• Title/Summary/Keyword: Catalytic Surface Reaction

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An organofunctionalized MgO∙SiO2 hybrid support and its performance in the immobilization of lipase from Candida rugosa

  • Kolodziejczak-Radzimska, Agnieszka;Zdarta, Jakub;Ciesielczyk, Filip;Jesionowski, Teofil
    • Korean Journal of Chemical Engineering
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    • v.35 no.11
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    • pp.2220-2231
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    • 2018
  • Lipase from Candida rugosa was immobilized on $MgO{\cdot}SiO_2$ hybrid grafted with amine, thiol, cyano, phenyl, epoxy and carbonyl groups. The products were analyzed using Fourier transform infrared spectroscopy, nuclear magnetic resonance, low-temperature $N_2$ sorption and elemental analysis. Additionally, the degree of coverage of the oxide material surface with different functional groups and the number of surface functional groups were estimated. The Bradford method was used to determine the quantity of immobilized enzyme. The largest quantity of enzyme (25-28 mg/g) was immobilized on the hybrid functionalized with amine and carbonyl groups. On the basis of hydrolysis reaction of p-nitrophenyl palmitate to p-nitrophenol, it was determined how the catalytic activity of the obtained biocatalysts is affected by pH, temperature, storage time, and repeated reaction cycles. The best results for catalytic activity were obtained for the lipase immobilized on $MgO{\cdot}SiO_2$ hybrids with amine and carbonyl groups. The biocatalytic system demonstrated activity above 40% in the pH range 4-10 and in the temperature range $30-70^{\circ}C$. Lipase immobilized on the $MgO{\cdot}SiO_2$ systems with amine and epoxy groups retains, respectively, around 80% and 60% of its initial activity after 30 days of storage, and approximately 60-70% after 10 reaction cycles.

Hydrogen Production Through Catalytic Dehydrogenation of Decalin over Pt/C Catalyst Using Activated Carbon Aerogel

  • Lee, Gihoon;Kang, Ji Yeon;Jeong, Yeojin;Jung, Ji Chul
    • Korean Journal of Materials Research
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    • v.25 no.4
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    • pp.191-195
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    • 2015
  • To improve its textural properties as a support for platinum catalyst, carbon aerogel was chemically activated with KOH as a chemical agent. Carbon-supported platinum catalyst was subsequently prepared using the prepared carbon supports(carbon aerogel(CA), activated carbon aerogel(ACA), and commercial activated carbon(AC)) by an incipient wetness impregnation. The prepared carbon-supported platinum catalysts were applied to decalin dehydrogenation for hydrogen production. Both initial hydrogen evolution rate and total hydrogen evolution amount were increased in the order of Pt/CA < Pt/AC < Pt/ACA. This means that the chemical activation process served to improve the catalytic activity of carbon-supported platinum catalyst in this reaction. The high surface area and the well-developed mesoporous structure of activated carbon aerogel obtained from the activation process facilitated the high dispersion of platinum in the Pt/ACA catalyst. Therefore, it is concluded that the enhanced catalytic activity of Pt/ACA catalyst in decalin dehydrogenation was due to the high platinum surface area that originated from the high dispersion of platinum.

Transition-State Structures for Solvolysis of Methanesulfonyl Chloride

  • 양기열;강금덕;구인선;이익준
    • Bulletin of the Korean Chemical Society
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    • v.18 no.11
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    • pp.1186-1191
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    • 1997
  • Solvolyses of methanesulfonyl chloride (CH3SO2Cl) in water and methanol have been studied theoretically using ab initio self-consistent reaction field (SCRF) molecular orbital method. All stationary structures including transition state on the potential energy surface in solution have been found and compared with the gas phase structures. The overall reaction occurs via a concerted SN2 mechanism with a non-cyclic trigonal bipyramidal transition state, and the activation barrier is lowered significantly in solution. The transition state for the hydrolysis reaction is looser than that for the methanolysis reaction, and this is in accord with the experimental findings that an SN2 type mechanism, which is shifted toward an SN1 process or an SAN process in the hydrolysis and alcoholysis reaction, respectively, takes place. The catalytic role of additional solvent molecules appears to be a purely general-base catalysis based on the linear transition structures. Experimental barrier can be estimated by taking into account the desolvation energy of nucleophile in the reaction of methanesulfonyl chloride with bulk solvent cluster as a nucleophile.

