• Applied Chemistry for Engineering
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• v.10 no.7
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• pp.1035-1040
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• 1999

Photocatalytic degradation of trichloroethylene has been carried out with UV-illuminated $TiO_2$-coated pyrex reactor in gas phase. Three commercial $TiO_2$ oxides were used as catalysts. The effect of reaction conditions, initial concentration of trichloroethylene, concentration of oxidant and light intensity on the photocatalytic activity were examined. Anatase-type catalyst showed higher activity than rutile-type, but P-25 catalyst showed the highest activity. The degradation rate increased with the decrease of flow rate and initial trichloroethylene concentration. It was preferable to use air as an oxidant. In addition, reactants with the water vapor decreased the activity and the degradation rate increased with the increase of light intensity, but it was very low with solar light. Photocatalytic deactivation was not observed at low concentration of trichloroethylene.

• 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.

• Clean Technology
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• v.22 no.2
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• pp.82-88
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• 2016

The loss of activity by coke is an important cause of catalyst deactivation during industrial operation. In this study, hydrogen ratio of reaction condition, which has influenced on coke formation over Pt-Sn catalyst, and regeneration of catalysts activity by coke burning, Pt sintering of coke burning as coke contents, effects of coke formation and deactivation with different Sn contents were confirmed. Pt-Sn-K catalyst supported on θ-alumina and γ-alumina was prepared progressively. Activity of regenerated catalyst for propane dehydrogenation was compared with fresh catalyst by coke burning, after propane dehydrogenation was carried out with different hydrogen ratio at 620 ℃ on fresh catalyst. Regenerated catalyst’s physical characterization such as BET, coke analysis and XRD was investigated. Through catalytic activity test and characterization, Sn contents of catalyst and hydrogen ratio in feed stream could affect coke formation on catalyst surface. Excessive coke makes loss of activity and Pt sintering during air regeneration process.

• Journal of Power System Engineering
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• v.14 no.6
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• pp.13-19
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• 2010

이 논문에서는 디젤자동차용 LNT와 SCR 촉매의 NO, $NH_3$ 흡착 및 탈리의 기본 특성과 수열화 온도와 시간 및 정량화된 황피독 농도에 대한 de-$NO_x$ 촉매의 내구성을 평가하였다. LNT 촉매는 열적으로 열화됨에 따라 Pt 및 Ba의 소결 및 응집으로 활성이 떨어져 $NO_x$ 전환율은 감소하였다. 반면에 Pt의 비활성화로 중간생성물인 $NH_3$ 생성량은 증가하였으며, 이때 생성된 $NH_3$는 LNT+SCR 복합시스템의 SCR 촉매의 환원제 역할을 담당한다. 1.0 g/L 이상의 황이 피독된 LNT 촉매는 탈황을 하여도 질소 산화물 흡장물질(Ba) 의 성능이 회복이 되지 않아 $NO_x$ 전환율은 회복되지 않았으며, 탈황 후 Pt 재활성화로 인해 NO2 및 SCR 환원제인 $NH_3$ 생성량은 증가하였다. SCR 촉매의 $NO_x$ 전환율은 $700^{\circ}C$ 36h, $800^{\circ}C$ 24h로 수열화 시킨 촉매는 전이금속 입자 성장 및 zeolite 구조 파괴로 인하여 급격하게 떨어졌으며, 0.36 g/L 황 피독된 촉매는 zeolite가 가지는 강산성 특정으로 내피독성이 강하여 탈황시 $NO_x$ 전환율은 회복되었다.

• Journal of Energy Engineering
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• v.3 no.1
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• pp.18-27
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• 1994

석탄액화반응에서 촉매 세공구조가 촉매 불활성화에 미치는 영향을 조사하기 위하여 간단한 모델을 전개하였다. 촉매의 세공수 분포에 근거하여 두 개의 Dirac delta 함수분포를 갖는 다공질 촉매구조를 제안하였으며 촉매 세공구조와 반응속도상수와의 관계를 유도하기 위하여 단순화된 반응계를 가정하였다. 균일 코드피복 가정에서 본 모델을 촉매 불활성화 예측에 적용하였으며 계산과정에서 세공율, 세공 크기 등의 촉매 특성치에 대해서는 실제값을 이용하였다. 본 모델연구에 의하면 unimodal 촉매에 비해 bimodal 촉매가 촉매 불활성화에 덜 민감하였다.

