• Title/Summary/Keyword: $CO_2/H_2O$ Co-Reduction

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Preparation of Copper Nanoparticles in Cellulose Acetate Polymer and the Reaction Chemistry of Copper Complexes in the Polymer

  • Shim, Il-Wun;Noh, Won-Tae;Kwon, Ji-Woon;Jo, Jung-Young;Kim, Kyung-Soo;Kang, Dong-Hee
    • Bulletin of the Korean Chemical Society
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    • v.23 no.4
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    • pp.563-566
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    • 2002
  • Copper complexes have been directly incorporated into cellulose acetate (CA) and the resulting light blue colored homogeneous films of 5-20 wt.% copper acetate complex concentrations are found to be thermally stable up to 200 $^{\circ}C$. The reaction chem istry of Cu in CA has been investigated by reacting them with small gas molecules such as CO, H2, D2, O2, NO, and olefins in the temperature range of 25-160 $^{\circ}C$, and various Cu-hydride, -carbonyl, -nitrosyl, and olefin species coordinated to Cu sites in CA are characterized by IR and UV/Vis spectroscopic study. The reduction of Cu(II) complexes by reacting with H2 gas at the described conditions results in the formation of Cu2O and copper metal nanoparticles in CA, and their sizes in 30-120 nm range are found to be controlled by adjusting metal complex concentration in CA and/or the reduction reaction conditions. These small copper metal particles show various catalytic reactivity in hydrogenation of olefins and CH3CN; CO oxidation; and NO reduction reactions under relatively mild conditions.

Coal gasification and A new IGCC system (석탄가스화와 새로운 IGCC 시스템)

  • Kim, Hyun-Yong
    • 한국신재생에너지학회:학술대회논문집
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    • 2008.05a
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    • pp.361-363
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    • 2008
  • 탄소 개질반응은 $1200^{\circ}C$(도1) 이상에서 모든 탄화물질과 수분 또는 $CO_2$ 사이에서 흡열/환원반응이 일어나서 합성가스를 생성한다. 개질반응로는 산화반응로와 연결되어, 수소가스와 CO 가스의 혼합인,합성가스가 산화반응로 내에서 산소가스와 연소하여 열과 $H_2O+CO_2$를 생성하여 환원 반응로 내로 유입되어, 환원 반응로를 $1200^{\circ}C$ 이상으로 유지하고, $H_2O$$CO_2$는 석탄 속의 모든 탄소를 CO로 개질한다(도2). 동시에 수소가스가 생성되어 합성가스를 생성하게 된다. 석탄 속의 비탄소 물질인 슬래그(Slag)는 개질로 내에 남게 되는데, 개질로를 슬래그 융점(non-fluid point) 이하에서 고체상태로 포집함으로서 Fly-ash로 처리된다. 개질로 내의 온도를 $1200{\sim}1300^{\circ}C$(석탄 슬래그 융점)로 유지함으로서 개질반응이 지속되어 합성가스가 생성된다. IGCC 시스템에서는 합성가스를 가스터빈 속에서 $O_2E가스와 연소하여 고온의 가스를 생성하여 터빈을 가동해 발전을 하고 배출가스를 $1500{\sim}1700^{\circ}C$에서 배출한다. 재래식 IGCC(도4)에서는 ${\sim}1500^{\circ}C$의 배출가스를 열교환 시스템에 의해 증기를 생성하여 Steam turbine(증기터빈)을 가동하여 추가 전력을 생산했다. 그러나 본 시스템에서는 배출가스(증기와 $CO_2E 가스)를 위의 개질로에 유입하여 개질로 온도를 $1200{\sim}1300^{\circ}C$로 유지함으로서 더 많은 합성가스를 생성 하게 된다(도3). 이렇게 하여 Oxidation-reduction cycle을 형성하게 된다. 새로운 IGCC 시스템에서 가스 터빈의 배출가스가 석탄 개질로에 연결되고 석탄개질로의 합성가스 출구가 가스터빈의 가스 입구에 연결됨으로서,외부에너지 주입 없이 지속 가능한 가스화 반응과 터빈 사이클(Cycle)을 완성하여 IGCC 시스템의 석탄 열효율을 1단계 상승시켰다. 이렇게 설계된 석탄가스화기는 Lurgi형 석탄가스화 기와 달리 석탄개질반응의 효율을 높일 수 있고, 슬래그 처리가 간단하기 때문에 석탄가스화기가 소형화 될 수 있으며 슬래그(Slag)용융에 따른 석탄가스화기의 외벽손상을 피할 수 있다.

