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변형된 Zeolite 촉매상에서 o-toluidine의 N-알킬화 반응에 관한 연구

A study on N-alkylation of o-toluidine over Modified Zeolite Catalysts

영남대학교 응용화학공학부, 경산 712-749
School of Chemical Engineering and Technology, Yeungnam University, Kyongsan 712-749, Korea
HWAHAK KONGHAK, April 2000, 38(2), 123-128(6), NONE
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Abstract

국내의 염료 중간체 제조 분야에서 고체상 촉매를 이용한 반응공정의 연구에 관심이 모아지고 있다. 이런 관점에서 K, Cs, K-Mg, MgO를 각각 사용하여 변형시킨 H/zeolite-X 촉매상에서 ether에 의한 o-toluidine의 N-알킬화 반응 연구를 수행하였다. H/zeolite-X의 경우, 300℃에서, 알칼리금속에 의한 변형으로 인하여 산도가 저하된 촉매들의 경우 K/zeolite-X와 Cs/zeolite-X는 320℃에서, K-Mg/zeolite-X는 350℃에서, MgO/zeolite-X는 400℃의 상대적으로 높은 반응온도에서 각각 최대 전화율을 나타내었다. H/zeolite-X 촉매와 K, Cs, K-Mg 가 각각 이온교환된 zeolite-X 촉매들은 300~420℃의 반응온도 범위에서 온도가 상승함에 따라 N-ethyl-o-toluidine을 생성하는 N-알킬화 반응의 활성이 급속히 감소되고 6-ethyl-o-toluidine을 생성하는 C-알킬화 반응의 활성은 증가되는 경향을 나타내었다. 그 반면에, 이들 촉매보다 더 높은 염기도를 가진 MgO/zeolite-X는 온도 상승에 따른 N-alkylates와 C-alkylates 생성량의 변화정도가 상대적으로 훨씬 작음을 알 수 있었다. 또한 Cs등의 알칼리금속에 의해 변형된 zeolite-X 촉매는 비록 산도가 낮아졌으나 측쇄 알킬화 반응이 주로 이루어져 N-alkylatles가 지배적으로 생성되었다. o-toulidine과 ether 간의 반응물질 구성 몰비가 1 : 4일 때 가장 높은 전화율을 나타내었으며, 알칼리금속으로 이온교환된 촉매들은 산도가 낮아짐에 따라서 반응의 최대활성을 나타내는 온도가 H/zeolite-X에 비해서, 상대적으로 높아짐을 알 수 있었다. 한편, Cs/zeolite-X 촉매에서는 Cs 담지량이 1 wt%인 촉매가 가장 높은 전화율을 나타내었다.
A study of reaction processes using solid catalysts has drawn attention of domestic dyestuff intermediate manufacturers. From this viewpoint, N-alkylation of o-toluidine with ether was conducted on H/zeolite-X catalysts modified with K, Cs, K-Mg, and MgO, respectively. While H/zeolite-X gave rise to maximum conversion at 300℃, those zeolite-X catalysts of lowered acidity due to modification by alkali metal exhibited maximum conversions at relactively higher temperatures: 320℃ for K/zeolite-X and Cs/zeolite-X, 350℃ for K-Mg/zeolite-X, 400℃ for MgO/zeolite-X. For H/zeolite-X and zeolites modified by ion exchange with K, Cs, or K-Mg, as the reaction temperature increased in 300-420℃ range, the activity of N-alkylation forming N-ethyl-o-toluidine decreased rapidly whereas the activity of C-alkyation forming 6-ethyl-o-toluidine increased. Meanwhile, for the same temperature increase, MgO/zeolite-X having higher basicity showed relatively much smaller variation of N-alkylates or C-alkylates yield. Those zeolite-X catalysts modified with alkali metals incuding Cs selectively catalzed side-chain alkylation producing N-alkylates predominantly. Maximum conversions were brought about at o-toludine: ether mole ratio of 1:4 in the reaction mixture, and lowered acidity of the catalysts modified by ion exchange with alkali metals were responsible for the increase of reaction temperature for maximum activity, relative to H/zeolite-X. In the case of Cs/zeolite-X catalysts, Cs loading of 1 wt% gave rise to the highest conversion of o-toluidine.

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