Kinetics of homogeneous 5‐hydroxymethylfurfural oxidation to 2,5‐furandicarboxylic acid with Co/Mn/Br catalyst

• Published in: AIChE journal Vol. 63; no. 1; pp. 162 - 171
• Main Authors: Zuo, Xiaobin, Chaudhari, Amit S., Snavely, Kirk, Niu, Fenghui, Zhu, Hongda, Martin, Kevin J., Subramaniam, Bala
• Format: Journal Article
• Language: English
• Published: New York American Institute of Chemical Engineers 01.01.2017
• Subjects: 2,5‐furandicarboxylic acid; 5‐hydroxymethylfurfural; Acetic acid; Batch reactors; Catalysts; Chemical engineering; Chemical engineers; Co/Mn/Br catalyst; Droplets; Kinetics; Mass transfer; Oxidation; Oxygen; Reactors; Sampling; semi‐batch reactor model
• ISSN: 0001-1541; 1547-5905
• DOI: 10.1002/aic.15497

2,5‐furandicarboxylic acid (FDCA) is a potential non‐phthalate based bio‐renewable substitute for terephthalic acid‐based plastics. Herein, we present an investigation of the oxidation rate of 5‐hydroxymethylfurfural (HMF) to FDCA in acetic acid medium using Co/Mn/Br catalyst. Transient concentration profiles of the reactant (HMF), intermediates [2,5‐diformylfuran (DFF), 5‐formyl‐2‐furancarboxylic acid (FFCA)], and the desired product (FDCA) were obtained for this relatively fast reaction in a stirred semi‐batch reactor using rapid in‐line sampling. Comparison of the effective rate constants for the series oxidation steps with predicted gas–liquid mass transfer coefficients reveals that except for the FFCA → FDCA step, the first two oxidation steps are subject to gas–liquid mass transfer limitations even at high stirrer speeds. Novel reactor configurations, such as a reactor in which the reaction mixture is dispersed as fine droplets into a gas phase containing oxygen, are required to overcome oxygen starvation in the liquid phase and further intensify FDCA production. © 2016 American Institute of Chemical Engineers AIChE J, 63: 162–171, 2017