A one-pot reaction for biorefinery: Combination of solid acid and base catalysts for direct production of 5-hydroxymethylfurfural from saccharides

Article abstract of DOI:10.1039/b914087e

5-Hydroxymethylfurfural (HMF), one of the most important intermediates derived from biomass, was directly produced from monosaccharides (fructose and glucose) and disaccharides (sucrose and cellobiose) by a simple one-pot reaction including hydrolysis, isomerization and dehydration using solid acid and base catalysts under mild conditions.

Full text of DOI:10.1039/b914087e

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A one-pot reaction for biorefinery: combination of solid acid and base
catalysts for direct production of 5-hydroxymethylfurfural from
saccharidesw
Atsushi Takagaki, Mika Ohara, Shun Nishimura and Kohki Ebitani*
Received (in Cambridge, UK) 14th July 2009, Accepted 18th August 2009
First published as an Advance Article on the web 7th September 2009
DOI: 10.1039/b914087e
5-Hydroxymethylfurfural (HMF), one of the most important
intermediates derived from biomass, was directly produced from
monosaccharides (fructose and glucose) and disaccharides
(sucrose and cellobiose) by a simple one-pot reaction including
hydrolysis, isomerization and dehydration using solid acid and
base catalysts under mild conditions.
Here, we report selective HMF formation from glucose over
solid acid and base catalysts via a one-pot reaction under mild
conditions. Simple use of conventional solid acids and bases
has afforded the efficient production of HMF. Our strategy
involves separating HMF synthesis from glucose into two
reactions, (1) isomerization of glucose into fructose catalyzed
by solid base and (2) dehydration of fructose into HMF by
solid acid. Such an approach has never been adopted for liquid
acid–base pair due to their neutralization.
The efficient utilization of biomass has recently received
considerable attention as a potential alternative to petroleum
for the production of fuels and chemicals.1,2 One of the most
desired processes is the transformation of lignocellulosic bio-
mass because of its inedibility, abundance and worldwide
distribution.3 Glucose, an abundant monosaccharide obtained
from the depolymerization of cellulose, is further converted
to 5-hydroxymethylfurfural (HMF) via isomerization into
fructose and subsequent dehydration, as shown in Fig. 1.
HMF is considered to be a significant intermediate for the
synthesis of a wide variety of chemicals and alternative fuels.4
Selective formation of HMF is therefore highly desirable to
establish successful biorefinery.
To select efficient heterogeneous catalysts for the one-pot
reaction, two individual reactions were first tested, the
isomerization of glucose and dehydration of fructose. Iso-
merization of glucose to fructose is known as the Lobry–de
Bruyn–van Ekenstein transformation and is generally
catalyzed by base.11 Among solid bases tested, Mg–Al
À
hydrotalcite (HT), consisting of layered clays with HCO3
groups on the surface,12 was found to display the highest
activity for isomerization (see ESIw Table S1w).13 For acid-
catalyzed dehydration of fructose into HMF, ion-exchange
resins, such as Amberlyst-156 and Nafion NR50, as well as
sulfated zirconia exhibited high activity, whereas niobic acid
and H-type zeolites were inactive under the conditions listed in
Table 1. The transformation of glucose over solid acids, also
shown in Table 1, indicates that ion-exchange resins did
not produce HMF directly from glucose but caused intra-
molecular dehydration into anhydroglucoses (1,6-anhydro-b-
D-glucopyranose and 1,6-anhydro-b-D-glucofuranose).14 This
is one of the major drawbacks in using only an acid catalyst
for the direct formation of HMF from glucose. From these
results, HT and Amberlyst-15 were chosen as the solid base
and acid, respectively. It was confirmed that these catalysts
could be recycled for each reaction at least three times without
loss of the activity. Although the appearance of humins on the
HMF is selectively formed from fructose by dehydration in
the presence of liquid5 or solid acids.6 Direct production of
HMF from glucose is, however, unsuccessful because iso-
merization of glucose into fructose seems to be more difficult
by acid catalysis,2 resulting in poor selectivity and considerable
amounts of by-products such as levulinic acid and oligomers.
