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A Study on the Reaction Characteristics of Carbon Dioxide Methanation Catalyst for Full-Scale Process Application (이산화탄소 메탄화 공정 적용을 위한 Ni/CeO2-X 촉매의 반응 특성 연구)

  • Lee, Ye Hwan;Kim, Sung Su
    • Applied Chemistry for Engineering
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    • v.31 no.3
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    • pp.323-327
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    • 2020
  • The reaction characteristics of Ni/CeO2-X which is highly efficient at a low temperature was investigated for an application to carbon dioxide methanation process. The CeO2-X support was obtained by the heat treatment of Ce(NO3)3 at 400 ℃ and the catalyst was prepared by impregnation process. The operating parameters of the experiment were the internal pressure of the reactor, the composition of oxygen, methane, and hydrogen sulfide in the inlet gas and the reaction temperature. When Ni/CeO2-X was used for the carbon dioxide methanation reaction, the CO2 conversion rate increased by more than 25% as the pressure increased from 1 to 3 bar. The increase was large at a low reaction temperature. When both oxygen and methane were in the inlet gas, the CO2 conversion rate of the catalyst decreased by up to 16 and 4%, respectively. As the concentration of oxygen and methane increased, the reduction rate of the CO2 conversion rate tended to increase. In addition, the hydrogen sulfide in the inlet gas reduced the CO2 conversion rate by up to 7% and caused catalyst deactivation. The results of this study will be useful as basic data for the carbon dioxide methanation process.

Preparation and Reactivity of Cu-Zn-Al Based Hybrid Catalysts for Direct Synthesis of Dimethyl Ether by Physical Mixing and Precipitation Methods (물리혼합 및 침전법에 의한 DME 직접 합성용 Cu-Zn-Al계 혼성촉매의 제조 및 반응특성)

  • Bang, Byoung Man;Park, No-Kuk;Han, Gi Bo;Yoon, Suk Hoon;Lee, Tae Jin
    • Korean Chemical Engineering Research
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    • v.45 no.6
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    • pp.566-572
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    • 2007
  • Two hybrid catalysts for the direct synthesis of DME were prepared and the catalytic activity of these catalysts were investigated. The hybrid catalyst for the direct synthesis of DME was composed as the catalytic active components of methanol synthesis and dehydration. The methanol synthesis catalyst was formed from the precursor contained Cu and Zn, the methanol dehydration catalyst was used ${\gamma}-Al_2O_3$. As PM-CZ+D and CP-CZA/D, Two hybrid catalysts were prepared by physical mixing method (PM-CZ+D) and precipitation method (CP-CZA/D), respectively. PM-CZ+D was prepared by physically mixing methanol synthesis catalyst and methanol dehydration catalyst, CP-CZA/D was prepared by depositing Cu-Zn or Cu-Zn-Al components on ${\gamma}-Al_2O_3$. The crystallinity and the surface morphology of synthesized catalyst were analyzed by X-ray diffraction (XRD) and scanning electron microscope (SEM) to investigate the physical property of prepared catalyst. And BET surface area by $N_2$ adsorption and the surface area of Cu by $N_2O$ chemisorption were investigated about the hybrid catalysts. In addition, catalytic activity of these hybrid catalysts was examined with varying reaction conditions. At that time, the reaction temperature of $250{\sim}290^{\circ}C$, the reaction pressure of 50~70 atm, the $[H_2]/[CO]$ mole ratio of 0.5~2.0 and the space velocity of $1,500{\sim}6,000h^{-1}$ were investigated the catalytic activity. From these results, it was confirmed that the reactivity of CP-CZA/D was higher than that of PM-CZ+D. When the conditions of reaction temperature, pressure, $[H_2]/[CO]$ ratio and space velocity were $260^{\circ}C$, 50 atm and 1.0, $3,000h^{-1}$ respectively, CO conversion using CP-CZA/D hybrid catalyst was 72% and the CO conversion of CP-CZA/D was more than 20% compared with the CO conversion of PM-CZ+D. It was known that Cu surface area of CP-CZA/D hybrid catalyst was higher than that of hybrid PM-CZ+D catalyst using $N_2O$ chemisorption. It was assumed that the catalytic activity was improved because Cu particle of hybrid catalyst prepared by precipitation method was well dispersed.

