Dehydration of fructose into 5-hydroxymethylfurfural catalyzed by phosphorylated activated carbon catalyst

Article abstract of DOI:10.14233/ajchem.2015.18344

Surface functionalized activated carbon catalysts with phosphate group were synthesized and used to catalyze dehydration of fructose into 5-hydroxymethylfurfural. The surface oxygen-containing functional groups of phosphorylated activated carbon were characterized and analyzed by XPS, infrared spectroscopy and Boehm titration techniques. The catalysts exhibit high dehydration activity of fructose but low 5-hydroxymethylfurfural selectivity using water as the solvent. Organic solvent can effectively improve the 5-hydroxymethylfurfural selectivity and yield. The highest 5-hydroxymethylfurfural yield of 66.6 % was achieved using DMSO as the solvent at 160 °C for 30 min. It was found that the amount of phosphate group is correlated with the fructose conversion, but higher concentration of phosphate group leads to the decrease of 5-hydroxymethylfurfural selectivity.

Full text of DOI:10.14233/ajchem.2015.18344

Asian Journal of Chemistry; Vol. 27, No. 8 (2015), 2979-2982
A
SIAN
J
OURNAL OF HEMISTRY
C
http://dx.doi.org/10.14233/ajchem.2015.18344
Dehydration of Fructose into 5-Hydroxymethylfurfural
Catalyzed by Phosphorylated Activated Carbon Catalyst
*
LI YANG, MIAOFENG WANG, XIAOPEI YAN, YILAN WANG and HAIAN XIA
Jiangsu Key Lab of Biomass-Based Green Fuels and Chemicals, College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037,
P.R. China
*
Corresponding author: Fax: +86 411 85428873; Tel: +86 25 85427635; E-mail: haxia@dicp.ac.cn
Received: 18 June 2014; Accepted: 11 September 2014; Published online: 27 April 2015;
AJC-17176
Surface functionalized activated carbon catalysts with phosphate group were synthesized and used to catalyze dehydration of fructose
into 5-hydroxymethylfurfural. The surface oxygen-containing functional groups of phosphorylated activated carbon were characterized
and analyzed by XPS, infrared spectroscopy and Boehm titration techniques. The catalysts exhibit high dehydration activity of fructose
but low 5-hydroxymethylfurfural selectivity using water as the solvent. Organic solvent can effectively improve the 5-hydroxymethylfurfural
selectivity and yield. The highest 5-hydroxymethylfurfural yield of 66.6 % was achieved using DMSO as the solvent at 160 °C for 30 min.
It was found that the amount of phosphate group is correlated with the fructose conversion, but higher concentration of phosphate group
leads to the decrease of 5-hydroxymethylfurfural selectivity.
Keywords: Phosphorylated activated carbon, Fructose dehydration, 5-Hydroxymethylfurfural, Phosphate.
In this work, we use a novel phosphate group functionalized
activated carbon, phosphorylated activated carbon, to catalyze
dehydration of fructose to produce 5-hydroxymethylfurfural.
The surface properties of the functionalized activated carbon
were tailored through the incorporation of different concen-
tration of phosphate group. The catalytic activities of these
materials were evaluated by the fructose dehydration using
INTRODUCTION
In recent years, much effort has been taken to the develop-
ment of alternatives to the fossil-based industry of today. The
development of a new, long term, environmentally friendly
and sustainable chemical source has received wide attention.
5
-Hydroxymethylfurfural, a versatile and key renewable plat-
form chemical produced from biomass feedstock, can be trans-
formed into fuels and various valuable chemicals through catalytic
conversion, such as the gasoline additives-2,5-dimethylfuran
H O and DMSO as the solvents. The relationship of the activity
2
and selectivity of these samples with the amount of surface
oxygen-containing functional groups is discussed.
(
DMF), an alternative polymer precursor-2,5-furandicar-
1
-16
EXPERIMENTAL
boxylic acid (FDCA) and levulinic acid
.
In past years, the production of 5-hydroxymethylfurfural
was performed by mineral acid-catalyzed hydration of biomass,
Preparation of catalysts: The preparation of phospho-
rylated activated carbon is similar to the method reported in
1,17,18
32
such as glucose, fructose and inulin
. The drawback of mineral
the literature . Coconut activated carbon was used as support.
acid is that it leads to the severe environmental pollution. In recent
years, some novel and green methods have been developed. Ionic
liquid system is a hot topic due to excellent catalytic performance
of producing high yield of 5-hydroxymethylfurfural yield
The support was impregnated with aqueous solution of H
at room temperature and then the mixture was stirred for 2 h.
Subsequently, water was removed from the mixture through
heating it at 90 °C. The dry samples were activated under N
flow in a quatz reactor heated by tubular furnace. Different
activation temperatures [350, 450 and 550 °C and impregnation
3
PO
4
2
19-23
through catalytic hydrolysis of biomass feedstock . In addition,
2
4
heterogeneous solid acid catalysts, such as sulfated zirconia
25-28
and acid zeolite , have been also attracted wide attention.Among
all the solid acid catalyst suitable for aqueous reactions, sulfonated
carbon materials have received much attention since its surface
acidity and the hydrophilic/hydrophobic character are easily tuned
ratios (1 and 0.5)], defined as H
to synthesize the samples with different amount of phosphate
group. The calcined samples were cooled under N flow and
3 4
PO /AC weight ratio, were used
2
then washed with distilled water until neutral pH and dried at
120 °C overnight. The activated carbon obtained are denoted
29-31
and it has more stable at hydrothermal reaction condition
.

