Researcher Database

Takao Masuda
President/Vice-Presidents
Executive/Vice-President

Researcher Profile and Settings

Affiliation

  • President/Vice-Presidents

Job Title

  • Executive/Vice-President

Degree

  • Doctor of Engineering(Kyoto University)

URL

J-Global ID

Research Interests

  • 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   

Research Areas

  • Manufacturing technology (mechanical, electrical/electronic, chemical engineering) / Chemical reaction and process system engineering
  • Manufacturing technology (mechanical, electrical/electronic, chemical engineering) / Transfer phenomena and unit operations
  • Manufacturing technology (mechanical, electrical/electronic, chemical engineering) / Catalytic processes and resource chemistry
  • Manufacturing technology (mechanical, electrical/electronic, chemical engineering) / Catalytic processes and resource chemistry
  • Manufacturing technology (mechanical, electrical/electronic, chemical engineering) / Chemical reaction and process system engineering
  • Manufacturing technology (mechanical, electrical/electronic, chemical engineering) / Transfer phenomena and unit operations

Academic & Professional Experience

  • 2020/10 - Today Hokkaido University Executive Director,Vice President
  • 2001 - Today Hokkaido University
  • 2017/04 - 2019/03 Hokkaido University Faculty of Engineering
  • 2014 - 2017/03 Hokkaido University Faculty of Engineering
  • 1994 - 2001 Kyoto University Faculty of Engineering
  • 1989 - 1994 Kyoto University Faculty of Engineering
  • 1982 - 1989 Kyoto University Faculty of Engineering

Education

  •        - 1982/10  Kyoto University  Graduate School of Engineering  Department of Chemical Engineering
  •        - 1981  Kyoto University  Graduate School of Engineering  Department of Chemical Engineering
  •        - 1979  Kyoto University  Faculty of Engineering

Association Memberships

  • THE CHEMICAL SOCIETY OF JAPAN   石油学会   ゼオライト学会   触媒学会   化学工学会   

Research Activities

Published Papers

  • Hiroki Konno, Yuta Nakasaka, Kousuke Yasuda, Miho Omata, Takao Masuda
    Catalysis Today in press 0920-5861 2020 [Refereed][Not invited]
     
    © 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 0947-6539 2019/09/20 [Refereed][Not invited]
     
    © 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 1385-8947 2019/07/15 [Refereed][Not invited]
  • Nakasaka Yuta, Kanda Takumi, Shimizu Ken-ichi, Kon Kenichi, Shibata Gen, Masuda Takao
    CATALYSIS TODAY 332 64 - 68 0920-5861 2019/07/15 [Refereed][Not invited]
  • 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 2058-9883 2019/03/01 [Refereed][Not invited]
  • Fujitsuka, Hiroyasu, Terai, Kazuhiro, Hayashi, Masanori, Yoshikawa, Takuya, Nakasaka, Yuta, Masuda, Takao, Tago, Teruoki
    JOURNAL OF THE JAPAN PETROLEUM INSTITUTE 62 (6) 319 - 328 1346-8804 2019 [Refereed][Not invited]
     
    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 0306-2619 2018/05/15 [Refereed][Not invited]
     
    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 1759-7277 2018/05/04 [Refereed][Not invited]
     
    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 1387-1811 2018/04/01 [Refereed][Not invited]
     
    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 0009-2673 2018/03 [Refereed][Not invited]
     
    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 1867-3899 2018/01/23 [Refereed][Not invited]
     
    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 0366-7022 2018 [Refereed][Not invited]
     
    © 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 1520-5029 2017/12/21 [Refereed][Not invited]
     
    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 1867-3880 2017/07 [Refereed][Not invited]
     
    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 1346-8804 2017/05 [Refereed][Not invited]
     
    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 1385-8947 2017/03 [Refereed][Not invited]
     
    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 2267-1242 2017 [Refereed][Not invited]
     
    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 1349-273X 2017 [Refereed][Not invited]
     
    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 0887-0624 2016/12 [Refereed][Not invited]
     
    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 0887-0624 2016/11 [Refereed][Not invited]
     
    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 0922-6168 2016/07 [Refereed][Not invited]
     
    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 0378-3820 2016/05 [Refereed][Not invited]
     
    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 1387-1811 2016/04/01 [Refereed][Not invited]
     
    © 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 1876-1070 2016/04 [Refereed][Not invited]
     
    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 1011-372X 2016/03 [Refereed][Not invited]
     
    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 1941-4900 2016/03 [Refereed][Not invited]
     
    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 0016-2361 2016/03 [Refereed][Not invited]
     
    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 1387-1811 2016/03 [Refereed][Not invited]
     
    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 0016-2361 2016/03 [Refereed][Not invited]
     
    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 1011-372X 2016/02 [Refereed][Not invited]
     
    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 0887-0624 2016/02 [Refereed][Not invited]
     
    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 1463-9262 2016 [Refereed][Not invited]
     
    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 0165-2370 2015/11 [Refereed][Not invited]
     
    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 1385-8947 2015/10 [Refereed][Not invited]
     
    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 1387-1811 2015/05 [Refereed][Not invited]
     
    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 1387-1811 2015/04 [Refereed][Not invited]
     
    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.
  • KONDO HISAKI, NAKASAKA YUTA, TAGO TERUOKI, MASUDA TAKAO
    J Jpn Inst Energy 94 (1) 67 - 73 0916-8753 2015/01/20 [Not refereed][Not invited]
  • MASUDA TAKAO, NAKASAKA YUTA, YOSHIKAWA TAKUYA, TAGO TERUOKI
    アロマティックス 66 242 - 251 0365-6187 2014/11/25 [Not refereed][Not invited]
  • 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 0165-2370 2014/11 [Refereed][Not invited]
     
    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 0016-2361 2014/11 [Refereed][Not invited]
     
    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 Trans Tech Publications 625 311  1662-7482 2014/09 [Refereed][Not invited]
  • Teruoki Tago, Yuta Nakasaka, Takao Masuda
    JOURNAL OF THE JAPAN PETROLEUM INSTITUTE The Japan Petroleum Institute 57 (5) 197 - 207 1346-8804 2014/09 [Not refereed][Not invited]
     
    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.
  • Teruoki Tago, Yuta Nakasaka, Takao Masuda
    JOURNAL OF THE JAPAN PETROLEUM INSTITUTE 石油学会 57 (5) 197 - 207 1346-8804 2014/09 [Refereed][Not invited]
     
    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 1387-1811 2014/08 [Refereed][Not invited]
     
    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 0961-9534 2014/07 [Refereed][Not invited]
     
    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.
  • YOKOI TOSHIYUKI, MASUDA TAKAO, TATSUMI TAKASHI
    ペトロテック 37 (4) 290 - 295 0386-2763 2014/04/01 [Not refereed][Not invited]
  • Hiroki Konno, Teruoki Tago, Yuta Nakasaka, Gaku Watanabe, Takao Masuda
    APPLIED CATALYSIS A-GENERAL 475 127 - 133 0926-860X 2014/04 [Refereed][Not invited]
     
    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 0926-3373 2014/03 [Refereed][Not invited]
     
    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 0926-3373 2014/03 [Refereed][Not invited]
     
    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 2190-6823 2014 [Refereed][Not invited]
     
    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 - + 1660-9336 2014 [Refereed][Not invited]
     
    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 2044-4753 2014 [Refereed][Not invited]
     
    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.
  • MASUDA TAKAO, TAGO TERUOKI, NAKASAKA YUTA, OBA KIYOSHI
    化学工学 77 (12) 862 - 866 0375-9253 2013/12/05 [Not refereed][Not invited]
  • Yuta Nakasaka, Takuya Okamura, Hiroki Konno, Teruoki Tago, Takao Masuda
    MICROPOROUS AND MESOPOROUS MATERIALS 182 (182) 244 - 249 1387-1811 2013/12 [Refereed][Not invited]
     
    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 0888-5885 2013/11 [Refereed][Not invited]
     
    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.
  • TAGO TERUOKI, YOSHIKAWA TAKUYA, NAKASAKA YUTA, MASUDA TAKAO
    触媒 55 (5) 270 - 275 0559-8958 2013/10/10 [Not refereed][Not invited]
  • Hiroki Konno, Teruoki Tago, Yuta Nakasaka, Ryota Ohnaka, Jun-ichi Nishimura, Takao Masuda
    MICROPOROUS AND MESOPOROUS MATERIALS 175 25 - 33 1387-1811 2013/07 [Refereed][Not invited]
     
    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 1387-1811 2013/07 [Refereed][Not invited]
     
    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 1385-8947 2013/06 [Refereed][Not invited]
     
    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 0378-3820 2013/04 [Refereed][Not invited]
     
    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 0378-3820 2013 [Refereed][Not invited]
     
    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 0378-3820 2013 [Refereed][Not invited]
     
    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 0016-2361 2013/01 [Refereed][Not invited]
     
    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 1385-8947 2012/10 [Refereed][Not invited]
     
    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 1385-8947 2012/10 [Refereed][Not invited]
     
    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 1571-1013 2012/09 [Refereed][Not invited]
     
    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 0065-7727 2012/08/19 [Refereed][Not invited]
  • Teruoki Tago, Yuta Nakasaka, Takao Masuda
    Zeolites: Synthesis, Chemistry and Applications 171 - 190 2012/08/01 [Not refereed][Not invited]
  • Hiroki Konno, Takuya Okamura, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    JOURNAL OF THE JAPAN PETROLEUM INSTITUTE 55 (4) 267 - 274 1346-8804 2012/07 [Refereed][Not invited]
     
    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.
  • MASUDA Takao
    觸媒 = Catalyst 54 (4) 0559-8958 2012/06/10 [Not refereed][Not invited]
  • Teruoki Tago, Yuta Nakasaka, Takao Masuda
    JOURNAL OF THE JAPAN PETROLEUM INSTITUTE 55 (3) 149 - 159 1346-8804 2012/05 [Refereed][Not invited]
     
    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 [Refereed][Not invited]
  • 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 [Refereed][Not invited]
  • TAGO TERUOKI, NAKASAKA YUTA, MASUDA TAKAO
    触媒 53 (7) 409 - 414 0559-8958 2011/12/10 [Not refereed][Not invited]
  • Takuya Yoshikawa, Teruoki Tago, Ayaka Nakamura, Aya Konaka, Mitsushi Mukaida, Takao Masuda
    RESEARCH ON CHEMICAL INTERMEDIATES Springer Nature 37 (9) 1247 - 1256 0922-6168 2011/11 [Refereed][Not invited]
     
