기상 TCE 제거반응용 $CrO_x/TiO_2$계 복합 산화물 촉매 디자인

• Yang, Won-Ho (Department of Environmental Engineering, Daegu University) ;
• Kim, Moon-Hyeon (Department of Occupational Health, Catholic University of Daegu)
• 양원호 (대구대학교 환경공학과) ;
• 김문현 (대구가톨릭대학교 산업보건학과)
• Published : 2006.04.30

Abstract

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.

순수한 아나타제 구조로 이루어진 DT51D $TiO_2$$CrO_x,\;FeO_x,\;MnO_x,\;LaO_x,\;CoO_x,\;NiO_x,\;CeO_x,\;CuO_x$와 같은 단일 산화물 촉매를 각각 5 wt.% 담지하여 모델반응으로 선택한 기상 TCE 제거반응을 수행하였으며, 이로부터 얻어진 결과를 바탕으로 $CrO_x/TiO_2$-based 복합 산화물 촉매상에서 TCE 산화반응을 연구함으로써 유해 중금속의 사용량을 최소화하기 위한 최적의 촉매 디자인 방법을 도출하고자 하였다. DT51D $TiO_2$에 담지된 여러 단일 금속 산화물들 중에서 기상 TCE 제거반응에 대하여 $CrO_x$가 가장 우수한 촉매활성을 보이는 것으로 나타났으며, 반응온도의 함수로 얻어진 TCE 제거반응의 활성은 $CrO_x$의 담지량에 의존하였다. 5 wt.% $CrO_x$-based 복합 산화물 촉매는 10 wt.% $CrO_x$만으로 이루어진 단일 산화물 촉매와 거의 동일한 수준의 TCE 제거반응 활성을 보였을 뿐만 아니라 이 복합 산화물 촉매들은 10 wt.% $CoO_x,\;MnO_x,\;FeO_x,\;NiO_x$ 등과 같은 단일 산화물 촉매들보다 높은 반응활성을 갖는 것으로 나타났다. 단일 산화물 촉매의 반응활성과 비교하였을 때 5 wt.% $CrO_x$-based 복합 산화물 촉매상에서 TCE 제거반응 동안에 얻어지는 반응활성의 증가 정도는 $420^{\circ}C$ 이하의 반응온도 기준으로 약 $10{\sim}80%$ 이상이었다. 따라서, CVOCs 제거반응을 위하여 널리 사용되고 있는 단일 $CrO_x/Al_2O_3$ 촉매보다는 $CrO_x$의 사용량을 최소화하면서도 우수한 반응활성을 얻을 수 있는 $CrO_x/TiO_2$-based복합 산화물 촉매가 보다 바람직하며 하나의 대안적인 촉매 디자인 방법으로 응용될 수 있을 것으로 생각된다.

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