of bioethanol from biomass has been known in almost worldwide. Grain-based bioethanol production generally yields a by-product known as DDGS (dried distiller grains with soluble). DDGS is potentially convertible into biocrude oil due to the lipid, carbohydrate, and protein content. One of the technologies for the production of biocrude oil from solid biomass is hydrothermal liquefaction. In this study, hydrothermal liquefaction of DDGS was conducted using ethanol solution as a reaction medium. The process was carried out under various temperatures, ratios of DDGS to reaction medium, and ethanol concentrations (15–99.5%). A high yield of biocrude oil was recovered at 280°C and ratio between DDGS and 75% of ethanol solution as 1:20. It was found that around 38.2% of biocrude oil was recovered from DDGS. Thus, DDGS has the potential to be converted into biocrude oil.
  • Anas K. Jamil, Oki Muraza, Mohamed H. Ahmed, Ahmad Zainalabdeen, Kenta Muramoto, Yuta Nakasaka, Zain H. Yamani, Takuya Yoshikawa, Takao Masuda
    Microporous and Mesoporous Materials 260 30 - 39 2018年04月01日 [査読有り][通常論文]
     
    To enhance the textural properties and the hydrothermal stability of porous catalysts, ZSM-22 zeolite samples were treated with different concentrations of HF aqueous solutions (0.7, 1.0 and 1.5 wt%). ZSM-22 samples that were treated with 0.7 and 1.0 wt% HF aqueous solutions showed a selective removal of aluminum atoms from TON framework. On the other hand, more concentrated HF (1.5 wt %) caused the leaching of silicon atom from the zeolites framework. The HF treated ZSM-22 samples showed smaller crystals size, better hydrothermal stability as reflected by intact textural properties as well as their mesoporosity. The modified samples also showed enhanced acidity with lower Brønsted acidity than the parent ZSM-22. ZSM-22 samples modified with low HF concentrations (0.7 and 1.0 wt%) showed better initial conversions in steam catalytic cracking (SCC) of hexane, which can be attributed to the enhancement in the acidity. However, deactivation rate was not enhanced after the HF treatment. The HF modified ZSM-22 samples showed more BTX selectivity which can be attributed to their larger external surface areas. The HF-treated samples lost more acidity, especially Brønsted acidity, after SCC reaction than the parents ZSM-22 zeolite.
  • 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][通常論文]
     
    Zeolites demonstrating better SCR of NOx performance due to wide temperature activity, hydrothermal stability and N-2 selectivity have been identified under a joint research initiative by the Research Association of Automotive Internal Combustion Engines (AICE), Japan. Based on the AICE's standards, over 25 zeolites with different structures and pore dimensions were investigated and their SCR efficiency and durability have been compared. While the performances of the top contenders cannot be related to a single parameter, the results suggest that the SAR, Cu quality/quantity, pore dimensions, diffusivity and acidity play a combined role in deciding the SCR activity and selectivity.
  • Ching-Tien Chen, Chi Van Nguyen, Zheng-Yen Wang, Yoshio Bando, Yusuke Yamauchi, Manar Tareq Saleh Bazziz, Amanullah Fatehmulla, W. Aslam Farooq, Takuya Yoshikawa, Takao Masuda, Kevin C.-W. Wu
    ChemCatChem 10 2 361 - 365 2018年01月23日 [査読有り][通常論文]
     
    An effective and selective method for the oxidation of 5-hydroxymethylfurfural (HMF) by using hydrogen peroxide (H2O2) as the liquid oxygen source and activated-carbon-supported ruthenium (Ru/AC) as the catalyst was developed. This reaction system allowed HMF to be oxidized in water under mild reaction conditions efficiently, as it was shown to have lower mass-transfer resistance than gaseous oxygen-assisted oxidation systems. In addition, we could selectively control the components of the oxidation products by adjusting the reaction conditions. We optimized several reaction parameters such as the reaction temperature (75 °C), time (t=1 or 6 h), base additive (sodium carbonate), and the HMF/catalyst ratio (50 or 10) to attain the desired products in maximum yields. Thus, 5-formyl-2-furoic acid was obtained in a high yield up to 92 % with a HMF/catalyst ratio of 50 and a reaction time of 1 h, whereas 2,5-furandicarboxylic acid was obtained in a maximum yield of 91.3 % with a HMF/catalyst ratio of 10 and a reaction time of 6 h. A possible mechanism for the selective oxidation of HMF was also discussed. We envision that the H2O2-mediated oxidation systems proposed in this study would be of great benefit to other organic oxidation systems.
  • Hiroki Konno, Seiya Sasaki, Yuta Nakasaka, Takao Masuda
    Chemistry Letters 47 5 620 - 623 2018年 [査読有り][通常論文]
     
    © 2018 The Chemical Society of Japan. In this study, zeolitic imidazolate framework-8 immobilized on aramid microfibrils (ZIF-8@AMF) with different crystal sizes were prepared in an aqueous solution at room temperature, and were used as adsorbents for the adsorptive removal of 1,4-dioxane from water. It was revealed that the immobilization of the ZIF-8 nanoparticles on the microfibrils improves the water permeation performance without impairing the adsorption performance.
  • Mohamed H. M. Ahmed, Oki Muraza, Shota Nakaoka, Anas K. Jamil, Alvaro Mayoral, Victor Sebastian, Zain H. Yamani, Takao Masuda
    Energy and Fuels 31 12 14097 - 14103 2017年12月21日 [査読有り][通常論文]
     
    Hierarchical ZSM-48, a one-dimensional pore system zeolite with the presence of mesopores, was obtained by post-synthesis alkaline and acid treatments. Hierarchical ZSM-48 exhibited excellent hexane cracking activity compared to parent ZSM-48, which can be attributed to better diffusion as a result of the created mesoporosity. Moreover, the post-synthesis treatment allowed for manipulation of the distribution of active sites. Consequently, better stability and higher propylene selectivity were accomplished. The spent catalyst was regenerated by removing the deposited coke from the pores, and the regenerated catalyst was characterized again to investigate the recyclability of the hierarchical structure achieved. Parent ZSM-48 showed the same textural and acidic properties after regeneration, while the structure of the post-treated sample suffered from serious defects. The defects severely decreased the number of active sites as measured by pyridine Fourier transform infrared spectroscopy and caused major structural collapse as observed by scanning electron microscopy and transmission electron microscopy.
  • Yuta Nakasaka, Takuya Yoshikawa, Yuki Kawamata, Teruoki Tago, Shinya Sato, Toshimasa Takanohashi, Yoshihito Koyama, Takao Masuda
    CHEMCATCHEM 9 14 2875 - 2880 2017年07月 [査読有り][通常論文]
     
    Fractionation of a lignin-derived liquid using a water/1-butanol mixture was investigated with the aim of developing a source of phenols. The effect of various phases on lignin depolymerization by using a water/1-butanol mixture with a solid acid catalyst was investigated. The water/1-butanol solvent was confirmed to be heterogeneous under the reaction conditions, and the liquid phase was essential for effective depolymerization of lignin. To make optimum use of the depolymerized lignin and to understand its chemical structure, solvent fractionation was performed by using a water/tetrahydrofuran solution, ethyl acetate, and n-hexane as solvents. Catalytic cracking of the n-hexane soluble fraction was performed over an iron oxide catalyst by using a high-pressure fixed-bed flow reactor at 673 K. The production of phenol was confirmed, and the demethoxylation reaction was examined by using model compounds. In addition, as the heavy components were extracted during the solvent fractionation, as confirmed by analysis of the molecular structures of the fractionated components, the formation of solid products could be suppressed to a level below 2.5 mol(C)% based on lignin.
  • Gaku Watanabe, Yuta Nakasaka, Takao Masuda
    JOURNAL OF THE JAPAN PETROLEUM INSTITUTE 60 3 146 - 153 2017年05月 [査読有り][通常論文]
     
    Aluminosilicate and ferrisilicate with the MTW-type zeolite structure were hydrothermally prepared and used to catalyze the methylation of 2-methylnaphthalene (2-MN) under supercritical conditions in a batch-type reactor. Dimethylnaphthalene (DMN) and 1-methylnaphthalene (1-MN) yields increased with decreasing Si/Al ratio of the zeolite. In contrast, ferrisilicate with the MTW-type zeolite structure (Si/Fe = 100) exhibited higher DMN selectivity and the beta,beta-DMN fraction in total DMNs was higher than that over aluminosilicate with MTW structure (Si/Al = 100). Kinetic analysis of 2-MN methylation over MTW zeolites was conducted, to obtain the reaction rate constants and apparent activation energies. The activation energy for the methylation of 2-MN over aluminosilicate with MTW structure was 176 kJ mol(-1), which was almost the same as that for the ferrisilicate with MTW structure. This indicates that the mechanism for methylation is independent of hetero-atoms species in the MTW zeolite framework. The introduction of Fe atoms into the framework significantly decreased the rate constant for the isomerization of 2-MN compared with that for the methylation of 2-MN. Therefore, ferrisilicate with MTW structure is effective for 2-MN methylation due to the decrease of the isomerization rate.
  • Gaku Watanabe, Yuta Nakasaka, Taichi Taniguchi, Takuya Yoshikawa, Teruoki Tago, Takao Masuda
    CHEMICAL ENGINEERING JOURNAL 312 288 - 295 2017年03月 [査読有り][通常論文]
     
    Methylation of 2-methylnaphthalene (2-MN) under high-pressure reaction conditions over MTW-type zeolites (Si/Al = 100) was carried out using a batch-type reactor. Compared with macro-sized MTW-type zeolites, nano-sized MTW-type zeolites exhibited higher 2-MN conversion and dimethylnaphthalene (DMN) selectivity. In addition, coke formation on the catalyst could be suppressed due to improvement of the produced DMN solubility by increasing the bulk phase pressure, which enabled kinetic analysis of 2-MN methylation over MTW-type zeolites. Kinetics analysis of 2-MN methylation over MTW-type zeolites with different crystal sizes was successfully carried out, and reaction rate constants and activation energies for methylation and isomerization of 2-MN over MTW-type zeolites were obtained. The apparent reaction rate constants of 2-MN methylation were improved by decreasing MTW-type zeolite crystal size due to decrease in diffusion resistance. Moreover, the effectiveness factors for methylation of 2-MN were estimated based on the rate constants of 2-MN methylation and crystal sizes of the MTW-type zeolites. As a result, it was revealed that the crystal size of MTW-type zeolite (Si/Al = 100) required for methylation of 2-MN to achieve the reaction-limiting condition was below 240 nm. (C) 2016 Elsevier B.V. All rights reserved.
  • Yuangsawad Ratanaporn, Na-Ranong Duangkamol, Tago Teruoki, Masuda Takao
    INTERNATIONAL CONFERENCE ON ADVANCES IN ENERGY SYSTEMS AND ENVIRONMENTAL ENGINEERING (ASEE17) 22 2017年 [査読有り][通常論文]
     
    A two-step process consisting of pyrolysis of dried sludge and catalytic upgrading of pyrolysed liquid was proposed. Wastewater from a palm oil mill was separated to solid cake and liquid by filtration. The solid cake was dried and pyrolysed at 773 K. Liquid product obtained from the pyrolysis had two immiscible aqueous and oil phases (PL-A and PL-O). Identification of chemicals in PL-A and PL-O indicated that both phases contained various chemicals with unsaturated bonds, such as carboxylic acids and alcohols, however, most of the chemicals could not be identified. Catalytic upgrading of PL-A and PL-O over ZrO2.FeOx were separately performed using a fixed bed reactor at various conditions, T = 513-723 K and mass of catalyst to feed rate = 0.25-10 h. The main components in the liquid products of PL-A upgrading were methanol and acetone whereas they were acetone and phenol in the case of PL-O upgrading. More than 15% of carbon in raw material was deposited on the catalyst. To reduce the carbon deposition, the used catalyst was treated with air at 823 K. This simple treatment could reasonably regenerate the catalyst only for the case of PL-A catalytic upgrading.
  • Yuta Nakasaka, Teruoki Tago, Takao Masuda
    Journal of the Japan Petroleum Institute 60 6 277 - 287 2017年 [査読有り][通常論文]
     
    A review covers the preparation of macro-, and nano-sized ferrisilicate and ferroaluminosilicate with MFI and MTW-type zeolite structures and its application to light olefins production from oxygenated organic compounds, e.g., acetone and methanol. Nano-sized ferrisilicate with MFI-type zeolite structure showed more stable activity compared to macro-sized zeolite in the acetone to olefin and methanol to olefin reactions. Metallosilicates containing Fe-atoms in the zeolite framework had higher selectivity for light olefins compared to aluminosilicate due to suppression of the consecutive reactions forming aromatics and coke. Ferroaluminosilicate containing two types of Bronsted acid sites, derived from both Fe and Al atoms in the framework, was the most effective catalyst for light olefins production from methanol.
  • Hisaki Komioh, Natsumi Hasegawa, Takuya Yoshikawa, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    ENERGY & FUELS 30 12 10358 - 10364 2016年12月 [査読有り][通常論文]
     
    The behavior of a CeO2- ZrO2-Al2O3-FeOx catalyst typically employed during heavy oil decomposition was investigated in conjunction with the addition of H2O, as a means of improving the upgrading activity and suppressing coke formation on the catalyst. The upgrading of oil sand bitumen diluted with benzene was examined with this catalyst at various FH2.0/Fbitumer, ratios [where Frizo is the water flow rate (g h(-1)) and F-bitumen is the bitumen feedstock flow rate (g h(-1))] in a fixed bed flow-type reactor. Under optimal conditions (F/H2O/F-bitumen equal to approximately 20) and at a reaction temperature of 693 K, effective catalytic decomposition of the bitumen was observed with the lighter component (gas oil and vacuum gas oil) yield reaching 71 mol % C. In addition, the formation of coke on the catalyst was decreased to less than 14 mol % C. Analyses using quadrupole mass spectrometry determined that this catalyst upgrades the heavy oil through oxidation reactions, in which the lattice oxygen of the iron oxide is consumed and, subsequently, regenerated by the decomposition of water molecules over the catalyst.
  • Mohammed A. Sanhoob, Oki Muraza, Taichi Taniguchi, Teruoki Tago, Gaku Watanabe, Takao Masuda
    ENERGY & FUELS 30 11 9679 - 9685 2016年11月 [査読有り][通常論文]
     
    One of the most interesting processes in energy-related catalysis is steam-assisted catalytic cracking. Herein, ZSM-12 (MTW) zeolite was modified by impregnation to improve the selectivity to olefins in the presence of steam. ZSM-12 zeolite was synthesized hydrothermally and modified by incorporating ZSM-12 zeolite with lanthanum (La), cerium (Ce), and boron (B). Two different ammonium solutions were used in the ion-exchange of the synthesized ZSM-12 zeolite, namely, ammonium nitrate and ammonium fluoride. Each group was impregnated with 2 wt % of lanthanum, cerium, or boron. Catalytic performance was evaluated using steam catalytic cracking of n-hexane. H-ZSM-12 zeolite exchanged with ammonium nitrate and impregnated with lanthanum and cerium has conversion above SO C-mol %. However, impregnation with boron reduced the active sites, and the conversion was 20 C-mol %. On the other hand, exchanging the samples with ammonium fluoride led to the loss of the active sites and the conversion was around 20 C-mol % in the presence of lanthanum, cerium, and boron.
  • Mohammed A. Sanhoob, Oki Muraza, Teruoki Tago, Taichi Taniguchi, Gaku Watanabe, Takao Masuda
    RESEARCH ON CHEMICAL INTERMEDIATES 42 7 6437 - 6448 2016年07月 [査読有り][通常論文]
     
    Desilicated MTW zeolite was evaluated in methylation of 2-methylnaphthalene (2-MN) in a fixed-bed flow reactor at 450 degrees C. Mesoporous MTW was fabricated via a microwave-assisted desilication process using a harsh alkaline solution to improve the pore volume and the surface area. H-ZSM-12 zeolite was treated with 0.3 M of NaOH solution with different treatment times. Due to the harsh alkaline treatment, micropores were blocked by the deposition of the removed atoms. Due to the importance of methylnaphthalenes intermediates, modified MTW zeolites were evaluated in methylation of 2-MN. Methanol (MeOH), 2-MN and 1,3,5-trimethylbenzene (TMB) were fed to the reactor with a molar ratio of 15:15:70. Higher selectivity to 1-methylnaphthalene (1-MN) was observed rather than dimethylnaphthalene and trimethylnaphthalene with a yield of 13.6, 8 and 2.5 mol%, respectively. Moderate conversion up to 24.1 mol% was reached for 30 min reaction.
  • Hisaki Kondoh, Yuta Nakasaka, Tatsuya Kitaguchi, Takuya Yoshikawa, Teruoki Tago, Takao Masuda
    FUEL PROCESSING TECHNOLOGY 145 96 - 101 2016年05月 [査読有り][通常論文]
     
    Upgrading of oil sand bitumen was examined using a catalyst consisting of CeO2-ZrO2-Al2O3-FeOx and sub- and super-critical water in two reactor types: batch-type and fixed-bed flow-type. Bitumen diluted with benzene was used as a feedstock, and the effects of reaction pressure and temperature on product yield were investigated. Under conditions of high pressure (approximately 19 MPa), catalytic decomposition of bitumen proceeded effectively over the FeOX-based catalyst, with the yield of lighter components such as gas oil and vacuum gas oil (VGO) reaching 70 mol%-C at a reaction temperature of 693 K. Moreover, because coke formation on the catalyst was suppressed (less than 10 mol%-C under optimized reaction pressure and temperature), the FeOX-based catalyst showed excellent durability and reusability for catalytic decomposition of bitumen. (C) 2016 Elsevier B.V. All rights reserved.
  • Taichi Taniguchi, Yuta Nakasaka, Keitaro Yoneta, Teruoki Tago, Takao Masuda
    Microporous and Mesoporous Materials 224 74 - 74 2016年04月01日 [査読有り][通常論文]
     
    © 2015 Elsevier Inc.A series of Al- and Fe-MFI zeolites was synthesized using a hydrothermal treatment, and nano-sized MFI zeolites were obtained by an emulsion method. UV-vis spectra and ac-NH3-TPD profiles demonstrated that Fe atoms were incorporated into the frameworks of the MFI structures and that almost all of the Fe3+ species were well dispersed without forming bulky iron oxide particles. The selective production of iso-butylene from acetone was examined using Al- and Fe-MFI zeolites with different crystal sizes. The nano-sized MFI zeolite exhibited a long catalyst lifetime compared with the macro-sized MFI zeolite. Although iso-butylene is normally an intermediate during acetone conversion over zeolite catalysts, the weak acidity of the Fe-MFI zeolite suppressed the completion of excessive reaction, leading to high selectivity for iso-butylene.
  • Galal A. Nasser, Teguh Kurniawan, Teruoki Tago, Idris A. Bakare, Taichi Taniguchi, Yuta Nakasaka, Takao Masuda, Oki Muraza
    JOURNAL OF THE TAIWAN INSTITUTE OF CHEMICAL ENGINEERS 61 20 - 25 2016年04月 [査読有り][通常論文]
     
    Cost-effective and efficient catalysts for pyrolysis and catalytic cracking can be derived from low-cost and abundantly available natural minerals. Herein, we report the fabrication of hierarchical mordenite (MOR) zeolites with an enhancement in micropore properties, which were obtained by ion exchange followed by dealumination of natural zeolites. Crystallinity, textural properties and morphologies of the hierarchical catalysts were characterized by using X-ray diffraction (XRD), nitrogen physisorption and field-emission scanning electron microscopy (SEM). The XRD patterns show that the parent minerals contain natural mordenite as the dominant phase (73-83 wt%). The severity of the dealumination was studied by applying different concentrations of nitric acid (HNO3). Dealumination affected crystallinity, Si/Al ratio, mesoporosity of mordenite, and selectivity of products in n-hexane cracking. Crystallinity of hierarchical MOR decreased with higher HNO3 concentrations. High selectivity to propylene with propylene/ethylene ratio of 1.26 was achieved over mordenite treated with mild dealumination by HNO3 (1 M). These cost-effective catalysts derived from natural zeolites are potentially applied in chemical industries. (C) 2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
  • Taichi Taniguchi, Yuta Nakasaka, Keitaro Yoneta, Teruoki Tago, Takao Masuda
    CATALYSIS LETTERS 146 3 666 - 676 2016年03月 [査読有り][通常論文]
     
    The synthesis of metallosilicates with a MTW structure was achieved using tetraethylammonium bromide (TEABr) and methyltriethylammonium chloride (MTEACl) as organic structure-directing agents (OSDAs). MTW zeolites (Al-MTW, Si-MTW, Fe-MTW and (Al, Fe)-MTW) were obtained by hydrothermal synthesis. The crystal size of the resulting MTW zeolite strongly depended on the type of OSDA, in which the column-like and agglomerated nano-sized crystals could be produced by using MTEACl and TEABr, respectively as an OSDA. Isomorphous substitution of Fe for Si was demonstrated by UV-vis spectra and ac-NH3-TPD profiles. These analyses indicated that Fe atoms were incorporated into the lattice framework and that almost all of the Fe species were well-dispersed without forming bulky iron oxide particles. The ac-NH3-TPD profiles showed that the acid strength of the Fe-MTW zeolite was weaker than that of the Al-MTW zeolite. Al-MTW zeolites with different crystal sizes were applied to methanol-to-propylene reactions. The nanosized Al-MTW zeolite exhibited a longer catalyst life time compared to the macro-sized Al-MTW zeolite. Since decreasing the acid strength of the MTW zeolite inhibited excessive reactions followed by the formation of aromatics, the (Al, Fe)-MTW zeolite exhibited higher yields of propylene and butenes and a lower yield of aromatics compared with the Al-MTW zeolite.
  • Chi Van Nguyen, Yang-Chuang Chang, Takuya Yoshikawa, Takao Masuda, Kevin C. -W. Wu
    NANOSCIENCE AND NANOTECHNOLOGY LETTERS 8 3 273 - 276 2016年03月 [査読有り][通常論文]
     
    Here, we present a new catalytic system to produce 5-hydroxymethylfurfural (HMF) from cellulose under milder conditions (<140 degrees C). A high 5-hydroxymethylfurfural (HMF) yield of 45 mol% was achieved by direct hydrolysis, isomerization, and dehydration of cellulose in [BMIM] Cl at 120 degrees C for 2 h with the presence of CrCl3 center dot 6H(2)O as the catalyst. The optimized ratio of CrCl3 center dot 6H(2)O/boric acid was determined to be 10/50 mol% based on cellulose loading. We also found that when the reaction time was increased it would reduce HMF production and lead to the formation of levulinic acid and formic acid.
  • Hisaki Kondoh, Kumiko Tanaka, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    FUEL 167 288 - 294 2016年03月 [査読有り][通常論文]
     
    Heavy oil upgrading was examined over titania-zirconia mixed oxide (TiO2-ZrO2) catalysts using fixedbed flow-type reactors. Catalytic cracking of atmospheric residual oil (AR) and oil sand bitumen into lighter fuels such as gas oil and vacuum gas oil (VGO) was carried out in a superheated steam. The upgrading mechanisms were found to occur by carbon-carbon bond cleavage and naphthalene-ring opening caused by cracking, oxidation, or hydrogenolysis. The carbon-carbon bond cleavage reaction over acid sites is a well-known FCC (Fluid Catalytic Cracker) process, whereas coke formation on catalysts is a serious problem. Hence, repetition of the sequence of reactions over a short period of time and immediate regeneration of the catalyst is required. We previously developed a CeO2-ZrO2-Al2O3-FeOX iron oxide catalyst for heavy oil conversion into lighter fuels (Funai et al., 2010a, b; Kondoh et al., 2015). When this catalyst was applied to the degradation of heavy oil, the lattice oxygen in the catalyst was the main active site, and it decomposed the heavy oil through partial oxidative cracking. Although the catalyst showed a high upgrading activity, it was gradually deactivated due to carbon deposition. In contrast, we found TiO2-ZrO2 catalysts exhibited acidic cracking activity for heavy oil cracking under superheated steam conditions. In this study, we conducted experiments with TiO2-ZrO2 catalysts for upgrading heavy oil. The effect of the catalyst composition on the yield of the lighter fuels, catalyst activity, and stability after the reaction was examined. As a result, the yield of light fractions from AR decomposition reached 71 mol%-C when using a TiO2-ZrO2 catalyst comprising TiO2 and ZrO2 in equimolar amounts and the catalyst structure remained intact after the reaction. (C) 2015 Elsevier Ltd. All rights reserved.
  • Yaqi Zhang, Aya Hirata, Yuta Nakasaka, Teruoki Tago, Taichi Taniguchi, Takao Masuda
    MICROPOROUS AND MESOPOROUS MATERIALS 222 178 - 184 2016年03月 [査読有り][通常論文]
     
    MTW-type zeolite nanocrystal-layered membranes composed of nanocrystal and protection layers were successfully prepared by a secondary growth method under hydrothermal conditions. The separation abilities of the membranes during pervaporation were investigated by studying the separation of water from water/2-propanol solutions. Both the nanocrystal and protection layers were found to play important roles in the separation process. The crystal size and morphology of the MTW-type zeolite in the protection layer formed on the MTW nanocrystal layer could be controlled by varying the organic structure directing agent (OSDA), such that small crystals approximately 50 nm in size were obtained when using tetraethylammonium bromide as the OSDA. Membranes with nanometer-sized crystals in the protection layer exhibited 4 times higher water flux values and enhanced separation factor as compared with membranes having micrometer-sized crystals. In both layers, zeolite crystals with higher Al contents generated higher water fluxes due to their enhanced hydrophilicity. Moreover, the membranes with nanocrystal layer thicknesses of 7.5, 10, 12 and 17 mu m were prepared, and the water flux through the membranes was observed to increase as the nanocrystal layer thickness was decreased. (C) 2015 Elsevier Inc. All rights reserved.
  • Umer Khalil, Oki Muraza, Hisaki Kondoh, Gaku Watanabe, Yuta Nakasaka, Adnan Al-Amer, Takao Masuda
    FUEL 168 61 - 67 2016年03月 [査読有り][通常論文]
     
    Production of lighter hydrocarbons were maximized by steam-assisted catalytic cracking of heavy oil over silane treated Beta catalysts. Steaming environment may cause dealumination of zeolites and affect the stability of zeolites. Herein, we improved the hydrophobicity and stability of the Beta zeolite catalyst (SiO2/Al2O3 = 150) by modifying its surface using triphenyl silane through vapor phase deposition technique. Parent Beta and silane treated Beta catalysts were tested in fixed-bed flow reactor for steamassisted catalytic cracking of atmospheric residue. It was found that the modified Beta catalyst retained its crystallinity and phase purity after reaction. Moreover, coke formation was also reduced significantly over silane treated Beta catalysts. This indicates the increase in the stability of catalysts. Furthermore, the yields of gases, gasoline (C-7-C-13) and gas oil (C-14-C-20) over a silane treated Beta zeolite catalyst were 11.6 mol%, 55.7 mol% and 3.7 mol% respectively for 2 h reaction time. (C) 2015 Elsevier Ltd. All rights reserved.
  • Taichi Taniguchi, Keitaro Yoneta, Shota Nakaoka, Yuta Nakasaka, Toshiyuki Yokoi, Teruoki Tago, Takao Masuda
    CATALYSIS LETTERS 146 2 442 - 451 2016年02月 [査読有り][通常論文]
     
    A series of MFI aluminosilicate (Al-MFI), MFI ferrisilicate (Fe-MFI) and MFI ferroaluminosilicate ((Al,Fe)-MFI), with crystal sizes of approximately 100 nm, were synthesized using an emulsion method. UV-vis spectra and ac-NH3-TPD profiles confirmed the isomorphous substitution of Fe for Si into the MFI framework and showed that almost all Fe3+ species were well dispersed without forming bulky iron oxide particles. In addition, the presence of Bronstead acid sites in MFI ferroaluminosilicate, derived from both Al and Fe, was confirmed from IR spectra. The selective production of propylene from methanol was examined using MFI ferrisilicate with different crystal sizes. The nano-sized MFI ferrisilicate exhibited a longer catalyst lifetime and gave a higher propylene to ethylene ratio compared with the macro-sized MFI ferrisilicate. Although the weak acidity of the MFI ferrisilicate suppressed the formation of aromatics to a greater extent than was found with the MFI aluminosilicate, the former generated a lower propylene yield. The MFI ferroaluminosilicate gave a high propylene yield of 47.9 C-mol% together with a low aromatics yield of 1.9 C-mol%.Product yield for methanol conversion reaction at 723 K over nano-sized MFI aluminoferrisilicate.[GRAPHICS]
  • Umer Khalil, Oki Muraza, Hisaki Kondoh, Gaku Watanabe, Yuta Nakasaka, Adnan Al-Amer, Takao Masuda
    ENERGY & FUELS 30 2 1304 - 1309 2016年02月 [査読有り][通常論文]
     
    The surface of beta zeolite (SiO2/Al2O3 = 150) was modified using triphenyl silane in a liquid phase, and a series of catalysts was applied in cracking of heavy oil in the presence of steam. Steam reduces the coke formation, but at the same time, zeolite catalysts may be degraded in an aqueous environment at high temperatures. This problem was overcome using the surface-modified zeolite catalyst. The silane treatment of the zeolite surface not only reduced the coke amount but also stabilized the catalyst by increasing the hydrophobicity of the external surface of zeolite. Moreover, an atmospheric residue, which was used as a heavy oil feedstock, effectively decomposed into a lighter hydrocarbon (gasoline, kerosene, and gas oil) over silane-treated beta zeolite. Different reaction times were evaluated for modified beta zeolite in steam-assisted catalytic cracking of the atmospheric residue. The yield of the lighter hydrocarbon (C-7-C-35) was increased significantly up to 50.4 mol % in the product stream over silane-treated catalysts after 2 h of reaction time, while the gasoline production was increased to 35.4 mol % compared to 30.9 mol % over a parent beta catalyst. This indicates an improvement on the stability of beta catalysts after silane treatment.
  • Chi Van Nguyen, Yu-Te Liao, Ting-Cih Kang, Jeffrey E. Chen, Takuya Yoshikawa, Yuta Nakasaka, Takao Masuda, Kevin C. -W. Wu
    GREEN CHEMISTRY 18 22 5957 - 5961 2016年 [査読有り][通常論文]
     
    We report a metal-free catalysis of the aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acids (FDCA), employing zeolitic-imidazole framework (ZIF-8) derived, nitrogen-doped nanoporous carbon (denoted as NNC) as an effective heterogeneous catalyst. The effect of high graphitic nitrogen loading in the NNC on the catalytic production of FDCA was demonstrated and discussed.
  • Idris A. Bakare, Oki Muraza, Taichi Taniguchi, Teruoki Tago, Galal Nasser, Zain H. Yamani, Takao Masuda
    JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS 116 272 - 280 2015年11月 [査読有り][通常論文]
     
    Steam-assisted catalytic cracking is an interesting process to produce petrochemicals. Herein, we report the incorporation of lanthanum (La) into MIT zeolite to improve its stability in the presence of steam. A series of La modified MIT zeolite was prepared in a microwave-assisted ion-exchange. The activity of parent and modified MU zeolites have been investigated in the steam catalytic cracking of n-hexane. Both parent and La modified zeolites showed excellent selectivity to olefins in the steam-assisted catalytic cracking of n-hexane. The incorporation of La into the cation exchange sites of MIT zeolite enhanced its selectivity to light olefins, especially propylene. La-modified MIT zeolites exhibited better resistance to steam. The modification of MIT with a rare earth metal is a promising approach to improve the stability of aluminosilicate in steam-assisted reactions. (C) 2015 Elsevier B.V. All rights reserved.
  • Yuta Nakasaka, Jun-ichi Nishimura, Teruoki Tago, Takao Masuda
    CHEMICAL ENGINEERING JOURNAL 278 159 - 165 2015年10月 [査読有り][通常論文]
     
    Diffusivity and adsorption properties of n-hexane within coked MFI-type zeolites, the micropore volume, and number of acid sites were measured to investigate the deactivation mechanism of MFI-type zeolite during n-hexane cracking. The coked MFI-type zeolite was prepared by n-hexane cracking over the zeolite at 923 K. The diffusivity and adsorption isotherm of n-hexane within the coked zeolite was obtained using the constant volume method. Micropore volume and acid sites number of the coked zeolite decreased with increasing coke loading, resulting in a decrease in n-hexane adsorption on the coked zeolite. In contrast, intracrystalline diffusivity of n-hexane within the coked zeolite increased with coke loading, and effective diffusivity remained constant regardless of coke loading. Coke formation on the acid site inside the zeolite pores caused a decrease in n-hexane adsorption onto the acid site, resulting in geometrical limitations that promoted the major mass transfer resistance. Effect of diffusivity on MFI-type zeolite deactivation during n-hexane cracking was small. The main cause of the deactivation was considered to be a decrease in reaction rate due to the decrease in the number of acid sites for n-hexane cracking by coke formation. (C) 2014 Elsevier B.V. All rights reserved.
  • Yaqi Zhang, Yuta Nakasaka, Teruoki Tago, Aya Hirata, Yuki Sato, Takao Masuda
    MICROPOROUS AND MESOPOROUS MATERIALS 207 39 - 45 2015年05月 [査読有り][通常論文]
     
    Mordenite nanocrystal-layered membranes consisting of a mordenite nanocrystal layer and protection layer were successfully prepared. The obtained mordenite membranes were applied to the separation of water from water/organic solutions (organic solvents: ethanol, acetone, iso-propanol, or acetic add) using a pervaporation method at temperatures from 60 to 100 degrees C. Water permeance through the mordenite membrane in each water/organic solution system was almost identical regardless of organic solvent types in the feed solution. In contrast, the permeance of the organic molecules depended on their polarities. The pre-aging temperature of the mother liquid and the heating rate for formation of the protection layer affected the secondary growth process that formed the protection layer, leading to different morphologies and sizes of the crystals in the protection layer. Water flux increased with decreasing crystal size in the protection layer because the number of non-zeolitic pores among the mordenite crystal increased as the crystal size decreased. (C) 2015 Elsevier Inc. All rights reserved.
  • Oki Muraza, Adedigba Abdul-lateef, Teruoki Tago, Asep B. D. Nandiyanto, Hiroki Konno, Yuta Nakasaka, Zain H. Yamani, Takao Masuda
    MICROPOROUS AND MESOPOROUS MATERIALS 206 136 - 143 2015年04月 [査読有り][通常論文]
     