• 한국전기화학회:학술대회논문집
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• 2005.07a
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• pp.317-322
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• 2005

[ $Pt/CeO_2$ ] 촉매에 Zr을 첨가하여 우수한 저온 수성가스전화반응의 활성을 가진 촉매를 만들었다. $Pt/ZrO_2-CeO_2$ 촉매는 $Pt/ZrO_2$나 $Pt/CeO_2$ 촉매에 비해 Ce와 Zr의 상호작용에 의한 시너지 효과로 인해 CO chemisorption으로 측정한 Pt area가 증가하고 담체에 Pt가 잘 분산되었다. 또한, Zr이 첨가된 $Pt/CeO_2$는 Ce의 redox 능력을 향상시켜 support의 reducibility를 향상시켰다. 담체에 고르게 잘 분산되고 support의 산소저장능력과 reducibility가 향상된 $3\;wt\%\;Pt/ZrO_2-CeO_2$ 촉매들은 반응물에 수소와 이산화탄소의 첨가 유무와 상관없이 $3\;wt\%\;Pt/ZrO_2$나 $3\;wt\%\;Pt/CeO_2$ 촉매보다 우수한 활성을 보였다.

• Clean Technology
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• v.26 no.4
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• pp.286-292
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• 2020

This study confirmed the effect of the Cu/CeO2-X catalyst on the CO oxidation activity at low temperature through the catalyst's structure and reaction characteristics. The catalyst was prepared by the wet impregnation method. Cu/CeO2_X catalysts were manufactured by loading Cu (active metal) using CeO2 (support) formed at different calcination temperatures (300-600 ℃). Manufactured Cu/CeO2_X catalysts were evaluated for the low-temperature activity of carbon monoxide. The Cu/CeO2_300 catalyst showed an activity of 90% at 125 ℃, but the activity gradually decreased as the calcination temperature of the CeO2-X and Cu/CeO2_600 catalysts showed an activity of 65% at 125 ℃. Raman, XRD, H2-TPR, and XPS analysis confirmed the physicochemical properties of the catalysts. Based on the XPS analysis, the lower the calcination temperature of the CeO2 was, the higher the unstable Ce3+ species (non-stoichiometric species) ratio became. The increased Ce3+ species formed a solid solution bond between Cu and CeO2-X, and it was confirmed by the change of the CeO2 peak in Raman analysis and the reduction peak of the solid solution structure in H2-TPR analysis. According to the result, the formation of the solid solution bond between Cu and Ce has been enhanced by the redox properties of the catalysts and by CO oxidation activity at low temperatures.

• Korean Chemical Engineering Research
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• v.53 no.6
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• pp.824-830
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• 2015

The influence of phosphorous precursors, $NH_4H_2PO_4$, $(NH_4)_2HPO_4$, $H_3PO_4$, $(C_2H_5)_3PO_4$, and $P_2O_5$, on the catalytic performance of the $BiFe_{0.65}MoP_{0.1}$ catalysts in the oxidative dehydrogenation of 1-butene to 1,3-butadiene was studied. The catalysts were characterized by XRD, $N_2$-sorption, ICP, SEM and TPRO analyses. It was not observed big difference on the physical properties of catalysts in accordance with used different phosphorous precursors, however, the catalytic performance was largely depended on the nature of the phosphorous precursors. Of various precursors, the $BiFe_{0.65}MoP_{0.1}$ oxide catalyst, which was prepared from a phosphoric acid precursor, showed the best catalytic performance. Conversion and yield to butadiene of the catalyst showed 79.5% and 67.7%, respectively, after 14 h on stream. The cation of phosphorous precursors was speculated to affect the lattice structure of the catalysts during catalyst preparation and this difference was influenced on the re-oxidation ability of the catalysts. Based on the results of TPRO, it was proposed that the catalytic performance could be correlated with re-oxidation ability of the catalysts.

