• Title/Summary/Keyword: CO 산화반응

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PWR 정지시 일차계통 산성-환원 및 산화단계의 용존기체 제어조건

  • 성기웅;강덕원;성기방;정홍호
    • Proceedings of the Korean Nuclear Society Conference
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    • 1998.05a
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    • pp.357-362
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    • 1998
  • PWR 정지시 일차계통 수화학 제어의 주요대상은 계통표면에 침적된 부식생성물의 주성분인 비화학양론적 니켈(코발트)페라이트로서, 산성-환원 단계에서 용존수소에 의해 Ni$^{\circ}$ (또는 Co$^{\circ}$)로 환원되고 산성-산화 단계에서 용존산소에 의해 Ni$^{2+}$ (또는 CO$^{2+}$)로 산화되어 이온교환기에 의해 제거된다 본 연구에서는, 니켈 및 코발트 산화물의 25~300 $^{\circ}C$ 환원 또는 산화반응 시 표준자유에너지의 변화 및 용존수소 또는 용존산소의 요구농도를 계산하여, 원자로 정지시 일차계통수 용존 기체의 제어조건을 고찰하였다. 산성-환원 단계의 냉각재 온도인 300~82$^{\circ}C$ 범위에서 용존수소가 충분할 경우 열역학적으로 $^{58}$ Co(또는 $^{60}$Co)Fe$_2$O$_4$$\longrightarrow$Co의 역반응이 억제되므로서 노심외 계통부위 침적이 감소될 수 있기 때문에, 용존수소를 온도에 따라 요구농도 곡선 위로 약간 높게 유지하는 것보다 25~50 cc/kg-$H_2O$로 유지하는 방식이 바람직한 반면, 용존산소를 제공하는 과산화수소 농도가) 2.7 ppm일 때 NiFe$_2$O$_4$$\longrightarrow$Ni$_2$O$_4$(+$\alpha$-Fe$_2$O$_3$) 반응이 일어날 수 있기 때문에, 산성-산화 단계에서는 과산화수소의 냉각재 농도를 이보다 낮게 유지하는 것이 바람직하다.

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Oxidation of 2,6-Dimethylnaphthalene by Co-Mn-Br Based Homogeneous Catalyst (Co-Mn-Br계 균일촉매를 이용한 2,6-Dimethylnaphthalene의 산화반응)

  • Kim, Dong-Bum;Park, Seungdoo;Cha, Woonou;Roh, Hang-Duk;Kwak, Kyu Dae
    • Applied Chemistry for Engineering
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    • v.10 no.6
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    • pp.863-870
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    • 1999
  • The catalytic performance of Co-Mn-Br system was performed in the 2,6-dimethylnaphthalene(DMN) oxidation at relatively mild reaction conditions such as $160^{\circ}C$ and $6kg/cm^2$. Experiments were conducted using a $2{\ell}$ batch reactor with varying the concentrations of catalysts. The reaction route of DMN oxidation was considered by measuring the concentration of intermediate species. As the intermediate species, 2-formyl-6-naphthoic acid, 2-methyl-6-naphthoic acid and 2-hydroxymethyl-6-methylnaphthalene are found. It was found that the yield of 2,6-naphthalene dicarboxylic acid(NDA) is largely dependent on the Co and Br concentrations. In addition, it was observed that color-b was closely related with Mn concentration in this experimental range. The burning loss of solvent could be reduced by controlling the concentration of Mn and Br. Addition of small amount of Ce and Cu compounds led to increase the NDA yields and decrease the burning amount of solvent.

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Partial Oxidation Of Methane over Transiton metal-substituted Hydrotalcite Catalysts (전이금속으로 치환된 하이드로탈사이트 촉매에 의한 메탄의 부분산화)

