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Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom
a r t i c l e
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Article history:
Received 14 December 2008
Received in revised form 3 April 2009
Accepted 14 April 2009
Available online 24 April 2009
Keywords:
Glucose
5-Hydroxymethylfurfural
SO42/ZrO2
SO42/ZrO2Al2O3
a b s t r a c t
SO42/ZrO2 and SO42/ZrO2Al2O3 catalysts were prepared by impregnation of Zr(OH)4 and Zr(OH)4
Al(OH)3 with ethylene dichloride solution of chlorosulfonic acid, and characterized by ICP-AES, BET,
XRD, NH3-TPD, CO2-TPD and FTIR of adsorbed pyridine. The catalysts were used in the catalytic conversion of glucose to 5-hydroxymethylfurfural. An optimized 5-hydroxymethylfurfural yield of 47.6% was
obtained within 4 h at 403 K over SO42/ZrO2Al2O3 with ZrAl mole ratio of 1:1. The catalyst with higher
acidity and moderate basicity was more favorable for the formation of the target product.
2009 Published by Elsevier B.V.
1. Introduction
Increasing interest has been devoted in recent years to the
selective dehydration of hexose to 5-hydroxymethylfurfural
(HMF) [14], as HMF and its derivatives have potential applications
in the production of ne chemicals, pharmaceuticals, plastics [3]
and liquid alkanes [5]. HMF could be formed with high yield by
the acid-catalyzed dehydration of fructose [1,69]. However, one
of the key problems for the use of fructose is its high cost. Another
hexose, glucose, which is the unit compound of cellulose, is one of
the most important starting chemicals from biomass. With its low
cost and wide supply, the conversion of glucose to HMF has attracted the interests of researchers [2,1013]. For gaining a high
HMF yield, the choice of catalysts is very important. Several kinds
of catalysts, such as CrCl2 in the 1-alkyl-3-methylimidazolium
chloride [2], H2SO4 [9], and TiO2 (anatase) [10,12,13] were employed. However, the catalysts mentioned above have some disadvantages, such as pollution, low yield, separation and recycling
problems. Therefore, the development of environmentally benign
catalysts with high activity is expected.
SO42/ZrO2 and modied SO42/ZrO2 solid acid catalysts have
attracted considerable interests due to their strong acidity and catalytic activity, and have been widely used to catalyze dehydration,
isomerization, acylation, esterication, alkylation reactions and so
on [1417]. H2SO4, (NH4)2SO4 and (NH4)2S2O8 solutions were usually employed as sulfating agents [18,19]. Recently, Yadav et al. reported a novel SO42/ZrO2 catalyst by the introduction of ethylene
* Corresponding author. Tel./fax: +86 28 85411105.
E-mail addresses: gchem@scu.edu.cn, chwehu@mail.sc.cninfo.net (C. Hu).
1566-7367/$ - see front matter 2009 Published by Elsevier B.V.
doi:10.1016/j.catcom.2009.04.020
1559
Turnover number
moles of HMF formed
1
mmolg1 h
mass of catalyst retention time
Table 1
The BET surface areas, pore volume, and ZrAl mole ratio of various catalysts.
Catalyst
Zr:Al controlled
(mol ratio)
Zr:Al (mol
ratio)a
Surface area
(m2/g)
Pore volume
(cm3/g)
CSZ
CSZA-1
CSZA-2
CSZA-3
CSZA-4
CSZA-5
9:1
7:3
1:1
3:7
1:9
9:0.9
7:2.5
1:1
3:7
1:8.7
6.87
11.1
28.2
27.3
26.6
66.0
0.008
0.015
0.034
0.038
0.042
0.090
1560
highest among all the catalysts. The total amounts of acid sites on
CSZA catalysts were lower than that on CSZ catalyst due to the
addition of Al, and decreased gradually with increasing amount
of Al, varying from 1.79 mmol/g for CSZA-1 to 0.95 mmol/g for
CSZA-5. The NH3-TPD proles were shown in Fig. 2a. It is shown
that all the catalysts afforded a broad desorption proles over
the range from 373 to 973 K, suggesting a broad distribution of
heterogeneous acid sites. The acid sites existed on the samples,
were articially divided into three categories which has weak-,
middle-, and strong acidity, respectively, according to the classication in the literatures [2829]. The amount of acid sites on the
CSZ sample was the highest; however, CSZA-1 and CSZA-3 catalysts exhibited stronger acidity than CSZ catalyst. This was also observed by Hua et al. [18] when adding small amount of Al2O3 into
SO42/ZrO2. It was reported that the increase of acid strength was
caused by the formation of AlOZr generating additional acidic
active sites. However, when the amount of Al increased further,
the acid strength of the CSZA catalysts decreased gradually. There
were several strong acid sites on CSZA-3, which gave NH3-TPD
peaks at 693, 743 and 823 K, respectively. Combined with the results of XRD, the enhanced acid strength on the CSZA-3 catalyst
might be related to the formation of tetragonal ZrO2 phase [20].