• 한국신재생에너지학회:학술대회논문집
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• 2009.11a
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• pp.232-232
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• 2009

최근 WGS반응용 Pt 촉매의 성능 향상을 위한 다양한 담체 및 조촉매(Promotor) 개발에 대한 연구가 활발하게 진행되고 있다. 선행 연구결과, 입방(Cubic)구조를 가지는 $Ce_{0.8}Zr_{0.2}O_2$ 담체는 정방 입계(Tetragonal)구조를 가지는 $Ce_{0.2}Zr_{0.8}O_2$ 담체 또는 혼합산화물(Mixed oxide)구조를 가지는 $Ce_{0.5}Zr_{0.5}O_2$ 담체 보다 높은 활성과 안전성을 가진다. 이것은 촉매의 성능 향상이 Ce-$ZrO_2$의 결정구조에 의존한다는 것을 나타낸다. 따라서 WGS 반응에서 Ce/Zr 비에 따라 변화된 담체 특성이 Pt 촉매의 활성에 영향이 있을 것으로 예상되며 실험결과 1% Pt/$CeO_2$ 촉매가 가장 높은 활성을 나타내었다. 따라서 Pt/Ce-$ZrO_2$ 촉매의 성능 향상을 위해 Ce-$ZrO_2$ 담체에 조촉매인 Ni을 첨가하여 촉매적 활성을 비교하여 보았다. 촉매는 2%의 Pt과 15%의 Ni로 고정하였고 Ce/Zr 비를 제조변수로 하였다. 제조된 모든 담체는 공침법(Co-precipitation)을 사용하여 제조하였으며 $500^{\circ}C$에서 6시간 소성하였다. Pt 촉매는 함침법 (Incipient wetness impregnation)으로 담지 시켰다. 2% Pt/Ce-$ZrO_2$ 촉매와 2% Pt/15% Ni-Ce-$ZrO_2$ 촉매는 저온영역($200^{\circ}{\sim}320^{\circ}C$)에서 비슷한 CO 전환율을 나타내었으나 고온영역($360^{\circ}C{\sim}400^{\circ}C$)에서는 2% Pt/15% Ni-Ce-$ZrO_2$ 촉매가 더 높은 CO의 전환율을 나타내었다. 이것은 Ni의 영향으로 고온에서 부반응인 메탄화 반응(Methanation reaction)이 생긴 것으로 판단되어 메탄($CH_4$)의 선택도를 살펴본 결과 2% Pt/15% Ni-Ce-$ZrO_2$ 촉매가 고온영역($360^{\circ}{\sim}400^{\circ}C$)에서 급격하게 증가하는 것으로 나타나 메탄화 반응이 일어난 사실을 증명한다.

• Applied Chemistry for Engineering
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• v.19 no.5
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• pp.574-581
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• 2008

The optimum regeneration conditions for the regeneration of three way spent catalysts (TWCs), which were taken from automobiles with different driving conditions, were investigated to evaluate the suitability as alternative catalysts for removing VOCs. The spent catalysts were washed with five different acids ($HNO_3$, $H_2SO_4$, $C_2H_2O_4$, $C_6H_8O_7$, and $H_3PO_4$) to remove contaminants and examine the optimum conditions for recovering the catalytic activity. The physicochemical properties of spent and its regenerated TWCs were evaluated by using nitrogen adsorption-desorption isotherms, XRD, and ICP. The relative atomic ratios of contaminants and platinum group metals (PGMs) of the spent TWCs were greatly dependent on the placed positions. The main contaminants formed were lubricant oil additives and metallic components. Also, the regeneration treatment increased the PGMs ratio, BET surface area, and average pore diameter of TWCs. The catalytic activity results indicated that the spent TWCs have the possibility for removing VOCs. Moreover, the employed acid treatments greatly enhanced the catalytic activity of the spent TWCs. Especially, nitric and oxalic acids provided the most improvement in the catalytic behavior. The catalytic activities of the regenerated TWCs were significantly influenced by the containing platinum ratios rather than the removal ratios of contaminants and the changes in the structural properties offered by the acid treatments.