    There is an increased demand for facile and rapid synthesis of one-dimensional pore zeolites with controlled crystal size in the nanometer range. Here, we report for the first time, the rapid synthesis of ZSM-22 (TON) by using microwave-assisted hydrothermal synthesis (MAHyS) to control nucleation and growth. ZSM-22 crystals were synthesized rapidly in 24 h (instead of 72 h in conventional synthesis). Effect of synthesis time under microwave irradiation on the crystallinity of TON zeolites from 8 to 24 h was investigated. The conventional hydrothermal synthesis was used for comparison. Under microwave-assisted synthesis, uniform crystal size with lower crystal aspect-ratio (length/width) was obtained and high agglomeration was prevented. Surface modification was applied by deposition of silica on the external surface of ZSM-22 using catalytic cracking of diphenyl silane. The protonated H-ZSM-22 prepared by the MAHyS and the surface-modified TON zeolites were applied in catalytic cracking of n-hexane. The modified MAHyS zeolites showed superior selectivity to propylene and lower selectivity to aromatics. Stability against deactivation was clearly observed over surface-modified ZSM-22 zeolites. The physico-chemical properties of modified zeolite-catalysts were characterized by using XRD, FE-SEM, N-2 adsorption-desorption, Al-27 MAS NMR and NH3-TPD. (C) 2014 Elsevier Inc. All rights reserved.
  • 近藤永樹, 中坂佑太, 多湖輝興, 増田隆夫
    J Jpn Inst Energy 94 1 67 - 73 2015年01月20日 [査読無し][通常論文]
  • 増田隆夫, 中坂佑太, 吉川琢也, 多湖輝興
    アロマティックス 66 242 - 251 2014年11月25日 [査読無し][通常論文]
  • A. K. Jamil, O. Muraza, M. Sanhoob, T. Tago, H. Konno, Y. Nakasaka, T. Masuda
    JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS 110 110 338 - 345 2014年11月 [査読有り][通常論文]
     
    Valorization Of naphtha, a derived intermediate from crude oil is still a crucial subject. Here we report an effort to control catalytic cracking of naphtha using nanosized TON zeolite, which was synthesized by microwave assisted hydrothermal synthesis (MAHyS) in the presence of polyoxyethylene-based surfactant. The effects polyoxyethylene (POE) surfactant on the crystal size, morphology and the crystal aspect-ratio were studied. The crystals with lengths in the range of 90-300 nm were obtained. The addition of polyoxyethylene surfactant reduced the agglomeration rate of ZSM-22 zeolite crystals. The. polyoxyethylene surfactant was added with POE/Al from 2.5 to 10. Effect of Si/Al in the presence of POE surfactant was studied by changing the Si/AI ratio from 45 to 80. Naphtha was simulated using a model compound, n-hexane. Excellent selectivity toward propylene was obtained over ZSM-22 zeolite crystals in n-hexane cracking. High selectivity to propylene was maintained over different size of ZSM-22 zeolite crystals. Decreasing crystal length from 300 to 90nm considerably increased the catalytic activity of ZSM-22 crystals. (C) 2014 Elsevier B.V. All rights reserved.
  • Oki Muraza, Idris A. Bakare, Teruoki Tago, Hiroki Konno, Taichi Taniguchi, Adnan M. Al-Amer, Zain H. Yamani, Yuta Nakasaka, Takao Masuda
    FUEL 135 135 105 - 111 2014年11月 [査読有り][通常論文]
     
    Catalytic cracking of naphtha over one-dimensional (1D) pore zeolite was targeted by using n-hexane as a model compound. Novel hierarchical H-ZSM-23 (MTT), a 1D pore zeolite, was specially designed to maximize propylene yield from catalytic cracking. Very high propylene-to-ethylene ratio of 2.5 was achieved. The ZSM-23 with mesopores displayed an enhanced deactivation resistance compared to microporous parent crystals. Hierarchical ZSM-23 was synthesized rapidly by applying microwave-assisted hydrothermal synthesis (MAHyS) followed by microwave-assisted alkaline treatment and moderate acid treatment. Pore volume of hierarchical ZSM-23 was improved considerably compared with the ones of parent crystals. Physico-chemical properties of hierarchical ZSM-23 were studied by characterization techniques such as XRD, FE-SEM, N-2 adsorption-desorption, Al-27 and Si-29 MAS NMR, NH3-TPD, and TEM. (C) 2014 Elsevier Ltd. All rights reserved.
  • Takao Masuda, Teruoki Tago, Takuya Yoshikawa
    Applied Mechanics and Materials 625 311  Trans Tech Publications 2014年09月 [査読有り][通常論文]
  • 多湖 輝興, 中坂 佑太, 増田 隆夫
    Journal of the Japan Petroleum Institute 57 5 197 - 207 The Japan Petroleum Institute 2014年09月 [査読無し][通常論文]
     
    酸化鉄系触媒によるグリセロールからの有用化学物質合成を実施した。反応実験は反応温度623 K,常圧下,固定床流通式反応器にて実施した。グリセロールからの有用化学物質転換反応では,主にアリルアルコール,プロピレン,ケトン類が得られた。これらの有用化学物質は反応経路I(アリルアルコール,プロピレン)と反応経路II(ヒドロキシアセトン,アクロレイン)に従って生成し,経路IIに含まれるヒドロキシアセトンは容易にカルボン酸へと転化し,カルボン酸のケトン化反応によりケトンへと転化された。W/F値(触媒量/供給原料比)を増加させると,アリルアルコールからのプロピレン生成,およびカルボン酸からのケトン生成の各逐次反応が進行し,生成物はプロピレン(収率約24 mol%-Carbon)とケトン類(収率約25 mol%-Carbon)に収束した。また,アルカリ金属を触媒に添加することにより,アリルアルコールの収率が効果的に向上することを見出した。本論文では,試薬グリセリン,および粗製グリセリンからの有用化学物質合成を報告するとともに,触媒組成と反応条件が生成物収率に及ぼす影響を反応機構の観点から議論する。
  • 多湖 輝興, 中坂 佑太, 増田 隆夫
    Journal of the Japan Petroleum Institute 57 5 197 - 207 石油学会 2014年09月 [査読有り][通常論文]
     
    Catalytic conversion of glycerol with iron oxide-based catalysts was investigated for the production of useful chemicals. The catalytic reaction was carried out in a fixed-bed flow reactpr at 623 K under atmospheric Pressure. Useful chemicals such as allyl-alcohol, propylene and ketones were produced from glycerol through two main pathways: formation of allyl alcohol and propylene (Pathway I), and formation of hydroxyacetone and acrolein (Pathway II). Hydroxyacetone in Pathway II is easily converted into carboxylic acids followed by ketonization to form acetone, methyl ethyl ketone and pentanone. An increase in the W/F (weight ratio of catalyst to feedstock) value allowed the consecutive reactions to progress and the final products were 24 mol%-carbon of propylene and 25 mol%-carbon of ketones. Moreover, addition of alkaline metals to the catalyst increased the yield of allyl alcohol. This study demonstrates the production of useful chemicals from glycerol (crude glycerol and reagent glycerol). The effects of catalyst composition and experimental conditions on these yields are discussed, based on investigations of the reaction pathways and mechanisms.
  • Mohammed Sanhoob, Old Muraza, Zain H. Yamani, Eid M. Al-Mutairi, Teruoki Tago, Belabbes Merzougui, Takao Masuda
    MICROPOROUS AND MESOPOROUS MATERIALS 194 194 31 - 37 2014年08月 [査読有り][通常論文]
     
    The effect of synthesis parameters on morphology of ZSM-12 (MTW) zeolite with tetra ethyl ammonium bromide (TEABr) as an organic-structure directing agent was investigated systematically. Aluminum sulfate octahydrate (Al-2(SO4)(3)center dot 18H(2)O) was used as an aluminum (Al) source. The Si/Al ratio was varied from 40 to 180 and alkalinity ratio (NaOH/Si) was set between 0.132 and 0.160. Effects of crystallization temperature and time were studied. The contribution of the aging period on the final morphology of ZSM-12 was investigated in the range of 1.5-6 h. Phase identification of as-synthesized ZSM-12 was confirmed by X-ray diffraction and morphology of crystals was studied by electron microscopy. The alkalinity was one of the most substantial factors that induced the formation of ZSM-5 (MFI) nuclei as a competing phase. Pure ZSM-12 was obtained with Si/Al of 80 at 145 degrees C. Different agglomeration shapes of ZSM-12 were observed by changing Si/Al ratio. Prolonged aging time up to 6 h induced the formation of ZSM-5 nuclei. (C) 2014 Published by Elsevier Inc.
  • Dieni Mansur, Teruoki Tago, Takao Masuda, Haznan Abimanyu
    BIOMASS & BIOENERGY 66 66 275 - 285 2014年07月 [査読有り][通常論文]
     
    Recently, much attention has been devoted the generation of useful chemicals from biomass. Cacao pod husks, a waste biomass, are one of the agricultural crop residues that can be utilized for this purpose. The husks were treated by pyrolysis to produce pyrolysis oil that contained several chemical compounds such as ketones, carboxylic acids, aldehydes, furans, heterocyclic aromatics, alkyl benzenes, phenols and benzenediols. Therefore, this biomass-derived pyrolysis oil is potentially a rich source of useful chemicals. The pyrolysis oil was upgraded over iron oxide catalysts. During the catalytic upgrade, ketonizadon, selective oxidation and demethoxylation reactions occurred and selectively produced aliphatic ketones (acetone, 2-butanone), phenol and alkyl phenols (cresol, xylenol, ethylphenol). (C) 2014 Elsevier Ltd. All rights reserved.
  • 横井俊之, 増田隆夫, 辰巳敬
    ペトロテック 37 4 290 - 295 2014年04月01日 [査読無し][通常論文]
  • Hiroki Konno, Teruoki Tago, Yuta Nakasaka, Gaku Watanabe, Takao Masuda
    APPLIED CATALYSIS A-GENERAL 475 127 - 133 2014年04月 [査読有り][通常論文]
     
    In the acetone to olefins (ATO) reaction using ZSM-5 zeolites, isobutylene is initially produced via decomposition of an acetone dimer, followed by dimerization of the isobutylene and its cracking to form ethylene and propylene. Nano-scale ZSM-5 zeolite exhibited stable activity during the ATO reaction compared with that of macro-scale ZSM-5.1n order to further improve the catalytic stability of the nano-scale ZSM-5, control of the acidity of nano-scale ZSM-5 zeolites through SiO2 unit formation was examined using phenyl silane and triphenyl silane as new deactivators. This modification led to an increase in the olefins yield and an improvement in the catalyst lifetime. In particular, the regioselective deactivation of acid sites located on the external surface of the zeolite inhibits the formation of aromatics. Moreover, the acidity control within the pores significantly improved the catalyst lifetime. Notably, the modified nano-scale ZSM-5 zeolite exhibited a stable olefins yield above 55C-mol% for 180h. (C) 2014 Elsevier B.V. All rights reserved.
  • Aya Konaka, Teruoki Tago, Takuya Yoshikawa, Ayaka Nakamura, Takao Masuda
    APPLIED CATALYSIS B-ENVIRONMENTAL 146 267 - 273 2014年03月 [査読有り][通常論文]
     
    The catalytic conversion of glycerol was performed with iron oxide-based catalysts for production of allyl alcohol using a fixed-bed flow reactor at 623 K under atmospheric pressure. The glycerol dehydration proceeds on acid sites of catalysts while the allyl alcohol production is assumed to be catalyzed by non-acidic sites of catalysts through a hydrogen transfer mechanism. Different alkali metals, including Na, K, Rb, and Cs were supported on ZrO2-FeOx and all of them gave impressively higher allyl alcohol yield and suppressed glycerol dehydration due to the reduced catalyst acidic property. K-supported ZrO2-FeOx (K/ZrO2-FeOx) was chosen for further studies, and allyl alcohol yield remarkably increased up to 27 mol% C at the K content of 3-5 mol%. Since no external hydrogen gas is supplied to the system, the hydrogen transfer mechanism should take place between the reaction of glycerol and either hydrogen atoms derived from formic acid forming during the reaction, or active hydrogen species produced from the decomposition of H2O by ZrO2.Addition of Al2O3 to K/ZrO2-FeOx (K/Al2O3-ZrO2-FeOx) was examined in order to improve structure stability during the glycerol conversion. Al2O3 addition to the catalyst was effective to achieve higher structure stability, leading to high glycerol conversion with stable allyl alcohol yield of above 25 mol% C. Moreover, K/Al2O3-ZrO2-FeOx can be applicable to the conversion of crude glycerol which is the waste solution obtained from biodiesel production. (C) 2013 Elsevier B.V. All rights reserved.
  • Takuya Yoshikawa, Satoshi Shinohara, Taichi Yagi, Naonori Ryumon, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    APPLIED CATALYSIS B-ENVIRONMENTAL 146 146 289 - 297 2014年03月 [査読有り][通常論文]
     
    A two-step process consisting of depolymerization and catalytic cracking without hydrogen addition was carried out to produce phenols from lignin. In the first step, lignin was depolymerized using a silica-alumina catalyst in a water/1 -butanol solution at 623 K for 2 h. After the reaction, lignin-derived slurry liquid was obtained in 67 C-mol% yield. From the model studies, it was considered that lignin was mainly depolymerized via hydrolysis of aryl ether bonds between lignin units. For the second step, the catalytic reaction of the 1-butanol phase of the slurry liquid was carried out over an iron oxide catalyst using a high pressure fixed-bed flow reactor at 673 K. The catalytic reaction under high pressure steam conditions was effective for the suppression of the formation of solid products. In addition, the recovery fraction of phenols increased as the F-H2O/F value (the flow rate ratio of steam to the slurry liquid) increased, resulting in 17% of phenols at F-H2O/F = 5 for 2-4h. From the model studies and our previous results, catechol and methoxyphenol in the slurry liquid were considered to be converted into phenols, cresols and other alkyl phenols over the iron oxide catalyst. (C) 2013 Elsevier B.V. All rights reserved.
  • Kaori Ishida, Shiho Matsuda, Masaru Watanabe, Haruyuki Kitajima, Aya Kato, Masayuki Iguchi, Taku M. Aida, Richard Lee Smith, Xinhua Qi, Teruoki Tago, Takao Masuda
    Biomass Conversion and Biorefinery 4 4 323 - 331 2014年 [査読有り][通常論文]
     
    Selective glucose production by cellulose hydrolysis with initial or sequential water addition in the presence of solid acid catalysts in 1-butyl-3-methyl-imidazolium chloride ([bmIm][Cl]) under microwave irradiation was investigated at 120 °C and 1.2 MPa of N2 atmosphere. For revealing the effect of water on cellulose hydrolysis in [bmIm][Cl], the phase behavior during the reaction was observed. Colored compounds formed at lower amounts of water, while some amounts of cellulose precipitated at higher amounts of water. Glucose yield was highest (65 mol%) at 25 wt% water in [bmIm][Cl] for the case of initial water addition. To improve the glucose yield, sequential water addition in which water was added in steps as the reaction proceeded was examined. Glucose yields in the presence of Amberlyst-15 in [bmIm][Cl] were 68.5 and 75.0 mol% by two-step and three-step water addition, respectively. Employing three-step water addition, Dowex 50wx8-100 (ion-exchange resin), hydrothermally synthesized carbon catalyst and three types of nano-zeolites were assessed. The carbon catalyst-modified fuming sulfuric acid and H-type zeolites (mordenite and faujasite) gave comparable glucose yields as Amberlyst-15. Sequential water addition is an effective technique for improving reaction efficiency in cellulose/solid acid catalyst/ionic liquid reaction systems.
  • Takao Masuda, Teruoki Tago, Takuya Yoshikawa
    PROCESS AND ADVANCED MATERIALS ENGINEERING 625 311 - + 2014年 [査読有り][通常論文]
     
    We developed iron-oxide catalysts for producing petroleum-related chemicals from inedible biomass wastes containing water by oxidative cracking. These catalysts composed basically of iron-oxide and zirconia. The usefulness of the catalysts was examined by the reactions of several inedible biomass wastes, such as palm waste, livestock excreta, fermentation residue, raw glycerin, raw bioethanol and lignin. It was found that ketones, mainly acetone, were produced from palm waste, livestock excreta, fermentation residue and raw bioethanol at high yields. Phenol was obtained from palm waste. In the case of raw glycerin, even if high contents of alkali, allyl-alcohol, propene and acetone were successfully produced. Furthermore, phenols could be recovered from lignin.
  • Hiroki Konno, Ryota Ohnaka, Jun-ichi Nishimura, Teruoki Tago, Yuta Nakasaka, Takao Masuda
    CATALYSIS SCIENCE & TECHNOLOGY 4 12 4265 - 4273 2014年 [査読有り][通常論文]
     
    The catalytic cracking of model naphthenes (cyclohexane and methylcyclohexane) over ZSM-5 zeolites of different crystal sizes (macro-and nano-ZSM-5) was examined at reaction temperatures ranging from 748 to 923 K under atmospheric pressure, focusing on the associated reaction rate constants and activation energies. The catalytic cracking was found to follow first-order kinetics with respect to the naphthene concentrations and the activation energies for cyclohexane and methylcyclohexane cracking over nano-ZSM- 5 were determined to be 119 and 116 kJ mol(-1), respectively. In order to elucidate the rate-limiting step in the cracking process, the Thiele modulus and the effectiveness factor obtained from cracking over the two ZSM-5 zeolites were evaluated. Cracking with nano-ZSM-5 proceeded under reaction-limiting conditions, whereas the reaction over macro-ZSM-5 at 923 K took place under transition conditions between reaction-and diffusion-limiting. Nano-ZSM-5 was applied to the catalytic cracking of a model naphtha and the results demonstrated that this catalyst was both effective and stable and generated a high yield of light olefins.
  • 増田隆夫, 多湖輝興, 中坂佑太, 大庭潔
    化学工学 77 12 862 - 866 2013年12月05日 [査読無し][通常論文]
  • Yuta Nakasaka, Takuya Okamura, Hiroki Konno, Teruoki Tago, Takao Masuda
    MICROPOROUS AND MESOPOROUS MATERIALS 182 182 244 - 249 2013年12月 [査読有り][通常論文]
     
    A kinetic study of n-hexane cracking over MFI-type zeolite was conducted in the temperature range from 748 to 923 K using a fixed-bed flow reactor under atmospheric pressure. The n-hexane cracking reaction exhibited first-order kinetics with respect to n-hexane concentration. In contrast, the activation energy for n-hexane cracking at high temperatures (823-923 K) was greater than that at low temperatures (748-823 K) because the major reaction mechanism shifted from monomolecular cracking to bimolecular cracking as reaction temperature decreased. Crystal size of the MFI-type zeolite needed to achieve reaction-control conditions, in which the active sites within zeolite are fully utilized during n-hexane cracking, was investigated using the kinetic data. The effect of crystal size and Si/Al ratio of the zeolite on the rate-limiting step of the n-hexane cracking could be expressed using the Thiele modulus. Results indicated that the size of the zeolite must be less than several hundred nanometers for the reaction to proceed under reaction-control conditions. (C) 2013 Elsevier Inc. All rights reserved.
  • Aya Konaka, Teruoki Tago, Takuya Yoshikawa, Hirofumi Shitara, Yuta Nakasaka, Takao Masuda
    Industrial and Engineering Chemistry Research 52 15509 - 15515 2013年11月 [査読有り][通常論文]
     
    In this study, catalytic conversion of crude glycerol was performed over ZrO2-FeOx catalysts for the production of useful chemicals. A crude glycerol solution obtained from biodiesel production was used as a feedstock, and a catalytic reaction was carried out in a fixed-bed flow reactor at 623 K under atmospheric pressure. The reaction was found to involve a series of consecutive reactions in which allyl alcohol, propylene, hydroxyacetone, carboxylic acids, acrolein, and ketones are included as intermediate and terminated products. Although the crude glycerol contained methanol, free-fatty acids, and potassium as impurities, using a ZrO 2-FeOx catalyst, the glycerol in the feedstock converted into these useful chemicals, the composition of which were identical regardless of the crude glycerol concentration. Moreover, an increase in the W/F (weight ratio of catalyst to feedstock) value allowed the consecutive reactions to progress, and the products were summed up in 24 mol % C of propylene and 25 mol % C of ketones. © 2013 American Chemical Society.
  • 多湖輝興, 吉川琢也, 中坂佑太, 増田隆夫
    触媒 55 5 270 - 275 2013年10月10日 [査読無し][通常論文]
  • Hiroki Konno, Teruoki Tago, Yuta Nakasaka, Ryota Ohnaka, Jun-ichi Nishimura, Takao Masuda
    MICROPOROUS AND MESOPOROUS MATERIALS 175 25 - 33 2013年07月 [査読有り][通常論文]
     
    The catalytic cracking of representative hydrocarbons of naphtha (n-hexane, cyclohexane, and methyl-cyclohexane) over ZSM-5 zeolite catalysts was examined at reaction temperatures ranging from 823 K to 923 K under atmospheric pressure. It was found that the Si/Al ratio of the zeolite affected the product selectivity and conversion. In order to investigate the effects of the crystal size of the ZSM-5 zeolites on catalyst lifetime, macro- and nano-scale ZSM-5 (Si/Al = 150) with crystal sizes of 2300 nm and 90 nm, respectively, were used for the cracking of representative naphtha hydrocarbons. In the cracking of naphthenes (cyclohexane and methyl-cyclohexane), coke was readily formed from the beginning of the reaction leading to significant deactivation of the catalyst for the macro-scale ZSM-5. In contrast, the nano-scale ZSM-5 exhibited a high conversion and high light olefins yield with stable activity, regardless of the type of reactant. As a result, the application of nano-scale ZSM-5 zeolites to the catalytic cracking of naphtha was effective and gave light olefins with high yield and excellent stable activity. (C) 2013 Elsevier Inc. All rights reserved.
  • Hiroki Konno, Teruoki Tago, Yuta Nakasaka, Ryota Ohnaka, Jun-ichi Nishimura, Takao Masuda
    MICROPOROUS AND MESOPOROUS MATERIALS 175 175 25 - 33 2013年07月 [査読有り][通常論文]
     
    The catalytic cracking of representative hydrocarbons of naphtha (n-hexane, cyclohexane, and methyl-cyclohexane) over ZSM-5 zeolite catalysts was examined at reaction temperatures ranging from 823 K to 923 K under atmospheric pressure. It was found that the Si/Al ratio of the zeolite affected the product selectivity and conversion. In order to investigate the effects of the crystal size of the ZSM-5 zeolites on catalyst lifetime, macro- and nano-scale ZSM-5 (Si/Al = 150) with crystal sizes of 2300 nm and 90 nm, respectively, were used for the cracking of representative naphtha hydrocarbons. In the cracking of naphthenes (cyclohexane and methyl-cyclohexane), coke was readily formed from the beginning of the reaction leading to significant deactivation of the catalyst for the macro-scale ZSM-5. In contrast, the nano-scale ZSM-5 exhibited a high conversion and high light olefins yield with stable activity, regardless of the type of reactant. As a result, the application of nano-scale ZSM-5 zeolites to the catalytic cracking of naphtha was effective and gave light olefins with high yield and excellent stable activity. (C) 2013 Elsevier Inc. All rights reserved.
  • Oki Muraza, Idris A. Bakare, Teruoki Tago, Hiroki Konno, Abdul-lateef Adedigba, Adnan M. Al-Amer, Zain H. Yamani, Takao Masuda
    CHEMICAL ENGINEERING JOURNAL 226 367 - 376 2013年06月 [査読有り][通常論文]
     
    The nucleation and growth of MTT zeolite, an important 10-membered ring (10 MR) zeolite, was controlled by a microwave-assisted hydrothermal synthesis. The effect of irradiation time (12,18, and 24 h), seed-assisted synthesis with 1 wt.% seeds for 6 h and desilication under microwave irradiation on crystallinity and porosity were investigated. Under microwave-assisted synthesis, uniform crystal size, with lower crystal aspect-ratio and suppressed phase-impurity has been obtained. The tendency of column-like crystal to form bundle of columns was reduced significantly. Seeded growth further reduced synthesis time to 6 h. Post-synthetic treatment was used to obtain larger pore volume of MTT zeolites. Some of the protonated MTT samples were tested in n-hexane cracking as model reaction. Characterization techniques such as XRD, FE-SEM, N-2 adsorption-desorption, Al-27 MAS NMR and NH3-TPD have been carried out to obtain insight in the physico-chemical properties of zeolite catalysts. (C) 2013 Elsevier B.V. All eights reserved.
  • Takuya Yoshikawa, Taichi Yagi, Satoshi Shinohara, Tetsuya Fukunaga, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    FUEL PROCESSING TECHNOLOGY 108 69 - 75 2013年04月 [査読有り][通常論文]
     
    Production of phenols from lignin was investigated using a new conversion process consisting of two reaction steps. In the first step, depolymerization of lignin was carried out in an autoclave reactor using a silica-alumina catalyst in a water/1-butanol solution. The yield of lignin-derived liquid product reached 85-88 C-mol% under the appropriate reaction conditions. In the second step, catalytic cracking of the liquid products from the first step was carried out using a fixed-bed flow reactor over an iron oxide catalyst. With this method, total recovered fraction of phenols and the conversion of methoxy phenol reached 6.6-8.6% and 92-94%, respectively. (C) 2012 Elsevier B.V. All rights reserved.
  • Dieni Mansur, Mana Shimokawa, Kiyoshi Oba, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    Fuel Processing Technology 108 139 - 145 2013年 [査読有り][通常論文]
     
    Many countries develop ethanol from biomass by fermentation because ethanol is one of the current alternative fuels in use. This process uses biomass such as corn, wheat, and irregular wheat as feedstock. Production of ethanol from cereal grains generates stillage as a fermentation residue. The stillage mainly contains proteins and unconverted carbohydrates. Both of these components have a potential to produce organic chemicals with lower molecular weight. The stillage derived from fermentation of irregular wheat for ethanol production was converted into aliphatic ketones by a two-step process of hydrothermal treatment followed by catalytic reaction over a ZrO2-FeOX catalyst. During hydrothermal treatment, the stillage was converted into oxygen-containing liquid tar that consisted of cyclic compounds containing nitrogen atoms, aromatics, ketones, ethers, esters, carboxylic acids, aldehydes, and some undetectable compounds. The ZrO2-FeOX has been considered as an appropriate catalyst to produce aliphatic ketones from oxygen-containing tar. Catalytic reaction of the liquid tar over the catalyst, cyclic compounds containing nitrogen atoms were converted into heavy components because of polymerization reaction. Meanwhile, esters and carboxylic acids were converted into aliphatic ketones via hydrolysis, oxidation, and ketonization reactions. As a result, aliphatic ketones were selectively produced from the fermentation stillage by the two-step process. © 2012 Elsevier B.V. All rights reserved.
  • Dieni Mansur, Mana Shimokawa, Kiyoshi Oba, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    Fuel Processing Technology 108 108 139 - 145 2013年 [査読有り][通常論文]
     
    Many countries develop ethanol from biomass by fermentation because ethanol is one of the current alternative fuels in use. This process uses biomass such as corn, wheat, and irregular wheat as feedstock. Production of ethanol from cereal grains generates stillage as a fermentation residue. The stillage mainly contains proteins and unconverted carbohydrates. Both of these components have a potential to produce organic chemicals with lower molecular weight. The stillage derived from fermentation of irregular wheat for ethanol production was converted into aliphatic ketones by a two-step process of hydrothermal treatment followed by catalytic reaction over a ZrO2-FeOX catalyst. During hydrothermal treatment, the stillage was converted into oxygen-containing liquid tar that consisted of cyclic compounds containing nitrogen atoms, aromatics, ketones, ethers, esters, carboxylic acids, aldehydes, and some undetectable compounds. The ZrO2-FeOX has been considered as an appropriate catalyst to produce aliphatic ketones from oxygen-containing tar. Catalytic reaction of the liquid tar over the catalyst, cyclic compounds containing nitrogen atoms were converted into heavy components because of polymerization reaction. Meanwhile, esters and carboxylic acids were converted into aliphatic ketones via hydrolysis, oxidation, and ketonization reactions. As a result, aliphatic ketones were selectively produced from the fermentation stillage by the two-step process. © 2012 Elsevier B.V. All rights reserved.
  • Dieni Mansur, Takuya Yoshikawa, Koyo Norinaga, Jun-Ichiro Hayashi, Teruoki Tago, Takao Masuda
    Fuel 103 103 130 - 134 2013年01月 [査読有り][通常論文]
     
    Catalytic upgrading of pyroligneous acid, by-product from slow pyrolysis of woody biomass for char production, was carried out using zirconia-supported iron-oxide catalysts under a steam atmosphere at temperatures ranging from 623 to 723 K, and the effect of ZrO2 content in the ZrO 2-FeOX catalysts on catalytic activity and ketone yields was investigated. It was demonstrated that hydroxyacetone and carboxylic acids (acetic and propionic acids) in the pyroligneous acid were converted into aliphatic ketones (acetone and 2-butanone) via a ketonization reaction over the ZrO2-FeOX catalyst. However, reaction inhibition by metal impurities in the pyroligneous acid such as potassium (K) and magnesium (Mg) was also observed. These metal impurities could be removed from the pyroligneous acid without changing the organic composition by using an ion-exchange resin. The removal of the metal impurities was effective in increasing the ketone yields. Moreover, as the W/F value (W: Amount of catalyst, and F: Flow rate of the pyroligneous acid in the feed) increased, the ketone yield increased up to approximately 30 C mol%, and the ketone fraction in the liquid product reached 55 C mol%. © 2012 Elsevier Ltd. All rights reserved.
  • Yuta Nakasaka, Teruoki Tago, Hiroki Konno, Akihiro Okabe, Takao Masuda
    CHEMICAL ENGINEERING JOURNAL 207 368 - 376 2012年10月 [査読有り][通常論文]
     
    Kinetic analysis of burning regeneration of coked MFI-type zeolite obtained by catalytic cracking of n-hexane was studied using a multiple-reaction model. Hydrogen contained in the coke was oxidized faster than carbon, and subsequently carbon remaining after the hydrogen combustion was gradually oxidized. Reaction rates of carbon and hydrogen correlated with the Arrhenius equation: and activation energies for the combustion of carbon and hydrogen were 156 kJ/mol and 140 kJ/mol, respectively, regardless of the coke loading. Regeneration of coked MFI-type zeolite in the fixed-bed reactor was simulated numerically using reaction rates obtained from the kinetic analysis. The numerical result for changes in gas composition with time at the reactor outlet agreed well with the experimental results. Axial distribution of the temperature and concentration of water vapor in the catalyst bed was obtained numerically and results showed that the temperature and water vapor near the outlet were higher than other location in the reactor. (C) 2012 Elsevier B.V. All rights reserved.
  • Hiroki Konno, Takuya Okamura, Takahito Kawahara, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    CHEMICAL ENGINEERING JOURNAL 207 490 - 496 2012年10月 [査読有り][通常論文]
     
    The catalytic cracking of n-hexane over ZSM-5 zeolite (MFI-type zeolite, Si/Al = 150 and 240) catalysts was examined at reaction temperatures ranging from 823 to 923 K under atmospheric pressure. The reaction rate constants and activation energies of n-hexane cracking over ZSM-5 zeolites with various crystal sizes and Si/Al ratios were evaluated. The catalytic cracking of n-hexane was first order with respect to the n-hexane concentration, and the activation energies of n-hexane cracking over ZSM-5 zeolites were found to be approximately 123-128 kJ mol(-1). Compared with the macro-sized zeolite, the nano-sized zeolites exhibited high n-hexane conversion with stable activity for 50 h. This is because the cracking reaction with nano-sized zeolite proceeded under reaction-limiting conditions, whereas the reaction with macro-sized zeolite proceeded under transition conditions between reaction- and diffusion-limiting conditions. As a result, the application of nano-zeolite to the catalytic cracking of n-hexane was effective and gave light olefins with high yield and excellent stable activity. (C) 2012 Elsevier B.V. All rights reserved.
  • Teruoki Tago, Hiroki Konno, Yuta Nakasaka, Takao Masuda
    CATALYSIS SURVEYS FROM ASIA 16 3 148 - 163 2012年09月 [査読有り][通常論文]
     
    For the application of zeolites as heterogeneous catalysts, low diffusion resistance for hydrocarbons within the micropore is essential for improving product selectivity and catalyst lifetime. This problem has been overcome by reducing the crystal size. This review introduces size-controlled preparation of nano-sized zeolites via hydrothermal synthesis in water/surfactant/organic solvent (emulsion method) and their application to heterogeneous catalysts. The ionicity of the hydrophilic group in surfactant molecules and the concentration of the Si source affected the crystallinity and morphology of zeolites prepared using the emulsion method. When using a non-ionic surfactant, mono-dispersed silicalite-1 nanocrystals similar to 60 nm in diameter were successfully prepared. Nano- and macro-ZSM-5 zeolites with crystal sizes of similar to 150-200 nm and 1.5 mu m, respectively, were prepared and applied to n-hexane cracking and acetone-to-olefin reactions to investigate the effect of zeolite crystal size on catalytic stability and light olefin yield. Application of nano-zeolite to light olefin production was effective in achieving faster mass transfer of hydrocarbon molecules within the micropore, which led to improvements in olefin yields and catalyst lifetime.
  • Koyama Yoshihito, Ryumon Naonori, Yoshikawa Takuya, Nakasaka Yuta, Tago Teruoki, Masuda Takao
    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY 244 2012年08月19日 [査読有り][通常論文]
  • Teruoki Tago, Yuta Nakasaka, Takao Masuda
    Zeolites: Synthesis, Chemistry and Applications 171 - 190 2012年08月01日 [査読無し][通常論文]
  • Hiroki Konno, Takuya Okamura, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    JOURNAL OF THE JAPAN PETROLEUM INSTITUTE 55 4 267 - 274 2012年07月 [査読有り][通常論文]
     
    Catalytic cracking of n-hexane over MFI-type zeolite catalysts was examined at a reaction temperature of 823 K under atmospheric pressure. Conversion of n-hexane depended on the Si/Al ratio of the MFI-type zeolite catalyst, so the relationships between the product yields and n-hexane conversion could be fitted as single, smooth curves. To investigate the effect of crystal size of MFI-type zeolite on the catalytic activity, light olefin yield and product composition, nano- and macro-sized MFI-type zeolites with crystal sizes of approximately 150-200 nm and 1.5 mu m, respectively, were prepared. The nano-sized zeolite exhibited a high n-hexane conversion with stable activity for 18 h compared with the macro-sized zeolite. The high activity of the nano-sized MFI-type zeolite is considered to be due to rapid diffusion of the produced light olefins out of the intracrystalline pores of the nano-zeolite due to the low diffusion resistance. Accordingly, the nano-sized zeolite achieved high yield of light olefins (approximately 35 %) and long catalyst lifetime.
  • 増田 隆夫
    觸媒 = Catalyst 54 4 2012年06月10日 [査読無し][通常論文]
  • Teruoki Tago, Yuta Nakasaka, Takao Masuda
    JOURNAL OF THE JAPAN PETROLEUM INSTITUTE 55 3 149 - 159 2012年05月 [査読有り][通常論文]
     
