P -Hydroxybenzenesulfonic acid-formaldehyde solid acid resin for the conversion of fructose and glucose to 5-hydroxymethylfurfural

Article abstract of DOI:10.1039/c7ra03155f

A novel solid p-hydroxybenzenesulfonic acid-formaldehyde resin (SPFR) was prepared via a straightforward hydrothermal method. The catalytic properties of SPFR solid acids were evaluated in the dehydration reaction of fructose and glucose to 5-hydroxymethylfurfural (HMF). SEM, TEM, N₂ adsorption-desorption, elemental analysis (EA), thermogravimetric analysis (TGA), and FT-IR were used to explore the effects of catalyst structure and composition on the HMF preparation from fructose. The effects of reaction time and temperature on the dehydration of fructose and glucose were also investigated. An HMF yield as high as 82.6% was achieved from fructose at 140 °C after 30 min, and 33.0% was achieved from glucose at 190 °C in 30 min. Furthermore, the recyclability of SPFR for the HMF production from fructose in 5 cycles was good.

Full text of DOI:10.1039/c7ra03155f

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p-Hydroxybenzenesulfonic acid–formaldehyde
solid acid resin for the conversion of fructose and
glucose to 5-hydroxymethylfurfural†
Cite this: RSC Adv., 2017, 7, 27682
a
a
b
c
d
Wenzhi Li,
Hason Jameel, Hou-min Chang and Gang Pei
Tingwei Zhang, * Haosheng Xin, Mingxue Su, Longlong Ma,*
e
e
a
A novel solid p-hydroxybenzenesulfonic acid–formaldehyde resin (SPFR) was prepared via a straightforward
hydrothermal method. The catalytic properties of SPFR solid acids were evaluated in the dehydration
reaction of fructose and glucose to 5-hydroxymethylfurfural (HMF). SEM, TEM, N
2
adsorption–
desorption, elemental analysis (EA), thermogravimetric analysis (TGA), and FT-IR were used to explore
the effects of catalyst structure and composition on the HMF preparation from fructose. The effects of
reaction time and temperature on the dehydration of fructose and glucose were also investigated. An
Received 17th March 2017
Accepted 9th May 2017
ꢀ
HMF yield as high as 82.6% was achieved from fructose at 140 C after 30 min, and 33.0% was achieved
DOI: 10.1039/c7ra03155f
ꢀ
from glucose at 190 C in 30 min. Furthermore, the recyclability of SPFR for the HMF production from
rsc.li/rsc-advances
fructose in 5 cycles was good.
catalysts, including mineral acids (H
2 4 3 4
SO , H PO , and HCl),
Introduction
metal chlorides (CrCl and AlCl ), and ionic liquids have been
3
3
12–14
In recent years, the utilization of renewable biomass resources applied for the production of HMF.
Li et al. found that 1-
as feedstocks for the production of sustainable biofuels and butyl-3-methylimidazolium bromide, without using any other
valuable chemicals has been regarded as a promising strategy to additive or catalyst, unexpectedly showed catalytic activity in the
deal with limited petroleum reserves and environmental prob- fructose to HMF conversion at mild temperatures, and the yield
1,2
12
lems.
In this context, 5-hydroxymethylfurfural (HMF), of HMF was 95%. In addition, homogeneous catalysts used
a pivotal and versatile biomass-derived platform compound, together with a solid catalyst that contained Brønsted acid sites
plays a crucial role in the synthesis of many ne chemicals, and/or Lewis acid sites were effective in the conversion of
3
–6
15–20
biofuels, liquid alkanes, polymer monomers and solvents.
carbohydrates to HMF.
Zhang et al. developed a hierarchi-
Although the conversion of fructose to HMF is rather compli- cally carbonaceous catalyst with Brønsted–Lewis acid sites,
cated due to the occurrence of a number of side reactions, HMF which was used to prepare HMF from cellulose in the ionic
can be readily obtained via acid-catalyzed dehydration of fruc- liquid 1-butyl-3-methylimidazolium chloride, and an HMF yield
7,8
19
tose because of its fructofuranose structure. However, the of 43.1% was achieved. However, reactor corrosion, difficult
conversion of glucose to HMF is more difficult, and involves an downstream separation of the catalyst and the high cost of ionic
initial isomerization of glucose to fructose, followed by dehy- liquids limited the application of the abovementioned methods
9
–11
dration of fructose to HMF.
for HMF production.
