STUDY OF THE SEQUENTIAL CONVERSION OF CITRIC TO ITACONIC TO METHACRYLIC-ACID IN NEAR-CRITICAL AND SUPERCRITICAL WATER

Citric acid rapidly reacts in hot (250-degrees-C), compressed (34.5 MPa) liquid water to form itaconic and citraconic acids with a combined selectivity that exceeds 90 %. At higher temperatures (360-degrees-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. Under 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.