View Article Online

Green
View Journal

Chemistry
Accepted Manuscript

This article can be cited before page numbers have been issued, to do this please use: J. Cui, J. Tan, T. S.
Deng, X. Cui, Y. L. Zhu and Y. Li, Green Chem., 2015, DOI: 10.1039/C5GC01948F.

This is an Accepted Manuscript, which has been through the

Royal Society of Chemistry peer review process and has been
accepted for publication.

Accepted Manuscripts are published online shortly after

acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.

You can find more information about Accepted Manuscripts in the

Information for Authors.

Please note that technical editing may introduce minor changes

to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.

www.rsc.org/greenchem
 Page 1 of 7 Please do notChemistry
Green adjust margins
View Article Online
DOI: 10.1039/C5GC01948F

Journal Name

Conversion of carbohydrates to furfural via selective cleavage of

carbon-carbon bond: cooperative effect of zeolite and solvent
Published on 29 October 2015. Downloaded by National University of Singapore on 03/11/2015 08:49:50.

Received 00th January 20xx,

Accepted 00th January 20xx Jinglei Cui,ab Jingjing Tan, ab Tiansheng Deng,a Xiaojing Cui,a Yulei Zhu*ac and Yongwang Liac
Furfural is one of the most valuable biomass-derived platform molecules which is primarily produced from hemicellulose.

Green Chemistry Accepted Manuscript

DOI: 10.1039/x0xx00000x
It is of significant importance but still highly challenging to produce furfural from hexoses, which are extensively
www.rsc.org/
distributed in nature. In this paper, the carbohydrates (cellulose, starch, inulin, maltose, sucrose, glucose and fructose)
were transformed into furfural efficiently over Hβ zeolite in γ-butyrolactone-water solvent. The key process for converting
hexoses into furfural is the selective cleavage of C-C bond in hexoses to pentoses. Hβ zeolite was discovered to induce the
formation of acyclic hexoses, and the synergy between Hβ and solvent enables the selective C-C bond cleavage of acyclic
hexoses into pentoses and promotes the subsequent dehydration of pentoses into furfural. Furfural yields for converting
fructose and glucose reached 63.5% and 56.5% at milder condition (150 oC), respectively. Moreover, a favorable yield of
38.5% for furfural can be achieved by direct conversion of cellulose.

from cellulose or its derived hexoses are scarce. Hu et al.

Introduction reported that furfural can be obtained with a low yield (<2%)
8
The shortage of fossil fuels and increasing environmental by transforming levoglucosan over Amberlyst-70 in DMSO.
destruction have stimulated the seeking for safety and clean Luijkx et al. reported that the formation of furfural from
energies and chemicals.1 Biofuel is an ideal complement as it is glucose and cellobiose with a yield of 3.2% and 6.7% can be
o 9
produced from abundant and renewable biomass. observed under hydrothermal conditions at 340 C. The low
Furthermore, many useful chemicals can be obtained by the furfural yields in this catalytic process arise from the slow
2
utilization of biomass. Among them, furfural is considered as kinetics of selective cleavage of the C-C bond, and fast
one of the top-valued platforms with an annual yield of more dehydration of hexoses into 5-hydroxymethylfurfural (HMF).
3
than 200,000 tonnes in the worldwide. As a typical biomass- Recently, in the pioneering work of Dumesic et al., a
derived chemical, furfural can complement the fossil resources
4 considerable yield of 37% for furfural was obtained from
for producing resins, lubricants, adhesives and plastics. It is o
glucose at 170 C over H-mordenite catalyst in γ-valerolactone
also the feedstock for the synthesis of many valuable 10
chemicals, including furfuryl alcohol, tetrahydrofurfuryl (GVL)-water solvent. It would be more desirable but highly
alcohol, 2-methylfuran and 2-methyltetrahydrofuran.5 challenging to develop a more efficient process for furfural
Crop waste, particularly corncob, is typically chosen as the production from C6-derived carbohydrates, particularly from
raw material for industrial producing of furfural. The cellulose.
production processes include the decomposition of In this work, an efficient strategy was presented for
hemicellulose of corncob to pentoses and their subsequently conversion of cellulose and C6 sugars-derived carbohydrates
6
dehydration to furfural catalysed by mineral acid. However, (fructose, glucose, maltose, sucrose, inulin, starch) into furfural
the current method cannot transform cellulose and its derived using acidic zeolite catalysts (Hβ, HZSM-5 and H-Mordenite)
C6 sugars of corncob into furfural. Therefore, a large amount and γ-butyrolactone (GBL) solvent. The unique pore structure
of cellulose and its derived C6 sugars are abandoned as wastes. of Hβ zeolite favours the formation of the acyclic hexose,
Moreover, cellulose and its derived C6 sugars are most which facilitates its following selective C-C bond cleavage to
abundant in biomass resources.7 To improve the efficiency of produce pentose. The synergy between Hβ zeolite and GBL
biomass utilization, it is of significant importance and industrial solvent largely promotes this selective C-C bond cleavage and
interest to produce valuable platforms, such as furfural, from the subsequently dehydration of pentose to furfural. High
cellulose and its derived C6 sugars. Many efforts have been yields of 63.5 % and 56.5% for furfural can be obtained from
made for improving the production efficiency of furfural from fructose and glucose, respectively. Moreover, a comparable
hemicellulose, while those on the efficient synthesis of furfural furfural yield of 38.5% can be achieved by direct converting
cellulose over Hβ zeolite in GBL-water solvent.

