Recycl. Catal. 2015; 2: 36–60
Review Article
Open Access
Yunxiang Qiao, Nils Theyssen, Zhenshan Hou*
Acid-Catalyzed Dehydration of Fructose
to 5-(Hydroxymethyl)furfural
Abstract: Hydroxymethylfurfural (abbreviated as HMF),
also 5-(hydroxymethyl)furfural, is an organic compound
derived from dehydration of certain sugars. HMF is primarily
considered as a starting material for liquid transportation
fuels and polyester building block chemicals. The most
convenient synthetic method of HMF is based on acidcatalyzed triple dehydration of fructose. Although there are
many studies about fructose dehydration to 5-HMF since this
field started to be investigated, it is necessary to provide a
new review about fructose dehydration to 5-HMF. In the
following, we will make a summary (in detail) of catalytic
systems of fructose dehydration to HMF achieved by different
acid catalysts, including mineral and organic acids, metal
complexes, heteropoly acid-based materials, Ionic Liquids,
ion-exchange resins, zeolites, functionalized carbonaceous
materials and mesoporous silica materials. It has been
demonstrated that nearly full conversion of fructose and
100% HMF selectivity could be obtained with some acidic
catalytic systems up to now.
Keywords: Dehydration; Fructose; 5-(hydroxymethyl)
furfural; Acid Catalysis; Recycling
DOI 10.1515/recat-2015-0006
Received November 27, 2014; accepted March 24, 2015
1 Introduction
Hydroxymethylfurfural (abbreviated as HMF), also
5-(hydroxymethyl)furfural, is an organic compound
derived from dehydration of certain sugars. The molecule
consists of a furan ring with one aldehyde and one
*Corresponding author: Zhenshan Hou: Key Laboratory for Advanced Material, Research Institute of Industrial Catalysis, East China
University of Science and Technology, 130 Meilong Road, Shanghai
200237 (P. R. China), E-mail: [email protected]
Yunxiang Qiao, Nils Theyssen: Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, D-45470 Mülheim an der Ruhr,
Germany
alcohol functional group. HMF is primarily considered
as a starting material for liquid transportation fuels and
polyester building block chemicals (Scheme 1). [1,2]
The most convenient synthetic method of HMF
is based on acid-catalyzed triple dehydration of
fructose (Scheme 2). Compared with other feedstocks,
the production of HMF from fructose is much easier
because the fructofuranoic structure is more reactive to
dehydration. Therefore, fructose was chosen as an ideal
model substrate to evaluate the performance of catalytic
systems for biomass conversion [3-9]. HMF synthesis
begins with removal of one or two water molecules from
fructose to form partially dehydrated intermediates. A
further dehydration of these intermediates leads to the
final product (HMF), but inter-molecular reactions of
these intermediates lead to condensation products, such
as soluble polymers and insoluble humins. Another
possible source of byproduct formation is the rehydration
of HMF to give levulinic acid. Thus, the design of an
effective catalyst, which can promote further dehydration
of partially dehydrated intermediates and suppress the
hydrolysis of HMF, is quite important.
Until now, there are several papers published
reviewing HMF production systems [1,2,10-13]. Various
acid catalysts have been used to transform carbohydrates
into HMF, for example mineral acids, metal chlorides
(Cr, Al, Ge, Zn, et al.), metal oxides, heteropolyacids
(HPAs), Ionic liquids (ILs), ion-exchange resins, zeolites,
functionalized carbonaceous materials, mesoporous
silica materials, ammonium or hydrotalcite-based
materials [14-17] and sub- and super-critical water [18-21]
or acetone [22]. Dimethyl sulfoxide (DMSO) was found to
be the most efficient solvent, promising high HMF yield
could be obtained even without any catalyst [3,23-25].
In the following, we will make a detailed summary of
catalytic systems of fructose dehydration to HMF achieved
by different acid catalysts. And all literatures cited are
published before the end of September, 2014.
© 2015 Yunxiang Qiao et al. licensee De Gruyter Open.
This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivs 3.0 License.
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Acid-Catalyzed Dehydration of Fructose to 5-(Hydroxymethyl)furfural
O
RO
O
O
O
Caprolactone
N
O
H
Caprolactam
H
HO
OH
1,6-Hexanediol
5-Alkoxymethylfurfural
O
O
O
O
HO
O
HO
OH
HO
O
O
OH
O
H
2,5-Furandicarboxylic acid
HO
OH
OH
O
Levulinic acid
5-Hydroxymethylfuroic acid
OH
Adipic acid
O
HMF
O
37
OH
O
O
O
O
O
O
H
2,5-Dimethylfuran
2,5-Bishydroxymethylfuran
O
H
Bis(5-methylfurfuryl)ether
Scheme 1. HMF as a platform chemical. Reprinted from Chem. Rev. 2013, 113, 1499-1597 with permission from American Chemical Society.
HOH2C
O
CH2OH
O
catalyst, solvent
OH
O
-3H2O
OH
HO
OH
Fructose
HMF
Scheme 2. Dehydration of fructose to HMF
2 Mechanism of fructose dehydration to HMF
3 Homogeneous catalytic dehydration over acidic catalysts
As it was illustrated in literatures, [1,2,12] mechanism
of fructose dehydration to HMF reaction is not clear. In
general, two different pathways involving cyclic or acyclic
intermediates have been proposed for HMF formation
(Scheme 3).
3.1 Mineral and organic acids
Continuous process for HMF production from fructose
using mineral acids (H3PO4, HCl) was already reported
in 1977. [26,27] For fructose dehydration reaction, it was
Pathway A
CH2OH
CHO
H
O
OH
H
HO
H
HO
H
OH
H
OH
H
OH
H
OH
CH2OH
CH2OH
Glucose
Fructose
CH2OH
CH2OH
O
-H2O
HO
OH
CH2OH
CHOH
O
HO
OH
OH
-H2O
CH2OH
O
Pathway B
OH
CHO
H
HO
CHO
OH
H
CHO
OH
H
-H2O
H
OH
H
OH
H
OH
H
OH
CH2OH
Glucose
CHO
CH2OH
-H2O
O
H
-H2O
H
H
OH
CH2OH
-H2O
O
HO
O
HMF
Scheme 3. Possible fructose dehydration pathways. Reprinted from Green Chem. 2011, 13, 754-793 with permission
from Royal Society of Chemistry.
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38 Y. Qiao et al.
found that regardless of the nature of the acid, only the
H+ acidity was responsible for the conversion rates, while
the associated anions only led to some differences in
selectivity towards HMF (Table 1) [28].
From Table 1, we can see that up to 99% HMF yield
can be obtained with conventional acids using ILs or
DMSO as solvents. And around 90% HMF yield can be
obtained with continuous flow reactors. Problems arise
from corrosion and difficult separation methodologies.
3.2 Metal chlorides
Lewis acidic metal chlorides are also interesting materials
for acid catalyzed dehydration reactions and they were
also widely studied for HMF production from fructose
(Table 2).
Besides the common Lewis acid AlCl3,[50] all
lanthanide(III) ions,[51] zinc ions,[52] LiCl,[53] InCl3,
[54,55] NbCl5,[56] CuCl2, CrCl2 and FeCl3 [57-64] and NH4Cl
Table 1. Conversion of fructose to HMF using mineral acids
Entry
mfructose
Reaction conditions
Solv.
T
/oC
t
Conv. /% sel. /% Yield /%
toluene:2-butanol (mass ratio
5:5) + H2O (v/v 3.2)
H2O
MIBK/2-butanol + H2O + DMSO
180
3 min
64
78
50
29
200
185
1 min
1 min
95
96
55
85
53
82
30
31
8-15 min
87
82
71
32
8 min
1h
n.d.
n.d.
n.d.
92.0
n.d.
n.d.
88.8
97
82
81.7
33
34
35
3h
n.d.
n.d.
85.3
36
2h
2h
2h
97.3
89.0
84.5
71.2
33.3
48.2
69.3
29.6
40.7
37
38
38
0.6
mL/min
15 min
≈98
≈92
90.3
39
n.d.
n.d.
74
40
1h
30 min
n.d.
94
n.d.
68
67.2
64
41
42
30 min
100
95
95
43
5h
8h
6h
15 h
n.d.
n.d.
n.d.
44
n.d.
n.d.
93
99
99
99
61
45
0-90 min
≈80
≈46
≈37
46
ca. 5 min
n.d.
n.d.
75
47
70 min
98.3
70.4
69.2
48
≈10 min
100
≈55
≈55
49
30 wt%
HCl (0.25 M)
2a
3
27 wt%
30 wt%
HCl (0.01 M)
HCl (0.1M)
4
30 wt%
HCl (Ph=0.6)
8
9
10
11
12
13
14
15a
16
17
18
19
20
21
22
Ref.
catalyst
1
5
6
7b
Post- reaction details
1-butanol + H2O
180
(V:V = 3.2)
0.4 g
HCl (0.2 mmol)
[BMIM]Cl (4.0 g)
80
0.45 g
HCl (5 mol%)
isopropanol (5 mL)
120
4g
HCl (0.3 mol/L)
H2O (60 mL) + 1-butanol (180 mL) 170
+ NaCl (8 g)
1 mmol
HCl (0.05 mmol)
isopropanol (1.94 mL) + H2O
120
(0.06 mL)
3.75 g
HCl (6.24 mmol)
DMSO (8.75 g)
90
10 w/v%
HCl (pH=1.1 buffer solution)
125
10 w/v%
HCl (pH=1.1 buffer solution) + carbon BP2000 adsorbent 125
(60 g/L)
Fructose solution (c=100 mg/mL) was premixed with hydrochloric acid 180
(c=1 mol/L) in a 10:1 ratio (v/v)
D-fructose (1 g/10 mL 0.25 M HCl aq., 0.33 mL/min) and MIBK (1.00 140
mL/min)
180 mg
H3PO4 (1 mmol)
[BMIM]Cl (10 mmol)
80
10 wt%
0.5 M H3PO4
H2O
150
/0.5 M NaH2PO4
(PH = 2.1)
1g
H2SO4 (40 μL, 0.75
[BMIM]Cl (20 g)
120
mmol)
3.6 g
10 mol% H2SO4
DMSO (10 mL)
100
or HCOOH
150
or Oxalic acid
150
or CH3COOH
150
137.5 mg conc. H2SO4
DMA (1 mL) + toluene (10 mL)
80
(2.5 μl) + LiCl (120 mg)
65 g·L-1
H2SO4
H2O
137
(33–300 mM)
2 mmol
H2SO4
10 mL GVL
130
(1.5 mL, 5 M)
1g
HCOOH (2.5 M)
water/n-butanol volume
170
ratio=1:3; 25 wt.% NaCl
50 mL of fructose– HCOOH (13.8 mg H2O (20 mL)
200
mL-1) mixture
a
MW irradiation
b
Mechanical stirring, 1000 rpm
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Acid-Catalyzed Dehydration of Fructose to 5-(Hydroxymethyl)furfural
39
Table 2. Conversion of fructose to HMF using metal chlorides
Entry
mfructose
Reaction conditions
catalyst
1a
5 wt%
2
0.20 M
3
2g
4
0.1 g
5
1.0 g
6
1.0 g
7
1.0 mmol
8
50 mg
9
1.0 g
10
1.0 g
11
0.1 g
12
1.00 g
13
1.0 g
14
180 mg
15
1.0 g
16
1.0 g
17
1.0 g
18
0.15 g
19
0.1 g
20
180 mg
21
180 mg
22
0.625 g
Post- reaction details
Solv.
