hzsm5分子筛膜的二次生长及其超临界催化裂解烃类性能研究-secondary growth of hz sm5 molecular sieve membrane and its supercritical catalytic cracking performance for hydrocarbons.docx

摘 要碳氢燃料在高超声速飞行器的换热通道内流动时，可通过裂解反应吸收热量 以满足飞行器的结构冷却要求。在高超声速飞行中，碳氢燃料的流动条件是高温、 高压、高速，因此，催化膜反应器以其低流动和传热阻力的特点而成为一种理想 的反应器型式。本文采用二次生长法合成 HZSM-5 分子筛膜，研究了分子筛膜的 微介观结构与其合成条件的关系及其对超临界正十二烷催化裂解性能的影响。通过调节二次生长的次数，制备出厚度为 5.7-13.8 μm、负载量为 0.68-2.05 mg/cm2 的 HZSM-5 膜。发现，生长次数不仅可调控分子筛膜的厚度，而且影响 分子筛膜的表面致密性。增加分子筛膜的厚度，可以增加催化活性位的数量，但 导致膜的致密性增加，使其容积碳能力下降。重复生长三次可得到厚度为 11.6 ?m 的分子筛膜。该膜具有较好的催化活性和高的容积碳能力。通过调节 Al 源的加入量，制备出不同硅铝比的 HZSM-5 分子筛膜。发现， 硅铝比对分子筛膜的表面形貌和酸位数量有较大影响。增加硅铝比，可以增大 HZSM-5 晶粒的交织生长程度，但 Br?nsted 酸量减少、膜表面致密性增加。低硅 铝比的分子筛膜表面具有较高的 Br?nsted 酸量，在反应的初始阶段存在快速的活 性下降行为。适当增加分子筛膜的硅铝比，可以减缓反应初始阶段的活性下降速 度，从而明显提高 HZSM-5 分子筛膜的催化活性。但过高的硅铝比使分子筛膜表 面的酸量大幅减少、致密性增加，不利于裂解反应。Si/Al=125 的 HZSM-5 分子 筛膜具有最高的反应活性和初始活性稳定性。探索了碱处理方法对 HZSM-5 分子筛膜催化裂解性能的影响。发现，弱碱处 理不改变分子筛膜的骨架结构，仅对分子筛膜内杂晶和无定形物质起清理作用。 强碱处理能够选择性地脱除骨架 Si，在保留大部分微孔的同时构建介孔。两者皆 能有效地改善分子筛膜的催化裂解活性。关键词： HZSM-5 分子筛膜，二次生长，硅铝比，碱处理，催化裂解ABSTRACTFor future hypersonic aircraft, hydrocarbon fuels not only provide propulsion power via combustion, but also play a crucial role as an ideal coolant to offer a necessary sufficient cooling capacity (heat sink) for the advanced cooling technologies of engines and combustors. Importantly, the removal of the waste heat can be achieved through endothermic cracking reactions of hydrocarbon fuels when they flow inside the microchannels of the heat exchangers, which is operated at elevated temperature and pressure. Specially, owing to its low pressure drop and thermal resistance, the catalytic membrane reactor (CMR) with zeolite membrane on the inner wall is an ideal candidate. In this paper, a series of cracking reactions of model fuel were carried out in the CMR under the simulated conditions of the supercritical state that hypersonic aircrafts actually worked in.The HZSM-5 membranes were prepared on the inner surface of stainless steel tubes by the secondary-growth method. The membranes were testified by the catalytic cracking of n-dodecane under supercritical conditions and the product distribution and deactivation mode were carefully