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Enhanced Catalytic Activity of Cu/ZnO/Al2O3 Catalyst by Mg Addition for Water Gas Shift Reaction (Mg 첨가에 따른 수성가스전이반응용 Cu/ZnO/Al2O3 촉매의 활성 연구)

  • Park, Ji Hye;Baek, Jeong Hun;Hwang, Ra Hyun;Yi, Kwang Bok
    • Clean Technology
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    • v.23 no.4
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    • pp.429-434
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    • 2017
  • To investigate the effect of magnesium oxide addition, $Cu/ZnO/MgO/Al_2O_3$ (CZMA) catalysts were prepared using co-precipitation method with fixed molar ratio of Cu/Zn/Mg/Al as 45/45/5/5 mol% for low-temperature water gas shift reaction. Synthesized catalysts were characterized by using BET, $N_2O$ chemisorption, XRD, $H_2-TPR$ and $NH_3-TPD$ analysis. The catalytic activity tests were carried out at a GHSV of $28,000h^{-1}$ and a temperature range of $200{\sim}320^{\circ}C$. At the same condition, magnesium oxide added catalyst (CZMA 400) showed that the lowest reduction temperature and stable presence of $Cu^+$, that is active species and abundant weak acid site. Also magnesium oxide added catalysts (CZMA) showed higher catalytic activity at temperature range above $240^{\circ}C$ than the catalyst without magnesium oxide (CZA). Consequently, CZMA 400 catalyst is considered to be excellent catalyst showing CO conversion of 77.59% without deactivation for about 75 hours at $240^{\circ}C$, GHSV $28,000h^{-1}$.

Oxygen Sensitivity of Carbon Monoxide-Dependent Hydrogen Production Activity in Citrobacter sp.

  • Kim, Jung-Rae;Oh, You-Kwan;Yoon, Yeo-Joon;Lee, Eun-Yeol;Park, Sung-Hoon
    • Journal of Microbiology and Biotechnology
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    • v.13 no.5
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    • pp.717-724
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    • 2003
  • A newly isolated Citrobacter sp. Y19 catalyzes the CO-dependent $H_2$ production (biological water-gas shift reaction) by the actions of CO dehydrogenase (CODH) and hydrogenase. Y 19 requires $O_2$ for fast growth, but its $H_2$ production activity is significantly inhibited by $O_2$. In the present study, the effect of $O_2$ on the activities of CODH ard hydrogenase was investigated quantitatively in both whole cells and broken cells, based on CO-dependent or methyl viologen (MV)-dependent $H_2$ production in addition to CO-dependent MV reduction. In crude cell extracts, CODH activity was mostly found in the soluble fraction. Inactivation of CODH and hydrogenase activities by $O_2$ followed the first-order decay kinetics, and the dependence of the rate constants on $O_2$ partial pressure could be expressed by the Michaelis-Menten equation. In whole cells, the maximum deactivation rate constants ($k_{d,max}$ of hydrogenase and CODH were quite similar: $0.07{\pm}0.03 min^{-1}\;and\;0.10{\pm}0.04 min^{-1}$, respectively. However, the first-order rate constant ($k_{d,max}/K_s$) of CODH ($0.25\;min^{-1}\;atm^{-1}$) at low $O_2$ partial pressures was about 3-fold higher than that of the hydrogenase, since the half-saturation constant ($K_s$) of CODH was about half of that of hydrogenase. In broken cells, both enzymes became significantly more sensitive to $O_2$ compared to the unbroken cells, while $k_{d,max}/K_s$ increased 37-fold for hydrogenase and 6.7-fold for CODH. When whole cells were incubated under anaerobic conditions after being exposed to air for 1 h, hydrogenase activity was recovered more than 90% in 2 h suggesting that the deactivation of hydrogenase by $O_2$ was reversible. On the contrary, CODH activity was not recovered once deactivated by $O_2$ and the only way to recover the activity was to synthesize new CODH. This study indicates that $O_2$ sensitivity of $H_2$ production activity of Citrobacter sp. Y19 is an important drawback as in other $H_2-producing$ bactria.