T
/oC
t
Conv. /% sel. /% Yield /% Catalyst
reuse
140
5 min
n.d.
n.d.
70.1
five runs
50
120
2h
n.d.
n.d.
92.6
51
120
n.d.
97.3
55
53.3
n.d. (no
data)
n.d.
100
2h
n.d.
n.d.
67
n.d.
53
180
10 min
100
76.5
76.5
three runs
54
180
10 min
100
76
76
n.d.
55
80
30 min
n.d.
n.d.
79
n.d.
56
80
3h
90
18
100
93
17
67
84
3
67
n.d.
57
100
1h
n.d.
n.d.
73
n.d.
58
100
1h
n.d.
n.d.
92
n.d.
58
100
1.5 h
n.d.
n.d.
69
five runs
59
100
3h
n.d.
n.d.
96
n.d.
60
90
2h
100
86
86
n.d.
61
80
2h
n.d.
n.d.
83.4
n.d.
62
90
1h
n.d.
n.d.
56.1
n.d.
63
100
2h
n.d.
n.d.
79.6
n.d.
63
100
2h
n.d.
n.d.
82.3
n.d.
63
120
1h
>90
>90
>80
n.d.
64
90
40 min
n.d.
n.d.
84.3
ten runs
65
100
12 h
97
37
36
n.d.
66
ipropanol
120
(2 mL)
DMSO (11.875 90
g)
12 h
100
68
68
five runs
66
2h
98.9
92.0
91.0
n.d.
37
DMSO
AlCl3
(50 mol%)
LaCl3
DMSO
(10.0 mM)
ZnCl2 (63 g) +
H2O
HCl (405 mg)
(37 mL)
LiCl
sulfolane
(100 mg)
(1.40 g)
InCl3
H2O
(30 mg)
(20 mL)
InCl3
H2O
(30 mg)
(20 mL)
NbCl5
[BMIM]Cl
(0.20 mmol)
(10.0 mmol)
CuCl2
[EMIM]Cl
FeCl2
(500 mg)
CrCl2
(MCl2/hexose=
0.06)
SnCl4
DMAc
(9.5 mol %) + NH4Br
(10 mL)
(0.16 M)
CrCl3
DMAc
(9.5 mol %) + NH4Br
(10 mL)
(0.16 M)
CrCl3·6H2O
Bu-DBUCl
(10 mg)
(1 g)
CrCl3·6H2O (0.39 mmol)[BMIM]-[HSO4]
(0.70 g)
FeCl3
NMP
(0.56 mmol) + Et4NBr (10 mL)
(1.0 mmol)
FeCl3
[BMIM]Cl
(0.01 mmol)
(2.5 g) + EtOH
(2.5 g)
NBS
NMP
(10.0 mol%)
(12 mL)
FeCl3 + NBS (10.0
NMP
mol%)
( 12 mL)
SnCl4 + NBS (10.0
NMP
mol%)
( 12 mL)
TfOH/ H2SO4/CuCl2 / [BMIM]Cl
FeCl3 (0.1 g)
(5.0 g)
Cr(III)-Al2O3
[BMIM]Cl
(0.1 g)
(1.0 g)
NH4Cl
EtOH
(0.5 mmol)
(2 mL)
NH4Cl
(0.5 mmol)
Hexachlorocyclotriphosphazene (HCCP,
0.347 mmol)
Ref.
52
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40 Y. Qiao et al.
Table 2. Conversion of fructose to HMF using metal chlorides
continued
Entry
mfructose
Reaction conditions
catalyst
23
400 mg
24
25
26
91.0 mg
91.0 mg
2.5 wt%
27
28
100 mg
100 mg
29
100 mg
30
5 wt%
31
100 mg
32
0.1 g
33
50 mg
34
90 mg
35
2g
36
500 mg
Post- reaction details
Solv.
T
/oC
p-Toluenesulfonic acid choline chloride 100
(10.0 mol%)
(ChCl) (600 mg)
1.47 g of ChoCl /citric acid
80
1.47 g of ChoCl /citric acid + EtOAc
80
DES derived from choline chloride (ChCl) 80
and p-toluene sulfonic acid monohydrate
(p-TSA)
GeCl4 (10 mol%)
[BMIM]Cl (2.0 g) 100
GeCl4 (10 mol%)
DMSO (0.5 g) + 25
[BMIM]Cl (2.5 g)
HfCl4 (10 mol%)
[BMIM]Cl
100
(2.0 g)
Zr(O)Cl2
[BMIM]Cl/MIBK 120
(10 mol%)
(1:1 v/v)
WCl6
[BMIM]Cl
50
(10 mol%)
(500 mg)
Hexachlorotriph-ospha- [BMIM]Cl
80
zene (N3P3Cl6, 5 mg)
(2.0 g)
NHC–Cr
[BMIM]Cl
100
(9 mol%)
(500 mg)
polymer-supported
DMSO
100
NHC–FeIII (2 mol%)
(2 mL)
IrCl3·(1-2)H2O (65 mg) [OMIM]Cl
180
/CrCl3·6H2O (49 mg)
(20 g)
(ca 7 mol% based on
fructose)
MIL-101(Cr)-SO3H (300 DMSO
120
mg)
(5 mL)
Ref.
t
Conv. /% sel. /% Yield /% Catalyst
reuse
0.5 h
n.d.
n.d.
67
n.d.
67
1h
1h
1h
93.2
97.6
n.d.
83.5
93.6
n.d.
77.8
91.4
90.7
n.d.
eight runs
n.d.
68
68
69
5 min
12 h
n.d.
n.d.
n.d.
n.d.
92.1
≈70
five runs
n.d.
70
71
30 min
100
77.5
77.5
n.d.
72
5 min
n.d.
n.d.
84
five runs
73
4h
n.d.
n.d.
63
eight runs
74
20 min
n.d.
n.d.
92.8
five runs
75
6h
n.d.
n.d.
≈90
four runs
76
3h
97
75
73
ten runs
77
10 min
n.d.
n.d.
92.5
five runs
78
1h
>99
91
90
five runs
79
DMAc: N,N-dimethylacetamide; DBU: 1,8-Diazabicyclo[5.4.0]undec-7-ene; NMP: N-methylpyrrolidone; NBS: N-bromosuccinimide; a microwave heating.
[66] were reported to be effective for fructose dehydration
to HMF. Ammonium salt NH4Br, [58] DBU-based ILs,
[59] and choline chloride (ChCl) [67,68] were found to be
effective promoters. Acidic DES derived from ChCl and
p-toluene sulfonic acid monohydrate (p-TSA) was also
investigated to dehydrate fructose to HMF (90.7% yield)
in Al-Duri group [69]. The use of ChCl–p-TSA plays a dual
role, being a hydrogen bond donor (HBD) and catalyst for
the dehydration reaction, thus obviating the addition of
an external acid.
Due to the special characteristics of ILs, they were
widely used in fructose dehydration reaction to promote
both fructose conversion and HMF selectivity. CrIII-Al2O3/
[Bmim]Cl, [65] CrCl3/[BMIM][HSO4], [60] GeCl4/[BMIM]Cl,
[70,71] HfCl4/[BMIM]Cl [72] and Zr(O)Cl2/ [BMIM]Cl-MIBK,
[73] as well as WCl6/THF–[BMIM]Cl [74] catalytic systems
were proved to be efficient for fructose conversion to
HMF. After reaction, the catalyst can be recycled without
a significant loss in its activity by simple extraction
of organic products. Organic chlorides, including
hexachlorotriphosphazene (N3P3Cl6), trichloromelamine
(C3N6H3Cl3) and NBS were also studied in ILs [75].
NHC–Cr/IL system and polymer-supported NHC–FeIII
catalytic system were also developed for HMF production
[76,77]. Excellent efficiencies were achieved with HMF
yields of 96% and 73% from fructose for the two systems
above, respectively. Furthermore, both NHC-metal
catalysts could also be reused without significant loss of
catalytic activity.
As more and more novel catalytic systems are being
developed for the dehydration of carbohydrates, an
effective way to separate the dehydration product HMF
is also required for industrial manufacturing. Wei et al.
developed a process called EIVRD (entrainer-intensified
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Acid-Catalyzed Dehydration of Fructose to 5-(Hydroxymethyl)furfural
vacuum reactive distillation) to separate HMF from the
dehydration solutions of carbohydrates catalyzed by a
metal chloride/1-methyl-3-octyl imidazolium chloride
([OMIM]Cl) IL, in which high vacuum and entrainers were
applied to intensify the distillation of HMF as well as the
dehydration of fructose or glucose. In such an EIVRD
process, the average recoveries of HMF dehydrated from
fructose is around 93% and it can be successfully repeated
during the whole five recycled reactions (Table 5, entry 38)
[78].
A series of sulfonic acid-functionalized metalorganic frameworks (MOF-SO3H), including sulfonic acidfunctionalized MIL-101(Cr) [MIL-101(Cr)-SO3H], UIO-66(Zr)
[UIO-66(Zr)-SO3H], and MIL-53(Al) [MIL-53(Al)-SO3H],
were further tested for fructose dehydration. With MIL-
41
101(Cr)-SO3H as catalyst, 90% HMF yield with full fructose
conversion was obtained after 60 min in DMSO at 120 °C.
Moreover, MIL-101(Cr)-SO3H behaves as a heterogeneous
catalyst and can be easily recovered and reused (Table
5, entry 39) [79]. Meanwhile, bimetallic RhRe/C was also
found to be an active catalyst for fructose dehydration
(50% HMF selectivity with 30% fructose conversion),
providing evidence for Brønsted acidity over Re atoms on
the surface of this RhRe/C catalyst in liquid water [80].
3.3 Metal complexes and oxides
Besides metal chlorides, inexpensive metal oxides as well
have been used as catalysts for fructose dehydration to
HMF in different media (Table 3).
Table 3. Conversion of fructose to HMF using heterogeneous metal oxides
Entry
mfructose
1
40 mg
2
1M
3
4
6 wt%
6 wt%
5
1.2 g
6
0.8 g
7
0.1 mL·min-1
8
9
0.1 mL·min-1,
0.3 M
0.1 g
10
600 mg
11
600 mg
12
0.1 g
13a
1.0 g
14
0.09 mL·min-1
15
0.133 M
Reaction conditions
Post-reaction details
Ref.
catalyst
Solv.
T
/oC
t
Conv. /% Sel. /% Yield /% Catalyst
reuse
Sc(OTf)3
(4 mg)
Al(OTf)3
(50 mM)
H3PO4-treated niobic acid
Niobium phosphate
DMSO
(2 g)
DMSO
120
2h
100
83.3
83.3
n.d.
81
120
1h
100
69
69
n.d.