2
980 Yang et al.
Asian J. Chem.
by the letterAC-x-T, where x and T correspond to the impreg-
nation ratio and the activation temperature in degree celsius,
respectively.
Catalyst characterization: X-Ray photoelectron spectro-
scopy (XPS) was carried out on anAXIS ULTRA DLD instru-
is achieved using water as the solvent at 140 °C for 30 min.
When H
3
PO is used as the catalyst at 140 °C, the fructose
4
conversion is about 96.8 % and the 5-hydroxymethylfurfural
yield is 38.9 %. The reason is that the acid strength of phosphate
group anchored activated carbon is weaker than H
3
PO ,
4
ment (SHIMADZU company) using Al K
mine the oxygen-containing functional groups and the value-
state of phosphorus elements. The samples were pressed into
a sample holder and then were evacuated to 10 Pa. The spectra
were analyzed and processed with the use of XPSpeak software.
Boehm titrations was used to quantify surface oxygen-
containing functional groups on activated carbon . Surface
oxygen-containing functional groups including carboxyl
α
radiation to deter-
resulting in a decrease in the activity of phosphorylated
activated carbon sample. The influence of the reaction time
on fructose conversion as well as 5-hydroxymethylfurfural
yield and selectivity was also analyzed. As can be seen from
Table 1, the fructose conversion increases but the 5-hydroxy-
methylfurfural yield and selectivity decrease with increasing
the reaction temperature. This is because 5-hydroxy-
methylfurfural can be further rehydrated to produce levulinic
acid and polymerized into humin, leading to a decrease of
5-hydroxymethylfurfural yield and selectivity. It was reported
that DMSO can effectively inhibit the degradation of 5-hydroxy-
methylfurfural to by-products, thus DMSO was selected as
-6
33
(
R-COOH), lactone (R-OCO), phenol (Ar-OH) and carbonyl
groups were determined using different reactants. The proce-
dure was described as follows: 0.10 g of each sample was mixed
in a closed flask with 50 mL of a 0.1 mol/L aqueous reactant
9,35,36
solution (NaOH, Na
2
CO
3
3
or NaHCO ). The mixtures were shaken
the reaction solvent
. As DMSO was used as the solvent,
for 24 h at room temperature and then filtered off. Back-
titrations of the filtrate were then carried out with standard
HCl (0.01 mol/L) to determine the oxygenated functional
group contents.
the 5-hydroxymethylfurfural yield and selectivity achieve
about 60.1 and 68.2 % at 140 °C and the highest 5-hydroxy-
methylfurfural yield and selectivity achieve 66.6 % and 79.1 %
at 160 °C, respectively.
Catalytic reaction: Reactions were conducted in a 100
mL autoclave equipped with a thermostat and an electronically
XPS has been shown to be a useful tool for analyzing the
surface oxygenated functional groups of carbon materials. It
allows for semi-quantitative analysis of surface oxygenated
functional groups by measuring the shift in binding energy
and thus the local chemical state. Fig. 1a presents the XPS
