(583cz) Efficient Production of 5-Hydroxymethylfurfural From Fructose Via Mechanical Stirring Control and High-Fructose Solution Addition

The production of transportation biofuels and
chemicals from renewable biomass has been regarded as the most promising
process for reducing our dependence on fossil feedstocks (Roman-Leshkov et al., 2007). However, the efficient utilization of biomass in multiple
catalytic processes is still needed to be further investigated. Among current
biochemicals, 5-hydroymethylfurfural (HMF) converted from carbohydrates has
attracted intensely scientific interest. HMF is a versatile intermediate in the
production of high value chemicals, such as alternative fuels, diesel fuel
additives, industrial solvents and bio-derived polymers (Chheda et al., 2007). Among
current carbohydrate resources of HMF production, such as cellulose, glucose,
fructose and some other potentially industrial residues (Rosatella et al., 2011), fructose is the most effective monosaccharide in the research of
acid-catalyzed conversion from biomass to HMF (Qi et al., 2011). The production
of HMF from fructose can be accomplished in variety of processes. However, the
major research for HMF preparation focused on the design of the catalyst and
the choice of proper extraction solution to improve the reaction efficiency of
the biphasic system in high sugar solution. However, several process
intensification issues, such as the method for increasing the concentration of
sugar solution, the control of stirring speed in the reactor, the type of the
impeller, the size of the reactor and the separation of products from solvent,
were still needed to be thoroughly investigated.

In this work, two simple operations,
mechanical stirring control and high-fructose solution addition, were applied
to the water/butanol system for enhancing fructose-to-HMF reaction using HCl as
catalyst (Fig. 1a). The optimization of stirring speed led to a high HMF yield of
81.7% with 92.0% fructose conversion at 0.3mol/L HCl and 1000rpm (Fig. 1b). High-speed
stirring promoted the reaction efficiency by enhancing the transfer rate of HMF
and decreasing the water around HMF and fructose. During different reaction
periods, the mass transfer rate of HMF has different effect on HMF yield. Via
studying the kinetics of fructose-to-HMF reaction, it demonstrated that the lower
value of reaction rate constant was benefit to obtain higher HMF yield in
queous/butanol media. In order to stablely and continuously obtain a high yield
of HMF with a high conversion of fructose, the high-fructose solution (54.6wt%)
addition was investigated. The application of this simple process led to a
maximum HMF yield of 83.3% with a fructose conversion of 93.8%, meanwhile HMF
yields were all above 55% during the whole reaction process (Fig. 1c). The simple addition
process greatly reduced the side-reaction and made the operation more
continuously and stablely, and thus provided a practical and effective method
toward HMF preparation in high-fructose solution.

This work was supported by
the NSF of China (51173128, 31071509, 21276192), the Ministry of Science and
Technology of China (Nos. 2012YQ090194, 2013AA102204, 2012BAD29B05), the
Program for New Century Excellent Talents in Chinese University (NCET-08-0386;
NCET-11-0372), and Beiyang Young Scholar Program (2012).

References

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[2]     Qi, X.H., Guo, H.X., Li, L.Y. (2011) Efficient Conversion of
Fructose to 5-Hydroxymethylfurfural Catalyzed by Sulfated Zirconia in Ionic
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7985-7989.

[3]     Roman-Leshkov, Y., Barrett, C.J., Liu, Z.Y., Dumesic, J.A. (2007)
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[4]     Rosatella, A.A., Simeonov, S.P., Frade, R.F.M., Afonso, C.A.M. (2011)
5-Hydroxymethylfurfural (HMF) as a building block platform: Biological
properties, synthesis and synthetic applications. Green Chemistry,
13(4), 754-793.

Figure 1 Dehydration of fructose to HMF. a) A typical reaction scheme for
HMF production by mechanical stirring in biphasic phases; b) Effect of stirring
type on fructose conversion and HMF yield in aqueous/butanol media; c) Effect
of high-fructose solution addition process on HMF yield and mass ratio
(fructose: water).