Characteristics of Nickel-Diamond Composite Powders by Electroless Nickel Plating (무전해 니켈 도금법으로 제조된 니켈-다이아몬드 복합분체의 특성)

  • ;;Hoang Tri Hai
    • Journal of Powder Materials
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    • v.11 no.3
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    • pp.224-232
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    • 2004
  • Ni-diamond composite powders with nickel layer of round-top type on the surface of synthetic diamond (140/170 mesh) were prepared by the electroless plating method (EN) with semi-batch reactor. The effects of nickel concentration, feeding rates of reductant, temperature, reaction time and stirring speeds on the weight percentage and morphology of deposited Ni, mean particle size and specific surface area of the composite powders were investigated by Atomic Adsortion Spectrometer, SEM-EDX, PSA and BET. It was found that nucleated Ni-P islands, acted as catalytic sites for further deposition and grown into these relatively thick layers with nodule-type on the surface of diamond by a lateral growth mechanism. The weight percentage of Ni in the composite powder increased with reaction time, feeding rate of reductant and temperature, but decreased with stirring speed. The weight percentage of Ni in Ni-diamond composite powder was 55% at 150 min., 200 rpm and 7$0^{\circ}C$ .

The Chemically Induced Hot Electron Flows on Metal-Semiconductor Schottky nanodiodes During Hydrogen Oxidation

  • Lee, Hyosun;Lee, Youngkeun;Lee, Changhwan;Kim, Sunmi;Park, Jeong Young
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.08a
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    • pp.152-152
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    • 2013
  • Mechanism of energy conversion from chemical to electrical during exothermic catalytic reactions at the metal surfaces has been a fascinating and crucial subject in heterogeneous catalysis. A metal-semiconductor Schottky nanodiode is novel device for direct detection of chemically induced hot electrons which have sufficient energy to surmount the Schottky barrier. We measured a continuous chemicurrent during the hydrogen oxidation under of 760 Torr of O2 and 6 Torr of H2 by using Pt/Si and Pt/TiO2 nanodiodes at reaction temperatures and compared the chemicurrent with the reaction turnover rate. The thermoelectric current was measured by carrying out an experiment under O2 condition for elimination of the background current. Gas chromatograph and source meter were used for measurement of the chemical turnover rate and the chemicurrent, respectively. The correlation between the chemicurrent and the chemical turnover rate under hydrogen oxidation implies how hot electrons generated on the metal surface affect hydrogen oxidation.

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Numerical Study on Operating Parameters and Shapes of a Steam Reformer for Hydrogen Production from Methane (천연가스로부터 수소를 생산하기 위한 수증기 개질기의 작동조건과 형상에 대한 수치해석 연구)

  • Park, Joong-Uen;Lee, Shin-Ku;Lim, Sung-Kwang;Bae, Joong-Myeon
    • Transactions of the Korean Society of Mechanical Engineers B
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    • v.33 no.1
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    • pp.60-68
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    • 2009
  • The steam reformer for hydrogen production from methane is studied by a numerical method. Langmuir- Hinshelwood model is incorporated for catalytic surface reactions, and the pseudo-homogeneous model is used to take into account local equilibrium phenomena between a catalyst and bulk gas. Dominant chemical reactions are Steam Reforming (SR) reaction, Water-Gas Shift (WGS) reaction, and Direct Steam Reforming (DSR) reaction. The numerical results are validated with experimental results at the same operating conditions. Using the validated code, parametric study has been numerically performed in view of the steam reformer performance. As increasing a wall temperature, the fuel conversion increases due to the high heat transfer rate. When Steam to Carbon Ratio (SCR) increases, the concentration of carbon monoxide decreases since WGS reaction becomes more active. When increasing Gas Hourly Space Velocity (GHSV), the fuel conversion decreases due to the heat transfer limitation and the low residence time. The reactor shape effects are also investigated. The length and radius of cylindrical reactors are changed at the same catalyst volume. The longer steam reformer is, the better steam reformer performs. However, system energy efficiency decreases due to the large pressure drop.

The Influence of a Second Metal on the Ni/SiC Catalyst for the Methanation of Syngas

  • Song, Lanlan;Yu, Yue;Wang, Xiaoxiao;Jin, Guoqiang;Wang, Yingyong;Guo, XiangYun
    • Korean Chemical Engineering Research
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    • v.52 no.5
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    • pp.678-687
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    • 2014
  • The catalytic performance of silicon carbide supported nickel catalysts modified with or without second metal (Co, Cu and Zn) for the methanation of CO has been investigated in a fixed-bed reactor using a feed consisting of 25% CO and 75% $H_2$ without any diluent gas. It has been found that the introduction of Co species can clearly improve the catalytic activity of Ni/SiC catalyst, whereas the addition of Cu or Zn can result in a significant decrease in the catalytic activity. The characterizations by means of XRD, TEM, XPS, CO-TPD and $H_2$-TPR indicate that the addition of Co could decrease the particle size of active metal, increase active sites on the surface of methanation catalyst, improve the chemisorption of CO and enhance the reducibility of methanation catalysts. Additionally, the special interaction between Co species and Ni species is likely favorable for the dissociation of adsorbed CO on the surface of catalyst, and this may also contribute to the high activity of 5Co-Ni/SiC catalyst for CO methanation reaction. For 5Cu-Ni/SiC catalyst and 5Zn-Ni/SiC catalyst, Cu and Zn species could cover partial nickel particles and decrease the chemisorption amount of CO. These could be responsible for the low methanation activity. In addition, a 150h stability test under 2 MPa and $300^{\circ}C$ showed that 5Co-Ni/SiC catalyst was very stable for CO methanation reaction.