results of C1s excitation of AC-0.5-450. The spectra were
deconvoluted into five components according to the literature
controlled magnetic stirrer charged with N (5 bar). The
2
fructose concentration of 2 wt % was used as the feedstock
and the catalyst (substrate/catalyst = 4/1 wt/wt) were mixed in
solvent (total volume 50 mL). The reactor was pressurized
at 5 bar of N and ramped to desired temperature. Once the
2
37
reaction temperature was reached, the monitoring of the
reaction started. The catalysts were removed periodically and
analyzed by high-performance liquid chromatography (HPLC)
using a column (Zorbax SB-C18) with UV detector to analyze
results . The components are assigned to carbide, graphitic
carbon, carbon species in ether groups and alcohol, carbon in
37
carbonyl groups, carboxyl and/or ester groups , their corres-
ponding binding energies and area percentages as illustrated
in Table-2. It can be seen that the amounts of carboxyl group
and R-OH+C-O-C or C-O-P of AC-0.5-450 are greater than
three other samples. Fig. 1b indicates the XPS results of P 2p
excitation of AC-0.5-450. The phosphorous spectra can be
convoluted into two peaks at 132.9 and 133.8 eV attributed to
5
-hydroxymethylfurfural yield. Aqueous solution was used
as a flow phase. The quantitative analysis of 5-hydroxy-
methylfurfural was performed by external standard method.
The reducing sugar was detected by DNS method according
34
to the reference .
32
tetra coordinated phosphorus (PO tetrahedra) . It is noted
4
RESULTS AND DISCUSSION
that XPS results of three other samples are similar to that of
AC-0.5-450 (not shown), suggesting that the samples contain
mainly phosphate groups.
Table-1 shows effect of reaction temperature, water and
solvent on the dehydration reaction of fructose catalyzed by
AC-0.5-450. It can be seen that phosphorylated activated
carbon could effectively catalyze the dehydration of fructose
into 5-hydroxymethylfurfural. The fructose conversion increases
with the reaction temperature, but the 5-hydroxymethylfurfural
yield does not always increase and its highest yield of 29.6 %
To further identify the nature of the oxygen-containing
functional groups over phosphorylated activated carbon, IR
spectroscopy was conducted (Fig. 2). As can be seen from
-1
Fig. 2, two weak bands at 3435 and 1146 cm are observed
for the activated carbon catalyst (Fig. 2a), while four IR peaks
TABLE-1
FRUCTOSE CONVERSION, YIELD OF 5-HYDROXYMETHYLFURFURAL, AND 5-HYDROXYMETHYLFURFURAL SELECTIVITY
IN THE DEHYDRATION OF FRUCTOSE CATALYZED BY AC-0.5-450 USING WATER AND DMSO AS SOLVENTS
o
Catalyst
AC-0.5-450
AC-0.5-450
AC-0.5-450
AC-0.5-450
AC-0.5-450
AC-0.5-450
AC-0.5-450
Temperature ( C)
Time (min)
Solvent
Conversion (%)
47.4
5-HMF yield (%)
5-HMF selectivity (%)
120
140
160
140
140
140
160
140
30
30
30
60
90
30
30
30
H O
18.2
29.6
28.5
28.1
21.9
60.1
66.6
43.7
38.4
35.0
30.7
32.6
23.9
68.2
79.1
44.8
2
H O
84.5
92.8
86.1
91.6
88.1
84.2
97.4
2
H O
2
H O
2
H O
2
DMSO
DMSO
H O
2
H PO4
3

