Transesterification membrane reactor with organosilica membrane in batch and continuous flow modes

• BTESA membranes were applied to transesterification to produce butyl acetate (BA). • Batch and CST membrane reactors showed higher yield than plug-flow. • In liquid phase reaction higher BA yields were achieved at 100° C than at 60° C. • Plug flow membrane reactor in gas phase reduced concentration polarization. • Simulation results could predict the experimental values with high accuracy. A membrane reactor (MR) using a 1,2-bis(triethoxysilyl)acetylene (BTESA)-derived organosilica membrane was applied for the transesterification reaction by extracting methanol (MeOH) in batch and flow modes. The BTESA membrane exhibited a MeOH flux exceeding 10 kg/(m 2 h) for MeOH/butyl acetate (BA) binary pervaporation with 10 wt% MeOH at 100 °C and a MeOH separation factor exceeding 10 3 . The effect of temperature on the liquid-phase batch MR (Batch-MR) performance was investigated at 60–100 °C. The BA yield for methyl acetate (MA)/n-butanol (BuOH) = 1 at 100 °C reached 84% after 10 h, which was significantly higher than that achieved at equilibrium (48%). Moreover, the performances of the Batch-MR, continuous stirred tank MR (CST-MR), and plug flow MR (PF-MR) were compared under the same reaction conditions. The PF-MR exhibited a low MeOH permeance owing to concentration polarization, whereas the Batch-MR and CST-MR exhibited a higher permeance because of vigorous agitation, leading to higher BA yields. Furthermore, the gas-phase PF-MR by vapor permeation (PF-VPMR) was used to prevent concentration polarization. The MeOH permeance of the PF-VPMR was three times higher than that of the liquid-phase PF-MR (PF-PVMR); however, the BA yield at 100° C of the PF-VPMR was similar to that of the PF-PVMR due to the formation of ethers as by-products. Nevertheless, the BA yield at 80 °C of the PF-VPMR was enhanced by more than 10% in relation to that of the PF-PVMR. Thus, the transesterification MR with the BTESA membrane can be used for efficient ester production.