Both homogeneous and heterogeneous catalytic systems
Prompted by the disadvantages of homogeneous catalyst,
were studied for HMF production from hexoses. Homogeneous tremendous efforts have been made for developing heteroge-
neous catalysts for the synthesis of HMF in organic solvents
and/or water. The generated HMF in a heterogeneous catalytic
system remains more stable. The dehydration of fructose over
a
Department of Thermal Science and Energy Engineering, University of Science and
Technology of China, Hefei 230026, PR China. E-mail: ztwei@mail.ustc.edu.cn
b
1
,3,21
a variety of solid catalysts such as functionalized silica,
Institute of Materials and Chemical Engineering, Anhui Jianzhu Univerisity, Hefei
22,23
24
25
carbon-based solid acids,
zeolites, ion-exchange resins,
2
c
30022, PR China
26
27
Department of Chemistry, University of Science and Technology of China, Hefei metal phosphate, and heteropoly acids has been investi-
2
30026, PR China
gated. Alamillo et al. synthesized an ordered mesoporous acid-
functionalized silica catalyst by the introduction of poly
d
CAS Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion,
Chinese Academy of Sciences, Guangzhou 510640, PR China
(vinylpyrrolidone) (PVP). PVP improved the HMF selectivity
e
Department of Forest Biomaterials, North Carolina State University, Raleigh, NC
from fructose, and a HMF yield of 87% was achieved at a rela-
2
†
1
7695-8005, USA
ꢀ
tively low temperature (130 C) in a mixture of tetrahydrofuran
Electronic supplementary information (ESI) available. See DOI:
0.1039/c7ra03155f
28
and water. Mazzotta et al. prepared a porous sulfonated
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2 2
carbonaceous TiO catalyst (Glu-TsOH-Ti) containing Brønsted glucose to HMF were studied in a mixture of GVL/H O. GVL,
and Lewis acid sites by a one-pot hydrothermal method. A good a nontoxic and eco-friendly solvent, may favour the conversion of
9
catalytic activity of Glu-TsOH-Ti in the conversion of fructose to fructose to HMF. In addition, GVL can be separated from the
HMF was evidenced by the high HMF yield of 59% and 99% in reaction media by distillation. The structure and elemental
a methyltetrahydrofuran/H
dimethyl sulfoxide (DMSO), respectively. Previously, our group TEM, N
2
O biphasic solvent system and composition of the SPFR catalysts were characterized by SEM,
29
2
adsorption–desorption isotherms, elemental analysis
synthesized a strong solid Brønsted acid PTSA–POM resin via (EA), thermogravimetric analysis (TGA) and FT-IR, and the effect
copolymerization of paraformaldehyde (POM) and p-toluene- of structure and composition on HMF production from fructose
sulfonic acid (PTSA), which was used for fructose dehydration, were studied. Furthermore, the effect of reaction time and
and a HMF yield of 78.1% was obtained in g-valerolactone temperature on fructose and glucose dehydration were also
7
(
GVL)/H O. Ordomskyet et al. studied the effect of organic studied, along with the reusability of SPFR.
2
solvents on fructose dehydration catalyzed by a series of zeolites
MOR, ZSM-5, BEA, amorphous aluminosilicate) in a bisphasic
system, and found that the addition of methyl isobutyl ketone
(
Experimental
signicantly improved HMF selectivity. Especically, the Formaldehyde solution (AR, 37–40%), acetic acid (GR), acetone
improvement in selectivity decreased in the following order: (AR), and sodium chloride (NaCl, AR) were supplied by Sino-
24
MOR > ZSM-5 > BEA > amorphous aluminosilicate. In pharm Chemical Reagent Co., Ltd. (Shanghai, China). D-
summary, fructose dehydration over solid acids is an efficient (+)-glucose (GC, 99.5%), D-fructose (99%), chitosan (degree of
and convenient way to synthesize HMF.
deacetylation $ 95%), HMF (99%), p-hydroxybenzenesulfonic
Glucose, the most abundant hexose in nature, which can acid hydrate (85%), and sodium hydroxide standard solution
even be obtained from non-edible agricultural and forestry (0.02 M) were purchased from Aladdin Industrial, Inc.
waste, has promising prospects in a number of applications. A (Shanghai, China). GVL (95%) was obtained from LangFang
considerable body of research has been conducted on the Hawk Technology and Development Co., Ltd. All chemicals
transformation of glucose into HMF over heterogeneous cata- were used without further purication.
4–6,30–34
lysts.