Vol. 27, No. 8 (2015)
Dehydration of Fructose into 5-Hydroxymethylfurfural 2981
(A)
(e)
B
C
(d)
c)
A
(
D
E
(
b)
a)
294
292
290
288
286
284
282
280
Binding energy (eV)
(
1146
(B)
4
000
3500
3000
Wavenumber (cm )
Fig. 2. IR spectra of (a) AC and phosphorylated activated carbon: (b) AC-
.5-450; (c) AC-1-350; (d) AC-1-450; (e) AC-1-550
2500
2000
1500
1000
–
1
0
2P3/2
that the samples contain phosphate group and polyphosphates
after H PO treatment.
3
4
To further explore the impact of surface oxygenated
groups of the catalysts on the fructose conversion, 5-hydroxy-
methylfurfural yield and 5-hydroxymethylfurfural selectivity,
Boehm titration method was utilized to quantitatively analyze
the amounts of surface oxygenated functional groups.
2P1/2
Table-3 represents the concentration of the surface oxyge-
nated functional groups of these samples. Boehm titration
results show that AC-0.5-450 has more strong acid sites in
comparison with three other samples, which is good agreement
with XPS results (Table-2). The phosphorus content increases
with increasing the calcination temperature, suggesting high
temperature activation favors the formation of C-O-P bond.
Fig. 3 shows the correlation of fructose conversion, 5-
hydroxymethylfurfural yield and selectivity with the surface
oxygenated functional groups. It seems that the activity of the
sample is correlated with the phosphorous content, while
5-hydroxymethylfurfural selectivity is not associated with the
phosphorous content. It should be noted that no remarkable
correlation is observed between the fructose conversion and
the amount of carboxyl, lactonic and phenolic acid groups
measured by Boehm titrations (Table-3). As well known, the
1
42 140 138 136 134 132 130 128 126 124
Binding energy (eV)
Fig. 1. X-Ray photoelectron spectrum of (A) C1s and (B) P 2p peaks of
AC-0.5-450. For details see Table-2
-1
appear at 3435, 1588, 1175 and 1066 cm after the treatment
-1
by H
3
PO . The band at 1175 cm is assigned to the stretching
4
vibration of hydrogen-bond P=O groups from phosphates and
polyphosphates of O-C stretching vibrations in the P-O-C
linkage and of O=P-OH groups . This result support the results
discussed in the XPS analysis. Moreover, it is observed that the
intensity of the band at 1175 cm increases with the phosphorous
content. The band at 1066 cm is ascribed to P-O- in acid phos-
phate esters and the symmetrical vibration in polyphosphate
32
-1
-1
32
chain P-O-P . Thus, IR spectral result further demonstrates
TABLE-2
DEVOLUTION RESULTS OF XPS SPECTRA OF THE SAMPLES
AC-0.5-450 AC-1-350 AC-1-450
P (eV) P (eV) P (eV)
AC-1-550
P (eV)
283.7
284.2
284.7
285.7
288.5
Assignment
A (%)
16.9
27.9
23.5
17.1
14.5
A (%)
6.4
A (%)
12.02
52.1
12.8
10.4
A (%)
15.5
41.0
15.5
13.1
12.3
Carbide
Graphite
R-OH+C-O-C or C-O-P
C=O + >C=O
283.8
284.2
284.6
285.7
288.6
283.7
284.2
284.6
285.8
288.7
83.7
284.3
285.0
286.1
288.9
34.1
23.4
16.4
13.2
COOH+ C-O-C
12.6
P-Position; A-Area percent

2
982 Yang et al.
Asian J. Chem.
TABLE-3
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