    The strong acidity and remarkable molecular sieving effect of zeolites makes them especially important materials in industrial reactions and separation processes. The use of zeolites as membranes combines the advantages of inorganic membranes (high temperature stability and solvent resistance) with the zeolitic properties. Such zeolite membranes have potential uses as separation and reaction membranes, and as simultaneous reaction/separation membranes. A number of approaches have proved effective for modifying the properties of zeolite membranes, including the use of nano-crystalline zeolites for membrane preparation, regioselective deactivation of acid sites, and modification of zeolitic pore size. This review describes the synthesis of nano-crystalline zeolites by an emulsion method and the regioselective deactivation of acid sites by the catalytic cracking of silane (CCS) method. The effects of the crystal size and CCS treatment on the performance of the zeolite membrane are reviewed.
  • Production of ketones from pyroligneous acid of woody biomass pyrolysis over an iron-oxide catalyst
    D. Mansur, T. Yoshikawa, K. Norinaga, J. Hayashi, T. Tago, T. Masuda
    Fuel 16 148 - 163 2012年 [査読有り][通常論文]
  • Zeolites: Synthesis, Chemistry and Applications, Chapter 6 "Synthesis of nanocrystalline zeolites and their applications"
    T. Tago, Y. Nakasaka, T. Masuda
    Nova Scientific publisher 171 - 189 2012年 [査読有り][通常論文]
  • 多湖輝興, 中坂佑太, 増田隆夫
    触媒 53 7 409 - 414 2011年12月10日 [査読無し][通常論文]
  • Takuya Yoshikawa, Teruoki Tago, Ayaka Nakamura, Aya Konaka, Mitsushi Mukaida, Takao Masuda
    Research on Chemical Intermediates 37 9 1247 - 1256 Springer Nature 2011年11月 [査読有り][通常論文]
     
    Conversion of glycerol to useful chemicals was examined using a zirconia-iron oxide catalyst. An aqueous glycerol solution was used as feedstock, and the catalytic reaction was carried out in a fixed-bed flow reactor at 623 K under atmospheric pressure. Useful chemicals, for example propylene, allyl alcohol, carboxylic acids, and ketones, were obtained from the aqueous glycerol solution. The reaction was found to involve a series of consecutive reactions, with allyl alcohol and carboxylic acids as reaction intermediates which were converted to propylene and ketones, respectively. Moreover, the catalyst had high and stable activity in the reaction of a 50 wt% glycerol solution.
  • 今野大輝, 多湖輝興, 中坂佑太, 増田隆夫
    化学工業 62 10 741 - 748 2011年10月01日 [査読無し][通常論文]
  • Teruoki Tago, Hiroki Konno, Mariko Sakamoto, Yuta Nakasaka, Takao Masuda
    APPLIED CATALYSIS A-GENERAL 403 1-2 183 - 191 2011年08月 [査読有り][通常論文]
     
    Production of light olefins such as ethylene, propylene and isobutylene from acetone was examined over ZSM-5 zeolites. These light olefins are produced from acetone over the acid sites of the zeolite via a series of consecutive reactions where olefins such as ethylene and propylene are obtained by cracking of isobutylene produced from aldol condensation products of acetone. Macro- and nano-sized ZSM-5 zeolites were prepared by conventional hydrothermal and emulsion methods, respectively, and the ZSM-5 zeolites with nearly the same acidity and BET surface area were obtained regardless of the crystal sizes. From SEM observations, the crystal sizes of the zeolites were approximately 2000 nm and 30-40 nm. These zeolites with different crystal sizes were applied to light olefins synthesis from acetone, and the effect of crystal size on catalytic activity and stability was investigated. As compared with the macro-seized zeolite, the nano-sized zeolite exhibited a high activity over a long lifetime. However, because the nano-sized zeolite possesses a large external surface area, undesirable reactions to form aromatics from the produced light olefins occurred on the acid sites located near the external surface. To inhibit aromatics formation, selective deactivation of the acid sites located near the outer surface of the zeolite was achieved via the catalytic cracking of silane (CCS) method using diphenyl silane (DP-silane). The CCS method was effective in deactivating the acid sites located near the external surface of the ZSM-5 zeolite. Moreover, the nano-size zeolite after the CCS treatment using DP-silane exhibited high olefins and low aromatics yields under high acetone conversion conditions. (C) 2011 Elsevier B.V. All rights reserved.
  • 中坂佑太, 多湖輝興, 増田隆夫
    ゼオライト 28 2 47 - 54 2011年06月10日 [査読無し][通常論文]
  • Kazuyuki Iwakai, Teruoki Tago, Hiroki Konno, Yuta Nakasaka, Takao Masuda
    Microporous and Mesoporous Materials 141 167 - 174 2011年05月 [査読有り][通常論文]
     
    The preparation of nano-crystalline MFI zeolites (Silicalite-1 and ZSM-5) was carried out by hydrothermal synthesis in a water/surfactant/organic solvent using fumed silica and aluminum sulfate as the Si and Al source, respectively. It was confirmed that the surfactant in the solution affected the nucleation rate of the MFI zeolite. Moreover, the crystal size of the MFI zeolite decreased with increasing surfactant concentration, and nanometer-sized MFI zeolites was obtained at a surfactant concentration of 0.25-0.5 mol/L. The successful preparation of MFI zeolite nanocrystals was ascribed to the stabilization of the MFI zeolite precursors and/or crystals by the adsorbed surfactant on their surface. This method was applied to the preparation of nano-crystalline ZSM-5 zeolite. ZSM-5 zeolite with a crystal size of approximately 50 nm was obtained. The nano-crystalline ZSM-5 zeolite was well-crystallized without octahedral Al atoms in the external framework, and exhibited almost the same acidity as a reference ZSM-5 zeolite. © 2010 Elsevier Inc. All rights reserved.
  • Nozomu Sonoyama, Kazunari Nobuta, Tokuji Kimura, Sou Hosokai, Jun-ichiro Hayashi, Teruoki Tago, Takao Masuda
    FUEL PROCESSING TECHNOLOGY 92 4 771 - 775 2011年04月 [査読有り][通常論文]
     
    Iron oxide catalysts containing metal promoters were tested to evaluate whether they could be applied to the coal tar obtained from the pyrolysis of Loy Yang coal. Catalytic cracking of the coal tar in a steam atmosphere was conducted in a fixed-bed reactor at 773 K and ambient atmospheric pressure. For iron oxide catalysts containing cerium, zirconium, and aluminium, the total yield of monocyclic aromatic hydrocarbons, phenols, and ketones exceeded 40 mol-C% on a tar basis, while about 97 wt.% of the initial heavy tar was decomposed. The combination of cerium, zirconium, and aluminium improved the activity of the iron oxide catalyst. Moreover, the addition of steam to the tar vapour increased the yield of ketones and made the catalyst more durable. (C) 2010 Elsevier B.V. All rights reserved.
  • Satoshi Funai, Teruoki Tago, Takao Masuda
    CATALYSIS TODAY 164 1 443 - 446 2011年04月 [査読有り][通常論文]
     
    The disposal of biomass waste containing large amounts of water by burial in the ground or burning causes environmental problems. Therefore, efficient methods for the treatment of biomass waste are required. In this study, conversion of livestock manure, a significant biomass waste, to useful chemicals such as ketones was carried out using a new conversion process consisting of hydrothermal treatment and reaction in the presence of an iron oxide. We succeeded in the selective production of acetone from a livestock manure-derived slurry liquid using the iron oxide catalyst. Moreover, the acetone yield in the product liquid was increased with increasing concentration of acetic acid in the slurry liquid. (C) 2010 Elsevier B. V. All rights reserved.
  • Teruoki Tago, Hiroki Konno, Syoko Ikeda, Seiji Yamazaki, Wataru Ninomiya, Yuta Nakasaka, Takao Masuda
    Catalysis Today 164 158 - 162 2011年04月 [査読有り][通常論文]
     
    Selective production of isobutylene from acetone was examined over BEA zeolites. Isobutylene production from acetone proceeds over solid-acid catalysts via a series of consecutive reactions, which include propylene and ethylene formation by cracking and coke formation. Because the isobutylene is an intermediate chemical in this process, low diffusion resistance of the isobutylene within the pore of the catalyst is needed to prevent its further conversion. To achieve this goal, we selected a BEA-type zeolite with 12-membered rings and a 3-dimensional pore structure. To obtain high yields of isobutylene, it is also important to inhibit undesired reactions of isobutylene and other intermediates that produce aromatics and coke. In this study, the acidity of the BEA zeolites was controlled using an ion-exchange method with alkali metals. The order of catalytic activity of the ion-exchanged BEA zeolites is as follows: H-BEA, Na-BEA, K-BEA, Rb-BEA, Cs-BEA, and is the same as the order of acidity of the zeolites. Though H-BEA zeolite showed a high acetone conversion at an initial reaction time, the activity of the catalyst drastically decreased due to coke formation. In contrast, the alkali metal ion-exchanged BEA zeolites exhibited high isobutylene selectivity at high acetone conversion conditions. Moreover, the amount of coke deposited on the catalyst decreased as compared to H-BEA zeolite. In K-BEA zeolite, the isobutylene yield reached 55%. © 2010 Elsevier B.V. All rights reserved.
  • 増田 隆夫
    ペトロテック = Petrotech 34 3 2011年03月01日 [査読無し][通常論文]
  • 多湖輝興, 吉川琢也, 増田隆夫
    Bio Ind 28 2 45 - 50 2011年02月12日 [査読無し][通常論文]
  • 吉川琢也, 多湖輝興, 増田隆夫
    ペトロテック 34 1 24 - 29 2011年01月01日 [査読無し][通常論文]
  • 多湖輝興, 吉川琢也, 増田隆夫
    JETI 58 10 36 - 38 2010年09月16日 [査読無し][通常論文]
  • FUNAI Satoshi, SATOH Yumi, SATOH Yasuharu, TAJIMA Kenji, TAGO Teruoki, MASUDA Takao
    Top Catal 53 7/10 654-658  2010年06月 [査読無し][通常論文]
  • Takuya Yoshikawa, Duangkamol Na-Ranong, Teruoki Tago, Takao Masuda
    Journal of the Japan Petroleum Institute 53 3 178 - 183 Japan Petroleum Institute 2010年05月 [査読有り][通常論文]
  • 舟井啓, 多湖輝興, 増田隆夫
    J Jpn Inst Energy 89 3 231 - 236 2010年03月20日 [査読無し][通常論文]
  • 舟井啓, 多湖輝興, 増田隆夫
    化学工学 74 2 57 - 59 2010年02月05日 [査読無し][通常論文]
  • Satoshi Funai, Eri Fumoto, Teruoki Tago, Takao Masuda
    CHEMICAL ENGINEERING SCIENCE 65 1 60 - 65 2010年01月 [査読有り][通常論文]
     
    In petroleum industry, it is desirable to produce lighter hydrocarbons such as gasoline, kerosene and gas-oil from unused heavy oils. Thus we have developed zirconia-supporting iron oxide catalysts (ZrO(2)-FeOx catalyst) to decompose petroleum residual oil (atmospheric distilled residual oil) with steam. In addition, we have found that the incorporation of Al(2)O(3) among FeO(X) crystals is effective in improving the catalytic activity and stability of the ZrO(2)-FeO(X) catalyst. In this study, the effects of Al(2)O(3) and ZrO(2) content in FeO(X)-based catalysts on catalytic activity and stability were investigated. Furthermore, the FeO(X)-based catalyst was applied to the decomposition of extra heavy oils such as vacuum distilled residual oil and Orimulsion. These extra heavy oils were effectively decomposed over the ZrO(2)-Al(2)O(3)-FeO(X) catalyst with steam, and the yields of lighter hydrocarbon reached to above 60% (C) 2009 Elsevier Ltd. All rights reserved.
  • Yuta Nakasaka, Teruoki Tago, Kazuhisa Yano, Takao Masuda
    Chemical Engineering Science 65 226 - 231 2010年01月 [査読有り][通常論文]
     
    The intracrystalline diffusivities of benzene within a series of porous materials in the liquid phase (cyclohexane was used as solvent) were measured by a constant volumetric method using Raman spectroscopy at a temperature range from 323 to 393 K. Silicalite-1, mono-dispersed mesoporous silica spheres (MMSS), silica gel, γ-Al2O3, and SiO2-Al2O3 were used as adsorbents. The intracrystalline diffusivity was calculated by parameter fitting using theoretical equations and the experimental transient change of benzene concentrations with time in response to the adsorption. The intracrystalline diffusivities of benzene within mesoporous silicas were almost the same as that within the micropore of silicalite-1, though the pore diameters of silicalite-1 and mesoporous silicas were different from each other. It is considered that the pore walls as well as the solvent molecules of cyclohexane affect the diffusion of benzene molecules in the mesopore region. Crown Copyright © 2009.
  • Yuta Nakasaka, Teruoki Tago, Kazuhisa Yano, Takao Masuda
    Chemistry Letters 38 1064 - 1065 2009年12月 [査読有り][通常論文]
     
    The intracrystalline diffusivities of benzene within porous materials in isopropanol solution were measured by the conven- tional constant volume method. The diffusivities within mesoporous silicas in isopropanol solution were smaller than those in cyclohexane solution. This means the effective pore diameter for the benzene diffusion in the presence of isopropanol is small, because isopropanol are preferentially adsorbed on the pore surface with silanol group due to the hydrophilic affinity. Copyright © 2009 The Chemical Society of Japan.
  • 舟井啓, 多湖輝興, 増田隆夫
    J Jpn Inst Energy 88 3 187 - 192 2009年03月20日 [査読無し][通常論文]
  • Teruoki Tago, Daichi Aoki, Kazuyuki Iwakai, Takao Masuda
    Topics in Catalysis 52 865 - 871 2009年 [査読有り][通常論文]
  • Tago Teruoki, Sakamoto Mariko, Iwakai Kazuyuki, Nishihara Hirotomo, Mukai Shin R, Tanaka Tsunehiro, Masuda Takao
    Journal of Chemical Engineering of Japan 42 S162 - S167 2009年 [査読有り][通常論文]
  • Teruoki Tago, Kazuyuki Iwakai, Mieko Nishi, Takao Masuda
    JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY 9 1 612 - 617 2009年01月 [査読有り][通常論文]
     
    In this paper, we report a method for preparing mono-dispersed silicalite-1 nanocrystals via hydrothermal synthesis in a water-surfactant-organic solvent consisting of a polyoxyethylene (15) oleyl-ether/cyclohexane system. Mono-dispersed silicalite-1 nanocrystals of approximately 60 nm diameter were successfully prepared. It was found that the crystal size depended on both the surfactant concentration and the amount of water solution added to the surfactant-organic solvent. The effects of the surfactant concentration and the amount of water solution on crystal morphology and size were investigated to clarify the mechanism underlying the formation of silicalite-1 nanocrystals in water-surfactant-organic solvent. Since the surfactant coexisted in the synthetic solvent, it was considered that the micellar structure and/or surfactants affected the rates of nucleation and crystal growth of silicalite-1, thus affecting crystal size. Crystal size was controllable within the range of 60 to 1000 nm by changing the W/S values.
  • Teruoki Tago, Yuta Nakasaka, Ayaka Kayoda, Takao Masuda
    Microporous and Mesoporous Materials 115 176 - 183 2008年10月 [査読有り][通常論文]
     
    Separation of water from a water-acetone solution was carried out by a pervaporation method using a hydrophilic silicalite-1 membrane. Silicalite-1 nanocrystals were piled up on the outer surface of cylindrical alumina ceramic filters, followed by a hydrothermal synthesis to form a silicalite-1 protection layer on the nanocrystal layer. In other words, the membrane consisted of a silicalite-1 nanocrystal layer and a silicalite-1 protection layer (the nanocrystal-layered membrane). In order to achieve high hydrophilic properties of the membrane with the remaining silanol group, the liquid-phase oxidation technique was applied to remove the template. From the SEM observation, the nanocrystal layer and the protection layer were clearly observed, and the silicalite-1 protection layer was uniformly formed on the nanocrystal layer. Pervaporation experiments to separate water from the water-acetone solution were conducted using the nanocrystal-layered membrane. It was considered that the secondary growth of the nanocrystals around the interface between the nanocrystal and protection layers affected the separation properties. The effects of the nanocrystal size on the separation properties were examined. The membrane exhibited selective permeation as well as a high flux of water, and these properties were improved with a decrease in the size of the nanocrystals. Moreover, the layered membrane exhibited high hydrophilic properties regardless of the acetone concentrations. © 2008 Elsevier Inc. All rights reserved.
  • Yuta Nakasaka, Teruoki Tago, Kazutoshi Odate, Takao Masuda
    Microporous and Mesoporous Materials 112 162 - 169 2008年07月 [査読有り][通常論文]
     
    A new method is proposed for measuring the diffusivities of hydrocarbons within solid catalysts in the liquid phase using Raman spectroscopy. This method was applied to measuring the intracrystalline diffusivity of benzene within silicalite-1 (SL) and γ-Al2O3 in cyclohexane solution at a temperature range from 323 to 413 K. From Raman spectra of benzene/cyclohexane solution, the proportional relationship between the benzene concentration and the intensity ratio of benzene to cyclohexane was obtained, which enables us to measure the benzene concentration in the solution. From this relationship, the transient change in benzene concentrations in the solution due to its adsorption and diffusion within the catalysts can be measured. The intracrystalline diffusivity (Dad) in the liquid phase was calculated using theoretical equations, and the experimental results of the concentration change with time. The Arrhenius plots of the diffusivity of benzene within SL (micro pore region) in the gas and liquid phase were correlated with a single line, regardless of the existence of solvent in the liquid phase. This result indicates that in the structure-sensitive diffusion region (diffusion of benzene within the micropore of SL), the diffusion mechanism in the gas phase is the same as that in the liquid phase. In contrast, the diffusivity of benzene within macro-pores of γ-Al2O3 in the liquid phase was approximately 107 times higher than that within SL. The diffusivity of benzene within γ-Al2O3 was almost the same as that of the theoretical molecular diffusion coefficient in cyclohexane solution calculated from the Wilke-Chang equation. © 2007 Elsevier Inc. All rights reserved.
  • 多湖輝興, 岩貝和幸, 増田隆夫
    ケミカルエンジニヤリング 53 6 432 - 439 2008年06月01日 [査読無し][通常論文]
  • Teruoki Tago, Yuta Nakasaka, Ayaka Kayoda, Takao Masuda
    Separation and Purification Technology 58 7 - 11 2007年12月 [査読有り][通常論文]
     
    Hydrophilic silicalite-1 nanocrystal-layered membrane was successfully prepared on an alumina ceramic filter. The silicalite-1 nanocrystals were layered on the outer surface of cylindrical alumina ceramic filters, followed by a hydrothermal synthesis to form a silicalite-1 layer (protection layer) on the nanocrystal layer. In order to achieve high hydrophilic properties of the membrane with the remaining silanol group, the liquid phase oxidation technique was applied to remove the template. From the SEM observation, the nanocrystal layer and the protection layer were clearly observed, and the silicalite-1 protection layer was uniformly formed on the nanocrystal-layer. Pervaporation experiments to separate water from water-acetone solution (acetone: 90 wt%) were conducted using the silicalite-1 nanocrystal-layered membrane. The membrane exhibited the selective permeation as well as the high flux of water. In the nanocrystal-layered membrane, water-silanol networks were formed on the non-zeolitic pores surface among the nanocrystals, which were the main channels for water permeation. The increase in the number of pores among the silicalite-1 crystals leads to a high flux of water through the membrane. © 2007 Elsevier B.V. All rights reserved.
  • 中坂佑太, 多湖輝興, 矢野一久, 増田隆夫
    膜 32 6 332 - 339 2007年11月01日 [査読無し][通常論文]
  • 筒井俊雄, 増田隆夫, 二井晋, 長谷川泰久, 西岡将輝, 外輪健一郎, 尾上薫, 霜垣幸浩
    化学工学 71 10 661 - 669 2007年10月05日 [査読無し][通常論文]
  • 多湖輝興, 岩貝和幸, 坂元真梨子, 増田隆夫
    触媒 49 6 495 - 497 2007年09月05日 [査読無し][通常論文]
  • 多湖 輝興, 麓 恵里, 増田 隆夫
    化学工業 58 7 522 - 527 化学工業社 2007年07月 [査読無し][通常論文]
  • 多湖輝興, 麓恵里, 増田隆夫
    化学工業 58 7 522 - 527 2007年07月01日 [査読無し][通常論文]
  • Eri Fumoto, Teruoki Tago, Takao Masuda
    CHEMISTRY LETTERS 35 9 998 - 999 2006年09月 [査読有り][通常論文]
     
    Zirconia-including iron catalyst with high durability was successfully prepared which had high activity for recovering lighter fuels from petroleum residual oil in a steam atmosphere. Zirconia dispersed highly in iron catalyst supplied enough amount of active oxygen species from steam into iron oxide lattice. Lattice oxygen in iron oxide reacted with heavy oil. Thus, oxidative cracking of heavy oil with steam was accelerated over iron catalyst with highly dispersed zirconia without any lack of lattice oxygen of iron oxide.
  • Hirotomo Nishihara, Shin R. Mukai, Yusuke Fujii, Teruoki Tago, Takao Masuda, Hajime Tamon
    Journal of Materials Chemistry 16 3231 - 3236 2006年08月11日 [査読無し][通常論文]
     
    Macroporous monoliths of SiO2-Al2O3 cryogels were prepared. Macropores were generated by using ice crystals as the template, while the walls which surround the macropores were tailored as porous cryogels by freeze drying. Macropores and walls formed honeycomb-like structures, which were confirmed from scanning electron microscopy images of cross-sections of the samples. It was confirmed that the sizes of the macropores and the wall thicknesses were respectively in the ranges of 10-20 m and 200-500 nm. Al mapping analysis by energy dispersive X-ray diffractometry showed that Al atoms were homogeneously dispersed throughout the samples without local aggregation. Moreover, Raman spectroscopy and 27Al NMR spectroscopy indicated that Al atoms were incorporated into the silica framework by forming an Al-O-Si polymeric network. Nitrogen adsorption-desorption measurements indicated that the walls were micro/mesoporous with high BET surface areas (>700 m2 g-1) and large pore volumes (>0.45 cm 3 g-1). Moreover, NH3-TPD measurements revealed that the samples had acid sites, which allowed this material to be used as a solid acid catalyst. © The Royal Society of Chemistry 2006.
  • Takao Masuda, Teruoki Tago
    Feedstock Recycling and Pyrolysis of Waste Plastics: Converting Waste Plastics into Diesel and Other Fuels 161 - 192 2006年06月07日 [査読有り][通常論文]
     
    This chapter contains sections titled: Introduction Recovery of Heavy Oil from Waste Plastic Upgrading of Waste-plastics-derived Heavy Oil Over Catalysts Continuous Production of Fuels from Waste Plastics References.
  • Teruoki Tago, Kazuyuki Iwakai, Mieko Nishi, Takao Masuda
    NEW DEVELOPMENT AND APPLICATION IN CHEMICAL REACTION ENGINEERING, 4TH ASIA-PACIFIC CHEMICAL REACTION ENGINEERING SYMPOSIUM (APCRE 05) 159 185 - 188 2006年 [査読有り][通常論文]
  • 多湖輝興, 増田隆夫
    ゼオライト 22 3 68 - 74 2005年09月10日 [査読無し][通常論文]
  • TAGO Teruoki, OKUBO Yoshihito, MUKAI Shin R, TANAKA Tsunehiro, MASUDA Takao
    Appl. Catal. A: General 290 1-2 54 - 64 2005年08月18日 [査読無し][通常論文]
     
    We propose a new TPD method for simultaneously characterizing the acidic and basic properties of solid catalysts by utilizing the co-adsorption of NH3 and CO2 on catalysts. First CO2 was adsorbed on the catalyst sample; then NH3 was adsorbed on it. Another adsorption sequence of NH3 and CO2, and CO 2 and NH3 single adsorptions were also conducted. The TPD measurements were carried out by heating the catalyst sample from 373 to 773 K at a heating rate of 2.5 K min-1 in a helium stream under a total pressure of 1.3 kPa. In solid acid catalysts, there is little difference in the NH3-TPD spectra between single and co-adsorption systems. This results from the absence of any induction effect between the acid and base sites, because the number of base sites in the solid acid catalyst is very small. In contrast, in a solid acid-base catalyst of alumina, a remarkable difference in the NH3-TPD spectra was observed between single adsorption and co-adsorption systems. The difference in the TPD spectra between single and co-adsorption systems was ascribed to a strong induction effect appearing on the acid and base sites, which was proved by an in situ IR measurement. The validity of the TPD method was examined by correlating the number of the strong acid sites to catalytic activities of dehydrolysis of ethanol over solid acid and solid acid-base catalysts. In solid acid-base catalysts, the number of strong acid sites was calculated from the activation energy distribution for the desorption of NH3 in a co-adsorption system because of the strong induction effect. A proportional relationship between the intrinsic reaction rate constant, which is based on the concentration of ethanol within the catalyst, and the number of strong acid sites could be obtained, regardless of the catalysts or their types or pore structure. © 2005 Elsevier B.V. All rights reserved.
  • Teruoki Tago, Kazuyuki Iwakai, Ken Morita, Katsunori Tanaka, Takao Masuda
    Catalysis Today 105 3-4 662 - 666 2005年08月15日 [査読有り][通常論文]
     
    ZSM-5 zeolite membrane, which shows high selectivity toward olefins in the methanol conversion, was developed by controlling the location of the acid sites. First, the ZSM-5 zeolite catalyst membrane without pinholes was successfully prepared by synthesizing a ZSM-5 zeolite layer on an outer surface of a cylindrical alumina ceramic filter. The membrane was used as the catalytic membrane reactor to recover olefins from methanol. Though the olefins were successfully produced from methanol with high selectivity (ca. 80%), production of paraffin and aromatics was observed at the feed side of the zeolite membrane. To prevent the such production, the location of the acid site of the ZSM-5 zeolite membrane was controlled by a new method called the catalytic cracking of silane (CCS) method. Selective deactivation of acid sites at the outer surface of the zeolite membrane (feed side of reactant) by the CCS method allowed us to increase the selectivity of the olefins by 10% as compared to the untreated membrane. © 2005 Elsevier B.V. All rights reserved.
  • Naonobu Katada, Tatsuya Takeguchi, Tatsuya Suzuki, Toshihisa Fukushima, Kinya Inagaki, Setsuo Tokunaga, Hiromichi Shimada, Koichi Sato, Yasunori Oumi, Tsuneji Sano, Kohichi Segawa, Kazuyuki Nakai, Hiroshi Shoji, Peng Wu, Takashi Tatsumi, Takayuki Komatsu, Takao Masuda, Kazunari Domen, Eisuke Yoda, Junko N. Kondo, Toshio Okuhara, Takahide Kanai, Miki Niwa, Masaru Ogura, Masahiko Matsukata, Eiichi Kikuchi, Noriyasu Okazaki, Motoi Takahashi, Akio Tada, Shogo Tawada, Yoshihiro Kubota, Yoshihiro Sugi, Yasuhiko Higashio, Masahiko Kamada, Yukiyo Kioka, Kohei Yamamoto, Takayuki Shouji, Shigeo Satokawa, Yusaku Arima, Yasuaki Okamoto, Hideyuki Matsumoto
    Applied Catalysis A: General 283 1-2 75 - 84 2005年04月 [査読有り][通常論文]
     
    The undesired structural change of mordenite with Si/Al2 = 15 during the ion exchange and during calcination from the sodium form into proton form, especially the dealumination after the calcination, was studied. The 29Si NMR results clarified that calcination of the NH4-form mordenite with Si/Al2 = 15 at >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 27Al 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 <673 K. The 1H 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. © 2005 Elsevier B.V. All rights reserved.
  • Naonobu Katada, Tatsuya Takeguchi, Tatsuya Suzuki, Toshihisa Fukushima, Kinya Inagaki, Setsuo Tokunaga, Hiromichi Shimada, Koichi Sato, Yasunori Oumi, Tsuneji Sano, Kohichi Segawa, Kazuyuki Nakai, Hiroshi Shoji, Peng Wu, Takashi Tatsumi, Takayuki Komatsu, Takao Masuda, Kazunari Domen, Eisuke Yoda, Junko N. Kondo, Toshio Okuhara, Yasuyoshi Kageyama, Miki Niwa, Masaru Ogura, Masahiko Matsukata, Eiichi Kikuchi, Noriyasu Okazaki, Motoi Takahashi, Akio Tada, Shogo Tawada, Yoshihiro Kubota, Yoshihiro Sugi, Yasuhiko Higashio, Masahiko Kamada, Yukiyo Kioka, Kohei Yamamoto, Takayuki Shouji, Yusaku Arima, Yasuaki Okamoto, Hideyuki Matsumoto
    Applied Catalysis A: General 283 1-2 63 - 74 2005年04月 [査読有り][通常論文]
     
    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/Al2 = 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, N2 adsorption, 29Si and 27AlNMR, 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 Brønsted 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. © 2005 Elsevier B.V. All rights reserved.
  • Toshiro Tsuji, Satoshi Okajima, Akira Sasaki, Takao Masuda
    Journal of Chemical Engineering of Japan 38 10 859 - 864 2005年 [査読有り][通常論文]
     
    Steam reforming of oils derived from plastics has been investigated to produce gas from waste plastics. Two types of oils from polyethylene and from polystyrene, were produced by thermal decomposition at relatively low temperatures (350-450°C). Steam reforming of these oils was conducted at temperatures from 650 to 850°C under a pressure of 1 atm using three types of Ni-Al2O3 catalysts. Gas yield, gas composition, carbon conversion, and the coking ratio for these catalysts were measured. Although the plastic-derived oils contain heavy hydrocarbons or aromatics, they are gasified well with a low coking rate at temperatures above 800°C and a steam carbon ratio = 3.5 and LHSV = 1 h-1. Among the three catalysts, C11NK, which is a commercial steam reforming catalyst for naphtha, possessed moderate activity, but had the lowest rate of coking. Gas compositions agreed well with values calculated from chemical equilibria. Product gas contained approximately 72 vol% hydrogen for polyethylene-derived oil and 68 vol% for polystyrene-derived oil. Copyright © 2005 The Society of Chemical Engineers, Japan.
  • Teruoki Tago, Mieko Nishi, Yousuke Kouno, Takao Masuda
    Chemistry Letters 33 8 1040 - 1041 2004年08月05日 [査読有り][通常論文]
     
    Monodispersed silicalite nanocrystals with a diameter of 80-150 nm were successfully prepared in water-surfactant-oil solution. It was found that the ionicity of the surfactants used in preparation affected the crystallinity and structure of the silicalite, and that silicalite nanocrystals could be obtained when using a nonionic surfactant. Furthermore, silicalite nanocrystals with a diameter of approximately 80 nm could be obtained in even a high concentration region of Si source.
  • Shin R. Mukai, Mitsutaka Shimoda, Litsu Lin, Hajime Tamon, Takao Masuda
    Applied Catalysis A: General 256 1/2 107 - 113 2003年12月30日 [査読無し][通常論文]
     
    In this work, efforts were made to improve the preparation method of "ship-in-the-bottle" type 12-molybdophosphoric acid (PMo12) encaged Y-type zeolite catalysts. First, the possibilities of modifying other popular heteropoly acid synthesis methods to prepare encaged catalysts were examined. It was found that only the conventional method, which uses MoO3 and H3PO4 for PMo12 synthesis, led to a significant amount of PMo12 encaging. Next, using this conventional method, the influences of temperature and solvent addition during synthesis on the amount of PMo12 encaging and the stability of the resulting encaged catalyst were investigated. It was found that by adjusting the reaction temperature, the stability of the resulting encaged catalyst could be enhanced to higher levels. Moreover, it was found that by adding t-butyl alcohol (TBA) to the solution used for catalyst synthesis, an active and stable encaged catalyst can be prepared even at low synthesis temperatures. © 2003 Elsevier B.V. All rights reserved.
  • 増田隆夫
    Jasco Rep 75 - 81 2003年11月01日 [査読無し][通常論文]
  • 増田隆夫
    J Jpn Pet Inst 46 5 281 - 294 2003年09月 [査読無し][通常論文]
     
    Diffusion mechanisms of hydrocarbons within zeolites, especially MFI-type zeolite, were investigated by discriminating intracrystalline diffusivity from effective diffusivity. Intracrystalline diffusivity directly represents the mobility of molecules within pores. Effective diffusivity is obtained by multiplying the intracrystalline diffusivity by a partition factor given by the ration of the concentrations of molecules in zeolite crystals to that in gas phase. Intracrystalline diffusivity was the main subject of this study. Diffusion within MFI-type zeolite is dominated by the following mechanisms: (1) configurational diffusion, (2) resistance to mass transfer at pore mouths, (3) adsorption-control led diffusion and (4) co-existing molecules with slow diffusing molecules. Intracrystalline diffusivity in the adsorption process is lower than in desorption process for (1) and (2) if the minimum molecular size is larger than the pore diameter, such as ortho- and meta-xylenes. The resistance to mass transfer at pore mouths becomes dominant in the adsorption process. This tendency is also observed for paraffins. Model equations were proposed for evaluating intracrystalline diffusivity based on the molecular size, molecular weight and pore diameter. Overall intracrystalline diffusivity for (3) is correlated with the configurational diffusion and the trapping effect on acid sites. This effect disturbs the mass transfer, especially at temperatures below 573 K, for aromatics. Similar effects are observed for lighter paraffins and olefins within MFI-type zeolites with metal cations. Intracrystalline diffusivities for (4) for silicalite-1 in a multicomponent system were measured using a new desorption under reduced pressure method. The diffusivity of the slow component in the multicomponent system agreed well for that of a single component. However, the diffusivity of the fast component was largely decreased by co-existing slow molecules. A random walk simulation and an empirical equation could explain this tendency. Effective diffusivity was calculated from the intracrystalline diffusivity and the partition factor, which was obtained from the adsorption isotherm. The partition factor suggested a marked condensation effect for MFI-type zeolites. Intracrystalline and effective diffusivities for beta- and Y-type zeolites, and mordenite were also investigated.
  • Takao Masuda, Shu hei Otani, Toshiro Tsuji, Masahiro Kitamura, Shin R. Mukai
    Separation and Purification Technology 32 181 - 189 2003年07月01日 [査読無し][通常論文]
     
