Production of 5-hydroxymethylfurfural from fructose using a spherically fibrous KCC-1 silica catalyst

Article abstract of DOI:10.1039/c6ra03382b

In the present study, fibrous KCC-1 silica nanospheres were synthesized and functionalized with propylsulfonic acid groups and applied as an effectual and reusable catalyst for the production of 5-hydroxymethylfurfural (HMF) from the dehydration of fructose using DMSO as a solvent. The functionalized catalyst was characterized by SEM, TEM, BET, and FT-IR spectroscopy techniques. The effects of various factors such as reaction time, catalyst weight, different solvents and temperature on the formation of HMF has been investigated. Under the optimized conditions (162 °C, 30 min) 67.71% yield and 68.32% selectivity for the HMF at a 99.11% fructose conversion was achieved.

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Production of 5-hydroxymethylfurfural from fructose using spherically
fibrous KCC-1 silica catalyst
Alireza Najafi Chermahini,* Fereshte Shahangi, Hossein A. Dabbagh, Mohammad Saraji,
a
Department of Chemistry, Isfahan University of Technology, 84154-83111 Isfahan, Iran E-
mail: anajafi@cc.iut.ac.ir, Tel/Fax:+983133913250
Abstract:
In the present study, nanosphere fibrous KCCꢀ1 silica was synthesized and functionalized
with propylsulfonic acid groups and applied as effectual and reusable catalyst for production
of 5ꢀhydroxymethylfurfural (HMF) from dehydration of fructose using DMSO as the solvent.
The functionalized catalyst was characterized by SEM, TEM, BET, and FTꢀIR spectroscopy
techniques. The effect of various factors such as reaction time, catalyst weight, different
solvents and temperature on formation of HMF has been investigated. Under the optimized
situation (162 ºC, 30 min) 67.71 % yield and 68.32 % selectivity for the HMF at 99.11 %
fructose conversion achieved.
Keywords: KCCꢀ1, solid acid catalyst, fructose dehydration, 5ꢀhydroxymethylfurfural

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1. Introduction
The world is getting warmer; the environmental pollution is increasing and fossil fuel
resources coming to an end and all these things due to the indiscriminate use of human from
fossil fuels. In addition, the burning of fossil fuels and greenhouse gases are produced which
cause environmental pollution and the disappearance of the ozone layer and eventually,
global and the world warming. Because of this problems, in recent years human thought to
find suitable alternatives to fossil fuels for energy generation, fine chemicals and materials
and transportation fuels [1, 2]. In recent years, dehydration of fructose to 5ꢀ
hydroxymethylfurfural (5ꢀHMF) has gained considerable attention [3ꢀ5]. Because HMF is an
important intermediate for the production of fine chemicals, pharmaceuticals and biofuels,
petrochemical industries, polymer monomer [6,7], solvents and liquid alkanes [8,9]. HMF
can be obtained by the acidꢀcatalyzed dehydration of fructose, glucose, sucrose and cellulose
[10ꢀ14]. The formation of HMF from glucose requires an initial isomerization to fructose,
followed by dehydration of fructose, consequently acid dehydration of glucose to HMF
unselective and has low yield. So, many scientists have preferred fructose for production of
HMF [15ꢀ18]. In spite of the relative simple reaction, dehydration reaction of fructose to
HMF is a very complex reaction because of the possibility of different side reactions. By the
condensation of two molecules of fructose, difructodianhydrides and levulosans are produce
[19]. Polymerization of fructose with itself or with HMF makes insoluble polymers known as
humins [20]. Rehydration of HMF in aqueous mixture yield formic acid and levulinic acid
[21]. So it is notable that for production of 5ꢀHMF in high yield and to avoid byꢀproducts
formation in dehydration reaction of fructose, many parameters should be optimized [22ꢀ24].
In the acidꢀcatalyzed dehydration of fructose, the nature of the solvent is an important factor.
Water is not very selective for the production of HMF due to the possible HMF rehydration
side reaction to levulinic and formic acid that lead to low HMF yield [25ꢀ27]. Ionic liquids