    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.
  • KONNO HIROKI, TAGO TERUOKI, NAKASAKA YUTA, MASUDA TAKAO
    化学工業 62 (10) 741 - 748 0451-2014 2011/10/01 [Not refereed][Not invited]
  • Teruoki Tago, Hiroki Konno, Mariko Sakamoto, Yuta Nakasaka, Takao Masuda
    APPLIED CATALYSIS A-GENERAL 403 (1-2) 183 - 191 0926-860X 2011/08 [Refereed][Not invited]
     
    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.
  • NAKASAKA YUTA, TAGO TERUOKI, MASUDA TAKAO
    ゼオライト 28 (2) 47 - 54 0918-7774 2011/06/10 [Not refereed][Not invited]
  • Kazuyuki Iwakai, Teruoki Tago, Hiroki Konno, Yuta Nakasaka, Takao Masuda
    Microporous and Mesoporous Materials 141 167 - 174 1387-1811 2011/05 [Refereed][Not invited]
     
    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 0378-3820 2011/04 [Refereed][Not invited]
     
    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 0920-5861 2011/04 [Refereed][Not invited]
     
    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 0920-5861 2011/04 [Refereed][Not invited]
     
    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) 0386-2763 2011/03/01 [Not refereed][Not invited]
  • TAGO TERUOKI, YOSHIKAWA TAKUYA, MASUDA TAKAO
    Bio Ind 28 (2) 45 - 50 0910-6545 2011/02/12 [Not refereed][Not invited]
  • YOSHIKAWA TAKUYA, TAO TERUOKI, MASUDA TAKAO
    ペトロテック 34 (1) 24 - 29 0386-2763 2011/01/01 [Not refereed][Not invited]
  • TAGO TERUOKI, YOSHIKAWA TAKUYA, MASUDA TAKAO
    JETI 58 (10) 36 - 38 0289-4343 2010/09/16 [Not refereed][Not invited]
  • FUNAI Satoshi, SATOH Yumi, SATOH Yasuharu, TAJIMA Kenji, TAGO Teruoki, MASUDA Takao
    Top Catal 53 (7/10) 654-658  1022-5528 2010/06 [Not refereed][Not invited]
  • Takuya Yoshikawa, Duangkamol Na-Ranong, Teruoki Tago, Takao Masuda
    Journal of the Japan Petroleum Institute Japan Petroleum Institute 53 (3) 178 - 183 1349-273X 2010/05 [Refereed][Not invited]
  • FUNAI SATOSHI, TAGO TERUOKI, MASUDA TAKAO
    J Jpn Inst Energy 89 (3) 231 - 236 0916-8753 2010/03/20 [Not refereed][Not invited]
  • FUNAI SATOSHI, TAGO TERUOKI, MASUDA TAKAO
    化学工学 74 (2) 57 - 59 0375-9253 2010/02/05 [Not refereed][Not invited]
  • Satoshi Funai, Eri Fumoto, Teruoki Tago, Takao Masuda
    CHEMICAL ENGINEERING SCIENCE 65 (1) 60 - 65 0009-2509 2010/01 [Refereed][Not invited]
     
    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 0009-2509 2010/01 [Refereed][Not invited]
     
    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 0366-7022 2009/12 [Refereed][Not invited]
     
    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.
  • FUNAI SATOSHI, TAGO TERUOKI, MASUDA TAKAO
    J Jpn Inst Energy 88 (3) 187 - 192 0916-8753 2009/03/20 [Not refereed][Not invited]
  • TAGO TERUOKI
    Topics in Catalysis 52 865 - 871 2009 [Refereed][Not invited]
  • Tago Teruoki, Sakamoto Mariko, Iwakai Kazuyuki, Nishihara Hirotomo, Mukai Shin R, Tanaka Tsunehiro, Masuda Takao
    Journal of Chemical Engineering of Japan 42 S162 - S167 0021-9592 2009 [Refereed][Not invited]
  • Teruoki Tago, Kazuyuki Iwakai, Mieko Nishi, Takao Masuda
    JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY 9 (1) 612 - 617 1533-4880 2009/01 [Refereed][Not invited]
     
    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 1387-1811 2008/10 [Refereed][Not invited]
     
    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 1387-1811 2008/07 [Refereed][Not invited]
     
    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.
  • TAGO TERUOKI, IWAKAI KAZUYUKI, MASUDA TAKAO
    ケミカルエンジニヤリング 53 (6) 432 - 439 0387-1037 2008/06/01 [Not refereed][Not invited]
  • Teruoki Tago, Yuta Nakasaka, Ayaka Kayoda, Takao Masuda
    Separation and Purification Technology 58 7 - 11 1383-5866 2007/12 [Refereed][Not invited]
     
    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.
  • NAKASAKA YUTA, TAGO TERUOKI, YANO KAZUHISA, MASUDA TAKAO
    膜 32 (6) 332 - 339 0385-1036 2007/11/01 [Not refereed][Not invited]
  • TSUTSUI TOSHIO, MASUDA TAKAO, NII SUSUMU, HASEGAWA YASUHISA, NISHIOKA MASAKI, SOTOWA KEN'ICHIRO, ONOE KAORU, SHIMOGAKI YUKIHIRO
    化学工学 71 (10) 661 - 669 0375-9253 2007/10/05 [Not refereed][Not invited]
  • TAGO TERUOKI, IWAKAI KAZUYUKI, SAKAMOTO MARIKO, MASUDA TAKAO
    触媒 49 (6) 495 - 497 0559-8958 2007/09/05 [Not refereed][Not invited]
  • 多湖 輝興, 麓 恵里, 増田 隆夫
    化学工業 化学工業社 58 (7) 522 - 527 0451-2014 2007/07 [Not refereed][Not invited]
  • TAGO TERUOKI, FUMOTO ERI, MASUDA TAKAO
    化学工業 58 (7) 522 - 527 0451-2014 2007/07/01 [Not refereed][Not invited]
  • Eri Fumoto, Teruoki Tago, Takao Masuda
    CHEMISTRY LETTERS 35 (9) 998 - 999 0366-7022 2006/09 [Refereed][Not invited]
     
    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 0959-9428 2006/08/11 [Not refereed][Not invited]
     
    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 2006/06/07 [Refereed][Not invited]
     
    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 0167-2991 2006 [Refereed][Not invited]
  • TAGO TERUOKI, MASUDA TAKAO
    ゼオライト 22 (3) 68 - 74 0918-7774 2005/09/10 [Not refereed][Not invited]
  • Teruoki Tago, Yoshihito Okubo, Shin R. Mukai, Tsunehiro Tanaka, Takao Masuda
    Applied Catalysis A: General 290 (1-2) 54 - 64 0926-860X 2005/08/18 [Not refereed][Not invited]
     
    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 0920-5861 2005/08/15 [Refereed][Not invited]
     
    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 0926-860X 2005/04 [Refereed][Not invited]
     
    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 0926-860X 2005/04 [Refereed][Not invited]
     
    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 0021-9592 2005 [Refereed][Not invited]
     
    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 0366-7022 2004/08/05 [Refereed][Not invited]
     
    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
    Appl. Catal. A: General 256 (1/2) 107 - 113 0926-860X 2003/12/30 [Not refereed][Not invited]
     
    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.
  • MASUDA TAKAO
    Jasco Rep 75 - 81 0916-3492 2003/11/01 [Not refereed][Not invited]
  • T Masuda
    JOURNAL OF THE JAPAN PETROLEUM INSTITUTE 46 (5) 281 - 294 1346-8804 2003/09 [Not refereed][Not invited]
     
    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 1383-5866 2003/07/01 [Not refereed][Not invited]
     
    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 2003/05 [Refereed][Not invited]
  • Takao Masuda, Tadashi Asanuma, Mitsuru Shouji, Shin R. Mukai, Motoaki Kawase, Kenji Hashimoto
    Chem. Eng. Sci. 58 (3/6) 649 - 656 0009-2509 2003/02/01 [Not refereed][Not invited]
     
    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) 0559-8958 2003/01/15 [Not refereed][Not invited]
  • 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 1387-1811 2001/11/01 [Not refereed][Not invited]
     
    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 1385-8947 2001/03/15 [Not refereed][Not invited]
     
    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 0009-2509 2001/02/01 [Not refereed][Not invited]
     
    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
    Chem. Eng. Sci. 56 (3) 799 - 804 0009-2509 2001/02/01 [Not refereed][Not invited]
     
    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 0009-2509 2001/02/01 [Not refereed][Not invited]
     
    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 0133-1736 2000/12/01 [Not refereed][Not invited]
     
    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 1387-1811 2000/08 [Refereed][Not invited]
     
    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.
  • MASUDA Takao
    触媒 触媒学会 42 (1) 25 - 30 0559-8958 2000/01/15 [Not refereed][Not invited]
  • MASUDA TAKAO
    触媒 42 (1) 25 - 30 0559-8958 2000/01/15 [Not refereed][Not invited]
  • T Masuda, N Fukumoto, M Kitamura, Mukai, SR, K Hashimoto
    ADSORPTION SCIENCE AND TECHNOLOGY 411 - 415 2000 [Refereed][Not invited]
     
    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 0008-6223 2000 [Not refereed][Not invited]
  • Mukai, SR, T Masuda, T Harada, K Hashimoto
    CARBON 38 (13) 1801 - 1805 0008-6223 2000 [Not refereed][Not invited]
     
    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.
  • SHICHI AKIRA, KATAKI KENJI, OKUBO NAOTO, MASUDA TAKAO, SATSUMA ATSUSHI, HATTORI TADASHI
    触媒 41 (6) 424 - 426 0559-8958 1999/09/10 [Not refereed][Not invited]
  • MASUDA TAKAO
    混相流 13 (2) 101 - 108 0914-2843 1999/06/15 [Not refereed][Not invited]
  • MASUDA TAKAO
    化学工学 63 (4) 201 - 204 0375-9253 1999/04/05 [Not refereed][Not invited]
  • T Masuda, P Tomita, Y Fujikata, K Hashimoto
    CATALYST DEACTIVATION 1999 126 89 - 96 0167-2991 1999 [Refereed][Not invited]
     