Results and discussion

Initially, the conversion of fructose over a series of acidic
zeolites (HY, H-Mordenite, HZSM-5 and Hβ) was performed in
water (Table 1, entries 1-4). HY zeolite was inactive for the

This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 1

Please do not adjust margins

 Please do notChemistry
Green adjust margins Page 2 of 7
View Article Online
DOI: 10.1039/C5GC01948F
ARTICLE Journal Name

a
Table 1 The conversion of fructose over various catalysts
Yield %
Entry Catalyst Solvent Conv. %
Furfural HMF LA+FA Glucose
1b HY Water 69.8 trace 19.8 3.3 10.1
b
2 H-Mordenite Water 63.2 4.5 10.1 7.3 9.6
b
3 HZSM-5 Water 62.9 2.9 2.8 11.6 5.1
b g
4 Hβ Water 79.2 9.1 14.4 4.8 12.9
Published on 29 October 2015. Downloaded by National University of Singapore on 03/11/2015 08:49:50.

5 HY GBL-water 99.9 2.9 57.1 11.6 1.5

6 H-Mordenite GBL-water 99.1 18.7 37.7 1.5 2.5

Green Chemistry Accepted Manuscript

7 HZSM-5 GBL-water 99.5 17.4 26.7 18.7 1.2
h
8 Hβ GBL-water 99.9 63.5 12.6 12.9 trace
9 Hβ 1,4-dioxane-water 99.7 39.5 11.5 15.7 0.8
10c H2SO4 GBL-water 99.9 trace trace 59.9 trace
d
11 Amberlyst-15 GBL-water 99.9 trace 0.8 45.6 trace
e
12 AlCl3 GBL-water 99.9 trace 13.8 5.6 trace
f
13 Amberlyst-15+AlCl3 GBL-water 99.9 trace 14.5 5.2 2.4
a
: 0.1 g catalyst; 0.5 g fructose, 9 g GBL or 1,4-dioxane, 0.5 g water; 150 oC, 1 h, 2 MPa N2; b: 0.5 g zeolite catalyst, 0.5 g fructose, 9.5 g water; c: H2SO4 0.02 M; d:
Amberlyst-15, 0.1 g; e: AlCl3: 30 mg; f: 0.05 g A-15, 15 mg AlCl3; g: carbon balance: 54.6%；h: carbon balance: 83.1%, HCHO/furfural in product =0.41 mol/mol, the
tests for investigating formaldehyde loss were listed in Table S1, ESI. The XRD patterns of various zeolites were shown in Figure S2, in ESI.

