Catalytic Conversion of Glucose into 5-Hydroxymethyl Furfural Over Cu–Cr/ZSM-5 Zeolite

Article abstract of DOI:10.1007/s10562-019-02922-4

Abstract: Cu–Cr/ZSM-5 zeolite catalyst is successfully synthesized by loading Cu and Cr ions in the ZSM-5 zeolite particles using ion-exchange method. The as-obtained zeolite shows impressive efficiency when applied to the transformation reaction of glucose into 5-hydroxymethyl furfural (HMF). Technical conditions that influence HMF yield including solvent, catalyst dosage, reaction temperature, and reaction time are investigated. According to the results, suitable conditions leading to the highest yield of HMF of 50.4% are established. The synthesized Cu–Cr/ZSM-5 catalyst shows promising performance and can be considered as a potential catalyst for direct conversion of glucose to HMF. Biomass materials other than glucose might be of interest for further investigations. Graphic Abstract: Cu–Cr/ZSM-5 zeolite catalyst was prepared and applied for conversion of glucose to 5-hydroxymethyl furfural (HMF). [Figure not available: see fulltext.].

Full text of DOI:10.1007/s10562-019-02922-4

Catalysis Letters
https://doi.org/10.1007/s10562-019-02922-4
Catalytic Conversion of Glucose into 5‑Hydroxymethyl Furfural Over
Cu–Cr/ZSM‑5 Zeolite
Nguyen Hoang Chung1 · Vo Thi Oanh1 · Luong Kim Thoa2 · Phan Huy Hoang1
Received: 21 March 2019 / Accepted: 29 July 2019
© Springer Science+Business Media, LLC, part of Springer Nature 2019
Abstract
Cu–Cr/ZSM-5 zeolite catalyst is successfully synthesized by loading Cu and Cr ions in the ZSM-5 zeolite particles using
ion-exchange method. The as-obtained zeolite shows impressive efciency when applied to the transformation reaction of
glucose into 5-hydroxymethyl furfural (HMF). Technical conditions that infuence HMF yield including solvent, catalyst
dosage, reaction temperature, and reaction time are investigated. According to the results, suitable conditions leading to
the highest yield of HMF of 50.4% are established. The synthesized Cu–Cr/ZSM-5 catalyst shows promising performance
and can be considered as a potential catalyst for direct conversion of glucose to HMF. Biomass materials other than glucose
might be of interest for further investigations.
Graphic Abstract
Cu–Cr/ZSM-5 zeolite catalyst was prepared and applied for conversion of glucose to 5-hydroxymethyl furfural (HMF).
Keywords 5-Hydroxymethyl furfural · Glucose · Cu–Cr/ZSM-5 zeolite · Biomass derivatives
1 Introduction
or biofuels that help decreases the dependence of chemicals
on fossil fuels [1, 2]. Production of HMF from biomass or
cellulose derivatives such as glucose is, therefore, a state-of-
the-art direction that contributes signifcantly to both science
and industry.
5-Hydroxymethyl-furfural (HMF) is an important immediate
compound in chemical industry. HMF can be produced from
lignocellulose and transformed into value-added chemicals
The conversion of biomass and derivatives for produc-
tion of HMF has been investigated widely using diferent
catalysts or catalytic systems [2–4]. Xue et al. [3] have sum-
marized the conversion of glucose and cellulose to HMF
over heterogeneous catalysts. According to that, HMF
could be synthesized from cellulose and glucose over metal
oxides, such as TiO2, ZrO2. The application of zeolites like
H-ZSM-5 or bimodal-HZ-5 were also successfully used for
the dehydration of cellulose in water. More works on HMF
production over heterogeneous catalysts including zeolites,
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s10562-019-02922-4) contains
supplementary material, which is available to authorized users.
* Phan Huy Hoang
hoang.phanhuy@hust.edu.vn
1
School of Chemical Engineering, Hanoi University
of Science and Technology, 1 Dai Co Viet Street, Hanoi,
Vietnam
2
Viet Tri University of Industry, Viet Tri City,
Phu Tho Province, Vietnam
Vol.:(0123456789)
1 3

N. H. Chung et al.
metal oxides and minerals have also been reviewed thor-
oughly by Perez et al. [4]. Chheda et al. [5] used inorganic
acid solutions such as HCl, H2SO4, or H3PO4 for synthe-
sizing HMF and furfural from biomass via hydrolysis and
subsequent dehydration. Their results showed that conver-
sion yield of glucose into HMF was 41% and 48% when the
reaction was catalyzed with HCl and H2SO4, respectively.
