화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Clean Technology, Vol.25, No.1, 91-97, March, 2019
DOI10.7464/ksct.2019.25.1.091  Export Citation
Keggin형 헤테로폴리산 촉매를 이용한 선박용 경유의 산화 탈황
Oxidative Desulfurization of Marine Diesel Using Keggin Type Heteropoly Acid Catalysts
오현우, 우희철†
  • 부경대학교 화학공학과, 48547 부산광역시 남구 신선로 365
Hyeonwoo Oh, and Hee Chul Woo†
  • Department of Chemical Engineering, Pukyong National University, 365, Sinseon-ro, Nam-gu, Busan, 48547, Korea
E-mail:
초록
산화탈황반응은 디벤조티오펜(dibenzothiophenes, DBTs)과 같이 제거하기 어려운 구조의 황화합물들을 선택적으로 산화하여 설폭사이드(sulfoxide)와 설폰(sulfone) 등의 형태로 전환하고, 이들을 추출과 흡착에 의해 제거할 수 있기 때문에 최근 많은 주목을 받고 있다. 본 연구에서는 선박용 경유의 산화탈황반응을 회분식반응기에서 산화제 과산화수소(H2O2)와 함께 다양한 헤테로폴리산 담지촉매에 의해 수행하였다. 제조 촉매들은 X-선 회절분석(XRD), X-선 형광분석(XRF), X-선 광전자분광분석(XPS) 및 질소 흡착등온선 등의 기법에 의해 특성분석이 이루어졌다. 유망한 지지체인 실리카에 30 wt% 담지된 헤테로폴리산 촉매 활성 순위는 황 제거율 기준으로, 30 H3PW12/SiO2 > 30 H3PMo12/SiO2 > 30 H4SiW12/SiO2 순으로 나타났으며, 이는 헤테로폴리산의 고유 산세기에 기인한 것으로 판단된다. 30 H3PW12/SiO2 촉매는 반응 온도 30 ℃, 촉매량 0.025 g mL-1 (cat./oil), 반응 시간 1 h의 반응조건 하에서 약 66%의 가장 높은 초기 황 제거율을 보였다. 그러나 H3PW12/SiO2 촉매의 재사용성 실험을 통해 확연하게 활성이 저하됨을 확인하였으며 이는 활성 성분인 H3PW12의 용출에 기인한 것으로 보인다. H3PW12/SiO2 촉매로의 세슘 양이온(Cs+) 도입에 의한 용해도의 변화와 함께 촉매의 안정성이 개선되었으며, Cs+ 이온교환된 촉매는 최소 5회 이상 재사용이 가능함을 확인하였다.
Oxidative desulfurization (ODS) has received much attention in recent years because refractory sulfur compounds such as dibenzothiophenes can be oxidized selectively to their corresponding sulfoxides and sulfones, and these products can be removed by extraction and adsorption. In this work, The oxidative desulfurization of marine diesel fuel was performed in a batch reactor with hydrogen peroxide (H2O2) in the presence of various supported heteropoly acid catalysts. The catalysts were characterized by XRD, XRF, XPS and nitrogen adsorption isotherm techniques. Based on the sulfur removal efficiency of promising silica supported heteropoly acid catalysts, the ranking of catalytic activity was: 30 H3PW12/SiO2 > 30 H3PMo12/SiO2 > 30 H4SiW12/SiO2, which appears to be related with their intrinsic acid strength. The 30 H3PW12/SiO2 catalyst showed the highest initial sulfur removal efficiency of about 66% under reaction conditions of 30 ℃, 0.025 g mL-1 (cat./oil), 1 h reaction time. However, through the recycle test of the H3PW12/SiO2 catalyst, significant deactivation was observed, which was attributed to the elution of the active component H3PW12. By introducing cesium cation (Cs+) into the H3PW12/SiO2 catalyst, the stability of the catalyst was improved with changing the solubility, and the Cs+ ion exchanged catalyst could be recycled for at least five times without severe elution.
Keywords:Oxidative desulfurization;Marine diesel;Heteropoly acid (HPA);Hydrogen peroxide;Supported catalyst
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