82
H 2O
H2O
100
100
0.5 h
0.5 h
31.2
28.8
93.3
100
29
28.8
Niobium phosphate (0.1 H2O
g)
(20 mL) +
2-butanol (30
mL)
NbPO-pH2
H 2O
(0.8 g)
(10 mL)
Nb2O5
H 2O
(2-4 g)
160
50 min
90
99
89
n.d.
83
At least four 83, 84
runs
Seven runs
85
130
0.5 h
57.6
78.2
45
seven runs
86
100
13
6.5
45 h
87
Silica-niobia oxides
(2-4 g)
Carbon (25%) - niobia
(75%)
(0.01 g)
Nb2O5
(80 mg)
Nb2O5 and Nb2O5·MeO2
(Me = Ti, Zr, Ce) (80 mg)
Nb2O5 prepared at 400 oC
(0.01 g)
as-prepared HNb3O8 (0.02
g)
NbOPO4
Nb2O5·nH2O
Nb2O5
(3 g)
H 2O
100
≈21
≈15
100 h
88
DMSO (5.0 g)
120
2.5-7.1
50
min·
mL-1g
20-40 min· ≈72
mL-1 g
2h
100
76.5
76.5
n.d.
89
H 2O
(60 mL)
H2O
(60 mL)
DMSO
(5.0 g)
H 2O
(9 mL)
H2O
130
6h
82
50
41
Five runs
90
130
10 h
71-87
23-30
26-36
n.d.
91
120
2h
100
86.2
86.2
Five runs
92
155
18 min
85.1
66
55.9
Four runs
93
100
-
94
100
30 h
n.d.
n.d.
n.d.
200-230 h
H 2O
up to 73 n.d.
40
n.d.
n.d.
≈25
70 h
95
Unauthenticated
Download Date | 6/18/17 2:23 PM
42 Y. Qiao et al.
Table 3. Conversion of fructose to HMF using heterogeneous metal oxides
continued
Entry
mfructose
Reaction conditions
catalyst
16
17
18
19
20
21
22
23
24
25
26
27
28
29
Post-reaction details
Solv.
T
/oC
the fructose solution (ca. 0.3 M) was continuously sent
100
(0.1 mL min−1) to the catalyst (NBO, 3.5 g) at constant
contact time (ca. 36 min mL−1 g)
1.08 g
VOP (0.64 g)
H2O
80
6.02 g
FeVOP (0.11 g)
1.04 g
AlVOP (0.10 g)
1.84 g
CrVOP (0.06 g)
6 mmol
VOPO4·2H2O (VOP, 0.6 g) H2O
80
(30 mL)
0.25 mmol
Large-Pore Mesoporous H2O
150
Tin Phosphate
(1 mL) + MIBK
(LPSnP-1, 10 mg)
(2 mL)
0.1 g
Tin(IV) phosphonate
[EMIM]Br
100
(SnBPMA) and zirconium (1 g)
phosphonate (ZrBPMA)
(25 mg)
0.23 g
Vanadium phosphate and H2O (0.5 g)/
120
mesostructured cellular [BMIM][Tf2N]
foam
(3 g)
(VPO-MCF, 0.10 g)
20 g
coated ZrP/Al
H2O
135
foam (1 g)
(300 mL)
1.1 g
cubic ZrP2O7
H2O
100
and pyrophosphates
(10 mL)
TiP2O7 (0.6 g)
50 mg
Zirconium phosphate
sub-critical
240
(25 mg)
water
(5.0 mL)
0.5 g
silicoaluminophosp-hate H2O
175
(SAPO,
(5 mL)
0.143 g)
+ MIBK (25 mL)
206 mg
phosphonic acid polysil- H2O
130
sesquioxanes
(1.8 g)
(PAPSQ, 209 mg)
+ MIBK
/2-butanol (7:3,
2 g)
1.2 g
Tantalum hydroxide
H2O
160
(0.1 g)
(20 mL) +
2-butanol (30
mL)
0.1 g
Copper phosphate nanos- H2O
200
tructures
(1 mL)
α-Cu2P2O7-900 (0.01 g)
0.1 g
alkaline earth phosphate H2O
200
(α-Sr(PO3)2, 0.01 g)
(1 mL)
30
100 mg
TiO2
(100 mg)
31
100 mg
TiO2
(50 mg)
H2O
120
(2 mL)
DMSO
(2 mL)
DMA-LiCl (10%) 130
(2 g)
Ref.
t
Conv. /% Sel. /% Yield /% Catalyst
reuse
-
Up to 79 10-20
n.d.
up to 200 h
96
h
h
h
2.0 h
2h
50.2
70.8
75.9
58.2
50.1
78.7
84.1
75.8
87.8
81.5
41.9
59.6
57.6
51.1
41
n.d.
97
n.d.
98
20 min
n.d.
n.d.
77
Five runs
99
1.0 h
93
90
90
77.8
83.3
70.0
five runs
100
20 h
89
91
81
five runs
101
250 min
20
38
8
n.d.
102
1h
52.2
29.3
86
90.1
45
26.4
two runs
103
2 min
≈80
≈61
≈48.8
n.d.
104
1h
90
89
80
five runs
105
12 h
n.d.
n.d.
59
three runs
106
100 min
94
96
90
fifteen times 107
5 min
82.2
44
35.8
n.d.
108
5 min
88
44
39
n.d.
109
5 min
n.d.
n.d.
n.d.
n.d.
34
55
four runs
110
2 min
n.d.
n.d.
74.2
five runs
111
Unauthenticated
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Acid-Catalyzed Dehydration of Fructose to 5-(Hydroxymethyl)furfural
43
Table 3. Conversion of fructose to HMF using heterogeneous metal oxides
continued
Entry
mfructose
32
1 mmol
33
1 mmol
34
23 wt%
35
1.665 mM
36
0.1 g
37a
0.1 g
38
39
0.1 g
0.1 g
0.1 g
40
1.0 g
41
180 mg
42
600 mg
43
30 wt%
44
0.56 mmol
45
10 mg
Reaction conditions
Post-reaction details
Ref.
catalyst
Solv.
T
/oC
t
Conv. /% Sel. /% Yield /% Catalyst
reuse
Sulfated TiO2
(0.1 g)
TiO2 NPs
(0.1 g)
TiO2
MeOH
(20 mL)
THF
(20 mL)
n-BuOH: H2O
(1:3)
DMSO
(10 mL)
175
1h
82
40
33
150
3h
>99
54
200
3 min
n.d.
120
1h
100
sulfated ZrO2 hollow
nanostructure
(15 mg)
SO4/ZrO2
(SO4 coverage=0.8,
0.1 g)
sulfated zirconia
(0.02 g)
H 2O
(20 mL)
acetone
180
(3.5 g)- DMSO
(1.5 g)
TiO2 (50 mg)
H2O (5 g)
200
ZrO2 (50 mg)
H2O (5 g)
200
a-TiO2
H 2O
200
(0.1 g)
(1 mL)
sulfated SnO2-ZrO2
DMSO
120
(0.2 g)
(10 mL)
Tin-tungsten mixed oxide DMSO
80
(100 mg)
(5 mL)
tungstated zirconia oxides H2O
130
(80 mg)
(60 mL)
B(OH) 2 (100 g·L-1) - NaCl H2O-MIBK (v/ 150
(50 g·L-1)
v=1:4)
B2O3
[BMIM]Cl (0.6 g) 100
(0.28 mmol)
silicon semiconductor
H3PO4
80
coated with silanol groups (4.6 M) in
(Si-OH)
DMSO/H2O (2
(40 mg)
mL/2 mL)
54
at least two
runs
five runs
112,
113
112
n.d.
18
n.d.
114
n.d.
n.d.
64
n.d.
115
6h
25.4
32.6
8.3
n.d.
116
20 min
93.6
77.8
72.8
n.d.
117
5 min
5 min
5 min
83.6
65.3
96
45.6
46.9
23
38.1
30.6
22
n.d.
118
n.d.
119
2.5 h
n.d.
n.d.
76
five runs
120
12 h
>99
70
70
n.d.
121
4h
≈62
≈20
12.0
n.d.
122
45 min
92
65
60
n.d.
123
1h
98
n.d.
n.d.
n.d.
124
5h
n.d.
n.d.
97.1
n.d.
125
VOP: Vanadyl phosphate. a under microwave irradiation
Various rare earth metal trifluoromethanesulfonates,
i.e., Yb(OTf)3, Sc(OTf)3, Ho(OTf)3, Sm(OTf)3, Nd(OTf)3 as
catalysts were investigated for HMF production from
fructose in DMSO. It was found that the catalytic activity
increases with decreasing ionic radius of rare earth metal
cations. Among the examined catalysts, Sc(OTf)3 exhibits
the highest catalytic activity with full fructose conversion
and 83.3% HMF yield at 120°C after 2 h [81]. Chromium
and aluminium halides and triflates were also identified
as promising catalysts [82].
Niobium acid shows high acidity on the surface
corresponding to the acidity of 70% sulfuric acid. The
unusual solid acid exhibits quite high efficiency for
fructose dehydration reaction. It was found that H3PO4-
treated niobic acid catalysts display a lower selectivity at
high fructose conversion than niobium phosphate ones,
it is probably because of a slightly higher strength of
Lewis and Brønsted acid sites in the niobium phosphate
systems [83-85]. Mesoporous niobium phosphates, [86]
dispersed niobia phase in/on silica matrix,[87,88] ordered
mesoporous carbon-niobium oxide composites,[89] and
mesoporous Nb2O5-MeO2 (Me = Ti, Zr, Ce) mixed oxides
[90,91] also show promising dehydration efficiency. Effect
of calcination temperatures (300–700 °C) for Nb2O5 was
found to be an important factor on fructose conversion
[92]. The Nb2O5 prepared at 400 °C shows 100% fructose
conversion with 86.2% HMF yield in DMSO at 120 °C after
2 h. The activity of the catalyst decreases gradually during
Unauthenticated
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44 Y. Qiao et al.
recycle because of coke deposition; however, it can be fully
recovered by calcination at 400 °C for 2 h. In addition, the
fructose dehydration reaction was catalyzed by HNb3O8
in water [93]. 55.9% HMF yield was achieved possibly
due to the fast in situ exfoliation of layered HNb3O8 with
the aid of microwave irradiation, which leads to quasihomogeneous catalytic behavior. Moreover, the unique
restacking feature of the exfoliated HNb3O8 ensures at
least four runs of the catalyst.
Niobic acid (Nb2O5·nH2O) and niobium phosphate
(NbOPO4) were also used as catalysts in a continuous
flow reactor at different temperatures (90-110 °C) and
pressures (from 2 to 6 bar) in Carniti’s and Gervasini’s
group. Niobium phosphate showed higher activity and
selectivity to HMF than niobic acid; it is possibly because
of its higher effective surface acidity. Losses of activity
were observed for both catalysts after long time (around
100 h) on stream [94,95]. K-, Ba-, and Nd-doped niobic
acid (Nb2O5·nH2O, NBO) catalysts also show long-term
stability (up to 200 h) in a fixed catalytic bed flow reactor
at constant temperature of 100 °C by controlling activity,
and in particular, selectivity to HMF [96].