When using H3PO4, 43% of HMF was achieved over the raw
material. Lima et al. [6] investigated into the conversion of
polysaccharides to furans using liquid catalyst CrCl3 and
ionic liquid catalyst 1-alkyl-3 methyllimidazolium chloride
([BMIM][Cl]), resulting in high yield of HMF with approx.
91%. HMF was successfully prepared from fructose–glu-
cose mixture using acid catalyst HCl in presence of acetone
and water by Pedersen and co-workers [7]. HMF yield of
approx. 70% was achieved accordingly. In 2015, a study on
the conversion of glucose into HMF using acid salt Hf(OTf)4
in presence of water and HCl by Junjie Li et al. [8] resulted
in up to 60% of HMF. Focussing on efects of solvents used
during the glucose-to-HMF catalytic reaction, Cunshan
Zhou and partners [9] investigated the application of several
catalysts FeCl3·6H2O, CrCl3·6H2O, and AlCl3 in presence
of diferent solvents including H2O, DMSO, and [BMIM]
[Cl]. The highest yield of HMF of 54.4% was achieved when
using CrCl3·6H2O in DMSO. According to Su et al. [1],
the conversion of cellulose into HMF using liquid catalysts
such as mixture of CuCl2 and CrCl2 could yield in HMF of
57.5%, in which concentration of HMF in the product was
up to 96%. However, the application of liquid catalysts has
many drawbacks in catalyst recycling and reproducing, as
well as economic and environmental issues.
sulfonated carbon-based catalyst [11], or sulfonated
sporopollenin [12]. Hu et al. [18] reported the zeolite-
promoted transformation of glucose to 5-HMF in ionic
liquid. Jiménez-Morales et al. [19] developed a process
for selective dehydration of glucose forming 5-HMF
on acidic mesoporous tantalum phosphate catalyst. The
selective dehydration of glucose to HMF in a biphasic
medium (water/methylisobuthylketone) using diferent
catalysts based on mesoporous MCM-41 silica contain-
ing ZrO2 was also performed by Jiménez-Morales’s group
[20]. In another publication, Fang et al. [21] presented an
application of Cr-exchanged montmorillonite K-10 clay
as a solid catalyst for the conversion of carbohydrates into
HMF. SAPO-34 catalyst was prepared by Zhang et al. [22]
and used as catalyst to convert glucose into HMF in the
biomass-based solvent γ-valerolactone (GVL). The nano-
sized mesoporous Al2O3–B2O3 catalysts with diferent
molar ratios of Al/B and sizes were prepared and applied
as solid acids to the catalytic conversion of glucose to
5-hydroxymethylfurfural (HMF) [23].
It is well-known that metal ions once are present in
zeolite catalyst structure, they are able to improve cata-
lytic activity of the zeolite material, which is refected by
enhancements in its pore and surface structure [17]. Among
many available metal catalysts, Cu and Cr ions are proved
to be most efective. These catalysts have shown good per-
formance in the conversion of cellulose or glucose into
HMF resulting in high conversion yield. However, Cu and
Cr ions are used in form of salt solutions, which makes the
catalyst difcult to recover and reuse [1]. The motivation
of this work was, therefore, to take fully advantages ofered
by both zeolitic catalyst and metal catalyst for preparation
of solid acid Cu–Cr/ZSM-5 zeolite catalyst and applying
it to the conversion of glucose into HMF.
Solid catalysts have several advantages over inorganic
(liquid) acid catalysts [7, 8]. First of all, solid catalysts are
recycleable and possess high selectivity leading to fewer by-
products formed during the catalytic reactions. Second, the
reusability of solid catalysts helps reduce energy consump-
tion for the process. Another overview on the developments
and catalytic applications of sulfonic-acid-based mesostruc-
tures (SAMs) has been presented by Doustkhah et al. [10].
