活化分子氧用于油品深度脱硫新体系的构建及应用基础研究

Adsorption - oxidation is the most competitive technology of deep desulfurization for hydrogenation of catalytic cracking oil. But there are several problems needed to be done: a loss of octane number, costive operation process and complex technology, etc.. Therefore, it is the key to develop the functional adsorption material and construct a corresponding novel adsorption-oxidation technology. With a full analyses of the species and morphological of sulfide compounds in gasoline, this project is targeting to construct the functional adsorption material as the.starting point, develop modified zeolites as multifunctional carriers of adsorption catalytic material, with high saturation magnetization and high oxygen storage by self assembly chemical reaction, and make the metal complexes of schiff base encapsulated in zeolite, above all are expected to enhance a synergistic biomimetic catalytic performances. Then, the multifunctional adsorption materials are designed and set the shape selectivity of adsorption, magnetic separation, high oxygen storage properties in one of the objective. The study of adsorption reaction mechanism based on the fluidized bed system is aimed to reveal the structure-activity relationship between the multifunctional zeolite materials and the selective adsorption of sulfide, which is helpful to establish selective adsorption reaction process and magnetic separation for recovering functional material from gasoline with high efficiencies. Complete mineralization pathways and product species are explored for understanding the degradation of sulfides, all above are expected to the final construction of a adsorption-oxidation technology for deep desulfurization of gasoline based on innovated multifunctional materials.

吸附氧化是加氢催化裂化油品深度脱硫技术中最具竞争性的，但油品中辛烷值/十六烷值易损失，工艺操作复杂。实施材料功能化集成，以此构建油品深度脱硫新工艺，发展反应控制技术才是解决问题的关键。本课题基于催化油品中硫化物种类与形态分析，发展以等级孔分子筛为载体的多功能吸附/催化材料; 调控多元金属离子改性分子筛载体的离子交换与同质晶化自组装反应过程，赋予等级孔分子筛高磁饱和强度和高储氧的性能;将希夫碱金属络合物封装于分子筛结构中，建立以活化分子氧为催化活性中心的仿生催化技术。考察多元金属离子对硫化物吸附-催化的协同效应，建立等级孔分子筛结构与选择性吸附硫化物的构效关系，搭建流化床反应-磁分离-萃取联动工艺，考察气-液-固反应体系中仿生催化降解硫化物的促进机制，分析硫化物矿化途径及产物形态变化规律，完成基于材料创新的催化油品深度脱硫新工艺的构建。

吸附氧化是替代加氢催化裂化油品深度脱硫技术中最具竞争性的，实施材料功能化集成化，构建油品深度脱硫新工艺，发展反应控制技术是关键。.等级孔分子筛既具有微孔分子筛的水热稳定性和酸性，又具有介孔分子筛的优良扩散传质性能和选择性能。NaOH-柠檬酸复合处理两步法既可以产生介孔结构，又可以使分子筛的酸量和骨架结构得以保持，达到了制备等级孔结构的目的。等级孔β分子筛有效地改善不同分子大小硫化合物的吸附能力，吸附过程符合准二级吸附动力学模型和粒子内扩散方程。.Schiff碱配合物作为一种良好的氧载体,可以有效地活化分子氧；Y型分子筛作为一种优良的载体,可以有效地避免Schiff碱配合物的二聚。使用Fe2(SO4)3溶液与NaY分子筛进行离子交换，依次通过氮气和氢气氛围焙烧，制得磁性分子筛Fe3O4@NaY。在25℃时饱和磁化强度为9.154 emu/g，矫顽力为143 Oe。将Schiff碱钴配合物Co(Salen)通过“瓶中造船”的方法将配合物固定于磁性分子筛的超笼内，制备出磁性高效脱硫催化剂Fe3O4/Co(Salen)/NaY(N2)。在100℃，氧气氛围下，0.05 g催化剂对25 mL 300 ppm DBT正辛烷模拟油的氧化脱硫效率达66.94%，氧化DBT成为二苯并噻吩砜（DBTO2）的主要活性氧物种为超氧阴离子自由基（·O2-）。.研究发现，配体进入超笼过程是催化剂合成的限制步骤，在150℃，1 Mpa压力最优化条件下，固相合成催化剂的钴含量达到3.11%。在悬浮床反应器中氧化脱硫反应拟合回归到双曲线动力学方程 ，引入吸附参数K，解释了催化剂吸附-反应历程，适合描述非均相反应体系下Co(salen)Y氧化脱硫特征。.分别使用离子交换法和等体积浸渍法,将CeO2引入到分子筛的方钠石笼内,成功制备CeY催化材料，以“瓶中造船法”将Co(salen)封装于分子筛的“超笼”内,制备具有协同储氧/放氧作用的复合催化材料。将 CeO2-Co(salen)/NaY催化剂应用于 FCC 加氢柴油的催化氧化脱硫反应。结果表明该体系对柴油的总脱硫率为 91.61%，对 C1~C4 苯并噻吩和二苯并噻吩类有机硫化合物具有较好的脱除效果。.上述研究结果有助于构建催化油品深度脱硫新工艺，为油品深度净化提供新的思路。