    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.
  • MASUDA TAKAO, HASHIMOTO KENJI
    ケミカルエンジニヤリング 43 (12) 939 - 944 0387-1037 1998/12 [Not refereed][Not invited]
  • T Masuda, K Hashimoto
    DEACTIVATION AND TESTING OF HYDROCARBON-PROCESSING CATALYSTS 634 62 - 76 0097-6156 1996 [Refereed][Not invited]
     
    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 [Refereed][Not invited]
  • T MASUDA, H MIZOTA, K HASHIMOTO
    KAGAKU KOGAKU RONBUNSHU 20 (2) 170 - 177 0386-216X 1994/03 [Refereed][Not invited]
     
    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.
  • Takao Masuda, Hirotoshi Mizota, Kenji Hashimoto
    KAGAKU KOGAKU RONBUNSHU 20 (2) 170 - 177 1349-9203 1994 [Not refereed][Not invited]
     
    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 [Refereed][Not invited]
  • Kenji Hashimoto, Takao Masuda, Makoto Arai
    Journal of The Japan Petroleum Institute 33 (3) 166 - 172 0582-4664 1990 [Not refereed][Not invited]
  • Kenji Hashimoto, Kouji Takatani, Takao Masuda
    The Chemical Engineering Journal 29 (2) 85 - 96 0300-9467 1984 [Refereed][Not invited]
     
    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 0300-9467 1983 [Refereed][Not invited]
     
    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 0369-4577 1981 [Refereed][Not invited]
  • Kenji Hashimoto, Koti-Ichi Miura, Yutaka Miyoshi, Takao Masuda, Toshihiko Yamanishi
    Nippon Kagaku Kaishi The Chemical Society of Japan 1981 (11) 1815 - 1824 0369-4577 1981 [Not refereed][Not invited]
     
    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.
  • Kenji Hashimoto, Koti-Ichi Miura, Yutaka Miyoshi, Takao Masuda, Toshihiko Yamanishi
    Nippon Kagaku Kaishi 1981 (11) 1815 - 1824 0369-4577 1981 [Not refereed][Not invited]
     
    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.

Books etc

  • 室井 高城, 増田 隆夫 (Joint work)
    シーエムシー出版 2018/03 (ISBN: 4781313140) 295
  • 草壁 克己, 増田 隆夫 (Joint work)
    三共出版 2010/03 (ISBN: 4782706014) 126
  • Deactivation of Zeolite Catalysts by Coke
    American Chemical Society, Symposium Series 1996
  • 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
  • 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
  • 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
  • Transport Phenomena in Processes Using Catalysts
    1995
  • Production of Fuel from Waste Plastics Using Zeolite Catalysts
    1995
  • 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
  • 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
  • Synthesis of Gasoline from Waste Plastics using Solid Catalysts
    1994
  • Production of Gasoline from Waste Plastics -Recycling of Polyethylene-
    1994
  • 物理化学実験のてびき(分担執筆)
    化学同人 1993

Conference Activities & Talks

  • Synthesis of Isomorphous Substituted Ferrosilicate with MTW Structure and Their Catalytic Performance on the Methylation of b-Methylnaphthalene  [Not invited]
    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  2014/09
  • Selective synthesis of allyl compound from Glycerol over Iron-oxide Based Catalyst  [Not invited]
    Shitara Hitofumi, Terai Kazuhiro, Nakasaka Yuta, Tago Teruoki, Masuda Takao
    TOCAT7 pre-symposium  2014/05
  • 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  [Not invited]
    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  2014/03
  • 重質油分解軽質化におけるTiO2-ZrO2系触媒の効果  [Not invited]
    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  2014/01
  • Liginin Conversion to Aromatic Chemicals  [Not invited]
    Takuya Yoshikawa, Taichi Yagi, Satoshi Shinohara, Teruoki Tago, Takao Masuda
    the 6th Japan-China Workshop on Environmental Catalysis and Eco-Materials  2013/12
  • Selective Formation of β,β-DimethylNaphthalene by Methylation of 2-Methylnaphthalene over MTW-type Zeolite  [Not invited]
    Gaku Watanabe, Taichi Taniguchi, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    The 4th CSE Summer School Post ISHHC-16 CRC International Symposium  2013/08
  • 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  [Not invited]
    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  2013/03
  • Fe-MTW型ゼオライトの合成と特性評価  [Not invited]
    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  2013/03
  • 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  [Not invited]
    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  2013/03
  • 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  [Not invited]
    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  2013/03
  • 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  [Not invited]
    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  2013/03
  • Conversion of Biodiesel-Derived Crude Glycerol into Useful Chemicals over Zirconia-Iron Oxide Catalyst  [Not invited]
    Aya Konaka, Teruoki Tago, Takuya Yoshikawa
    3rd North American Symposium on Chemical Reaction Engineering (NASCRE-3)  2013/03
  • Isobutylene synthesis from water-containing acetone  [Not invited]
    Teruoki Tago, Hiroki Konno, Takuya Okamura, Yuta Nakasaka, Takao Masuda
    3rd North American Symposium on Chemical Reaction Engineering (NASCRE-3)  2013/03
  • 炭素資源転換における触媒技術の動向と展望  [Not invited]
    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  2013/02
  • 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  [Not invited]
    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  2013/01
  • 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  [Not invited]
    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  2013/01
  • 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  [Not invited]
    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  2013/01
  • 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  [Not invited]
    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  2013/01
  • MTW型ゼオライトの結晶サイズ制御と反応特性評価  [Not invited]
    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  2013/01
  • Production of phenolic compounds from lignin via depolymerization and catalytic cracking  [Not invited]
    Taichi Yagi, Takuya Yoshikawa, Satoshi Shinohara, Naonori Ryumon, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    The 25th International Symposium on Chemical Engineering  2012/12
  • Catalytic cracking of extra heavy oil over FeOx-based catalyst under subcritical water  [Not invited]
    Kumiko Tanaka, Tatsuya Kitaguchi, Yuma Takeda, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    The 25th International Symposium on Chemical Engineering  2012/12
  • n-Hexane Cracking for Light Olefins Selective Synthesis over Nano-scale ZSM-5 zeolite  [Not invited]
    Hiroki Konno, Takuya Okamura, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    The 25th International Symposium on Chemical Engineering  2012/12
  • Conversion of Inedible Biomass Wastes to Petroleum-related Useful Chemicals Using Iron Oxide Catalysts  [Not invited]
    Takao Masuda, Teruoki Tago
    22th Annual Saudi-Japan Symposium  2012/11
  • ZSM-5 を用いたn-ヘキサン接触分解の反応工学的解析  [Not invited]
    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  2012/11
  • 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  [Not invited]
    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  2012/11
  • Size/morphology controlled synthesis of zeolite crystals and their applications  [Not invited]
    Teruoki Tago, Takao Masuda
    10th Japan-Korea Symposium on Materials and Interfaces  2012/11
  • 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  [Not invited]
    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  2012/10
  • 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  [Not invited]
    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  2012/10
  • 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  [Not invited]
    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  2012/10
  • Catalytic Cracking of n-Hexane Cracking over MFI-Type Zeolites with Different Crystal Sizes  [Not invited]
    Yuta Nakasaka, Hiroki Konno, Akihiro Okabe, Teruoki Tago, Takao Masuda
    22th International Symposium on Chemical Reaction Engineering  2012/09
  • Production of Useful Chemicals from Lignin-derived Slurry Liquid using Iron Oxide Catalyst  [Not invited]
    Takuya Yoshikawa, Satoshi Shinohara, Taichi Yagi, Naonori Ryumon, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    7th International Conference on Environmental Catalysis (ICEC 2012)  2012/09
  • Conversion of Glycerol into Allyl Alcohol over Potassium-Supported Iron Oxide Catalyst  [Not invited]
    A. Konaka, T. Tago, T. Yoshikawa, A. Nakamura, T. Masuda
    7th International Conference on Environmental Catalysis (ICEC 2012)  2012/09
  • MTW型ゼオライトの結晶サイズ制御と n-hexaneeの 接触分解  [Not invited]
    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  2012/09
  • 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  [Not invited]
    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  2012/09
  • 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  [Not invited]
    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  2012/09
  • 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  [Not invited]
    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  2012/09
  • Controlled and Rapid Growth of MTT Zeolite Crystals with Low Aspect Ratio in a Microwave Reactor  [Not invited]
    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  2012/09
  • Upgrading of Oil Sand Bitumen over Iron-oxide Catalyst using Flow Type reactor unde Sub/Super-Critical Water Conditions  [Not invited]
    Tatsuya Kitaguchi, Yusuke Sato, Teruoki Tago, Takao Masuda
    22th International Symposium on Chemical Reaction Engineering  2012/09
  • 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  [Not invited]
    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  2012/08
  • 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  [Not invited]
    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  2012/08
  • 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  [Not invited]
    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  2012/08
  • 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  [Not invited]
    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  2012/08
  • Measurement of Intracrystalline Diffusivities of Aromatics within Si-beta in Cyclohexane Solution  [Not invited]
    Yuta Nakasaka, Sayuri Katsuta, Teruoki Tago, Satoshi Inagaki, Yoshihiro Kubota, Takao Masuda
    International Symposium on Zeolites and MicroPorous Crystals 2012  2012/07
  • Effect of surfactant addition and Na/Al ratio on crystal size of FAU zeolite  [Not invited]
    Taichi Taniguchi, Saori Fujiwara, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    International Symposium on Zeolites and MicroPorous Crystals 2012  2012/07
  • Kinetics for catalytic cracking of n-hexane over MFI-type zeolites with different crystal sizes  [Not invited]
    Takuya Okamura, Hiroki Konno, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    International Symposium on Zeolites and MicroPorous Crystals 2012  2012/07
  • Catalytic Cracking of n-Hexane over Mono-dispersed Nano-crystalline MFI-type Zeolite  [Not invited]
    Hiroki Konno, Takuya Okamura, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    International Symposium on Zeolites and MicroPorous Crystals 2012  2012/07
  • Production of Light Olefins from n-Hexane Cracking over MFI Zeolites with Nano- and Macro-Crystal Sizes  [Not invited]
    Teruoki Tago, Hiroki Konno, Takuya Okamura, Yuta Nakasaka, Takao Masuda
    The 15th International Congress on Catalysis  2012/07
  • Activity and Stability of iron oxide catalyst toward conversion of biomass tar into useful chemicals  [Not invited]
    Dieni Mansur, Mana Shimokawa, Teruoki Tago, Takao Masuda
    15th International Congress on Catalysis 2012  2012/07
  • Production of Useful Chemicals from Bio-diesel Derived Crude Glycerol over Zirconia-Iron Oxide Catalyst  [Not invited]
    Takuya Yoshikawa, Taichi Yagi, Satoshi Shinohara, Testuya Fukunaga, Yuta Nakasaka, Teruoki Tago, Takao Masuda
    15th International Congress on Catalysis 2012  2012/07
  • Kinetc Analysis of Burning Regeneration of Coked MFI-type Zeolites Obtained by Catalytic Cracking of n-Hexane  [Not invited]
    Teruoki Tago, Takuya Okamura, Hiroki Konno, Yuta Nakasaka, Takao Masuda
    22th International Symposium on Chemical Reaction Engineering  2012

