3D打印制造甲基铝氧烷（MAO）合成的多相流动化学反应系统

The discovery of methylaluminoxane (MAO) has promoted the rapid development of metallocene catalysts, while the synthesis of MAO encounters central challenges of high risk and poor process control. In China, the synthesis of MAO has not been commercialized so that the high price of the imported MAO products limited the development and innovation of the related fields. Recently, the development of chemical engineering discipline shows that micro-chemical systems have enabled new breakthroughs for the classic theory. As microreaction technology comes of age, flow chemistry has made tremendous progress, of which its intrinsic safety and better process control makes itself a valuable tool for synthesis of MAO. In this proposal, I plan to combine the chemical engineering processes with the “state-of-the-art” material fabrication technologies, aided by CFD simulation, to develop and optimize the design of reactors for MAO synthesis with high mass transfer performance and high product yield in continuous flow. Moreover, I aim to build reactors to handle the potential solid products during the synthesis of MAO in continuous flow process. On one hand, this project helps with the development of reactor design protocols for solving the universal solid handling problems in continuous flow process; on the other hand, it further facilitates the research of transport phenomena in confined chemical space and provides valuable information for the implementation of other similar processes.

甲基铝氧烷（MAO）推动了茂金属催化剂的迅猛发展，但是其合成工艺面临危险性高与可控性差的双重问题，我国目前也尚未成功研发可商业化生产MAO的工业装置，进口MAO昂贵的价格也制约了我国相关领域的发展创新。而近年来化学工程学科的发展趋势显示在微化工领域已为原有的理论体系带来了新的突破，随着微反应器技术走向成熟，流动化学技术也取得了较大发展，其本征安全可控无疑是探索MAO合成工艺的适定性思路。本项目提出将前沿化学工程问题和现代新型材料加工手段相结合，以CFD仿真模拟为理论指导，优化设计具有高传质特性和高产品收率的连续流MAO合成反应器。本项目也旨在通过连续流反应工艺解决MAO合成中可能面临的固体副产物沉积堵塞反应器的问题，一方面可以使我们探索出一套简单有效的构建高性能多相含固体产物的连续流反应器的普适方法，另一方面也将有利于探索受限空间内的化工传递过程，为其它类似反应工艺的设计提供有价值的参考。

甲基铝氧烷（MAO）是聚烯烃工业中最重要的助催化剂，其世界年总产能达近万吨，且价格高昂；但由于反应原料极为活泼、反应条件苛刻、反应工艺复杂，国内仍无法大规模生产高活性MAO产品，这已成为控制我国聚烯烃材料高性能化的关键“卡脖子”技术。本项目结合CFD与3D打印技术，并借助3D打印的高度加工灵活性和应用流动化学反应器处理固体的创新型设计，开发了适用于MAO合成这一气/液/液/固反应的多个核心微器件，构建了集成微混合-微反应-微分离于一体的微化工系统，形成了具有自主知识产权的微反应器MAO合成技术，实现了工艺流程的小型化、高效化和本征安全化，并将技术拓展到异丁基铝氧烷（IBAO）等产品，也为应用流动化学技术探索MAO的改性提供了有力支撑。项目取得的主要创新性成果包括：（1）应用3D打印开发了并联文丘里型微气泡发生器、毛细管式微液滴生成器、SAR微混合器、微型CSTR串联反应器等器件，提升了多相流体的混合，通过微器件的合理配置和反应优化大幅提高了MAO收率，产品具有高催化活性，解决了现有间歇合成工艺中存在的控制难、单程收率低和安全性差等问题；（2）将反应技术拓展到IBAO等长链烷基铝氧烷产品合成，并开发了基于在线紫外光谱的铝氧烷产物连续监测技术；（3）构建了基于热感相机的流动化学检测平台，首次测量出MAO/IBAO合成反应的反应焓变。项目执行期间总计发表学术论文9篇，其中SCI论文8篇、EI论文1篇，主要发表在Green Chemistry、Chemical Engineering Journal、AIChE Journal等化学化工领域权威期刊上；申请与MAO合成、后处理、改性相关的中国发明专利5项，已授权1项。