Journal of Energy Chemistry 22(2013)826–832

Dehydration of xylose to furfural over niobium phosphate

catalyst in biphasic solvent system
Boonrat Pholjaroena,b , Ning Lia∗ , Zhiqiang Wanga,c , Aiqin Wanga , Tao Zhanga
a. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
b. University of Chinese Academy of Sciences, Beijing 100049, China;
c. Department of Chemical Engineering, Sichuan University, Chengdu 610065, Sichuan, China
[ Manuscript received February 28, 2013; revised April 12, 2013 ]

Abstract
Phosphoric acid treated niobic acid (NbP) was used for the dehydration of xylose to furfural in biphasic solvent system, which was found
to exhibit the best performance among the tested catalysts. The excellent performance of NbP could be explained by the better synergistic
cooperation between Brönsted and Lewis acid sites. Moreover, NbP showed good stability and no obvious deactivation or leaching of Nb could
be observed after six continuous recycles.
Key words
xylose; furfural; dehydration; biphasic solvent system; solid acid catalyst; niobium phosphate

1. Introduction as sulfuric acid, phosphoric acid or superphosphate). These

catalysts are effective and give furfural yields of 40%–60%
In the viewpoint of declining petroleum resources and [13]. However, the utilization of these mineral acids has seri-
continuous increasing energy demand around the world, it ous drawbacks of extreme corrosion, high toxicity, excessive
is necessary to develop alternative ways to fulfill the energy waste disposal, difficulty in separation and recycling [14,15].
needs of industrialized society. Lignocellulosic biomass that For the environmental protection reason, some highly efficient
exists abundantly can be considered as a renewable source for solid acid catalysts should be developed for furfural produc-
chemicals, electricity and liquid fuel production [1]. There- tion. In the past years, many solid acid catalysts, such as in-
fore, catalytic transformations of lignocellulosic biomass and organic oxides [16], heteropolyacids [17], ion-exchange poly-
its derivatives have drawn a lot of attention recently [2−7]. mer resins [18], zirconium phosphate [19], vanadium phos-
Furfural is an important chemical that possesses a unique phate [20], sulfated metal oxides [21−23], as well as zeolites
advantage in production from renewable biomass, such as [24−26], have been reported to be active in the dehydration
agricultural wastes or forest residues which are rich in pen- of xylose to furfural.
tosan polymers [8]. As a non-petroleum-derived product, fur- As a side reaction for the dehydration of xylose to fur-
fural has been broadly used as the feedstock in the manu- fural, furfural can also react with xylose and produce humin,
facturing of furfuryl alcohol, 2-methylfuran, tetrahydrofuran which will decrease the selectivity towards furfural. To solve
(THF), 2-methyltetrahydrofuran (MeTHF), plastics, pharma- this problem, a biphasic solvent system was developed to
ceutics and agrochemicals [9–11]. Recently, it was found that extract the furfural from the aqueous phase, thus decreas-
furfural can also be used as the building block for renewable ing the chance for furfural to react with xylose [27]. The
diesel or jet fuel [12]. organic phases often used in biphasic system are toluene
The production of furfural usually involves the hydrolysis [14,25,26,28], methyl isobutyl ketone (MIBK) [14,26], 2-
of pentosan into pentoses (e.g. xylose) and the dehydration of butanol [27,29] and n-butanol [15,30].
the latter to form furfural in the presence of an acidic catalyst. Phosphoric acid treated niobic acid (NbP) catalyst is an
In conventionally commercial process, furfural is produced interesting solid acid material which has been reported to be
by a homogeneous reaction catalyzed by mineral acids (such highly active and selective for the dehydration of hexoses or
∗ Corresponding author. Tel: +86-411-84379738; Fax: +86-411-84685940; E-mail: lining@dicp.ac.cn
This work was supported by the Natural Science Foundation of China (No. 21106143), 100-talent project of Dalian Institute of Chemical Physics (DICP),
and the Independent Innovation Foundation of State Key Laboratory of Catalysis (No. R201113).