It was also reported that the presence of weak basic sites on the
SO42/ZrO2 catalysts was due to the basicity of ZrO2 [24]. As can be
seen from Fig. 2b, the highest CO2-TPD peak of all the samples was
over the range of 620670 K, which indicated the presence of
mainly middle strength base on the catalysts. The amount of base
sites of CSZ was 0.32 mmol/g, which was the lowest among all the
catalysts. Compared with CSZ catalyst, the amounts of base sites on
CSZA samples were higher, which increased from 0.35 to
0.98 mmol/g with the ZrAl mole ratio changing from 9:1 to 1:9.
This change was ascribed to the presence of aluminum species,
Fig. 2. NH3-TPD and CO2-TPD proles of the catalysts. (A) CSZ, (B) CSZA-1, (C) CSZA2, (D) CSZA-3, (E) CSZA-4 and (F) CSZA-5.
showing stronger basicity than ZrO2 [30]. Part of the base sites
based on aluminum species might not be affected by chlorosulfonic acid in the impregnation process.
3.4. FTIR studies
The results of FTIR of adsorbed pyridine were shown in Fig. 3.
Three peaks due to CC stretching vibrations of pyridine were
observed. The peak at 15401541 cm1 was assigned to pyridine
adsorbed on Brnsted acid sites, and that at 14891491 cm1
Table 2
NH3- and CO2-TPD data of the catalysts.
Catalyst
CSZ
CSZA-1
CSZA-2
CSZA-3
CSZA-4
CSZA-5
1.83
1.79
1.60
1.55
1.49
0.95
463,
633,
473,
693,
593,
643,
0.32
0.35
0.49
0.52
0.84
0.98
623
653
653
573, 613
623, 663
623
743, 853
813
603, 763
743, 823
703
683
1561
Fig. 3. FTIR spectra recorded after the chemisorption of pyridine on CSZ and CSZA
catalysts and evacuation at 473 K. (A) CSZ, (B) CSZA-1, (C) CSZA-2, (D) CSZA-3, (E)
CSZA-4 and (F) CSZA-5.
was characteristic of pyridine adsorbed on both Brnsted and Lewis acid sites while the peak around 1640 cm1 was related to pyridine adsorbed on Brnsted acid sites [31]. From the spectra we
can see that the amounts of acid sites decreased with increasing
amount of Al. This was consistent with the observation of NH3TPD. The quantity of Brnsted acids over SCZ sample was higher
than those over CSZA, while CSZA-5 had the lowest amount of
Brnsted acids. It was notable that no bands indicative of pyridine
adsorbed on Lewis acid sites were observed around 1450 cm1,
which was different from that obtained over SO42/ZrO2 when taking H2SO4 solution as sulfating agent. The absence of peak around
1450 cm1 was also found when SF4 was used as sulfating agent
[32].
3.5. Catalytic activity and catalyst stability
As seen from Table 3, in the absence of catalysts, the yield of
HMF was only 4.3%. By the use of CSZ, HMF yield was enhanced
signicantly with slight increase of glucose conversion. Vogel
et al. [9] has reported the increase of HMF yield from glucose when
H2SO4 was used as the catalyst, but the improvement was less evident than that when fructose was used as starting material. Compared with CSZ, the yield of HMF was further increased by the use
of CSZA catalysts. The CSZA-3 sample with the ZrAl mole ratio of
1:1 was found to be the most effective, leading to a yield of 47.6%
Table 3
Conversion of glucose to HMF in the presence of CSZ and CSZA catalystsa.