Jim ´e nez-Morales et al. prepared the Al-MCM-550
Two kinds of SPFR catalysts with different amounts of PHSA
catalyst, containing Brønsted and Lewis acid sites, for the were synthesized: SPFR-0.38 and SPFR-0.26. In a typical
dehydration of glucose in a MIBK/H O system. A HMF yield of synthetic procedure for SPFR-0.38, 0.45 g of chitosan were
2
3
1
6% and a glucose conversion of 87% were achieved aer added to 30 mL of distilled water (DIW) under constant
50 min at 195 C. Gallo et al. exploited the combination of magnetic stirring, and 0.6 mL of acetic acid were subsequently
ꢀ
35
Amberlyst-70 with Sn-based catalysts (Sn-SBA-15, Sn-beta) for added to completely dissolve chitosan. Aer the addition of
the production of HMF from glucose in different mixed solvent 3.1 g of p-hydroxybenzenesulfonic acid hydrate, mixture was
36
2 2 2
systems (THF/H O, g-hexalactone/H O and GVL/H O). The stirred for ten minutes. Then, 3 mL of formaldehyde solution
combination of Amberlyst-70 with Sn-based catalysts led to were added quickly to the mixture, and stirring was continued
a remarkable enhancement of the HMF selectivity. Sn-beta, with for further 5 minutes. The mixture was sealed in a 50 mL Teon-
ꢀ
higher Lewis acidity, showed a higher HMF selectivity than Sn- lined autoclave, and heated in an oven for 10 h at 120 C (SPFR
SBA-15, and the highest HMF yield, of 63%, was achieved in gels were also successfully synthesized at a larger scale without
a THF/H O system. In general, it is difficult to develop an effi- changing the concentrations of reactants or reaction time).
2
cient heterogeneous catalyst for producing HMF from glucose, Aer cooling down, the product of SPFR lled the reaction
and the synthesis for most of these catalysts is complicated and autoclave, because the autoclave is cylindrical, so nally
4–6
expensive. Therefore, the development of a simple, econom- columned SPFR gels formed. The gels were mashed to a paste,
ical and efficient catalyst for glucose dehydration is of great washed with acetone/DIW once, then washed with plenty of
importance.
DIW several times until the ltrate was neutral, and nally dried
ꢀ
Yu's group developed an energy and time efficient hydro- at 100 C overnight. The gels shrank signicantly during the
thermal method to synthesize a phenol–formaldehyde resin drying process (shrinkage for SPFR-0.38 was more pronounced
37
(PFR), which had interesting mechanical properties. PFR was than for SPFR-0.26). Moreover, the gels developed a brownish
obtained via polymerization of phenol and formaldehyde in colour during the drying process, so polymerization of the SPFR
acetic acid aqueous solution using chitosan as a so template. In gels by condensation must have occurred during drying. The as-
our work, according to Yu's method, a novel and straightforward obtained brownish solids were ground to a powder, and dried at
ꢀ
route for the synthesis of a solid acid resin catalyst was reported, 100 C to a constant weight.
where phenol was substituted with p-hydroxybenzenesulfonic
The microstructure and morphology of SPFR-x was analyzed
acid (PHSA). The as-prepared solid acid resins were named by SEM (FEI Sirion scanning electron microscope) and TEM
SPFR-x, where x is the molar ratio of PHSA to formaldehyde. (JEM 2010 electron microscope). The BET specic surface areas,
Since the raw materials used for the preparation of SPFR are BJH desorption pore diameters and total pore volumes of SPFR-
relatively inexpensive and their synthesis is straightforward, x were obtained based on the N2 adsorption–desorption
their large-scale production is feasible and thus, SPFR may have isotherms, which were recorded using an Autosorb iQ (Quan-
great potential applications in acid catalysis. The catalytic tachrome) device. Thermogravimetric analysis (TGA) was per-
activity of SPFR-x catalysts for the dehydration of fructose and formed on a TGA Q5000 analyzer. FTIR spectra were recorded
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on a Nicolet 8700 instrument (with KBr disks). The elemental resin, a certain content of –SO
3
H groups should be found in the
37,39
composition of the samples was determined with an Elementar resin (ESI, Scheme S1†).
model Vario EL III. The Brønsted acidity of SPFR-0.38 and SPFR- Fig. S1† shows the SEM and TEM images of the SPFR cata-
.26 was measured by acid base titration. The strong acid site lysts (SPFR-0.38 and SPFR-0.26). The majority of particles in
concentration for fresh SPFR-0.38 and SPFR-0.26 were 0.7 mmol SPFR-0.38 exhibited an irregular bulk-like structure with a rela-
38
0
ꢁ1
ꢁ1
g
and 0.23 mmol g , respectively.
tively uniform size. On the other hand, SPFR-0.26 exhibited
The experimental parameters, including the dose of a clustered irregular structure with a much larger particle size.