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are the other solvents for dehydration of fructose to hydroxymethylfurfural but using them on
an industrial scale because of economic problems is not favorable [28ꢀ30]. Consequently,
select of inexpensive solvents with favorable properties such as high boiling point and low
viscosity like DMSO is best idea for industrial applications [31ꢀ33]. The other essential issue
in fructose hydrolysis is catalyst. To date, different heterogeneous and homogeneous catalysts
have been proposed for dehydration of fructose to HMF. Homogenous acids such as H2SO4,
HCl, H3PO4 and soluble metal halides are lowꢀpriced and effectual for the dehydration
reaction at high temperature, but they have severe weakness related to the high price of the
catalyst recycling, equipment corrosion and their waste pollutes the environment [34ꢀ36].
Because of catalyst recyclability, facile product separation, high temperature tolerance and
modulation of surface properties (acidity, basicity and pore size) to achieve maximal HMF
selectivities and yields, nowadays the researchers want to use heterogeneous catalysts such as
ion exchange resins [37, 38] zeolites [39ꢀ41], transitionꢀmetal phosphates [42, 43],
heteropolyacids [44, 45], functionalized silicas [46] and sulfated zirconias [47]. Currently,
scientists use mesoporous silica materials as catalyst or catalyst support due to their high
surface area, large pore size and thermal and hydrothermal stabilities for carbohydrate
dehydration. MCMꢀ41 and SBAꢀ15 are two of these mesoporous silica materials that use for
carbohydrate dehydration. Morales et al. synthesized different mesoporous MCMꢀ41 silica
2ꢀ
containing ZrO2for glucose dehydration to HMF [48]. Jiang et al. used SO4 /TiꢀMCMꢀ41
catalyst for conversion of cellulose to HMF [49]. He and coꢀworkers synthesized five
different titanium containing MCMꢀ41 and showed, all these materials improve the
conversion of cellulose to HMF [50]. Lucas et al. examined the effect of Si/Al ratio on the
catalytic activity of AlSBAꢀ15 catalyst for the fructose dehydration to HMF [51].
Mesoporous silicates surfaces are typically covered by silanol groups, which make the
functionalization of the pore surface of the mesoporous materials adjustable. Moreover, the

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surface functionalization of mesoporous silicates could modify the chemical and physical
properties of these materials significantly [52]. Therefore, the surface functionalization of
mesoporous silicates has been intensively investigated. So, some researchers functionalized
mesoporous silicates with propylsulfunic acid and used this catalyst for fructose dehydration.
For example, Crisci et al. used a propylsulfunic acid catalyst supported on SBAꢀ15 silica in
deionized water and MIBK: 2ꢀbutanol as solvent for conversion of fructose to HMF [53].
Crisci et al. in another work used 3ꢀ((3ꢀ(trimethoxysilyl)ꢀpropyl) thio) propaneꢀ1ꢀsulfonic
acid supported on SBAꢀ15 for dehydration of fructose [40]. Guo et al. functionalized SBAꢀ15
with propylsulfunic acid groups and used it as catalyst for the selective synthesized of HMF
from dehydration of fructose in [BMIm]Cl ionic liquid as the solvent [54].
Lately, a new kind of silica nanosphere with unique fibrous morphology, named KCCꢀ1, was
synthesized, which has a high surface area because of the dendritic fibers [55]. In this work,
we used this silica material and functionalized it with propyl sulfonic acid groups to make a
novel acid catalyst for fructose dehydration to HMF.
2. Experimental section
2.1. Chemicals and instruments
Tetraethyl orthosilicate (TEOS> 98%), cetyltrimethyl ammonium bromide (CTAB > 99%),
urea, DMSO, DMF, NMP, DMA, and ethylene glycol were purchased from DaeꢀJung, S.
Korea. Cyclohexane, fructose, toluene, and 1ꢀpentanole were purchased from Merck. (3ꢀ
Mercaptopropyl) trimethoxysilane (MPTMS) was purchased from Aldrich. Deionized water
was used for the preparation of all aqueous solution. All chemicals were used as received.
The synthesized KCCꢀ1 and propylsulfonic acidꢀfunctionalized KCCꢀ1were confirmed by the
corresponding means of characterization. A JASCO Fourier transform infrared (FTꢀIR)ꢀ680
PLUS spectrometer was used to record IR spectra with KBr pellets. The size and morphology