Copyright©2013, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. All rights reserved.
 Journal of Energy Chemistry Vol. 22 No. 6 2013 827

hexosans (such as fructose, glucose, inulin and Jerusalem ar- temperature. The spectra of the samples at this stage were
tichoke juice) to 5-hydroxymethylfuran (HMF) [31−35]. In recorded as the background references. Subsequently, pyri-
this work, NbP was used as the catalyst for the dehydration dine vapor at room temperature (pressure ∼20.7 torr) was in-
of xylose in biphasic solvent system which exhibited the best troduced for 10 min followed by evacuation for 20 min to re-
catalytic performance among the tested catalysts. At the same move the physically adsorbed pyridine. Then, the samples
time, we also studied the effects of several factors such as or- were heated in vacuum at 160 ◦ C for 10 min. The spectra were
ganic phase, organic/aqueous volume ratio, catalyst loading, recorded after the IR cell was cooled to ambient temperature.
initial xylose concentration and reaction temperature on the Brönsted to Lewis acid site ratio (B/L ratio) for each cata-
conversion of xylose to furfural over NbP catalyst in biphasic lyst was evaluated by the ratio of the peak areas at 1540 cm−1
solvent system. Finally, we also examined the stability of NbP and 1450 cm−1 which have been assigned as the characteristic
catalyst under the optimal condition. peaks for pyridine adsorbed on Brönsted acid and Lewis acid,
respectively.
2. Experimental
2.2.3. NH 3 -TPD
2.1. Catalyst preparation
NH3 -TPD experiments were carried out to measure the
Niobium phosphate (NbP) was prepared according to the acidity of the tested catalysts. NH3 -TPD was conducted with
procedure described by Yang et al. [31]. 3.0 g hydrated Micromeritics AutoChem II 2920 automated catalyst charac-
niobium pentoxide (Nb2 O5 ·xH2 O, CBMM) was mixed with terization system. For each test, 100 mg catalyst was placed in
40 mL 1.0 M H3 PO4 . The mixture was stirred at room temper- a quartz reactor and heated at 500 ◦ C for 1 h in He flow to re-
ature for 52 h, aged at ambient condition for 12 h and filtrated. move the physically absorbed water. The adsorption of ammo-
The solid product was washed for 3 or 4 times with deionized nia was performed at 100 ◦ C. After saturation, the sample was
water until the pH value was neutral and then dried overnight heated linearly from 100 to 900 ◦ C at the rate of 10 ◦ C/min un-
at 60 ◦ C for 12 h. The product was dried at 110 ◦ C in vacuum der a constant He flow of 30 mL/min. Total acid sites of the
oven for 2 h and calcined in air at 300 ◦ C for 3 h. catalysts were measured by a Pfeiffer Vacuum OmniStarTM
Zirconium phosphate (ZrP) was prepared according to mass spectrometer at m/z = 16 from the amount of ammonia
the procedure reported in Ref. [36] by precipitation of desorbed within the temperature range from 120 to 600 ◦ C.
ZrCl2 O·8H2 O (1.0 M, 31.9 mL) and NH4 H2 PO4 (1.0 M,
63.8 mL) at a molar ratio of P/Zr = 2.0. The precipitate was 2.3. Activity tests
filtered, washed with deionized water, dried at 100 ◦ C, and
then calcined at 400 ◦ C for 3 h. The catalytic experiments were performed under argon
Sulfated zirconia (SZ) was prepared according to our pre- in a 100 mL stainless steel batch reactor. In a typical pro-
vious work [37] by impregnation of Zr(OH)4 with an aqueous cedure, 2.0 g xylose, 0.14 g powdered catalyst, 18 mL H2 O,
solution of 0.5 M (NH4 )2 SO4 at the ratio of 15 mL/g. The and 30 mL organic solvent were put into the reactor. The re-
slurry was stirred for 30 min, filtrated without washing, dried action mixtures were quickly heated to 160 ◦ C under stirring
at 110 ◦ C overnight, and then calcined at 600 ◦ C in air for 3 h. at 800 rpm. Zero time was taken when the reaction tempera-
H-β (SiO2 /Al2 O3 = 25) and H-Y (SiO2 /Al2 O3 = 4) zeo- ture was reached. The reaction was halted by stopping stirring
lite catalysts used in this work were provided by Nankai Uni- and then quenching the reactor to room temperature by cold
versity. water.
After the reaction, the aqueous and organic phases were
2.2. Characterization separated and filtered by a syringe filter. The concentra-
tion of xylose presented in the aqueous phase was quantified
2.2.1. BET surface area by an Agilent 1200 HPLC using a refractive index detector
(RID) equipped with a Shodex Sugar SC1011 column (i.d.
The specific surface areas and average pore sizes of the 8.0 mm×L 300 mm). While, the furfural contents in both
catalysts were determined by nitrogen adsorption at 77 K us- aqueous and organic phases were analyzed by an Agilent 1260
ing a Micromeritics ASAP 2010 apparatus. Before each ex- HPLC using a UV detector (at 280 nm) equipped with a ZOR-
periment, the sample was evacuated at 150 ◦ C for 3 h. BAX Eclipse XDB-C18 column (i.d. 4.6 mm×L 150 mm).
Methanol in water of 40 vol% was used as the mobile phase.
2.2.2. FT-IR spectroscopy
3. Results and discussion
The FT-IR spectra with pyridine as the molecular probe
were recorded on a Bruker Equinox 55 equipped with a DTGS 3.1. Characterization of catalysts
detector at a resolution of 4 cm−1 (120 scans). Before the ad-
sorption of pyridine, the samples were pretreated in vacuum Table 1 presents the specific BET surface areas (SBET ),
(<10−3 torr) at 400 ◦ C for 1 h, then cooled down to room Brönsted to Lewis acid site ratios (B/L ratio), and the amount
828 Boonrat Pholjaroen et al./ Journal of Energy Chemistry Vol. 22 No. 6 2013