Catalyst
Substrate
Rb (w/w)
Time (h)
Conversion (%)
Tonc
No
CSZ
CSZA-1
CSZA-2
CSZA-3
Glucose
Glucose
Glucose
Glucose
Glucose
Glucose
Glucose
Glucose
Glucose
Glucose
Glucose
5
5
5
2.5
5
5
5
16.7
5
5
4
4
4
4
4
4
6
15
4
4
4
94.0
95.2
97.3
98.1
99.1
97.2
100
100
98.1
97.8
95.2
4.3
19.2
27.3
41.5
48.0
47.6
47.9
47.6
39.2
43.1
37.0
1.32
1.87
2.85
1.67
3.31
2.22
0.88
9.03
2.98
2.57
CSZA-4
CSZA-5
a
b
c
(7.6 wt%)
(7.6 wt%)
(7.6 wt%)
(7.6 wt%)
(3.9 wt%)
(7.6 wt%)
(7.6 wt%)
(7.6 wt%)
(20 wt%)
(7.6 wt%)
(7.6 wt%)
1562
Fig. 4. (a) Effect of the retention time on the yield of fructose and HMF at 403 K over CSZA-3. (b) Effect of the amounts of base sites over different catalysts on the yield of
fructose at 22 min.
Table 4
Dehydration of fructose to HMF in the presence of CSZ and CSZA catalystsa.
Catalyst
Substrate
Rb (w/w)
Time (h)
Conversion (%)
Tonc
No
CSZ
Fructose
Fructose
Fructose
Fructose
Fructose
Fructose
Fructose
Fructose
Fructose
5
2.5
16.7
5
5
5
5
5
4
4
4
4
4
4
4
4
4
99.6
99.8
100
100
99.6
100
99.4
99.7
99.1
71.9
67.7
68.2
61.6
64.2
58.1
56.6
52.2
47.2
4.71
2.36
14.1
4.46
4.02
3.93
3.63
3.28
CSZA-1
CSZA-2
CSZA-3
CSZA-4
CSZA-5
a
b
c
(7.6 wt%)
(7.6 wt%)
(3.9 wt%)
(20 wt%)
(7.6 wt%)
(7.6 wt%)
(7.6 wt%)
(7.6 wt%)
(7.6 wt%)
mins and the removal of these species made the catalyst reactivated. How to improve the stability of the catalyst remained a
problem for future study.
4. Conclusions
The CSZ catalyst prepared contained monoclinic ZrO2 phase and
Zr(SO4)2 phase. The crystalline structure varied with the amount of
aluminum species on the series of CSZA. Both Brnsted and Lewis
acid sites existed on the catalysts and the former was stronger. The
amounts of acid sites decreased, while base sites increased with
increasing amount of Al. Basicity promoted the glucosefructose
isomerization. CSZA series catalysts were more active than CSZ
for the catalytic conversion of glucose to HMF. In particular, over
CSZA-3 with ZrAl mole ratio of 1:1, a yield of about 47.6% to
HMF was obtained with a turnover number (TON) of about 3.31.
The activity of catalyst could be recovered, and a stable HMF yield
of about 35% could be obtained.
Catalyst
Conversion (%)
1
2
3
4
5
CSZA-3
CSZA-3
CSZA-3
CSZA-3
CSZA-3b
97.2
92.3 (95.3)a
92.8 (94.8)
92.0 (93.9)
94.0
47.6
35.2 (21.6)a
35.8 (8.62)
35.5 (5.53)
33.6
[7]
[8]
[9]
[10]
[11]
[12]
Conversion of glucose and yield of HMF when the catalyst was reused without
calcination prior to the next run.
b
The catalyst successively used for four times without calcination (almost
completely deactivated) was calcined at 823 K for 2 h and reused.
[13]
[14]
[15]
[16]
[17]
[18]
[19]
Acknowledgements
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
References
[30]
[31]
[1]
[2]
[3]
[4]
[5]
[6]
[32]
[33]
[34]
[35]
1563