A Study of Non-thermal Plasma Generation on a Photocatalytic Reactor Using a Ceramic Honeycomb Monolith Substrate (세라믹 벌집형 담체를 사용한 광촉매 반응기의 플라즈마 생성에 관한 연구)

  • 손건석;윤승원;고성혁;김대중;송재원;이귀영
    • Transactions of the Korean Society of Automotive Engineers
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    • v.10 no.2
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    • pp.48-54
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    • 2002
  • Since photocatalysts are activated by lights of UV wavelengths, plasma is alternatively used as a light source for a photocatalytic reactor. Light intensity generated by plasma is proportional to the surface area of catalytic material, and this, in many practical applications, is prescribed by the geometry of a plasma generator. Thus, it is crucial to increase the surface area far sufficient light intensity for photocatalytic reaction. For example, in a pack-bed type reactor, multitudes of beads are used as a substrate in order to increase the surface area. Honeycomb monolith type substrate, which has very good surface area to volume ratio, has been difficult to apply plasma as a light source due to the fact that light penetration depth through the honeycomb monolith was too short to cover sufficient area, thus resulting in poor intensity for photocatalytic reaction. In this study, nonthermal plasma generation through a photocatalytic reactor of honeycomb monolith substrate is investigated to lengthen this short penetration depth. The ceramic honeycomb monolith substrate used in this study has the same length as a three way catalyst used fur automotive applications, and it is shown that sufficient light intensity for photocatalytic reaction can also be obtained with honeycomb monolith type reactor.

A Study on the Effectiveness of Remanufacturing Technology for the Diesel Oxidation Catalyst(DOC) Deactivated by Diesel Exhaust Gas (경유차 매연저감장치에 의해 비활성화된 DOC촉매의 재제조 효과에 관한 연구)

  • Park, Hea-Kyung
    • Clean Technology
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    • v.16 no.4
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    • pp.265-271
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    • 2010
  • The deactivated diesel oxidation catalyst(DOC) was remanufactured by ultrasonic wave treatment with various solutions, followed by active component re-impregnation. The catalytic performance and surface properties of remanufactured DOC were studied at various remanufacturing conditions. The proper ultrasonic-wave cleaning time at various solutions and optimal re-impregnation amounts of active component for the best catalytic performance were investigated. The catalytic performance tests on the conversions of CO and THC(total hydrocarbon) were also carried out at various temperatures by catalytic reaction test unit using bypass gas from the diesel engine dynamo system. It was found that the catalytic performance of DOC remanufactured with the high-temperature air washing, ultrasonic wave cleaning at acidic/basic solutions and active component re-impregnation method was recovered to 90% level of its activity compared to that of the fresh DOC, which was caused by removing the deactivating materials from the surface of the DOC through the analyses of catalyst performance test and their characterization by Optical microscope, EDX, ICP, TGA, and porosimeter.

Mesoporous Silica Catalysts Modified with Sulfonic Acid and Their Catalytic Activity on Ring Opening Polymerization of Octamethylcyclotetrasiloxane (술폰산으로 표면개질된 메조기공 실리카 촉매의 제조 및 Octamethylcyclotetrasiloxane 개환중합에서의 촉매 활성)

  • Lee, Yeonsong;Hwang, Ha Soo;Lee, Jiyoung;Lo, Nu Hoang Tien;Nguyen, Tien Giang;Lee, Donghyun;Park, In
    • Applied Chemistry for Engineering
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    • v.31 no.4
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    • pp.383-389
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    • 2020
  • Mesoporous silica solid catalysts modified with sulfonic acid were prepared for cationic ring-opening polymerization of octamethylcyclotetrasiloxane (D4). Two sets of MCM-41 (1.7 and 2.8 nm) and SBA-15 (8.1 and 15.9 nm) with different pore sizes were used as catalyst supports. The surface of silica materials was modified with (3-mercaptopropyl)trimethoxysilane by silylation reaction and oxidized to sulfonic acid. The structures of the prepared catalysts were examined by X-ray diffraction and nitrogen adsorption-desorption. The pore size, specific surface area, and pore volume of the modified solid catalysts decreased slightly. In addition, the modification of the sulfonic acid on the silica surface was confirmed by using infrared spectroscopy and nuclear magnetic resonance spectroscopy. To observe the effect of the particle size on the catalytic activity, it was observed with a scanning electron microscope. The catalysts were used to synthesize PDMS through a ring-opening polymerization of D4, and the conversion and polymerization rate of the polymerization reaction depended on the pore size, specific surface area, particle size, and particle agglomeration of the catalysts. In order for the polymerization rate, the catalyst prepared with SBA-15 of 8.1 nm pore size had the fastest reaction rate and showed the best catalytic activity.