Performance of Ru-based Preferential Oxidation Catalyst and Natural Gas Fuel Processing System for 1 kW Class PEMFCs System (Ru계 촉매의 CO 선택적 산화 반응 및 1 kW급 천연가스 연료처리 시스템의 성능 연구)

  • Seo, Yu-Taek;Seo, Dong-Joo;Seo, Young-Seog;Roh, Hyun-Seog;Jeong, Jin-Hyeok;Yoon, Wang-Lai
    • Transactions of the Korean hydrogen and new energy society
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    • v.17 no.3
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    • pp.293-300
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    • 2006
  • KIER has been developing a Ru-based preferential oxidation catalysts and a novel fuel processing system to provide hydrogen rich gas to residential PEMFCs system. The catalytic activity of Ru-based catalysts was investigated at different Ru loading amount and different support structure. The obtained result indicated that 2 wt% loaded Ru-based catalyst supported on ${\alpha}-Al_2O_3$ showed high activity in low temperature range and suppressed the methanation reaction. The developed prototype fuel processor showed thermal efficiency of 78% as a HHV basis with methane conversion of 92%. CO concentration below 10 ppm in the produced gas is achieved with separate preferential oxidation unit under the condition of $[O_2]/[CO]=2.0$. The partial load operation have been carried out to test the performance of fuel processor from 40% to 80% load, showing stable methane conversion and CO concentration below 10 ppm. The durability test for the daily start-stop and 8 h operation procedure is under investigation and shows no deterioration of its performance after 50 start-stop cycles. In addition to the system design and development.

Characterization of V/TiO2 Catalysts for Selective Reduction (V/TiO2 촉매의 선택적 촉매 환원 반응특성 연구)

  • Lee, Sang-Jin;Hong, Sung-Chang
    • Applied Chemistry for Engineering
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    • v.19 no.5
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    • pp.512-518
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    • 2008
  • The present work studied the selective catalytic reduction (SCR) of NO to $N_2$ by $NH_3$ over $V/TiO_2$ focusing on NOx control for the stationary sources. The SCR process depends mainly on the catalyst performance. The reaction characteristics of SCR with $V/TiO_2$ catalysts were closely examined at low and high temperature. In addition, adsorption and desorption characteristics of the reactants on the catalyst surface were investigated with ammonia. Seven different $TiO_2$ supports containing the same loading of vanadia were packed in a fixed bed reactor respectively. The interaction between $TiO_2$ and vanadia would form various non-stoichiometric vanadium oxides, and showed different reaction activities. There were optimum calcination temperatures for each samples, indicating different reactivity. It was finally found from the $NH_3-TPD$ test that the SCR activity was nothing to do with $NH_3$ adsorption amount.

CeO2-Promoted Highly Active Catalyst, NiSO4/CeO2-ZrO2 for Ethylene Dimerization

  • Pae, Young-Il;Shin, Dong-Cheol;Sohn, Jong-Rack
    • Bulletin of the Korean Chemical Society
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    • v.27 no.12
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    • pp.1989-1996
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    • 2006
  • The $NiSO_4/CeO_2-ZrO_2 $catalysts containing different nickel sulfate and $CeO_2$ contents were prepared by the impregnation method, where support, $CeO_2-ZrO_2$was prepared by the coprecipitation method using a mixed aqueous solution of zirconium oxychloride and cerium nitrate solution followed by adding an aqueous ammonia solution. No diffraction line of nickel sulfate was observed up to 20 wt %, indicating good dispersion of nickel sulfate on the surface of $CeO_2-ZrO_2$. The addition of nickel sulfate (or $CeO_2$) to $ZrO_2$ shifted the phase transition of $ZrO_2$ from amorphous to tetragonal to higher temperatures because of the interaction between nickel sulfate (or $CeO_2$) and $ZrO_2$. A catalyst (10-$NiSO_4/1-CeO_2-ZrO_2$) containing 10 wt % $NiSO_4$ and 1 mole % $CeO_2$, and calcined at $600{^{\circ}C}$ exhibited a maximum catalytic activity for ethylene dimerization. The catalytic activities were correlated with the acidity of catalysts measured by the ammonia chemisorption method. The role of $CeO_2$was to form a thermally stable solid solution with zirconia and consequently to give high surface area, thermal stability and acidity of the sample.

