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염기성 촉매를 이용한 o-xylene과 1,3-Butadiene의 알케닐화 반응

Alkenylation of o-xylene with 1,3-Butadiene Over Base Catalysts

이종석 이수출 길민호 최일석¹ 이재성² 김재창^†

Jong Seok Lee Soo Chool Lee Min Ho Kil Il Seok Choi¹ Jae Sung Lee² Jae Chang Kim^†

경북대학교 공과대학 화학공학과, 대구 702-701 ¹S-Oil(주), 울산 689-890 ²포항공과대학교 화학공학과, 포항 790-784

Department of Chemical Engineering, Kyungpook National University, Daegu 702-701, Korea ¹R & D Center, S-Oil Corporation, Ulsan 689-890, Korea ²Department of Chemical Engineering, Pohang University of Science and Technology(POSTECH), Pohang 790-784, Korea

kjchang@bh.knu.ac.kr

HWAHAK KONGHAK, December 2002, 40(6), 669-675(7), NONE

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Abstract

액상 NaK alloy, Na metal 그리고 지지체에 담지된 Na metal을 촉매로 이용하여 o-xylene과 1,3-butadiene의 alkenylation을 통한 OTP(ortho-tolyl pentene)의 합성 반응을 연구하였다. 액상의 NaK alloy 촉매인 경우 metal의 분산도를 증가시키기 위해서 ultrasound로 처리하였고 촉매상은 매우 작은 입자로 쪼개져 emulsion을 형성하면서 분산도를 증가시킬수록 전화율과 선택도를 향상시킬 수 있었다. Na metal의 경우 분산도를 증가시키기 위해 전처리가 필요하였으며 미립자로 분산이 진행되는 동안 지체(induction) 시간이 필요하였다. 지지체에 담지된 Na metal의 경우 지지체에 관계없이 80 % 이상의 전화율을 지체 시간 없이 얻을 수 있었다. 하지만 slurry 액상 반응계에서는 담지된 금속의 85 % 이상이 촉매에서 떨어져 나와 반응에 참여하는 것으로 보인다. 반응물인 1,3-butadiene과 생성물인 OTP간의 반응에 의한 부반응이 진행되어 1,3-butadiene의 양이 증가하면 부반응으로 생성된 oligomer 양이 증가하였으며 전화율이 증가하면 선택도가 반비례 관계로 감소하였다.

The alkenylation of o-xylene with 1,3-butadiene to make OTP(ortho-tolyl Pentene) was carried out over liquid phase NaK alloy, Na metal and the metallic sodium dispersed on the specific support such as NaX and Al2O3. Liquid phase NaK alloy showed the improved conversion and selectivity when they were pretreated by ultrasound to increase the dispersion. For the case of metallic sodium, the induction period for the formation of homogeneous metal sodium solution with high dispersion was needed before the reaction. In the case of metallic sodium dispersed on support, more than 80 % conversion could be obtained without induction period regardless of supports used. But 85 % of the metallic sodium was resolved into the reaction mixture after reaction for 7 hours. The amount of byproducts, oligomers, produced from OTP and 1,3-butadiene increased with the amount of 1,3-butadiene introduced and the selectivity to OTP was in inversely proportional to the conversion.

Keywords

Alkenylation OTP o-xylene 1,3-Butadiene Na Metal

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