Over ten most popular precursors for the sulfonation of
mesoporous structures have been listed, such as fuoro-based
sulfonic acid precursors (F-SAPs), phenylsulfonic acid silox-
ane-based precursors (Ph-SAPs), sulfonic acid-based carbon
mesoporous materials. More works on sulfonated solid acid
catalyst for preparation of furfural from diferent sources of
biomass have also been conducted by Wang et al. [11, 12].
Among several diferent sorts of solid acid catalysts,
zeolite ZSM-5 is one of the most popular ones, which is
efective in organic syntheses [13–17]. Study on zeolite-
catalyzed conversion of carbohydrates into hydroxym-
ethylfurfural (HMF) has been performed popularly and
still drawn much attention. The production of furfural
from D-xylose and xylan was investigated using over
Herein, we reported a promising solid acid catalyst,
Cu–Cr/ZSM-5 for transformation of glucose derived
biomass into HMF with outstanding advantages. In such
processes of biomass conversion that is mentioned above,
solvent also plays an important role. Among a variety of
solvents that can be used, DMSO and THF/H2O are most
efective ones [9]. Therefore, in this work, these solvents
were used for comparison and evaluation. The results pro-
vide a new direction and contribute signifcantly to HMF
synthesis from biomass and biomass derivatives.
2 Experimental
2.1 Materials
Chemicals were all analytical grades and mostly purchased
from Sigma Aldrich such as: CrCl3·6H2O, CuSO4·5H2O,
glucose, DMSO, THF.
1 3

Catalytic Conversion of Glucose into 5-Hydroxymethyl Furfural Over Cu–Cr/ZSM-5 Zeolite
(
)
2.2 Synthesis of Cu–Cr/ZSM‑5 Catalyst
Mole of glucose in products
Starting mole of glucose
Glucose conversion (%) = 1 −
× 100
Mesoporous zeolite ZSM-5 was synthesized according to
the work of Su et al. [1] using CTAB as mesoporogen. Gel
liquor consisting of several components with following ratio
was prepared: TEOS/TPAOP/NaAlO2/KOH/H2O/CTAB=
8/1.05/0.1/0.85/64/500/5. The gel liquor was poured into a
closed 1 L autoclave. It was placed in a roaster, which was
set at 175 °C for a specifc time depending on case study.
After the reaction time, products in form of micro-nano size
solid particles were separated by centrifugation and washed
for several times with distilled water. The obtained zeolite
ZSM-5 was dried at 100 °C and calcined at 550 °C for 8 h.
Chrome and copper ions were introduced to the ZSM-5
structure by ion exchange method. ZSM-5 in powder form
was well stirred in a mixed solution of 2 M CrCl3 and 2 M
CuSO4 at room temperature for 3 h. Solid product was then
washed with distilled water for several times before it was
separated from the solution by centrifugation. The product
was subsequently dried at 105 °C for 8 h and calcined at
550 °C for 5 h. Structural properties and features of the fnal
product were characterized by modern analytical techniques
such as XRD, IR, SEM–EDS.
Mole of HMF in products
HMF yield (%) =
× 100
Starting mole of glucose
3 Results and Discussion
3.1 Characterization of the Synthesized Cu–Cr/
ZSM‑5 Catalyst
Structure of Cu–Cr/ZSM-5 was characterized with XRD.
The result is shown in Fig. 1.
According to Fig. 1, the XRD pattern of Cu–Cr/ZSM-5
zeolite product coincides with that of the parent ZSM-5
zeolite. Comparing the two spectra, it can be seen that
the structure of ZSM-5 remains intact either with Cu or
Cr exchanged into its structure. Cu–Cr/ZSM-5 with high
crystallinity as observed at peaks 2θ = 7 ÷ 10 and 22 ÷ 25
is unchanged after the ion exchange of H with Cu and Cr
inside the ZSM-5 zeolite structure (see Fig. S1, Electronic
Supporting Information). In addition, new peaks appearing
at the 2θ=42, 43, and 50; and 2θ=36, 38, 48, and 59 are
assigned to Cr2O3 and CuO, respectively (see more Figs. S2
and S3, Electronic Supporting Information) [24]. This indi-
cates that Cu–Cr/ZSM-5 zeolite is successfully synthesized.
The obtained zeolite product is highly crystallined with MFI
zeolite structure.