    Hydrophilic and acid-proof silicalite-1 zeolite membrane was successfully prepared by repeating hydrothermal synthesis of silicalite-1 layer on an alumina ceramic filter (repeated batch synthesis) followed by a liquid phase oxidation method with H2O2 to remove template molecules. This prepared membrane has marked amount of silanol group both in the micro pores of silicalite-1 crystals and in the apertures among the crystals. Networks of water molecules are formed via hydrogen bond in silanol groups. These networks allow only water molecules to diffuse through the networks. Therefore, when this membrane was applied to the pervaporation of concentrated acetic acid (30-98 wt.%), only water molecules passed through the membrane. To examine the usefulness of the membrane, the pervaporation of two kinds of water solutions, acetone and ethanol, were conducted by this membrane. In both systems, only water was permeated, as well as the case of the water solution of acetic acid. The permeation rate at the pervaporation temperature was found to lie on a single line for acetone-water, ethanol-water and acetic acid-water systems. Thermogravimetric analysis of hydrophilic silicalite-1 powders indicated that dominant channels for the permeation of water molecules were apertures among fine silicalite-1 crystals of the membrane. © 2003 Elsevier Science B.V. All rights reserved.
  • Production of Hard Carbons for Lithium Ion Storage by the Co-Carbonization of Phenolic Resin Precursors
    Mukai, Shin, Tanigawa, Takahito, Harada, Takeshi, Tamon, Hajime, Masuda, Takao
    Adsorption Science and Technology,, pp. 313-315 2003年05月 [査読有り][通常論文]
  • Takao Masuda, Tadashi Asanuma, Mitsuru Shouji, Shin R. Mukai, Motoaki Kawase, Kenji Hashimoto
    Chemical Engineering Science 58 3/6 649 - 656 2003年02月01日 [査読無し][通常論文]
     
    A ZSM-5 zeolite catalyst membrane without pinholes was successfully prepared by synthesizing ZSM-5 zeolite layer on the outer surface of a cylindrical alumina ceramic filter. In the preparation of the membrane, to enhance the smoothness of the outer surface of the filter, a filter with pores of 0.1 μm in diameter was employed. Furthermore, the hydrothermal synthesis was repeated using the same samples. The obtained zeolite membrane showed a molecular sieving effect for the permeation of gaseous xylene and diethylbenzene isomers. The ratio of the permeability of the para-isomer to the meta-isomer was about 2.7 for xylene and 6.0 for diethylbenzene, respectively. The membrane was used as a catalytic membrane reactor to recover olefins from methanol. By adjusting the diffusion rate to the chemical reaction rate for producing olefins within the ZSM-5 zeolite layer, olefins were successfully produced at a high selectivity (about 80-90%) from methanol at high conversions of 60-98%. © 2003 Elsevier Science Ltd. All rights reserved.
  • 増田 隆夫
    触媒 = Catalysts & Catalysis 45 1 2003年01月15日 [査読無し][通常論文]
  • Takao Masuda, Takao Masuda, Naohiro Fukumoto, Masahiro Kitamura, Shin R. Mukai, Kenji Hashimoto, Tsunehiro Tanaka, Takuzo Funabiki
    Microporous and Mesoporous Materials 48 1/3 239 - 245 2001年11月01日 [査読無し][通常論文]
     
    Catalytic cracking of silane (CCS) is proposed as a new method for modifying the effective pore opening of a zeolite. In this method, first silane compounds which can penetrate into the pores of the zeolite are introduced and are pre-adsorbed on active sites within the zeolite, such as acid sites and metal cations. Next, the adsorbed species are cracked catalytically on the sites, leaving coke that contains Si atoms on the active sites. By the calcination of the coked material, mono SiO2 units are formed on active sites, thereby reducing the size of the pores. When this method is applied to powdery MFI-type zeolite, the adsorption capacity of benzene is markedly reduced, but that of CO2 is maintained constant. Furthermore, the proposed CCS method was applied to reduce the pore diameters of an MFI-type zeolite membrane. By use of the membrane, experiments of separating H2 from a mixture gas containing H2 and N2 or O2 were conducted in a flow system. The membrane showed a high H2 separation factor of about 90-140 (as compared with 1.4-4.5 for a non-treated MFI-type zeolite membrane). © 2001 Elsevier Science B.V. All rigths reserved.
  • T. Masuda, T. Kushino, T. Matsuda, S. R. Mukai, K. Hashimoto, S. Yoshida
    Chemical Engineering Journal 82 1/3 173 - 181 2001年03月15日 [査読無し][通常論文]
     
    A new reactor system was developed for recovery fuels from the waste plastic mixture in steam atmosphere. Firstly, the degradation mechanisms of eight kinds of plastics, two polyolefins (polyethylene and polypropylene), two polyamide resins (nylon-6 and nylon-6,6), polystyrene and three polyesters (polycarbonate, poly(butylene terephthalate) and poly(ethylene terephthalate), were investigated both in nitrogen and steam as the carrier gas. Plastics except for polyesters were degraded without any influences of the kinds of the carrier gas, leaving negligibly small amount of carbonaceous residue. Polyesters, which were degraded with producing large amount of the residue in nitrogen, were succeeded to be hydrolyzed at high reaction rates in steam with producing hardly the carbonaceous residue. Secondly, a mixture of the waste plastics was continuously degraded to produce heavy oil in steam atmosphere by using a new reactor system. This system was composed of three kinds of reactors connected in series. One was a reactor filled with stirred heat medium particles, which enabled the high heat transfer rate, the high holdup and the good contact of the melted plastics with steam. The second was a tank reactor. The last one was a fixed bed reactor with FeOOH catalyst particles, which showed the catalysis in steam for the decomposition both of a wax and sublimate materials generated by the degradation of plastics. Furthermore, the oil produced from the proposed reactor system was continuously upgraded to produce gasoline and kerosene over Ni-REY catalyst in steam atmosphere. © 2001 Elsevier Science B.V.
  • T. Masuda, Y. Kondo, M. Miwa, T. Shimotori, S. R. Mukai, K. Hashimoto, M. Takano, S. Kawasaki, S. Yoshida
    Chemical Engineering Science 56 897 - 904 2001年02月01日 [査読無し][通常論文]
     
    The possibility of recovering useful hydrocarbons from oil palm waste derived lignocellulose (palm shell oil) using steam tolerant catalysts was investigated. The examined catalysts were rare earth metal exchanged Y-type (REY) zeolites, nickel supporting REY zeolites and FeOOH catalysts. It was found that palm shell oil could be converted to a mixture which mainly contains phenol, acetone and butanone without hardly generating solid residues when a FeOOH catalyst was used. Therefore, by catalytic reaction, this waste-derived material may become a new and abundant chemical source. The catalytic activity of this FeOOH catalyst can be enhanced by supporting ZrO2 on it. It was found that oxygen transfer during reaction occurs mainly from H2O to the products, not from the oxygen of the catalyst. It is assumed that the supported ZrO2 plays a role of the decomposition of H2O adsorbed on the catalyst, yielding active hydrogen and oxygen species, which is also supported by the results of thermal desorption spectra and Mössbauer spectroscopy analysis of the catalyst. © 2001 Elsevier Science Ltd. All rights reserved.
  • S. R. Mukai, L. Lin, T. Masuda, K. Hashimoto
    Chemical Engineering Science 56 3 799 - 804 2001年02月01日 [査読無し][通常論文]
     
    The influences of the properties of the zeolite support on the amount of encapsulation of Keggin-type heteropoly acid (HPA) molecules in the supercages of Y-type zeolite were investigated to clarify the key factors for the production of a solid acid catalyst which maintains activity in aqueous solutions. The investigated properties were the SiO 2/A1 2O 3 ratio and the type and amount of counter cation occupying the cation sites of the zeolite support. It was found that in order to efficiently encapsulate HPA molecules, the zeolite support must have a moderate number of aluminum atoms in its framework, and cations which promote the formation of HPA precursors must occupy the cation sites induced by these aluminum atoms. It was also found that the degree of ion exchange of such cations must be high enough so that the cations can exist within the supercages, and therefore can contribute to the formation of HPAs. By controlling these factors, we succeeded in enhancing the catalytic activity of the encapsulated catalyst. © 2001 Elsevier Science Ltd. All rights reserved.
  • T. Masuda, Y. Okubo, S. R. Mukai, M. Kawase, K. Hashimoto, A. Shichi, A. Satsuma, T. Hattori, Y. Kiyozumi
    Chemical Engineering Science 56 3 889 - 896 2001年02月01日 [査読無し][通常論文]
     
    Intracrystalline and effective diffusivities of ethane, propane, ethylene and propylene were measured for several kinds of MFI-type zeolite, such as silicalite-1, H-MFI, Cu- and Co-MFI-type zeolites at temperatures ranging from 323 to 823 K. The intracrystalline diffusivity represents the mobility of molecules within zeolite crystals, and was found to be reduced to 1/100 for paraffins and 1/1000 for olefins by the existence of active sites (proton, Cu and Co ions), as compared with silicalite-1. The effective diffusivity was evaluated by multiplying the intracrystalline diffusivity by a partition factor. Although the intracrystalline diffusivity of olefins was about 1/10 to 1/100 of that of paraffins, the effective diffusivity of olefins was almost equal to that of paraffins. The calculated effective diffusivity of ethylene within Cu-MFI was in good agreement with those evaluated by the kinetic analysis of the catalytic decomposition of NO with ethylene over Cu-MFI catalyst. © 2001 Elsevier Science Ltd. All rights reserved.
  • Shin R. Mukai, Isao Ogino, Litsu Lin, Yumi Kondo, Takao Masuda, Kenji Hashimoto
    Reaction Kinetics and Catalysis Letters 69 2 253 - 258 2000年12月01日 [査読無し][通常論文]
     
    The stability of a "ship in the bottle" type 12-molybdophosphoric acid encaged catalyst was drastically enhanced by stabilizing the acidic species of the catalyst by partial exchange of its protons with cesium cations. This catalyst practically acted as a solid catalyst in the esterification of acetic acid with ethanol.
  • T Masuda, Y Fujiikata, H Ikeda, K Hashimoto
    MICROPOROUS AND MESOPOROUS MATERIALS 38 2-3 323 - 332 2000年08月 [査読有り][通常論文]
     
    Diffusivities within crystals of highly siliceous MFI-type zeolite in a binary component system were measured over a temperature range of 448-498 K and under a total pressure of 13.3 Pa by a newly developed DRP method using paraffins (n-heptane, n-octane) and aromatics (ortho- and meta-xylenes). The diffusivities of the fast diffusing molecules were strongly affected by the co-existence of slow diffusing molecules. The diffusion of the former decreased as the number of slow molecules increased and the intrinsic diffusion rate of the slow molecules decreased. In contrast, the diffusivities of the slow molecules were not affected by the co-existence of fast molecules. To account for the difference in the diffusivities in the single and binary component systems, the random walk simulation was conducted. The difference in the diffusivities simulated agreed well with the results found experimentally. An empirical equation is proposed for the simple prediction of the reduction of the diffusivity of fast molecules in a binary components system by modifying the previously reported equation for the decrease in diffusivity caused by coke deposition. The estimated value using the empirical equation agreed well with the experimental data and the data calculated by the random walk simulation. (C) 2000 Elsevier Science B.V. All rights reserved.
  • 増田 隆夫
    触媒 42 1 25 - 30 触媒学会 2000年01月15日 [査読無し][通常論文]
  • 増田隆夫
    触媒 42 1 25 - 30 2000年01月15日 [査読無し][通常論文]
  • T Masuda, N Fukumoto, M Kitamura, Mukai, SR, K Hashimoto
    ADSORPTION SCIENCE AND TECHNOLOGY 411 - 415 2000年 [査読有り][通常論文]
     
    A new method, catalytic silane cracking method, was developed for controlling the effective pore opening of MFI-type zeolite. In this method, silane is cracked catalytically on active sites (acid sites) of MFI-type zeolite to produce methane and ethane, leaving coke containing Si atom on acid sites. This coked sample is calcined in air stream. By this procedure, a mono SiO2 unit is deposited on an acid site. The pore diameter at the position of SiO2 deposit is decreased to about the minimum molecular diameter of carbon dioxide. By this method, the amount adsorbed of benzene was largely decreased, but the amount of CO2 was kept constant.
  • Mukai, SR, T Masuda, K Hashimoto, H Iwanaga
    CARBON 38 3 491 - 494 2000年 [査読無し][通常論文]
  • Mukai, SR, T Masuda, T Harada, K Hashimoto
    CARBON 38 13 1801 - 1805 2000年 [査読無し][通常論文]
     
    Silicon containing vapor grown carbon fibers have been rapidly produced from a mixture of benzene and phenyl silane, using the liquid pulse injection technique. Fibers with lengths up to 20 mm were obtained within 1 min at a carbon yield of 0.23. The inclusion of silicon led to the improvement in the oxidation resistivity of the fibers. Moreover, the obtained fibers possessed tensile strengths and electrical resistivities comparable to those of fibers without silicon inclusion. Electrochemical analysis suggests that the included silicon is highly dispersed within the structure of the fibers. (C) 2000 Elsevier Science Ltd. All rights reserved.
  • 志知明, 片木健二, 大久保尚人, 増田隆夫, 薩摩篤, 服部忠
    触媒 41 6 424 - 426 1999年09月10日 [査読無し][通常論文]
  • 増田 隆夫
    混相流 13 2 101 - 108 1999年06月15日 [査読無し][通常論文]
  • 増田隆夫
    化学工学 63 4 201 - 204 1999年04月05日 [査読無し][通常論文]
  • T Masuda, P Tomita, Y Fujikata, K Hashimoto
    CATALYST DEACTIVATION 1999 126 89 - 96 1999年 [査読有り][通常論文]
     
    Deactivation mechanism of high siliceous Y-type zeolite catalyst was analyzed for catalytic cracking of gas-oil. First, catalytic properties, such as the amount of strong acid sites, the intracrystalline diffusivity and the accessible pore space for reactant molecules, were measured for a series of coked Y-type zeolite catalysts with different coke loadings. The relations of the coke loading to the changes in the catalytic properties were obtained. Using these relations, model equations were proposed for representing the deactivation of Y-type zeolite catalyst under the reaction control condition and the diffusion control condition. The comparison of the calculated by the model equations with the experimental data clarified that the catalytic cracking of gas-oil proceeded under the diffusion control condition, and the reduction of accessible pore space for reactant molecules was dominant factor of the deactivation.
  • 増田隆夫, 橋本健治
    ケミカルエンジニヤリング 43 12 939 - 944 1998年12月 [査読無し][通常論文]
  • T Masuda, K Hashimoto
    DEACTIVATION AND TESTING OF HYDROCARBON-PROCESSING CATALYSTS 634 62 - 76 1996年 [査読有り][通常論文]
     
    Zeolite catalysts are widely used in conversion processes of hydrocarbons, because of their high activity and shape selectivity. The conversion rate and the shape selectivity are closely related to intracrystalline diffusion rate and acidic properties of the zeolite catalyst. Carbonaceous materials called coke deposit on the catalyst during reactions, leading to changes in catalytic properties (diffusivity and acidic properties) as well as the reaction performance. This presentation reviews the mechanisms of the deactivation of zeolite catalysts caused by coke deposition from the following points of view. (1) Characterization of coke. Examination of the location of coke formation. (2) Relationship between the changes in acidic properties, and the acid strength and the acid amount. Prediction of the reduction of diffusion rate taking account of pore structure and molecular size. (3) Development of models for predicting the change in the activity and the shape selectivity.
  • AR Songip, T Masuda, H Kuwahara, K Hashimoto
    POLYMER AND OTHER ADVANCED MATERIALS 603 - 609 1995年 [査読有り][通常論文]
  • T MASUDA, H MIZOTA, K HASHIMOTO
    KAGAKU KOGAKU RONBUNSHU 20 2 170 - 177 1994年03月 [査読有り][通常論文]
     
    A model was developed for representing the activity and the shape selectivity of HZSM-5 zeolite catalyst in an integral reactor for the methylation of toluene with methanol. This model took account of the catalytic properties, such as the intracrystalline diffusivity, and the acidic properties within and on the outer surface of the zeolite crystallite. These properties were directly measured by methods developed by the authors. Two kinds of HZSM-5 zeolites with different Si/Al ratios were prepared. The methylation of toluene was performed using an integral reactor at 673 to 773 K. The experimental results were found to be well predicted by the proposed model. A chart based on the model is also presented which predicts the influence of the size of the zeolite crystallite and of the acidic properties on shape selectivity in a wide range of the methanol conversions.
  • 増田隆夫, 溝田浩敏, 橋本健治
    化学工学論文集 20 2 170 - 177 1994年 [査読無し][通常論文]
     
    A model was developed for representing the activity and the shape selectivity of HZSM-5 zeolite catalyst in an integral reactor for the methylation of toluene with methanol. This model took account of the catalytic properties, such as the intracrystalline diffusivity, and the acidic properties within and on the outer surface of the zeolite crystallite. These properties were directly measured by methods developed by the authors. Two kinds of HZSM-5 zeolites with different Si/Al ratios were prepared. The methylation of toluene was performed using an integral reactor at 673 to 773 K. The experimental results were found to be well predicted by the proposed model. A chart based on the model is also presented which predicts the influence of the size of the zeolite crystallite and of the acidic properties on shape selectivity in a wide range of the methanol conversions. © 1994, The Society of Chemical Engineers, Japan. All rights reserved.
  • Kinetic analysis of the growth of polycrystalline silicon from silane, using a rod-substrate CVD reactor
    K. Hashimoto, K. Miura, T. Masuda, M. Toma, H. Sawai, M. Kawase
    International chemical engineering 32 2 360 - 369 1992年 [査読有り][通常論文]
  • 橋本 健治, 増田 隆夫, 荒井 誠
    石油学会誌 33 3 166 - 172 1990年 [査読無し][通常論文]
  • Kenji Hashimoto, Kouji Takatani, Takao Masuda
    The Chemical Engineering Journal 29 2 85 - 96 1984年 [査読有り][通常論文]
     
    A model is presented that predicts the transient changes in both the temperature and the conversion of a single coked catalyst pellet during its burning regeneration. The following assumptions are made in developing the model. The coke, consisting of carbon and hydrogen, is dispersed in fine particle form within the catalyst pellet. The hydrogen is first oxidized at a sharp interface in the coke particle and then the carbon remaining outside the interface is gradually oxidized to yield simultaneously CO and CO2. The temperature in the pellet is uniform and the pellet is in a pseudo steady state. In addition the intrapellet diffusion effect is taken into account. Transient profiles of both the temperature and the conversion in the catalyst pellet were measured during the burning regeneration of coked silica-alumina catalysts. The experimental results were in good agreement with the results predicted by the model. © 1984.
  • Kenji Hashimoto, Kouji Takatani, Hiroshi Iwasa, Takao Masuda
    The Chemical Engineering Journal 27 3 177 - 186 1983年 [査読有り][通常論文]
     
    A multiple-reaction model is presented for the burning reaction of carbonaceous deposits, usually termed coke, on fouled catalysts. The coke, consistin. © 1983.
  • K HASHIMOTO, K MIURA, Y MIYOSHI, T MASUDA, T YAMANISHI
    NIPPON KAGAKU KAISHI 11 1815 - 1824 1981年 [査読有り][通常論文]
  • 橋本 健治, 三浦 孝一, 三吉 裕, 増田 隆夫, 山西 敏彦
    日本化学会誌 1981 11 1815 - 1824 The Chemical Society of Japan 1981年 [査読無し][通常論文]
     
    5種類のフェノール樹脂廃棄物と1種類の純粋フェノール樹脂から水蒸気賦活法によって活性炭を製造し,賦活にともなう比表面積,吸着性能の変化を詳細に検討した。もっとも一般的なフェノール樹脂の廃棄物(試料A)から原料基準で0.25以上の高収率で1000m<SUP>2</SUP>/gの比表面積を有する活性炭が得られた。この活性炭のベンゼンならびにメタノール蒸気の吸着量は市販やし殻活性炭のそれらを上回った。さらに,ヨウ素吸着量も市販の活性炭(CAL)を上回った。以上の結果,試料Aから製造した活性炭は気相吸着用,あるいは液相での低分子物質吸着用に適すると考えられた。また,試料B,Cからも三池炭を原料とした場合と同程度の比表面積を有する活性炭が得られた。<BR>つぎに,試料Aから製造した活性炭について合成廃水の吸着と加熱再生からなるサイクルを5回くり返し,一連の操作にともなう比表面積,細孔径分布,吸着性能の変化などを検討し,その結果をCAL炭に対する同様の実験結果と比較した。両活性炭の再生特性には大差がみられず,フェノール樹脂廃棄物から製造した活性炭がくり返し再生利用の可能性においても市販品に匹敵することが明らかになった。0
  • 橋本 健治, 三浦 孝一, 三吉 裕, 増田 隆夫, 山西 敏彦
    日本化学会誌 1981 11 1815 - 1824 1981年 [査読無し][通常論文]
     
    Activated carbons were produced from five kinds of waste phenol-formaldehyde (PF) resins by the steam activation. The specific surface area of an activated carbon made from a most commonly used PF resin (sample A) reached more than 1000m2/g in about 25% yield. The amounts of benzene and methanol vapors adsorbed on the activated carbon were much larger than those adsorbed on a commercial carbon (Figs. 8, 9). The amount of phenol adsorbed from the dilute aqueous solution on the activated carbon was comparable to that of another commercial carbon (Fig. 10). The specific surface areas of activated carbons produced from other two PF resins (samples B and C) were also comparable to those of an activated carbon produced from the Miike coal (Fig. 6). The activated carbon made from sample A was rendered to the repeated cycles consisting of adsorption of waste water and thermal regeneration. Although the specific surface area and the adsorption capacity of the activated carbon decreased with an increase of the number of the cycle, the extents of the decrease were similar to those of a commercial carbon (CAL). Thus it was found that the activated carbons made from waste PF resins can serve for practical use. © 1981, The Chemical Society of Japan. All rights reserved.

書籍

  • 室井 高城, 増田 隆夫 (担当:共著)
    シーエムシー出版 2018年03月 (ISBN: 4781313140) 295
  • 草壁 克己, 増田 隆夫 (担当:共著)
    三共出版 2010年03月 (ISBN: 4782706014) 126
  • Deactivation of Zeolite Catalysts by Coke
    American Chemical Society, Symposium Series 1996年
  • 触媒プロセスにおける移動現象
    化学工学の進歩、槙書店 1995年
  • ゼオライト触媒による廃プラスチックの油化技術
    廃プラスチック油化技術の開発と実施動向、IVTS 1995年
  • 種類別触媒劣化メカニズムおよび防止対策-固体酸触媒-
    触媒劣化メカニズムと防止対策 1995年
  • Transport Phenomena in Processes Using Catalysts
    1995年
  • Production of Fuel from Waste Plastics Using Zeolite Catalysts
    1995年
  • 触媒作用を利用した廃プラスチックからのガソリン合成
    化学工学シンポジウムシリーズ 1994年
  • 廃プラスチックからのガソリン製造-ポリエチレンのリサイクル-
    リサイクル技術百科-プラスチック別冊- 1994年
  • Synthesis of Gasoline from Waste Plastics using Solid Catalysts
    1994年
  • Production of Gasoline from Waste Plastics -Recycling of Polyethylene-
    1994年
  • 物理化学実験のてびき(分担執筆)
    化学同人 1993年

講演・口頭発表等

  • Synthesis of Isomorphous Substituted Ferrosilicate with MTW Structure and Their Catalytic Performance on the Methylation of b-Methylnaphthalene  [通常講演]
    Taichi Taniguchi, Keitaro Yoneta, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    The 23rd International symposium on Chemical Reaction Engineering (ISCRE23), 7th Asia-Pacific Chemical Reaction Engineering Symposium 2014年09月 ポスター発表
  • Selective synthesis of allyl compound from Glycerol over Iron-oxide Based Catalyst  [通常講演]
    Shitara Hitofumi, Terai Kazuhiro, Nakasaka Yuta, Tago Teruoki, Masuda Takao
    TOCAT7 pre-symposium 2014年05月 ポスター発表
  • Fe-Ti系触媒を用いた過熱水蒸気雰囲気下における重質油の分解軽質化  [通常講演]
    近藤永樹, 武田祐磨, 田中久美子, 中坂佑太, 多湖輝興, 増田隆夫
    化学工学会第79年会 2014年03月 ポスター発表
  • 重質油分解軽質化におけるTiO2-ZrO2系触媒の効果  [通常講演]
    近藤永樹, 田中久美子, 武田祐磨, 中坂佑太, 多湖輝興, 増田隆夫
    化学系学協会北海道支部2014年冬季研究発表会 2014年01月 口頭発表(一般)
  • Liginin Conversion to Aromatic Chemicals  [通常講演]
    Takuya Yoshikawa, Taichi Yagi, Satoshi Shinohara, Teruoki Tago, Takao Masuda
    the 6th Japan-China Workshop on Environmental Catalysis and Eco-Materials 2013年12月 口頭発表(一般)
  • Selective Formation of β,β-DimethylNaphthalene by Methylation of 2-Methylnaphthalene over MTW-type Zeolite  [通常講演]
    Gaku Watanabe, Taichi Taniguchi, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    The 4th CSE Summer School Post ISHHC-16 CRC International Symposium 2013年08月 ポスター発表
  • コーク析出量がMFI型ゼオライト結晶内におけるナフサ関連物質の吸着・拡散現象に及ぼす影響  [通常講演]
    西村純一, 今野大輝, 中坂佑太, 多湖輝興, 増田隆夫
    第111回触媒討論会 2013年03月 ポスター発表
  • Fe-MTW型ゼオライトの合成と特性評価  [通常講演]
    谷口太一, 米田敬太郎, 中坂佑太, 多湖輝興, 増田隆夫
    第111回触媒討論会 2013年03月 ポスター発表
  • MFI型ゼオライト触媒を用いたメチルシクロヘキサン接触分解の反応速度解析  [通常講演]
    大仲亮太, 今野大輝, 中坂佑太, 多湖輝興, 増田隆夫
    第111回触媒討論会 2013年03月 ポスター発表
  • n-ヘキサン接触分解におけるZSM ZSM-5ゼオライトの反応工学的触媒設計  [通常講演]
    今野大輝, 岡村拓哉, 中坂佑太, 多湖輝興, 増田隆夫
    第111回触媒討論会 2013年03月 ポスター発表
  • MTW型ゼオライト膜による含水有機溶媒からの水の選択分離  [通常講演]
    平田彩, Zhang Yaqi, 中坂佑太, 多湖輝興, 増田隆夫
    化学工学会第78年会 2013年03月 口頭発表(一般)
  • Conversion of Biodiesel-Derived Crude Glycerol into Useful Chemicals over Zirconia-Iron Oxide Catalyst  [通常講演]
    Aya Konaka, Teruoki Tago, Takuya Yoshikawa
    3rd North American Symposium on Chemical Reaction Engineering (NASCRE-3) 2013年03月 口頭発表(一般)
  • Isobutylene synthesis from water-containing acetone  [通常講演]
    Teruoki Tago, Hiroki Konno, Takuya Okamura, Yuta Nakasaka, Takao Masuda
    3rd North American Symposium on Chemical Reaction Engineering (NASCRE-3) 2013年03月 ポスター発表
  • 炭素資源転換における触媒技術の動向と展望  [通常講演]
    多湖 輝興, 中坂 佑太, 増田 隆夫
    石炭・炭素資源利用技術第148委員会 第138回研究会 2013年02月 公開講演,セミナー,チュートリアル,講習,講義等
  • TiO2-ZrO2系触媒を用いた過熱水蒸気雰囲気下における重質油の分解軽質化  [通常講演]
    田中久美子, 武田祐磨, 近藤永樹, 北口達也, 中坂佑太, 多湖輝興, 増田隆夫
    化学系学協会北海道支部2013年冬季研究発表会 2013年01月 口頭発表(一般)
  • 固体酸触媒,水/ブタノール溶媒を反応場とするリグニン低分子化機構の検討とフェノール類の製造  [通常講演]
    八木太一, 吉川琢也, 篠原悟志, 龍門尚徳, 中坂佑太, 多湖輝興, 増田隆夫
    化学系学協会北海道支部2013年冬季研究発表会 2013年01月 口頭発表(一般)
  • MFI型ゼオライトを用いたヘキサン接触分解の反応速度解析  [通常講演]
    岡村拓哉, 今野大輝, 中坂佑太, 多湖輝興, 増田隆夫
    化学系学協会北海道支部2013年冬季研究発表会 2013年01月 口頭発表(一般)
  • 酸化鉄系触媒によるグリセリンからのアリルアルコールの選択合成  [通常講演]
    古仲彩, 中村文香, 吉川琢也, 中坂佑太, 多湖輝興, 増田隆夫
    化学系学協会北海道支部2013年冬季研究発表会 2013年01月 口頭発表(一般)
  • MTW型ゼオライトの結晶サイズ制御と反応特性評価  [通常講演]
    谷口太一, 米田敬太郎, 中坂佑太, 多湖輝興, 増田隆夫
    化学系学協会北海道支部2013年冬季研究発表会 2013年01月 口頭発表(一般)
  • Production of phenolic compounds from lignin via depolymerization and catalytic cracking  [通常講演]
    Taichi Yagi, Takuya Yoshikawa, Satoshi Shinohara, Naonori Ryumon, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    The 25th International Symposium on Chemical Engineering 2012年12月 ポスター発表
  • Catalytic cracking of extra heavy oil over FeOx-based catalyst under subcritical water  [通常講演]
    Kumiko Tanaka, Tatsuya Kitaguchi, Yuma Takeda, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    The 25th International Symposium on Chemical Engineering 2012年12月 ポスター発表
  • n-Hexane Cracking for Light Olefins Selective Synthesis over Nano-scale ZSM-5 zeolite  [通常講演]
    Hiroki Konno, Takuya Okamura, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    The 25th International Symposium on Chemical Engineering 2012年12月 口頭発表(一般)
  • Conversion of Inedible Biomass Wastes to Petroleum-related Useful Chemicals Using Iron Oxide Catalysts  [通常講演]
    Takao Masuda, Teruoki Tago
    22th Annual Saudi-Japan Symposium 2012年11月 口頭発表(招待・特別)
  • ZSM-5 を用いたn-ヘキサン接触分解の反応工学的解析  [通常講演]
    岡村拓哉, 今野大輝, 中坂佑太, 多湖輝興, 増田隆夫
    第28回ゼオライト研究発表会 2012年11月 口頭発表(一般)
  • MOR 型ゼオライトの構造規定剤フリー合成における界面活性剤添加効果  [通常講演]
    谷口太一, 藤原沙緒梨, 中坂佑太, 多湖輝興, 増田隆夫
    第28回ゼオライト研究発表会 2012年11月 口頭発表(一般)
  • Size/morphology controlled synthesis of zeolite crystals and their applications  [通常講演]
    Teruoki Tago, Takao Masuda
    10th Japan-Korea Symposium on Materials and Interfaces 2012年11月 口頭発表(招待・特別)
  • Fe-Ti系触媒を用いた過熱水蒸気雰囲気下での常圧残油の分解軽質化  [通常講演]
    武田祐磨, 北口達也, 田中久美子, 中坂佑太, 多湖輝興, 増田隆夫
    第42回石油・石油化学討論会 2012年10月 ポスター発表
  • 酸化鉄系触媒を用いた亜臨界水雰囲気下におけるビチューメン分解反応の速度解析  [通常講演]
    田中久美子, 北口達也, 武田祐磨, 中坂佑太, 多湖輝興, 増田隆夫
    第42回石油・石油化学討論会 2012年10月 口頭発表(招待・特別)
  • 酸化鉄触媒を用いた過熱水蒸気雰囲気下でのリグニン可溶化液からのフェノール類製造  [通常講演]
    篠原悟志, 吉川琢也, 八木太一, 龍門尚徳, 中坂佑太, 多湖輝興, 増田隆夫
    第42回石油・石油化学討論会 2012年10月 口頭発表(一般)
  • Catalytic Cracking of n-Hexane Cracking over MFI-Type Zeolites with Different Crystal Sizes  [通常講演]
    Yuta Nakasaka, Hiroki Konno, Akihiro Okabe, Teruoki Tago, Takao Masuda
    22th International Symposium on Chemical Reaction Engineering 2012年09月 ポスター発表
  • Production of Useful Chemicals from Lignin-derived Slurry Liquid using Iron Oxide Catalyst  [通常講演]
    Takuya Yoshikawa, Satoshi Shinohara, Taichi Yagi, Naonori Ryumon, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    7th International Conference on Environmental Catalysis (ICEC 2012) 2012年09月 口頭発表(一般)
  • Conversion of Glycerol into Allyl Alcohol over Potassium-Supported Iron Oxide Catalyst  [通常講演]
    A. Konaka, T. Tago, T. Yoshikawa, A. Nakamura, T. Masuda
    7th International Conference on Environmental Catalysis (ICEC 2012) 2012年09月 ポスター発表
  • MTW型ゼオライトの結晶サイズ制御と n-hexaneeの 接触分解  [通常講演]
    谷口太一, 藤原沙緒梨, 中坂佑太, 多湖輝興, 増田隆夫
    第110回触媒討論会 2012年09月 口頭発表(一般)
  • 結晶サイズの異なるZSM-5ゼオライトを用いたナフサ留分炭化水素の接触分解  [通常講演]
    今野 大輝, 岡村 拓哉, 中坂 佑太, 多湖 輝興, 増田 隆夫
    第110回触媒討論会 2012年09月 口頭発表(一般)
  • リグニンから芳香族化合物を製造する可溶化・接触分解反応プロセスの開発  [通常講演]
    八木太一, 吉川琢也, 篠原悟志, 龍門尚徳, 中坂佑太, 多湖輝興, 増田隆夫
    第110回触媒討論会 2012年09月 口頭発表(一般)
  • グリセリンからのアリルアルコールの選択合成を可能にする酸化鉄触媒の開発  [通常講演]
    古仲彩, 中村文香, 吉川琢也, 中坂佑太, 多湖輝興, 増田隆夫
    第110回触媒討論会 2012年09月 口頭発表(一般)
  • Controlled and Rapid Growth of MTT Zeolite Crystals with Low Aspect Ratio in a Microwave Reactor  [通常講演]
    Oki Muraza, Idris Bakare, Abdul-Lateef Adedigba, Teruoki Tago, Adnan M.J. Al-Amer, Zain H. Yamani, Takao Masuda
    22th International Symposium on Chemical Reaction Engineering 2012年09月 ポスター発表
  • Upgrading of Oil Sand Bitumen over Iron-oxide Catalyst using Flow Type reactor unde Sub/Super-Critical Water Conditions  [通常講演]
    Tatsuya Kitaguchi, Yusuke Sato, Teruoki Tago, Takao Masuda
    22th International Symposium on Chemical Reaction Engineering 2012年09月 口頭発表(一般)
  • ゼオライト触媒を用いたn-ヘキサンクラッキングにおける反応工学的解析  [通常講演]
    岡村拓哉, 今野大輝, 中坂佑太, 多湖輝興, 増田隆夫
    第52回オーロラセミナー 2012年08月 ポスター発表
  • 結晶サイズを制御したMTW型ゼオライトの合成及びn-hexane接触分解への展開  [通常講演]
    谷口太一, 藤原沙緒梨, 中坂佑太, 多湖輝興, 増田隆夫
    第52回オーロラセミナー 2012年08月 ポスター発表
  • 可溶化・接触分解反応プロセスによるリグニンからの有用化学物質製造  [通常講演]
    八木太一, 吉川琢也, 篠原悟志, 龍門尚徳, 中坂佑太, 多湖輝興, 増田隆夫
    第52回オーロラセミナー 2012年08月 ポスター発表
  • アルカリ金属担持酸化鉄触媒を用いたグリセリンからの有用化学物質の製造  [通常講演]
    古仲彩, 中村文香, 吉川琢也, 中坂佑太, 多湖輝興, 増田隆夫
    第52回オーロラセミナー 2012年08月 ポスター発表
  • Measurement of Intracrystalline Diffusivities of Aromatics within Si-beta in Cyclohexane Solution  [通常講演]
    Yuta Nakasaka, Sayuri Katsuta, Teruoki Tago, Satoshi Inagaki, Yoshihiro Kubota, Takao Masuda
    International Symposium on Zeolites and MicroPorous Crystals 2012 2012年07月 口頭発表(基調)
  • Effect of surfactant addition and Na/Al ratio on crystal size of FAU zeolite  [通常講演]
    Taichi Taniguchi, Saori Fujiwara, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    International Symposium on Zeolites and MicroPorous Crystals 2012 2012年07月 ポスター発表
  • Kinetics for catalytic cracking of n-hexane over MFI-type zeolites with different crystal sizes  [通常講演]
    Takuya Okamura, Hiroki Konno, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    International Symposium on Zeolites and MicroPorous Crystals 2012 2012年07月 ポスター発表
  • Catalytic Cracking of n-Hexane over Mono-dispersed Nano-crystalline MFI-type Zeolite  [通常講演]
    Hiroki Konno, Takuya Okamura, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    International Symposium on Zeolites and MicroPorous Crystals 2012 2012年07月 ポスター発表
  • Production of Light Olefins from n-Hexane Cracking over MFI Zeolites with Nano- and Macro-Crystal Sizes  [通常講演]
    Teruoki Tago, Hiroki Konno, Takuya Okamura, Yuta Nakasaka, Takao Masuda
    The 15th International Congress on Catalysis 2012年07月 ポスター発表
  • Activity and Stability of iron oxide catalyst toward conversion of biomass tar into useful chemicals  [通常講演]
    Dieni Mansur, Mana Shimokawa, Teruoki Tago, Takao Masuda
    15th International Congress on Catalysis 2012 2012年07月 ポスター発表
  • Production of Useful Chemicals from Bio-diesel Derived Crude Glycerol over Zirconia-Iron Oxide Catalyst  [通常講演]
    Takuya Yoshikawa, Taichi Yagi, Satoshi Shinohara, Testuya Fukunaga, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    15th International Congress on Catalysis 2012 2012年07月 口頭発表(一般)
  • Kinetc Analysis of Burning Regeneration of Coked MFI-type Zeolites Obtained by Catalytic Cracking of n-Hexane  [通常講演]
    Teruoki Tago, Takuya Okamura, Hiroki Konno, Yuta Nakasaka, Takao Masuda
    22th International Symposium on Chemical Reaction Engineering 2012年 口頭発表(一般)

