Efficient green catalysis for the conversion of fructose to levulinic acid

• Published in: Applied catalysis. A, General General, 2017-06, Vol.539, p.70-79
• Main Authors: Thapa, Indira, Mullen, Brian, Saleem, Ammar, Leibig, Cora, Baker, R. Tom, Giorgi, Javier B.
• Format: Article
• Language: English
• Subjects: Catalysis; Catalysts; Dowex; Fructose; Green catalysis; Hydroxymethylfurfural; Levulinic acid; Mass spectrometry; Polymerization; Polystyrene; Polystyrene resins; Substrates; Sulfonic acid
• ISSN: 0926-860X; 1873-3875
• DOI: 10.1016/j.apcata.2017.03.016

[Display omitted] •Demonstration of fructose to levulinic acid with very high activity and selectivity using Dowex 50×8-100 resin.•We obtained an efficient system capable to produce the transformation under benign conditions.•This work provides more flexibility than dual catalyst systems reported previously, behaving as a switchable catalyst for LA and HMF production depending on the nature of solvent.•Mechanistic insight provided on the formation of by-products leading to humins, the primary catalyst fouling mechanism for this reaction. Highly efficient and selective production of levulinic acid has been achieved from D-fructose in the presence of polystyrene-based sulphonic acid resin catalyst, Dowex 50×8-100, at mild reaction conditions of 120°C, over 24h in a 50:50 mixture of water/GVL resulting in 72mol% yield under optimized reaction conditions. Optimization of the effect of reaction temperature, time, pressure, catalyst to substrate ratio, fructose concentration and solvent was performed. Various polystyrene-based sulfonic acid resins were also investigated for quantitative production of LA from 5-hydroxymethylfurfural (5-HMF) in pure water. Catalyst recycling was carried out up to 6 cycles. Significant mechanistic information was obtained for the formation of “humins”, which are the primary cause of catalyst fouling, by the identification of soluble by-products and polymerization presursors using Q-Tof mass spectrometry based on accurate masses.