Works

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

MISC

  • 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  2017/12/01  [Not refereed][Not invited]
  • 中坂佑太, 増田隆夫  ゼオライト  34-  (4)  129‐138  2017/10/15  [Not refereed][Not invited]
  • 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  2017/07/01  [Not refereed][Not invited]
  • 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  2016/07  [Not refereed][Not invited]
  • 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  2016/04/10  [Not refereed][Not invited]
  • 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  2016/03/16  [Not refereed][Not invited]
  • 中坂佑太, 多湖輝興, 増田隆夫  ゼオライト  32-  (2)  53  -61  2015/06/10  [Not refereed][Not invited]
  • KONISHI RYOTA, KAWAMATA YUKI, SHINOHARA SATOSHI, YAGI TAICHI, KOYAMA YOSHIHITO, NAKASAKA YUTA, TAGO TERUOKI, MASUDA TAKAO  化学工学会年会研究発表講演要旨集(CD-ROM)  80th-  ROMBUNNO.XB237  2015/03/19  [Not refereed][Not invited]
  • WATANABE GAKU, TANIGUCHI TAICHI, NAKASAKA YUTA, TAGO TERUOKI, MASUDA TAKAO  触媒討論会講演予稿集  115th-  97  2015/03/10  [Not refereed][Not invited]
  • TANIGUCHI TAICHI, YONEDA KEITARO, NAKASAKA YUTA, TAGO TERUOKI, MASUDA TAKAO  触媒討論会講演予稿集  115th-  95  2015/03/10  [Not refereed][Not invited]
  • KONDOH Hisaki, NAKASAKA Yuta, TAGO Teruoki, MASUDA Takao  Journal of the Japan Institute of Energy  94-  (1)  67  -73  2015/01/20  [Not refereed][Not invited]
     
    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.
  • YONETA KEITARO, TANIGUCHI TAICHI, NAKASAKA YUTA, TAGO TERUOKI, MASUDA TAKAO  ゼオライト研究発表会講演予稿集  30th-  41  2014/11/26  [Not refereed][Not invited]
  • HASEGAWA MIHO, ZHANG YAQI, NAKASAKA YUTA, GUCUYENER CANAN, TAGO TERUOKI, GASCON JORGE, KAPTEIJN FREEK, MASUDA TAKAO  ゼオライト研究発表会講演予稿集  30th-  21  2014/11/26  [Not refereed][Not invited]
  • SHITARA HIROFUMI, TERAI KAZUHIRO, NAKASAKA YUTA, TAGO TERUOKI, MASUDA TAKAO  石油・石油化学討論会講演要旨  44th-  286  2014/10/16  [Not refereed][Not invited]
  • KONDO HISAKI, TANAKA KUMIKO, NAKASAKA YUTA, TAGO TERUOKI, MASUDA TAKAO  石油・石油化学討論会講演要旨  44th-  252  -253  2014/10/16  [Not refereed][Not invited]
  • NISHIMURA JUN'ICHI, ONAKA RYOTA, NAKASAKA YUTA, TAGO TERUOKI, MASUDA TAKAO  石油・石油化学討論会講演要旨  44th-  58  2014/10/16  [Not refereed][Not invited]
  • KONDOH Hisaki, TANAKA Kumiko, TAKEDA Yuma, NAKASAKA Yuta, TAGO Teruoki, MASUDA Takao  日本エネルギー学会大会講演要旨集  (23)  10  -11  2014/07/14  [Not refereed][Not invited]
     
    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  2014/01/01  [Not refereed][Not invited]
  • SATO Shinya, FUMOTO Eri, TAKANOHASHI Toshimasa, KOYAMA Yoshihito, MASUDA Takao  石炭科学会議発表論文集  (50)  20  -21  2013/10/21  [Not refereed][Not invited]
     
    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.
  • TAGO Teruoki, YOSHIKAWA Takuya, NAKASAKA Yuta, MASUDA Takao  觸媒 = Catalyst  55-  (5)  270  -275  2013/10/10  [Not refereed][Not invited]
  • SATO Shinya, TAKANOHASHI Toshimasa, KAJITANI Satoshi, MASUDA Takao  日本エネルギー学会大会講演要旨集  (22)  14  -15  2013/07/29  [Not refereed][Not invited]
     
    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.
  • Konno Hiroki, Tago Teruoki, Nakasaka Yuta, Masuda Takao  Proceeding of Annual/Fall Meetings of the Japan Petroleum Institute  2013-  (0)  157  -157  2013  [Not refereed][Not invited]
     
    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。
  • Shinohara Satoshi, Yoshikawa Takuya, Yagi Taichi, Koyama Yoshihito, Nakasaka Yuuta, Tago Teruoki, Masuda Takao  Proc. JPI  2013-  (0)  2013  [Not refereed][Not invited]
     
    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。
  • Shinohara Satoshi, Yoshikawa Takuya, Yagi Taichi, Kajitani Satoshi, Nakasaka Yuuta, Tago Teruoki, Masuda Takao  Proc. JPI  2013-  (0)  2013  [Not refereed][Not invited]
     
    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。
  • MASUDA TAKAO, TAGO TERUOKI  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  2011/06  [Not refereed][Not invited]
  • 多湖 輝興, 吉川 琢也, 増田 隆夫  Bio industry  28-  (2)  45  -50  2011/02  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
     
    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  [Not refereed][Invited]
  • Nakasaka Yuta, Okamura Takuya, Konno Hiroki, Kawahara Takahito, Tago Teruoki, Masuda Takao  Proceeding of Annual/Fall Meetings of the Japan Petroleum Institute  2011-  (0)  16  -16  2011  [Not refereed][Not invited]
     
    MFI型、BEA型ゼオライト触媒を用いた<I>n</I> -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<I>n</I> -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。
  • Yoshikawa Takuya, Yagi Taichi, Shinohara Satoshi, Fukunaga Tetsuya, Nakasaka Yuta, Tago Teruoki, Masuda Takao  Proc. JPI  2011-  (0)  176  -176  2011  [Not refereed][Not invited]
     
    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。
  • Kitaguchi Tatsuya, Tanaka Kumiko, Sato Yusuke, Takeda Yuma, Tago Teruoki, Masuda Takao  Proc. JPI  2011-  (0)  19  -19  2011  [Not refereed][Not invited]
     
    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。
  • Tanaka Kumiko, Kitaguchi Tatsuya, Sato Yusuke, Takeda Yuma, Tago Teruoki, Masuda Takao  Proc. JPI  2011-  (0)  20  -20  2011  [Not refereed][Not invited]
     
    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  [Not refereed][Not invited]
  • SONOYAMA Nozomu, YOSHIKAWA Takuya, HAYASHI Jun-ichiro, TAGO Teruoki, MASUDA Takao  石炭科学会議発表論文集  (47)  112  -113  2010/09/21  [Not refereed][Not invited]
     
    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  2010/09  [Not refereed][Not invited]
  • FUNAI Satoshi, TAGO Teruoki, MASUDA Takao  Journal of the Japan Institute of Energy  89-  (3)  231  -236  2010/03/20  [Not refereed][Not invited]
     
    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  2010/02/05  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • Yoshikawa Takuya, Funai Satoshi, Fukunaga Tetsuya, Tago Teruoki, Masuda Takao  Proc. JPI  2010-  (0)  118  -118  2010  [Not refereed][Not invited]
     
    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。
  • Sato Yusuke, Kitaguchi Tatsuya, Funai Satoshi, Morimoto Masato, Sato Shinya, Takanohashi Toshimasa, Tago Teruoki, Masuda Takao  Proc. JPI  2010-  (0)  173  -173  2010  [Not refereed][Not invited]
     
    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。
  • Kitaguchi Tatsuya, Sato Yusuke, Funai Satoshi, Tago Teruoki, Masuda Takao  Proc. JPI  2010-  (0)  174  -174  2010  [Not refereed][Not invited]
     
    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。
  • Kitaguchi Tatsuya, Sato Yusuke, Shinooka Miki, Hunai Satoshi, Tago Teruoki, Masuda Takao  Proc. JPI  2010-  (0)  10  -10  2010  [Not refereed][Not invited]
     
    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。
  • Takuya Yoshikawa, Duangkamol Na-Ranong, Teruoki Tago, Takao Masuda  Journal of the Japan Petroleum Institute  53-  (3)  178  -183  2010  [Not refereed][Not invited]
     
    The catalytic activity of iron oxide composite catalyst (ZrO 2-Al2O3-FeOx) was investigated for converting aromatic compounds derived from plant biomass into useful aromatics. Catalytic cracking of lignin constituent-related di-aroatics such as diphenyl ether, diphenyl methane, and 2-benzyloxyphenol, and mono-aromatics such as guaiacol, acetophenone, and 1-phenyl-1-propanol was carried out over ZrO 2-Al2O3-FeOx. The catalytic reactions were conducted in a fixed-bed reactor at 773 K under atmospheric pressure. Diphenyl ether and diphenyl methane were stable, whereas 2-benzyloxyphenol was thermally decomposed, followed by the production of toluene and phenol over ZrO2-Al2O3-FeO x. Guaiacol and acetophenone were selectively converted into 54 C-mol% of phenol and 29 C-mol% of benzene, respectively. The methoxy and carbonyl groups were decomposed into gaseous products mainly consisting of CO2, whereas dehydration of the aliphatic hydroxyl group in 1-phenyl-1-propanol mainly occurred to produce 1-phenyl-1-propene. ZrO 2-Al2O3-FeOx catalyst is effective for degrading alkyl ether bonds between aromatic rings, and the ring substituent methoxy and carbonyl groups.
  • SONOYAMA Nozomu, NOBUTA Kazunari, KIMURA Tokuji, HOSOKAI Sou, HAYASHI Jun-ichiro, TAGO Teruoki, MASUDA Takao  石炭科学会議発表論文集  (46)  4  -5  2009/11/26  [Not refereed][Not invited]
     