formation of furfural in water, while low yields of furfural were Hβ zeolite can catalyse efficiently the conversion of fructose
obtained over Hβ, HZSM-5 and H-Mordenite zeolites. into furfural, whereas the dehydration of fructose into HMF
Meanwhile, 5-hydroxymethylfurfural (HMF), levulinic acid (LA), was predominant and only trace amount of furfural was
formic acid (FA) and glucose were the major products over all obtained over HY zeolite under the same conditions (Table 1,
the zeolite catalysts. Compared with HZSM-5 and H- entry 5 and 8). To understand the effects of acid sites on the
Mordenite, Hβ and HY zeolite showed high activity and higher conversion of fructose to furfural, several typical Brønsted and
overall yields of HMF, LA and FA were achieved. As HMF is Lewis acid catalysts were selected for converting fructose in
formed by acid catalytic dehydration of fructose, which can GBL-water solvent (Table 1, entry 10-13). Brønsted acids
further dehydrate to produce LA and FA, the observed higher (H2SO4 and Amberlyst-15), Lewis acids (AlCl3) or their
overall yields are likely due to Hβ and HY zeolite have more combination (Amberlyst-15+AlCl3) are unable to transform
acid sites in respect to HZSM-5 and H-Mordenite (as seen in fructose to furfural. The above results indicate that the unique
Table S2, ESI). The yield of glucose was high over Hβ zeolite as pore structures of Hβ catalyst is of vital importance for high
it owns more Lewis acid sites that are active sites for the yield of furfural compared with HY zeolite and other Brønsted
11
isomerization of fructose to glucose. The carbon balances of or Lewis acid catalysts.
aqueous reactions are low (<60%). Considerable amounts of
humin were observed in the aqueous solutions after reactions,
which are responsible for the majority of mass loss. The above
results show that it is extremely insufficient for the
transforming of fructose into furfural over zeolites in water. A
solvent facilitating the formation of furfural from fructose is
required. It has been reported that γ-valerolcatone (GVL)
favours the conversion of fructose into furfural and a
10
comparable yield of 36% of furfural can be obtained.
However, a substantial amount of valuable GVL will be
consumed in the process using GVL as solvent. In contrast, γ-
butyrolactone (GBL) is a versatile commodity and has been
demonstrated to be a preferable solvent in the process of
12
sugars conversion in our latest work. Hence, the conversion
of fructose was performed in the GBL-water solvent (Table 1,
entry 5-8). The addition of GBL greatly enhanced the catalytic
activity and yield of furfural. A nearly full conversion of
fructose can be obtained with fewer amounts of catalysts. A
maximum furfural yield of more than 60% was achieved over
Hβ catalyst, which is the highest in literature concerning the
conversion of hexoses to furfural. Besides, the addition of 1, 4-
dioxane was identified to enhance the yield of furfural from
fructose compared with water (Table 1, entry 9). GBL was Figure 1 The FTIR spectra of (a) Hβ+ fructose + water; (b) Hβ + fructose+
1,4-dioxane-water (5wt%); (c) dealuminated-Hβ + fructose + water; (d)
finally chosen as the solvent because of its high ability for
dealuminated-Hβ+fructose+1,4-dioxane-water (5wt%); (e) HY + fructose +
conversion of hexoses into furfural. Notably, it is observed that water; (f) HY + fructose+1,4-dioxane-water (5 wt%).

2 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

Please do not adjust margins

 Page 3 of 7 Green Chemistry
View Article Online
DOI: 10.1039/C5GC01948F

a
Table 2 The effect of water content on the conversion of fructose
Yield mol%
Entry Solvent Conv. %
Furfural HMF LA+FA Glucose
1 GBL 99.9 48.2 9.5 4.6 trace
2 GBL-water (2.5 wt%) 99.9 61.5 9.9 7.9 trace
3 GBL-Water (5 wt%) 99.9 63.5 12.6 12.9 trace
4 GBL-Water (10 wt%) 99.1 52.7 11.2 12.5 1.2
5 GBL-Water (15 wt%) 97.5 35.3 13.1 9.4 2.6
Published on 29 October 2015. Downloaded by National University of Singapore on 03/11/2015 08:49:50.

6 GBL-Water (20 wt%) 90.5 25.2 12.3 11.7 3.7

7 GBL-Water (30 wt%) 82.2 19.1 13.4 11.1 6.5
8 GBL-Water (40 wt%) 80.4 10.3 12.1 9.4 9.6

Green Chemistry Accepted Manuscript

a
: 0.1 g Hβ catalyst; 10 g fructose/GBL-water solution for each run, fructose concentration 5 wt%; 150 oC, 1 h, 2 MPa N2.