of acid sites for various catalysts. Among the investigated cat- the B/L ratios of different catalysts measured by FT-IR, the
alysts, zeolites had higher SBET and higher total acid sites than amounts of Brönsted and Lewis acid sites on different cata-
those of sulfated metal oxides and metal phosphates. lysts can be estimated. The amount of Brönsted acid sites of
From the FT-IR spectra with pyridine as probe molecule, the tested catalysts was in the sequence of H-Y>ZrP>SZ>H-
the B/L ratios of different catalysts are in the sequence of β>NbP, while that of Lewis acid sites in the sequence of H-
ZrP>SZ>H-Y>NbP>H-β, as shown in Table 1. Based on β>H-Y>SZ>NbP>ZrP.
to the total amounts of acid sites measured by NH3 -TPD and

Table 1. BET surface areas, average pore sizes, Brönsted to Lewis acid site ratios and the amounts of
acid sites deduced from N2 -adsorption, FT-IR and NH3 -TPD results
BET surface Average Brönsted to Amount of acid sites (mmol/g)
Catalysts
area (m2 /g) pore size (nm) Lewis acid site ratio Brönsted Lewis total
NbP 114 7.1 0.32 0.097 0.305 0.402
ZrP 93 10.7 1.77 0.404 0.229 0.633
SZ 136 6.6 0.85 0.315 0.370 0.685
H-Y 617 0.66×0.67, 0.56×0.56 [38] 0.62 0.530 0.854 1.384
H-β 481 0.74×0.74 [38] 0.16 0.170 0.892 1.062

3.2. Activity tests Table 2. Xylose conversion, furfural yield and product
selectivity over different catalysts
3.2.1. Screen of catalysts Catalysts
Xylose Furfural Selectivity (%)
conversion (%) yield (%) furfural xylulose othersa
Table 2 shows xylose conversion, furfural yield and se- – 13.3 4.4 33.1 18.0 48.9
lectivity over different solid acid catalysts after reacting at NbP 51.8 22.5 43.4 13.1 43.5
ZrP 27.9 14.4 51.7 18.1 32.2
160 ◦ C in toluene/water system for 1 h. Even in the absence
SZ 44.9 16.1 35.8 32.2 32.0
of catalyst, furfural can be formed in a small amount under the H-Y 68.3 19.4 28.3 59.9 11.8
investigated condition, which can be attributed to the catalysis H-β 58.1 16.6 28.6 57.8 13.6
of the organic acids generated during the thermal decomposi- aOthers include humins and some unidentified products. Reaction
tion of xylose [8,39]. Among the tested catalysts, NbP exhib- conditions: 160 ◦ C, 1 h; 2.0 g xylose, 18 mL H2 O, 30 mL toluene
ited the best catalytic performance, over which furfural yield and 0.14 g catalyst were used for each reaction
up to 22.5% can be obtained after reacting at 160 ◦ C for 1 h.

