受限撞击射流场大孔/介孔二氧化硅的控制合成及应用研究

Preparation of mesoporous materials with pore size larger is difficult using traditional method because of dimension limitations of supermolecular templates. Continuous synthesis ordered mesoporous silica with extra-large pores via sequential confined impinging jets microreation. The supermolecular templating allows tuning the pore size of mesoporous silica in the once elusive range through simple control of synthetic variables (the Reynolds number, the supersaturation ratio and composite nanoparticles). By means of SAXS, FESEM and BET, the nucleation and growth of mesoporous silica nano-particles as well as their particle size controlling mechanisum will be explored. Precise tuning of mesoporous silica pore size distribution is a critical issue for us. As self-assembly is a complex process related to many aspects, computer simulation has become a convenient and efficient method to study the self-assembly of copolymer. Using Monte Carlo simulation, we study the self-assembly and the morphological transition of block copolymer solution under high Reynolds numbers and the wind-structure interaction effects respectively, and the formation mechanization of these systems. The mechanical of reducing Ostwald Ripening was studied by sequential microreation, by comparing the experimental results and theoretical results calculated based on LSW theory, the model function for the particle size of composite nanoparticles system will be set up. Finally, continuous synthesis petroleum resin hydrogenation catalyst with extra-large pores by nonionic block copolymer surfactants via sequential microreation. The structure property correlation and pore size distribution in the synthesis of mesoporous materials effect petroleum resin hydrogenation have been studied systematically. The ordered mesoporous silicas with extra large pores were used as the supports for petroleum resin hydrogenation, and catalysts showed high catalytic activities and stability. The ordered mesoporous silica with open porous networks and extra large pore size as the support provide optimal mass diffusion and improved efficiency.

针对共聚物静态自发自组装过程中存在的胶束尺寸局限，采用受限撞击射流微反应器快速可控制备超大孔/介孔材料，主要研究射流速度比、过饱和速率和包封率等对复合胶束及二氧化硅孔径的影响，将材料孔径调控问题转化为化工过程工艺参数控制问题，这是一种新的介孔材料尺寸调控理念。研究介孔材料在微反应中快速脱溶形核过程中粉体的生长规律，对喷雾干燥瞬间“冷冻”产物采用SAXS、FESEM、BET等手段研究其晶胞参数、孔径、形貌，实现大孔/介孔材料连续精准合成。采用蒙特卡罗法模拟共聚物在高雷诺数下湍流场中的自组装行为及形貌转变规律，对串联工艺抑制纳米粒子Ostwald熟化机理进行研究，利用修正的LSW方程预测粒子粒径与微流操作条件间的定量关系。采用该工艺制备树脂加氢催化剂，研究载体孔径及孔结构对碳五石油树脂加氢效果的影响，研究树脂催化加氢改性中载体孔径及其分布的影响，探索客体分子尺寸与加氢催化剂载体孔径间的匹配原理

纳米材料在催化、传感、储能及许多功能材料领域具有不可替代的重要价值。快速可控制备纳米材料是当今材料化工领域研究的重点问题。然而，常规方法制备纳米材料存在材料结构不可控、耗时、耗能且难以连续化制备等问题，这将严重阻碍其工业应用。瞬时纳米沉降法是一种制备纳米粒子的新方法。该方法利用受限撞击混合器（CIJR）或多入口涡流混合器（MIVM）将不同的反应流体在混合腔室内碰撞，从而制备出具有不同功能的纳米粒子。溶液在CIJR和MIVM中可以达到毫秒级的混合尺度，同时产生高能量耗散区域，这将大大增强混合效率，制备出的纳米粒子形貌均一、大小可控。. 本项目首先采用不同工艺及聚合方法，制备了几种不同分子量的嵌段共聚物和脂肪族聚酯。在成功设计开发受限撞击流反应器和多通道涡流反应器的基础上，利用CFD软件模拟优化流体流动参数，得到了不同流速下流体混合情况和剪切力场。利用微反应器能够瞬时形核的优势，我们合成了一系列不同种类的纳米材料，包括二氧化硅、水滑石、硫纳米粒子等。结果发现，通过调节微反应器的工艺参数，如雷诺数、过饱和度和微混程度，可以控制纳米粒子的形貌、尺寸及微纳结构。与传统的共沉淀方法相比，采用微反应器法原位生成的催化剂表现出优异的催化性能。项目借助DFT软件模拟，结合HADDF-STEM等先进的表征，系统地研究了纳米材料在FNP原位生成过程中的成核和组装规律，为工程化大规模制备纳米复合材料奠定了理论基础。