  • Lee, Seung-Hwan;Kwak, Jung-Hun;Nam, Suk-Woo;Lim, Tae-Hoon;Lim, Seong-Ahn;Yoon, Ki-June
    • 한국신재생에너지학회:학술대회논문집
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    • 2007.11a
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    • pp.85-88
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    • 2007
  • 고정층반응기에서 여러 가지 전이금속으로 치환된 하이드로탈사이트($[M_xMg_{6-x}Al_2(OH)_{16}(CO_3)^{2-}]{\cdot}H_2O;$ M: 전이금속(Ni, Mn, Co, Cu, Zn) x: 전이금속 치환비($x=0.5{\sim}6$))를 합성하고 이를 소성한 후 메탄의 부분산화 반응에 사용하였다. 반응 시 도입되는 $CH_4/O_2$비는 2로 하고 $VHSV=120,000cm^3/g$ h, 온도를 $500^{\circ}C$ 부터 $50^{\circ}C$ 간격으로 하여 $800^{\circ}C$까지 수행하였다. 실험결과 다른 전이금속들 중에서 니켈로 치환된 촉매가 대체적으로 부분산화반응을 촉진시키는데 좋은 것으로 나타났으며, 실험 결과 니켈의 hydrotalcite 중의 치환비(x)에 따른 차이는 별로 없었다.

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Reactivity and Preparation of Perovskite-Type Mixed Oxides LaBO3(B = Mn, Fe, Co) by Citrate Sol-Gel Method (Citrate Sol-Gel법에 의한 Perovskite형 복합 산화물 LaBO3(B = Mn, Fe, Co)의 생성 및 환원 반응성)

  • Hwang, Ho Sun;Park, Il Hyeon
    • Journal of the Korean Chemical Society
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    • v.38 no.4
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    • pp.276-282
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    • 1994
  • Perovskite-type mixed oxides LaBO$_3$(B = Mn, Fe, Co) were prepared by citrate sol-gel method in $air(850^{\circ}C$, 24h). The oxygen stoichiometries and structures of these oxides were determined by XRD and TPR results as followings; LaMnO$_{3.16}$(a = 5.507, c = 13.329 $\AA$, hexagonal), LaFeO$_{3.17}$(a = 5.554, b = 5.555, c = 7.863 $\AA$, orthorhomibic), LaCoO$_{3.0}$(a = 5.436, c = 13.095 $\AA$, hexagonal). The temperature programmed reduction(TPR) experiments in static 300 torr H$_2$ atmosphere shows that the reduction reaction of LaBO$_3$(B = Mn, Fe, Co) proceeds into two stages, and thermal stabilities of these oxides decreased in the order of LaMnO$_3$ > LaFeO$_3$ > LaCoO$_3$. According to the kinetic analysis the lowest activation energy was obtained for LaCoO$_3$.

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The Oxidation Behavior of Pitch based Carbon Fibers in ${CO}_2$ Gas and Air (${CO}_2$ gas및 공기중에서 피치계 탄소섬유의 산화거동)

  • No, Jae-Seung;Seo, Dong-Su
    • Korean Journal of Materials Research
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    • v.7 no.2
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    • pp.121-128
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    • 1997
  • Two-types of carbon fiber, anisotropic- and isotropic- pitch based, were expose to isothermal oxidation in air and $CO_{2}$ gas and the weight change rates was measured by TGA apparatus. Thc oxidation rate was laster in air than in $CO_{2}$ gas, and the oxidation rare of isotropic T- 101s liher was over 23 9 times faster than that of anisotropic HM-60 filler at $600^{\circ}C$ in air. The activation energy was 36-56 Kcal/mole at lower temperature range and 6- 13 Kcal/molc at higher temperature range. It was higher that the transition temperalure 01 reaction zone(zone 1. 2, :i) of 11M-GO fiber than that of T-101s fiber, and it was higher in $CO_{2}$ gas than in air. From SEM observation, it Lvas found that the oxidation of carbon fibers was progressed through the imperfection.

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A Design Approach to $CrO_x/TiO_2$-based Catalysts for Gas-phase TCE Oxidation (기상 TCE 제거반응용 $CrO_x/TiO_2$계 복합 산화물 촉매 디자인)

