“Green” MMA; an environmentally benign and economically attractive process for the production of methyl methacrylate

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Abstract
Over the last seven years Shell has developed a novel, economically attractive, and environmentally benign process for the production of methyl methacrylate (MMA). The process is based on the highly efficient Palladium‐catalysed methoxycarbonylation of propyne (methyl‐acetylene or MA) under mild, non‐corrosive reaction conditions (temperature ca. 50°C, CO pressure ca. 10 bar) according to the equation:MeOH + CO + HC ≡ C − Me(MA) → H2C = C(Me) − C(O)OMe(MMA)The activity (> 20000 mol‐MMA/mol‐Pd.h) and selectivity (> 99%mol) of the homogeneous Pd catalyst are very high making a once‐through process with minimal waste possible.The MA feedstock for the process, together with propadiene (PD), is separated from a steam‐cracker C3 stream by extractive distillation with DMF. Subsequently, PD is removed from this MA + PD/DMF mixture and isomerized over a heterogeneous K2O/Al2O3 catalyst to yield additional MA.Crude MMA obtained from the methoxycarbonylation of MA can easily be purified by a ‘topping and tailing’ procedure to yield MMA of very high purity (> 99.99 w%).This article describes some of the R&D work carried out at the ‘Koninklijke/Shell‐Laboratorium, Amsterdam’ which has enabled the design of a plant, based on this novel technology.

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