Two possible reaction pathways for the conversion of for 4 h, and then the zeolite was separated, washed and dried
13
fructose to furfural have been proposed. Specifically, one is at room temperature before the FTIR characterization
that fructose dehydrated into HMF, followed by the leaving of (detailed in method section in ESI). Considering that GBL also
9,14
a -CH2O group to generate furfural. The other is that the C-C owns C=O group, water and 1, 4-dioxane were chosen as the
bond in fructose was cleaved, leading to the formation of solvents for the diffusion of fructose into zeolite pores. HY was
pentose, followed by the dehydration of pentose to give also investigated for better comparison, as the dehydration of
10,15
furfural. The first reaction pathway was ruled out in our fructose into HMF was predominant on it (Table 1, entry 8).
-1 -1
reaction system by a HMF conversion test (as seen in Table S3, Clear adsorption bands at 1767 cm and 1731 cm , which are
ESI). HMF was dissolved in GBL-water solvent and contacted assigned to the stretching vibration of C=O group in acyclic
o o
with Hβ catalyst for 1 h at 150 C and 160 C, respectively, fructose, were observed in Hβ/fructose/water or
however no furfural was formed after the reactions. In Hβ/fructose/1,4-dioxane-water system (Figure 1 a, b), whereas
-1 -1
contrast, pentose (arabinose) and a certain amount of the bands at 921 cm and 867 cm which assigned to the
formaldehyde were observed when fructose or glucose was vibration of ring structure of fructose disappeared (The FTIR
18
the reactant under the same conditions (as seen in Table 1 and data of fructose was shown in Table S6, ESI). In contrast, the
-1
Table S4, ESI). Arabinose can convert to furfural efficiently over adsorption peaks for ring structure of fructose (921 cm and
-1
Hβ catalyst (as seen in Table S5, ESI). These results indicate 867 cm ) were found while the adsorption bands of C=O
that fructose was first degraded into arabinose and vibration were not detected in HY/fructose/water or
formaldehyde, followed by the dehydration of arabinose to HY/fructose/1,4-dioxane-water system (Figure 1 e, f). These
give furfural on Hβ catalyst. In other words, the selective results indicated that Hβ zeolite enables the formation of
cleavage of the C-C bond in fructose to form pentose is more acyclic fructose. When passing through the pores, acyclic
favoured on Hβ catalyst. fructose has a very good chance to cleave the C-C bond to
In solutions, more than 99% of D-fructose molecules usually
exist in the cyclic form, and the dehydration of cyclic fructose,
Table 3 The effect of temperature and substrate concentration
particularly for furanose, into HMF are demonstrated to a
16,17 on the conversion of fructose and glucose to furfural
readily occur in the presence of acid catalyst. This
suggested to us that the high yield of furfural over Hβ catalyst Sugar
o Furfural
may stem from the fact that fructose exists in acyclic Entry sugar T/ C concen. Conv.%
yield %
configuration in Hβ zeolite. Therefore, we assumed that the wt%
unique pore structures of Hβ can induce the formation of 1 Fructose 130 5 97.8 38.3
2 Fructose 140 5 99.9 49.7
acyclic fructose when fructose diffused into the Hβ zeolite. To
3 Fructose 150 5 99.9 63.5
verify this assumption, FTIR spectroscopy was selected to
4 Fructose 160 5 99.9 59.6
identify the different configurations of fructose (Figure 1). b
5 Fructose 150 2.5 99.9 62.3
This is based on the understanding that C=O group exists in c
6 Fructose 150 10 85.6 46.8
acyclic fructose, whereas it is absence in the cyclic form of
fructose. Zeolite, sugar and solvent were mixed and stirred 7 Glucose 140 5 95.4 41.5
d
O OH Hβ OH OH 8 Glucose 150 5 99.9 56.5
CH 2OH
OH OH
HOH2 C
OH OH
-HCHO
OHC
OH
CH2OH
9 Glucose 160 5 99.9 57.7
OH
O OH Hβ Hβ OH b
Acyclic fructose
O Hβ O
10 Glucose 150 2.5 99.9 54.6
OH Arabinose (acyclic) O
OH -3H 2O c
HO
HO
11 Glucose 150 10 78.6 42.2
Fructose (cyclic) Arabinose (cyclic) Furfural a
: 0.1 g Hβ catalyst; 10 g fructose or glucose/GBL-water solution for each run,
- 3H O
2O
O
H+ water concentration 5 wt%, reaction time: 1 h for fructose conversion, 2 h for
HO O OH + HCOOH