Figure 1. (a) The relationship among xylose conversion, furfural yield and the amount of Lewis acid site over different solid acid catalysts; (b) The relationship
of furfural selectivity at reaction time of 1 h and/or furfural selectivity at 70% xylose conversion with Brönsted to Lewis acid site (B/L) ratio over different solid
acid catalysts (Reaction conditions: 160 ◦ C, 1 h; 2.0 g xylose, 18 mL H2 O, 30 mL toluene and 0.14 g catalyst were used for each reaction)

The effects of acid sites on catalytic activity and prod- be explained by the two-step reaction mechanism (shown in
uct selectivity were further studied. From Figure 1(a), it can Scheme 1) proposed by Suzuki et al. [22] and Yang et al.
be seen that xylose conversion increased with the amount [40]. In the first step, xylose was isomerized to xylulose under
of Lewis acid sites on the catalysts. At the same time, it the catalysis of Lewis acid site. In the second step, xylulose
was also noticed from Figure 1(b) that furfural selectivity in- was dehydrated to furfural over Brönsted acid sites. The iso-
creased with the B/L ratio of the catalyst. These results were merization of xylose has been proved to be a beneficial step
consistent with the work of Weingarten et al. [19] and can in the dehydration of xylose to furfural. For example, in the
 Journal of Energy Chemistry Vol. 22 No. 6 2013 829

early work of Takagaki et al. [41], evidently higher furfural

yield was achieved by the synergism of Amberlyst-15 and hy-
drotalcite under moderate conditions. It was suggested that
xylose was isomerized to xylulose over hydrotalcite, and xy-
lulose was dehydrated to furfural over Amberlyst-15. Analo-
gously, evident synergy effects between Lewis acid (Sn-beta
or CrCl3 ) and Brönsted acid (such as Amberlyst-15 and HCl)
were also observed by Choudhary et al. [42,43] in their recent
works about the dehydration of xylose to furfural. In these
systems, Sn-beta or CrCl3 was used to catalyze the isomer-
ization of xylose to xylulose, while HCl or Amberlyst-15 pro-
moted the dehydration of xylulose to furfural. Because the
Brönsted acid-catalyzed-dehydration of xylulose to furfural
is faster than that of xylose to furfural, much higher furfural
yields were achieved at low temperature when these catalysts
were used together. Based on these results, we suggest that
xylose is isomerized to xylulose over Lewis acid sites of cata-
lyst, and then the generated xylulose is dehydrated to furfural
over Brönsted acid sites.

Scheme 2. Proposed structures of Lewis and Brönsted acid sites of different

catalysts. (a) NbP [44], (b) ZrP [19], (c) SZ [45−47], (d) H-Y and H-β [19]
Scheme 1. Suggested reaction mechanism of xylose dehydration over solid
acid catalyst
3.2.2. Ef fect of organic phase
From the suggested reaction mechanism, we can see that
Lewis acid sites are favorable for the conversion of xylose, Table 3 shows the effect of organic phase on xylose con-
and the higher the amount of Lewis acid sites of the catalyst, version and furfural yield over NbP catalysts. Among the in-
the higher xylose conversion is. However, because the Lewis vestigated organic phases, toluene provided the highest fur-
acid sites are more active than the Brönsted acid sites for the fural yield due to its lower polarity and higher affinity to fur-
side reaction between furfural and xylose to produce humin fural. It is very interesting that when n-butanol or 2-butanol
as the final product [19], excess Lewis acid sites will decrease was used as the organic phase, xylose conversion increased,
the selectivity and yield to furfural. Therefore, NbP exhibited while furfural yield decreased. According to the result of GC-
the best catalytic performance among the tested catalysts due MS analysis (not shown here), this result can be explained by
to its better synergistic effect between the Brönsted acid sites the acetalisation reaction between furfural and alcohol under
and Lewis acid sites on the catalyst surface. Scheme 2 sum- the catalysis of acid sites. Similar phenomenon was reported
marizes the structures of Brönsted and Lewis acid sites over by Lai and Zhang in their previous work about the production
the tested catalysts. According to Scheme 2, the Lewis acid of HMF from fructose [48]. Moreover, as listed in Table 3, xy-
sites over NbP catalyst were assigned to coordinatively un- lose conversion and furfural selectivity in hexane/water bipha-
saturated Nb5+ sites, whereas the Brönsted acid sites on NbP sic system were very close to those in aqueous phase due to
catalyst were attributed to either Nb–OH or P–OH sites [35]. that hexane is not a solvent having a good affinity to furfural.

