Study of the sequential conversion of citric to itaconic to methacrylic acid in near-critical and supercritical water

Abstract

Between 200 and 400 million lb of citric acid are produced annually in the USA by fermentation of molasses and other sugars using the microorganism Aspergillus niger. A lesser quantity of itaconic acid is manufactured by a similar technology using Aspergillus terreus. The recovery of citric acid from its fermentation broth via calcium salt precipitation is a costly, highly complex, sophisticated operation. USDOE estimates the cost of dry citric acid produced from a new plant to be about $0.59/lb, whereas the estimated cost of wet citric acid (in its fermentation broth) from a new plant is about $0.19/lb and from an old plant is about $0.15/lb. Citric acid rapidly reacts in hot (250 C), compressed (34.5 MPa) liquid water to form itaconic and citraconic acids with a combined selectivity that exceeds 90%. At higher temperatures (360 C), in the absence and presence of NaOH, itaconic acid decarboxylates to form methacrylic acid. The yield of methacrylic acid depends on the temperature, pH, and buffer strength of the medium, reaching a maximum of about 70% (by mole) of the itaconic acid feed. Conditions which favor the production of methacrylic acid also lead to the formation of its hydration product: hydroxyisobutyric acid. Undermore » optimum conditions the combined yield of methacrylic acid and hydroxyisobutyric acid from itaconic acid exceeds 80%. Results are consistent with well-established dehydration and decarboxylation mechanisms.« less