作品等

  • Efficient Recovery of Biomass Derived Energy
    2003年 -2005年
  • Development of an Integrated Urban and Solid Waste Treatment System Incorporating Technologies of Transforming Urban Garbage to value-added Products
    1998年 -2003年
  • Efficient Use of Oil Palm Wastes as Renewable Resource for Energy & Chemicals
    1998年 -2000年
  • Development of Processes Utilizing New Reaction Technologies
    1997年 -2000年

その他活動・業績

  • 吉川琢也, 小山啓人, 小山啓人, 佐藤信也, 増田隆夫 Cellulose Communications 24 (4) 175‐180 2017年12月01日 [査読無し][通常論文]
  • 多湖輝興, 吉川琢也, 中坂佑太, 藤墳大裕, 増田隆夫 オレオサイエンス 17 (7) 313‐319 2017年07月01日 [査読無し][通常論文]
  • 多湖 輝興, 吉川 琢也, 中坂 佑太, 藤墳 大裕, 増田 隆夫 Journal of the Japan Institute of Energy = 日本エネルギー学会誌 95 (7) 535 -540 2016年07月 [査読無し][通常論文]
  • 増田隆夫, 中坂佑太, 吉川琢也, 多湖輝興, 鷹觜利公, 佐藤信也, 小山啓人 触媒 58 (2) 74 -79 2016年04月10日 [査読無し][通常論文]
  • 奈良林直, 千葉豪, 小崎完, 増田隆夫, 中坂佑太, 佐藤修彰, 秋山大輔 日本原子力学会春の年会予稿集(CD-ROM) 2016 ROMBUNNO.1D20 2016年03月16日 [査読無し][通常論文]
  • 中坂佑太, 多湖輝興, 増田隆夫 ゼオライト 32 (2) 53 -61 2015年06月10日 [査読無し][通常論文]
  • 小西亮太, 川又勇来, 篠原悟志, 八木太一, 小山啓人, 中坂佑太, 多湖輝興, 増田隆夫 化学工学会年会研究発表講演要旨集(CD-ROM) 80th ROMBUNNO.XB237 2015年03月19日 [査読無し][通常論文]
  • 渡部岳, 谷口太一, 中坂佑太, 多湖輝興, 増田隆夫 触媒討論会講演予稿集 115th 97 2015年03月10日 [査読無し][通常論文]
  • 谷口太一, 米田敬太郎, 中坂佑太, 多湖輝興, 増田隆夫 触媒討論会講演予稿集 115th 95 2015年03月10日 [査読無し][通常論文]
  • 近藤 永樹, 中坂 佑太, 多湖 輝興, 増田 隆夫 日本エネルギー学会誌 94 (1) 67 -73 2015年01月20日 [査読無し][通常論文]
     
    From the perspective of diversification of energy resources, a technological development which can convert unused fossil resources into useful fuels has been required. Especially, oil sand bitumen is one of the promising candidates, of which the deposit is larger than that of the petroleum. Consequently, we have developed iron oxide (FeOx) composite catalysts which can convert heavy oil into lighter fuel in superheated steam condition. In this catalytic cracking system, the lattice oxygen in FeOx is main active sites to decompose heavy oil. When the lattice oxygen is consumed during the oxidative reaction, the crystal structure of FeOx changes from hematite to magnetite and the catalyst is deactivated. Therefore, zirconia (ZrO_2) and ceria (CeO_2) that exhibit an activity to produce active oxygen species from water are loaded on FeOx, and the detect of lattice oxygen is regenerated by active oxygen species. Moreover, we have succeeded in improving the resistance to sintering of FeOx by alumina (Al_2O_3 ) addition. In this study, catalytic cracking of oil sand bitumen (abbreviated as bitumen) into lighter fuels such as gas oil and VGO was carried out under high pressure superheated steam and super critical water atmospheres. The effects of reaction atmosphere on the yields of the light fuels and the amount of carbonaceous residue (coke on catalyst and residue on reactor wall) were examined.
  • 米田敬太郎, 谷口太一, 中坂佑太, 多湖輝興, 増田隆夫 ゼオライト研究発表会講演予稿集 30th 41 2014年11月26日 [査読無し][通常論文]
  • 長谷川実穂, ZHANG Yaqi, 中坂佑太, GUCUYENER Canan, 多湖輝興, GASCON Jorge, KAPTEIJN Freek, 増田隆夫 ゼオライト研究発表会講演予稿集 30th 21 2014年11月26日 [査読無し][通常論文]
  • 設楽裕史, 寺井和宏, 中坂佑太, 多湖輝興, 増田隆夫 石油・石油化学討論会講演要旨 44th 286 2014年10月16日 [査読無し][通常論文]
  • 近藤永樹, 田中久美子, 中坂佑太, 多湖輝興, 増田隆夫 石油・石油化学討論会講演要旨 44th 252 -253 2014年10月16日 [査読無し][通常論文]
  • 西村純一, 大仲亮太, 中坂佑太, 多湖輝興, 増田隆夫 石油・石油化学討論会講演要旨 44th 58 2014年10月16日 [査読無し][通常論文]
  • 近藤 永樹, 田中 久美子, 武田 祐磨, 中坂 佑太, 多湖 輝興, 増田 隆夫 日本エネルギー学会大会講演要旨集 (23) 10 -11 2014年07月14日 [査読無し][通常論文]
     
    From the perspective of diversification of energy resources, it has been required to develop a new technology to convert unused fossil resources into useful fuels. We have developed mixed metal oxide catalysts and conducted an upgrading of atmospheric residue (AR) under superheated steam using the catalyst. Moreover, we have found that TiO_2-ZrO_2 based catalysts exhibits an acidic cracking activity to decompose for heavy oil under superheated steam atmosphere. In this study, effect of the catalyst compositions on the decomposition activity was examined. Nb_2O_5, Al_2O_3, and CeO_2 were used as third catalytic components to TiO_2-ZrO_2. The TiO_2-ZrO_2-CeO_2 catalyst with the composition of Ti : Zr : Ce = 48 : 48 : 4 exhibited the high and stable activity. Furthermore, the coke formation on the catalyst was successfully suppressed, leading to the stable catalyst activity.
  • Teruoki Tago, Hirofumi Shitara, Kazuhiro Terai, Yuta Nakasaka, Takao Masuda Catalysis and Reaction Engineering Division 2014 - Core Programming Area at the 2014 AIChE Annual Meeting 2 991 2014年01月01日 [査読無し][通常論文]
  • 佐藤 信也, 麓 恵理, 鷹觜 利公, 小山 啓人, 増田 隆夫 石炭科学会議発表論文集 (50) 20 -21 2013年10月21日 [査読無し][通常論文]
     
    For the detailed average structure analysis of heavy hydrocarbons, the determinations of (1) tertiary and quaternary aromatic carbon distributions by ^<13>C-NMR using dept and quat methods, (2) carbonyls by FT-IR, and (3) hydroxyl groups by acetylation with trifluoroacetic acid anhydride followed by ^<19>F-NMR were performed besides the normal analyses. The detailed structures of aromatic rings were estimated using those data.
  • 多湖 輝興, 吉川 琢也, 中坂 佑太, 増田 隆夫 觸媒 = Catalyst 55 (5) 270 -275 2013年10月10日 [査読無し][通常論文]
  • 佐藤 信也, 鷹觜 利公, 梶谷 智史, 増田 隆夫 日本エネルギー学会大会講演要旨集 (22) 14 -15 2013年07月29日 [査読無し][通常論文]
     
    Determination of hydroxyl groups were conducted on heavy hydrocarbon fractions including lignin degradation products. The acetylation was conducted using trifluoroacetic anhydride and pyridine-d_5 in chloroform-d followed by the determination of trifluoromethyl group by ^<19>F-NMR. Phenolic and alcoholic hydroxyl groups were distinguished by the chemical shifts. The amounts of the hydroxyl groups were well agreed with the results by an average molecular structural analysis.
  • 今野 大輝, 多湖 輝興, 中坂 佑太, 増田 隆夫 石油学会 年会・秋季大会講演要旨集 2013 (0) 157 -157 2013年 [査読無し][通常論文]
     
    低級オレフィン合成を目的としたZSM-5ゼオライトによるアセトン転換反応を実施した。ゼオライトの結晶サイズを微小化することで触媒寿命が向上した。これは外表面積の増大によりコーク析出の影響が低減した為だと考えられる。さらなる寿命の向上を目的とし、シラン処理法によるZSM-5ゼオライトの位置選択的不活性化を行った。その結果、長時間の活性の維持と高い低級オレフィン収率を示した。
  • 篠原 悟志, 吉川 琢也, 八木 太一, 小山 啓人, 中坂 佑太, 多湖 輝興, 増田 隆夫 石油学会 年会・秋季大会講演要旨集 2013 (0) 2013年 [査読無し][通常論文]
     
    可溶化・接触分解から成る2段階反応プロセスによるリグニンからのフェノール類の製造を検討した。本研究では、可溶化反応における反応条件の最適化を行うと共に、リグニンの低分子化機構を検討し、フェノール類収率の向上を図った。その結果、反応条件の最適化によるフェノール類収率の向上に成功し、リグニンの低分子化は、構成単位間の全結合のうち約6割を占めるエーテル結合の加水分解により進行することを明らかにした。
  • 篠原 悟志, 吉川 琢也, 八木 太一, 梶谷 智史, 中坂 佑太, 多湖 輝興, 増田 隆夫 石油学会 年会・秋季大会講演要旨集 2013 (0) 2013年 [査読無し][通常論文]
     
    未利用木質資源であるリグニンは、アルキルフェノールの重縮合体であり、フェノール等の有用化学物質への転換が期待される。当研究室では、可溶化・接触分解プロセスによるリグニンからのフェノール類製造に成功している。本研究では、可溶化におけるリグニン低分子化機構の解明を目的とし、固体酸触媒存在下、水/アルコール溶媒中でリグニンモデル物質の可溶化を実施した。結果、可溶化によりリグニン中の約60 %の結合を分解できることが推察された。
  • 増田隆夫, 多湖輝興 石油産業活性化センター技術開発・調査事業成果発表会要旨集(技術開発事業関連)(CD-ROM) 2011 ROMBUNNO.S4.2.6 2011年06月 [査読無し][通常論文]
  • 多湖 輝興, 吉川 琢也, 増田 隆夫 バイオインダストリー 28 (2) 45 -50 2011年02月 [査読無し][通常論文]
  • 吉川 琢也, 八木 太一, 篠原 悟志, 福永 哲也, 中坂 佑太, 多湖 輝興, 増田 隆夫 石油学会年会・秋季大会講演要旨集 (2011) 257 -258 2011年 [査読無し][通常論文]
     
    木質バイオマスの主要成分であるリグニンは、アルキルフェノールの重縮合体であり、樹脂原料として需要の高いフェノール等の樹脂原料芳香族への転換が期待される。そこで本研究では、新規リグニン転換法として、リグニンを高温・高圧下で低分子化する段階と、得られたリグニン構成2量体や単量体を酸化鉄触媒により接触分解する段階から成る2段反応プロセスの開発を目的とし、各段階の反応形式と反応条件の最適化を検討した。
  • ゼオライトナノクリスタルの合成と応用
    今野大輝, 多湖輝興, 中坂佑太, 増田隆夫 月刊 化学工業 62 (10) 1 -8 2011年 [査読無し][招待有り]
  • 中坂 佑太, 岡村 拓哉, 今野 大輝, 川原 貴仁, 多湖 輝興, 増田 隆夫 石油学会 年会・秋季大会講演要旨集 2011 (0) 16 -16 2011年 [査読無し][通常論文]
     
    MFI型、BEA型ゼオライト触媒を用いたn -ヘキサン接触分解の反応速度解析を550~650℃の温度領域において行った。ゼオライト種に依らず反応速度はヘキサン濃度に比例し、反応速度定数の活性化エネルギーはゼオライトのトポロジーによって異なることがわかった。また、反応速度定数とゼオライト細孔内におけるn -ヘキサンの拡散係数から触媒有効係数について検討を行った。
  • 吉川 琢也, 八木 太一, 篠原 悟志, 福永 哲也, 中坂 佑太, 多湖 輝興, 増田 隆夫 石油学会 年会・秋季大会講演要旨集 2011 (0) 176 -176 2011年 [査読無し][通常論文]
     
    木質バイオマスの主要成分であるリグニンは、アルキルフェノールの重縮合体であり、樹脂原料として需要の高いフェノール等の樹脂原料芳香族への転換が期待される。そこで本研究では、新規リグニン転換法として、リグニンを高温・高圧下で低分子化する段階と、得られたリグニン構成2量体や単量体を酸化鉄触媒により接触分解する段階から成る2段反応プロセスの開発を目的とし、各段階の反応形式と反応条件の最適化を検討した。
  • 北口 達也, 田中 久美子, 佐藤 祐介, 武田 祐磨, 多湖 輝興, 増田 隆夫 石油学会 年会・秋季大会講演要旨集 2011 (0) 19 -19 2011年 [査読無し][通常論文]
     
    近年エネルギー資源の多様化により、埋蔵量の多い超重質油の有効利用が求められている。本研究では、酸化鉄触媒を用いて亜臨界水中でオイルサンドビチューメンの軽質燃料化を実施した。反応温度420 ℃、圧力約20 MPaにおいて分解実験を行うことで、水、希釈剤使用量を削減すると共に、Gas Oil等の有用成分収率70 %を維持することに成功した。また、高圧流通系では触媒上のコークを低減でき、かつ長時間の反応にも安定した分解活性を示した。
  • 田中 久美子, 北口 達也, 佐藤 祐介, 武田 祐磨, 多湖 輝興, 増田 隆夫 石油学会 年会・秋季大会講演要旨集 2011 (0) 20 -20 2011年 [査読無し][通常論文]
     
    本研究では、酸化鉄系触媒を用い常圧過熱水蒸気~超臨界水雰囲気下でのビチューメン改質反応を実施した。常圧過熱水蒸気雰囲気と比較し、反応圧力19MPa以上の高圧水蒸気~超臨界水雰囲気では、コーク生成を抑制しつつビチューメンの軽質化が効果的に進行した。ビチューメンから得られたマルテン成分とアスファルテン成分を原料に反応実験を行ったところ、超臨界水雰囲気下ではアスファルテン成分の軽質化とコーク生成抑制が可能であることが明らかとなった。
  • 守屋 由介, 増田 隆夫, 多湖 輝興 下水道研究発表会講演集 48 139 -141 2011年 [査読無し][通常論文]
  • 園山 希, 吉川 琢也, 林 潤一郎, 多湖 輝興, 増田 隆夫 石炭科学会議発表論文集 (47) 112 -113 2010年09月21日 [査読無し][通常論文]
     
    We carried out the catalytic cracking of pyrolytic oil derived from Loy Yang coal with an iron oxide catalyst bearing Ce, Zr and Al in a steam atmosphere. The durability of iron oxide catalysts was examined by powder X-ray diffractometry(XRD). Iron oxide catalysts required an appropriate amount of Ce, Zr and Al for the cracking of the pyrolytic oil in a steam atmosphere. The steam partial pressure of 87 kPa and the reaction temperature of 773 K were favorable to the durability of the iron oxide catalysts.
  • 多湖 輝興, 吉川 琢也, 増田 隆夫 ジェティ 58 (10) 36 -38 2010年09月 [査読無し][通常論文]
  • 舟井 啓, 多湖 輝興, 増田 隆夫 日本エネルギー学会誌 89 (3) 231 -236 2010年03月20日 [査読無し][通常論文]
     
    Recently, the demand for useful fuels such as gasoline and kerosene has grown every year. From a viewpoint of energy source diversification, new techniques to produce the fuels from unused heavy oils such as oil sand, oil shale and Orinoco tar are required. Especially, the deposits of oil sand and oil shale are larger than that of crude oil. Thus, we have developed iron oxide catalyst to decompose heavy oils with steam. In this article, we introduce decomposition of waste plastic, a biomass waste, and heavy oil using iron oxide catalyst. Moreover, a consumption-supply cycle of lattice oxygen in steam decomposition of heavy oil using iron oxide catalyst is investigated.
  • 舟井 啓, 多湖 輝興, 増田 隆夫 化学工学 = Chemical engineering 74 (2) 57 -59 2010年02月05日 [査読無し][通常論文]
  • 高含水バイオマス廃棄物からの石油化学関連物質生成触媒プロセス
    舟井啓, 多湖輝興, 増田隆夫 次世代バイオエタノール生産の技術革新と事業展開,フロンティア出版 249 -254 2010年 [査読無し][通常論文]
  • 触媒反応による未利用バイオマスからの基礎化学物質合成
    多湖輝興, 増田隆夫 未利用バイオマスの活用技術と事業性評価,サイエンス&テクノロジー株式会社 176 -182 2010年 [査読無し][招待有り]
  • 山崎 聖治, 今野 大輝, 中坂 佑太, 二宮 航, 多湖 輝興, 増田 隆夫 化学工学会 研究発表講演要旨集 2010 (0) 634 -634 2010年 [査読無し][通常論文]
  • 園山 希, 信田 一成, 木村 篤治, 細貝 聡, 林 潤一郎, 多湖 輝興, 増田 隆夫 化学工学会 研究発表講演要旨集 2010 (0) 625 -625 2010年 [査読無し][通常論文]
  • 舟井 啓, 多湖 輝興, 増田 隆夫 化学工学会 研究発表講演要旨集 2010 (0) 623 -623 2010年 [査読無し][通常論文]
  • 中村 文香, 吉川 琢也, 舟井 啓, 多湖 輝興, 増田 隆夫 化学工学会 研究発表講演要旨集 2010 (0) 622 -622 2010年 [査読無し][通常論文]
  • 吉川 琢也, 舟井 啓, 福永 哲也, 多湖 輝興, 増田 隆夫 石油学会 年会・秋季大会講演要旨集 2010 (0) 118 -118 2010年 [査読無し][通常論文]
     
    木質バイオマスの主要成分であるリグニンは、アルキルフェノールの重縮合体であり、樹脂原料として需要の高いフェノール等の樹脂原料芳香族への転換が期待される。そこで本研究では、新規リグニン転換法として、リグニンを高温・高圧下で低分子化する段階と、得られたリグニン構成2量体や単量体を酸化鉄触媒により接触分解する段階から成る2段階反応プロセスの開発を目的とし、樹脂原料芳香族の収率向上について検討した。
  • 佐藤 祐介, 北口 達也, 舟井 啓, 森本 正人, 佐藤 信也, 鷹觜 利公, 多湖 輝興, 増田 隆夫 石油学会 年会・秋季大会講演要旨集 2010 (0) 173 -173 2010年 [査読無し][通常論文]
     
    エネルギー資源の多様化の観点から、原油の代替として埋蔵量の多い超重質油を軽質化して有効利用する技術開発が求められている。そこで本研究では酸化鉄系触媒により安価な水を水素源として超重質油(ビチューメン)を軽質燃料化することを目的とした。水共存下で有効に作用する本触媒はビチューメンの軽質化に有効であり、さらに超臨界水雰囲気下、流通式反応器を利用することで触媒上に堆積する残渣を低減させることに成功した。
  • 北口 達也, 佐藤 祐介, 舟井 啓, 多湖 輝興, 増田 隆夫 石油学会 年会・秋季大会講演要旨集 2010 (0) 174 -174 2010年 [査読無し][通常論文]
     
    近年エネルギー資源の多様化により、埋蔵量の多い超重質油の有効利用が求められている。本研究では、酸化鉄触媒を用いた高圧過熱水蒸気・超臨界水雰囲気下で、超重質油(ビチューメン)の軽質燃料化を実施した。反応温度420℃においてビチューメン濃度を変化させたとき、圧力約27MPaでは反応性の濃度依存性はないが、圧力約23MPaではビチューメン濃度が下がると、軽質化が効果的に進行することが明らかとなった。
  • 北口 達也, 佐藤 祐介, 篠岡 実樹, 舟井 啓, 多湖 輝興, 増田 隆夫 石油学会 年会・秋季大会講演要旨集 2010 (0) 10 -10 2010年 [査読無し][通常論文]
     
    近年エネルギー資源の多様化により、埋蔵量の多い超重質油の有効利用が求められている。本研究では、酸化鉄触媒を用いた過熱加圧水~超臨界水雰囲気下で、超重質油(ビチューメン)の軽質燃料化を実施した。反応温度420℃、圧力18.9-22.3MPaのとき超重質油の軽質化が効果的に進行し、ガソリン+ケロセン成分を原料ビチューメンに比べ約3倍に増加させることに成功した。
  • 吉川 琢也, 多湖 輝興, 増田 隆夫 Journal of the Japan Petroleum Institute 53 (3) 178 -183 2010年 [査読無し][通常論文]
     
    酸化鉄複合触媒(ZrO2–Al2O3–FeOx触媒)を用いて,植物バイオマス由来芳香族を有用芳香族へ転換するためにその触媒活性について検討した。リグニン構成物質関連芳香族化合物として,2環芳香族化合物(ジフェニルエーテル,ジフェニルメタン,2-ベンジルオキシフェノール),および単環芳香族化合物(グアヤコール,アセトフェノン,1-フェニル-1-プロパノール)を原料にZrO2–Al2O3–FeOx触媒を用いて接触分解を行った。反応実験は常圧の固定床流通式反応器を用いて行い,反応温度773 Kとした。2環芳香族化合物を原料とした実験では,ジフェニルエーテルやジフェニルメタンは分解されず,2-ベンジルオキシフェノールは熱分解の後,ZrO2–Al2O3–FeOx触媒上での反応によりトルエンとフェノールが生成した。単環芳香族化合物を原料とした実験では,グアヤコールとアセトフェノンからフェノール(54 C-mol%)とベンゼン(29 C-mol%)がそれぞれ選択的に生成した。その際,メトキシ基とカルボニル基の酸化分解により主にCO2が生成したが,1-フェニル-1-プロパノールでは,主に脂肪族水酸基の脱水反応が起こり,1-フェニル-1-プロペンが生成した。したがって,本触媒は,芳香環どうしのアルキルエーテル結合,および芳香環に結合するメトキシ基とカルボニル基の分解に有効であることが分かった。
  • 園山 希, 信田 一成, 木村 篤治, 細貝 聡, 林 潤一郎, 多湖 輝興, 増田 隆夫 石炭科学会議発表論文集 (46) 4 -5 2009年11月26日 [査読無し][通常論文]
     
    We carried out catalytic cracking of pyrolytic oil derived from Loy Yang coal with an iron oxide catalyst bearing Zr and Al in a steam atmosphere. Although the pyrolytic oil contained 12.8% on an oil carbon basis of the chemicals that were monocyclic hydrocarbons, phenols and ketones, the total yield of the chemicals by the cracking with the catalyst was more than 25% on an oil carbon basis. The yield of product gas was less than 5.0% on an oil carbon basis. Also, the cracking was effective in decomposing the initial heavy tar. We indicated that the catalyst had a possibility of the production of oxygenated compounds from Loy Yang coal tar via not gasification but the cracking.
  • 舟井啓, 佐藤由実, 佐藤康治, 田島健次, 多湖輝興, 増田隆夫 触媒討論会討論会A予稿集 104th 138 2009年09月27日 [査読無し][通常論文]
  • 舟井 啓, 多湖 輝興, 増田 隆夫 日本エネルギー学会誌 88 (3) 187 -192 2009年03月20日 [査読無し][通常論文]
     
    Recently, the demand for useful fuels such as gasoline and kerosene has grown every year and approximately half of the primitive petroleum deposits have already been consumed. Therefore, new techniques to produce the fuels from unused heavy oils such as atomospheric- or vacuum-distilled residual oils, oil sand, and Orinoco tar are required. Especially, the deposit of Oil sand and Orinoco tar are larger than that of the petroleum deposit. Thus, we have developed zirconia, alumina, and iron oxide composite catalyst (ZrO_2-Al_2O_3-FeO_x catalyst) to decompose petroleum residual oil with steam. In this article, we introduce the production of lighter fuels from the heavy oil and extra heavy oil with steam using ZrO_2-Al_2O_3-FeO_x catalyst, and effects of the content of Al_2O_3 and ZrO_2 content in ZrO_2-Al_2O_3-FeO_x catalyst on catalytic activity and stability are investigated.
  • Eri Fumoto, Teruoki Tago, Takao Masuda Journal of Chemical Engineering of Japan 43 (3) 184 -190 2009年 [査読有り][通常論文]
  • 篠岡 実樹, 北口 達也, 佐藤 祐介, 舟井 啓, 多湖 輝興, 増田 隆夫 石油学会 年会・秋季大会講演要旨集 2009 (0) 18 -18 2009年 [査読無し][通常論文]
     
    近年化石資源の枯渇が懸念されており、埋蔵量の多い超重質油や、原油精製で副生する重質油を有効利用する技術が求められている。本研究では酸化鉄触媒を用いた水蒸気分解により重質油・超重質油を軽質燃料化することを目的とした。結果、重質油である常圧残油は十分に軽質化され、約50%のガソリン+ケロセンを生成することに成功した。また超重質油であるビチューメンでも反応実験を行い、十分に軽質化することがわかった。
  • 吉川 琢也, 舟井 啓, 多湖 輝興, 増田 隆夫 化学工学会 研究発表講演要旨集 2009 (0) 379 -379 2009年 [査読無し][通常論文]
  • 池田 翔子, 今野 大輝, 二宮 航, 中坂 佑太, 多湖 輝興, 増田 隆夫 化学工学会 研究発表講演要旨集 2009 (0) 380 -380 2009年 [査読無し][通常論文]
  • 佐藤 由実, 舟井 啓, 多湖 輝興, 増田 隆夫 化学工学会 研究発表講演要旨集 2009 (0) 386 -386 2009年 [査読無し][通常論文]
  • 増田 隆夫 触媒 = Catalysts & Catalysis 50 (4) 2008年06月10日 [査読無し][通常論文]
  • 多湖 輝興, 岩貝 和幸, 増田 隆夫 ケミカルエンジニヤリング 53 (6) 432 -439 2008年06月 [査読無し][通常論文]
  • Baohua Liu, Teruoki Tago, Eri Fumoto, Jun-ichirou Hayashi, Takao Masuda Journal of Chemical Engineering of Japan 41 (5) 369 -373 2008年 [査読有り][通常論文]
  • Duangkamol Na-Ranong, Ratanaporn Yuangsawad, Teruoki Tago, Takao Masuda Korean Journal of the Chemical Engineering 25 (3) 426 -430 2008年 [査読有り][通常論文]
  • 市川 龍也, 橋本 龍馬, 中坂 佑太, 多湖 輝興, 増田 隆夫 化学工学会 研究発表講演要旨集 2008 (0) 838 -838 2008年 [査読無し][通常論文]
  • 舟井 啓, 佐藤 由実, 多湖 輝興, 増田 隆夫 化学工学会 研究発表講演要旨集 2008 (0) 746 -746 2008年 [査読無し][通常論文]
  • 大堀武蔵, 田島健次, 佐藤康治, 多湖輝興, 増田隆夫 ゼオライト研究発表会講演予稿集 23rd 86 2007年11月07日 [査読無し][通常論文]
  • 麓 恵里, 松村 明光, 佐藤 信也, 鷹觜 利公, 多胡 輝興, 増田 隆夫 石炭科学会議発表論文集 (44) 82 -83 2007年10月11日 [査読無し][通常論文]
     
    To recover useful lighter hydrocarbons from heavy oil, catalytic cracking of petroleum residual oil was examined. The residual oil was converted into lighter hydrocarbons such as gasoline and kerosene in a steam atmosphere over zirconia-supporting iron oxide catalyst. Steam is decomposed on the catalyst, yielding active oxygen and hydrogen species. Heavy oil fractions are cracked on the catalyst and lighter fractions and coke precursors are generated. The active oxygen species react with coke precursors, producing carbon dioxide. The remaining active hydrogen species are added to the lighter fractions. Therefore, heavy oil was oxidatively cracked on the catalyst without any carbonaceous residue.
  • 増田 隆夫 化学工学 = CHEMICAL ENGINEERING OF JAPAN 71 (10) 2007年10月05日 [査読無し][通常論文]
  • 青木大地, 岩貝和幸, 多湖輝興, 増田隆夫 化学工学会年会研究発表講演要旨集 72nd (0) 673 -710 2007年02月19日 [査読無し][通常論文]
  • 劉 保華, 多湖 輝興, 林 潤一郎, 増田 隆夫 化学工学会 研究発表講演要旨集 2007 (0) 1117 -1117 2007年 [査読無し][通常論文]
  • 舟井 啓, 麓 恵里, 多湖 輝興, 増田 隆夫 化学工学会 研究発表講演要旨集 2007 (0) 1116 -1116 2007年 [査読無し][通常論文]
  • 信田 一成, 舟井 啓, 多湖 輝興, 増田 隆夫 石油学会 年会・秋季大会講演要旨集 2007 (0) 81 -81 2007年 [査読無し][通常論文]
     
    水蒸気を活性酸素と水素に分解し,その活性酸素による酸化的C-C結合の解裂と解裂部への水素補給による重質油の軽質化反応を実施した。触媒として活性酸素種の生成・貯蔵と供給能を有するセリアを含む鉄触媒を開発して適用した。
  • 坂元 真梨子, 岩貝 和幸, 中坂 佑太, 多湖 輝興, 増田 隆夫 化学工学会 研究発表講演要旨集 2007 (0) 725 -725 2007年 [査読無し][通常論文]
  • Toshiro Tsuji, Akito Hatayama, Shin Mukai, Takao Masuda Polymer Preprints, Japan 55 5603 -5604 2006年12月01日 [査読無し][通常論文]
     