2.3 Conversion of Glucose into HMF Using
the Synthesized Catalyst Cu–Cr/ZSM‑5
The catalytic reaction was taken place in a 150 mL pressur-
ized reactor. 0.5 g (o.d.) of glucose was placed in a beaker. A
specifc amount of catalyst together with 20 mL of solvent
were added. The mixture was then treated with ultrasound for
15 min before it was transferred to the reactor. The reactor was
placed in a glycerin bath, which was set at 120–140 °C and
kept there for 2–8 h according to experimental design. After
reaction time, the reactor was cooled down to room tempera-
ture. Products were separated from each other by centrifuga-
tion. The liquid part was collected and stored in a glass bottle
at 4 °C for sugar analysis using an HPLC (High Performance
Liquid Chromatogaphy) Agilent 1200 system located at the
Laboratory of Food Technology (HUST). Working conditions
were set as follows: temperature 5–50 °C, humidity 5–96%,
and using GLP/GMP compliance as standard. The system is
equipped with a G1322A vacuum pump; an Aminex HPX-
87P column; the stationary phase was in lead form with parti-
cle size of 9 µm, 8% cross linkage; mobile phase was ionized
water, which was fltered through a 0.45 µm flter and degassed,
working well at pH 5–9. Obtained data were analyzed with an
Agilent 2D LC ChemStation software (G2170BA).
IR spectra of the sample revealed all typical bands of
an MFI type zeolite. The bands observed at 450 cm−1 and
550 cm−1 refect internal vibrations of TO (tetrahedrons) and
vibrations of the secondary building units, respectively [13,
17]. Asymmetric stretching vibration of framework Si–O–Si
or Si–O–Al bonds corresponding to the band at 1099 cm−1
was also observed [25]. The IR spectra of Cu–Cr/ZSM-5
zeolite in Fig. 2 showed the presence of a peak at about
660 cm−1 for the Cr containing samples that were tentatively
ascribed to asymmetric vibration of the (Si–O–Cr)n groups
[13, 17]. The absorption peak at 695 cm−1 could be attrib-
uted to vibrational modes of CuO structures [26].
Moreover, the intensity of the band at 3450 cm−1 of
Cu–Cr/ZSM-5 zeolite is weaker than that of the parent
ZSM-5 zeolite. It can be explained that the Cu and Cr spe-
cies migrated the zeolite framework and occupied H+ posi-
tion resulting in decreasing of the intensity of this band [27].
This result is also consistent and confrmed by SEM and
EDS images, which are presented in Fig. 3. As seen from
SEM image (Fig. 3a), particle size of the Cu–Cr/ZSM-5 zeo-
lite is about 400 nm. On the one hand, the Cu–Cr/ZSM-5
zeolite shows high crystallinity, while its shape and size
are relatively uniform. On the other hand, the particles are
The solid catalyst was recovered by washing with dis-
tilled water, ethanol and subsequently dried at 105 °C. HMF
yield and glucose conversion were calculated according to
Hu et al. [18].
1 3

N. H. Chung et al.
Fig. 1 XRD spectrum of (a)
parent ZSM-5 and (b) Cu–Cr/
ZSM-5; (+) and (*) indicate
peak of CuO and Cr2O3, respec-
tively
Fig. 2 IR spectra of parent
ZSM-5 and Cu–Cr/ZSM-5
zeolite catalyst
100
80
60
40
20
0
ZSM-5
Cu-Cr/ZSM-5
3600
3200
2800
2400
2000
1600
1200
800
400
-1
Wavenumbers (cm
)
orthorhombic, which is a typical confguration of ZSM-5
structure.
indicates that Cr and Cu ions are successfully introduced to
the ZSM-5 structure. The ions are present on the surface or
inside pores by replacing H+ ions. This result is consistent
with and complements the analyzed XRD and IR data. It,
therefore, can be concluded that the Cu–Cr/ZSM-5 zeolite is
successfully synthesized by ion exchange method.
