Advanced stackable membrane microreactor for gas–liquid-solid reactions: Design, operation, and scale-up

We present a 3D-printed stackable miniature membrane reactor to handle gas–liquid-solid reactions effectively and showcase its application in the synthesis of alkylaluminoxanes. The combination of membrane dispersion and microreaction techniques allows for better process control of the ultrafast and highly exothermic reactions of alkylaluminums hydrolysis with pyrophoric reactants. Droplet generation experiments guide the optimization of the reactor structure and operating parameters, highlighting its ability to produce clustered microdroplets with a narrow size distribution and minimal energy consumption. Our visualized reactor design provides insights into the transient characteristics of alkylaluminoxanes formation, improving understanding of the complex chemistries and achieving room-temperature synthesis of highly active methylaluminoxane (MAO) and isobutylaluminoxane (IBAO) for ethylene polymerization. When scaled up, our compact and integrated five-layer stacked reactor demonstrates uniform flow distribution and consistent reaction performance among all layers, achieving an impressive production rate exceeding ten tons/year. Our work demonstrates a versatile membrane microreaction platform for the scalable and inherently safe production of highly reactive materials, offering a promising approach for other challenging chemical synthesis applications.