Although notable methods for HMF production from glucose
and/or fructose have been demonstrated using a two-phase
modifier7 and an ionic liquid containing chromium chloride,8
development of a more environmentally-benign system is
strongly preferred in order to realize green and sustainable
chemistry.9
One-pot reactions using heterogeneous catalysts afford
remarkably unique and environmentally-friendly benefits,
including avoidance of isolation and purification of intermediate
compounds, which saves time, energy and solvent.10 The
concept of site isolation can be realized by the coexistence
of acid and base without neutralization, which has been
demonstrated using acid–base pairs of polymers, sol–gel
matrices, porous silicas and layered clays.
School of Materials Science, Japan Advanced Institute of Science and
Technology (JAIST), 1-1 AsahidaiNomi, Ishikawa 923-1292, Japan.
E-mail: ebitani@jaist.ac.jp; Fax: +81-761-51-1625;
Tel: +81-761-51-1611
w Electronic supplementary information (ESI) available: Experimental
procedure, isomerization of glucose, recycle test, solvent effect. See
DOI: 10.1039/b914087e
Fig. 1 A typical reaction scheme for glucose transformation.
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Table 1 Transformations of fructose and glucose over solid acid
catalystsa
Yield (%)
HMF
AHGb
Substrate
Fructose
Catalyst
Conv. (%)
Amberlyst-15
Nafion NR50
SO4/ZrO2
499
499
57
73
45
21
0
0
0
0
0
0
0
0
0
0
0
0
Nb2O5ÁnH2O
8
H-ZSM5c
Trace
Trace
69
34
7
12
H-Betad
0
Glucose
Amberlyst-15
Nafion NR50
SO4/ZrO2
32
26
0
0
0
Nb2O5ÁnH2O
Fig. 2 Plot of glucose conversion (’), fructose yield (m) and
5-hydroxymethylfurfural (HMF) yield (K) for the transformation of
glucose as a function of reaction time. Amberlyst-15 was added after
2.5 h. Reaction conditions: glucose (0.1 g), hydrotalcite (0.2 g),
Amberlyst-15 (0.1 g), DMF (3 mL), 373 K.
H-ZSM5c
Trace
Trace
0
0
H-Betad
0
a
Reaction conditions: Substrate (0.1 g), catalyst (0.1 g), N,N-dimethyl-
b
formamide (3 mL), 373 K, 3 h. Anhydroglucose. SiO2/Al2O3 = 90,
d
JRC-Z-5-90H. SiO2/Al2O3 = 25, JRC-Z-HB25.
c
anhydroglucoses and other products were not detected
(mass balance: 76%).
surface of hydrotalcite was observed after isomerization of
glucose, the activity for isomerization remained unchanged
by washing with solvent and drying in vacuo for further
experiment.
The acid–base catalysts were simply recovered by decantation,
washing with the solvent (DMF, 6 mL) and drying in vacuo
overnight, and recycled for further reaction. It was confirmed
that a pair of HT and Amberlyst-15 could be reused for this
HMF synthesis at least three times without loss of activities
(see ESIw Fig. S2). HMF was also produced in other polar
aprotic solvents including N,N-dimethylacetamide and dimethyl
sulfoxide in the presence of both HT and Amberlyst-15
(see ESIw Fig. S3). It should be noted that HMF was formed
in acetonitrile which is a lower boiling solvent, so making it
much easier to separate HMF from solvent. Moreau et al.
have examined isomerization of glucose over NaOH and solid
base catalysts.13 Although high glucose conversion was
observed at high concentration of NaOH (pH 12.8), selectivity
to fructose was below 50%. In the pH range from 9.6 to 12.8,
moderate basicity (pH 11.4) gave the highest selectivity of
fructose though glucose conversion was about half to that in
the case of pH 12.8. The carbonate form of HT also exhibited
similar activity of NaOH solution with pH 11.4. The high
selectivity of HMF using Amberlyst-15 could be explained
Direct formation of HMF from glucose using solid acid and
base in the one-pot reaction is shown in Table 2 (see ESIw).