Promising results in terms of activity and selectivity
using vanadyl phosphate (VOP) as catalyst were also
achieved. Substitution with trivalent Fe, Cr, Ga, Mn and Al
was studied here. Fe-substituted VOP showed the highest
activity in the dehydration reaction [97,98]. Mesoporous tin
phosphate material [99,100]. nanostructured vanadium
phosphate-mesostructured cellular foam (VPO-MCF)
[101] and zirconium phosphate with or without support
of open-cell aluminum foam or coated aluminum foams
[100,102] showed quite promising activity and selectivity
for HMF production as well.
Meanwhile, layered zirconium and titanium
hydrogen phosphates with α and γ structural phase,
α-Zr(HPO4)2·H2O, γ-Zr(PO4)(H2PO4)·2H2O, α-Ti(HPO4)2·H2O,
γ-Ti(PO4)(H2PO4)·2H2O as well as their corresponding
α- and γ-layered pyrophosphates, α-ZrP2O7, and
cubic pyrophosphates TiP2O7 [103] showed similar
activities. Laboratory-made zirconium phosphate in
combination with sub-critical water (sub-CW),[104]
silicoaluminophosphate (SAPO) catalysts [105] and
even phosphonic acid polysilsesquioxanes, PAPSQ,
[(O3/2SiCH2R)x(O3/2­­- SiCHR(CH2)2SiO3/2)y]n where R stands for
CH2PO3H2 [106] as well as tantalum hydroxide [107] also
showed promising activities.
In 2012, Faungnawakij used nanostructured
copper hydrogen phosphate monohydrate and copper
pyrophosphate for fructose dehydration in hot compressed
water at 200 °C. Among all samples, the Cu2P2O7 catalysts
with weak acid strength (+3.3 ≤ H0 ≤ +4.8) were highly active
and selective for HMF production with 36% yield and
maximum turnover number, while no metal leaching was
observed after the reaction [108]. At the same time, they
reported another dehydration system with phosphates
of alkaline earth metals (calcium and strontium). It was
found that CaP2O6 and α-Sr(PO3)2 showed similar catalytic
performance toward the dehydration of sugars [109].
TiO2 NPs also can give relatively high HMF yield
[110,111]. SO42-/TiO2 catalysts treated with 0.50 mol/L
H2SO4 and calcined at 500 oC for 3 h, showed better
catalytic effect. The recovered catalyst after calcination
was found to show slower deactivation rate compared
to those without calcination [112,113]. Moreover, TiO2 in
a fixed bed catalytic reactor could afford HMF yields up
to 29% [114].
Hollow ZrO2 nanostructures and sulfated ZrO2 hollow
particles showed superior performance in dehydration of
fructose to HMF than the solid sulfated ZrO2 nanocatalyst
[115-117]. Dehydration activity of TiO2, ZrO2 and sulfated
zirconia, [117,118] TiO2 (anatase TiO2 or rutile TiO2) and ZrO2
(monoclinic/tetragonal mixt. ZrO2), [119] and Sn-based
catalyst (mixed SnO2-ZrO2 and sulfated SnO2-ZrO2) [120]
were tested for fructose dehydration also. It was found that
the suitable ratio of Sn/Zr is 0.5, and the catalytic activity
of sulfated SnO2-ZrO2 is higher than that of SnO2-ZrO2
with 75.0% HMF yield after 2.5 h at 120 °C. The catalytic
system can be reused for five times. Sn-W mixed oxide and
tungstated zirconia oxides were reported to be efficient for
fructose dehydration [121,122].
Due to the strong complexation between the
boron atom and the hexoses, B(OH)3 with various salts
or B2O3 alone were applied for fructose dehydration
[123,124]. Interestingly, silicon was found to be a suitable
semiconductor for fructose conversion to HMF compared
with α-Fe2O3, WO3, and TiO2. Remarkably, a silicon
semiconductor coated with silanol groups (Si-OH) affords
HMF in 97% yield even at 80 °C. This result suggests
that the Si-OH catalyst provides energy selectively to the
starting material fructose and not to desired product HMF,
preventing side-reactions [125].
3.4 ILs
Room temperature ILs as reaction media have attracted
great interest for decades due to their special properties,
being nonvolatile, nonflammable, highly polar, and
sometimes easy to separate from reactants and products.
Neutral ILs can promote dehydration due to enhanced
dissolution of catalysts and substrates. The use of ILs in
carbohydrate transformations was first suggested by Liu
et al. in 2005 [126].
Unauthenticated
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45
Acid-Catalyzed Dehydration of Fructose to 5-(Hydroxymethyl)furfural
Table 4. Conversion of fructose to HMF using ILs
Entry
mfructose
1
100 mg
2
0.5 g
3
0.5 g
4a
1.0 g
5
50 mg
6a
1.0 g
7
1.0 g
8
0.5 g
9
30 mg
10b
63 mg
11
0.05 g
12
1.0 g
13
1.5 g
14
180 mg
15
180 mg
16
180 mg
17
0.36 g
18
0.5 g
19
20b
21
22
23
24
25
8.6 wt%
0.33 g
90 mg
21.6 g
1.0 g
1.0 g
0.5 g
Reaction conditions
Post- reaction details
Ref.
catalyst
Solv.
T
/oC
t
Conv. /% Sel. /% Yield /% Catalyst
reuse
concentrated HCl
(8 mol%)
concentrated
sulfuric acid
(27 mg)
CrCl3·6H2O
(74 mg)
[NMM][CH3SO3] (0.104 g, 10.0
mol%)
[BMIM]Cl
(500 mg)
[BMIM]Cl
(5 g)
23
24 h
n.d.
n.d.
72
six runs
127
100
50 min 100
82.9
82.9
n.d.
128
2h
100
75.3
75.3
n.d.
128
2h
n.d.
n.d.
74.8
n.d.
129
5h
97
58
56
n.d.
130
2h
82.9
87.2
72.3
five runs
131
1h
93
78
72.8
five runs
132
1h
n.d.
n.d.
75
n.d.
133
0.5 h
100
88
88
n.d.
134
2 min n.d.
n.d.
83
n.d.
135
3h
n.d.
n.d.
81
five runs
136
3h
100
94.6
94.6
six runs
137
1.5 h
91.1
88
80.5
five runs
138
2h
100
95.7
95.7
six runs
139
45 min 99
84.9
84.9
five runs
140
10 min 97.9
100
95.4
97.2
93.4
97.2
n.d.
141
1h
95.6
99.8
95.5
five runs
142
1.5 h
89.2
97.7
87.1
three runs
142
1h
1.5 h
1h
44 min
40 min
40 min
8h
n.d.
97
>99
≈92
100
92
n.d.
n.d.
100
95
≈99
92.3
90
n.d.
67
97
95
92
92.3
83
91.6
n.d.
n.d.
six runs
five runs
five runs
Six runs
six runs
143
144
145
146
147
148
149, 150
[BMIM]Cl
100
(5 g)
DMF–LiBr solu- 90
tion (70:1, mass
ratio, 10 mL)
[BMIM]Cl
DMSO
80
(2.4 mg)
(2 mL)
N-methyl-2-pyrrolidonium
DMSO
90
methyl sulfonate [NMP][CH3SO3] (12 mL)
(7.5 mol%)
[PSMBIM]HSO4
DMSO
80
(0.1 g)
(10 mL)
1,3-dipropanesulfonic acidDMSO
100
imidazolium methanesulfonic (2 mL)
(2.78 mmol)
[EMIM][HSO4]
IBMK
100
(0.3 mL)
(0.7 mL)
1DMSO
100
methylimidazolium chlorosulfate(2.0 g)
([HMIm]SO3Cl, 0.175 mmol)
[MBCIm]SO3Cl
H2O (0.1g) +
80
(fructose/IL: 2 mol/mol)
CH3CN (2 g)
1-(4-sulfonic acid) butylH2O
120
3-methylimidazolium hydrogen (1 mL) + MIBK
sulfate (0.3 g)
(9 mL)
caprolactam
water: PGME = 105
hydrogen sulfate ([CPL]HSO4, 8.62.5:12.5 (W/W)
mmol)
[CMIm]Cl
DMSO
120
(2 mmol)
(5 mL)
1-allyl-3-methylimidazolium
DMF
100
chloride ([AMIM]Cl,
(2.5 mL)
2.5 mL)
[NMP][HSO4], [C3SO3HMIM][AMIM]Cl
100
[HSO4]
(2 mL)
(0.09 mmol)
[C6(Mpy)2][NiCl4]2- (1 g)
DMSO
110
(5 mL)
[C10(Epy)2]2Brnone
100
(1.5 g)
[BMIM][CH3SO3]
80
[BMIM]Cl (1.0 g)
175
[BMIM]Br (0.3 g)
100
1-H-3-methyl imidazolium chloride (0.6 mol)
90
[TetraEG(mim)2][OMs]2 (1.0 g)
120
[tetraEG(mpyri) (triethylamo)] [HSO4]2 (0.1 g)
70
[BMIM]OH
DMSO
160
(0.25 g)
(30 mL)
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46 Y. Qiao et al.
Table 4. Conversion of fructose to HMF using ILs
continued
Entry
mfructose
26b
63 mg
27
0.5 g
Reaction conditions
Post- reaction details
Ref.
catalyst
Solv.
T
/oC
t
Conv. /% Sel. /% Yield /% Catalyst
reuse
ILIS–SO3H
ILIS–SO2Cl
(0.175 mmol)
fiber supported ILs (FSILs, 7.5
mol%)
DMSO
(2.0 g)
160
4 min 100
100
70.1
67.2
70.1
67.2
seven runs 151
DMSO
(10 mL)
120
30 min n.d.
n.d.
82.9
ten runs
152
[NMP][HSO4]: N-methyl-2-pyrrolidonium hydrogen sulfate; PGME: proprylene glycol monomethyl ether; [C3SO3HMIM][HSO4]: 1-(4-sulfonic
acid)-propyl-3-methylimidazolium hydrogen sulfate; [C6(Mpy)2][NiCl4]2-: 1,1’-hexane-1,6-diylbis (3-methylpyridinium) tetrachloronickelate (II);
[C10(Epy)2]2Br-: 1,1’-decane-1,1’-diylbis (3-ethylpyridinium) dibromide; ILIS: ionic liquids immobilized on silica. a with microwave irradiation;
b under an N2 atmosphere.
HCl/H2SO4–[BMIM]Cl (catalyst–solvent) system at
ambient conditions would afford high HMF yields and
excellent recyclability [127,128]. Combination of ILs
(neutral, with only Brønsted or Lewis acidity and dual
Brønsted Lewis acidity) and organic solvents also showed
promising conversion and selectivity in the dehydration
reaction [129-142]. ILs can be recycled by distillation of
organic solvents and extraction of products after reaction
and be reused for several times without significant activity
loss.