substrate and catalyst, the amount of solvent, the reaction time, No net-like framework or nanoporous structures were observed
and the temperature, employed in this work were determined in SPFR-0.38 or SPFR-0.26, which was attributed to the thermal
7,9
according to previous studies published by our group. In drying process, in agreement with the results obtained by Yu
37
a typical dehydration experiment, 0.4 g of substrate (glucose or et al. Compared with PTSA–POM, a resin catalyst synthesized
fructose), 0.2 g of SPFR-0.38 and a mixture of GVL/DIW (1.5 mL/ without a template, the particle size of SPFR-0.38 was much
1
5 mL) were added to a 25 mL stainless steel reactor. Then, the smaller and therefore, the dispersibility of SPFR was expected to
reactor was sealed and heated to the target temperature within be better. The textural properties of SPFR-0.38, SPF-0.26 and
0 minutes under magnetic stirring at 500 rpm. Aer reaction PTSA–POM are summarized in Table 1. SPFR catalysts had
3
completion, the reactor was immersed in cool water to quench a small surface area, total pore volume and BJH desorption pore
the reaction immediately. The mixture was ltrated, and the diameter. The surface area and total pore volume of SPFR-0.38

ltrate was dissolved in DIW.
The dissolved samples were analyzed by HPLC (Waters 515 lysts exhibited a similar BJH desorption pore diameter of
pump, equipped with a Waters 2414 refractive index detector 1.42 nm. Also, the surface area and total pore volume of both
were slightly larger than those of SPFR-0.26, and the two cata-
9,38
using a Waters XBridge Amide column; and a Waters 2489 SPFR catalysts were higher than those of PTSA–POM.
ultraviolet detector using a Waters Symmetry C18 column) to The FTIR spectra of SPFR-0.38 and SPFR-0.26 were similar
determine the yield of HMF, as well as fructose and glucose (Fig. 1). The bands at 1040 cm (O]S]O stretching vibration)
ꢁ
1
7,9,38
ꢁ1
conversion.
3
Standard calibration curves were used for the and 1167 cm (SO –H stretching vibration) in the FTIR spectra
quantication of glucose, fructose and HMF in the diluted clearly revealed the presence of sulfonic acid groups in SPFR.
ꢁ1
samples.
The broad band at around 3436 cm was ascribed to the N–H
The HMF yield and selectivity, furfural yield, and glucose and O–H stretching vibrations, which were attributed to the
37
and fructose conversion were dened as follows:
amino groups and phenolic hydroxils in SPFR, respectively.
Table 2 summarizes the elemental composition of the SPFR
catalysts. The H, O and S content in SPFR-0.26 were higher than
in SPFR-0.38. The presence of N in the SPFR catalysts suggested
that a certain amount of chitosan was incorporated. According
HMF yield ¼ (moles of HMF produced/moles of starting glucose
or fructose) ꢂ 100%
HMF selectivity ¼ (HMF yield/glucose or fructose conversion) ꢂ
37
to Yu's work, a reaction between chitosan and SPFR occurred.
1
00%
The O/S ratio in the SPFR catalysts as calculated from the
elemental analysis was greater than 3, indicating that SPFR
catalysts contained other oxygen functional groups.
Fig. 2 shows the weight loss curves of the SPFR catalysts as
obtained by TGA. SPFR-0.38 (Fig. 2A) and SPFR-0.26 (Fig. 2B)