HY or other acid catalysts

H 2O O glucose conversion, 2 MPa N2; b: 0.05 g Hβ catalyst; c: 0.2 g Hβ catalyst; d:
HMF LA
HCHO/furfural in product=0.38 mol/mol, the tests for investigating
Scheme 1 Possible Pathways of fructose conversion over Hβ zeolite and
formaldehyde loss were listed in Table S1, ESI.
other acid catalysts

This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 3

Please do not adjust margins

 Please do notChemistry
Green adjust margins Page 4 of 7
View Article Online
DOI: 10.1039/C5GC01948F
ARTICLE Journal Name

Highest yields of 76% and 87% for furfural were obtained with
GBL as the solvent. Meanwhile, the degradation of furfural was
found to be suppressed drastically by GBL (as seen in Table S8,
ESI). A clear loss of furfural (25.2%) in water was detected,
while the degradation of furfural was much less in GBL-water
solvent. However, water is inevitable for the conversion of
sugars despite that it is unfavourable for the transformation of
21
sugars into furfural. Water is essential to dissolve sugars and
Published on 29 October 2015. Downloaded by National University of Singapore on 03/11/2015 08:49:50.

also as a product in dehydration process of sugars. Therefore,

the effect of water content in GBL-water solvent was
Figure 2 The conversion of (a) fructose and (b) glucose as a function of time.