    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  2009/09/27  [Not refereed][Not invited]
  • FUNAI Satoshi, TAGO Teruoki, MASUDA Takao  Journal of the Japan Institute of Energy  88-  (3)  187  -192  2009/03/20  [Not refereed][Not invited]
     
    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  [Refereed][Not invited]
  • Shinooka Miki, Kitaguchi Tatsuya, Sato Yusuke, Funai Satoshi, Tago Teruoki, Masuda Takao  Proc. JPI  2009-  (0)  18  -18  2009  [Not refereed][Not invited]
     
    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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 増田 隆夫  触媒 = Catalysts & Catalysis  50-  (4)  2008/06/10  [Not refereed][Not invited]
  • 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  2008/06  [Not refereed][Not invited]
  • Baohua Liu, Teruoki Tago, Eri Fumoto, Jun-ichirou Hayashi, Takao Masuda  Journal of Chemical Engineering of Japan  41-  (5)  369  -373  2008  [Refereed][Not invited]
  • Duangkamol Na-Ranong, Ratanaporn Yuangsawad, Teruoki Tago, Takao Masuda  Korean Journal of the Chemical Engineering  25-  (3)  426  -430  2008  [Refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  2007/11/07  [Not refereed][Not invited]
  • FUMOTO Eri, MATSUMURA Akimitsu, SATO Shinya, TAKANOHASHI Toshimasa, TAGO Teruoki, MASUDA Takao  石炭科学会議発表論文集  (44)  82  -83  2007/10/11  [Not refereed][Not invited]
     
    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)  2007/10/05  [Not refereed][Not invited]
  • AOKI DAICHI, IWAKAI KAZUYUKI, TAGO TERUOKI, MASUDA TAKAO  化学工学会年会研究発表講演要旨集  72nd-  (0)  673  -710  2007/02/19  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • Nobuta Kazunari, Funai Satoshi, Tago Teruoki, Masuda Takao  Proc. JPI  2007-  (0)  81  -81  2007  [Not refereed][Not invited]
     
    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  [Not refereed][Not invited]
  • Toshiro Tsuji, Akito Hatayama, Shin Mukai, Takao Masuda  Polymer Preprints, Japan  55-  5603  -5604  2006/12/01  [Not refereed][Not invited]
     
    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  [Not refereed][Not invited]
  • FUMOTO Eri, MIZUTANI Yosuke, TAGO Teruoki, MASUDA Takao  Applied Catalysis B, Enviromental  68-  (3-4)  154  -159  2006  [Not refereed][Not invited]
  • 増田 隆夫  化学工学会 研究発表講演要旨集  2006-  (0)  338  -339  2006  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  2004/10/05  [Not refereed][Not invited]
  • MASUDA TAKAO, KODA SHINOBU, SHIRAISHI FUMIHIDE, TSUTSUI TOSHIO, ITO NAOTSUGU, KUSAKABE KATSUMI, SHIMOGAKI YUKIHIRO  化学工学  68-  (10)  549  -556  2004/10/05  [Not refereed][Not invited]
  • T Tsuji, A Sasaki, S Okajima, T Masuda  KAGAKU KOGAKU RONBUNSHU  30-  (5)  705  -709  2004/09  [Not refereed][Not invited]
     
    Steam reforming of oils produced from waste plastics such as polyolefins has been investigated with a view of producing hydrogen. Steam reforming of oils produced by decomposition of plastics at relatively low temperatures (350-450degreesC) was carried out at temperatures from 600 to 800degreesC using commercial Ni/Al2O3 catalysts. Gas yield, gas composition, carbon conversion and coking characteristics were examined. Oils from both polyethylene and polystyrene were well gasified with very high carbon conversions and low coking rates at temperatures higher than 700degreesC. The gas components were consistent with calculated equilibrium compositions. The coking rate of polystyrene oil was lower than that of polyethylene oil, and the coking rate was the lowest at the temperature of 800degreesC.
  • FUMOTO E, TAGO T, TSUJI T, MASUDA T  Energy & Fuel  18-  (6)  1770  -1774  2004  [Not refereed][Not invited]
  • 筒井俊雄, 小島紀徳, 増田隆夫  アロマティックス  55-  296  -300  2003/11/25  [Not refereed][Invited]
  • Mukai, SR, Y Yamamoto, T Masuda, H Tamon  KAGAKU KOGAKU RONBUNSHU  29-  (2)  221  -225  2003/03  [Not refereed][Not invited]
     
    Si/C composites were synthesized by the co-carbonization of 3,5-xylenol-derived novolac resin with various polysilane polymers. A significant increase in the Li+ reversible capacity due to the inclusion of Si in the C matrix was observed. However, the Li+ irreversible capacities of the materials were also fairly large. The irreversible Li+ capacities were fand to be explainable by two factors: the consumption of Li+ due to the formation of solid electrolyte interface layers within the materials, the amount of which depends on the pore structure of the material, and the trapping of Li+ by the O included in the material. It was also found that the Si in the materials synthesized using polydiphenylsilane as the Si source could store up to an average of 2.4 Li+ per atom. These results indicate that by selecting a proper C source for the co-carbonization with polysilane polymers, an anode material for Li+ batteries with a large reversible capacity and small irreversible capacity can be obtained.
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 増田 隆夫  触媒  44-  (4)  290  -291  2002/06/10  [Not refereed][Not invited]
  • MASUDA TAKAO, OKUBO YOSHIHITO, TANAKA YOSHIHIRO, FUNABIKI TAKUZO  触媒  43-  (6)  434  -436  2001/09/10  [Not refereed][Not invited]
  • KUSUDA TETSUYA, SHIMIZU YASUTOSHI, SHIRAI YOSHIHITO, SAKAI KENJI, SHIBATA MASAO, FUNATSUKURI TOSHITAKA, MIURA KOICHI, MASUDA TAKAO, HARADA YOSHIFUMI  科学技術振興調整費試験研究実施計画  2001-  331  -335  2001/08  [Not refereed][Not invited]
  • 増田 隆夫  環境保全  (16)  3  -12  2001  [Not refereed][Not invited]
  • 増田 隆夫  触媒  42-  (1)  2000/01/15  [Not refereed][Not invited]
  • MUKAI SHIN, YAMAMOTO YUTAKA, MASUDA TAKAO, HASHIMOTO KENJI  炭素材料学会年会要旨集  26th-  38  -39  1999/12/01  [Not refereed][Not invited]
  • T Masuda, H Kuwahara, Mukai, SR, K Hashimoto  CHEMICAL ENGINEERING SCIENCE  54-  (13-14)  2773  -2779  1999/07  [Not refereed][Not invited]
     
    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.
  • MASUDA Takao  Kagaku k(0xFADE)gaku  63-  (4)  201  -204  1999/04/05  [Not refereed][Not invited]
  • 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  1999/01/01  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • Book Review of H. Scott Fogler, Elements of Chemical Reaction Engineering, third ed. Prentice-Hall PTR.
    Chemical Engineering Journal  1  -2  1999  [Not refereed][Not invited]
  • Diffusion Mechanism within Micro Pores of Zeolites
    Chemical Engineering of Japan  63-  (4)  201  -204  1999  [Not refereed][Not invited]
  • Mechanical and Electrical Properties of Rapidly Grown Vapor Grown Carbon Fivers
    Proceedings of the 24th Biennial Conference on Carbon  564  -565  1999  [Not refereed][Not invited]
  • Minimization of the Irreversible Li+ Capacity of Hard Carbons
    Proceedings of the 24th Biennial Conference on Carbon  540  -541  1999  [Not refereed][Not invited]
  • Process of Continuous Conversion of Waste Plastic Mixture to Fuels
    Japanese Journal of Multiphase Flow  13-  (2)  101  -108  1999  [Not refereed][Not invited]
  • 増田 隆夫, 橋本 健治  ケミカルエンジニヤリング  43-  (12)  939  -944  1998/12  [Not refereed][Not invited]
  • MASUDA Takao, ASANUMA Tadashi, KITAMURA Masahiro, HASHIMOTO Kenji, KOBAYASHI Yoshiteru, KOMAYA Takashi  Syokubai  40-  (6)  348  -351  1998/09/10  [Not refereed][Not invited]
  • T Masuda, Y Fujikata, Mukai, SR, K Hashimoto  APPLIED CATALYSIS A-GENERAL  172-  (1)  73  -83  1998/08  [Not refereed][Not invited]
     
    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  1998/08  [Not refereed][Not invited]
     
    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  1998/05  [Not refereed][Not invited]
     
    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  1998/02  [Not refereed][Not invited]
     
    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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • Continuous Recovery of Liquid Fuals from Waste Plastic Mixtures
    Chemical Engineering  43-  (12)  939  -944  1998  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • T Masuda, Y Miwa, K Hashimoto, Y Ikeda  POLYMER DEGRADATION AND STABILITY  61-  (2)  217  -224  1998  [Not refereed][Not invited]
     
    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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • Mukai, SR, T Masuda, Ogino, I, K Hashimoto  APPLIED CATALYSIS A-GENERAL  165-  (1-2)  219  -226  1997/12  [Not refereed][Not invited]
     
    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  1997/12  [Not refereed][Not invited]
     
    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  1997/11  [Not refereed][Not invited]
     
    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.
  • MASUDA Takao, FUJIKATA Yoshihiro, IKEDA Hideo, NISHIDA Tomonori, HASHIMOTO Kenji  触媒  39-  (6)  432  -435  1997/09/10  [Not refereed][Not invited]
  • 橋本 健治, 増田 隆夫  燃料及燃焼  64-  (7)  483  -492  1997/07  [Not refereed][Not invited]
  • MASUDA Takao, FUJIKATA Yoshihiro, HASHIMOTO Kenji  触媒  39-  (2)  1997/03/10  [Not refereed][Not invited]
  • 橋本 健治, 増田 隆夫  工業材料  45-  (2)  119  -123  1997/02  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • The Production of Silicon Included Vapor Grown Carbon Fibers Using the Liquid Pulse Injection Technique
    Proceedings of Carbon'97  284  -285  1997  [Not refereed][Not invited]
  • T Masuda, Y Miwa, A Tamagawa, Mukai, SR, K Hashimoto, Y Ikeda  POLYMER DEGRADATION AND STABILITY  58-  (3)  315  -320  1997  [Not refereed][Not invited]
     