Remarkably, HMF synthesis from glucose was successfully
achieved in the presence of both HT and Amberlyst-15 catalysts
(entry 1).15 64% of glucose conversion and 38% of HMF
selectivity were obtained at 373 K for 3 h. Anhydroglucoses
(AHG; 1,6-anhydro-b-D-glucopyranose and 1,6-anhydro-b-D-
glucofuranose) and a small amount of fructose were detected
as by-products (AHG selectivity: 28%, fructose selectivity 3%).
Other compounds including retro-aldol condensation products
such as erythlose and glycolaldehyde, and levulinic acid as
rehydration of HMF were not detected. The mass balance was
estimated to be 69% from the sum of amount of detected
products. Glucose conversion and HMF yield continually
increased with increasing reaction time. HMF selectivity was
almost the same after 3 h reaction. After 9 h, glucose was fully
converted (498%), resulting in HMF selectivity of 34%
(see ESIw, Fig. S1). At 353 K for 9 h, HMF selectivity was
58% at high glucose conversion (73%). It should be noted that
this one-pot reaction operates at lower temperature (353 K).
Increasing the temperature results in the formation of
anhydroglucose and oligomers by acid catalysis. The pair of
HT and Nafion NR50 also produces HMF from glucose
(glucose conversion: 60%; HMF selectivity: 27%) (entry 2).
As mentioned above, glucose was converted, not into HMF,
but fructose, over only solid base (HT) (entry 3) and anhydro-
glucoses over only solid acid (Amberlyst-15) (entry 4). On the
other hand, HMF was not formed using a liquid acid–base pair
(entry 6). A control experiment confirmed the occurrence of
sequential reactions, as the addition of solid acid (Amberlyst-15)
into a solution containing a considerable amount of fructose
(39%), which had formed from glucose in the presence of solid
base (HT), resulted in the disappearance of fructose and
simultaneous formation of HMF within 1 h (Fig. 2). 76% of
HMF selectivity was obtained after 4.5 h (Table 2, entry 1) and
Table 2 One-pot synthesis of 5-hydroxymethylfurfural (HMF) from
glucose using acids and basesa
Entry Base
Acid
Conv. (%)
HMF sel. (%)
1
2
3
4
HT
HT
HT
—
Amberlyst-15
Nafion NR50
—
Amberlyst-15
HCl (pH 1)
64, 73,b 60c 38, 58,b 76c
60
62
27
0
69
499
0
0
0
0
5
—
6d
Piperidine p-TsOHÁH2O
Reaction conditions: Glucose (0.1 g), HT (0.1 g), Amberlyst-15 (0.1 g),
a
b
N,N-dimethylformamide (3 mL), 373 K, 3 h. Using 0.2 g of HT,
c
353 K, 9 h. Using 0.2 g of HT, 4.5 h. Amberlyst-15 was added after
d
2.5 h. Piperidine (0.2 mmol), p-toluenesulfonic acid (0.07 mmol).
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Table 3 One-pot synthesis of 5-hydroxymethylfurfural (HMF) from
mono- and disaccharides using HT and Amberlyst-15a
Notes and references
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52
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HMF from disaccharides. It is considered that a small amount
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and results in satisfactory cascade reactions.
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15 Acid and base amounts of catalysts used are 4.8 mmol gÀ1 for
Amberlyst-15 and 0.7 mmol gÀ1 for HT, respectively. 0.2 mmol of
HMF was produced from 0.55 mmol of glucose in the presence of
Amberlyst-15 (25 mg, acid amount; 0.12 mmol) and hydrotalcite
(0.2 g, base amount; 0.14 mmol) in DMF (3 mL) at 373 K for 3 h.
TONs were estimated to be 1.7 and 1.4 for Amberlyst-15 and
hydrotalcite, respectively.
In conclusion, 5-hydroxymethylfurfural, one of the most
important intermediates derived from biomass, was directly
produced from monosaccharides (fructose and glucose) and
disaccharides (sucrose and cellobiose) by a simple one-pot
synthesis using a conventional solid acid and base under mild
reaction conditions.
This work was supported by a Grant-in-Aid for Young
Scientists (Start-up) (No. 20860038) of the Ministry of Education,
Culture, Sports, Science and Technology (MEXT), Japan.
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This journal is The Royal Society of Chemistry 2009
6278 | Chem. Commun., 2009, 6276–6278