    The thermal and oxidative degradation of polydnethyl methacrylate) were studied in atmospheres of Argon and Air by thermogravimetries under various heating rates. Distribution functions of the activation energies of degradation were analyzed for both thermal and oxidative degradation. In an argon atmosphere, there were one monodispersed peak attributed from chain end vinyl group and broadly distributed peak from random scission. In an air atmosphere, the activation energy of oxidative degradation was also widely distributed and the peak energy was lower than that of the degradation from chain end group.
  • FUMOTO Eri, TAGO Teruoki, MASUDA Takao Energy & Fuel 20 (1) 1 -6 2006年 [査読無し][通常論文]
  • FUMOTO Eri, MIZUTANI Yosuke, TAGO Teruoki, MASUDA Takao Applied Catalysis B, Enviromental 68 (3-4) 154 -159 2006年 [査読無し][通常論文]
  • 増田 隆夫 化学工学会 研究発表講演要旨集 2006 (0) 338 -339 2006年 [査読無し][通常論文]
  • 麓 恵里, 多湖 輝興, 増田 隆夫 化学工学会 研究発表講演要旨集 2006 (0) 758 -758 2006年 [査読無し][通常論文]
  • 多湖 輝興, 齋藤 聡敏, 田島 健次, 田口 精一, 佐藤 敏文, 佐藤 康治, 増田 隆夫 化学工学会 研究発表講演要旨集 2006 (0) 759 -759 2006年 [査読無し][通常論文]
  • 岩貝 和幸, 青木 大地, 多湖 輝興, 増田 隆夫 化学工学会 研究発表講演要旨集 2006 (0) 771 -771 2006年 [査読無し][通常論文]
  • 水谷 洋輔, 麓 恵理, 多湖 輝興, 増田 隆夫 化学工学会 研究発表講演要旨集 2005 (0) 947 -947 2005年 [査読無し][通常論文]
  • 奥村 哲孝, 多湖 輝興, 増田 隆夫 化学工学会 研究発表講演要旨集 2005 (0) 939 -939 2005年 [査読無し][通常論文]
  • 岩貝 和幸, 森田 健, 多湖 輝興, 増田 隆夫 化学工学会 研究発表講演要旨集 2005 (0) 921 -921 2005年 [査読無し][通常論文]
  • 向井 紳, 山本 裕, 増田 隆夫, 田門 肇 化学工学会 研究発表講演要旨集 2005 (0) 668 -668 2005年 [査読無し][通常論文]
  • 増田 隆夫, 香田 忍, 白石 文秀, 筒井 俊雄, 伊藤 直次, 草壁 克己, 霜垣 幸浩 化学工学 = CHEMICAL ENGINEERING OF JAPAN 68 (10) 549 -556 2004年10月05日 [査読無し][通常論文]
  • 増田隆夫, 香田忍, 白石文秀, 筒井俊雄, 伊藤直次, 草壁克己, 霜垣幸浩 化学工学 68 (10) 549 -556 2004年10月05日 [査読無し][通常論文]
  • 辻俊郎, 佐々木玲, 岡島聡, 増田隆夫 化学工学論文集 30 (5) 705 -709 2004年09月 [査読無し][通常論文]
     
    ポリオレフィン類廃プラスチックの水蒸気改質を, 水素製造を目的として, 検討した. プラスチックを低温で熱分解して得た油を, 市販のNi坦持アルミナ触媒を用いて, 600-800℃で水蒸気改質を行い, ガスの生成量, ガス成分, 炭素転化率, コーキングの程度を調べた. ポリエチレン, ポリスチレンの分解油とも700℃以上で非常に高い炭素転化率でガス化し, ガス組成は水性ガス転化反応と一酸化炭素のメタネーションの, 二つの反応からなる平衡組成に非常に近い値となった. 水素比率の少ないポリスチレン分解油の方が, コーキングの割合が高く, 800℃でコーキングの割合は最小となった.
  • FUMOTO E, TAGO T, TSUJI T, MASUDA T Energy & Fuel 18 (6) 1770 -1774 2004年 [査読無し][通常論文]
  • 筒井俊雄, 小島紀徳, 増田隆夫 アロマティックス 55 296 -300 2003年11月25日 [査読無し][招待有り]
  • 向井紳, 山本裕, 増田隆夫, 田門肇 化学工学論文集 29 (2) 221 -225 2003年03月 [査読無し][通常論文]
     
    主鎖がSiのみで形成されるSiポリマー(ポリシラン)と安価なフェノール樹脂とを共炭化し,Si/C複合材を作製した.得られた材料のLi+電池の負極材としての特性を測定したところ,Siの導入により材料のLi+可逆容量が大幅に増大することが確認できた.特にポリジフェニルシランをSi源に用いた場合には,複合材料中のSi原子1個あたり最大で2.4個ものLi+が吸蔵可能であることが明らかとなった.さらに,材料のLi+不可逆容量について詳細に検討したところ,不動態膜形成と酸化物形成によって生じていることが示唆され,材料のミクロ孔容積と酸素含有量によって不可逆容量が定量的に説明できることが分かった.
  • 辻 俊郎, 佐々木 玲, 岡島 聡, 増田 隆夫 化学工学会 研究発表講演要旨集 2003 (0) 346 -346 2003年 [査読無し][通常論文]
  • 大谷 修平, 北村 昌弘, 向井 紳, 辻 俊郎, 増田 隆夫 化学工学会 研究発表講演要旨集 2003 (0) 838 -838 2003年 [査読無し][通常論文]
  • 西原 洋知, 志知 星児, 藤井 勇佑, 向井 紳, 田門 肇, 多湖 輝興, 増田 隆夫 化学工学会 研究発表講演要旨集 2003 (0) 498 -498 2003年 [査読無し][通常論文]
  • 河野 陽介, 西 美詠子, 多湖 輝興, 辻 俊郎, 増田 隆夫 化学工学会 研究発表講演要旨集 2003 (0) 874 -874 2003年 [査読無し][通常論文]
  • 麓 恵里, 沢岡 大輔, 辻 俊郎, 多湖 輝興, 増田 隆夫 化学工学会 研究発表講演要旨集 2003 (0) 879 -879 2003年 [査読無し][通常論文]
  • 増田 隆夫 触媒 44 (4) 290 -291 2002年06月10日 [査読無し][通常論文]
  • 増田隆夫, 大久保尚人, 田中庸裕, 船引卓三 触媒 43 (6) 434 -436 2001年09月10日 [査読無し][通常論文]
  • 楠田哲也, 清水康利, 白井義人, 酒井謙二, 柴田昌男, 船造俊孝, 三浦孝一, 増田隆夫, 原田芳文 科学技術振興調整費試験研究実施計画 2001 331 -335 2001年08月 [査読無し][通常論文]
  • 増田 隆夫 環境保全 (16) 3 -12 2001年 [査読無し][通常論文]
  • 増田 隆夫 触媒 42 (1) 2000年01月15日 [査読無し][通常論文]
  • 向井紳, 山本裕, 増田隆夫, 橋本健治 炭素材料学会年会要旨集 26th 38 -39 1999年12月01日 [査読無し][通常論文]
  • T Masuda, H Kuwahara, Mukai, SR, K Hashimoto CHEMICAL ENGINEERING SCIENCE 54 (13-14) 2773 -2779 1999年07月 [査読無し][通常論文]
     
    Nickel and rate earth metal exchanged Y-type zeolite catalyst (Ni-REY) was prepared for producing light fuels (gasoline and kerosene) by the catalytic cracking of heavy oil from waste plastics in a steam atmosphere. The Ni in the catalyst was found to exhibit catalysis for transportation of hydrogen atoms from steam to hydrocarbons. In a steam atmosphere, strong acid sites of the catalyst, which usually cause excessive cracking, were covered with steam molecules, leading to a high yield of liquid fuels. Experiments using MFI zeolite in a nitrogen atmosphere were also conducted for comparison. During the repetition of sequences of reaction and regeneration of the catalysts, MFI zeolite was gradually deactivated, whereas Ni-REY was found to show constant activity. Furthermore, the selectivity towards gasoline was higher than MFI zeolite (Ni-REY in steam: 78%, MFI type zeolite in N-2: 35%). (C) 1999 Elsevier Science Ltd. All rights reserved.
  • 増田 隆夫 化学工学 63 (4) 201 -204 1999年04月05日 [査読無し][通常論文]
  • 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01日 [査読無し][通常論文]
  • Catalyst Decay Mechanism of HY-type Zeolite Catalyst due to cove Deposition during Gas-Oil Cracking
    Proceedings of Asia-Pacific Chemical Reaction Engineering Symposium 359 -364 1999年 [査読無し][通常論文]
  • Book Review of H. Scott Fogler, Elements of Chemical Reaction Engineering, third ed. Prentice-Hall PTR.
    Chemical Engineering Journal 1 -2 1999年 [査読無し][通常論文]
  • Diffusion Mechanism within Micro Pores of Zeolites
    Chemical Engineering of Japan 63 (4) 201 -204 1999年 [査読無し][通常論文]
  • Mechanical and Electrical Properties of Rapidly Grown Vapor Grown Carbon Fivers
    Proceedings of the 24th Biennial Conference on Carbon 564 -565 1999年 [査読無し][通常論文]
  • Minimization of the Irreversible Li+ Capacity of Hard Carbons
    Proceedings of the 24th Biennial Conference on Carbon 540 -541 1999年 [査読無し][通常論文]
  • Process of Continuous Conversion of Waste Plastic Mixture to Fuels
    Japanese Journal of Multiphase Flow 13 (2) 101 -108 1999年 [査読無し][通常論文]
  • 増田 隆夫, 橋本 健治 ケミカルエンジニヤリング 43 (12) 939 -944 1998年12月 [査読無し][通常論文]
  • 増田 隆夫, 浅沼 忠, 北村 昌弘, 橋本 健治, 小林 芳照, 駒谷 隆志 触媒 40 (6) 348 -351 1998年09月10日 [査読無し][通常論文]
  • T Masuda, Y Fujikata, Mukai, SR, K Hashimoto APPLIED CATALYSIS A-GENERAL 172 (1) 73 -83 1998年08月 [査読無し][通常論文]
     
    Changes in the acidic properties and catalytic activity of MFI-type zeolite catalysts caused by dealumination in a steam atmosphere were examined. The reaction rate constant of the cracking of n-hexane was used as an index of the catalytic activity. The zeolite catalysts were exposed to a steam atmosphere for 3-20 h under a steam partial pressure of 1.0-101 kPa, and a temperature of 773 K. The amounts of acid sites induced by each kind of aluminum atoms inside and on the outer surface of the steamed zeolite crystals were measured separately by TPD methods with ammonia and 2,6-diethylaniline. Dealumination in a steam atmosphere was found to proceed as follows: first, tetrahedral aluminum atoms are extracted out of the framework and transformed into partially distorted octahedral aluminum atoms, which also induce acid sites. These atoms move to the outer surface of the zeolite crystals. During this movement, a part of them is pushed out of the crystals and turn into perfectly octahedral ones, which never induce acid sites. The remaining partially distorted octahedral aluminum atoms arrive at the outer surface of the crystals, and then they are pushed out of the crystals and turn into perfectly octahedrally coordinated aluminum atoms. With the progress of the dealumination, the catalytic activity increased at the beginning of the process, reached a maximum value, and then decreased. This phenomenon was considered to be dependent on the change in the amount of partially distorted octahedral aluminum atoms on the outer surface of the zeolite crystals. (C) 1998 Elsevier Science B.V. All rights reserved.
  • T Masuda, Y Fujikata, T Nishida, K Hashimoto MICROPOROUS AND MESOPOROUS MATERIALS 23 (3-4) 157 -167 1998年08月 [査読無し][通常論文]
     
    The intracrystalline diffusivities of benzene, toluene and para-xylene in MFI-type zeolites with different amounts of acid sites were measured using the constant volume method at temperatures between 423 and 723 K and a pressure below 0.70 kPa. The intracrystalline diffusivities for the MFI-type zeolites with acid sites showed a different temperature dependence in high- and low-temperature regions. Ir: the high-temperature region, the magnitude of the diffusivity agreed well with that of an MFI-type zeolite without any acid sites (silicalite), regardless of the existence of acid sites. On the other hand, in the low-temperature region, the magnitude of the diffusivity decreased significantly with increasing amounts of acid sites in the zeolites. The activation energy of the diffusivity in the low-temperature region was almost equal to the adsorption enthalpy of the diffusion molecules, which was calculated from the adsorption isotherm. The critical temperature T-C between the high-temperature region (where the effect of acid sites on the diffusivity was negligibly small) and the low-temperature region (where the effect of acid sites on the diffusivity was significant) increased as the acid amount of the zeolites increased, and T-C also increased in the order benzene <toluene <para-xylene, especially for zeolites with a large number of acid sites. Semi-empirical equations were developed to predict the diffusivities within MFI-type zeolites with acid sites. These equations include the diffusivity within silicalite, the adsorption enthalpy of the diffusion molecules and the acid amount as parameters, The predicted values of the diffusivities were in fairly good agreement with the experimental data. (C) 1998 Elsevier Science B.V. All rights reserved.
  • Y Fujikata, T Masuda, H Ikeda, K Hashimoto MICROPOROUS AND MESOPOROUS MATERIALS 21 (4-6) 679 -686 1998年05月 [査読無し][通常論文]
     
    Diffusivities of aromatics and paraffins within crystals of MFI- and Y-type zeolites in desorption and adsorption processes were measured in the temperature range from 423 to 673 K by the constant volume method, and by a newly developed method: the desorption under reduced pressure method. In the case of Y-type zeolites, the diffusivities in the adsorption and desorption processes were equal to each other because the pore size was larger than the molecular size. In the case of MFI-type zeolites, when the aromatics had the same minimum molecular size as a benzene ring, there were no differences in diffusivities between the adsorption process and the desorption process. In contrast, when the minimum molecular size of the aromatics was larger than a benzene ring, the diffusivity in the adsorption process was much smaller than in the desorption process. The diffusivities of paraffins of above six carbon atoms exhibited the same trend. The comparison of diffusivities between adsorption and desorption processes yielded diffusion rates within the pores and at the pore mouths. The diffusivities and activation energies were found to be expressed by similar equations to those defined in the field of metallurgy for the diffusion of impurities contained in a metal lattice. (C) 1998 Elsevier Science B.V. All rights reserved.
  • Mukai, SR, T Masuda, Y Matsuzawa, K Hashimoto CHEMICAL ENGINEERING SCIENCE 53 (3) 439 -448 1998年02月 [査読無し][通常論文]
     
    In the production of vapor-grown carbon fibers, ultrafine iron catalyst particles play an important role in the elongation process of the fibers. The activity of the catalyst particles depends strongly on their sizes. Therefore, in this work, ultrafine iron catalyst particles were produced under various reaction conditions using the liquid pulse injection technique, and were collected to investigate the influence of the reaction conditions on the size distribution of the obtained particles. The varied conditions were, the concentration and amount of ferrocene, which was used as the source of the catalyst material, and the velocity of the carrier gas at a fixed temperature. Each of them had a significant influence on the size distribution. From the obtained distribution curves, the relationship between the amount of catalyst particles having diameters in the range 20-30 nm, and the yield of fibers produced under the same set of reaction conditions was investigated. It was found that the yield increases with the increase in the number of catalyst particles in the size range from 20 to 30 nm. Furthermore, a model was developed to predict the size distribution of particles produced under various reaction conditions. This model was found to well represent the experimental data. (C) 1997 Elsevier Science Ltd.
  • 廃プラスチック混合物の連続油化
    ケミカルエンジニアリング 43 (12) 939 -944 1998年 [査読無し][通常論文]
  • 円筒状MFI型ゼオライト触媒膜を用いた濃酢酸溶液からの水の選択透過とメタノールからの低級オレフィンの製造
    触媒 40 348 -351 1998年 [査読無し][通常論文]
  • 円筒状ZSM-5ゼオライト膜の合成と気体分離への適用
    RITE News 27 19 -19 1998年 [査読無し][通常論文]
  • Continuous Recovery of Liquid Fuals from Waste Plastic Mixtures
    Chemical Engineering 43 (12) 939 -944 1998年 [査読無し][通常論文]
  • Structure of Hard Carbons with Leads to Small Irreversible Capacities for Li Insertion
    Proceedings of the International Symposium on Carbon Science and Technology for New Carbons 304 -305 1998年 [査読無し][通常論文]
  • Application of Cylindrical Catalytic Membrane of MFI-type Zeolite to Selective Permeation of Water from Water Solution of Concentrated Acetic Acid, and to Reaction of Methanol to Olefins
    Catalysts & Catalysis 40 348 -351 1998年 [査読無し][通常論文]
  • T Masuda, Y Miwa, K Hashimoto, Y Ikeda POLYMER DEGRADATION AND STABILITY 61 (2) 217 -224 1998年 [査読無し][通常論文]
     
    When household waste plastics are thermally decomposed, sublimate materials such as terephthalic acid and benzoic acid are produced, which cause serious pipe blocking in plants built for the degradation of the waste. The sublimate materials produced have been successfully decomposed using FeOOH catalyst. The main products were acetophenone, phenol, benzene and carbon dioxide. Ni(OH)(2) and NiO showed low activity, and Fe2O3 was inactive. A reaction mechanism is proposed and kinetic equations derived. These model equations were found to represent the experimental data well. FeOOH catalyst was transformed into porous Fe2O3 with pores of about 50-10nm in diameter after steam treatment above 773 K. Many active sites are thought to be generated on the surface of the pores. As expected from this result, an iron ore containing a large amount of FeOOH was found to show high activity for the decomposition of terephthalic acid, whereas the activity of an iron ore containing Fe2O3 was negligible. This suggests that an iron ore with a large amount of FeOOH can be used as a cheap catalyst with high mechanical strength for the degradation of poly(ethylene terephthalate) without producing any sublimate. (C) 1998 Elsevier Science Limited. All rights reserved.
  • Synthesis of Cylindrical ZSM-5 Zeolite Membrane and Its Application to Gas Separation
    RITE NOW 27 19 -19 1998年 [査読無し][通常論文]
  • A Stable"Ship in the Bottle"Type 12-Molybdophosphoric Acid Encaged Y-type Zeolite Catalyst for Liquid Phase Reactions
    Proceedings of 15th International Symposium on Chemical Reaction Engineering 374 -375 1998年 [査読無し][通常論文]
  • Production of High Quality Gasoline from Waste Polyethylene Derived Heavy Oil over Ni/REY Catalyst in Steam Atmosphere
    Proceedings of 15th International Symposium on Chemical Reaction Engineering 258 -259 1998年 [査読無し][通常論文]
  • Selective Permeation of Co2 from Mixture Gas of Co2 and N2 through ZSM-5 Zeolite Membrane
    Proceedings of 5th International Conference on Inorganic Membranes 128 -131 1998年 [査読無し][通常論文]
  • Mukai, SR, T Masuda, Ogino, I, K Hashimoto APPLIED CATALYSIS A-GENERAL 165 (1-2) 219 -226 1997年12月 [査読無し][通常論文]
     
    12-molybdophosphoric acid encaged in the supercages of Y-type zeolite was synthesized from molybdenum oxide and phosphoric acid, in a slurry mixture of Y-type zeolite crystals and deionized water. After thorough washing in hot water, the 12-molybdophosphoric acid was found to remain in the Y-type zeolite, at an amount estimated to be 0.09 g (g-support)(-1). Catalysts thus obtained were found to show activity for the esterification of acetic acid with ethanol, indicating that this catalyst could be used as a solid acid catalyst in various liquid phase reactions which involve water. (C) 1997 Elsevier Science.
  • T Masuda, Y Fujikata, Mukai, SR, K Hashimoto APPLIED CATALYSIS A-GENERAL 165 (1-2) 57 -72 1997年12月 [査読無し][通常論文]
     
    A method, called the ac-TPD method, was presented for calculating the density distribution function of the adsorption enthalpy of ammonia by utilizing the temperature-programmed desorption (TPD) spectrum of ammonia from solid catalysts measured under complete adsorption equilibrium conditions. TPD spectra were measured using a gas stream containing ammonia, at a relatively large concentration compared to the amount of ammonia desorbed from the catalyst. Under these conditions, the concentrations of ammonia both inside the catalyst particles and in the gas phase are kept almost constant during the experiment. This situation meant that the amount of ammonia remaining on the catalyst was at an equilibrium state and dependent on the temperature and concentration of ammonia. Therefore, it could be assumed that the adsorption equilibrium of ammonia on acid sites can be expressed by a Langmuir-Hinshelwood type equation, which has an adsorption enthalpy and a pre-exponential adsorption equilibrium constant corresponding to the strength of an acid site. The overall TPD spectrum is represented by the sum of the spectra from acid sites with different acid strengths. Under these assumptions, the desorption temperature was related to the adsorption enthalpy of ammonia, and a relationship was derived between the overall TPD spectrum and the density distribution function of the adsorption enthalpy. The distribution function obtained by this method can be used for evaluating acidic properties of solid catalysts. The heat flux required for the desorption of ammonia from acid sites during the TPD experiment was calculated using the obtained distribution. The value was found to agree well with that directly measured by a differential scanning calorimetric apparatus. The density distribution of the adsorption enthalpy (Q) was compared to the distribution of activation energy for desorption of ammonia (E) by a method, called dc-TPD, which was reported previously by us. This comparison gave the relationship between Q and E, and it was found that the Q value was smaller than the E value by about 15 kJ mol(-1). (C) 1997 Elsevier Science B.V.
  • T Masuda, Y Fujikata, H Ikeda, S Matsushita, K Hashimoto APPLIED CATALYSIS A-GENERAL 162 (1-2) 29 -40 1997年11月 [査読無し][通常論文]
     
    A method, called the dc-TPD method, was presented for calculating the density distribution function of the activation energy for ammonia desorption by utilizing the temperature-pro rammed desorption (TPD) spectrum of ammonia from solid catalysts measured under desorption control conditions. TPD spectra were measured in a helium stream under low pressure (about 0.13 kPa) to realize desorption control conditions by removing ammonia desorbed from a catalyst quickly. The measured TPD spectra showed only one peak corresponding to stronger acid sites, and were found to be dependent not on the time factor (ratio of the catalyst weight to the gas flow rate), but only on the heating rate. The TPD spectrum thus obtained was assumed to be the sum of the spectra from a series of acid sites with different acid strengths distributed on the catalyst. The desorption of ammonia from the acid sites was approximated as an irreversible first-order reaction rate equation with the activation energy and frequency factor whose values correspond to the acid strength of the acid sites. Using these assumptions, the relation between the TPD spectrum and the activation energy distribution for desorption was derived. The distribution functions obtained can be used for characterizing the acidic properties of solid catalysts. The shape of the distribution function was found to have little dependence on the heating rate in the TPD experiment. The acidic properties of silica-alumina, H-mordenite, and HY-type and MFI-type zeolites were well characterized by the distribution function of the activation energy for ammonia desorption. (C) 1997 Elsevier Science B.V.
  • 増田 隆夫, 藤方 恒博, 池田 英雄, 西田 知則, 橋本 健治 触媒 39 (6) 432 -435 1997年09月10日 [査読無し][通常論文]
  • 橋本 健治, 増田 隆夫 燃料及燃焼 64 (7) 483 -492 1997年07月 [査読無し][通常論文]
  • 増田 隆夫, 藤方 恒博, 橋本 健治 触媒 39 (2) 1997年03月10日 [査読無し][通常論文]
  • 橋本 健治, 増田 隆夫 工業材料 45 (2) 119 -123 1997年02月 [査読無し][通常論文]
  • 廃プラスチックからのガソリン製造技術
    工業材料 45 119 -123 1997年 [査読無し][通常論文]
  • NH3の昇温脱離過程における脱着熱量の直接測定
    触媒 39 201 1997年 [査読無し][通常論文]
  • The Production of Silicon Included Vapor Grown Carbon Fibers Using the Liquid Pulse Injection Technique
    Proceedings of Carbon'97 284 -285 1997年 [査読無し][通常論文]
  • T Masuda, Y Miwa, A Tamagawa, Mukai, SR, K Hashimoto, Y Ikeda POLYMER DEGRADATION AND STABILITY 58 (3) 315 -320 1997年 [査読無し][通常論文]
     
    Poly(ethylene terephthalate) (PET) waste was successfully decomposed in a steam atmosphere, yielding an amount of terephthalic acid predicted from the chemical formula of PET. It was found that steam accelerated the hydrolysis of PET, yielding terephthalic acid and oxygen-containing compounds such as aldehyde and ester with less than 1% carbonaceous residue. The amount of carbonaceous residue decreased with an increase in the fraction of steam in the carrier gas and was about 16% in nitrogen steam and below 1% in steam. The amount of terephthalic acid predicted from the chemical formula of PET (about 87%) was recovered at about 723 K in a carrier gas containing 70% steam and 30% nitrogen. Kinetic equations are proposed by considering both the hydrolysis and thermal pyrolysis of PET. (C) 1997 Elsevier Science Limited.
  • The Production of Silicon Included Vapor Grown Carbon Fibers Using the Liquid Pulse Injection Technique
    23rd Biennial Conference on Carbon(Carbon '97) 2 284 -285 1997年 [査読無し][通常論文]
  • Chemical Process for Recovery of Gasoline from Waste Plastics
    Industrial Materials 45 119 -123 1997年 [査読無し][通常論文]
  • The Development of a Solid Acid Catalyst which Catalyzes Aqueous Phase Reactions by the Immobilization of 12-Molybdophosphoric Acicl in the Super Cages of Y-type Zeolite
    International Symposium on Zeolites and Microporous Crystals 233 1997年 [査読無し][通常論文]
  • Difference in Intracrystalline Diffusivities of Zeolites between Adsorption and Desorption Processes
    International Symposium on Zeolites and Microporous Crystals OC22 1997年 [査読無し][通常論文]
  • A New Technique to Measure TPD Spectrum under Desorption Control Conditions
    International Symposium on Acid-Base Catalysis III 28 1997年 [査読無し][通常論文]
  • Measurement of Heat Flux Caused by Desorption of NH3
    Catalysts & Catalysis 39 201 1997年 [査読無し][通常論文]
  • 増田 隆夫, 藤方 恒博, 池田 英雄, 松下 俊一, 橋本 健治 触媒 38 (6) 490 -493 1996年09月10日 [査読無し][通常論文]
  • 増田 隆夫 触媒 38 (6) 466 -467 1996年09月10日 [査読無し][通常論文]
  • 向井 紳, 増田 隆夫, 原田 武志, 橋本 健治 化学工学 60 (7) 481 -482 1996年07月05日 [査読無し][通常論文]
  • 橋本 健治, 増田 隆夫 高分子 45 (5) 311 -315 1996年05月01日 [査読無し][通常論文]
     
    橋本健治
  • T Masuda, K Fukada, Y Fujikata, H Ikeda, K Hashimoto CHEMICAL ENGINEERING SCIENCE 51 (10) 1879 -1888 1996年05月 [査読無し][通常論文]
     
    Intracrystalline diffusivities of Y type zeolite were measured in the temperature range of 323-573 K for four aromatics: benzene, toluene, and ortho-, and para-xylene, and four paraffins: n-hexane, n-heptane, n-octane and iso-octane. Three model equations for calculating the intracrystaline diffusivity were derived each based on one of the factors thought to control the diffusion: the probability for a molecule to jump from a supercage to a neighbouring supercage through a narrow window. the Lennard Jones (12.6)-potential induced by the van der Waals attraction and the electrostatic field formed in a supercage. The measured intracrystalline diffusivity was found to be well represented by the model equations based on the electrostatic field mechanism.
  • 脱着律速下でのNH3-TPDスペクトルの測定と酸強度評価法の開発
    触媒 38 490 -493 1996年 [査読無し][通常論文]
  • ポリエチレンテレフタレート(PET)からの燃料油の製造
    コンバーテック (2) 40 -41 1996年 [査読無し][通常論文]
  • Hydrocarbons Contributing Production of Vapor Grown Carbon Fibers by Liquid Pulse Injection Technique
    60 481 -482 1996年 [査読無し][通常論文]
  • Preparation of ZSM-5 Zeolite Mem brane and Its Application to Pervaporation
    The 1996 Asian-Pacific Chemical Reaction Engineering Forum 2 435 -440 1996年 [査読無し][通常論文]
  • Catalytic Cracking of Heavy Oil Obtained from Waste Polyethylene to Produce High Quality Gasoline
    The 1996 Asian-Pacific Chemical Reaction Engineering Forum 1 23 -28 1996年 [査読無し][通常論文]
  • Method for Characterization of Acidic Properties Using NH3-TPD Spectra Measured under Desorption Control Conditions
    Catalysts & Catalysis 38 490 -493 1996年 [査読無し][通常論文]
  • Intracrystalline Diffusivities of MFI-and Y-type Zeolites
    Catalysts & Catalysis 38 466 -467 1996年 [査読無し][通常論文]
  • Mukai, SR, T Masuda, T Harada, K Hashimoto CARBON 34 (5) 645 -648 1996年 [査読無し][通常論文]
     
    Benzene and several light paraffins were used as the initial carbon source for vapor grown carbon fiber production to clarify the dominant hydrocarbon which contributes to fiber growth. When light paraffins were used as the initial carbon source, methane, ethylene and benzene were found to be the main hydrocarbons which exist at the reaction zone for fiber growth. It was found that benzene is the actual contributor to fiber growth, because a linear relationship between the benzene concentration at the reaction zone and the initial growth rate of the fibers was observed. No relationships were observed for other hydrocarbons. Copyright (C) 1996 Elsevier Science Ltd
  • Production of Fuel from Polyethylene Terephthalate (PET)
    Converting Technology (2) 40 -41 1996年 [査読無し][通常論文]
  • Degradation of Waste Polyethylene Terephthalate -Minimizing Carbonaceous Residue-
    Prodeeding of 7th Asian Pacific Confederation 94 -98 1996年 [査読無し][通常論文]
  • K HASHIMOTO, T MASUDA ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY 210 32 -PETR 1995年08月 [査読無し][通常論文]
  • M ARAI, Y NISHIYAMA, T MASUDA, K HASHIMOTO APPLIED SURFACE SCIENCE 89 (1) 11 -19 1995年05月 [査読無し][通常論文]
     
    A method has been developed that can calculate the distribution of activation energy for desorption of hydrogen from temperature-programmed desorption (TPD) spectra for characterizing the heterogeneity of the surfaces of supported metal catalysts. This method is based on the idea of Hashimoto et al. [Stud. Surf. Sci. Catal. 28 (1986) 503] who determined the distribution of acid strength of solid acid catalysts from the TPD spectra of ammonia. The surface of a catalyst is regarded as a collection of groups of desorption sites with identical activation energy in each group. These groups are experimentally sampled from a series of TPD spectra and a set of desorption kinetic parameters are determined for each group. An overall TPD spectrum is given by the summation of the contribution from each group characterized by a particular activation energy. The fitting of a calculated spectrum to an experimental one determines the activation energy distribution. This method has been applied to study the surfaces of silica-supported nickel catalysts in the present work. The surface state of the catalysts is influenced by various preparation variables, and their influence is expressed in terms of the distribution of activation energy for hydrogen desorption.
  • 増田 隆夫, 向井 紳, 秋山 崇, 藤方 恒博, 橋本 健治 化学工学論文集 21 (6) 1133 -1139 1995年 [査読無し][通常論文]
     
    希土類金属イオン交換Y型 (REY) ゼオライトによる廃プラスチック熱分解油の接触分解反応のコーク付着にともなう活性劣化を表すモデル式を提出した.コーク付着によって触媒の酸点が被覆されるとともに, 付着したコーク粒子によりゼオライト結晶内の拡散速度が低下し, その結果, 触媒活性は低下する.コーク付着した触媒の強酸点量と拡散係数を実測し, 両者のコーク付着量への依存性を表す実験式を求めた.これら関係式を用いて接触分解反応の活性と反応生成物の収率の経時変化を表すモデル式を提出した.本モデルによる予測値は実験結果をよく表現した.また, 本モデルによる触媒活性の長期予測を行ったところ, 拡散抵抗が存在する粒径の大きい触媒を用いた方が触媒活性を長期に維持できることが分かった.
  • MUKAI, SR, T MASUDA, Y FUJIKATA, T HARADA, K HASHIMOTO CARBON 33 (5) 733 -735 1995年 [査読無し][通常論文]
  • T MASUDA, H HARA, M KOUNO, H KINOSHITA, K HASHIMOTO MICROPOROUS MATERIALS 3 (4-5) 565 -571 1995年01月 [査読無し][通常論文]
     
    An A-type zeolite film was prepared on the outer surface of an alumina ceramic filter by repeated hydrothermal syntheses using the same sample (referred to as repeated batch synthesis). The thickness of the film was found to increase to 35 mu m by precipitating the crushed zeolite crystal on the ceramic filter and to 50 mu m by precipitating the crushed alumina before repeated batch synthesis. The structure and atomic composition of the zeolite film obtained were found to be the same as those of the corresponding original zeolite using several spectrometric methods: X-ray diffraction (XRD), Si-29 magic-angle spinning nuclear magnetic resonance (MAS NMR) and electron-probe microanalysis (EPMA). The morphology and thickness of the zeolite film were dependent on the reaction time and temperature, and especially on the types of silica and alumina sources. The preferred silica and alumina sources were Na2SiO3, and Al(OH)(3), respectively; these are different from the usual sources for the synthesis of powdery A-type zeolites.
  • M KAWASE, Y IKUTA, T TAGO, T MASUDA, K HASHIMOTO CHEMICAL ENGINEERING SCIENCE 49 (24A) 4861 -4870 1994年12月 [査読無し][通常論文]
     
    SiC whisker-reinforced Al2O3 composite was made by the chemical vapor infiltration (CVI) method. A porous preform was made from commercial SiC whiskers. Aluminum triisopropoxide was used as the reactant to deposit alumina. Reaction kinetics of the Al2O3 deposition were investigated experimentally. By inductive heating, it was possible to increase the temperature in the area closer to the center of the preform than at the outer surface. This led to a favorable deposition rate distribution in the preform, avoiding pore plugging. Infiltration proceeded from the center to the outer area of the preform. Hence, dense composite was obtained in a short processing time. A numerical model was developed to simulate this thermal-gradient CVI process. The experimental and calculated results were in good agreement. For the purpose of comparison, the conventional isothermal CVI method was also simulated. It was verified that by applying a temperature gradient the processing time could be significantly reduced.
  • M KAWASE, T MASUDA, M NAGASHIMA, T MAKI, Y MIYAMOTO, K HASHIMOTO JAPANESE JOURNAL OF APPLIED PHYSICS PART 1-REGULAR PAPERS SHORT NOTES & REVIEW PAPERS 33 (7A) 3830 -3836 1994年07月 [査読無し][通常論文]
     
    Hydrogenated amorphous silicon (a-Si:H) was prepared on substrates located away from rf plasma of hydrogen-diluted silane at 3 Torr. Physical and chemical structures of the films were changed by altering the distance between the plasma and the substrates. An optimum separation distance between the plasma and the substrates was found. The effects of substrate temperature and hydrogen dilution on film properties were also examined. The changes in film properties were explained by taking into account three types of film precursors: favorable radicals of lower sticking probability, unfavorable sticky ones and unfavorable polymerized ones.
  • T MASUDA, A SATO, H HARA, M KOUNO, K HASHIMOTO APPLIED CATALYSIS A-GENERAL 111 (2) 143 -150 1994年04月 [査読無し][通常論文]
     