Continuous High Pressure Carbon Dioxide Processing of Mandarin Juice

  • Lim, Sang-Bin;Yagiz, Yavuz;Balaban, Murat O.
    • Food Science and Biotechnology
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    • v.15 no.1
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    • pp.13-18
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    • 2006
  • Mandarin juice was processed using a continuous high pressure $CO_2$ system. Response surface methodology was used to investigate the effects of the processing parameters such as temperature, pressure, residence time, and %(w/w) ratio of $CO_2$ to juice on total aerobic count (TAC), pectinesterase (PE) activity, cloud level, $^{\circ}Brix$, pH, and titratable acidity (TA) of the juices. Maximum log reduction (3.47) of TAC was observed at $35^{\circ}C$, 41.1 MPa, 9 min residence time, and 7% $CO_2$. PE was inactivated by 7-51%. The cloud was not only retained but was also enhanced by 38%. Lightness and yellowness increased, and redness decreased. The processing temperature and % $CO_2$/juice ratio significantly affected high pressure $CO_2$ processing of the juice in terms of pasteurization, PE inactivation, cloud increase, and color change. The $^{\circ}Brix$, pH, and TA before and after treatment remained unchanged.

Kinetic Investigation of CO2-CH4 Reaction over Ni/La2O3 Catalyst using Photoacoustic Spectroscopy

  • Oh, Hyun-Jin;Kang, Jin-Gyu;Heo, Eil;Lee, Sung-Han;Choi, Joong-Gill
    • Bulletin of the Korean Chemical Society
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    • v.35 no.9
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    • pp.2615-2620
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    • 2014
  • Ni/$La_2O_3$ with a high dispersion was prepared by reduction of $La_2O_3$ perovskite oxide to examine the catalytic activity for the $CO_2-CH_4$ reaction. The Ni/$La_2O_3$ catalyst was found to be highly active for the reaction. The ratios of $H_2$/CO were measured in a flow of the reaction mixture containing $CO_2/CH_4$/Ar using an on-line gas chromatography system operated at 1 atm and found to be varied with temperature between 0.66 and 1 in the temperature range of $500-800^{\circ}C$. A kinetic study of the catalytic reaction was performed in a static reactor at 40 Torr total pressure of $CO_2/CH_4/N_2$ by using a photoacoustic spectroscopy technique. The $CO_2$ photoacoustic signal varying with the concentration of $CO_2$ during the catalytic reaction was recorded as a function of time. Rates of $CO_2$ disappearance in the temperature range of $550-700^{\circ}C$ were obtained from the changes in the $CO_2$ photoacoustic signal at early reaction stage. The plot of ln rate vs. 1/T showed linear lines below and above $610^{\circ}C$. Apparent activation energies were determined to be 10.4 kcal/mol in the temperature range of $550-610^{\circ}C$ and 14.6 kcal/mol in the temperature range of $610-700^{\circ}C$. From the initial rates measured at $640^{\circ}C$ under various partial pressures of $CO_2$ and $CH_4$, the reaction orders were determined to be 0.43 with respect to $CO_2$ and 0.33 with respect to $CH_4$. The kinetic results were compared with those reported previously and used to infer a reaction mechanism for the Ni/$La_2O_3$-catalyzed $CO_2-CH_4$ reaction.

Catalytic Characteristic of Water-Treated Cu/ZnO/MgO/Al2O3 Catalyst for LT-WGS Reaction (LT-WGS 반응을 위한 Cu/ZnO/MgO/Al2O3 촉매의 수분처리에 의한 촉매 특성 분석)

  • PARK, JIHYE;BAEK, JEONG HUN;JO, GWANG HUI;RASHEED, HAROON UR;YI, KWANG BOK
    • Transactions of the Korean hydrogen and new energy society
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    • v.30 no.2
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    • pp.95-102
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    • 2019
  • In order to investigate the effect of water treatment on activity of WGS catalyst, $Cu/ZnO/MgO/Al_2O_3$ (CZMA) catalysts were synthesized by co-precipitation method. The prepared catalysts were water-treated at two different temperature (250, $350^{\circ}C$). Synthesized catalysts were characterized by using BET, SEM, $N_2O$ chemisorption, XRD, $H_2-TPR$ and XPS analysis. The catalytic activity tests were carried out at a GHSV of $28,000h^{-1}$ and a temperature range of $180-320^{\circ}C$. The reduction temperature decreased with water treatment and CZMA_250 catalyst showed the lowest reduction temperature and retained a large amount of $Cu^+$. Water-treated catalysts showed increased reactivity compared to untreated catalyst and the CZMA_250 catalyst showed higher catalytic activity on WGS reaction.