A Study on NOx Removal Efficiency using SNCR Process in the Industrial Waste Incineration Plant (산업폐기물 소각로에서 SNCR공정에 의한 NOx 제거효율에 관한 연구)

  • Ryu Hae-Yeol;Kim Min-Choul;Jung Jong-Hyeon;Lee Gang-Woo;Chung Jin-Do
    • Journal of Environmental Health Sciences
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    • v.31 no.4 s.85
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    • pp.332-339
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    • 2005
  • The environmental regulations in the world has been reinforced and many nations has devoted themselves to the development of cost-effective technology. Selective catalyst reduction(SCR) and selective non-catalyst reduction (SNCR) processes are mainly used to treat nitrogen oxidants generated from fossil-fuel combustion. One of these typical technologies for reduction of do-NOx is SNCR process has increased continuously because of the low cost for building and maintenance. Nevertheless the researches on the application to real scale plant by the reductant like Urea are rarely studied. In this paper, an experimental investigations were performed on the SNCR process in the industrial waste incineration plant. With no reducing agent, the concentration of NOx stayed in around 180 ppm $(O_2\;12\%)$ with the exhausting temperature of $950^{\circ}C$ and changed within the range of 20 ppm to remain relatively consistent. When $10\;wt\%)$ of a solution was added, the efficiency of denitrification reached above $61.4\%$ with the NSR of 2.0 and the exhausting temperature of $950^{\circ}C.$ When the concentration of the urea solution was set to $10\;wt\%$ and the sprinkling to four nozzles, the reaction temperature was reduced to about $50~100^{\circ}C$ with a mixture of $10\;wt\%\;CH_3OH\;and\;5wt\%\;Na_2CO_3$ in $40\;wt\%$ of the solution. The NOx removal efficiency increased to $78.4\%,$ achieving a broader and expansive range of reaction temperatures than the addition of an unmixed pure solution.

Synthesis of Methoxy Polyoxyethlene Dodecanoates (Methoxy Polyoxyethylene Dodecanoate의 합성)

  • Kang, Yun-Seog;Noh, Sueng-Ho;Choi, Seung-Ok;Nam, Ki-Dae
    • Applied Chemistry for Engineering
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    • v.9 no.5
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    • pp.749-753
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    • 1998
  • Methoxy polyoxyethylene dodecanoates, kinds of nonionic surfactants, could be obtained from addition of ethylene oxide (5, 7, 9, and 12mol) with fatty acid methyl ester utilizing solid catalyst, metal oxide. Because ethylene oxide (EO) couldn't react directly in acid or alkali catalyst with dodecanoic acid methyl ester (DME) that had no active hydrogen, the reaction to add EO was carried out using active solid catalyst. By using IR, HPLC and $^1H$ NMR analysis, structural confirmation of methyl polyoxy ethylene dodecanate showed high yield ranging from 93 to 97%. EO unit mol number of reacted products was 5.2, 7.1, 9.2 and 12.1 mol respectively. Also, EO adduct distrobution of ethoxylated methyl laurate (MPD) had normal distribution curve like polyoxyethylene alkyl ether (AE).

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Catalytic Reduction of Nitric Oxide by Carbon Monoxide over Perovskite-Type Oxide (페롭스카이트형 산화물에서 일산화탄소에 의한 질소산화물의 환원반응)

  • Moon, Haeng-Chul;Sun, Chang-Bong;Lee, Gun-Dae;Ahn, Byuong-Hyun;Lim, Kwon-Taek;Hong, Seong-Soo
    • Applied Chemistry for Engineering
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    • v.10 no.3
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    • pp.407-414
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    • 1999
  • We have studied the reduction of NO by CO over perovskite-type oxides prepared by malic and method. The catalysts were modified to enhance the activity by substitution of metal into A or B site of perovskite oxides. In the $LaCoO_3$ type catalyst, the partial substitution of Sr into A site enhanced the catalytic activity on the conversion of NO at less than $350^{\circ}C$. In the $La_{0.6}Sr_{0.4}Co_{1-x}Fe_xO_3$ catalyst, the partial substitution of Fe or Mn into B site enhanced the conversion of NO, but excess amount of Fe decreased the conversion of NO. In addition, $La_{0.6}Sr_{0.4}Co_{0.8}Fe_{0.2}O_3$ mixed with $SnO_2$ or $MnO_2$ showed the synergy effect on the reduction of NO. The introduction of water into reactants feed decreased the catalytic activity but the deactivation was shown to be reversible. The introduction of $SO_2$ into reactants feed also decreased the catalytic activity.