Table 3. Xylose conversion, furfural yield and selectivity over NbP catalyst
Organic/aqueous Xylose conversion Furfural yield (%) Furfural
solvent systems (%) aqueous organic total selectivity (%)
Only watera 44.1 17.4 − 17.4 39.5
Toluene/water 51.8 3.8 18.7 22.5 43.4
MIBK/water 52.6 2.0 20.1 22.1 42.1
n-butanol/water 64.2 2.4 13.6 16.0 25.0
2-butanol/water 58.9 3.1 13.7 16.8 28.6
Hexanol/water 43.5 9.6 3.8 13.4 30.7
a
5.0 g xylose, 45 mL H2 O, 0.35 g catalyst were used. Reaction conditions: 160 ◦ C, 1 h; 2.0 g xylose, 18 mL H2 O, 30 mL organic solvent and 0.14 g
catalyst were used for each reaction
830 Boonrat Pholjaroen et al./ Journal of Energy Chemistry Vol. 22 No. 6 2013

3.2.3. Ef fect of organic/aqueous volume ratio is shown in Figure 3. Xylose conversion and furfural yield
increased as the catalyst amount increased from 0 to 0.14 g.
The effect of organic/aqueous volume ratio on xy- This result can be rationalized by the increase of acid sites
lose conversion and furfural yield is shown in Figure 2. which are active for the dehydration of xylose. Further in-
Toluene/water was used as the biphasic solvent system with an creasing of the catalyst amount to 0.21 g, no evident effect on
organic/aqueous volume ratio ranging from 0 to 2.0. To facili- xylose conversion and furfural yield could be observed. So,
tate the comparison, the mass ratio of catalyst : xylose : water 0.14 g catalyst was used in the following work.
was kept constant at 0.07 : 1 : 9. As we mentioned before, the
presence of toluene increased xylose conversion and furfural 3.2.5. Ef fect of initial xylose concentration
yield. The promotion effect of toluene was evident even at
low toluene/water volume ratio (0.5). With further increase of The effect of initial xylose concentration on xylose con-
toluene/water volume ratio from 0.5 to 2.0, similar conversion version and furfural yield over NbP catalyst was also studied.
of xylose and yield of furfural were obtained, indicating that As shown in Figure 4, xylose conversion, furfural yield, and
the amount of toluene has no significant impact on the con- furfural selectivity decreased continuously when the initial
version of xylose and the yield of furfural when toluene/water xylose concentration in aqueous phase increased from 1 wt%
volume ratio is greater than 0.5. to 15 wt%. This phenomenon is similar to what was observed
by Yemiş and Mazza [49] and it can be explained by the for-
mation of humin via the condensation reaction between fur-
fural and xylose. With the increase of initial xylose concentra-
tion, the probability for furfural to react with xylose increases.
And so, more humin will be generated, which will lead to the
plugging of the catalyst pores and the decrease the accessibil-
ity of acid sites.