Without utilizing any other additive or catalyst,
imidazolium ILs (act both as solvent and catalyst) were
found to be unexpectedly effective for fructose conversion
[143-148]. The acidic C-2 hydrogen of imidazolium cations
was shown to play a major role in the reaction in absence
of a catalyst. Both the alkyl groups of imidazolium cations
and the type of anions affected the reactivity of the
carbohydrates. ILs based on bis(N-methylimidazolium)
cations containing short oligo ethylene glycol linkers
and mesylate (CH3SO3−) anions could afford 92.3% HMF
yield from fructose in 40 min with one equivalent of
[TetraEG(mim)2][OMs]2 at 120 °C [147].
Interestingly, the basic IL 1-Butyl-3-methylimidazolium
Hydroxide ([BMIM]OH), can also be used as a catalyst in
the conversion of fructose to 5-HMF. The maximum yield
of 5-HMF was 91.6% at 160 °C after 8 h with a mass ratio
IL:fructose of 0.5 using DMSO as solvent [149,150].
3.5 Heteropoly acid-based materials
HPA is a class of acidic compounds made up of a particular
combination of hydrogen and oxygen with certain metals
and non-metals. They have been widely used as both
homogeneous and heterogeneous catalysts for acid
catalyzed and oxidation reactions due to their special
physicochemical properties, especially those based on
the Keggin structures [153-155]. It was proved that HPAs
are potentially promising candidates for the catalytic
conversion of fructose to HMF (Table 5).
Since HPAs possess properties like good thermal
stability, high acidity and high oxidizing ability, it’s
logical for researchers to apply HPAs for dehydration of
fructose to HMF that was performed in acidic condition.
Classic H3PW12O40 (PW12) and H4SiW12O40 (SiW12) were used
as effective catalysts for promoting this dehydration in the
presence of [BMIM]Cl as solvent. HMF can be obtained
in yields of up to 99% under mild condition (80 oC, only
5 min). Moreover, the used [BMIM]Cl and HPAs could be
recycled and reused with only slight decrease of reactivity
for at least ten times [156].
A new Brønsted–Lewis–surfactant-combined
C16H3PW11CrO39(H2O) (abbreviated as C16H3PW11Cr, C16:
cetyltrimethyl ammonium) was designed and used as
heterogeneous catalyst for fructose dehydration. 40.6%
HMF yield with 90.3% fructose conversion can be obtained
due to its dual acidity and hydrophobicity, which can
prevent further decomposition of HMF to levulinic acid
and formic acid. Moreover, C16H3PW11Cr can be recycled for
six runs [157]. Cesium exchanged dodecatungstophophoric
acid (Cs2.5H0.5PW12O40) with strong acidity catalyst was also
tested. It was performed in water–MIBK biphasic system
with 74.0% HMF yield and 94.7% HMF selectivity. More
important is that Cs2.5H0.5PW12O40 is tolerant to such high
concentration of 50 wt% fructose and its possibility for
recycling [158]. Ag3PW12O40 [159] and silver exchanged
silicotungstic acid (AgSTA) [160] were also proved to be
active recyclable catalyst for fructose dehydration to HMF
due to its moderate Lewis acidity of Ag.
To avoid the large usage and difficult separation
of ILs, HPA–IL composites have also been reported
and utilized as catalysts for acid-catalyzed reactions
[165,166]. 1-(3-sulfonic acid)propyl-3-methylimidazolium
Unauthenticated
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47
Acid-Catalyzed Dehydration of Fructose to 5-(Hydroxymethyl)furfural
Table 5. Conversion of fructose to HMF using heteropoly acid-based catalysts
Entry
mfructose
Reaction conditions
catalyst
1
0.5 g
2
0.6 g
3
0.6 g
4
2.4 g
5
1.0 g
6
0.5 g
7
50 mg
8
50 mg
9
50 mg
Post- reaction details
Solv.
H3PW12O40 or H4SiW12O40
(0.1 mmol)
C16H3PW11Cr
(0.1 mmol)
Cs2.5H0.5PW12O40
(128 mg)
T
/oC
[BMIM]Cl
80
(0.6 g)
H2O
130
(2 mL)
H2O
115
(2 mL) + MIBK
(6 mL)
Ag3PW12O40
H2O (8 mL) +
120
(80 mg)
MIBK (18 mL)
Ag4[Si(W3O10)4]·nH2O (10 wt%) H2O
120
(10 mL)
[MIMPS]3PW12O40 (0.25 g)
sec-butanol (100120
mL)
[SO3H-IL]3[PW12O40]2
DMSO
100
(2.5 mol% relative to fructose) (2 mL)
poly(VMPS)-PW
DMSO
130
(30 mg)
(0.5 mL)
PTA(3.0)/MIL-101
[EMIM]Cl
80
(20 mg)
(0.5 g)
Ref.
t
Conv. /% sel. /% Yield /% Catalyst
reuse
5 min
>99
99
99
1.5 h
90.3
45
40.6
at least ten 156
runs
six runs
157
1h
78
94.7
74.0
six runs
158
1h
83
93.8
77.7
six runs
159
120 min 98
87
85.7
eight runs
160
2h
99.7
98.8
99.1
six runs
161
1h
>99
92
92
five runs
162
1h
98
85
83
five runs
163
1h
84
74
63
Three runs
164
[MIMPS]3PW12O40: 1-(3-sulfonicacid)propyl-3-methyl imidazolium phosphotungstate; poly(VMPS)-PW: Poly(1-vinyl-3-propane sulfonate
imidazolium)-H3PW12O40; [EMIM]Cl: 1-ethyl-3-methylimidazolium chloride;
SO3H-IL: N,N,N’,N’-tetramethyl-N,N’-dipropanesulfonic acid ethylenediammonium salt.
phosphotungstate ([MIM-PS]3PW12O40) [161] and [SO3HIL]3[PW12O40]2 [162] can both catalyze dehydration of
fructose to HMF in 99% yield and they can be reused for
at least five times.
4 Heterogeneous catalytic dehydration over solid acid catalysts
4.1 Supported ILs and HPAs
Although excellent fructose conversion and HMF
selectivity can be obtained in IL-based system, isolation
of IL is still a big disadvantage. Supported-IL catalysts
(SILCs, Table 4, entries 26-27), like silica gel supported
ILs, [151] fiber supported ILs (FSILs) [152] and nanosized amorphous silica particles supported IL NPs
(SILnPs, covalently bonded) [167] exhibited improved
results for the dehydration reaction in terms of activity
and reusability compared with mineral acids and other
homogeneous catalytic systems. Functional polymeric
ILs (FPILs) were also prepared by coupling of SO3Hfunctionalized polymeric ILs with different counterpart
anions. The catalytic activity of the prepared solid FPILs
with the presence of DMSO-mediated solvents, produced
moderate to excellent yields of HMF under atmosphere
pressure [168].
Supported HPA catalysts were also investigated with
polymers or MIL-101 (a chromium-based metal–organic
framework) as supports (Table 5, entries 8 & 9). The
obtained Brønsted-acidic poly(1-vinyl-3-propane sulfonate
imidazolium)-H3PW12O40 [poly(VMPS)-PW] [165] and
MIL-101 encapsulated H3PW12O40 (PTA/MIL-101) [166] were
used as active heterogeneous catalysts.
4.2 Ion-Exchange Resins
An ion-exchange resin or ion-exchange polymer is an
insoluble matrix (or support structure) normally in
the form of small (0.5-1 mm diameter) beads, usually
white or yellowish, fabricated from an organic polymer
substrate. The two main classes of ion-exchange resins
are based upon styrene-based sulfonic acids (Amberlyst®
and Dow type resins), [169-171] which show very high
activity for esterification and etherification. Due to their
special characteristics, they were widely used in fructose
dehydration to HMF (Table 6) [172-178].
The pioneering work for HMF production was
published in Science in 2006 by Dumesic and coworkers
Unauthenticated
Download Date | 6/18/17 2:23 PM
48 Y. Qiao et al.
Table 6. Conversion of fructose to HMF using heterogeneous ion-exchange resins
Entry
mfructose
Reaction conditions
Cat.
Sol.
7:3 (8:2
90
Water:DMSO):PVP (5
g) /7:3 MIBK:2-butanol
(5 g)
H2O
135
(300 mL)
THF
120
(10 mL)
dioxane
100
(100 mL)
DMSO
120
(3 ml)
DMSO
140
(5.0 g)
1
30 wt %
ion-exchange resin
(30 wt %)
2
20 g
Amberlyst-15 (4 g)
3
0.25 g
Amberlyst-15 (0.29 g)
4a
9g
Amberlyst-15 (10 g)
5
0.4 g
Amberlyst-15 (0.1 g)
6
0.38 g
Amberlyst-70 (0.20
mmol H+)
7b
306 mg
8
30 mg
Amberlyst-15 powder
(0.02 g) in a size of
0.15–0.053 mm
Amberlyst-70
(50 mg)
Amberlyst-70 (50 mg)
9
10
11
12
13
14
15
16 c
17 c
18
19
20
21
22
Post- reaction details
DMSO
(10 g)
T
/oC
120
H2O (1.5 mL) + DHMTHF 130
(96 g)
30 mg
GVL (1.35 g)
130
+ H2O (0.15 g)
30 mg
Amberlyst-70 (50 mg) GHL (1.35 g)
130
+ H2O (0.15 g)
30 mg
Amberlyst-70 (50 mg) THF (1.35 g)
130
+ H2O (0.15 g)
300 mg
acidic polystyrene-codi- H2O (3 mL) +
130
vinylbenzene resin
2-MTHF
(50 mg)
(20 mL)
4.5 g
Ion-exchange resin (10 DMSO
80
meq.)
(50 mL)
270 mg
Amberlyst-15 (70 mg) 1,4-dioxane
100
(4.5 mL) + DMSO (0.5
mL)
feed solution: 1,4-dioxane (450 mL), DMSO (50 mL), and
110
D-fructose (27 g)
0.1 g
Dowex
acetone (3.5 g)- H2O 150
(1.5 g)
50wx8-100
(0.1 g)
0.1 g
Dowex
acetone (3.5 g)-DMSO 150
50wx8-100
(1.5 g)
(0.1 g)
0.1 g
Amberlyst-15 (0.1 g)
DMF
100
(3 mL)
0.1 g
Amberlyst-15 (0.1 g)
DMF
100
(3mL)
72 mg
Amberlyst-15
[BMIM][BF4] (0.5 mL) + 80
(70 mg)
DMSO (0.3 mL)
72 mg
Amberlyst-15
[BMIM][PF6] (0.5 mL) + 80
(70 mg)
DMSO (0.3 mL)
50 mg
Amberlyst-15 (50 mg) [BMIM]Cl (1 g) +
25
acetone (50 mg)
Ref.
t
Conv. /% Sel. /% Yield /% Cat. reuse
8-16 h
83
65
54
n.d.
179
400 min ≈ 31
≈ 54
≈ 17
n.d.
180
20 min 98
49
48
Eleven runs181
3h
98
82
80
Five runs
1h
100
82
82
seven runs 183
1h
100
93
93
Three runs 184
2h
100
100
100
n.d.
185
29 min 87
70
61
n.d.
186
9 min
89
80
71
n.d.
187
10 min 91
81
74
n.d.
187
10 min 91
85
77
n.d.
187
1h
≈ 84
≈ 60
50
n.d.