displayed similar weight loss trends, which could be divided
Furfural yield ¼ (moles of furfural produced/moles of starting
fructose) ꢂ 100%
Glucose or fructose conversion ¼ 1 ꢁ (moles of glucose or fruc-
tose in products/moles of starting glucose or fructose) ꢂ 100%
into 3 stages during the decomposition process. In stage 1 (30 to
ꢀ
1
40 C), the weight loss was more pronounced for SPFR-0.38.
The weight loss in this stage corresponded to the evaporation
of water, mainly in the form of physically adsorbed water and
Results and discussion
water weakly bonded to SPFR via hydrogen bonds. In stage 2
ꢀ
Chitosan can dissolve well in an acetic acid solution and form (160 to 410 C), the weight loss was higher for SPFR-0.26, and
a viscous and transparent gel. It can absorb p-hydrox- probably corresponded to the elimination of strongly bonded
ybenzenesulfonic acid (PHSA) and can be cross-linked by water via hydrogen bonds, sulfonic acid groups and thermal
40
ꢀ
formaldehyde. Moreover, PHSA and formaldehyde can poly- decomposition of chitosan. In stage 3 (410 to 760 C), the
merize in an acetic acid solution. This way, chitosan was used as weight loss was again higher for SPFR-0.26, and could be
a template in which formaldehyde reacted with PHSA and chi- attributed to the decomposition and carbonization of the
tosan concurrently. The rapidly generated SPFR micro- phenolic–formaldehyde resin. Throughout the whole process,
molecules gradually deposited on the chitosan template to form more carbonization products formed from the thermal
the SPFR gels. During the hydrothermal process, chitosan gels decomposition of SPFR-0.38. This was ascribed to the higher
were gradually dissolved away, and only SPFR gels were carbon content and the more rigid structure of SPFR-0.38,
retained. The SPFR gels were washed with distilled water (DIW), which is in good agreement with the results obtained by EA,
ꢀ
and nally dried in an oven at 100 C to afford a brownish solid, SEM and TEM. However, SPFR-0.26 was more stable in the low
the SPFR catalyst. Since PHSA was used to prepare the phenolic temperature stage. This may be ascribed to
a further
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Table 1 Textural parameters of SPFR-0.26 and SPFR-0.38
a
2
ꢁ1
b
3
ꢁ1
c
p
d
P
Sample
S
BET (m g
)
V
P
(cm g
)
r
(nm)
r
(nm)
Refs.
SPFR-0.26
SPFR-0.38
PTSA–POM
21.13
27.98
0.4503
23.96
21.65
0.06
0.11
0.001
0.06
0.05
1.42
1.42
—
—
—
11.74
15.48
—
9.70
9.28
This work
This work
38
This work
This work
First used SPFR-0.38
th
5
used SPFR-0.38
a
b
c
d
Multipoint BET. Total pore volume. BJH desorption pore diameter. Average pore diameter.
HMF in GVL/H O. No insoluble polymers or clogging in the
2
reactor were observed during the experiments.
The effect of temperature and reaction time on HMF
production from fructose using SPFR-0.38 as the catalyst was
ꢀ
investigated by performing the reaction at 120–150 C for 10–
50 min. The results, shown in Fig. 3, indicate that SPFR-0.38 is
an effective catalyst for fructose dehydration. In addition, the
reaction temperature and time play a crucial role in the
ꢀ
conversion of fructose to HMF. At a temperature of 120 C for
1
0 min, the HMF yield was of only 32.0%, with a fructose
ꢀ
conversion of 60.2%. At 120 and 130 C, the HMF yield
increased with reaction time. Upon further increasing the
temperature to 140 C, the HMF yield initially increased (for
ꢀ
Fig. 1 FT-IR spectra of SPFR-0.26 and SPFR-0.38.
a reaction time of 10–30 min), and then decreased as reaction
time increased. At 150 C, the HMF yield decreased with reac-
ꢀ
tion time. A higher temperature promoted the formation of
condensation polymerization in SPFR-0.38, which would lead to HMF, but also favoured undesired side reactions. Fructose
a more pronounced weight loss at low temperatures.
conversion increased with time and/or temperature. A HMF
The catalytic activity of the SPFR catalysts was evaluated in yield as high as 82.6% with a fructose conversion of 99.3% was
ꢀ
terms of the dehydration rate of fructose and glucose to form achieved at 140 C in 30 min, and complete conversion was
Table 2 Element composition of SPFR-0.26 and SPFR-0.38
Atomic ratio (%)
S content mmol
g
Strong acid acidity mmol
H /g
ꢁ
1
+
Sample
C
H
O
N
S
SPFR-0.26
SPFR-0.38
29.04
31.99
55.33
53.12
13.87
13.38
0.76
0.53
1.00
0.98
1.48
1.42
0.23
0.7
Fig. 2 Weight loss curves of SPFR-0.38 (A) and SPFR-0.26 (B).
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Fig. 3 Effect of temperature and reaction time on HMF yield (A) and fructose (0.40 g) conversion to HMF (B) in GVL/DIW (10/1 v/v) catalyzed by
SPFR-0.38 (0.20 g).
reached under harsher reaction conditions. Although the vari- with the addition of more water. Furthermore, it was found that
ation trend in the HMF selectivity is complicated, it was the formation of furfural was hindered when water was added,
concluded that a high HMF selectivity of 87.3% and yield of thus promoting HMF formation. Actually, several secondary
ꢀ
6
7.2% can be achieved at 130 C in 20 min (Fig. S2†). Compared reactions were prevented by the addition of water, which would
with the much stronger pure Brønsted acid catalyst PTSA–POM explain the increase in HMF yield. Thus, GVL/DIW is an ideal
ꢁ
1
(
2.4 mmol g ), the HMF yield with SPFR-0.38 was slightly mixture of solvents for HMF production.
