- D.S. Es van (1)
- E. Giling (1)
- E.L.V. Goetheer (1)
- E. Goetheer (2)
- R. Heck van (1)
- R. Latsuzbaia (1)
- H. Meer van der (1)
- M. Roelands (1)
- T.M. Slaghek (1)
- M.S. Yagüe (1)
- M. Zijlstra (2)
Identification of more benign cathode materials for the electrochemical reduction of levulinic acid to valeric acid
Bisselink, R.J.M. ; Crockatt, M. ; Zijlstra, M. ; Bakker, I.J. ; Goetheer, E. ; Slaghek, T.M. ; Es, D.S. van - \ 2019
ChemElectroChem 6 (2019)13. - ISSN 2196-0216 - p. 3285 - 3290.
sustainable chemistry, deoxygenation, electrocatalysis, renewable resources, clemmensen reduction
The electrochemical production of valeric acid from the renewable bio‐based feedstock levulinic acid has the potential to replace the oxo‐process which uses fossil‐based feedstock 1‐butylene. The electrochemical reduction of the ketone functionality in levulinic acid using lead or mercury cathodes is already known for over 100 years. However, large scale electrochemical production of valeric acid might be limited due to the toxicity of these materials. In this study, we identified three additional cathode materials, cadmium, indium and zinc, which selectively and efficiently produce valeric acid. Of these materials, indium and zinc are considered more benign. More specifically, at indium there is no formation of the side product γ‐valerolactone, thus resulting in the highest selectivity towards valeric acid. For the electrochemical reduction a reaction mechanism involving formation of an organometallic compound is proposed. Furthermore, a possible processing strategy is outlined to enable continuous electrochemical production of valeric acid on large scale.
Electrochemical method for producing valeric acid
Bisselink, R.J.M. ; Crockatt, M. ; Goetheer, E.L.V. - \ 2019
Octrooinummer: WO2019035715, verleend: 2019-02-21.
The invention is directed to a method of electrochemically producing valeric acid. The method of the invention comprises - contacting a solution of levulinic acid with an anode and a cathode in an electrochemical cell; and - electrochemically reducing levulinic acid at the cathode to form valeric acid, wherein the cathode comprises one or more materials selected from the group consisting of cadmium, zinc, and indium.
Continuous electrochemical oxidation of biomass derived 5-(hydroxymethyl)furfural into 2,5-furandicarboxylic acid
Latsuzbaia, R. ; Bisselink, R. ; Anastasopol, A. ; Meer, H. van der; Heck, R. van; Yagüe, M.S. ; Zijlstra, M. ; Roelands, M. ; Crockatt, M. ; Goetheer, E. ; Giling, E. - \ 2018
Journal of Applied Electrochemistry 48 (2018)6. - ISSN 0021-891X - p. 611 - 626.
Continuous production - Electroorganic synthesis - FDCA - HMF - Nickel oxy-hydroxide electrode
Abstract: A continuous electrochemical process with integrated product separation has been developed for production of 2,5-furandicarboxylic acid (FDCA) by oxidation of 5-(hydroxymethyl)furfural (HMF) in aqueous alkaline media on non-noble Ni/NiOOH foam electrodes at ambient conditions. Initially, voltammetry studies were performed in both, acid and alkaline media, on various catalyst materials: Au, Au3Pd2, Pt, PbO2, Ni/NiOOH and graphite. Preparative electrolysis was performed on Au, Au3Pd2, Pt, PbO2, Ni/NiOOH electrodes in a divided glass cell and Ni/NiOOH showed the best performance with an FDCA yield of ≈ 90% and a Faradaic efficiency of ≈ 80%. The electrolysis conditions were then optimized to industrially relevant conditions in a filter-press type flow reactor with Ni/NiOOH foam anode. HMF concentrations as high as 10 wt% were converted to FDCA at pH 12 in a buffer free 0.1 M Na2SO4 electrolyte with continuous addition of NaOH to maintain constant pH. An FDCA separation yield up to 95% was achieved via pH shift crystallization. The electrolysis and FDCA separation results were used for the design and construction of a bench-scale system where continuous FDCA production, including integrated product separation, was tested and reported in this work. This publication for the first time presents a continuous electrochemical FDCA production system with integrated product separation at industrially relevant product concentrations, 10 wt% HMF, and utilizing non-noble electrode materials. Graphical Abstract: [Figure not available: see fulltext.]