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of the catalyst was evaluated by field emission scanning electron microscopy (FEꢀSEM)
analysis on a HITACHI Sꢀ4160 microscope and highꢀresolution transmission electron
microscopy (HRTEM) was performed on a philips CN120 device. The nitrogen
adsorption/desorption isotherms were measured at liquid nitrogen temperature (ꢀ196 ⁰C)
using a PHSꢀ1020(PHSCHINA) instrument. HMF content was analyzed by high performance
liquid chromatography (HPLC), by using a RIGOL liquid chromatograph equipped with a
quaternary pump (Lꢀ3240), a UVꢀVIS detector (Lꢀ3500), column oven (Lꢀ3400) using a
LICHROSPHER C18 column (125 mm × 4.6 mm × 5 ꢁm), (eluted with methanol : water
10:90 as the mobile phase). The disappearance or conversion of fructose and HMF selectivity
was analyzed by using a HEWLETT PACKARD (SERIES II)liquid chromatograph equipped
with refractive index detector, using a aminꢀNH2 COLUMN (150 mm × 3 mm × 3 ꢁm),
(eluted with acetonitrile : water 75:25 as the mobile phase). Elemental analysis was
performed by Vario EL III.
2.2 Catalyst preparation
2.2.1 Synthesis of KCC-1
The KCCꢀ1 fibrous material was prepared based to the published procedure with some
modification [53]. In order to synthesize KCCꢀ1, at first cetyltrimethyl ammonium bromide
(CTAB 1 g, 0.0027 mol) and urea (0.6 g, 0.01 mol) was dissolved in deionized water. This
solution was stirred for about 3h until all of CTAB was dissolved. Then this solution was
added to solution of tetraethyl orthosilicate (TEOS, 2.5 g, 0.012 mol), cyclohexane (30 mL),
and pentanol (1.5 mL). This mixture was stirred for 30 min at room temperature, and the
resulting solution was refluxed at 120⁰C under stirring in oil bath for 4h. This solution placed
in oven at 80 ºC for 24h. Then the mixture was allowed to cool to room temperature and the
silica formed was isolated by centrifugation (30 min, 6000 rpm), then washed with deionized

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water and acetone repeatedly and airꢀdried for 24 h. The asꢀsynthesized material was then
calcined at 550 ⁰C for six hours in air.
2.2.2. Synthesis of propylsulfonic acid-functionalized KCC-1 (KCC-1-Pr-SO3H)
After calcination, silicas were functionalized with sulfonic acid groups by post grafting
method. For this propose, 1 g of KCCꢀ1 was added to a solution containing 30 mL of toluene
and 1 mL of mercaptopropyltrimethoxysilane (MPTS). The resulting solution was then
refluxed at 120 °C under magnificent for 24 h, then the resulting solid was filtered, washed
with methanol using a soxhlet extractor and dried at 80 °C overnight. For changed thiol
groups into −SO3H ones, 30 mL of 30% hydrogen peroxide was added to solid by permanent
stirring at room temperature for 24 h. The consequential sulfonated solid was centrifuged,
washed with methanol three times, and finally dried at room temperature. Elemental analysis
show 0.20 mmol gꢀ acid loaded on surface of catalyst.
2.3. Catalytic dehydration of fructose.
For fructose dehydration, the catalytic reaction was down in a 10 mL roundꢀbottom flask in
the oil bath with the temperature range of 142ꢀ182⁰C, with a magnetic stirring rate of 800
rpm. The reaction was performed with 3 mL DMSO, 0.25 g fructose and 0.05 g catalyst at
desired temperature (162⁰C) for 15ꢀ150 min of reaction time. After that, the roundꢀbottom
flask was removed from oil bath and cooled to room temperature. Then the sample analysis
was performed by high performance liquid chromatography (HPLC). Fructose conversion
and the yield and selectivity of HMF were calculated according to the following equations:
Mass of starting fructose − mass of remaining fructose × 100
Fructose conversion =
Mass of starting fructose
Moles of produced product × 100
HMF selectivity =
Moles of fructose reacted