    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  [Not refereed][Not invited]
  • Chemical Process for Recovery of Gasoline from Waste Plastics
    Industrial Materials  45-  119  -123  1997  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • Difference in Intracrystalline Diffusivities of Zeolites between Adsorption and Desorption Processes
    International Symposium on Zeolites and Microporous Crystals  OC22  1997  [Not refereed][Not invited]
  • A New Technique to Measure TPD Spectrum under Desorption Control Conditions
    International Symposium on Acid-Base Catalysis III  28  1997  [Not refereed][Not invited]
  • Measurement of Heat Flux Caused by Desorption of NH3
    Catalysts & Catalysis  39-  201  1997  [Not refereed][Not invited]
  • MASUDA Takao, FUJIKATA Yoshihiro, IKEDA Hideo, MATSUSHITA Shunichi, HASHIMOTO Kenji  触媒  38-  (6)  490  -493  1996/09/10  [Not refereed][Not invited]
  • MASUDA Takao  触媒  38-  (6)  466  -467  1996/09/10  [Not refereed][Not invited]
  • 向井 紳, 増田 隆夫, 原田 武志, 橋本 健治  化学工学  60-  (7)  481  -482  1996/07/05  [Not refereed][Not invited]
  • HASHIMOTO Kenji, MASUDA Takao  Kobunshi  45-  (5)  311  -315  1996/05/01  [Not refereed][Not invited]
     
    橋本健治
  • T Masuda, K Fukada, Y Fujikata, H Ikeda, K Hashimoto  CHEMICAL ENGINEERING SCIENCE  51-  (10)  1879  -1888  1996/05  [Not refereed][Not invited]
     
    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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • Hydrocarbons Contributing Production of Vapor Grown Carbon Fibers by Liquid Pulse Injection Technique
    60-  481  -482  1996  [Not refereed][Not invited]
  • Preparation of ZSM-5 Zeolite Mem brane and Its Application to Pervaporation
    The 1996 Asian-Pacific Chemical Reaction Engineering Forum  2-  435  -440  1996  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • Method for Characterization of Acidic Properties Using NH3-TPD Spectra Measured under Desorption Control Conditions
    Catalysts & Catalysis  38-  490  -493  1996  [Not refereed][Not invited]
  • Intracrystalline Diffusivities of MFI-and Y-type Zeolites
    Catalysts & Catalysis  38-  466  -467  1996  [Not refereed][Not invited]
  • Mukai, SR, T Masuda, T Harada, K Hashimoto  CARBON  34-  (5)  645  -648  1996  [Not refereed][Not invited]
     
    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  [Not refereed][Not invited]
  • Degradation of Waste Polyethylene Terephthalate -Minimizing Carbonaceous Residue-
    Prodeeding of 7th Asian Pacific Confederation  94  -98  1996  [Not refereed][Not invited]
  • K HASHIMOTO, T MASUDA  ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY  210-  32  -PETR  1995/08  [Not refereed][Not invited]
  • M ARAI, Y NISHIYAMA, T MASUDA, K HASHIMOTO  APPLIED SURFACE SCIENCE  89-  (1)  11  -19  1995/05  [Not refereed][Not invited]
     
    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.
  • Takao Masuda, Shin Robert Mukai, Takashi Akiyama, Yoshihiro Fujikata, Kenji Hashimoto  KAGAKU KOGAKU RONBUNSHU  21-  (6)  1133  -1139  1995  [Not refereed][Not invited]
     
    A model has been developed to represent the deactivation of REY zeolite caused by coke deposition during catalytic cracking of heavy oil obtained from pyrolysis of waste plastics. Coke deposition not only leads to coverage of the acid sites, which contribute to the reaction, but also leads to a decrease in the intracrystalline diffusivity of the zeolite due to the reduction in effective pore opening, resulting in deactivation of the catalyst. In this work, firstly the amount of strong acid sites and the diffusivity of catalysts with different amounts of coke loading were measured, and empirical equations, which represent the relationships between the amount of coke loading and these two values, were obtained. Finally, a model was developed to calculate the transient change of the catalyst activity and the concentration distributions of the components within the reactor by employing the obtained empirical equations. The calculated results agreed well with experimental results. Using this model, it was found that the deactivation rate of the catalyst was reduced under diffusion control conditions, and large catalyst particles could maintain their activity longer than small catalyst particles. © 1995, The Society of Chemical Engineers, Japan. All rights reserved.
  • MUKAI, SR, T MASUDA, Y FUJIKATA, T HARADA, K HASHIMOTO  CARBON  33-  (5)  733  -735  1995  [Not refereed][Not invited]
  • T MASUDA, H HARA, M KOUNO, H KINOSHITA, K HASHIMOTO  MICROPOROUS MATERIALS  3-  (4-5)  565  -571  1995/01  [Not refereed][Not invited]
     
    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  1994/12  [Not refereed][Not invited]
     
    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  1994/07  [Not refereed][Not invited]
     
    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  1994/04  [Not refereed][Not invited]
     
    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  [Not refereed][Not invited]
  • ゼオライト  11-  2  -17  1994  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • Deactivation of Zeolite Catalyst Caused by Coke Deposition
    Petrotech  17-  1052  -1058  1994  [Not refereed][Not invited]
  • Zeolite News Letters  11-  2  -17  1994  [Not refereed][Not invited]
  • S. R. Mukai, T. Masuda, Y. Fujikata, K. Hashimoto  CHEMICAL ENGINEERING SCIENCE  49-  (24B)  4909  -4916  1994  [Not refereed][Not invited]
     
    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  [Not refereed][Not invited]
  • AR SONGIP, T MASUDA, H KUWAHARA, K HASHIMOTO  ENERGY & FUELS  8-  (1)  136  -140  1994/01  [Not refereed][Not invited]
     
    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  [Not refereed][Not invited]
     
    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  1994/01  [Not refereed][Not invited]
     
    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  [Not refereed][Not invited]
  • AR SONGIP, T MASUDA, H KUWAHARA, K HASHIMOTO  APPLIED CATALYSIS B-ENVIRONMENTAL  2-  (2-3)  153  -164  1993/06  [Not refereed][Not invited]
     
    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  [Not refereed][Not invited]
  • Catalytic Reforming of Heavy Oil from waste plastics on Zeolite Catalysts
    Proceeding of International Symposium on Zeolites and Microporous crystals  349-350-  1993  [Not refereed][Not invited]
  • T MASUDA, MUKAI, SR, K HASHIMOTO  CARBON  31-  (5)  783  -787  1993  [Not refereed][Not invited]
     
    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  1992/08  [Not refereed][Not invited]
  • T MASUDA, N MURAKAMI, K HASHIMOTO  CHEMICAL ENGINEERING SCIENCE  47-  (9-11)  2775  -2780  1992/06  [Not refereed][Not invited]
     
    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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • Preparation of Zeolite Membrane on Ceramic Filter
    Chemical Engineering  (8)  9  -11  1992  [Not refereed][Not invited]
  • T MASUDA, MUKAI, SR, K HASHIMOTO  CARBON  30-  (1)  124  -126  1992  [Not refereed][Not invited]
  • K HASHIMOTO, T MASUDA, H KASHIHARA  APPLIED CATALYSIS  75-  (2)  331  -342  1991/08  [Not refereed][Not invited]
     
    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  [Not refereed][Not invited]
  • K HASHIMOTO, T MASUDA, N MURAKAMI  ZEOLITE CHEMISTRY AND CATALYSIS  69-  477  -484  1991  [Not refereed][Not invited]
  • 増田 隆夫, 橋本 健治  触媒  32-  (4)  p253  -256  1990/06  [Not refereed][Not invited]
  • K HASHIMOTO, K MIURA, T MASUDA, M TOMA, H SAWAI, M KAWASE  KAGAKU KOGAKU RONBUNSHU  16-  (3)  438  -446  1990/05  [Not refereed][Not invited]
     
    Polycrystalline silicon ingots, which are intermediate products of single crystalline silicon wafers, are produced from silane by thermal CVD under atmospheric pressure. A rod-substrate reactor with a double tube was designed for analyzing the kinetics of this process. Growth rates of polycrystalline silicon were measured at 10731173K under low pressures of silane (0.512.0kPa) diluted with hydrogen. The simple configuration of the reactor allowed exact simulations of the distributions of gas velocity, temperature and silane concentration in the reactor by use of the Navier-Stokes equations, and the axial profile of silicon growth rates on the substrate was calculated. The surface reaction rate constant was estimated by comparing the calculated and the experimental profiles of the growth rates. Two approximate models were also developed. One is a simplified laminar-flow model, in which axial gradients of velocity and temperature are neglected, and the other is a film model, in which resistances to mass transfer are confined to the film around the substrate. Results of the three kinds of model analyses indicated that the experiments were performed under nearly surface reaction-controlling regions. The surface reaction rate constants were thus estimated in the higher temperature regime using the rod-substrate reactor.
  • K HASHIMOTO, K MIURA, T MASUDA, M TOMA, H SAWAI, M KAWASE  JOURNAL OF THE ELECTROCHEMICAL SOCIETY  137-  (3)  1000  -1007  1990/03  [Not refereed][Not invited]
  • Kenji Hashimoto, Takao Masuda, Makoto Arai  Journal of The Japan Petroleum Institute  33-  (3)  166  -172  1990  [Not refereed][Not invited]
     