The Effect of Organic Solvents on the Activity for the Synthesis of 12wt% Co-based FT Catalyst (12wt% Co 담지 FT 촉매 제조시 유기용매가 촉매활성에 미치는 영향연구)

  • LEE, JIYUN;HAN, JA-RYOUNG;CHUNG, JONGTAE;BAEK, YOUNGSOON
    • Transactions of the Korean hydrogen and new energy society
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    • v.26 no.4
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    • pp.339-346
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    • 2015
  • The synthesis of Fischer-Tropsch (FT) oil is the catalytic hydrogenation of CO to give a range of products, which can be used for the production of high-quality diesel fuel, gasoline and linear chemicals. This studied catalyst was prepared Cobalt-supported alumina and silica by the incipient wet impregnation of the nitrates of cobalt, promoter and organic solvent with supports. Cobalt catalysts were calcined at $350^{\circ}C$ before being loaded into the FT reactors. After the reduction of catalyst has been carried out under $450^{\circ}C$ for 24h, FT reaction of the catalyst has been carried out at GHSV of 4,000/hr under $200^{\circ}C$ and 20atm. From these experimental results, we have obtained the results as following; In case of $SiO_2$ catalysts, the activity of 12wt% $Cobalt-SiO_2$ synthesized by organic solvent was about 2 or 3 times higher than the activity of 12wt% $Cobalt-SiO_2$ catalyst synthesized without organic solvent. In particular, the activity of the $Cobalt-SiO_2$ catalyst prepared in the presence of an organic solvent P was two to three times higher than that of the $Cobalt-SiO_2$ catalyst prepared without the organic solvent. Effect of Cr and Cu metal as a promoter was found little. 200 h long-term activity test was performed with a $Co/SiO_2$ catalyst prepared in the presence of an organic solvent of Glyoxal solution.

Process TAC Time Reduction Technology for Improving the Efficiency and Throughput of the PDP (PDP 효율 및 생산성 향상을 위한 공정단순화 기술)

  • Kwon, Sang Jik
    • Journal of the Semiconductor & Display Technology
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    • v.12 no.2
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    • pp.45-50
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    • 2013
  • This paper focuses on the fundamental issues for improving the efficiency and throughput of the AC PDP (Plasma Display Panel) manufacturing. The properties of the MgO protective layer affect the PDP efficiency. Especially, the secondary electron emission efficiency was affected on the deposition rate of MgO during the evaporation. In this study, the deposition rate of 5 $\AA$/s has given the maximum efficiency value of 0.05 It is demonstrated that the impurity gases such as $H_2O$, $CO_2$, CO or $N_2$, and $O_2$ can be remained inside the PDP panel before sealing and the amount of the impurity gases decreased rapidly as the base vacuum level increased, especially near $10^{-5}$ torr. The fundamental solution in order to overcome these problems is the vacuum in-line sealing process from the MgO evaporation to the final sealing of the panel without breaking the vacuum. We have demonstrated this fundamental process technology and shown the feasibility. The firing voltage was reduced down to 285 V at the base vacuum value of $10^{-6}$ torr, whreras it was about 328 V at the base vacuum value of $10^{-3}$ torr.

Hydrothermal Synthesis and Characterization of BaTiO3 Fine Powders (BaTiO3 미세 분말의 수열합성 및 특성분석)

  • Park, Jung-Hoon;Park, Sangdo
    • Korean Chemical Engineering Research
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    • v.45 no.5
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    • pp.448-454
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    • 2007
  • Hydrothermal synthesis was conducted with starting material as Barium hydroxide and hydrous titania ($TiO_2{\cdot}xH_2O$) to obtain barium titanate fine Powder. The conversion, crystal structure and properties of as-prepared powder were investigated according to reaction temperature, time and concentration. The effect of variables on conversion was in order of time < temperature < concentration and the maximum conversion reached to 99.5% in the case of hydrothermal synthesis at $180^{\circ}C$ for 2 h with 2.0 M reactant concentration. At low concentration such as 0.25 M, formation of unreacted $BaCO_3$ and $TiO_2$ was not inevitable at even high reaction temperature and these components converted into $BaTi_2O_5$ at high temperature and remained as impurity. As concentration of reactant increased, the size of as-synthesized $BaTiO_3$ powder deceased and Ba/Ti molar ratio approached into 1, showing Ba/Ti ratio of $1{\pm}0.005$ for reaction at $180^{\circ}C$ for 2 h with 2.0 M concentration.