Vol.:(0123456789) 1 3
Catal Lett
DOI 10.1007/s10562-017-2191-5
Aqueous-Phase Oxidation of Furfural to Maleic Acid Catalyzed
by Copper Phosphate Catalysts
Tomáš Soták
1
· Milan Hronec
1
· Miroslav Gál
2
· Edmund Dobročka
3
·
Jaroslava Škriniarová
4
Received: 19 July 2017 / Accepted: 13 September 2017
© Springer Science+Business Media, LLC 2017
Graphical Abstract
Keywords Furfural · Oxidation · Metal pyrophosphates ·
Maleic acid · Furoic acid
1 Introduction
The major challenge today is to convert biomass as feedstock
into useful chemicals for the chemical and pharmaceutical
industries in an economically viable fashion. Furfural is a
renewable resource coming from agricultural byproducts,
hemicelluloses, by dehydration in acidic media. Currently
it is used as a solvent and as a platform compound for syn-
thesis of variety of chemicals and engine fuels [1, 2]. Selec-
tive oxidation of biomass-based furfural to maleic acid or
anhydride which is currently manufactured from benzene
and/or butane is an alternative route to the on-going fossil
based processes. Maleic acid is applied in the synthesis of
plasticizers, copolymers, resins, surface coatings, lubricants
and agricultural chemicals.
In literature is described oxidation of furfural in both
vapor and liquid phases using various types of metal cata-
lysts [3, 4]. In spite of oxidation of furfural in vapor phase
where the main products are maleic anhydride and carbon
dioxide, the oxidation in the liquid phase, depending on the
catalyst and solvent, can produce 2-furancarboxylic acid
(furoic acid) eventually its esters or furan-ring opening
Abstract This work describes catalytic aqueous-phase
oxidation of furfural to maleic acid. The heterogeneous Cu-
phosphate catalysts were prepared by coprecipitation method
at diferent atomic ratios of precursors and characterized by
various techniques. The CaCu-phosphate catalyst showed
the best catalytic performance. Using this catalyst under
reaction conditions (115 °C and 0.8 MPa of O
2
) 37.3 mol%
yield and 54.8% selectivity of maleic acid were achieved.
This catalyst can be recycled more than four times producing
practically the same selectivity as fresh one by 13% decrease
in furfural conversion. The proposed mechanism involves
furoic acid as an intermediate in the formation of maleic
acid.
Electronic Supplementary Material The online version
of this article (doi:10.1007/s10562-017-2191-5) contains
supplementary material, which is available to authorized users.
* Tomáš Soták
tomas.sotak@stuba.sk
* Milan Hronec
milan.hronec@stuba.sk
1
Department of Organic Technology, Catalysis and Petroleum
Chemistry, Slovak University of Technology, Radlinského 9,
812 37 Bratislava, Slovakia
2
Department of Inorganic Technology, Slovak University
of Technology, Radlinského 9, 812 37 Bratislava, Slovakia
3
Institute of Electrical Engineering, Slovak Academy
of Sciences, Dúbravská cesta 9, 845 41 Bratislava, Slovakia
4
Institute of Electronics and Fotonics, Slovak University
of Technology, Ilkovičova 3, 812 19 Bratislava, Slovakia