    The motor gasoline is commercially produced from n-paraffin and naphtene by catalytic reforming reaction, and is composed mainly of hydrocabon molecules of high octane rating such as aromatics and side-chained hydrocarbons. A part of the gasoline is incompletely burned and is exhausted, resulting in air pollution. Hence, in order to completely burn the gasoline, it is desired to increase the fraction of side-chained hydrocarbons, which is completely burned, without reducing its octane rating. These molecules are produced from n-paraffin by isomerization reaction over metal catalysts supported on solid acid catalysts.The main objective of this paper is to investigate the relationship between selectivity of the side-chained hydrocarbon molecules and acidic properties of catalysts by performing isomerization of n-hexane over platinum catalysts supported on Y type zeolites at 603K. On the basis of results obtained, catalyst of high selectivity of isomerization was prepared. Furthermore, the changes in its catalytic activity caused by thiophene poisoning the continual cycle of reaction and regeneration were examined.Firstly, a series of Y type zeolites with different acidic properties were prepared, by varying sodium content in Y type zeolite by the technique of ion exchange applied to sodium ion. Secondly, platinum was supported, about 0.5-0.6wt%, on the prepared Y type zeolites, yielding platinum catalysts supported on Y type zeolites. By measuring amounts of chemisorbed hydrogen on the catalysts and contents of platinum in these catalysts, it was confirmed that platinum was supported on Y type zeolites in the same manner (Fig. 1). The acid strength distributions of the catalysts were measured by the amine titration method. Isomerization of n-hexane was performed over the catalysts at 603K. From the results of reaction and measurement of acidic properties, the selectivity of isomerization was found to be closely related to the acid strength of acid sites distributed on the catalyst, as follows:1) acid sites having Hammett acidity function (H0) smaller than -8.2 (stronger acid sites) accelerate the cracking reaction of n-hexane as well as the isomerization.2) acid sites having acid strength H0 in the range from -2 to -6 enhance only isomerization.3) acid sites with weak acid strength (H0>2) on the catalyst are inactive in isomerization and cracking reactions.The platinum catalyst supported on Y type zeolite, which was prepared by exchanging 45% of proton with sodium ion, (Na(45)Y), had a number of acid sites of acid strengths H0 in the range from -2 to -6 (Fig. 3). Hence, this catalyst accelerated only the isomerization of n-hexane, and its selectivity was 90% (Fig. 2). The deactivated Na(45)Y catalyst was found to be completely regenerated by burning reaction. Furthermore, the reaction rate of the Na(45)Y catalyst was reduced only 16%, when the catalyst was used for 2h with thiophene of 60ppm in the reactant gas, while the platinum catalyst supported on activated alumina was completely deactivated under the same conditions.
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • K HASHIMOTO, T MASUDA, Y HARIGUCHI  NIPPON KAGAKU KAISHI  (3)  575  -582  1989/03  [Not refereed][Not invited]
     
    A model is developed which describes the activity and shape selectivity for the methylation of toluene to produce xylene isomers over HZSM-5 zeolite catalysts by taking account of both intracrystalline diffusion and acid strength distributions inside and outside crystallite. Effective intracrystalline diffusivities were directly measured by use of high-silica HZSM-5 zeolite which had no catalytic activity for the methylation of toluene in a high temperature range (473-673 K). The ratio among the diffusivities of p-, m- and o-xylene was about 10: 1: 1in the above temperature range. The acid sites inside and outside the crystallite were discriminated from each other, and each acid strength distribution function was measured by combining the two methods developed by 0urselves. Rate constants of methylation and isomerizations of xylenes inside and outside the crystallite were estimated by performing these reactions over two kinds of catalysts: one has acid sites only inside the crystallite, the other only o4tsicle the crystallite. Using these values, the proposed model was found to predict satisfactorily the apparent shape selectivity. A chart (Fig.11) based on the proposed model is also presented which gives a guide in preparing highly selective HZSM-5 catalysts for the methylation of trthiene.
  • 橋本 健治, 増田 隆夫, 播口 陽一  日本化学会誌  1989-  (3)  p575  -582  1989/03  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • K. Hashimoto, T. Masuda, M. Kawase  Studies in Surface Science and Catalysis  46-  (C)  485  -494  1989/01/01  [Not refereed][Not invited]
     
    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  1988/10  [Not refereed][Not invited]
  • K HASHIMOTO, T MASUDA, K ISOBE  JOURNAL OF CHEMICAL ENGINEERING OF JAPAN  21-  (3)  249  -255  1988/06  [Not refereed][Not invited]
  • K HASHIMOTO, T MASUDA, T MORI  CHEMICAL ENGINEERING SCIENCE  43-  (8)  2275  -2280  1988  [Not refereed][Not invited]
  • 橋本 健治, 増田 隆夫, 高木 嘉則  触媒  29-  (6)  p406  -409  1987/09  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • Relationship between Activation Energy of Desorption of
    Catalysts & CatalysisNH3 and Hammett Acidity Function Ho  29-  406  -409  1987  [Not refereed][Not invited]
  • 橋本 健治, 増田 隆夫, 森 達生  触媒  28-  (6)  p401  -404  1986/09  [Not refereed][Not invited]
  • K HASHIMOTO, T MASUDA, H MOTOYAMA, H YAKUSHIJI, M ONO  INDUSTRIAL & ENGINEERING CHEMISTRY PRODUCT RESEARCH AND DEVELOPMENT  25-  (2)  243  -250  1986/06  [Not refereed][Not invited]
  • K HASHIMOTO, T MASUDA, H UEDA, N KITANO  APPLIED CATALYSIS  22-  (1)  147  -156  1986/04  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • K. Hashimoto, T. Masuda, T. Mori  Studies in Surface Science and Catalysis  28-  (C)  503  -510  1986  [Not refereed][Not invited]
     
    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  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • Measurement of Lewis and Broensted Acid Strength Distributions of Solid Catalyst by Indicator Adsorption Method
    Catalysts & Catalysis  26-  333  -335  1984  [Not refereed][Not invited]
  • K HASHIMOTO, K TAKATANI, T MASUDA  CHEMICAL ENGINEERING JOURNAL AND THE BIOCHEMICAL ENGINEERING JOURNAL  29-  (2)  85  -96  1984  [Not refereed][Not invited]
  • Change in Surface Area of Silica-Alumina Catalysts Owing to Sintering in Steam
    Proceeding of 3rd Pacific Chemicla Engineering Congress  244  -249  1983  [Not refereed][Not invited]
  • K HASHIMOTO, K TAKATANI, H IWASA, T MASUDA  CHEMICAL ENGINEERING JOURNAL AND THE BIOCHEMICAL ENGINEERING JOURNAL  27-  (3)  177  -186  1983  [Not refereed][Not invited]
  • 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  [Not refereed][Not invited]
  • Measurement of Acid Strength Distribution of Solid Acid Catalyst by Adsorption Method
    Catalysts & Catalysis  23-  168  -170  1981  [Not refereed][Not invited]
  • Properties of Adsorption and Regeneration of Activated Carbon Produced from Phenol Resin Waste
    Bulletin of Chemical Society of Japan  (11)  1815  -1824  1981  [Not refereed][Not invited]
  • The Production of Carbon Fibers from Light Paraffins in the Gas Phase
    Proceding of Carbon '95  1995-  [Not refereed][Not invited]
  • 4
    /,308-309  1995-  [Not refereed][Not invited]

Industrial Property Rights

Awards & Honors

  • 2018 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 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 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 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 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

Research Grants & Projects

  • 文部科学省:科学研究費補助金基盤研究(A)
    Date (from‐to) : 2019 -2022 
    Author : 増田 隆夫
  • 文部科学省:科学研究費挑戦的研究(萌芽)
    Date (from‐to) : 2019 -2021 
    Author : 増田 隆夫
  • 文部科学省:科学研究費挑戦的研究(萌芽)
    Date (from‐to) : 2017 -2019 
    Author : 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)
    Date (from‐to) : 2012 -2019 
    Author : 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
    Date (from‐to) : 2017/04 -2018/03 
    Author : 増田 隆夫
  • 文部科学省:科学研究費補助金(基盤研究(A))
    Date (from‐to) : 2015 -2017 
    Author : 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
    Date (from‐to) : 2015 -2016 
    Author : 増田 隆夫
  • 文部科学省:科学研究費補助金(挑戦的萌芽研究)
    Date (from‐to) : 2015 -2016 
    Author : 増田 隆夫
  • 文部科学省:科学研究費補助金(基盤研究(B))
    Date (from‐to) : 2012 -2014 
    Author : 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
    Date (from‐to) : 2000 -2014 
    Author : 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
    Date (from‐to) : 2014 
    Author : 増田 隆夫
  • 文部科学省:科学研究費補助金(挑戦的萌芽研究)
    Date (from‐to) : 2012 -2013 
    Author : 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
    Date (from‐to) : 2009 -2013 
    Author : 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)
    Date (from‐to) : 2011 -2012 
    Author : 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
    Date (from‐to) : 2012 
    Author : 増田 隆夫
  • Ministry of Education, Culture, Sports, Science and Technology:Grants-in-Aid for Scientific Research(基盤研究(B))
    Date (from‐to) : 2009 -2011 
    Author : Takao MASUDA, 多湖 輝興
     
    We have successfully developed a preparation method for size-controlled synthesis of MFI, MOR and FAU zeolites in organic-structure-directing agents (OSDA) free condition. Nano-sized zeolite possesses advantages, such as low-diffusion resistance for hydrocarbons and high external surface area. By applying the advantages, a ZSM-5 nanocrystal layered membrane was prepared and used as a catalytic membrane for acetone-to-olefin reaction. As compared with a conventional fixed-bed reactor, the catalytic membrane exhibited a high acetone conversion and high olefin yields.
  • 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
    Date (from‐to) : 2011 
    Author : 増田 隆夫
  • 文部科学省:科学研究費補助金(挑戦的萌芽研究)
    Date (from‐to) : 2009 -2010 
    Author : 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
    Date (from‐to) : 2007 -2009 
    Author : 増田 隆夫
  • 文部科学省:科学研究費補助金(萌芽研究)
    Date (from‐to) : 2007 -2008 
    Author : 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.
  • Ministry of Education, Culture, Sports, Science and Technology:Grants-in-Aid for Scientific Research(基盤研究(B))
    Date (from‐to) : 2007 -2008 
    Author : Takao MASUDA, 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
    Date (from‐to) : 2008 
    Author : 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)
    Date (from‐to) : 2008 
    Author : 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
    Date (from‐to) : 2006 -2007 
    Author : 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
    Date (from‐to) : 2006 -2007 
    Author : 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
    Date (from‐to) : 2007 
    Author : 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
    Date (from‐to) : 2007 
    Author : 増田 隆夫
  • 文部科学省:科学研究費補助金(基盤研究(C))
    Date (from‐to) : 2006 -2006 
    Author : 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。
  • Ministry of Education, Culture, Sports, Science and Technology:Grants-in-Aid for Scientific Research(基盤研究(B))
    Date (from‐to) : 2005 -2006 
    Author : Taka MASUDA, 辻 俊郎, 多湖 輝興
     