In addition, a variety of elements including O, Al, Si, Cr,
and Cu are present as observed in EDS spectrum (Fig. 2b)
of the Cu–Cr/ZSM-5 zeolite. The Cu–Cr/ZSM-5 consists
of approx. 0.2 wt% of Cr, 0.6 wt% of Cu, 45.6 wt% of
Si, and 1 wt% of Al. On the other hand, Si/Al ratio in the
parent ZSM-5 zeolite is 48, no Cu and Cr detected. This
Calculation of BET data (Fig. S4, Electronic Support-
ing Information) shows that the surface area of Cu–Cr/
1 3

Catalytic Conversion of Glucose into 5-Hydroxymethyl Furfural Over Cu–Cr/ZSM-5 Zeolite
Fig. 3 SEM image (a) and EDS spectrum (b) of Cu–Cr/ZSM-5; SEM image of the parent ZSM-5 (c)
ZSM-5 (456 m2 g−1) is slightly smaller than that of the par-
ent ZSM-5 (487 m2 g−1). Similarly, the pore size of Cu–Cr/
ZSM-5 (5.0 nm) is also slightly smaller than that of the par-
ent ZSM-5 (6.1 nm). This indicates that Cu and Cr ions are
dispersed on the surface and/or mitigated into ZSM-5 pores.
NH3-TPD (see Fig. S5, Electronic Supporting Informa-
tion) was used to characterize the concentration and strength
of acid sites by the amount of desorbed NH3 and the location
of desorption peak. It is known that total amount of ammo-
nia desorbed (mmol/g) could correspond to the number of
acid sites of catalysts. The result showed that acidity of the
parent ZSM-5 zeolite is relatively high with acid concen-
tration of 0.3 mmol/g, which is comparable to the results
reported in the literature [14]. The acidity of catalyst after
loading of metal ions is improved with the acid concentra-
tion of the Cu–Cr/ZSM-5 is around 2.35 mmol/g.
ZSM-5 catalyst was applied to a conversion reaction of glu-
cose instead of using traditional catalysts. Factors infuenc-
ing the yield of HMF by catalytic conversion of glucose
including solvent, temperature, catalyst dosage, and time are
investigated to fnd the most suitable reaction conditions.
The main purpose of using solvents is to dissolve reac-
tants making them able to contact well with each other as
well as with catalyst if available, and therefore facilitate the
reaction. In this work, DMSO and THF/H2O solvents were
used alternately, while other parameters were kept constant.
After the reaction, the catalyst was separated from the main
product by centrifugation. The product was subject to HPLC
analysis for determination of the conversion efency. Infu-
ence of solvent on the HMF yield is illustrated in Fig. 4.
As can be seen from Fig. 4, the conversion efciency is
improved remarkably when switching solvent from THF/
H2O to DMSO or in other words solvent infuences obvi-
ously HMF yield. The HMF yield when using THF/H2O is
11.4%, while it is 2.5 times higher (28%) when DMSO was
used. Hydrogen bonds formed between the acidic site of the
Cu–Cr/ZSM-5 and THF, H2O are believed to be the reason
that leads to this phenomenon. These hydrogen bonds would
reduce the acidity and catalytic activity of acidic zeolite cata-
lyst. In addition, low solubility of the reaction mixture in
THF/H2O due to low polarity of the two components also
3.2 Application of the Synthesized Cu–Cr/ZSM‑5
Catalyst for Conversion of Glucose into HMF
The conversion of glucose into HMF includes two steps:
isomerization of glucose to form fructose and followed by
dehydration of the fructose producing HMF. This reaction
is often catalyzed by inorganic acids. In order to determine
catalytic activity of the as-synthesized zeolite, Cu–Cr/
1 3

N. H. Chung et al.
30
20
10
0
30
20
10
0
28
27.6
30
24.8
20
16.2
10
11.4
40
11.4
DMSO
THF/H2O
Solvent
Zeolite Cu-Cr/ZSM-5 dosage (%)
Fig. 4 Infuence of solvent on glucose-to-HMF conversion efciency
(experimental conditions: glucose: 0.5 g, catalyst dosage: 30%; reac-
tion time: 2 h; temperature: 130 °C; solvent volume: 20 mL)
Fig. 5 Infuence of catalyst proportion on HMF yield (experimental
conditions: glucose: 0.5 g; temperature: 130 °C; solvent: 20 mL of
DMSO, time: 2 h)
limits the interaction between the reactants resulting in low
reaction efciency. Furthermore, the presence of water may
negatively afect the fructose dehydration for HMF forma-
tion. Possessing higher polarity than THF and H2O, DMSO
is a great solvent for dissolving reagents like glucose. Thanks
to this property, DMSO facilitates the mixing of glucose
molecules and catalyst. On the other hand, as an anhydrous
solvent, DMSO can absorb water to promote the dehydration
reaction resulting in high conversion efciency. According to
the obtained results, DMSO was chosen for further investiga-
tions including glucose hydrolysis for HMF [9].
transformation reactions. Therefore, in this work, reaction
temperature was varied from 120 to 140 °C to study the
efect of temperature on the conversion yield, while other
conditions were maintained constant. Infuence of reaction
temperature on HMF yield is summarized in Fig. 6.