    Thin films of ZSM-5 zeolite were prepared on the outer surface of an alumina ceramic filter by hydrothermal synthesis at 473 K. Their structure and atomic composition were shown to be the same as those of the corresponding original zeolite using several spectrometric methods: X-ray diffraction, Si-29 magic angle spinning nuclear magnetic resonance and electron probe microanalysis. The acidic properties of the membrane were evaluated using the conventional temperature-programmed desorption spectrum of ammonia. The morphology and thickness of the zeolite film were dependent on the silica source. Water glass is typically used as the silica source in the preparation of powdery ZSM-5 zeolite. A dense zeolite film could be prepared using Na2SiO3 as the silica source, but could not be obtained using water glass as the silica source.
  • コーク付着に伴うゼオライト触媒の劣化
    ペトロテック 17 1052 -1058 1994年 [査読無し][通常論文]
  • ゼオライト 11 2 -17 1994年 [査読無し][通常論文]
  • Production of Gasoline by Catalytic Cracking of Heavy Oil from Waste Plastics over Ni Supported REY Zeolite in Steam Atmosphere
    Prodeeding of 44th Canadian Chemical Engineering Conference 579 -580 1994年 [査読無し][通常論文]
  • Deactivation of Zeolite Catalyst Caused by Coke Deposition
    Petrotech 17 1052 -1058 1994年 [査読無し][通常論文]
  • Zeolite News Letters 11 2 -17 1994年 [査読無し][通常論文]
  • S. R. Mukai, T. Masuda, Y. Fujikata, K. Hashimoto CHEMICAL ENGINEERING SCIENCE 49 (24B) 4909 -4916 1994年 [査読無し][通常論文]
     
    Vapor grown carbon fibers were successfully produced from benzene, toluene and xylene, and also from mixtures of these hydrocarbons using the liquid pulse injection technique developed by the authors. This indicates the possibility of the usage of this kind of low-cost material as the Carbon source for fiber production. From the analysis of the growth curves of the fibers for each of the carbon sources, it was found that the initial growth rate of the fibers decreases as the average number of methyl groups per benzene ring of the carbon source increases. This decrease may be attributed to the inhibiting effect of the methyl group. The rate constants of fiber growth using benzene, toluene and xylene as the carbon source were calculated. They were 1.7 x 10(-3), 0.85 x 10(-3) and 0.65 x 10(-3) M-4/(Mol S) for benzene, toluene and xylene, respectively.
  • Activity and Selectivity of Methylation of Toluene over HZSM-5 Zeolite Taking into Account Intracrystalline Diffusivity and Acidic Properties within and on the Outer Surface of Crystal.
    Kagaku Kogaku Ronbunshu 20 170 -177 1994年 [査読無し][通常論文]
  • AR SONGIP, T MASUDA, H KUWAHARA, K HASHIMOTO ENERGY & FUELS 8 (1) 136 -140 1994年01月 [査読無し][通常論文]
     
    The effects of reaction conditions and properties of the catalysts used on the product yields and quality of the gasoline fraction from the catalytic cracking of heavy oil obtained from waste plastics over rare-earth metal exchanged Y-type (REY) zeolites were examined. Gasoline with high contents of isoparaffins and low contents of n-paraffins and aromatics is desired in order to increase the research octane number and to achieve complete burning. A large amount of gasoline with these favorable components was obtained by the catalytic cracking of heavy oil over,a REY zeolite catalyst under the condition of a time factor (ratio of the mass of the catalyst to the mass flow rate of the feed oil) of 0.75-1 kg-cat.kg-oil(-1).h, a reaction temperature of 673 K, and a catalyst of small crystal size that has a moderate amount of sites of strong acid strength.
  • T MASUDA, K HASHIMOTO ZEOLITES AND MICROPOROUS CRYSTALS 83 225 -232 1994年 [査読無し][通常論文]
     
    The influence of the amount of hydrocarbons, which were adsorbed on the outer surface of ZSM-5 zeolite crystallites, on the evaluated intracrystalline diffusivity was investigated. Six kinds of hydrocarbons; n-hexane, n-heptane, n-octane, benzene, toluene and p-xylene, were used as adsorbates. The uptake curves of the amounts of these hydrocarbons adsorbed on high siliceous ZSM-5 zeolites with different sizes and shapes were measured. The amount adsorbed on the outer surface of zeolite crystallites and the intracrystalline diffusivities were evaluated from a theoretical equation and the obtained uptake curves. The magnitude of the amount adsorbed on the outer surface was found to be about 10 to 50% of the total amount adsorbed (zeolite crystal size: 0.1 to 2 mu m) The adsorption potential theory of Polanyi was found to well represent the adsorption isotherms considering only the outer surface of zeolite crystallite. The intrinsic uptake curve of the amount adsorbed within the zeolite crystallites was obtained by subtracting the amount adsorbed on the outer surface of the crystallite from the total amount adsorbed. Using the amount adsorbed within the crystallite, the intracrystalline diffusivities were reevaluated. These values were found to be about one-tenth of those evaluated from the uptake curves of the total amount adsorbed.
  • AR SONGIP, T MASUDA, H KUWAHARA, K HASHIMOTO ENERGY & FUELS 8 (1) 131 -135 1994年01月 [査読無し][通常論文]
     
    A kinetic model was developed to represent the catalytic cracking of heavy oil from waste plastics by rare-earth metal exchanged Y-type (REY) zeolite to produce gasoline. The influences of reaction conditions on the product distributions were previously reported by us. On the basis of these results, a reaction pathway was proposed and a set of differential equations was developed, The kinetic parameters were determined by nonlinear least-squares regression of the experimental data. These parameters were found to be proportional to the amount of strong acid sites of the used catalysts. The calculated values of the product distribution were found to be in good agreement with the experimental data.
  • Rapid Vapor Grown Carbon Fiber Production Using the Intermittent Liquid Pulse Injection Technique
    Materials & Manufacturing Processes 9 237 -248 1994年 [査読無し][通常論文]
  • AR SONGIP, T MASUDA, H KUWAHARA, K HASHIMOTO APPLIED CATALYSIS B-ENVIRONMENTAL 2 (2-3) 153 -164 1993年06月 [査読無し][通常論文]
     
    A method which combines pyrolysis and catalytic reforming is a more efficient and pollution-free recovery method for processing large amounts of waste plastics than a combustion-based process. Several solid acid catalysts such as HY, rare earth metal-exchanged Y-type (REY), and HZSM-5 zeolites and silica-alumina (SA) were used for catalytic reforming of heavy oil produced by pyrolysis of waste polyethylene, to yield gasoline. REY zeolite was found to be the most suitable catalyst for the reaction having the highest research octane number (RON) of 67 and a gasoline yield of 48 wt.-%. In contrast, high siliceous and ordinary HZSM-5 zeolites gave the lowest RON value (23) and gasoline yield (18 wt.-%), respectively.
  • 劣化のない触媒は誕生するか
    化学工学誌 57,706-709 1993年 [査読無し][通常論文]
  • Catalytic Reforming of Heavy Oil from waste plastics on Zeolite Catalysts
    Proceeding of International Symposium on Zeolites and Microporous crystals 349-350 1993年 [査読無し][通常論文]
  • T MASUDA, MUKAI, SR, K HASHIMOTO CARBON 31 (5) 783 -787 1993年 [査読無し][通常論文]
     
    Long vapor grown carbon fibers (VGCFs) have been obtained using a new method, . the liquid pulse injection (LPI) technique. A benzene solution of ferrocene was injected to the surface of the hot wall of the reactor. Ferrocene was rapidly heated and decomposed, yielding ultra-fine iron catalyst particles, on which VGCFs were grown. VGCFs as long as 44 mm were obtained within 30 seconds using this new technique. Furthermore, the maximum average growth rate of them was over 2500 mum/s, which is much higher than those of conventional VGCFs. This growth rate permits the production of VGCFs longer than 10 mm within a few seconds.
  • 増田 隆夫, 佐藤 敦司, 橋本 健治 ケミカルエンジニヤリング 37 (8) p657 -659 1992年08月 [査読無し][通常論文]
  • T MASUDA, N MURAKAMI, K HASHIMOTO CHEMICAL ENGINEERING SCIENCE 47 (9-11) 2775 -2780 1992年06月 [査読無し][通常論文]
     
    The high shape selectivity of HZSM-5 zeolite catalyst is affected strongly by the intracrystalline diffusivities of reactants and products. Carbonaceous materials, called coke, are deposited on the zeolite catalysts during reactions, resulting in the change in the magnitude of the diffusivity. The diffusivities of five aromatics and four paraffins within the HZSM-5 zeolite crystallite with different amounts of coke deposition were directly measured in the temperature range of 373-773 K. The diffusivity was found to decrease with the coke deposition (e.g. 70% at 2 wt% coke deposition). Furthermore, the network of the pores within the zeolite crystallite was assumed to be of lattice. Coke particles and hydrocarbon molecules were marked partially on lattice points, and the random movements of the molecules were simulated and the magnitude of the diffusivity was estimated. The obtained diffusivity was found to be in good agreement with the experimental data.
  • 化学工学テクニカルレポートNO.33"廃棄物・廃水・循環利用技術の動向 第7集"うち3章担当 "固体触媒を用いたポリエチレン廃棄物からのガソリン製造",51-57
    1992年 [査読無し][通常論文]
  • 1992年度触媒開発工学特別研究会報告書"触媒活性劣化に関する報告書(]G0002[)",第3章担当,52-92
    1992年 [査読無し][通常論文]
  • セラミックスフィルター上に形成したゼオライト分離膜の形成
    ケミカル・エンジニアリング (8) 9 -11 1992年 [査読無し][通常論文]
  • A New Method for Continuously Producing Long Vapor Grown Carbon Fibers at High Growth Rates -Intermittent Liquid Pulse Injection Technique-
    Proceding of Carbon '92 498 -500 1992年 [査読無し][通常論文]
  • Preparation of Zeolite Membrane on Ceramic Filter
    Chemical Engineering (8) 9 -11 1992年 [査読無し][通常論文]
  • T MASUDA, MUKAI, SR, K HASHIMOTO CARBON 30 (1) 124 -126 1992年 [査読無し][通常論文]
  • K HASHIMOTO, T MASUDA, H KASHIHARA APPLIED CATALYSIS 75 (2) 331 -342 1991年08月 [査読無し][通常論文]
     
    A binary oxide of titanium and zirconium supporting a platinum catalyst (titania-zirconia), which has both acid and base sites, was used in the catalytic reforming of n-hexane. The relationships of the acid- and base-amounts in the catalyst to the rates of the cracking, isomerization, cyclic and aromatization reactions (steps in the catalytic reforming reaction) were investigated. The acid-and base-amounts were varied by changing the composition of titanium oxide in the catalyst. When the distance between the acid and base sites on the catalyst is shorter than the length of the rectant molecule, the active sites on the support of the catalyst are of two types: an adjacent pair of acid-base sites and a lone acid site. The rates of the cyclic and aromatization reactions increased linearly with the number of adjacent pairs of acid-base sites. The reaction rates for cracking and isomerization were proportional to the number of lone acid sites. The selectivity in the cyclic and aromatization reactions therefore can be enhanced by increasing the number of adjacent pairs of acid-base sites and decreasing the number of lone acid sites. The titania-zirconia catalyst with a 50% content of titanium oxide (Ti-50) has more adjacent pairs of acid-base sites and fewer lone acid sites than does the commercial catalyst PR-6. Hence, the selectivity of the sum of the cyclic and aromatization reactions over the Ti-50 catalyst is higher (62%) than that of PR-6 (38%).
  • ゼオライト固体触媒の特異な拡散現象と形状選択性
    ゼオライト 8 1 -11 1991年 [査読無し][通常論文]
  • K HASHIMOTO, T MASUDA, N MURAKAMI ZEOLITE CHEMISTRY AND CATALYSIS 69 477 -484 1991年 [査読無し][通常論文]
  • 増田 隆夫, 橋本 健治 触媒 32 (4) p253 -256 1990年06月 [査読無し][通常論文]
  • 橋本 健治, 三浦 孝一, 増田 隆夫, 当麻 正明, 沢井 宏之, 河瀬 元明 化学工学論文集 16 (3) 438 -446 1990年05月 [査読無し][通常論文]
     
    単結晶シリコン基板の中間原料となる多結晶シリコン塊はシランから常圧熱CVD法で製造される.その速度解析のための研究用実験装置として棒状基板型二重管反応器を考案し, 入口シラン分圧0.51~2.0kPa, 水素雰囲気, 1073~1173Kの条件で多結晶シリコン層の成長速度を測定した.反応器形状が単純なため, Navier-Stokes方程式を用いて厳密な解析ができた.モデル計算により反応器内のガス流速・温度・シラン濃度を解析し, シリコンの成長速度分布を推定した.得られた成長速度分布の計算値と実測値との比較から表面反応速度定数を求めることができた.また, 近似解析法として, 軸方向の速度・温度変化を無視した単純層流モデルとさらに半径方向の温度・濃度分布も単純化した境膜モデルとを検討した.3種のモデル解析の結果, 実験は表面反応律速に近い条件で行われたことが示され, 本反応器を用いて, 高温域でも表面反応速度定数を求められることが確認できた.
  • K HASHIMOTO, K MIURA, T MASUDA, M TOMA, H SAWAI, M KAWASE JOURNAL OF THE ELECTROCHEMICAL SOCIETY 137 (3) 1000 -1007 1990年03月 [査読無し][通常論文]
  • 橋本 健治, 増田 隆夫, 荒井 誠 石油学会誌 33 (3) 166 -172 1990年 [査読無し][通常論文]
     
    固体酸性の異なる白金担持Y型ゼオライトをn-ヘキサンの異性化反応に適用し, 反応の選択性に対する固体酸性の影響を明らかにした。固体酸性はY型ゼオライトのNa+の含有率をイオン交換法で変えることにより制御した。酸度関数H0≦-8.2の強酸点は分解反応と異性化反応を促進する。H0=-2~-6の中間強度の酸点は異性化反応のみを促進する。H0≧2の弱酸点はこの反応には不活性であった。Na+で45%イオン交換したY型ゼオライトを担体とした白金触媒の酸点のほとんどはH0=-2~-6の酸強度を持つ。そのため, この触媒は分解活性を示さず異性化反応に対して90%という高い選択性を示した。さらに, 反応•再生の繰り返し操作に対して安定であり, チオフェンに対する耐被毒性も高い。
  • 触媒、vol.32"定容法によるゼオライト結晶内有効拡散係数の測定",253-256
    1990年 [査読無し][通常論文]
  • 触媒工学若手の会"研究・調査および活動報告書"第2集の内"シリカ・アルミナ固体酸触媒のシンタリングに伴う触媒活性の変化,"
    1990年 [査読無し][通常論文]
  • Influence of Acidic and Basic Properties on Selectivity of Reforming Reaction of n-hexane by Titania-Zirconia Catalyst Supporting Platinum
    Proceeding of 5th Acian Pacific Confederation on Chemical Engineering 22 -28 1990年 [査読無し][通常論文]
  • 橋本 健治, 増田 隆夫, 播口 陽一 日本化学会誌 (3) 575 -582 1989年03月 [査読無し][通常論文]
     
    HZSM-5類似ゼオライト触媒を用いたトルエンのメチルイ化反応の形状選択牲を表現するモデルを提出した。このモデルでは結晶内拡散と結晶の内・外表面の酸強度分布曲線の形状選択性への影響を考慮している。反応温度での結晶内の有効拡散係数はトルエンのメチル化反応の温度範囲 (473~673K) で活性をもたない高シリカの HZSM-5 を用いて直接測定した。p-, m- および o-キシレンの拡散係数の比はおよそ 10:1=1 であった。結晶内と結晶外表面の酸強度分布曲線を著者らがすでに提出した方法により分離測定した。結晶内部と結晶外表面でのトルエンのメチル化反応とキシレンの異性化反応の速度定数は2種類の触媒を用いて推定した。一つは結晶内部のみに酸点をもつ触媒, 他は結晶外表面にのみ酸点をもつ触媒である。これらの特性値を用いてモデルを検討した結果, モデル式は見かけの形状選択性をよく予測することがわかった。さらに,本解析法を用いることで, トルエンのメチル化反応に対して高い形状選択性をもつ HZSM-5 ゼオライトを調製するための指針を与える線図を得た。
  • ケミカル・エンジニアリング(4)"低温プラズマによる薄膜形成",29-33
    1989年 [査読無し][通常論文]
  • 化学工学テクニカルレポートNO.24"パソコンを用いた実験データの取り込みと解折処理-NH3-TPD",108-115
    1989年 [査読無し][通常論文]
  • HZSM-5ゼオライト触媒によるトルエンのメチル化反応の形状選択性の解析-結晶内および外表面の寄与-
    日本化学会誌 3,575-582 1989年 [査読無し][通常論文]
  • K. Hashimoto, T. Masuda, M. Kawase Studies in Surface Science and Catalysis 46 (C) 485 -494 1989年01月01日 [査読無し][通常論文]
     
    A model is developed which describes the activity and the shape selectivity of methylation of toluene to produce xylenes over HZSM-5 zeolite catalysts by taking account of both intracrystalline diffusion and acid strength distributions inside and outside the crystallite. The shape selectivity is strongly affected by the relative rates of intracrystalline diffusions of hydrocarbon molecules. Uptake curves of amounts of benzene, toluene and xyleneisomers adsorbed on high-silica HZSM-5 zeolites, which have no catalytic activities, were measured in the range of temperature from 373–673 K. Effective intracrystalline diffusivities were calculated from the uptake curves over the temperature range. The ratio among the diffusivities of para-, meta-and ortho-xylene was about 10:1:1 in the above temperature range. Each acid strength distribution of acid sites inside and outside the crystallite was measured by combining the two methods developed by us. Rate constants of methylation and isomerizations of xylenes inside and outside the crystallite were estimated by performing these reactions over two kinds of the catalysts: one has acid sites only inside the crystallite, the other only outside the crystallite. Using these values, the proposed model was found to predict well the apparent shape selectivity. A chart based on the proposed model was also presented which provides a guide in preparing more highly selective HZSM-5 catalysts for the methylation of toluene. © 1989, Elsevier Science & Technology. All rights reserved.
  • K HASHIMOTO, T MASUDA, H SASAKI INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH 27 (10) 1792 -1797 1988年10月 [査読無し][通常論文]
  • K HASHIMOTO, T MASUDA, K ISOBE JOURNAL OF CHEMICAL ENGINEERING OF JAPAN 21 (3) 249 -255 1988年06月 [査読無し][通常論文]
  • K HASHIMOTO, T MASUDA, T MORI CHEMICAL ENGINEERING SCIENCE 43 (8) 2275 -2280 1988年 [査読無し][通常論文]
  • 橋本 健治, 増田 隆夫, 高木 嘉則 触媒 29 (6) p406 -409 1987年09月 [査読無し][通常論文]
  • NH3の脱離の活性化エネルギーとHammettの酸度関数Hoとの対応関係
    触媒 29 406 -409 1987年 [査読無し][通常論文]
  • Relationship between Activation Energy of Desorption of
    Catalysts & CatalysisNH3 and Hammett Acidity Function Ho 29 406 -409 1987年 [査読無し][通常論文]
  • 橋本 健治, 増田 隆夫, 森 達生 触媒 28 (6) p401 -404 1986年09月 [査読無し][通常論文]
  • K HASHIMOTO, T MASUDA, H MOTOYAMA, H YAKUSHIJI, M ONO INDUSTRIAL & ENGINEERING CHEMISTRY PRODUCT RESEARCH AND DEVELOPMENT 25 (2) 243 -250 1986年06月 [査読無し][通常論文]
  • K HASHIMOTO, T MASUDA, H UEDA, N KITANO APPLIED CATALYSIS 22 (1) 147 -156 1986年04月 [査読無し][通常論文]
  • NH3の昇温脱離スペクトルを用いた固体触媒の酸特性の評価と他の測定法との関係
    触媒 28 401 -404 1986年 [査読無し][通常論文]
  • Change in Catalytic Acativity of Silica-Alumina Catalysts during Sintering at High Temperature and Steam Atmosphere
    Proceding of World Congress (]G0003[) on Chemical Engineering 124 -127 1986年 [査読無し][通常論文]
  • Acidic Properties of Solid Catalyst Measured Using temperature -Programmed Desorption Spectrum of NH3 and Its Relation to those by Other Methods
    Catalysts & Catalysis 28 401 -404 1986年 [査読無し][通常論文]
  • K. Hashimoto, T. Masuda, T. Mori Studies in Surface Science and Catalysis 28 (C) 503 -510 1986年 [査読無し][通常論文]
     
    A method is presented which calculates a density distribution function of the activation energy for desorption of ammonia by utilizing the temperature-programmed desorption (TPD) spectrum of ammonia. The distribution function can be used for evaluating acidic properties of solid acid catalysts. The shape of the distribution curve obtained was found to be less dependent on the heating rate in the TPD experiment. The acidic properties of solid catalysts including zeolites and silica-aluminas were well characterized by the distribution function of the activation energy.
  • K HASHIMOTO, T MASUDA JOURNAL OF CHEMICAL ENGINEERING OF JAPAN 18 (1) 71 -78 1985年 [査読無し][通常論文]
  • 指示薬法による固体触媒上のルイス酸点およびブレンステッド酸点の酸強度分布の測定
    触媒 26 333 -335 1984年 [査読無し][通常論文]
  • Measurement of Lewis and Broensted Acid Strength Distributions of Solid Catalyst by Indicator Adsorption Method
    Catalysts & Catalysis 26 333 -335 1984年 [査読無し][通常論文]
  • K HASHIMOTO, K TAKATANI, T MASUDA CHEMICAL ENGINEERING JOURNAL AND THE BIOCHEMICAL ENGINEERING JOURNAL 29 (2) 85 -96 1984年 [査読無し][通常論文]
  • Change in Surface Area of Silica-Alumina Catalysts Owing to Sintering in Steam
    Proceeding of 3rd Pacific Chemicla Engineering Congress 244 -249 1983年 [査読無し][通常論文]
  • K HASHIMOTO, K TAKATANI, H IWASA, T MASUDA CHEMICAL ENGINEERING JOURNAL AND THE BIOCHEMICAL ENGINEERING JOURNAL 27 (3) 177 -186 1983年 [査読無し][通常論文]
  • 吸着法による固体酸触媒の酸強度分布の測定
    触媒 23 168 -170 1981年 [査読無し][通常論文]
  • Measurement of Acid Strength Distribution of Solid Acid Catalyst by Adsorption Method
    Catalysts & Catalysis 23 168 -170 1981年 [査読無し][通常論文]
  • Properties of Adsorption and Regeneration of Activated Carbon Produced from Phenol Resin Waste
    Bulletin of Chemical Society of Japan (11) 1815 -1824 1981年 [査読無し][通常論文]
  • The Production of Carbon Fibers from Light Paraffins in the Gas Phase
    Proceding of Carbon '95 1995 [査読無し][通常論文]
  • 4
    /,308-309 1995 [査読無し][通常論文]

特許

受賞

  • 2018年 石油学会 平成29年度石油学会学会賞(学術的)
     酸化鉄系触媒を用いた難処理炭素資源の軽質化に関する反応工学的研究 
    受賞者: 増田 隆夫
  • 2012年 触媒学会 平成24年度触媒学会学会賞(学術部門)
     含水バイオマス廃棄物からの化学品生成触媒プロセスに関する研究 
    受賞者: 増田 隆夫
  • 2008年 化学工学会 平成19年化学工学会研究賞(實吉雅郎記念賞)
     ゼオライト触媒に関する触媒分子反応工学的研究 
    受賞者: 増田 隆夫
  • 2003年 化学工学会 (化学工学論文集) 平成15年度優秀論文賞
     フェノール樹脂とポリシランの共炭化によるSi/C複合材の作成とLi+電池用負極財への応用 
    受賞者: 増田 隆夫
  • 1996年 触媒学会 触媒学会奨励賞
     固体酸触媒の劣化と選択性に関する反応工学的研究 
    受賞者: 増田 隆夫

共同研究・競争的資金等の研究課題

  • 文部科学省:科学研究費補助金基盤研究(A)
    研究期間 : 2019年 -2022年 
    代表者 : 増田 隆夫
  • 文部科学省:科学研究費挑戦的研究(萌芽)
    研究期間 : 2019年 -2021年 
    代表者 : 増田 隆夫
  • 文部科学省:科学研究費挑戦的研究(萌芽)
    研究期間 : 2017年 -2019年 
    代表者 : 増田 隆夫
  • 天然多環芳香族からの単環芳香族の単離・製造技術開発、リグニン可溶化条件の探索とフェノール類生成触媒の開発、並びに研究の総括
    (独)科学技術振興機構:先端的低酸素化技術開発(ALCA)
    研究期間 : 2012年 -2019年 
    代表者 : 増田 隆夫
  • DOC再生制御中に供給されたミストを含む燃料の排気管および酸化触媒上の現象解明とモデル化研究における現象解明
    自動車用内燃機関技術研究組合:共同研究
    研究期間 : 2017年04月 -2018年03月 
    代表者 : 増田 隆夫
  • 文部科学省:科学研究費補助金(基盤研究(A))
    研究期間 : 2015年 -2017年 
    代表者 : 増田 隆夫
  • 革新的NOx低減触媒研究でのゼオライト特性向上における数値計算
    自動車用内燃機関技術研究組合:共同研究
    研究期間 : 2015年 -2016年 
    代表者 : 増田 隆夫
  • 文部科学省:科学研究費補助金(挑戦的萌芽研究)
    研究期間 : 2015年 -2016年 
    代表者 : 増田 隆夫
  • 文部科学省:科学研究費補助金(基盤研究(B))
    研究期間 : 2012年 -2014年 
    代表者 : 増田 隆夫, 多湖 輝興, 中坂 佑太
     
    本研究の目的は,各種ゼオライト触媒のナノ結晶の合成と,それを用いて機能性樹脂の原料を生産する精密形状選択的反応プロセスを開発することである.平成25年度は次の成果を得た.(1)未着手のゼオライトの ナノ結晶合成: 研究実施者らが開発したエマルション法を適用し,平成24年度で未着手であったFAU型ゼオライトについて単分散のナノ結晶を合成することに成功した.(2)ナノ結晶ゼオライトによる芳香族のアルキル化反応の速度解析:メタノールを用いたナフタレンのアルキル化は,ナフタレンからメチルナフタレン(MN)が生成し,ついでジメチルナフタレン(DMN)が生成する逐次反応であることを確認した.また,ナノ結晶として合成したゼオライトを用いた反応実験によりMTWゼオライトが最も活性が安定し,高いβ,β-DMNの選択性を与えた.さらに,DMNは異性体の混合物であるが,その中でβ,β-DMNの選択性を向上させる触媒特性を調べるため2-MNのアルキル化反応を気相で実施した.その結果,ゼオライト結晶のナノ化が有効であり,ゼオライトの酸性を抑制することが必要であった.そこで,リン酸を担持して酸性を抑制したところ,活性・選択性の両面で向上することに成功した.(3)液相系のナフタレン類の拡散係数の測定:単環芳香族について液相の拡散係数を測定した.ナフタレンの拡散を測定に取り掛かる時に,吸着にともなう液相の濃度の経時変化測定用のレーザーラマン分光器が故障した.そのためナフタレンに関するデータの蓄積ができなかった.現在,修理中であり,修理後に測定を開始する.(4)β,βジメチルナフタレン合成用ゼオライト触媒の最適な触媒特性の決定: 反応にはMTW型ゼオライトのナノ結晶を触媒として用いることが適していた.さらにゼオライトの酸性の抑制は必要であった.更に,活性低下を抑制するために液相の反応が好ましい知見を得た.
  • 鉄系微粒子触媒を用いた重視梅雨の水蒸気分解プロセス
    石油学会:石油産業活性化センター委託研究
    研究期間 : 2000年 -2014年 
    代表者 : 増田 隆夫
  • 既存ゼオライトの特性向上における数値計算
    自動車用内燃機関技術研究組合:共同研究
    研究期間 : 2014年 
    代表者 : 増田 隆夫
  • 文部科学省:科学研究費補助金(挑戦的萌芽研究)
    研究期間 : 2012年 -2013年 
    代表者 : 増田 隆夫, 多湖 輝興, 中坂 佑太
     
    本研究では,直鎖多価アルコールから,二重結合を有するアリル化合物の直接合成を可能とする触媒反応プロセス開発を実施する.触媒としては,酸化鉄(Fe2O3)を基材とし,酸化活性の向上を目的とした成分(MOx:ジルコニアなど)と塩基性の賦与を目的とした成分(アルカリ金属)を担持した触媒を開発する.平成24年度の成果により,酸化鉄系触媒を用いるとグリセリン水溶液の反応では,水素移行反応によりアリルアルコールが得られることを見出している.さらに,水素供与体であるギ酸を反応系に併給するとギ酸由来の活性水素種により水素移行反応が促進され,アリルアルコール収率が向上した.さらに,触媒にKを担持すると触媒酸点上で進行する副反応の脱水反応が抑制されることが分かった.そこで, 平成25年度は本触媒をグリセリン以外の多価アルコールからの有用化学物質の合成に適用した.グリセリンは炭素数3であるため,反応原料として新たに炭素数2のエチレングリコール(2つの水酸基)と炭素数4のエリスリトール(4つの水酸基),そして芳香族としてカテコールを用いた.また,触媒として酸性制御の観点からK-ZrO2-FeOxの他にK-FeOx,K-Al2O3-FeOx,K-TiO2-FeOxを調製して研究に用いた.エチレングリコールとギ酸の混合物を原料とした場合,期待されるように主生成物としてエチレンが水素移行反応により得られた.K-Al2O3-FeOxを用いた場合,最も高いエチレン収率が得られた.これは,Al2O3による水素スピルオーバーによって水素が効率的に使用されたためと考えられる.エリスリトールとギ酸の混合物をK-Al2O3-FeOxを触媒として反応をすると,水素移行反応によりエリスリトールからはブタジエンが,カテコールからはフェノールが高い収率で得らることに成功した.
  • 触媒を用いる革新的ナフサ分解プロセス基盤技術開発
    NEDO(独)新エネルギー・産業技術総合開発機構:グリーン・サステナブルケミカルプロセス基盤技術開発
    研究期間 : 2009年 -2013年 
    代表者 : 巳, 増田
  • リグニンからフェノール類生成プロセスの開発
    (独)科学技術振興機構:先端的低炭素化技術開発(ALCA)
    研究期間 : 2011年 -2012年 
    代表者 : 増田 隆夫
  • ペトロリオミクス技術に係る新規要素技術の調査研究
    (社)石油学会:受託研究
    研究期間 : 2012年 
    代表者 : 増田 隆夫
  • 文部科学省:科学研究費補助金(基盤研究(B))
    研究期間 : 2009年 -2011年 
    代表者 : 増田 隆夫, 多湖 輝興
     
    構造規定剤フリー合成条件において,MFI,MOR,FAUの各ゼオライトの合成と結晶サイズ制御に成功した.ゼオライト結晶のナノサイズ化は,拡散抵抗の低減,および結晶外表面積の増大に効果がある.これらの特徴を利用し,低級オレフィン選択合成用のゼオライト反応・分離膜を開発した.H-ZSM5(MFIゼオライト)ナノクリスタル積層触媒膜型反応器を用いた,アセトンからの低級オレフィンの選択的合成では,充填層反応器と比較し,アセトン転化率とオレフィン収率を向上させることができた.
  • 植物由来バイオエタノールからエチレングリールへの転換技術開発
    (財)十勝圏振興機構:受託研究
    研究期間 : 2011年 
    代表者 : 増田 隆夫
  • 文部科学省:科学研究費補助金(挑戦的萌芽研究)
    研究期間 : 2009年 -2010年 
    代表者 : 増田 隆夫, 多湖 輝興
     
    本研究の目標は、BDFの廃棄物である"アルカリ性グリセリン水溶液"をアセトン、プロピレン、アクロレイン等の石油関連化学物質に変換可能な触媒の開発とその触媒の反応機構の解明である。昨年度は酸化鉄系触媒の最適組成とその調製法を確立した。そこで、本年度はBDF製造時に副生する実際の粗グリセリンの反応を350℃で常圧流通式反応器を用いて実施した。最初に試薬のグリセリンを原料として反応を実施した結果、アリルアルコール→プロピレンの反応(反応1)とアルデヒド→カルボン酸→ケトンの反応(反応2)の二種類が進行した。これら有用成分を合計70%炭素収率(アルデヒドを除くと60wt%弱)で得ることに成功した。さらに、後者の反応はアルカリ金属を触媒に担持することで抑制されるが、前者の反応は抑制されないことを見出し、それが、前者の(反応1)の選択性の向上に繋がることを予測した。一方、粗グリセリンにはカリウムを5wt%、メタノールと有機酸を合わせて30wt%、ガスクロで同定が難しい物質を20wt%以上含まれ、グリセリンは40wt%ほどである。予備実験から期待されたように、粗グリセリンに含まれるカリウムにより(反応2)が抑制され、(反応1)が優先的に進行することを実証した。開発した酸化鉄系触媒の活性種は格子酸素である。反応により消費する格子酸素を水分解により生成する活性酸素によって補充する。そのため、触媒の劣化の主な要因は格子酸素の過度の消費となる。この現象は触媒中の酸化鉄のヘマタイトがマグネタイトに変化することで観測される。分析した結果、反応後の触媒はヘマタイト相を維持しており、粗グリセリンに不純物として含まれる存在するメタノールと有機酸によって触媒が劣化しないことを見出した。
  • 超臨界水を利用した重視梅雨の水熱分解・改質技術の開発
    (財)石油産業活性化センター:共同研究
    研究期間 : 2007年 -2009年 
    代表者 : 増田 隆夫
  • 文部科学省:科学研究費補助金(萌芽研究)
    研究期間 : 2007年 -2008年 
    代表者 : 増田 隆夫, 多湖 輝興
     