188
5h
n.d.
n.d.
89
n.d.
189
3h
n.d.
n.d.
75
n.d.
190
3 min
98
94
92
96 h
190
15 min 95.1
77
73.4
Five runs
191
20 min 97.6
90
88.1
Five runs
192
3h
>99
73
73
n.d.
193
1h
100
91
91
n.d.
194
32 h
n.d.
n.d.
75
n.d.
195
24 h
n.d.
n.d.
70
n.d.
195
6h
90.3
86.5
78.1
n.d.
196
182
Unauthenticated
Download Date | 6/18/17 2:23 PM
Acid-Catalyzed Dehydration of Fructose to 5-(Hydroxymethyl)furfural
49
Table 6. Conversion of fructose to HMF using heterogeneous ion-exchange resins
continued
Entry
mfructose
Reaction conditions
Cat.
23
24
25
26
27
28
29
30
31
32
0.1 g
Post- reaction details
Sol.
D001-cc resin (0.1 g)
T
/oC
[Bmim]Cl
75
(1.5 g)
25 mg
Amberlyst-15
[BMIM][BF4]/[BMIM]
25
(25 mg)
Cl binary mixture (XCl=
0.5, 0.5 g)
0.1 g
Amberlyst-15 (ground, [BMIM]Cl
80
50 mg)
(0.65 g)
10 wt%
Dowex®
[BMIM]Cl
100
50Wx8-200 (10%)
(3 mL)
1g
Amberlyst-70 (0.1 equiv [BMIM]Cl
110
H+)
(2.5 g)
1g
Amberlyst-70 (0.1 equiv [BMIM]Cl/glyce-rol (2.5 110
H+)
g, 65:35 wt%)
1g
Amberlyst-70 (0.1 equiv [BMIM]Cl/glyce-rol car- 110
H+)
bonate (2.5 g, 65:35
wt%)
50 mg
sulfonic ion-exchange [BMIM]Cl
80
resin (50 mg)
(1 g)
2g
Amberlyst-15 (10%)
tetraethylammonium 100
bromide (TEAB, 18 g) /
H2O (2 g)
1 g of fructose in TEAB (20 g)-water (5 g) through a glass
100
reactor containing Amberlyst-15 (3.5 g)
t
Ref.
Conv. /% Sel. /% Yield /% Cat. reuse
20 min n.d.
n.d.
93.0
Seven runs 197
3h
n.d.
56
n.d.
198
10 min 99
82.8
82
n.d.
199
3h
n.d.
n.d.
60
n.d.
200
15 min n.d.
n.d.
94
n.d.
201
8 min
n.d.
n.d.
70
n.d.
201
35 min n.d.
n.d.
98
n.d.
201
10 min 98.6
84.5
83.3
Seven runs 202
15 min 100
100
100
Six runs
203,
204
0.9 mL/ n.d.
min
n.d.
90
n.d.
203,
204
n.d.
PVP: polyvinylpyrrolidone; MIBK: methyl isobutyl ketone; THF: tetrahydrofuran; DHMTHF: 2,5-(dihydroxymethyl)-tetrahydrofuran; GVL:
γ-valerolactone; GHL: γ-hexalactone; 2-MTHF: 2-methyltetrahydrofuran; [BMIM][BF4]: 1-butyl-3-methylimidazolium tetrafluoroborate; [BMIM]
[PF6]: 1-butyl-3-methylimidazolium hexaphosphate; [BMIM]Cl: 1-butyl-3-methylimidazolium chloride; DMF: dimethylformamide. a 9 g Fructose corresponds to 14.3 g HFCS-90 (high fructose corn syrup) and 10 g Amberlyst-15 corresponds to 47 mmol of -SO3H. b The reaction was
typically performed under evacuation at 0.97 × 105 Pa or under 1.01 × 105 Pa N2 without evacuation; c Microwave irradiation
[179]. A biphasic system to separate HMF from the
aqueous phase using 7:3(8:2 Water:DMSO):PVP mixture
as a reaction media and equivalent mixture of 7:3 MIBK:2butanol as an extraction phase was first reported. 65%
of HMF selectivity at 83% of fructose conversion at 30 wt
% fructose concentration was achieved with acidic resin
catalyst (Table 6, entry 1).
It is clear to see that with ion-exchange resin as
catalyst, high HMF selectivity and yields can be obtained
in biphasic systems,[180] organic solvents,[181-194] and
ILs [195-202,205]. The combination of IL with ion-exchange
resin catalyst reduces the reaction time, and the conversion
of fructose to HMF in ILs is highly selective. Furthermore,
microwave heating showed remarkable accelerating effect
both on fructose conversion and HMF yield [191,192].
Also, IL-like structure salt, tetraethylammonium bromide
(TEAB) was used as reaction media in Simeonov’s
and Afonso’s group for HMF production from fructose
[203,204].
Decreasing in the particle size of Amberlyst-15
resin was found to be an effective way to improve HMF
yield [185]. Acidic polystyrene-co-divinylbenzene resin
catalysts were also reported and the cross-linker content
of the resin was found to be the most influential factor for
fructose dehydration to HMF [188].
Continuous dehydration of D-fructose was already
carried out under mild conditions in early 1980, using
acidic ion-exchange resin with a low divinylbenzene
content as the catalyst and DMSO as a solvent, to give 89%
HMF yield [189]. In 2012, Aellig and Hermans reported
HMF production from fructose under continuous flow
with 92 % HMF yield. The space–time yield was found to
be 75 times higher than that of the batch reaction [190].
Internal and external mass transfer limitations could be
eliminated by changing the particle size and by adjusting
the flow rate. Furthermore, the catalyst was stable over
96 h.
Unauthenticated
Download Date | 6/18/17 2:23 PM
50 Y. Qiao et al.
Table 7. Conversion of fructose to HMF using zeolites
Entry
mfructose
Reaction conditions
catalyst
1
3.5 g
2
3.5 g
3
20 g
4
10 wt%
5
218 mg
6
1g
7
600 mg
8
5 wt%
9
5 wt%
10
180 mg
11
180 mg
12
0.625 g
Post- reaction details
Solvents
Ref.
T
/oC
t
Conv. /% Sel. /% Yield /% Catalyst
reuse
mordenite
H2O (35 mL) + MIBK
(Si/Al = 11)
(175 mL)
(1 g)
mordenite
H2O (35 mL) + MIBK
(Si/A1 = 11)
(175 mL)
(1 g)
zeolite mordenite
H2O (300 mL) + MIBK
(4 g)
(900 mL)
H-BEA-18 (SiO2/Al2O3 = 18, H2O
Al/fructose molar ratio=0.1)
zeolite microspheres (18
DMSO
mg)
(8 g)
165
1h
76
91
69
n.d.
165
2h
93
78
73
several runs 208
165
≈75
≈65
49
130
400
min
6h
≈24
≈15
4
At least two 209
runs
three runs 210
120
5h
100
77
77
n.d.
211
H-Beta
(0.15 g)
BetaM
(80 mg)
Sn-Mont
(0.2 g)
Sn-Mont (0.2 g) + NaCl
(0.37 g)
K-10 clay-Cr (120 mg)
165
1h
93
43
40
n.d.
212
130
8h
75
15
11
n.d.
213
160
3h
n.d.
n.d.
≈78
n.d.
214
160
3h
n.d.
n.d.
78.8
six runs
214
100
3h
n.d.
n.d.
75.7
six runs
215
120
3h
n.d.
n.d.
93.2
six runs
216
150
4h
80
≈23
≈18
n.d.
217
H2O (10 mL) + MIBK
(50 mL)
H2O
(60 g)
THF (4.2 mL) –DMSO
(1.8 mL)
H2O (1 mL) +
THF (5 mL)
DMSO
(5 mL)
K-10 clay-Al (150 mg)
DMSO
(5 mL)
H-Beta (0.62 g) + 2% carbon H2O
adsorbent BP2000
(52.4 g)
4.3 Zeolites
Zeolites are microporous, aluminosilicate minerals
commonly used as commercial adsorbents and catalysts.
Zeolites have large open cage-like structures that form
channels. These channels allow the easy movement of
ions and molecules into and out of the structure. This
ability assigns zeolites to the class of materials known as
“molecular sieves”. Zeolites may offer advantages over
other acidic catalysts in sugar dehydration, including
simple catalyst separation relative to homogeneous acid
catalysts, stability in high-temperature aqueous systems
compared to Amberlyst resins, and stability to thermal
regeneration. Indeed, zeolite catalysts have frequently
been investigated for fructose dehydration reactions
(Table 7).
Early in 1990th, Moreau and Rivalier used H-form
zeolites as catalysts for fructose dehydration at 165°C and
in a mixed solvent of water and MIBK (1:5 by vol.) [206-208].
Fructose conversion and selectivity to HMF were found to
depend on both acidic and structural properties of the
catalysts used. H-mordenite with Si/Al ratio of 11 showed
206,
207
the promising fructose conversion and HMF selectivity,
and they can be used for several runs without loss of both
activity and selectivity [209]. Similar materials, such as
H-BEA zeolite with SiO2/Al2O3 = 18 (abbreviated as H-BEA18), [210] zeolite microspheres (ZMSs),[211] USY, Beta and
ZSM-5 zeolites with alkaline,[212,213] Sn-Mont,[214] as
well as cation-exchanged montmorillonite K-10 clay and
chromium-exchanged K-10 clay (K-10 clay-Cr)[215,216]
were also attempted to use for fructose dehydration. Most
of the catalysts could be effectively recycled several times
without significant loss of activity. And HMF selectivity
was also found to be dependent on the acid sites strength
of the investigated zeolites. Higher selectivities towards
HMF were detected for all modified zeolites, compared to
the parent ones [213].
Carbon black (BP2000) was used as an adsorbent
for fructose dehydration using zeolite catalysts in
aqueous phase [217]. BP2000 carbon black exhibited
high selectivity and capacity for the adsorption of HMF
and furfural, which was due to the large surface area,
hydrophobic nature and micropore structure. With using
the carbon adsorbent, furan selectivity (selectivity of HMF
Unauthenticated
Download Date | 6/18/17 2:23 PM
Acid-Catalyzed Dehydration of Fructose to 5-(Hydroxymethyl)furfural
and furfural) over zeolite beta was improved from 27% to
44% with a furan yield of 41%.
It was reported by Nikolakis group that for fructose
dehydration with zeolite catalysts, about 1-2% of the
zeolite dissolves, resulting in a solution of aluminosilicate
species with Al contents between 1.2-26.2 mg/L and Si
contents up to 226 mg/L. The actual concentration of these
species depends on the zeolite type used and on its Si/
Al ratio. And these species homogeneously catalyze side
reactions of fructose and sequential reactions of HMF, but
not glucose-fructose isomerization [218].
4.4 Functionalized carbonaceous materials
Due to the high stability of carbon materials and
complementary properties on forms of hydrophobicity,
various (mainly sulfonated) carbonaceous materials were
also used as solid catalysts for fructose dehydration to
HMF (Table 8).