higher. This was attributed to the higher dispersibility of SPFR- The recyclability of the SPFR catalysts is very relevant for
.38, which may favour HMF production. As shown in Fig. 4, potential industrial applications. A ve-cycle experiment was
7
0
a small amount of furfural was generated in this reaction conducted to assess the stability of the SPFR catalysts. Aer
system, which is in good agreement with Dumesic et al. each cycle, the used solid acids were washed with DIW and
4
1
ꢀ
studies. Furfural yield increased with temperature and time in acetone, and dried at 80 C. The results of the reusability test are
all experiments. shown in Fig. 5. The yield of HMF decreased from 82.6% to
The effect of adding different amounts of water (0–30 wt%, 64.2% with reused SPFR-0.38 aer ve cycles. The leaching of
+
based on GVL) on HMF production from fructose was studied, H from the SO
3
–H groups during the 5 cycles may be respon-
and the results are shown in Table S1.† The addition of a certain sible for the reduction in the HMF yield. This hypothesis was
ꢁ
1
3
amount of water had a signicant improvement on the veried by the attenuated band at 1167 cm (SO –H stretching
conversion of fructose to HMF, and higher HMF yields were vibration) in the IR spectrum of the catalyst aer 5 cycles. This
obtained compared with the pure GVL solvent system. Upon band was so attenuated that it was almost covered by the band
ꢁ
1
adding 10 wt% water, a HMF yield as high as 82.6% was ach- at 1208 cm (Fig. 2). Furthermore, the surface area, total pore
ieved. However, the conversion of fructose to HMF became slow
Fig. 5 Reusability study for the SPFR catalysts. Reaction conditions:
ꢀ
ꢀ
Fig. 4 Effect of temperature and reaction time on fructose (0.40 g) 0.40 g of fructose, catalyst (0.20 g of SPFR-0.38 or 175 C-treated
conversion to furfural in GVL/DIW (10/1 v/v) catalyzed by SPFR-0.38 SPFR-0.38, 0.30 g of SPFR-0.26), GVL/DIW (10/1 v/v), 140 C, 30 min
(
0.2 g).
reaction time.
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Fig. 6 Effect of temperature and reaction time (A and B) on glucose (0.40 g) conversion to HMF in GVL/DIW (10/1 v/v) catalyzed by SPFR-0.38
0.20 g).
(
volume and average pore diameter of the used catalyst glucose to HMF conversion. When performing the reaction at
ꢀ
decreased, indicating that insoluble byproducts may form and 160 and 170 C, the HMF yield increased with reaction time. By
ꢀ
deposit on the catalyst, blocking the pores (Table 2). This may contrast, when performing the reaction at 180 and 190 C, the
be another reason for the reduction in the HMF yield. However, HMF yield initially increased with time (10–30 min), and
despite this, the recyclability of SPFR-0.38 was still considered thereaer decreased (40–60 min). A high HMF yield of 33.0%
ꢀ
to be good.
with glucose conversion of 97.6% was achieved at 190 C in
SPFR-0.26 was also used for the conversion of fructose to 30 min. Glucose conversion increased as time and temperature
ꢀ
ꢀ
HMF at 140 C for 30 min, but the catalytic activity was low, only increased, and conversion was complete at 190 C and 60 min.
7
0
0.2% HMF yield was obtained even with the use of 0.3 g SPFR- Compared with PTSA–POM, a relatively higher HMF yield was
.26 (Fig. 5). In addition, the recyclability of SPFR-0.26 was poor, obtained using SPFR-0.38. The introduction of nitrogen func-
with a HMF yield of only 16.0% aer the 5th cycle (Fig. 5). tional groups in SPFR may promote glucose isomerization,
7
According to the characterization results, the main differences thereby increasing the yield of HMF.
between SPFR-0.26 and SPFR-0.38 lie in the morphology,
microstructure and Brønsted acidity. Thus, we inferred that the
higher Brønsted acidity and relatively small and uniform
Conclusions
particle size of SPFR-0.38 played a key role in its high catalytic
activity.