  • Yang, Won-Ho;Kim, Moon-Hyeon
    • Journal of Korean Society of Environmental Engineers
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    • v.28 no.4
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    • pp.368-375
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    • 2006
  • Single and complex metal oxide catalysts supported onto a commercial DT51D $TiO_2$ have been investigated for gas-phase TCE oxidation in a continuous flow type fixed-bed reaction system to develop a better design approach to catalysts for this reaction. Among the $TiO_2$-supported single metal oxides used, i.e., $CrO_x,\;FeO_x,\;MnO_x,\;LaO_x,\;CoO_x,\;NiO_x,\;CeO_x\;and\;CuO_x$, with the respective metal contents of 5 wt.%, the $CrO_x/TiO_2$ catalyst was shown to be most active for the oxidative TCE decomposition, depending significantly on amounts of $CrO_x\;on\;TiO_2$. The use of high $CrO_x$ loadings greater than 10 wt.% caused lower activity in the catalytic TCE oxidation, which is probably due to production of $Cr_2O_3$ crystallites on the surface of $TiO_2$. $CrO_x/TiO_2$-supported $CrO_x$-based bimetallic oxide catalysts were of particular interest in removal efficiency for this TCE oxidation reaction at reaction temperatures above $200^{\circ}C$, compared to that obtained with $CrO_x$-free complex metal oxides and a 10 wt.% $CrO_x/TiO_2$ catalyst. Catalytic activity of 5 wt.% $CrO_x-5$ wt.% $LaO_x$ in the removal reaction was similar to or slightly higher than that acquired for the $CrO_x$-only catalyst. Similar observation was revealed for 5 wt.% $CrO_x$-based bimetallic oxides consisting of either 5 wt.% $MnO_x,\;CoO_x,\;NiO_x\;or\;FeO_x$. These results represent that such $CrO_x$-based bimetallic systems for the catalytic TCE oxidation on significantly minimize the usage of $CrO_x$ that is well known to be one of very toxic heavy metals, and offer a very useful technique to design new type catalysts for reducing chlorinated volatile organic substances.

Selective Oxidation of Hydrogen Over Palladium Catalysts in the Presence of Carbon Monoxide: Effect of Supports (Pd 촉매상에서 일산화탄소 존재 하 수소의 선택적 산화반응: 담체 효과)

  • Kim, Eun-Jeong;Kang, Dong-Chang;Shin, Chae-Ho
    • Korean Chemical Engineering Research
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    • v.55 no.1
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    • pp.121-129
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    • 2017
  • Pd based catalysts were prepared by impregnating palladium precursor using incipient wetness method on $TiO_2$, $Al_2O_3$, $ZrO_2$, and $SiO_2$ and were applied for the selective oxidation of $H_2$ in the presence of CO. Their physicochemical properties were studied by X-ray diffraction (XRD), $N_2$-sorption, temperature programmed desorption of CO (CO-TPD) and (CO+$H_2O$)-TPD, temperature programmed reduction of CO (CO-TPR) and XPS a. The results of CO- and (CO+$H_2O$)-TPD showed the correlation between peak temperature of TPD and catalytic activities for $H_2$ and CO conversion. The $Pd/ZrO_2$ catalyst exhibited the highest conversion of $H_2$. The addition of $H_2O$ vapor promotes the conversion of $H_2$ and CO by inducing easy desorption of CO and $H_2$ in the competitive adsorption of $H_2O$, CO and $H_2$.

A Study on the Characteristics of CO Oxidation by NO Poisoning in Pt/TiO2 Catalyst (Pt/TiO2 촉매에서의 NO 피독에 의한 CO 산화반응특성 연구)

  • Kim, Min Su;Kim, Se Won;Hong, Sung Chang
    • Clean Technology
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    • v.25 no.4
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    • pp.296-301
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    • 2019
  • This study was conducted to investigate the characteristics of CO oxidation by NO poisoning in Pt/TiO2 catalyst prepared by wet impregnation method and calcined at 400 ℃. In order to confirm the NO poisoning effect of the Pt/TiO2 catalyst, the change of reaction activity was observed when NO was injected during the CO+O2 reaction where it was ascertained that the CO conversion rate rapidly decreased below 200 ℃. Also, CO conversion was not observed below 125 ℃. Recovery of initial CO conversion was not verified even if NO injection was blocked at 125 ℃. Accordingly, various analyses were performed according to NO injection. First, as a result of the TPD analysis, it was confirmed that NO pre-adsorption in catalyst inhibited CO adsorption and conversion desorption from adsorbed CO to CO2. When NO was pre-adsorbed, it was confirmed through H2-TPR analysis that the oxygen mobility of the catalyst was reduced. In addition, it was validated through FT-IR analysis that the redox cycle (Pt2+→Pt0→Pt2+) of the catalyst was inhibited. Therefore, the presence of NO in the Pt/TiO2 catalyst was considered to be a poisoning factor in the CO oxidation reaction, and it was determined that the oxygen mobility of the catalyst is required to prevent NO poisoning.

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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