    The main objective of this research is to develop a zeolite membrane exhibiting shape-selective oxidation properties. The major results are described below.A)Preparation of mono-dispersed ZSM-5 zeolite nanocrystals: Two types of zeolites with different crystal size, 2.0 micro-meter (micro-zeolite) and 50 nano-meter (nano-zeolite), could be prepared. These zeolites show the same acidity, pore volume, and crystalinity regardless of the different crystal size. Methanol reaction was carried out over the ZSM-5 zeolites, which is a series of reactions from methanol to ether, olefins, paraffins, and aromatics. Though the decrease in the catalytic activity was observed just after the reaction in the micro-zeolite, the nano-zeolite exhibited the high activity and the long life-time.B)Selective-deactivation of the acid sites at the outer surface: Acid sites of the zeolite at the outer surface were successfully deactivated by using phenyl-slilane compound. The intermediate of the dimthyl-ether could be selectively produced over the zeolite.C)Preparation of nanocrystal-layered membrane: The ZSM-5 zeolite nanocrystals were piled up on an alumina filter. The thickness of the nanocrystals could be controlled in the range from 20 to 40 micrometer. The methanol reaction was carried out using the nanocrystal-layered membrane, and the selectivity of the intermediate such as ether and olefins successfully increased up to 90 %.D)Ni-supporting zeolite for selective-oxidation system: Since the acid sites at the outer surface of the zeolite were deactivated, Ni ions could be selectively exchanged for protons at the inner pore of the ZSM-5 zeolite nanocrystals. Accordingly, Ni-supporting zeolite nanocrystals and membrane, which realizes the shape-selective oxidation, could be prepared.
  • 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
    Date (from‐to) : 2006 
    Author : 増田 隆夫
  • 文部科学省:科学研究費補助金(萌芽研究)
    Date (from‐to) : 2004 -2005 
    Author : 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
    Date (from‐to) : 2005 
    Author : 増田 隆夫
  • Ministry of Education, Culture, Sports, Science and Technology:Grants-in-Aid for Scientific Research(基盤研究(B))
    Date (from‐to) : 2003 -2004 
    Author : Takao MASUDA, 多湖 輝興, 辻 俊郎
     
    The main objective of this research is to develop a zeolite membrane showing high separation performance in acidic solution. The major results are described below.a)Silicalite-1 with hydrophilic properties : A method, called liquid phase oxidation method, was proposed for removing template molecules in as-prepared high siliceous MFI-type zeolite (Silicalite-1) crystals in water solution with hydrogen peroxide. Silicalite-1 treated by this method has many silanol groups in it, and showed high hydrophilic properties, leading to a rigid network of water molecules by hydrogen bonds, in which water molecules are selectively allowed to pass through.b)Preparation of nano-crystals of zeolites : First, a micro emulsion was formed by using TEOS, template molecule, surfactant, water and organic solvent. This emulsion was hydrothermally treated to yield mono-dispersed nano-crystals of MFI-type zeolite. The crystal size could be controlled in the range of 60 to 300nm.c)Preparation of zeolite membrane with high separation performance : First, nano-crystals of Silicalite-1 were prepared by the method b). Then the crystals were treated by the method a) to yield nano-crystals of Silicalite-1 with hydrophilic properties. The crystals thus obtained were piled on an alumina ceramic filter and hydrothermally treated to fix the crystals on the filter, producing the zeolite membrane. This membrane was applied to the pervaporation of acetone/water and acetic acid/water solutions. The separation factor for water was infinite, and the permeance for water was faster than that of a zeolite membrane without any pinholes by 100 times.
  • 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)
    Date (from‐to) : 2001 -2003 
    Author : 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。
  • Ministry of Education, Culture, Sports, Science and Technology:Grants-in-Aid for Scientific Research(基盤研究(C))
    Date (from‐to) : 2001 -2002 
    Author : Takao MASUDA
     
    Zeolites are crystalline alumino-silicate, and widely used as catalysts and adsorbents. MFI-type zeolite has fine pores within its crystals, the diameter of which is almost the same as the molecular size of benzene. Hence, the zeolite shows high molecular-sieving effect. When the zeolite is succeeded to be prepare in the shape of membrane, the membrane can enable to realize new separation and simultaneous reaction and separation with high performance. The main objective of this project is to development of MFI-type zeolite catalytic membrane, and to apply it to high separation and simultaneous reaction and separation processes. We obtained the following results through this research work :In fiscal year of 2001 :(1) MFI-type catalytic membrane was succeeded to prepared without any pin-holes by a new method, well-mixed hydrothermal synthesis.(2) Hydrophilic zeolite membrane with high acid-proof was successively prepared by the liquid phase oxidation method. This membrane allows the permeation for only water.(3) We developed a new method, called "Catalytic Cracking of Silane (CCS) method", for controlling the pore diameter and the location of acid sites distribution of zeolite. When diethoxymethyl-silane was employed for the CCS method, the effective pore diameter was decreased in pores. On the other hand, tri-phenyl silane was used, the effective pore diameter was decreased only at pore months.In fiscal year of 2002 :The CCS method with tri-phenyl sliane was applied to contorol the distribution of active sites (acid sites) on the zeolite membranes, to prepared the membrane with acid sites only within pores. When the reaction of methanol was conducted by use of this treated membrane, useful olefins were produced at selectivity above 85% under the conditions of the conversion of methanol of around 0 to 70% and zero pressure drop between the permeate and the feed sides.
  • Ministry of Education, Culture, Sports, Science and Technology:Grants-in-Aid for Scientific Research(基盤研究(C))
    Date (from‐to) : 1999 -2000 
    Author : Takao MASUDA, 向井 紳, 河瀬 元明
     
    Zeolites are crystalline alumino-silicate, and widely used as catalysts and adsorbents. MFI-type zeolite has fine pores within its crystals, the diameter of which is almost the same as the molecular size of benzene. Hence, the zeolite shows high molecular-sieving effect. When the zeolite is succeeded to be prepare in the shape of membrane, the membrane can enable to realize new separation and simultaneous reaction and separation with high performance. The main objective of this project is to development of MFI-type zeolite catalytic membrane, and to apply it to high separation and simultaneous reaction and separation processes. We obtained the following results through this research work :In fiscal year of 1999 :(1) MFI-type catalytic membrane was succeeded to prepared without any pin-holes by a new method, wellmixed hydrothermal synthesis.(2) When this membrane was applied to the pervaporation of concentrated acetic acid solutions, this membrane allowed only water to permeate in the range of the concentration of acetic acid from 30 to 98wt%.(3) We developed a new method, called "Catalytic Cracking of Silane (CCS) method", for decreasing the pore diameter of zeolite. The zeolite membrane treated by this method showed high separation factor of H_2 from mixture gases of H_2 and N_2 or O_2, about 100, as compared with 1.4 to 3 for a fresh zeolite membrane.In fiscal year of 2000 :Zeolites are crystalline alumino-silicate, and widely used as catalysts and adsorbents. MFI-type zeolite has fine pores within its crystals, the diameter of which is almost the same as the molecular size of benzene. Hence, the zeolite shows high molecular-sieving effect. When the zeolite is succeeded to be prepare in the shape of membrane, the membrane can enable to realize new separation and simultaneous reaction and separation with high performance. The main objective of this project is to development of MFI-type zeolite catalytic membrane, and to apply it to high separation and simultaneous reaction and separation processes. We obtained the following results through this research work :
  • 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
    Date (from‐to) : 1998 -2000 
    Author : 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
    Date (from‐to) : 1998 -2000 
    Author : 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
    Date (from‐to) : 1997 -1999 
    Author : 増田 隆夫
  • Ministry of Education, Culture, Sports, Science and Technology:Grants-in-Aid for Scientific Research(基盤研究(C))
    Date (from‐to) : 1997 -1998 
    Author : Takao MASUDA, 向井 紳, 河瀬 元明
     
    Zeolites are crystalline alumino-silicate, and widely used as catalysts and adsorbents. MFI-type zeolite has fine pores within its crystals, the diameter of which is almost the same as the molecular size of benzene. Hence, the zeolite shows high molecular-sieving effect. When the zeolite is succeeded to be prepare in the shape of membrane, the membrane can enable to realize new separation and simultaneous reaction and separation with high performance. The main objective of this project is to development of MFI-type zeolite catalytic membrane, and to apply it to high separation and simultaneous reaction and separation processes.In fiscal year of 1997, we conducted the following research work :MFI-type catalytic membrane was succeeded to prepared without any pin-holes by a new method, well-mixed hydrothermal synthesis. This membrane was found to show high proof against thermal and mechanical shocks and to be used at above 773 K.The separation factor of para- to ortho-isomers of xylene and diethyl-benzene was 3 and 7, respectively.In fiscal year of 1998, the membrane was applied to high separation and simultaneous reaction and separation processes, and the following results were obtained :1) Selective permeation of water from concentrated acetic acid : only water can permeate through the membrane under the conditions of temperature from 343 K to 363 K and the concentration of acetic acid from 20 to 98%.2) Selective separation of hydrogen from mixtures of hydrogen with nitrogen, oxygen and carbon dioxide : the separation factor of hydrogen to the other gas was found to be about 100 in the flow system at 483 K.3) Simultaneous reaction and regeneration : Reaction of methanol is a consecutive reaction, such as methanol (]SY.tri-substituted left.[) ether (]SY.tri-substituted left.[) olefin (]SY.tri-substituted left.[) paraffin+aromatics. Methanol diffuses through the catalytic zeolite membrane undertaking the reaction. When methanol is converted to olefin, they pass completely through the membrane, attaining high selectivity of olefin. The selectivity of olefin was enhanced up to 85% as compared with only 7% for the usage of conventional fixed bed reactors.
  • 文部科学省:科学研究費補助金(基盤研究(C))
    Date (from‐to) : 1996 -1996 
    Author : 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))
    Date (from‐to) : 1995 -1995 
    Author : 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))
    Date (from‐to) : 1993 -1993 
    Author : 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

Educational Activities

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Campus Position History

  • 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

Position History

  • 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


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