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Mole of HMF × 100
HMF yield % =
Initial fructose ꢀmoleꢁ
The identification of products was achieved based on GCꢀMS technique
3. Result and discussion
Scheme 1. Schematic illustration for the synthesis of KCCꢀ1ꢀPrꢀSO3H
3.1. Catalyst synthesis and characterization
The synthesis of KCCꢀ1ꢀPrꢀSO3H involved several steps. A schematic procedure for the
catalyst preparation is shown in (Scheme 1). For look into size details and morphology of
KCCꢀ1, the scanning electron microscopy (SEM) was down. As can be seen in (Fig. 1), the
sample consists of sphere particles with uniform sizes. Highꢀresolution transmission electron
microscopy (HRTEM) was used to found structural details of catalyst (Fig. 2). A closed look
at Fig.2 shows that the catalyst has fibrous morphology. It seems that fibers emergence from
the center of the particle and distributed regularly in all directions. The HRTEM images of
KCCꢀ1ꢀPrꢀSO3H indicate that after modification the morphology of KCCꢀ1 is not change.

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Fig. 1. SEM images of silica nanospheres KCCꢀ1.
Fig. 2.HRTEM images of a) KCCꢀ1 b) KCCꢀ1ꢀPrꢀSO3H.
The FTꢀIR spectra of KCCꢀ1, KCCꢀ1ꢀPrꢀSH and KCCꢀ1ꢀPrꢀSO3H are presented in (Fig. 3).
For KCCꢀ1 the broad absorption bands at 1093 cmꢀ1 and 3745 cmꢀ1 are attributed to SiꢀOꢀSi
unsymmetrical stretching and OH respectively. Two peaks at 808 cmꢀ1 and 464 cmꢀ1 for SiꢀOꢀ
Si symmetrical stretching and bending respectively. The bond at 1627 cmꢀ1 ascribed water
molecules absorbed on the KCCꢀ1 surface. The FTꢀIR spectra of KCCꢀ1ꢀPrꢀSH show another
peak at 2854 cmꢀ1 that can be assigned to the stretching vibrations of aliphatic CꢀH, that

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indicate a successful grafting of mercapto propyl groups on KCCꢀ1 surface. At the FTꢀIR
spectra of KCCꢀ1ꢀPrꢀSO3H catalyst, unsymmetrical and symmetrical stretching of O=S=O
group are respectively at 1110ꢀ1240 cmꢀ1 and 1020 ꢀ1080 cmꢀ1, but in the present spectra this
peaks are overlapped with broad stretching bond of SiꢀOꢀSi. The band at 2982 cmꢀ1 can be
assigned to the stretching vibrations of aliphatic CꢀH bonds.
Fig. 3. FTꢀIR spectra of (a) KCCꢀ1 (b) KCCꢀ1ꢀPrꢀSH (c) KCCꢀ1ꢀPrꢀSO3H.
The respectively N2 adsorption/desorption isotherms of KCCꢀ1 and KCCꢀ1ꢀPrꢀSO3H
materials are presented in (Fig. 4). KCCꢀ1 and KCCꢀ1ꢀPrꢀSO3H show analogous IV
isotherms and typical H1ꢀhysteresis loops, demonstrating the mesoporous character of KCCꢀ1
and KCCꢀ1ꢀPrꢀSO3H materials. The textural properties of KCCꢀ1 and KCCꢀ1ꢀPrꢀSO3H are

