ChemComm
Communication
reaching a maximum after 15 h. When reaction time exceeded (50%) without the need for isolating LA. This has not been
5 h, yields tended to diminish, probably by degradation. accomplished in the past; only model solutions have been
The behavior of GVL yield observed in Fig. 1 indicates that studied. Finally, GVL could easily be isolated from the reaction
the conversion of LA into GVL by Fe-carbonyls is not a straight- mixture using simple solvent extraction.
1
forward process. The long induction time observed suggests
We would like to thank the FAPESP (Research Supporting
that the initial Fe-carbonyl species is being converted into a Foundation of the State of Sao Paulo) for financial support
more active catalyst, before the conversion of LA into GVL. X-ray (2013/25504-1) and a fellowship to G.M. (2013/17271-7). We also
analysis after reaction work-up reveals no [Fe
3
(CO)12] at the end thank CNPq for a research fellowship to A.C.B.B. (301079/2012-9),
of the reaction, but Fe (0.2–0.8 microns) as the only Fe IQSC-USP for facilities and NMR analysis, and Prof. D.W. Franco
2 3
O
species (see ESI†). Although merely speculative, this indicates and D.R. Cardoso (IQSC-USP) for the use of the ESI-MS (FAPESP
that [Fe (CO) ] may be a catalyst precursor and that the real 2004/15985-3). The authors are also indebted to CTBE (Adriano
3
12
catalytic species is being converted into Fe O at the end of the Siqueira and Caio Soares) for the kind donation of biomass
2
3
reaction or during reaction work-up. Although not detected in hydrolysis liquor containing LA, Prof. Antonio A. S. Curvelo
our system, some authors suggest that Fe-carbonyls may be (IQSC-USP) and Prof. Peter C. Ford (UCSB) for discussions and
4
5–48
49,50
converted into Fe nanoparticles (Fe-NP)
or Fe
clusters Prof. Laudemir C. Varanda (IQSC-USP) for X-ray and MEV
when heated to high temperatures. The exponential shape of analysis and discussions.
the curve in Fig. 1 also suggests that the process is related to a
heterogeneous catalyst process.
5
1,52
Notes and references
One of the greatest challenges in biomass processing, the
conversion of LA into GVL, is the extrapolation of model
reactions (solvent, LA + FA, and catalyst) to existing industrial
situations (crude liquors obtained directly from biomass hydro-
1
2
3
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8
lysis containing LA + FA). Such extrapolation is important in
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5
2
biorefining. Although a single example employing an LA and FA
mixture from the acid hydrolysis of commercial glucose is
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Science, 2012, 337, 695.
2
4
described in the literature, the use of the mixture directly
from a biomass source has not been explored. Herein, we show
that our catalyst system can be used to form GVL from crude
biomass hydrolysis liquors. As depicted in Fig. 2, a sample
collected directly from a 300-L Pope reactor after the acid
hydrolysis of a sugarcane bagasse (containing 20% LA) was
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of LA and FA from crude biomass hydrolysis liquor has been
shown to form GVL, mimicking a biorefinery situation.
In conclusion, we have converted LA into GVL in the presence
of FA in high yields (up to 92%) using Fe(0) compounds as
catalyst precursors. This result exceeds the traditional limits
found when noble metals are employed. Moreover, to mimic a
biorefinery setting, crude liquor from the acid hydrolysis of
1
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Fig. 2 Conversion of LA into GVL from crude liquor after sugarcane
biomass hydrolysis.
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