According data shown in Fig. 6, HMF yield clearly
depends on reaction temperature. Increasing reaction tem-
perature from 120 to 140 °C results in a signifcant increase
in HMF yield from 14.4 to 38.5%, respectively. This can
be explained by the thermodynamics theory. As tempera-
ture rises, difusivity as well as number of efective colli-
sions between reactant molecules and with acid sites of the
catalyst are improved. Reaction temperature is, therefore,
selected at 140 °C for further study.
It is well known that catalyst plays a very important role
in organic syntheses. In this work, efect of catalyst loading
on the acquisition of HMF obtained by glucose conversion
using the Cu–Cr/ZSM-5 catalyst was investigated. Catalyst
dosage was varied from 10 to 40% based on dried weight
of the glucose, while other parameters were kept contstant.
Infuence of catalyst dosage on HMF yield is presented in
Fig. 5.
To investigate the efects of reaction time on the con-
version of glucose into HMF, the conversion reaction was
carried out for diferent periods of time ranging from 2 to
8 h. Other conditions such as solvent, catalyst dosage, and
temperature were kept constant. As seen from Fig. 7, both
It can be seen from Fig. 5, the Cu–Cr/ZSM-5 catalyst
amount has infuenced clearly the glucose conversion for
HMF. Increasing the zeolite dosage from 10 to 20%, HMF
yield is improved dramatically from 16.2 to 24.8%. How-
ever, as the dosage increases from 20 to 30%, the efciency
of HMF acquisition only rises insignifcantly from 24.8 to
27.6%. When using higher amount of the catalyst, i.e. 40%,
HMF yield decreased dramatically. The reason is clear as
using a large amount of catalyst results in partial precipi-
tation and deposition of the catalyst on the bottom of the
reactor. It is, therefore, difcult for the glucose to approach.
In addition, side reactions and adsorption into pores of cata-
lyst particles can also reduce HMF yield. Considering both
efciency and economic issue, the catalyst dosage of 20% is
chosen for further investigations.
40
30
20
10
0
38.5
140
24.8
14.4
120
130
Reaction temperature (ºC)
Fig. 6 Infuence of reaction temperature on HMF yield (experimental
conditions: glucose: 0.5 g; catalyst dosage: 20%; solvent: 20 mL of
DMSO, reaction time: 2 h)
According to thermodynamics law, temperature is one
of the key factors that afect the performance of chemical
1 3

Catalytic Conversion of Glucose into 5-Hydroxymethyl Furfural Over Cu–Cr/ZSM-5 Zeolite
HMF Glucose conversion
catalytic activity and efciency in the glucose conversion.
In addition, suitable conditions for the acquisition of HMF
from glucose have also established. The suitable parameters
are as follows: dosage of Cu–Cr/ZSM-5 zeolite catalyst: 20%
based on dried weight of glucose; reaction temperature:
140 °C; reaction time: 4 h; using DMSO as solvent. Under
these conditions, approx. 50.4% of HMF is achieved from
glucose. The obtained results show that Cu–Cr/HZSM-5
zeolite can be considered as a promising catalyst for con-
version of glucose to HMF as well as for lignocellulosic
processing.
60
40
20
0
66.8
62.7
57.5
52.6
50.4
51.5
43.7
38.5
2
4
6
8
Reaction time (h)
Acknowledgements This work was funded by the Hanoi University of
Science and Technology (HUST) under project number T2019-TĐ-002.
Fig. 7 Infuences of reaction time on yield of HMF and glucose con-
version (experimental conditions: glucose: 0.5 g; catalyst dosage:
20%; solvent: 20 mL of DMSO; temperature: 140 °C)
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4 Conclusions
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