Sulfonated carbonaceous material (Glu-TsOH)
bearing –SO3H, –OH, and –COOH groups via one-step
hydrothermal carbonization of glucose and p-toluene
sulfonic acid was prepared under mild conditions
and Wang’s group reported its application in fructose
dehydration. Besides the high HMF yield obtained, this
catalyst also displayed a good reusability; the conversion
and selectivity still retain 99.9% and 89.1% even after
five cycles. This remarkable catalytic performance is
ascribed to the good affinity of fructose on the catalyst
and the synergic effect between surface carboxylic acid
and sulfonic acid groups [219]. Similar cellulose-derived
carbonaceous solid acid catalyst (abbreviated as CCC)
containing –SO3H, –COOH and phenolic –OH groups,[220]
cellulose sulfuric acid,[221] lignin-derived solid acid
catalyst (abbreviated as LCC)[222] and porous sulfonated
carbonaceous TiO2 material (Glu-TsOH-Ti),[223] as well
as phosphorylated mesoporous carbons (PMCs)[224] and
superhydrophobic mesoporous acid (P-SO3H-154)[225]
were reported for fructose dehydration in succession.
Lignosulfonic acid (LS, C18H22.4O11S1N0.14), which is
a waste byproduct from paper industry, can catalyze
fructose dehydration in ILs with 94.3% HMF yield.
Furthermore, the material can also be recycled for six runs
with only slight activity decrease [226]. Ultra-low ash Taixi
coal was also functionalized with sulfonic acid group to
form coaled carbon-based solid acid (Coal-SO3H) [235].
Porous polydivinylbenzene (PDVB) was also treated with
H2SO4 at 250°C to form sulfated porous carbon (PC-SO3H)
[227]. Both materials were tested by fructose dehydration
reaction and can be reused for several times without
significant activity loss.
51
Other sulfonic acid functionalized carbon materials
(C–SO3H), including poly(p-styrenesulfonic acid)-grafted
carbon nanotubes (CNT-PSSA), poly(p-styrenesulfonic
acid)-grafted
carbon
nanofibers
(CNF-PSSA),
benzenesulfonic acid-grafted CMK-5 (CMK-5-BSA), and
benzenesulfonic acid-grafted carbon nanotubes (CNTBSA) were reported in Chen’s group. Among these four
materials, CNT-PSSA exhibits the highest acid density as
well as the best performance on fructose dehydration with
HMF yield of 89%. It can also be reused for at least three
runs [228].
Polyethylene fiber was used as support to graft
acrylonitrile and vinylsulfonic acid (or vinylphosphonic
acid) monomers on the surface. The obtained material
proved to be an effective catalyst for fructose dehydration
solely in water. It is likely that sulfonic and phosphonic
acid groups on the polymer surface have a strong
interaction with water, creating a branched environment
easily accessible to fructose [229]. Sulfonated carbon
foam,[230] polyethylene glycol (PEG)-bound sulfonic
acid (PEG-OSO3H), polystyrene-poly(ethylene glycol)
(PS-PEG) resin-supported sulfonic acid (PS-PEG-OSO3H)
[231] also showed encouraging activity and selectivity for
fructose dehydration and HMF production. Carbon–silica
composites containing SO3H groups were reported to be
effective acid catalysts for the production of furanic ethers
and levulinate esters (bioEs), and HMF was also produced
as intermediate product [232].
Graphite derivatives such as graphite oxide (GO),
reduced graphite oxide (RGO) and sulfated reduced
graphite oxide (GSO3H) were applied for the fructose
dehydration reaction. Among these materials, GO was
proved to be the most efficient. Besides the active sulfonic
groups, oxygen-containing groups (alcohols, epoxides,
carboxylates), which can form strong hydrogen-bonding
interactions with fructose, also have an important
synergic effect in maintaining the high performance of
GO. Moreover, GO can be used for several runs with slight
deactivation [233,234].
4.5 Functionalized mesoporous materials
A mesoporous material is a material containing pores
with diameters between 2-50 nm. Mesoporous materials
have been widely studied in catalysis due to their special
properties, like the large surface area of the pores.
Therefore, functionalized mesoporous materials were
also investigated as solid acid catalysts for fructose
dehydration to HMF (Table 9).
In the last few years, Scott and Dumesic designed
several kinds of acid-functionalized SBA-15-type silica
Unauthenticated
Download Date | 6/18/17 2:23 PM
52 Y. Qiao et al.
Table 8. Conversion of fructose to HMF using functionalized carbonaceous materials
Entry
mfructose
T
/ oC
t
Conv. /% Sel. /% Yield /% Catalyst
reuse
Glu-TsOH
(0.4 g)
Cellulose-derived carbonaceous solid acid catalyst
(40 mg)
Cellulose sulfuric acid (50 mg)
DMSO
(6 mL)
[BMIM]Cl
(1 g)
130
1.5 h
99.9
91.2
91.2
five runs
219
160
15 min n.d.
n.d.
81.4
five runs
220
DMSO
100
(3 mL)
0.1 g
Lignin-derived solid acid cata- DMSO (0.8 g)110
lyst (LCC) (0.1 g)
[BMIM]Cl (1.2 g)
0.2 mmol
porous sulfonated carbonace- H2O (1 mL) +
180
ous TiO2 (22 mg)
MeTHF (2 mL)
5 wt%
Phosphorylated mesoporous H2O
120
carbon (P/N-0.25, P/N-0.50
and P/N-0.75) (2.5 wt%)
100 mg
superhydrophobic solid acid DMSO (5 g) or
100
(p-SO3H-154, 50 mg)
THF (3 g) –DMSO
(2 g)
0.2 g of P-SO3H-154, 2.0 wt% fructose in THF–DMSO solution 100
(weight ratio of 1.5), reaction flux: 0.2 mL·min-1
0.2 g
lignosulfonic Acid
[Bmim]Cl
100
(LS, 0.05 g)
(2.0 g)
0.1 g
sulfonated porous carbon (PC- THF (3 g) – DMSO 110
SO3H, 50 mg)
(2 g)
150 mg
CNT-PSSA
DMSO
120
(15 mg)
(1.5 mL)
5.6 wt%
HSO3–fiber
H2O
120
(8.6 wt %)
5.6 wt%
H2PO3–fiber
H2O
120
(8.6 wt%)
10 g
sulfonated polystyrene- poly- H2O (150 mL) + 135
propylene (2 g)
MIBK (450 mL)
10 g
Carbon Foam supported sulfo- H2O (150 mL) + 135
nated polystyrene
MIBK (450 mL)
(2 g)
0.36 g
LiCl (0.3 g)
H2O
120
PEG-OSO3H (0.7 g, 0.23 mmol) (2 mL) + DMSO
(4 mL)
0.36 g
LiCl (0.3 g)
H2O
120
PS-PEG-OSO3H
(2 mL) + DMSO
(0.2 g,
(4 mL)
0.66 mmol)
0.33 M
carbon–silica composite
Ethanol–water 170
(10 gcat dm-3)
90 mg
graphene oxide
DMSO
120
(8 mg)
(2 mL)
1.0 g
graphite oxide
DMSO
120
(25 mg)
(10 mL)
45 min 100
93.6
93.6
six runs
221
10 min 98
85.7
84
five runs
222
60 min 99
59.6
59
four runs
223
16 h
16 h
16 h
10 h
48
68
78
n.d.
70
63
53
n.d.
34
43
41
>99.0
six runs
224
n.d.
225
-
40-50
>99
40-50
45 h
225
10 min n.d.
n.d.
94.3 six runs
226
4h
n.d.
68.3
four runs
227
30 min >99
89
89
three runs
228
6h
72
47
34
four runs
229
6h
79
34
27
four runs
229
4.5 h
23
78
18
n.d.
230
4.5 h
27
75
19
three runs
230
1.5 h
>99
90
90
seven runs 231
1h
99
95
94
seven runs 231
1h
78
55
43
n.d.
232
6h
100
93
93
four runs
233
4h
n.d.
n.d.
60.8
five runs
234
2
100 mg
3
180 mg
6b
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Ref.
Solv.
0.5 g
5
Post- reaction details
catalyst
1
4a
Reaction conditions
n.d.
Glu-TsOH: sulfonated carbonaceous material; MeTHF: methyltetrahydrofuran; Phosphorylated mesoporous carbon composites P/N-0.25,
P/N-0.50, P/N-0.75: H3PO4/HNO3 in molar ratio of 0.25, 0.50 and 0.75; CNT-PSSA: poly(p-styrenesulfonic acid)-grafted carbon nanofibers. a
With microwave irradiation (power 100W); b PN2=3 atm
Unauthenticated
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Acid-Catalyzed Dehydration of Fructose to 5-(Hydroxymethyl)furfural
53
Table 9: conversion of fructose to HMF using functionalized mesoporous materials
Entry
mfructose
Reaction conditions
catalyst
1
450 mg
2
450 mg
3
2 wt%
4
30 mg
5
30 mg
6
30 mg
7
120 mg
8
120 mg
9
0.2 g
10
0.18 g
11
0.22 g
12
0.33 M
13
0.33 M
14
0.23 g
15
0.375 g
16a
0.1 g
17
7g
18
1g
Post- reaction details
Solv.
propylsulfonic
H2O (1.05 g) + (7:3
acid-functionalized silica MIBK:2-butanol 3.0
(Taa-SBA-15, 50 mg)
g).
TESAS-SBA-15
H2O (1.05 g) + (7:3
(142 mg, 64 μmol of
MIBK:2-butanol 3.0
acid)
g).
acid-functionalized SBA- THF and H2O
15-type periodic meso- (4:1 w/w)
porous organosilicas
PVP modified
THF (1.2 g)-H2O
silica-based material
(0.3 g)
(PVP-pSO3H-SS, 100 mg)
PVP modified
THF (1.2 g)-H2O
silica-based material
(0.3 g)
(PVP-pSO3H-SBA-15,
100 mg)
PVP modified
THF (1.2 g)-H2O
silica-based material
(0.3 g)
(PVP-pSO3H-MCM-41,
100 mg)
sulfonic acid-functiona- H2O
lized organosilica (SBA- (2 mL)
C2Ph-coc,
DMSO
6 mg)
(2 mL)
SBA-15-SO3H
[BMIM]Cl
(20 mg)
(2.0 g)
mesoporous sulfonic
H2O (0.5 mL)
acids (SBA-15-PrSO3H, + nitromethane (4.5
2 mol%, 17 mg)
mL)
sulfonic acid functiona- water (0.5 mL) +
lized periodic mesopo- MIBK/2-butanol
rous organosilica (PMO) (70/30; 1.5 mL)
materials (Ph-PMOPrSO3H, 37 mg)
C/SBA (Si/Al molar ratio: H2O
45)
(10 gcat dm-3)
C/MCF(Si/Al molar ratio: H2O
63)
(10 gcat dm-3)
Poly(4-styrenesulfonic H2O
acid) brush-grafted silica (3.5 mL)
particles (0.10 g)
Nafion(15)/Mesocellular DMSO
Silica Foam
(11 mL)
(acid amount:
0.06 mmol H+)
SiO2-gel
H2O
(50 mg)
(6 mL)
SiO2-gel
H2O (6 mL) + MIBK
(0.1 g)
(50 mL)
AlSBA-15 (Si/Al=40)
H2O (10 mL) + MIBK
(0.15 g)
(50 mL)
Ref.
