Industrial & Engineering Chemistry Research, Vol.33, No.8, 1989-1996, 1994
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.
Keywords:PLUG-FLOW IDEALIZATION;1-PROPANOL DEHYDRATION;HIGH-TEMPERATURE;ACRYLIC-ACID;REACTOR DATA;LACTIC-ACID;MECHANISM;KETOSES;ALDOSES