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The Effect of $MnO_2$ Addition on the $V_2O_5/TiO_2$ Catalytic Filters for NO Reduction (NO 환원반응을 위한 $V_2O_5/TiO_2$계 촉매필터의 $MnO_2$ 조촉매 효과)

  • Shin, Hae-Joong;Choi, Jae-Ho;Song, Young-Hwan;Lee, Ju-Young;Jang, Sung-Cheol;Choi, Joo-Hong
    • Proceedings of the SAREK Conference
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    • 2008.11a
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    • pp.363-368
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    • 2008
  • Nitrogen oxides (NO, $NO_2$ and $N_2O$) have been controlled effectively by the SCR catalysts coated on monolith or honeycomb in commercial sites with ammonia as reductant at high temperature range $300{\sim}400^{\circ}C$. However, the catalytic filter has much merit on the point of controlling the particles and nitrogen oxides simultaneously. It will be more advanced-system if the catalytic working temperature is reduced to the normal filtration temperature of under $200^{\circ}C$. This study has focus on the development of the catalytic filter working at the low temperature. So the additive effect of the components such as Pt and Mn (which are known the catalytic component of $V_2O_5/TiO_2$ was investigated. The $V_2O_5-WO_3$ catalytic filter exhibited high activity and selectivity at $250{\sim}320^{\circ}C$ showing more than 95% NO conversion for the treatment of 600 ppm NO at face velocity 2 cm/s. The Pt-$V_2O_5-WO_3$ catalytic filter shifted the optimum working temperature towards the lower temperature ($170{\sim}200^{\circ}C$). And NO conversion was 100% and higher than that of $V_2O_5-WO_3$ catalyst at $250{\sim}320^{\circ}C$. The $MnO_X-V_2O_5-WO_3$ catalytic filter showed the wide temperature range of $220{\sim}330^{\circ}C$ for more than 95% NO conversion. This is a remarkable advantage when considered the $MnO_X$ catalytic filter presents the maximum activity at $150{\sim}250^{\circ}C$ and $V_2O_5-WO_3$ catalytic filter shows the maximum activity at $250{\sim}320^{\circ}C$.

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Continuous Wet Oxidation of TCE over Supported Metal Oxide Catalysts (금속산화물 담지촉매상에서 연속 습식 TCE 분해반응)

  • Kim, Moon Hyeon;Choo, Kwang-Ho
    • Korean Chemical Engineering Research
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    • v.43 no.2
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    • pp.206-214
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    • 2005
  • Heterogeneously-catalyzed oxidation of aqueous phase trichloroethylene (TCE) over supported metal oxides has been conducted to establish an approach to eliminate ppm levels of organic compounds in water. A continuous flow reactor system was designed to effect predominant reaction parameters in determining catalytic activity of the catalysts for wet TCE decomposition as a model reaction. 5 wt.% $CoO_x/TiO_2$ catalyst exhibited a transient period in activity vs. on-stream time behavior, suggesting that the surface structure of the $CoO_x$ might be altered with on-stream hours; regardless, it is probable to be the most promising catalyst. Not only could the bare support be inactive for the wet decomposition reaction at $36^{\circ}C$, but no TCE removal also occurred by the process of adsorption on $TiO_2$ surface. The catalytic activity was independent of all particle sizes used, thereby representing no mass transfer limitation in intraparticle diffusion. Very low TCE conversion appeared for $TiO_2$-supported $NiO_x$ and $CrO_x$ catalysts. Wet oxidation performance of supported Cu and Fe catalysts, obtained through an incipient wetness and ion exchange technique, was dependent primarily on the kinds of the metal oxides, in addition to the acidic solid supports and the preparation routes. 5 wt.% $FeO_x/TiO_2$ catalyst gave no activity in the oxidation reaction at $36^{\circ}C$, while 1.2 wt.% Fe-MFI was active for the wet decomposition depending on time on-stream. The noticeable difference in activity of the both catalysts suggests that the Fe oxidation states involved to catalytic redox cycle during the course of reaction play a significant role in catalyzing the wet decomposition as well as in maintaining the time on-stream activity. Based on the results of different $CoO_x$ loadings and reaction temperatures for the decomposition reaction at $36^{\circ}C$ with $CoO_x/TiO_2$, the catalyst possessed an optimal $CoO_x$ amount at which higher reaction temperatures facilitated the catalytic TCE conversion. Small amounts of the active ingredient could be dissolved by acidic leaching but such a process gave no appreciable activity loss of the $CoO_x$ catalyst.