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Synthesis of tricyclopentadiene from dicyclopentadiene over aluminosilicate catalysts 원문보기

  • 저자

    곽경열

  • 학위수여기관

    Graduate School, Korea University

  • 학위구분

    국내석사

  • 학과

    化工生命工學科

  • 지도교수

    李寬榮

  • 발행년도

    2014

  • 총페이지

    xi, 84장

  • 키워드

    heterogeneous catalysis tricyclopentadiene dicyclopentadiene cycloaddition Al-MCM-41;

  • 언어

    eng

  • 원문 URL

    http://www.riss.kr/link?id=T13541935&outLink=K  

  • 초록

    Dicyclopentadiene (DCPD) is important raw material of various chemical processes which can be obtained from C5 stream after naphtha cracking. DCPD has been mainly utilized for raw material of polymers. However, it also can be used in various organic synthesis producing high added-value chemicals. Specifically in jet fuel industry, high energy-density fuel has become important in volume limited systems. DCPD derivatives have attractive properties using for high energy-density fuel, which show high mass density and volumetric energy contents due to their cyclic structure. Tricyclopentadiene (TCPD) is an important raw material of high energy-density fuel. TCPD is synthesized through a cycloaddition between DCPD and CPD. Despite the promising properties of TCPD, there are only a few studies about synthesizing TCPD. Non-catalytic process for synthesizing TCPD is low DCPD conversion and low selectivity of TCPD. Mobil Oil applied zeolite in this reaction and reported somewhat enhanced activity comparing to non-catalytic process, however, it still show low activity and little is known about the relation between catalyst properties and reaction activity. The molecular size of the DCPD and TCPD is large enough to cause diffusion limitation over microporous zeolites. To overcome this problem, there have been many studies about the mesoporous catalyst to substitute microporous zeolites in other bulky molecule involved reactions. In this study, microporous ZSM-5, HY zeolite and mesoporous Al-MCM-41 with various Si/Al ratios were applied. Mesoporous Al-MCM-41 shows higher catalytic activity than microporous zeolites in reactant conversion and product yield. From the acid property studies of prepared Al-MCM-41, the Brönsted acidity was not monotonically increased as total acid amounts increased. Among the Al-MCM-41, the sample with the highest fraction of Brönsted acid site showed the highest TCPD yield although it had low acidity compared to the other one which had higher total acid sites. On the other hand, Al-MCM-41 has relatively low acidity comparing to zeolite, NH4F was employed to improve the acidity of the Al-MCM-41, specifically Brönsted acidity. The activity was strongly influenced by the average pore size and the Brönsted acidity of the catalyst. Among the tested catalysts, the NH4F-treated Al-MCM-41 catalyst, which had meso-sized pores and enhanced Brönsted acidity, exhibited the best DCPD conversion, TCPD selectivity and yield. The average pore size of the catalyst also influenced the isomer distribution of the TCPD products: the mesoporous catalysts produced mixtures of exo- and endo-TCPD, which favored the exo-fraction compared to the microporous catalysts. The differences in the reaction pathways followed by the zeolites and Al-MCM-41 catalysts were discussed.


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