Previously, we found that for PTSA–POM, a further drying
treatment at high temperatures signicantly improved thermal
In summary, a novel and highly efficient solid acid resin cata-
lyst, SPFR, was successfully synthesized by a straightforward
hydrothermal route. The catalytic activity of SPFR was evaluated
in the dehydration of fructose and glucose. Different amounts
stability and water resistance. The PTSA–POM catalyst obtained
of PHSA were added for the synthesis of SPFR to obtain SPFR-
by this procedure exhibited a higher catalytic activity in the
0.38 and SPFR-0.26: SPFR-0.38, with a higher acidity, shows
38
furfural production from xylose. Therefore, the catalytic
a better catalytic activity and recyclability for the HMF produc-
tion from fructose than SPFR-0.26. The morphology and
microstructure of the SPFR catalysts plays an important role in
the catalytic activity. A HMF yield as high as 82.6% was obtained
activity of SPFR-0.38 aer a further treatment at a high
ꢀ
temperature (175 C) was examined in a reaction conducted at
ꢀ
1
40 C for 30 min. The additional drying treatment was con-
ꢀ
ducted in an oven at 175 C for 6 h the SPFR-0.38 catalyst that
had previously been dried at 100 C. There was no obvious
ꢀ
from fructose at 140 C in 30 min, and 33.0% was achieved from
ꢀ
ꢀ
glucose at 190 C in 30 min. Compared with PTSA–POM,
distinction in the HMF yield and catalyst reusability between
a relatively higher HMF yield was achieved with SPFR-0.38. This
may be explained by the presence of nitrogen functional groups
in SPFR-0.38, which may promote glucose isomerization. Also,
quite importantly, the recyclability of SPFR-0.38 was good.
ꢀ
the SPFR catalyst dried at 100 C and the same catalyst aer
ꢀ
a further drying treatment at 175 C (Fig. 5), indicating that the
thermal stability and water resistance of SPFR-0.38 was already
ꢀ
optimal aer the drying treatment at 100 C, and a further
thermal treatment was not necessary.
Finally, glucose was used as the substrate for HMF produc- Acknowledgements
tion, and the effect of temperature and reaction time were
studied using SPFR-0.38 as the catalyst. As shown in Fig. 6, the
temperature and time were also important factors for the
This study was nancially supported by the State Key Program
of the National Natural Science Foundation of China
(51536009), the National Key Technology R&D Program of China
This journal is © The Royal Society of Chemistry 2017
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(No. 2015BAD15B06) and the Science and Technological Fund 20 L. Hu, Z. Wu, J. Xu, Y. Sun, L. Lin and S. Liu, Chem. Eng. J.,
of the Anhui Province for Outstanding Youth (1508085J01).
2014, 244, 137–144.
2
2
1 Z. Yang, W. Qi, R. Huang, J. Fang, R. Su and Z. He, Chem.
Eng. J., 2016, 296, 209–216.
2 J. M. R. Gallo, R. Alamillo and J. A. Dumesic, J. Mol. Catal. A:
Chem., 2016, 422, 13–17.
Notes and references
1
H. Hazi, A. N. Chermahini, M. Saraji and 23 J. Zhao, C. M. Zhou, C. He, Y. H. Dai, X. L. Jia and Y. H. Yang,
G. Mohammadnezhad, Chem. Eng. J., 2016, 294, 380–388.
Catal. Today, 2016, 264, 123–130.
G. Tsilomelekis, M. J. Orella, Z. Lin, Z. Cheng, W. Zheng, 24 V. V. Ordomsky, J. Van der Schaaf, J. C. Schouten and
2
V. Nikolakis and D. G. Vlachos, Green Chem., 2016, 18(7),
T. A. Nijhuis, J. Catal., 2012, 287, 68–75.
1983–1993.
25 G. Sampath and S. Kannan, Catal. Commun., 2013, 37, 41–44.
3
4
5
A. N. Chermahini, F. Shahangi, H. A. Dabbagh and M. Saraji, 26 L. Yang, X. Yan, S. Xu, H. Chen, H. Xia and S. Zuo, RSC Adv.,
RSC Adv., 2016, 6(40), 33804–33810.
2015, 5(26), 19900–19906.
P. Zhou and Z. Zhang, Catal. Sci. Technol., 2016, 6(11), 3694– 27 C. Fan, H. Guan, H. Zhang, J. Wang, S. Wang and X. Wang,
712.
Biomass Bioenergy, 2011, 35(7), 2659–2665.
R. J. van Putten, J. C. van der Waal, E. D. De Jong, 28 R. Alamillo, A. J. Crisci, J. M. R. Gallo, S. L. Scott and
3
C. B. Rasrendra, H. J. Heeres and J. G. de Vries, Chem. Rev.,
J. A. Dumesic, Angew. Chem., 2013, 125(39), 10539–10541.
29 M. G. Mazzotta, D. Gupta, B. Saha, A. K. Patra, A. Bhaumik
and M. M. Abu-Omar, ChemSusChem, 2014, 7, 2342–2350.
30 T. D. Swi, H. Nguyen, Z. Erdman, J. S. Kruger, V. Nikolakis
and D. G. Vlachos, J. Catal., 2016, 333, 149–161.
