(631b) Catalytic Conversion of 5-Hydroxymethylfurfural into Tetrahydrofuran–Dimethanol in Aqueous Media Using a Continuous-Flow Reactor

AIChE meeting 2016

Catalytic
Conversion of 5-Hydroxymethylfurfural into tetrahydrofuran–dimethanol
in aqueous media using a continuous-flow reactor

Sérgio Lima, Klaus Hellgardt, David Chadwick

Chemical
Engineering Department, Imperial College London , London SW7 2AZ, United
Kingdom

During the coming decades,
the world is being challenged to reach its goals to replace a major part of its
use of oil based feedstock for the production of new commodity chemicals and
fuels. In this context, a particular attention is now given to the introduction
of renewable carbon (e.g. biomass) in the chemical industry. Among the large
variety of biomass available on earth, lignocellulosic biomass, a non-edible resource,
has the potential to provide a direct access to valuable chemicals, ideally
with similar or improved properties as compared to fossil-derived chemicals.
Its high oxygen content, low accessibility to (bio)catalysts
and its polyfunctionality makes the transposition of
current catalytic processes to lignocellulosic biomass rather challenging. Tetrahydrofuran–dimethanol (THFDM) is a key derivative for the production
of a wide range of non-petroleum-derived chemicals. In particular it can be
used for the production of 1,6-hexanediol (1,6-HD;
Scheme 1). 1,6-HD can be used to produce caprolactam, the monomer for nylon-6, a widely used
synthetic polymer and is extensively used in the production of polyesters for
polyurethane elastomers, coatings, adhesives, and polymeric plasticizers.[1,2]

In this work we
wish to report on the heterogeneous catalysed continuous synthesis
of tetrahydrofuran–dimethanol
(THFDM) from 5-hydroxymethylfurfural
(5-HMF) in water using a continuous-flow reactor. Raney-Cu and
Raney-Ni were found to be
effective catalysts for this reaction, using water as solvent in a two-steps
process. The highest
yield of THFDM (higher than 90 %) was achieved
by first hydrogenation of 5-HMF to 2,5-furandimethanol (FURDM) in the presence of Raney-Cu follow by hydrogenation of FURDM
to THFDM under 90 bar H₂ at 90 ºC. Results
indicate that large-scale production of low-cost platform and commodity chemicals
for the polymer industries from carbohydrate biomass can be achieved in
continuous flow processes.

Scheme
1

1.      Buntara T., Noel S., Phua
P. H., Cabrera I. M., de Vries J. G., Heeres H. J., Angew. Chem. Int. Ed.
2011, 50, 7083-7087.

2.     
Figueiredo F. C. A., Jorda E., Carvalho W. A., Appl.
Catal. A 2008,
351, 259-266.