【作者】 汪哲明；

【导师】 林励吾； 田志坚；

【作者基本信息】 中国科学院研究生院（大连化学物理研究所） ， 物理化学， 2006， 博士

【摘要】 烷烃加氢异构化催化剂的研究和开发,对高品质润滑油和柴油生产有重要意义。本论文通过调控分子筛的孔结构、酸性与晶粒尺寸,研究了载Pt双功能催化剂异构化活性与其酸性、金属性以及分子筛的择形性之间的关系。不同分子筛的异构化性能的比较显示,具有温和酸度与一维十元环直孔道的SAPO-11担载铂催化剂,具有最高的异构化收率。硅烷化处理可以选择性覆盖外表面的酸性位,抑制裂化反应,同时也窄化了SAPO-11的孔口尺寸。水热合成SAPO-11的研究发现,硅凝胶的单独析出,是导致杂晶相的生成,抑制其硅含量与结晶度提高的原因。通过老化与动态晶化的组合,抑制了硅凝胶的析出,合成出具有较高硅含量与酸度的分子筛,提高了催化剂异构化性能。溶剂热合成研究显示,多元醇较强的形成氢键能力,有利于SAPO-11分子筛的成核与晶化,进而提高其硅含量及酸性。本文首次以正硅酸乙酯、异丙醇铝为原料,乙二醇为溶剂合成出晶粒尺寸为50¹00nm的SAPO-11分子筛。相应的Pt/SAPO-11催化剂具有优异的异构化性能,在250oC、WHSV=1.0h^-1, H_2/n-C₁₂=15.0,1atm,正十二烷的转化率89%,选择性可达90%,反应温度比常规水热合成的活性最好的催化剂的反应温度低30oC。模拟工业操作条件,在氢压8.0MPa的滴流床反应器中考察了催化剂的异构化性能,结果证实所设计催化剂对高压苛刻操作条件具有良好的适应性。更多还原

【Abstract】 Paraffin isomerization is involved in the refining processes of producing environmentally benign high octane gasoline, high-cetane diesel fuel, and high viscosity lubricant base stocks with low pour points. With the increasingly strict environmental legislation and continual consumption of unregenerative petroleum resource, the importance of paraffin isomerization for improving motor fuel properties is growing. Therefore, the development of the hydyisomerization catalyts with high selectivity and activities is of great interest and significance.In the thesis, the molecular sieves with different pore structures, pore size and acidity, e.g. SAPO-11, SAPO-41, SAPO-34, ZSM-23, MCM-41, were synthesized through hydrothermal and/or solventhermal methods, and the hydroisomerization of the dodecane over the bi-functional molecular sieve supported Pt catalysts were also evaluated. By using NH3-TPD, H2-chemisorption, BET, 29Si NMR, Pyridine-IR, XRD, and SEM, etc., the influence of acidity, pore structures, crystal size and hydrogenation-dehydrogenation property on the hydroisomerization performance of the catalysts were investigated.Among the above molecular sieves, SAPO-11 and SAPO-41 supported Pt catalysts exhibited the highest hydroisomerization selectivity due to their mild acidity and monodimensional 10-member ring pore structures. A silanization process could selectively passivate the acide sites on the exterior surface of SAPO-11, and thus suppress the unselective hydrocracking reactions. Meanwhile, the silanization could also narrow the pore mouth size of SAPO-11, resulting in a更多还原