Methylformate from CO2: an integrated process combining catalytic hydrogenation and reactive distillation

摘要: An integrated two-step process for the production of methylformate (MF) from CO2, H2 and MeOH was developed. In first step, hydrogenation CO2 to a formate-amine adduct is carried out in biphasic system comprising n-decane as catalyst phase product phase. second resulting methanol solution containing subjected reactive distillation esterification isolation methylformate. The selection amine played an important role devising overall process. Whereas step basic amines work best, medium low are preferred step. 1,2-Dimethyl-imidazole (1,2-DMI) identified effective compromise integration both steps. bis(diphenylphosphino)methane ligand tailored with long alkyl chains ensured retention Ru-catalyst non-polar allowing straightforward reuse semi-continuous set-up, repetitive (8 cycles) led total turnover number (TTON) 38 000 at average frequency (TOF) 1400 h−1 cumulative leaching only 1.4 mol% P 2.0 Ru. Reactive demonstrated continuously operated rectification unit leading MF head column purity 91.5%.