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summarized in Table 1. It is obvious that the related BET surface area and pore volume of
KCCꢀ1ꢀPrꢀSO3H decrease after functionalization.
Fig. 4. N2 adsorption and desorption isotherm of (a) KCCꢀ1 and (b) KCCꢀ1ꢀPrꢀSO3H.
Table 1
Textural parameters of KCCꢀ1 and KCCꢀ1ꢀPrꢀSO3H.
Sample
SBET (m2gꢀ1)
VP (cm3 gꢀ1)
rp (nm)
KCCꢀ1
KCCꢀ1ꢀPrꢀSO3H
781.36
612.32
2.18
1.47
4.60
4.40
3.2. Acid catalyzed dehydration of fructose
In the present study, our aim is to conversion of fructose to HMF with KCCꢀ1ꢀPrꢀSO3H.
Scheme 2 shows dehydration of fructose to HMF can yields different products. Since the
reaction is related to various parameters, in following the effect of these factors was
evaluated.

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HO
O
HO
OH
OH
HO
O
O
O
H+
H+
H+
H
H
OH
H
H
OH
ꢀH2O
ꢀH2O
ꢀH2O
H
H
OH
H
H
HO
H
HO
HO
O
HO
O
H
H+ , + 2 H2O
Condensation products
HMF
O
Polymers , humins
HO
O
HO
+
O
Levulinic acid
Formic acid
Scheme 2. Acidꢀcatalyzed dehydration of fructose to HMF and possible by products.
3.2.1. The effect of reaction temperature
At first the dehydration reaction of fructose with KCCꢀ1ꢀPrꢀSO3H was evaluated at different
temperatures that range from 142ꢀ182 ⁰C. The results in (Fig. 5) show that the yield and
selectivity of HMF and conversion of fructose in dehydration reaction of fructose related to
reaction temperature. A closer look at the (Fig. 5) reveals that with increase the reaction
temperature from 142 ⁰C to 162 ⁰C yield and selectivity of HMF increase from 58.08 to
67.71 and 63.42 to 68.32, respectively. But, at the higher temperature (172ꢀ182 ⁰C) both yield
and selectivity of HMF decreases (64.64 to 64.44 and 65.20 to 65.14 respectively). At the
relative low temperatures byꢀproduct formation is negligible, but at the same time for higher
temperature byꢀproduct formation is serious. Consequently, both yield and selectivity of
HMF decrease at higher temperatures. So temperature of 162 ⁰C was selected as optimum
temperature for the fructose dehydration to HMF over KCCꢀ1ꢀPrꢀSO3H.

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Fig. 5. Effect of temperature on dehydration of fructose with KCCꢀ1ꢀPrꢀSO3H catalyst.
3.2.2. The effect of the fructose catalyst ratios
In the following, the effect of different amounts of catalyst was examined. Thus, three
different fructose /catalyst ratios of 3, 5, 10 (fructose = 0.25, catalyst = 25, 50 and 83 mg)
was selected. The results in the (Fig. 6) show that fructose conversion is nearly constant, but
HMF yield and selectivity increased for catalyst weights of 50 mg and 83 mg. This attributed
to increase in the number of active sites of catalyst. Therefore, 50 mg of catalyst was found to
be the best amount for this reaction.