Green Chemistry Accepted Manuscript

investigated (Table 2). Without water in the solvent, the yield
Conditions: 0.1 g Hβ, 10 g fructose or glucose/GBL-water solution for each
o
of furfural was low and the colour of solution after reaction
run, fructose or glucose concentration 5 wt%, 150 C, 2 MPa N2.
became dark, indicating the formation of soluble humins.22,23
With the increasing content of water in the solvent, the
produce arabinose and subsequently dehydration to produce
resulting solution became lighter and higher levels of furfural
furfural on the acid sites in the pores. In contrary, HMF, other
were achieved with a water content of 2.5-10 wt%. A clear
than furfural, is the main product from fructose with HY or
decline in both fructose conversion and furfural yield were
other conventional acids as the catalysts due to the cyclic
observed when the water content exceeded 15 wt%.
fructose favours dehydration. The possible reaction pathways
The strategy for converting fructose was further applied for
over Hβ and HY catalysts were proposed based on FTIR and the transforming glucose to furfural, and the effect of reaction
above test results (Scheme 1). temperature on converting both fructose and glucose was also
Additionally, a clear difference in the peak position of C=O studied (Table 3). Higher temperature facilitated the
vibration in acyclic fructose was found in 1,4-dioxane-water conversion of fructose and glucose and the yield of furfural
and in pure water (Figure 1 a, b). This indicated that solvents achieved a high level at 150 o C. Meanwhile, the effect of the
may affect the interactions between the acid sites of zeolite concentration of fructose or glucose in the reactions was
16,17,19
and C=O in fructose. In such case, the removing of studied. The declines in the furfural yield were observed with
solvents or lessening of acid sites might reduce this difference. the content of fructose or glucose increased to 10 wt% as the
A long period of time or a heating process is required for the high concentration of sugar promotes the formation of
removal of solvent, especially water, from zeolite, which would humins.24,25 Noticeably, a high yield of 56.5% for furfural can
lead to the conversion of fructose. Therefore, the be obtained using glucose as the raw material. The recycle of
dealuminizing of zeolite was performed to obtain an Hβ with Hβ zeolite in converting fructose and glucose to furfural was
20
much less acid sites (details in ESI). The FTIR characterization further studied. A slight decrease of furfural yield was found
of dealuminated-Hβ/fructose/water or dealuminated- after three recycling runs (Table S9, ESI). Meanwhile, a certain
Hβ/fructose/1,4-dioxane-water system were further mass loss was observed in the recycled Hβ catalyst by TG
investigated. The difference in the band positions for C=O analysis (Figure S4), and the colour of used Hβ zeolite changed
adsorption in 1, 4-dioxane and water was greatly reduced to 2 from dark gray into white after TG analysis, indicating that the
cm-1 (Figure 1 c, d). This result apparently clarifies that the observed mass loss can be ascribed to the removal of the
solvent has a remarkable effect on the interactions between carbon deposition on the Hβ zeolite. Therefore, the Hβ zeolite
acid sites and -C=O. Meanwhile, the synergy between acid after three recycling runs was calcined at 600 oC for 2 h (air
sites and solvent greatly promotes the selective C-C bond atmosphere) and used for next run. Furfural yields from
cracking of hexose into pentose. fructose and glucose reached 62.1% and 53.2% respectively
The promotional effect of solvents was further investigated (Table S9, entries 5, 10), which are the same level with that
by the dehydration of arabinose or xylose (Table S7, ESI). The over fresh Hβ zeolite.
furfural yield is below 20% in water, whereas it was greatly The effect of reaction time on the conversions of fructose
enhanced when 1, 4-dioxane or GBL was applied as the solvent. and glucose was further investigated (Figure 2). The
conversion of fructose was completed within 60 minutes while
a
80 minutes was required for a quantitative conversion of
Table 4 The conversion of carbohydrates to furfural glucose. The reaction of glucose is slower than that of fructose,
Yield % implying that an isomerization for glucose to fructose is
Entry Substrate Conv. % 10
Furfural HMF LA+FA required in the transformation of glucose to furfural. As
1 Maltose 99.9 45.2 11.9 6.7 glucose and fructose can be produced from cellulose or other
2 Sucrose 99.9 53.7 11.4 9.4 carbohydrates, the above results suggested that the combined
3 Inulin 99.9 62.8 10.2 6.2 Hβ zeolite and GBL-water solvent are likely to convert other
4b Starch 99.9 48.1 13.5 8.7 carbohydrates to furfural efficiently. Therefore, maltose,
5c Cellulose 99.9 38.5 25.6 5.6 sucrose, inulin and starch were applied for producing furfural,
a
: 0.1 g Hβ catalyst; 10 g substrate/GBL-water solution, substrate respectively (Table 4). The furfural yields for these
concentration 5 wt%; water concentration 5 wt%, 2 MPa N2, t=2 h, 150 oC; b: carbohydrates were more than 40%, and the conversion of
0.2 g Hβ catalyst, t=3 h, 170 oC; c: 0.3 g Hβ catalyst, 0.5 g cellulose, 10 g GBL-
o inulin gave a yield of 62.8% for furfural. Sucrose is a
water solvent with water content 5 wt%, t=6 h, 180 C.
disaccharide, and the hydrolysis of sucrose into glucose and
fructose (1:1, mol/mol) is required before its further

