【作者】 姜锋；

【导师】 吕连海； 荣泽明；

【作者基本信息】 大连理工大学 ， 精细化工， 2011， 硕士

【摘要】 稠环芳烃存在于石油和煤焦油中,其选择性催化加氢产物不但可以作为煤液化反应的供氢溶剂,而且也是重要的功能材料和医药中间体。本文将骤冷法制备的改性骨架镍(MS-Ni)催化剂应用于稠环芳烃萘、芘、菲选择性加氢的研究中。系统考察了反应参数对萘、芘、菲加氢反应的影响,并考察了不同催化体系下芘和菲催化加氢的反应历程。将MS-Ni催化剂应用于萘催化加氢制备四氢萘,催化剂展现出较高的活性和选择性。以环己烷为溶剂,在50℃,1.OMPa的条件下,萘转化率为100%,四氢萘选择性可达100%,催化剂连续套用10釜后仍保持活性和选择性不变。同时考察了MS-Ni催化体系下反应参数对萘催化加氢制备十氢萘的影响,结果表明,在此催化体系下140℃为最佳反应温度,提高反应温度和降低反应压力有利于提高反式结构十氢萘的选择性。将MS-Ni催化剂应用于芘催化加氢制备1,2,3,6,7,8-六氢芘,催化剂表现出较高选择性,以环己烷为溶剂,在150℃,0.6MPa条件下,芘转化率为100%,1,2,3,6,7,8-六氢芘的选择性达76.9%；并考察了负载型贵金属(Rh/C/、Ru/C、Pd/C)催化体系下芘催化加氢反应历程,实验结果表明,在负载型贵金属催化体系下,可使4,5,9,10-四氢芘成为加氢主产物,催化剂活性高低顺序为：Rh/C>Ru/C>Pd/C,主产物选择性高低顺序与其相反。将MS-Ni催化剂应用于菲催化加氢制备1,2,3,4,5,6,7,8-八氢菲,获得了较高选择性,以环己烷为溶剂,在150℃,1.OMPa条件下,菲转化率为100%,1,2,3,4,5,6,7,8-八氢菲的选择性高达95.1%；并考察了Pd/C催化体系下菲加氢反应历程,研究表明,在该催化体系下,可使9,10-二氢菲成为加氢主产物。更多还原

【Abstract】 Polycyclic aromatic hydrocarbons (PAHs) are derived from coal tar and petroleum compounds. The hydrogenation products of PAHs can be used not only as hydrogen donor solvents in coal liquefaction but also as the intermediates for function materials and medicines. In this thesis, selective hydrogenation of naphthalene, pyrene and phenanthrene over modified skeletal Ni (MS-Ni) prepared by rapidly quenching technique was investigated. The effects of reaction parameters such as solvent type, temperature, pressure and initial concentration of the substrate were investigated. The reaction pathways of pyrene and phenanthrene hydrogenation over different catalysts were studied.The hydrogenation of naphthalene to tetralin over MS-Ni was investigated. Under optimal conditions of 50℃, 1.0MPa, both the conversion of naphthalene and the selectivity to tetralin were up to 100%. The MS-Ni catalyst was repeatedly used for 10 times, the activity and high selectivity of tetralin was maintained, indicating the excellent stability of catalyst. Moreover, the effects of reaction parameters on the hydrogenation of naphthalene to decalin were investigated over MS-Ni catalyst. Results revealed that the optimized reaction temperature was 140℃. The high reaction temperature and low reaction pressure significantly improved the mass ratio of trans-decalin to cis-decalin.Selective hydrogenation of pyrene over MS-Ni catalyst in liquid phase gave rise mainly to 1,2,3,6,7,8-hexahydropyrene. High selectivity of 1.2,3,6,7,8-hexahydropyrene was up to 76.9% under 150℃and 0.6MPa when the conversion was 100%. The reaction pathways of pyrene hydrogenation over Rh/C, Ru/C, Pd/C were studied and results showed that the main product was 4,5,9,10-tetrahydropyrene. Catalytic activity for pyrene hydrogenation was found in the order of Rh/C>Ru/C>Pd/C, which was opposite to the order of the main product selectivity.The application of MS-Ni catalyst was studied by hydrogenation of phenanthrene to 1,2,3,4,5,6,7,8-octahydropyrene. The MS-Ni catalyst showed excellent selectivity to 1,2,3,4,5, 6,7,8-octahydropyrene. Excellent 100% phenanthrene conversion and 95.1% 1,2,3,4,5,6,7,8-octahydropyrene selectivity were obtained in one-pot reaction under 150℃and 1.0MPa. The reaction pathway of phenanthrene hydrogenation over Pd/C catalysts was investigated and results showed that the main product was 9,10-dihydrophenanthrene.更多还原