Producing acrylic acid and the four primary acrylate derivatives generates over 16 million kg CO<sub>2</sub>/yr through today’s dominant petrochemical process, the 2-step oxidation of propylene. But, these chemicals are necessary for modern life due to broad application across super-absorbent polymers, paints, coatings, and adhesives industries. What if we could instead sustainably produce a bio-based acrylic at cost parity? We focus on the use of feeds derived from lactic acid, a C3 oxygenate sustainably fermented from a range of bio-derived sugar sources.<br/>To tune selectivity in the well-known lactic-to-acrylic dehydration reaction, we co-feed an inert and site-selective chemical titrant to form an inorganic / organic composite can provide desirable selectivity tuning. Here, a yield enhancement from 60 to upwards of 90 C % was demonstrated for methyl lactate dehydration to methyl acrylate and acrylic acid. Dehydration occurs over a composite Na-FAU based zeolite catalyst using several classes of amines as titrants to suppress side reactions on in situ-generated Brønsted acid sites (BASs). We evaluate the effectiveness of BAS titration by considering both the basicity and steric properties of the titrant molecule with the goal to maximize the selectivity enhancement and present here the results of several different amine titrants which outperform the previously studied pyridine derivatives. In particular, we showcase results using a class of diamine titrants which achieve greater than 90% acrylics yield.

Dehydration of C3 oxygenates to bio-based acrylics over inorganic-organic composite catalysts

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ACS Fall 2022

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