4 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

Please do not adjust margins

 Page 5 of 7 Please do notChemistry
Green
Journal Name
transformation into furfural. This suggested to us that the
hydrolysis process may reduce the efficiency of the total
processes, leading to a low yield of furfural. To verify this
assumption, the conversion of mixture of 1.46 mmol fructose
and 1.46 mmol glucose was also investigated. The yield of
furfural is 59.7% (Table S10, in ESI), which is higher than that
from 1.46 mmol sucrose (Table 4, entry 2). This result indicates
the negative effect of the hydrolysis process of sucrose on the
Published on 29 October 2015. Downloaded by National University of Singapore on 03/11/2015 08:49:50.
yield of furfural. As the most abundant biomass, the utilization
of cellulose is of significant importance but highly challenging.
In this study, the production of furfural from cellulose was also
studied. A considerable yield of 38.5% for furfural was
achieved, which is, to date, not reported in literature. This
result shows a great potential of the combined Hβ and GBL-
water system for large-scale producing furfural considering the
abundant of cellulose in nature.
Conclusion
An efficient strategy was proposed for the conversion of
carbohydrates (cellulose, starch, inulin, maltose, sucrose,
glucose and fructose) to furfural by using Hβ zeolite and GBL.
In this work, it was discovered that the key process for the
production of furfural is the selective cleavage of C-C bond in
hexoses to pentoses, while the formation of acyclic hexoses is
required for this C-C bond cleavage. Hβ zeolite can induce the
formation of acyclic hexoses. Solvents affect the interactions
between zeolite acid sites and C=O in fructose. The synergy
between acid sites of Hβ and GBL greatly promotes the
selective cleavage of C-C bond in hexose to pentose. Besides,
GBL can promote the dehydration of pentose into furfural and
suppress the degradation of furfural, favouring a high yield of
furfural. In contrast, the cyclic hexoses incline to dehydrate
into HMF over HY zeolite and other acid catalysts. Furfural
yields for converting fructose and glucose reached 63.5% and
56.5% over Hβ zeolite in GBL-water (5 wt%) at 150 oC,
respectively. The yield of furfural from starch, inulin, maltose
and sucrose reached more than 40%. Moreover, a favourable
yield of 38.5% for furfural can be achieved by direct conversion
of cellulose, indicating the great potential of combined Hβ
zeolite and GBL-water system for industrial production of
furfural.
Experimental Section
All experiments were performed in a batch reactor (30 ml)
with a magnetic stirrer. Typically, sugar (0.5 g) and a certain
volume of solvent were added in the vessel, followed by the
addition of catalyst. Before each run the vessel was sealed and
filled with 2 MPa N2. After the reaction, the vessel was cooled
down. The reaction products were centrifuged for 10 min and
then filtrated to obtain a clear solution. The samples were
analyzed by HPLC (Agilent 1260) with a Shodex SH-1821
capillary column (300 mm × 8 mm × 0.6 μm). Standard
solutions were used to obtain the calibration curves to
calculate concentrations of the compounds by the external
standard method.
Acknowledgements
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins
adjust margins
View Article Online
DOI: 10.1039/C5GC01948F
ARTICLE
The authors gratefully acknowledge the financial support of
the Major State Basic Research Development Program of China
(973 Program) (no. 2012CB215305).
Notes and references
1 a) T. S. Deng, X. J. Cui, Y. Q. Qi, Y. X. Wang, X. L. Hou and Y. L.
Zhu, Chem. Commun., 2012, 48, 5494-5496; b) J. J. Tan, J. L.
Cui, T. S. Deng, X. J. Cui, G. Q. Ding, Y. L. Zhu and Y. W. Li,
ChemCatChem, 2015, 7, 508-512.
2 a) A. Corma, S. Iborra and A. Velty, Chem. Rev., 2007, 107,
Green Chemistry Accepted Manuscript