    本研究では, ZrO_2-FeO_x触媒を用い, 木質バイオマスの一種であるリグニンの分解と高付加価値樹脂原料芳香族への転換を目的としている.多環芳香族を主成分とするリグニンから有用化学物質を合成する反応プロセス開発を実施した. 先ず, 先ず, 多環芳香族のモデル物質として, 石油生成プロセスで副製する常圧残油の軽質化を行った. ZrO_2, FeO_xの各触媒成分の機能を明確にするため, それぞれの担持量の異なる触媒を調製し, 反応実験を行った. その結果, FeO_xの格子酸素を酸素源として常圧残油を効果的に軽質化することに成功した. さらに, 反応系に共存する水分子がZrO_2上で分解し酸素活性種を生成することで, 消費された格子酸素が補われ, 反応サイクルが進むことを明らかにした. 続いて同触媒を用いて, リグニン構造のモデル物質であるアセトフェノンとグアヤコルの分解を実施したところ, アシル結合とアルキルアルコール結合の官能基を分解し, フェノールを生成することを明らかにした.上記検討の結果を基に, パームシェルの熱分解タールの軽質化を実施した. 熱分解タールにはフェノール系の芳香環以外に多量の不明成分と水分が含まれる. 水蒸気雰囲気下、350℃〜450℃でZrO_2-FeO_x触媒を用い, 熱分解タールを反応させたところ, これら不明成分を選択的に分解することに成功したさらに, フェノール類とケトン類が新たに生成した. 熱分解タールに含まれる不明成分が分解し、フェノールとケトンが生成したと考えられる. しかし、450℃以上では生成した有用成分(フェノール, ケトン類など)の完全酸化分解とFeO_x触媒の劣化(ヘマタイト(α-Fe_2O_3)からマグネタイト(Fe_3O_4)への結晶性の変化)が進行した.
  • 文部科学省:科学研究費補助金(基盤研究(B))
    研究期間 : 2007年 -2008年 
    代表者 : 増田 隆夫, 多湖 輝興
     
    水/界面活性剤/有機溶媒を利用するゼオライト合成法により, モルデナイト結晶のナノサイズ化に成功した. ナノサイズモルデナイト結晶の外表面酸点を, 有機シラン化合物由来シリカにより選択的に不活性化させた構造性活性点を有する触媒の開発, およびモルデナイトナノクリスタルを積層させた膜型構造体触媒反応器の開発に成功した. 同モルデナイト触媒はナフタレンからの2,6-ジメチルナフタレン選択合成に高活性を示した.
  • 畜産糞尿などの有機物に係る余剰窒素成分のエネルギー・化成品原料化システムの開発
    経済産業省:低炭素社会に向けた技術シーズ発掘・社会システム実証モデル事業
    研究期間 : 2008年 
    代表者 : 増田 隆夫
  • バイオエタノールからの有用石油関連物質生産プロセスのための減圧浸透気化高速脱水用ハニカム状ゼオライトナノ結晶積層膜の開発
    (独)科学技術振興機構(JST):シーズ発掘試験(発展B)
    研究期間 : 2008年 
    代表者 : 増田 隆夫
  • “パイロコーキング技術による木質系バイオマスを原料とするSOFC発電プロセスの開発”バイオコース物性評価、バイオコース水性ガス化速度解析
    環境省:温暖化対策技術開発事業
    研究期間 : 2006年 -2007年 
    代表者 : 増田 隆夫
  • 畜産糞尿の石油系プラスチック原料化とNH3製造システムの構築
    北海道経済産業局:地域新生コンソーシアム研究開発事業
    研究期間 : 2006年 -2007年 
    代表者 : 増田 隆夫
  • 含水バイオエタノールからの有用石油関連物質合成
    (独)科学技術振興機構(JST):シーズ発掘試験
    研究期間 : 2007年 
    代表者 : 増田 隆夫
  • 水蒸気を酸素および水素供給減とした酸化鉄系による未利用超重視梅雨の軽質燃料化プロセスの開発
    (独)石油天然ガス・金属鉱物資源機構:平成19年度石油・天然ガス基礎研究委託事業
    研究期間 : 2007年 
    代表者 : 増田 隆夫
  • 文部科学省:科学研究費補助金(基盤研究(C))
    研究期間 : 2006年 -2006年 
    代表者 : 増田 隆夫, 五十嵐 哲, 田川 智彦, 草壁 克己, 岸田 昌浩, 尾上 薫
     
    持続可能な発展のためのグリーン触媒プロセスを開発するためには,ナノ反応場である触媒とマクロ反応場である反応器が一体となる構造体触媒を開発する必要がある。この反応システムついて調査研究を行い,次の成果を得た。1)報告会(3回):平成18年9月12日(苫小牧),平成18年11月1-2日(名古屋)平成19年1月5日(東京)2)出版:化学工学会編「進化する反応工学-持続可能社会に向けて-」槇書店(2006年10月)に,研究代表者と研究分担者は構造体触媒反応システムに関して,計91頁執筆した。これらの活動により,構造体触媒反応システムを学理と実理の両面で具体化するためには,目的の反応が所望の場所で高速かつ選択的に進行するように,活性点周りの分子レベルから反応器のマクロレベルにわたって物質・エネルギー移動を所望のベクトル(方向と速度)で制御できる構造化された反応場の設計・合成・操作法を構築する必要がある。そのためには,「構造化反応場」を軸にして,(1)ミクロレベルの機能分離型構造化反応場,(2)物質移動ベクトル制御型構造化反応場,(3)エネルギー移動ベクトル制御型構造化反応場,の3つの課題に分割して体系化を図る必要があることを明確にした。さらに,上記の成果を基に,構造体触媒反応システムの研究を推進するため,初期の目的である特定領域研究『構造化触媒反応場:物質・エネルギー移動のベクトル制御型グリーン反応システムの構築』(研究代表者:工学院大学五十嵐哲)研究期間:平成19-21年度,を申請した。
  • 文部科学省:科学研究費補助金(基盤研究(B))
    研究期間 : 2005年 -2006年 
    代表者 : 増田 隆夫, 辻 俊郎, 多湖 輝興
     
    結晶性のアルミノ珪酸塩であるゼオライトは、高い分子篩い能と強い固体酸性を示す。特に、ZSM-5ゼオライトでは、その結晶細孔がベンゼン等の芳香環と同程度であるため、形状選択的反応への展開が図られている。しかし、1)細孔径が反応分子と同程度であるため拡散律速になる、2)結晶外表面上酸点での反応では形状選択性が発現しない、という問題点がある。本研究ではこれらの問題を解決するため、結晶サイズが100nm以下のZSM-5ゼオライトナノクリスタルの調製と結晶外表面酸点の選択的不活性化、膜型反応器作製、Ni固定化に関して検討を進めた。1)結晶性、固体酸性質が同じで、結晶サイズのみが異なるZSM-5ゼオライト(サイズ2μm;マイクロゼオライト、50nm;ナノゼオライト)の作製に成功した。これらZSM-5ゼオライトによるメタノールの反応実験を行った。マイクロゼオライトでは、反応開始直後から触媒の活性劣化が進行したが、ナノゼオライトでは6時間以降も高活性を維持した。2)ナノゼオライトの結晶外表面酸点を、フェニルシラン系化合物を用いて選択的に不活性化することに成功した。同触媒により反応中間体であるジメチルエーテルの選択性を向上させることができた。3)上記ナノゼオライトをアルミナフィルター上に積層し、ナノクリスタル積層膜を作製した。ナノクリスタル積層量を20mm〜40mmの範囲で制御することに成功した。ナノクリスタル積層膜では、メタノールの反応において、反応中間体であるジメチルエーテルとオレフィンを、選択率90%以上で合成することに成功した。4)ZSM-5ナノゼオライト酸点にNiをイオン交換法より固定化した。ナノゼオライトの結晶外表面酸点を不活性化することにより、結晶外表面酸点にはNiが固定化されていない。形状選択的な酸化反応を可能とするナノゼオライト、及び積層膜型反応器の調製に成功した。
  • ゼオライトナノクリスタル積層反応分離膜を用いた液相反応の非平均化プロセス
    (独)科学技術振興機構(JST):シーズ発掘試験
    研究期間 : 2006年 
    代表者 : 増田 隆夫
  • 文部科学省:科学研究費補助金(萌芽研究)
    研究期間 : 2004年 -2005年 
    代表者 : 増田 隆夫, 辻 俊郎, 多湖 輝興
     
    ゼオライトはその結晶内に低級炭化水素の最小分子径とほぼ等しい径の細孔を有するため、高い分子篩能に由来する得意な触媒活性と分離能を示す。しかし、細孔内の拡散速度が極めて遅いため、その性能を最大限に生かしていない。研究実施者はゼオライトの結晶をナノサイズに調製することでこれらゼオライト使用時に問題となる点を克服できるとの着想に至った。そのため、平成16年度は、1)単分散ゼオライトナノクリスタルの開発について研究を実施し、珪素、アルミナ源とテンプレート分子が溶解した水溶液と、界面活性剤(O-15)および有機溶媒(シクロヘキサン)を浪合してミクロサイズのエマルションを形成し、その後水熱処理することで、シリカライトとZSM-5について60-200nmの範囲で単分散のゼオライトのナノクリスタルを合成することに成功した。そこで、平成17年度は平成16年度に開発したゼオライトナノクリスタルを利用して、次の研究を展開し、所望の成果を得た。2)水の選択的高速分離膜の開発:上記1)で合成したシリカライトのナノクリスタルを、アルミナフィルターの表面に吸引濾過固定化し、さらに水熱処理によって固着・薄膜化することで、膜厚が数百nmから数ミクロンの範囲でゼオライト薄膜を合成した。この膜を用いて浸透気化法により高濃度アセトン水溶液(アセトン/水=90/10)から水の選択透過に成功した。透過速度は、緻密な膜に比べて100倍の高速に達した。3)メタノールからのオレフィン選択合成用触媒膜の開発:ZSM-5のナノクリスタルを用いて2)と同様の方法により触媒膜を作成した。本触媒膜により、緻密な膜に比べて200倍以上の処理速度でメタノールからオレフィンを60%以上の選択率で合成することに成功した。
  • 各種極性物質の高濃度水溶液からの水の選択的高速分離用シリカライトナノクリスタル膜の開発
    (独)科学技術振興機構(JST):シーズ育成試験
    研究期間 : 2005年 
    代表者 : 増田 隆夫
  • 文部科学省:科学研究費補助金(基盤研究(B))
    研究期間 : 2003年 -2004年 
    代表者 : 増田 隆夫, 多湖 輝興, 辻 俊郎
     
    本研究は耐酸性が高いゼオライト分離膜を創成することを最終目的として研究を実施し次に示す成果を得た。a)ゼオライト細孔の微小化:ゼオライトの酸点にシラン化合物を化学吸着させ、それを空気焼成することで酸点上にSiO_2ユニットを形成させるシラン接触分解法を開発している。本法にゼオライト細孔の径よりも大きいトリフェニルシラン(TPS)と径よりも小さいジエトキシメチルシラン(DES)を用いたところ、DESの場合は細孔を0.1nmだけ微小化できること、TPSでは細孔経を変化せず、ゼオライト結晶外表面の酸点を選択的に不活性化できることを見出した。b)ゼオライトの親水化:水熱合成したゼオライトの結晶内に残存するテンプレート分子を過酸化水素水により液相酸化することでシラノール基を結晶外表面と細孔内に多く有するゼオライトを得た。このゼオライトは高い親水性を有した。c)ゼオライトナノクリスタルの製造:TEOS、テンプレート分子、界面活性剤、水と有機溶媒から成るマイクロエマルション相を水熱処理することでゼオライトナノクリスタルを合成することに成功した。得られる結晶はサイズが60nm〜300nmの範囲で制御された単分散であった。d)ゼオライトナノクリスタルを積層した親水性ゼオライト膜の調製:c)の方法でシリカライトのナノクリスタルを調製し、a)とb)の方法で処理した後、アルミナフィルター上に積層させることにより、親水性ゼオライト分離膜を作製した。この膜を用いて90wt%アセトン水溶液からの水分離を30〜110℃で実施した。その結果、膜は水のみを高速度に透過し、実際の蒸留塔の留出液の濃縮にほぼ適用できることが可能であり、高度分離が可能であることを明らかにした。
  • 文部科学省:科学研究費補助金(特定領域研究(B), 特定領域研究)
    研究期間 : 2001年 -2003年 
    代表者 : 増田 隆夫, 辻 俊郎, 多湖 輝興
     
    中間体を目的物質として逐次反応を実施する際,反応率と選択率の両者を同時に向上させるものとして,構造体触媒であるゼオライト触媒膜が考えられる。そこで、MFI型ゼオライト膜型反心器を用いてメタノールの反応を行い、中間体であるオレフィンの選択合成(MTO反応)を検討した。緻密な膜は反応率55〜98%でオレフィン選択率が80%を越えた。この膜の選択性の向上のためには、メタノール供給側の活性点(酸点)を不活性化する必要がある。そこで、最小分子径の異なるシラン化合物を用いて酸点に化学吸着させ、分解することでSi原子を含むコークを生成後、酸化することで酸点上にSiO_2粒子を形成させることで酸点を不活性化した。本法にトリフェニルシランを用いることで、ゼオライト結晶外表面の酸点を選択的に不活性化できることを見いだした。その結果、反応率5〜70%の範囲でオレフィン選択率90%を実現した。さらに、膜透過速度の向上を目的として、ゼオライトナノクリスタルを積層した膜が高い選択性を維持しながら透過速度を向上できることを見いだした。そこで、まずW/Oエマルション技術により約100nmの単分散MFI型ゼオライトナノクリスタルの調製法を開発した。ついで、その結晶を用いて触媒膜を作製し,原料と生成物の膜透過速度の向上を図った。その結果、透過速度を10倍以上に向上できた。さらに、シラン処理することで、芳香族の生成を無視小にできることに成功した。
  • 文部科学省:科学研究費補助金(基盤研究(C))
    研究期間 : 2001年 -2002年 
    代表者 : 増田 隆夫
     
    MFI型ゼオライトは0.数〜数μmの大きさのアルミノケイ酸塩の結晶であり、それを膜状にしたMFI型ゼオライト膜は分子節能を有する触媒膜の特性を示す。この膜を逐次反応に適用すると、反応物質の活性点との接触時間を均一にすることができる。その結果、逐次反応の中間体生成に適用すると、従来の充填層では観測されない選択率を得ることができると考えて研究を実施し、次に記載する成果を得た。(1)ゼオライト膜の合成:強制撹拌式水熱合成法を開発し、分子節能を示すMFI型ゼオライト層を円筒状アルミナセラミックスフィルター外表面に合成することに成功した。(2)濃酢酸水溶液からの水の選択分離:膜の緻密性を実証するために、合成した膜を98wt%濃酢酸水溶液からの水の選択分離に適用した。水の選択性を向上させるため、膜をH_2O_2で処理して親水性を向上させることで水のみを透過させることに成功した。この結果は分子レベルで膜が緻密であることを実証するものである。(3)ゼオライト触媒の酸点分布と有効径の制御:ゼオライト触媒膜を構成するゼオライト微結晶の外表面を選択的に不活性化するため、分子径の大きいトリフェニルシラン(TPS)を用いたシラン接触分解(CCS)法を開発した。(4)酸特性評価法の開発:触媒膜の活性点分布を精度良く評価するため、NH_3とCO_2の共吸着試料か減圧下で脱離スペクトルを測定する減圧TPDを開発した。(5)逐次反応の中間体選択的生成反応:反応としてメタノールからのオレフィン生成反応を取り挙げた。未処理の膜はオレフィン選択率は80%(従来の充填層は7-50%)であったものが、TPS処理した膜は50〜98%の反応率でオレフィンを85%以上の選択率で得ることに成功した。
  • 文部科学省:科学研究費補助金(基盤研究(C))
    研究期間 : 1999年 -2000年 
    代表者 : 増田 隆夫, 向井 紳, 河瀬 元明
     
    ゼオライトは結晶性アルミノケイ酸塩であり、その一つであるMFI型ゼオライトはその結晶内にベンゼン環とほぼ同じ径の細孔を持つため、分子篩効果を示す。一般には0.0数〜数ミクロンの粉末として合成されるが、膜として合成できれば高度分離や反応・分離同時プロセスへの応用が期待される。そこで、本研究では、このMFI型ゼオライト膜を種々の高度分離および反応・分離同時プロセスに適用することを目的として実施した。平成11年度は(1)膜の合成条件を検討することで、現在達成している分子篩能をさらに向上させることに成功した。(2)高度分離の一つとして濃酢酸溶液からの水の選択透過を実施し、化学〓業で切望されている95%以上の濃酢酸溶液からの水の選択透過に成功した。また,ガス分離として多様な分子の分離が可能となるように(3)シリカを細孔内表面の触媒活性点上へ選択的に付着させる全く新しい方法により細孔の有効径を制御する新規なシラン接触分解法を開発した。この方法をMFI型ゼオライト膜に適用して、水素と窒素(または酸素)の混合ガスから水素を分離係数100の状態で選択透過させることに成功した。平成12年度は、平成11年度に開発したシラン接触分解法をゼオライト膜の活性点である酸点の分布制御法に展開した。その結果、膜供給側の酸点のみを不活性化するする手法を開発した。この触媒膜を用い手メタノールの反応を実施したところ、供給側と透過側の差圧ゼロの状態においてもオレフィン(反応中間体)を選択率85%で得る(MTO反応)ことに成功した。
  • 都市ゴミの生分解性プラスチック化による生活排水・廃棄物処理システムの構築
    科学技術庁:科学技術振興調整費
    研究期間 : 1998年 -2000年 
    代表者 : 増田 隆夫
  • パーム廃棄物再生可能なエネルギー資源の高度利用技術の開発
    NEDO:国際共同研究助成
    研究期間 : 1998年 -2000年 
    代表者 : 増田 隆夫
  • ゼオライト触媒を用いた分離および反応・分離同時プロセスの開発
    NEDO:次世代化学プロセス技術開発費補助金
    研究期間 : 1997年 -1999年 
    代表者 : 増田 隆夫
  • 文部科学省:科学研究費補助金(基盤研究(C))
    研究期間 : 1997年 -1998年 
    代表者 : 増田 隆夫, 向井 紳, 河瀬 元明
     
    ゼオライトは結晶性アルミノケイ酸塩であり、その一つであるMFI型ゼオライトはその結晶内にベンゼン環とほぼ同じ径の細孔を持つため、分子篩効果を示す。一般には0.0数〜数ミクロンの粉末として合成されるが、膜として合成できれば高度分離や反応・分離同時プロセスへの応用が期待される。そこで、本研究では欠陥細孔の無い膜状のMFI型ゼオライトの開発と、その高度分離と反応・分離への適用を目的として研究を実施した。平成9年度には、全く新しい強制攪拌式粋熱合成法を開発して、円筒状セラミックスフィルター外表面に分子篩能を示すMFI型ゼオライト触媒膜を合成することに成功した。この膜はキシレンとジエチルベンゼンそれぞれのパラ体とオルト体の透過速度比がそれぞれ3と7であることを確認した。さらに、773Kまでの加熱と放冷を繰り返したり、強い機械的衝撃(ダイヤモンドカッターによる切断)を加えても、上記の等加速度比が変化せず高い耐熱性と機械的強度を有することを確認した。平成10年度では、ゼオライト触媒膜を高度分離および反応・分離プロセスに適用した。高度分離では1)高濃度の酢酸溶液からの水の選択透過と、2)新規なシラン接触分解法による細孔径制御を開発して、無機ガス中に含まれる水素の選択透過を実施した。その結果、1)においては数10〜98wt%の酢酸水溶液から水を選択的に透過できた。2)では水素/窒素(または酸素、二酸化炭素)の混合系において分離係数=約100を達成することに成功した。一方、反応・分離プロセスではゼオライト膜が触媒能を有することを利用し、膜外側から膜内側にメタノール蒸気を流した。この反応はメタノール→エーテル→オレフィン→パラフィン+芳香族の逐次反応であり、メタノールがオレフィンに転換したときに膜を透過し終わるようにした。その結果、通常の充填層型反応器では90%以上の反応率において、オレフィン選択率は7%程度であったものが85%にまで向上させることに成功した。
  • 文部科学省:科学研究費補助金(基盤研究(C))
    研究期間 : 1996年 -1996年 
    代表者 : 増田 隆夫, 向井 紳, 河瀬 元明
     
    産業廃棄物の廃プラスチックはほとんどの場合特定のプラスチックで構成されている。その中で熱分解技術が困難なプラスチックはポリ塩化ビニル(PVC),ポリオレフィンとポリエチレンテレフタレート(PET)である。そこで,これらプラスチックについて,熱分解機構を解析し,軽質な有用炭化水素への転換反応条件と操作法について研究を進めた。PVCについては,400℃以上の温度で熱分解すると含塩素化合物を生成するが,昇温すると300〜350℃で塩素原子が塩酸や塩素ガスとして完全に脱離し,400℃以上では重量で25%の炭化水素が得られ,残さが14%残った。そこで,300-350℃で一度脱塩素した後,400℃以上に加熱することで含塩素化合物を生成せずに炭化水素が得られることが分かった。また,見かけの反応は350℃以下で支配的なPVC主鎖からのランダムな脱塩素と,それに続くZipper反応と,400℃以上で支配的な主鎖の分解反応の3種類の並列反応で表せることが明らかになった。ポリオレフィンについては代表的なポリエチレン(PE)を用いて研究を行った。PEは400℃以上で分解反応が進行し,550℃までで,2%程度の残さを残して,ほとんどが炭素数1〜25程度の炭化水素に分解する。また,分解反応は主鎖のrandamな分解反応速度式で表せた。液状物はNi/REY触媒により市販のハイオクガソリンと同等のオクタン価を有する高品位ガソリンに改質でき,さらにその速度式を導出した。PETについては,水酸化鉄,酸化鉄,酸化ニッケルが触媒活性を示したが,水酸化鉄を用いた場合にはフタル酸が全く生成しないことを見出した。液状成分としてアセトフェノン,ベンゼン,フェノールが,ガス成分として主に二酸化炭素が得られ,残さは数%であった。また,新規な反応機構を提案し,それに含まれる全ての反応速度定数の温度依存性を明らかにした。
  • 文部科学省:科学研究費補助金(一般研究(C))
    研究期間 : 1995年 -1995年 
    代表者 : 増田 隆夫, 向井 紳, 河瀬 元明
     
    ゼオライトは結晶性アルミノケイ酸塩であり、その結晶内に低級炭化水素の最小分子径とほぼ同じ径のミクロ孔を持つ。そのため、分子形状により分子を篩い分けることができる(分子篩い効果)。さらに、ゼオライトの中には触媒作用を有するものがあり、現在、石油精製で多量に用いられている。一般にゼオライトは0.数〜数μmの粉末として合成されるが、セラミックスフィルター表面に膜状に形成することで高い分離能と触媒作用を期待することができる。そこで、A型ゼオライトと触媒機能を有するZSM-5についてアルミナフィルター外表面に膜状に形成する研究を行った。従来の粉末ゼオライト合成と異なり、Si源としてケイ酸ナトリウム、Al源としてA型では推算化アルミニウムが、ZSM-5では硫酸アルミニウムが膜形成に有用であることを見いだした。さらに、同じ材料を用いて3回合成を繰り返し、さらに、各合成前に粉砕したゼオライト結晶を塗布することで、50μmの厚みの膜を合成できることを発見した。現在、高分子膜では分離が困難なアルコール/トルエンの分離を高分子膜よりも透過速度が早く、克つ130以上の分離係数を達成できた。また、meta-ジエチルベンゼンとpara-ジエチルベンゼンの混合系において、para-体をmeta-対の2倍の速度で透過できることが分かった。これは欠陥細孔が1×10^<-5>%しか存在しないことになり、非常に緻密な膜が形成できたことになる。さらに、メタノールの反応に適用した結果、膜を透過した物質はC2-C4のオレフィンを反応率85%で70%以上含み、膜透過しない場合の4倍以上の値が得られた。
  • 文部科学省:科学研究費補助金(奨励研究(A))
    研究期間 : 1993年 -1993年 
    代表者 : 増田 隆夫
     
    高い活性・選択性を示す固体酸触媒の設計法を構築するためには活性点である酸点尾強度分布を精度よく測定する必要がある。酸強度分布はNH_3の昇温脱離(TPD)スペクトルを用いているが、酸強度の尺度として脱離温度を用いている。さらに、従来の実験条件では脱離過程がNH_3の脱着律速と吸着平衡の状態の中間の状態であるため、解析が困難であった。そこで、本研究では完全な吸着平衡状態でTPDスペクトルを測定する全く新しい実験法を開発すると共に、酸強度分布としてTPDスペクトルからNH_3の吸着エンタルピー分布を求める解析法を提出した。研究成果として以下結果が得られた。(1)固体酸触媒からのNH_3の昇温脱離スペクトルを用いたNH_3の吸着エンタルピー分布測定法の開発:NH_3を吸着した触媒を定速昇温する際に、脱離するNH_3と比較して数10倍以上のNH_3を含むHeをキャリヤ-ガスとして用いることで、昇温速度が10K/min以下でNH_3の脱離が完全な吸着平衡状態で進行することを明らかにした。この状態で測定されるTPDスペクトルは強度の異なる酸点からのNH_3の脱離の総和で表せるとすると、脱離温度と吸着エンタルピーが、脱離速度と脱離温度をエンタルピーの密度分布関数に関係づけることができる。本方法を代表的な固体酸触媒であるZSM-5、HY型ゼオライトとモルデナイトに適用し、酸強度分布として吸着エンタルピー分布関数を求めることに成功した。(2)吸着エンタルピーと吸着熱との比較:TPDの測定と同じ条件で熱量計によりNH_3の脱離に伴う吸熱量を脱離温度に対して測定した。また、(1)の方法で求めた吸着エンタルピー分布を用いて脱離に伴う吸熱量の経時変化を計算することができる。両者は非常に良く一致した。また、他の研究者が測定した微分吸着熱の値とエンタルピー分布のピーク値は一致し、これらの結果より、本方法の妥当性を実証した。
  • 廃プラスチックからの燃料油の製造バイオマス由来廃液からの石油関連製品の生産
  • ゼオライト結晶内の拡散係数の測定とその推算法の開発
  • セラミックフィルター表面に形成したゼオライト膜の合成と反応・分離への適用
  • Production of Petrochemical Related Materials from Biomass-derived Waste Fluids
  • Measurement of Diffusivity within Zeolite Crystal and Its Estimation Method
  • Development of Zeolite Thin Film on Ceramic Filter and Its Application to Reaction and Separation Process

教育活動情報

主要な担当授業

  • 応用化学特別講義
    開講年度 : 2019年
    課程区分 : 修士課程
    開講学部 : 総合化学院
    キーワード : 触媒反応工学,触媒化学,化学プロセス
  • 応用分子化学A(プロセス工学)
    開講年度 : 2019年
    課程区分 : 修士課程
    開講学部 : 総合化学院
    キーワード : 化学プロセス,プロセスシミュレーション,最適化,プロセスフロー,経済収支
  • 基礎プロセス工学
    開講年度 : 2019年
    課程区分 : 学士課程
    開講学部 : 工学部
    キーワード : 化学プロセス 物質・エネルギー収支 プロセス設計

大学運営

学内役職歴

  • 2014年4月1日 - 2016年3月31日 大学院工学研究院副研究院長
  • 2016年4月1日 - 2017年3月31日 大学院工学研究院副研究院長
  • 2017年4月1日 - 2019年3月31日 工学部長
  • 2017年4月1日 - 2019年3月31日 大学院工学研究院長
  • 2017年4月1日 - 2019年3月31日 教育研究評議会評議員
  • 2020年10月1日 - 2022年3月31日 研究戦略室室長
  • 2020年10月1日 - 2022年3月31日 創成研究機構長
  • 2020年10月1日 - 2022年9月30日 産学・地域協働推進機構長

委員歴

  • 2019年07月 - 現在   国立研究開発法人新エネルギー・産業技術総合開発機構   NEDO技術委員
  • 2019年05月 - 現在   国立研究開発法人 科学技術振興機構   外部専門家・分科会委員
  • 2019年04月 - 現在   公立大学法人公立千歳科学技術大学   公立大学法人公立千歳科学技術大学経営審議会委員
  • 2019年04月 - 現在   国立研究開発法人科学技術振興機構   領域アドバイザー
  • 2019年04月 - 現在   大地みらい信用金庫   NoMaps釧路・根室実行委員会 副委員長
  • 2013年06月 - 現在   科学技術振興機構   領域アドバイザー
  • 2018年05月 - 2020年05月   北海道生産性本部   理事
  • 2018年05月 - 2020年05月   公益社団法人 石油学会   理事
  • 2019年07月 - 2020年03月   北海道環境生活部   循環資源利用促進研究開発補助事業意見聴取会評価委員
  • 2018年04月 - 2020年03月   国立研究開発法人 新エネルギー・産業技術総合開発機構   分野横断的公募事業の事前書面審査員
  • 2018年07月 - 2019年06月   独立行政法人 日本学術振興会   特別研究員等審査会委員会等
  • 2017年06月 - 2019年06月   公益社団法人 日本工学教育協会   事業企画委員会委員
  • 2017年06月 - 2019年06月   公益社団法人 日本工学教育協会   理事
  • 2017年04月 - 2019年04月   一般社団法人 八大学工学系連合会   理事
  • 2013年04月 - 2019年04月   化学工学会   高度生産システム検討委員会 委員長
  • 2018年10月 - 2019年03月   国立大学法人 大阪大学   非常勤講師
  • 2018年06月 - 2019年03月   北海道   リサイクル技術研究開発補助事業評価意見徴収会評価委員
  • 2017年08月 - 2019年03月   旭川工業高等専門学校   運営懇話会委員
  • 2017年06月 - 2019年03月   北海道職業能力開発大学校   北海道職業能力開発大学校部会委員
  • 2017年06月 - 2019年03月   国立研究開発法人 科学技術振興機構(JST)   領域アドバイザー
  • 2016年05月 - 2018年05月   石油学会   副会長
  • 2017年06月 - 2018年   公益財団法人 北洋銀行中小企業新技術研究助成基金   技術審査委員
  • 2015年05月 - 2016年05月   石油学会   北海道支部 支部長
  • 2014年06月 - 2016年05月   石油学会   理事
  • 2012年05月 - 2016年05月   石油学会   理事
  • 2015年04月 - 2016年03月   石油学会   海外協力合同セミナー事業分科会委員
  • 2015年04月 - 2016年03月   石油学会   海外協力受入事業分科会委員
  • 2014年04月 - 2016年03月   科学技術振興機構   研究成果最適展開支援プログラム専門委員
  • 2014年04月 - 2016年03月   新エネルギー・産業技術総合開発機構   分野横断的公募事業に係る事前書面審査
  • 2014年03月 - 2016年02月   触媒学会   代議員
  • 2014年11月 - 2015年10月   ゼオライト学会   会長
  • 2015年09月   化学工学会第47回秋季大会   実行委員長
  • 2014年09月 - 2015年08月   経済産業省   石油精製技術開発評価検討委員会 委員
  • 2015年06月   ZMPC2015   Chair man
  • 2014年05月 - 2015年05月   触媒学会   北海道支部幹事
  • 2013年05月 - 2015年05月   触媒学会   経営・予算委員会 委員
  • 2014年06月 - 2015年03月   北海道   循環資源利用促進税研究開発補助事業審査委員会 委員
  • 2013年03月 - 2015年03月   化学工学会   理事
  • 2010年04月 - 2015年03月   石油学会   海外協力分科会 委員
  • 2012年12月 - 2014年10月   新エネルギー・産業技術総合開発機構   「グリーン・サステイナブルケミカルプロセス基盤技術開発/触媒を用いる革新的ナフサ分解プロセス基盤技術開発/高性能ゼオライト触媒を用いる革新的ナフサ分解プロセスの開発」プロジェクトのプロジェクトリーダー
  • 2013年07月 - 2014年03月   北海道   循環資源利用促進税研究開発補助事業審査委員会 委員
  • 2012年12月 - 2014年03月   新エネルギー・産業技術総合開発機構   分野横断的応募事業に係る事前書面審査の依頼について
  • 2012年04月 - 2014年03月   科学技術振興機構   研究成果最適展開支援プログラム専門委員
  • 2013年04月 - 2014年02月   触媒技術研究組合   ナフサ接触分解プロジェクト総合調査研究委員会
  • 2013年03月 - 2014年02月   触媒学会   代議員
  • 2012年08月 - 2013年07月   日本学術振興会   特別研究員等審査会専門委員及び国際事業委員会書面審査員
  • 2012年02月 - 2013年04月   化学工学会   高度生産システム検討委員会 委員長
  • 2012年04月 - 2013年03月   触媒技術研究組合   ナフサ接触分解プロジェクト総合調査研究委員会
  • 2010年06月 - 2013年03月   北海道   循環資源利用促進税研究開発補助事業審査委員会 委員
  • 2012年03月 - 2013年02月   触媒学会   代議員
  • 2011年05月 - 2013年01月   石油学会   研究助成委員会
  • 2012年06月 - 2012年07月   経済産業省   平成24年度地域イノベーション創出実証研究補助事業の採択審査に係る委員
  • 2011年08月 - 2012年07月   日本学術振興会   特別研究員等審査会専門委員及び国際事業委員会書面審査員
  • 2010年05月 - 2012年05月   石油学会   理事
  • 2012年01月 - 2012年03月   産業技術総合研究所   平成24年新設研究ユニット設計に係る諮問委員会委員
  • 2011年04月 - 2012年03月   新エネルギー・産業技術総合開発機構   事前書面審査
  • 2010年06月 - 2012年03月   科学技術振興機構   研究成果最適展開支援事業専門委員
  • 2010年04月 - 2012年03月   文部科学省   大学設置分科会 専門委員
  • 2011年03月 - 2012年02月   触媒学会   教育企画委員会 委員
  • 2011年03月 - 2012年02月   触媒学会   支部幹事
  • 2011年03月 - 2012年02月   触媒学会   国際交流委員
  • 2010年04月 - 2012年02月   触媒技術研究組合   ナフサ接触分解プロジェクト総合調査研究委員会 委員
  • 2010年09月 - 2011年09月   石油学会   表彰推薦委員会 委員長
  • 2011年03月 - 2011年03月   触媒学会   設立理事
  • 2010年12月 - 2011年03月   経済産業省   地域イノベーション創出研究開発事業
  • 2010年08月 - 2011年03月   化学技術戦略推進機構   交流連携 バイオマス利活用研究会 委員
  • 2010年07月 - 2011年03月   科学技術振興機構   地域イノベーション創出総合支援事業査読評価委員
  • 2010年04月 - 2011年03月   日本化学会   学術賞・進歩賞選考委員会分野別選考委員
  • 2010年03月 - 2011年02月   触媒学会   北海道地区幹事
  • 2009年03月 - 2011年02月   日本化学会   理事
  • 2000年 - 2001年   ゼオライト学会   理事   ゼオライト学会
  • 1990年 - 1991年   触媒学会   幹事   触媒学会
  • 1990年 - 1991年   化学工学会   幹事、反応工学部会庶務、触媒反応工学分科会副代表   化学工学会


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