T
/oC
t
Conv. /% Sel. /% Yield /% Catalyst
reuse
180
30 min 66
74
49
n.d.
236
130
141
min
84
71
60
n.d.
237
130
-
up to 95 60 to 75 Up to 71 up to 190 h 238
130
≈83
min
48
64
31
four runs
239
130
≈54
min
52
87
45
n.d.
239
130
≈
2h
57
85
48
n.d.
239
120
3h
1
100
1
n.d.
240
120
3h
>99
83
83
n.d.
240
120
1h
99.2
81
81
four runs
241
140
30 min 93
75
70
three runs
242
160
75 min 95
61
58
two runs
243
140
6h
89
44
39
two runs
244
140
4h
83
47
39
two runs
244
120
6h
80
34
27
five runs
245
90
2h
94
95.0
89.3
five runs
246
160
65 min 50
100
50
n.d.
247
88
8h
n.d.
n.d.
47
n.d.
247
165
1h
59
88
51.9
n.d.
248
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54 Y. Qiao et al.
Table 9: conversion of fructose to HMF using functionalized mesoporous materials
continued
Entry
mfructose
19
0.5 g
20
600 mg
21
100 mg
22
100 mg
23
15 mg
24
15 mg
25
50.0 mg
26
0.18 g
27
20 mg
Reaction conditions
Post- reaction details
Ref.
catalyst
Solv.
T
/oC
t
Conv. /% Sel. /% Yield /% Catalyst
reuse
AlSBA-15 (Si/Al=40)
(75 mg)
borosilicate, B-TUD-1
(200 mg)
none
DMSO
(20 mL)
water (2 mL) +
toluene (6 mL)
[BMIM]HSO4
(1 g)
[BMIM]HSO4
(1 g)
120
2h
96
190
H3BO3–SiO2
(15 mg, 0.02 mmol of
boric acid),
LPMSN-based catalysts [EMIM]Cl
(4 mg)
(150 μL)
[HSO3 + (ILs/CrCl2)]-MSN DMSO
(4 mg)
(0.5 mL)
Silica supported IL nano- DMSO
particle catalyst (40 mg) (0.5 mL)
Fe3O4-SBA-SO3H
DMSO
(0.1 g)
(3 mL)
Fe3O4@Si/Ph-SO3H (10 DMSO
mg)
(1.0 mL)
77
74
four runs
248
40 min 90
66.7
60
three runs
249
120
2
n.d.
n.d.
72
n.d.
250
120
1.5
n.d.
n.d.
88
four runs
250
120
3h
n.d.
n.d.
66-70
n.d.
251
90
3h
97.0
74.8
72.5
five runs
252
130
30 min 99.9
63.0
63.0
seven runs 253
110
2h
>99
81
81
five runs
254
110
3h
>99
82.3
82.3
three runs
255
TESAS-SBA-15: 3-((3-(trimethoxysilyl)-propyl)thio)propane-1-sulfonic acid functionalized SBA-15; MCF: mesostructured cellular foam; LPMSN:
Mesoporous silica nanoparticles (MSNs) with large pore size; [HSO3 + (ILs/CrCl2)]-MSN: Mesoporous silica nanoparticles (NPs) functionalized with both sulfonic acid (HSO3) and Ionic liquid (ILs). a In autoclave with 20 bar of synthetic air.
catalysts and applied them to fructose dehydration to
HMF. In 2010, they incorporated propylsulfonic acid to
thiopropyl-functionalized mesoporous silica (Tp-SBA-15)
and the obtained material Taa-SBA-15 achieved 74% HMF
selectivity with 66% fructose conversion [236]. In 2011, they
incorporated a bifunctional silane, 3-((3-(trimethoxysilyl)
propyl)thio)propane-1-sulfonic acid (TESAS), into SBA15-type silica by co-condensation, the thioether group of
TESAS was further oxidized by H2O2 to the sulfone in a
comparative case. Interestingly, the thioether-containing
TESAS-SBA-15 shows higher activity in the fructose
dehydration, as well as higher selectivity towards HMF
(71% at 84% conversion) than its sulfone derivative,
possibly because of its more hydrophobic nature [237]. In
2012, they reported another system for HMF production in
a single-phase solution of THF and H2O (4:1 w/w) using
several supported acid catalysts in tubular reactors. Three
propylsulfonic acid-functionalized, ordered porous silicas
(one inorganic SBA-15-type silica, and two ethane-bridged
SBA-15-type organosilicas) were compared with that of a
propylsulfonic acid-modified, non-ordered, porous silica.
The HMF selectivity of the catalysts with ordered pore
structures ranged from 60 to 75%, whereas the selectivity
of the non-ordered catalyst under the same reaction
conditions peaked at 20%. But deactivation under
flow conditions was observed [238]. Later in 2013, they
designed a nanocomposite catalyst, acid-functionalized
mesoporous
silica
with
poly(vinylpyrrolidone)
intercalated and cross-linked inside and also applied it for
fructose dehydration. Although fructose conversions were
lower than the former two cases, the HMF selectivities
were higher. All PVP intercalated materials show higher
conversions and selectivities than the corresponding PVPfree materials [239].
Similar catalytic dehydration systems were also
reported using sulfonic-acid functionalized SBA-15
materials (SBA-15-SO3H), [240-242] sulfonic acid
functionalized periodic mesoporous organosilica
(Ph-PMO-PrSO3H) materials, [243] mesoporous (SO3H)functionalised-carbon/silica (C/Si) composites with large
pores and high density of acid sites (up to 2.3 mmol g-1)
[244] and poly(4-styrenesulfonic acid) brush-grafted silica
particles, [245] as well as Nafion-modified mesocellular
silica foam (MCF) materials [246]. It was reported by B.
Karimi’s group that the hydrophilic surface of solid acids
might improve HMF selectivity via faster departure of HMF
from the mesopores and thus retarding the rehydration
of HMF to unwanted by-products [242]. Among all the
investigated materials, ordered mesoporous silicas MCF
and SBA-15 were found to be the favorable support for
Unauthenticated
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Acid-Catalyzed Dehydration of Fructose to 5-(Hydroxymethyl)furfural
fructose dehydration to HMF [244]. Pure silica-gel could
afford 100% HMF selectivity [247].
Aluminosilicate mesoporous MCM-41 [256] and
Al-SBA-15 catalysts with different Si/Al ratios [248] were
also applied for fructose dehydration. It was found that
5% Al addition to MCM-41 leads to the reaction activity
enhanced by more than twice. Furthermore, sulfonated
MCM-41 material showed higher reactivity with 51.8%
HMF yield and 83.3% fructose conversion [256]. It was
also found that part of aluminium is substituted into
tetrahedral positions and the material with lower acid
site density but medium to strong acid strength favours
selective formation of HMF. 51.9% HMF yield with 59%
fructose conversion can be obtained with Al-SBA-15 (Si/
Al=40, actual ratio was 65 determined from ICP-OES).
Leaching of aluminium was observed with water as
solvent, while activity can be retained when DMSO is used
as solvent [248].
Amorphous mesoporous borosilicate, B-TUD-1 is also
efficient for HMF production from fructose. Leaching of
boron occurred in pure water solution and the leached
boron was demonstrated to be the active species but
the catalyst can be reused for three runs in total [249].
Silica-supported boric acid and its application in fructose
dehydration in IL [BMIM]HSO4 was reported with 88% HMF
yield. The catalyst and the solvent system can be recycled
for up to four consecutive cycles without a significant loss
in conversion [250]. Mesoporous silica NPs (with large
pore size around 30 nm) was also functionalized with acid
(-SO3H), base (-NH2) and both acid-base (-SO3H and -NH2)
functional groups (namely, LPMSN-SO3H, LPMSN-NH2
and LPMSN-both, respectively) in Wu’s group. These
materials could easily convert fructose into 5-HMF in the
IL [EMIM]Cl system at 120 oC with 66-70% HMF yield due
to the favorable HMF production system with IL and high
reaction temperature [251]. Wu group also functionalized
mesoporous silica NPs with both sulfonic acid (HSO3-) and
ionic liquid (ILs) and applied it for HMF production from
fructose with 72.5% HMF yield [252]. Similar supported
IL NPs (SILnPs) having particle size ranging from 293
± 2 to 610 ± 11 nm by immobilization of IL, 1-(tri-ethoxy
silyl-propyl)-3-methyl-imidazolium hydrogen sulfate
(IL-HSO4), on the surface of silica NPs were reported by
Sidhpuria and Coutinho. Around 63.0% HMF yield with
99.9% fructose conversion can be obtained using silica
supported IL NP catalyst and it can be recycled for seven
runs without significant loss in both fructose conversion
and HMF yield [253].
Due to obvious advantages of magnetic separation,
magnetically recyclable acid catalysts composed of Fe3O4
core and sulfonic acid functionalized silica shell were
55
applied for fructose dehydration to HMF. Fu’s group
used Fe3O4-SBA-SO3H as heterogeneous catalyst and
81% HMF yield with >99% fructose conversion can be
obtained [254]. Wang and Xu synthesized similar Fe3O4@
Si/Ph-SO3H material and it showed higher activity than
the conventional Amberlyst-15 catalyst and comparable
activity to several homogeneous sulfonic acid catalysts
for fructose dehydration to HMF. 82% HMF yield with
99% fructose conversion in DMSO after 3 h at 110°C can
be obtained [255]. Both materials could be magnetically
separated and recycled several times without significant
loss in activity.
5 Conclusion
Different kinds of acidic catalytic systems have been
developed for dehydration reaction of fructose to HMF.
Nearly full conversion of fructose and 100% HMF selectivity
could be obtained. Compared with homogeneous catalytic
system, it is easier to separate product and to recycle
the catalyst using a heterogeneous system. In addition,
heterogeneous acid catalysts can offer high selectivity
towards HMF and have the potential for industrial process.
But the separation and purity of HMF from the reaction
system is still a challenge for scientists, and fructose is
relatively expensive compared to other sugars as starting
material. Thus HMF production directly from other
carbohydrates would be more favorable. At the moment,
dehydration of glucose and glucose-based polymers are
relatively difficult because of the additional isomerization
process. Furthermore, economical commercial-scale
production of HMF is still a big challenge although many
improvements of HMF production in lab-scale have been
achieved. Therefore, further efforts are still needed in
the near future for economical and high-quality HMF
production.
Acknowledgements: This work was performed as part
of the Cluster of Excellence ‘‘Tailor–Made Fuels from
Biomass’’, which is funded by the Excellence Initiative
of the German federal and state governments to promote
science and research at German universities. The authors
also gratefully acknowledge the Max–Planck–Institut für
Kohlenforschung. Moreover, the authors are grateful for
support from the National Natural Science Foundation
of China (21373082), Innovation Program of Shanghai
Municipal Education Commission (15ZZ031), and the
Fundamental Research Funds for the Central Universities.
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Download Date | 6/18/17 2:23 PM
56 Y. Qiao et al.
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