31 X. Yi, I. Delidovich, Z. Sun, S. Wang, X. Wang and
R. Palkovits, Catal. Sci. Technol., 2015, 5(4), 2496–2502.
32 A. Osatiashtiani, A. F. Lee, D. R. Brown, J. A. Melero,
G. Morales and K. Wilson, Catal. Sci. Technol., 2014, 4(2),
333–342.
2013, 113, 1499–1597.
6
7
8
9
A. Mukherjee, M. J. Dumont and V. Raghavan, Biomass
Bioenergy, 2015, 72, 143–183.
W. Li, Z. Xu, T. Zhang, G. Li, H. Jameel, H. M. Chang and
L. Ma, BioResources, 2016, 11(3), 5839–5853.
X. Wang, H. Zhang, J. Ma and Z. H. Ma, RSC Adv., 2016, 6(49),
43152–43158.
T. Zhang, W. Fan, W. Li, Z. Xu, H. Xin, M. Su, Y. Lu and L. Ma,
Energy Technol., 2017, 5, 747–755.
1
1
1
1
1
1
0 A. Takagaki, M. Ohara, S. Nishimura and K. Ebitani, Chem. 33 V. V. Ordomsky, J. van der Schaaf, J. C. Schouten and
Commun., 2009, 41, 6276–6278.
T. A. Nijhuis, ChemSusChem, 2013, 6(9), 1697–1707.
1 E. Nikolla, Y. Rom ´a n-Leshkov, M. Moliner and M. E. Davis, 34 I. Jim ´e nez-Morales, J. Santamar ´ı a-Gonz ´a lez, A. Jim ´e nez-
ACS Catal., 2011, 1, 408–410.
L ´o pez and P. Maireles-Torres, Fuel, 2014, 118, 265–271.
2 Y. N. Li, J. Q. Wang, L. N. He, Z. Z. Yang, A. H. Liu, B. Yu and 35 I. Jimenez-Morales, M. Moreno-Recio, J. Santamaria-
C. R. Luan, Green Chem., 2012, 14(10), 2752–2758.
3 J. N. Chheda, Y. Rom ´a n-Leshkov and J. A. Dumesic, Green
Chem., 2007, 9(4), 342–350.
Gonzalez, P. Maireles-Torres and A. Jim ´e nez-L ´o pez, Appl.
Catal., B, 2015, 164, 70–76.
36 J. M. R. Gallo, D. M. Alonso, M. A. Mellmer and J. A. Dumesic,
Green Chem., 2013, 15, 85–90.
4 Y. Yang, C. W. Hu and M. M. Abu-Omar, Green Chem., 2012,
1
4(2), 509–513.
37 Z. L. Yu, Z. Y. Wu, S. Xin, C. Qiao, Z. Y. Yu, H. P. Cong and
S. H. Yu, Chem. Mater., 2014, 26(24), 6915–6918.
5 V. Choudhary, S. H. Mushrif, C. Ho, A. Anderko,
V. Nikolakis, N. S. Marinkovic, A. I. Frenkel, S. I. Sandler 38 Z. P. Xu, W. Z. Li, Z. J. Du, H. Wu, H. Jameel, H. M. Chang
and D. G. Vlachos, J. Am. Chem. Soc., 2013, 135, 3997–4006.
and L. L. Ma, Bioresour. Technol., 2015, 198, 764–771.
6 B. Kim, J. Jeong, D. Lee, S. Kim, H. J. Yoon, Y. S. Lee and 39 J. M. Li, X. G. Meng, C. W. Hu and J. Du, Bioresour. Technol.,
J. K. Cho, Green Chem., 2011, 13(6), 1503–1506.
2009, 100(3), 1168–1173.
7 Y. Zhang, Y. Chen, Y. Shen, Y. Yan, J. Pan, W. Shi and L. Yu, 40 J. Zawadzki and H. Kaczmarek, Carbohydr. Polym., 2010,
ChemPlusChem, 2016, 81, 108–118.
80(2), 394–400.
8 Y. Li, H. Liu, C. Song, X. Gu, H. Li, W. Zhu, S. Yin and C. Han, 41 E. I. G u¨ rb u¨ z, J. M. R. Gallo, D. M. Alonso, S. G. Wettstein,
1
1
1
1
Bioresour. Technol., 2013, 133, 347–353.
W. Y. Lim and J. A. Dumesic, Angew. Chem., Int. Ed., 2013,
52, 1270–1274.
9 Y. Zhang, Y. Shen, Y. Chen, Y. Yan, J. Pan, Q. Xiong and
L. Yu, Chem. Eng. J., 2016, 294, 222–235.
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