Figure 2. Effect of organic/aqueous volume ratio on xylose conversion

and furfural yield over NbP catalyst (Reaction conditions: 160 ◦ C, 1 h;
toluene/water was used as the biphasic solvent system with the total vol-
ume of 50 mL. The mass ratio of catalyst : xylose : water was kept constant at
0.07 : 1 : 9)

3.2.4. Ef fect of catalyst loading

The effect of catalyst loading on the dehydration of

xylose to furfural over NbP catalyst in toluene/water system Figure 4. Effect of initial xylose concentration on xylose conversion, fur-
fural yield, and furfural selectivity over NbP catalyst (Reaction conditions:
160 ◦ C, 1 h; 18 mL H2 O, 30 mL toluene and 0.14 g catalyst were used for
each reaction)

3.2.6. Ef fect of reaction temperature

From the result illustrated in Figure 5, xylose conversion

and furfural yield increased obviously with the increase of
reaction temperature. Furfural yield up to 44.7% could be
obtained after reacting at 210 ◦ C for 1 h. A reasonable ex-
plaination why high reaction temperature is more favorable
to the dehydration of xylose than the condensation is that the
adsorption of xylose under high reaction temperature is get-
ting weaker. Recently Ordomsky et al. [50] reported the de-
Figure 3. Effect of catalyst amounts on xylose conversion and furfural yield
over NbP catalyst (Reaction conditions: 160 ◦ C, 1 h; 2.0 g xylose, 18 mL hydration of fructose over solid acids that carbohydrates are
H2 O and 30 mL toluene were used for each reaction) relatively easier to be adsorbed and activated on the Lewis
 Journal of Energy Chemistry Vol. 22 No. 6 2013 831

acid sites than on the Brönsted acid sites. Such a higher ad- conditions. After each run, the used catalyst was filtered by
sorption of carbohydrates over Lewis acid may be responsible a 0.2 µm membrane, washed thoroughly with deionized wa-
for the higher conversion of xylose over the catalysts with a ter, and dried at 120 ◦ C overnight. From the result shown
higher amount of Lewis acid sites, but the higher adsorption in Figure 6, no obvious change in the catalytic performance
of carbohydrates over the Lewis acid sites also facilitates the of NbP catalyst could be observed after 6 continuous recy-
side reaction (i.e., condensation) between furfural and xylose cles, indicating that NbP catalyst was very stable under the
with humin as the final product. Under high temperature, the investigated conditions. ICP analysis also showed there was
adsorption of carbohydrate on Lewis acid sites is weakened, no niobium species in the aqueous product. Therefore, the
which may be helpful for the suppressing of unexpected con- leaching of Nb could be excluded. These results were con-
densation reaction. However, with further increase of reaction sistent with the reports on the dehydration of xylose over
temperature to 220 ◦ C, xylose conversion increased whereas microporous and mesoporous niobium silicates [52], meso-
furfural yield slightly decreased. This indicates that some fur- porous niobium phosphate [53], and niobate and titanoniobate
fural decomposition reactions such as furfural decarbonyla- nanosheets [54].
tion [51] can be promoted at high temperature and thus de-
creasing furfural yield. 4. Conclusions

Niobium phosphate (NbP) was used as a catalyst for the

dehydration of xylose in biphasic solvent system and it exhib-
ited the best catalytic performance among the tested catalysts.
The higher xylose conversion and furfural yield over NbP can
be rationalized by the better synergistic cooperation between
Brönsted acid sites and Lewis acid sites on the catalyst sur-
face. Organic solvent, catalyst loading, initial xylose concen-
tration and reaction temperature also had some obvious effects
on the catalytic performance of NbP catalyst. The presence of
non-polar organic solvents with low solubility in water and
higher affinity to furfural could extract furfural from aqueous
phase and thus exhibiting evident promotion effect on the con-
version of xylose to furfural. Among the investigated organic
Figure 5. Effect of reaction temperature on xylose conversion and furfural
solvents, toluene provided the highest furfural yield. Xylose
yield over NbP catalyst (Reaction conditions: 1 h; 2.0 g xylose, 18 mL H2 O, conversion and furfural yield increased with the increase of
30 mL toluene and 0.14 g catalyst were used for each reaction) catalyst loading and reaction temperature but decreased with
the increase of the initial xylose concentration. NbP catalyst
was very stable under the investigated condition, no loss of
3.2.7. Stability of NbP catalyst catalytic performance or leaching of Nb could be observed
during 6 continuous recycles.
Finally, we also examined the stability of NbP catalyst.
First of all, we investigated the effect of recycle time on the Acknowledgements
catalytic performance of NbP catalyst under the optimal Miss Hua Wang and Dr. Lin Li are appreciated for their techni-
cal helps on GC-MS and FT-IR analysis.

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