2411-2502; b) Y. H. Liao, Q. Y. Liu, T. J. Wang, J. X. Long, L.
L. Ma and Q. Zhang, Green Chem., 2014, 16, 3305-3312; c) J.
J. Tan, J. L. Cui, G. Q. Ding, T. S. Deng, Y. L. Zhu and Y. W.
Li, Catal. Sci. Technol., 2015, doi: 10.1039/C5CY01374G.
3 S. Dutta, S. De, B. Saha and Md. I. Alam, Catal. Sci. Technol.,
2012, 2, 2025-2036.
4 H. G. Bernal, L. Bernazzania and A. M. R. Galletti, Green
Chem., 2014, 16, 3734-3740.
5 X. L. Li, J. Deng, J. Shi, T. Pan, C. G. Yu, H. J. Xu and Y. Fu,
Green Chem., 2015, 17, 1038-1046.
6 J. P. Lange, E. van der Heide, J. van Buijtenen and R. Price,
ChemSusChem, 2012, 5, 150-166.
7 a) P. R. Patwardhan, R. C. Brown and B. H. Shanks,
ChemSusChem, 2011, 4, 636-643; b) R. Sahu and P. L.
Dhepe, ChemSusChem, 2012, 5, 751-761.
8 X. Hu, L. P. Wu, Y. Wang, D. Mourant, C. Lievens, R.
Gunawan and C. Z. Li, Green Chem., 2012, 14, 3087-3098.
9 G. C. A. Luijkx, F. van Rantwijk and H. van Bekkum,
Carbohyd. Res., 1993, 242, 131-139.
10 E. I. Gürbüz, J. . R. Gallo, D. M. Alonso, S. G. Wettstein, W. Y.
Lim and J. A. Dumesic, Angew. Chem. Int. Ed., 2013, 52,
1270-1274.
11 Y. R omán-Leshkov, M. Moliner, J. A. Labinger, and M. E.
Davis, Angew. Chem. Int. Ed., 2010, 49, 8954-8957.
12 J. L. Cui, J. J. Tan, T. S. Deng, X. J. Cui, H. Y. Zheng, Y. L. Zhu
and Y. W. Li, Green Chem., 2015, 17, 3084-3089.
13 a) F. M. Jin and H. Enomoto, Energy Environ. Sci., 2011, 4,
382-397; b) T. M. Aida, Y. Sato, M. Watanabe, K. Tajima, T.
Nonaka, H. Hattori and K. Arai, J. Supercrit. Fluids, 2007, 40,
381-388.
14 Y. Takeuchi, F. Jin, A. Kishita and H. Enomoto, Proceedings
of the 14th International Conference on the Properties of
Water and Steam, Maruzen Co. Ltd., 724-728.
15 G. C. A. Luijkx, F. V. Rantwijk, H. V. Bekkum and M. J. Antal,
Carbohyd. Res., 1995, 272, 191-202
16 a) G. Avigad, S. England and I. Listowsky, Carbohyd. Res.,
1970, 14, 365-373; b) D. Steele, J. Lall and J. Pamnani,
Carbohyd. Res., 1984, 133, 313-318; c) V. A. Yaylayan, A. A.
Ismail and S. Mandeville, Carbohyd. Res., 1993, 248, 355-
360.
17 a) M. J. Antal, W. S. L. Mok and G. N. Richards, Carbohyd.
Res., 1990, 199, 91-109; b) M. A. Camblor, A. Corma, S.
Iborra, S. Miquel, J. Primo and S. Valencia, J. Catal., 1997
172, 76-84; c) J. Jae, G. A. Tompsett, A. J. Foster, K. D.
Hammonda, Scott M. Auerbach, R. F. Lobo and G. W. Huber,
J. Catal., 2011, 279, 257–268.
18 J. Y. Guo and X. M. Zhang, Carbohyd. Res., 2004, 339, 1421-
1426.
19 H. Yoshida, Y. Onodera, S. Fujita, H. Kawamori and M. Arai,
Green Chem., 2015, 17, 1877-1883.
20 a) C. E. Hédoire, C. Louisa, A. Davidson, M. Breysse, F.
Maugé and M. Vrinat, J. Catal., 2003, 220, 433-441, b) L. Li,
J. H. Ding, J. G. Jiang, Z. G. Zhu and P. Wu, Chinese J. Catal.,
2015, 36, 820-828.
21 J. N. Chheda, Y. Román-Leshkov and J. A. Dumesic, Green
Chem., 2007, 9, 342-350.
J. Name., 2013, 00, 1-3 | 5
 Please do notChemistry
Green adjust margins Page 6 of 7
View Article Online
DOI: 10.1039/C5GC01948F
ARTICLE Journal Name

22 K. J. Zeitsch, The Chemistry and Technology of Furfural and

its many By-Products, Elsevier, Amsterdam, 2000.
23 M. J. Antal, T. Leesomboon, W. S. Mok and G. N. Richards,
Carbohydr. Res., 1991, 217, 71-85.
24 T. F. Wang, M. W. Noltea and B. H. Shanks, Green Chem.,
2014, 16, 548-572.
25 C. Moreau, R. Durand, D. Peyron, J. Duhamet and P.
Rivalier, Ind. Crops Prod., 1998, 7, 95-99.
Published on 29 October 2015. Downloaded by National University of Singapore on 03/11/2015 08:49:50.

Green Chemistry Accepted Manuscript

6 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

Please do not adjust margins

 Page 7 of 7 Green Chemistry
View Article Online
DOI: 10.1039/C5GC01948F
Published on 29 October 2015. Downloaded by National University of Singapore on 03/11/2015 08:49:50.

Green Chemistry Accepted Manuscript

Cooperative effect of zeolite and solvent enables the efficient conversion of
carbohydrates to furfural via selective cleavage of carbon-carbon bond.