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Fig. 6. Effect of catalyst weight on dehydration of fructose with KCCꢀ1ꢀPrꢀSO3H catalyst.
3.2.1. The effect of reaction time
In the following, a series of dehydration reaction of fructose was done at different time ranges
from 15 min to 150 min. The results in presented in (Fig. 7) show that the yield and
selectivity of HMF in dehydration reaction of fructose are greatly depend on time of reaction.
With increase the reaction time from 15 to 30 min, yield and selectivity of HMF increase
from 60.74 to 67.71 and 61.54 to 68.32 respectively. However, by increasing the reaction
time from 60 min to 150 min HMF yields and selectivity slowly reduced. With increasing
time, the probability of occurrence of side reactions and humins production increase (The
reaction mixture becomes dark brown). Humins placed on the catalyst surface and covered
active sites of catalyst as a result HMF yields and selectivity slowly reduced. Consequently,
30 min was selected as ideal time for fructose dehydration to HMF with KCCꢀ1ꢀPrꢀSO3H. For
more evaluation of effect of the solid acid catalyst in the reaction, dehydration reaction of
fructose was done without catalyst. Under the optimized condition (162 ºC, 30 min), 50.57 %
yield and 50.82 % selectivity for HMF was observed. The HMF yield about 17.14% and
HMF selectivity is about 17.5% lower than the reaction with solid acid catalyst.

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Fig. 7. Effect of time on dehydration of fructose with KCCꢀ1ꢀPrꢀSO3H catalyst.
3.2.4. The effect of solvent
The effect of solvent on dehydration of fructose is considered by using different polar solvent
such as Dimethylformamide (DMF), Dimethylacetamide (DMAC), NꢀMethylꢀ2ꢀpyrrolidone
(NMP) and ethylene glycol. Results are shown in (Table 2). Among the various solvent
(DMSO) show best yield and selectivity of HMF and conversion of fructose in dehydration
reaction of fructose. And other solvent have not significant yield. Thus we concluded that in
addition of polarity, boiling point of solvent is an important factor for this reaction.
Table 2
Effect of different solvents on dehydration of fructose with KCCꢀ1ꢀPrꢀSO3H catalyst.
Solvent
Boiling Point (ºC)
Yield (%)
Selectivity (%)
Conversion (%)
DMSO
NMP
189
67.71
56.72
6.10
1.3
68.32
57.15
7.39
99.11
99.24
81.86
57.6
202ꢀ204
165
DMAc
DMF
153
2.26
Ethylene glycol 197.3
0.84
0.84
99.5

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4. The reusability of catalyst
In the developing of heterogeneous catalysts for carbohydrate dehydration, the catalyst
reusability is an essential factor. Therefore, the reusability of catalyst was considered over
four extra cycles. As shown in (Fig. 8), no significant loose of HMF yield was observed. It
means that the grafted propylsulfonic acids have low leach during the process. Also, the HMF
selectivity decrease slowly from 68.32 to 55.31 for first and forth cycle and decrease in
fructose conversion was also small (99.11 for first and 97.66 for forth cycle of reaction). It is
also important to note that this catalyst can be reused by easily separation with centrifugation
of the reaction mixture, followed by simple washing with deionized water and dried in the
oven.
Fig.8. Reusability test of catalyst for fructose dehydration.
The TEM images of reused catalyst in different magnifications are presented in Fig. 9. The
images of KCCꢀ1ꢀPrꢀSO3H show that the morphology of recycled catalyst is not change after
four cycles.

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Fig. 9. TEM images of recycled KCCꢀ1ꢀPrꢀSO3H after four cycles.
4. Conclusions
KCCꢀ1ꢀPrꢀSO3H synthesized and characterized using various techniques. The heterogeneous
catalyst was used for the selective synthesis of HMF from dehydration of fructose using
DMSO as the solvent. The optimum conditions consists 67.71 % yield of HMF with 68.32
selectivity and 99.11 conversions were obtained for 30 min at 162 ºC. When NMP was used
as the solvent good yields was obtained. Compared with other work that has been done in this
area, although the acid loading on our catalyst surface was low, but the result was acceptable.
This good result is due to the unique dendritic fibrous morphology of the support, which
made the active site accessible. The catalyst was simply reusable and offer environmentally
friendly process for heterogeneous catalytic manufacture of 5ꢀHMF.

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Acknowledgments
The authors wish to acknowledge the financial supports from the Isfahan University of
Technology (Iran) for the research work. In addition, authors would like to thanks the Iranian
National Science Foundation (INSF) for financial support of this work.
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