Applied Catalysis A: General 183 (1999) 295302

Selective saccharides dehydration to 5-hydroxymethyl-2-furaldehyde

by heterogeneous niobium catalysts
Carlo Carlinia,*, Mario Giuttaria, Anna Maria Raspolli Gallettia, Glauco Sbranaa,
Tiziana Armarolib, Guido Buscab
a
Dipartimento di Chimica e Chimica Industriale, University of Pisa, Via Risorgimento 35, I-56126, Pisa, Italy
b
Istituto di Chimica, Facolta di Ingegneria, University of Genoa, Fiera del Mare, I-16129, Genova, Italy

Received 25 November 1998; received in revised form 2 March 1999; accepted 2 March 1999

Abstract

Selective dehydration of different substrates, such as fructose, sucrose and inulin, to 5-hydroxymethyl-2-furaldehyde has
been studied in aqueous medium by using heterogeneous niobium-based catalysts. Batch experiments have been performed in the
presence of both commercial niobium phosphates and catalysts prepared by treatment of niobic acid with phosphoric acid. Flow
experiments on catalyst packed beds have been also examined. Finally, batch catalytic experiments, characterized by combination
of reaction and products extraction steps, have been also carried out. # 1999 Elsevier Science B.V. All rights reserved.

Keywords: 5-Hydroxymethyl-2-furaldehyde; Carbohydrates dehydration; Niobium phosphate catalysts; Fructose; Sucrose; Inulin

1. Introduction anhydrous organic or biphasic water-cosolvent solution,

Increasing attention has been recently devoted to
the selective acid catalysed dehydration of hexoses
and fructose-based oligo- and poly-saccharides to 5-
hydroxymethyl-2-furaldehyde (HMF) [1,2]. HMF, due
to its potential versatility as starting material for ne
chemicals and polymers [3,4] is expected to be one of the
most important compounds derived from renewable
biomass and agriculture surpluses. In this respect, strong
mineral acids [59], ammonium salts [10], zirconium
phosphate [11], strong acid cation exchange resins
[1218] and more recently H-form zeolites [1921] as
well as supported heteropolyacids [22], in aqueous,
*Corresponding author. Fax: +39-050-918260; e-mail:
carlini@dcci.unipi.it
have been proposed as catalysts for the carbohydrates
dehydration to HMF. However, acid catalysts may also
promote a subsequent rehydration reaction of HMF, thus
causing carboncarbon bond cleavage on the aldehyde
to yield levulinic and formic acids [1]. Moreover, in
acidic media, oligomerization of fructose and/or HMF
may occur, leading to both insoluble humins and
soluble polymeric by-products (Scheme 1).
Indeed, in homogeneous acid catalysed processes
too low selectivities (3050%) towards HMF were
observed at a quite high substrate conversion (50
70%), owing to the subsequent aldehyde degradation
to levulinic and formic acids [1,2]. Moreover, serious
drawbacks, in terms of separation and recycling of the
mineral acid as well as of plant corrosion, are
expected. Therefore, with the aim of potential indus-

0926-860X/99/$ see front matter # 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 9 9 ) 0 0 0 6 4 - 2
296 C. Carlini et al. / Applied Catalysis A: General 183 (1999) 295302
Scheme 1. Possible reaction products of the acid catalyzed dehydration and subsequent rehydration of fructose and related compounds.
trial applications, processes based on heterogeneous
acid catalysts were more recently considered, but the
catalytic performances achieved up to now are still
unsatisfactory.
As far as the reaction medium is concerned, water
was the most frequently used solvent, due to its
excellent substrate solution properties and low cost.
However, under the above conditions rehydration of
HMF to levulinic and formic acids easily occurred [6],
strongly limiting the use of the aqueous media. Anhy-
drous solvents, such as DMF [23], acetonitrile [24]
and DMSO [25], were therefore used leading to HMF
yields generally higher than with water and strongly
reducing humins formation. However, the removal of
these organic solvents and the purication of HMF
may give rise to additional technical difculties and to
environmental problems. Moreover, with hydrosolu-
ble raw materials, as the above carbohydrates, a large
amount of organic solvents is required, due to their
scarce solution capability, thus implying high sub-
strate dilution and consequently reduced productivity.
The use of mixed solvents in homogeneous aqueous
solution has been also suggested in order to improve
the selectivity towards the target product, a positive
effect being observed when either butanol [26] or
dioxane [27] were added to water. Moreover, biphasic
systems were also applied, the organic component
behaving as extracting agent. When methyl isobutyl
ketone (MIBK) was used as organic co-solvent [28],
the extraction of HMF strongly inhibits its degradation
to levulinic and formic acids, although the high dilu-
tion, owing to the limited extracting capacity of this
organic component, and long heating times reduced
the above existing advantages.
Despite the fact that dehydration of hexoses to HMF
is a well-known reaction for many years, the search for
nding both the most suitable catalytic system and the
best reaction medium is still actual, no denitive
industrial technology being realized up to now.
In this context, a procedure for obtaining HMF from
different carbohydrate resources in the presence of
various heterogeneous acid niobium-based catalysts
was reported by us [29]. Indeed, niobium pentoxide
and niobium phosphate are known to display quite
high Brnsted acid strength [3032].
Very recently, we have spectroscopically investi-
gated niobic acid and different niobium phosphate
samples and characterized their active sites in terms of
Brnsted and Lewis acidity [33]. Preliminary experi-
ments on fructose dehydration in aqueous medium in
the presence of the above examined catalysts have
allowed to conclude that no levulinic and formic acids
were obtained and selectivities to HMF higher than
90% were accomplished, although at quite low con-
version (<30%) [33].
Therefore, in the present paper a more exhaustive
investigation of fructose dehydration to HMF in
aqueous solution by niobium-based catalysts and its
extension to other carbohydrate substrates, such as
sucrose and inulin, are reported. Flow experiments
in a column reactor packed with catalyst pellets,
with the aim to approach pilot plant conditions
are also described. Two-step batch experiments
consisting of the reaction and subsequent solvent
extraction are nally depicted with the aim of
removing the formed HMF, thus avoiding its further
degradation.
2. Experimental
2.1. Materials
Niobic acid (Nb2O5
nH2O, containing 20 wt%
H2O) (NA sample) and niobium phosphate samples
(NP1 and NP4) were supplied by CBMM (Companhia
Brasileira de Metalurgia e Minerac,ao). NP2 and NP3
were prepared by treating NP1 at 528 and 423 K for
 C. Carlini et al. / Applied Catalysis A: General 183 (1999) 295302
6 h under high vacuum (5 Pa), respectively. NP5
sample was obtained by heating NP4 at 423 K for
6 h under high vacuum (5 Pa). P/N1 sample was
prepared by stirring 6.35 g of NA with 120 ml of
1M H3PO4 aqueous solution for 48 h at room tem-
perature. The precipitate, as a powdered solid, was
centrifugated, suspended in water (50 ml) and again
centrifugated. This procedure was repeated three
times and nally the washed solid was transferred
into a crucible and calcined by ignition with slow
heating. P/N2 sample was analogously prepared
starting from the same amount of reagents as for
P/N1, but its occulation was promoted by adding
30 ml of 5% NaCl aqueous solution. Before calcina-
tion of the solid, water washings were accomplished
with the same procedure as described for P/N1, until
the centrifugate was free of chlorides (checked by
AgNO3).
Niobium and phosphorus content of noncommer-
cial catalysts was determined by gravimetric and
titrimetric standard procedures, respectively [34].
Some relevant characteristics of the above samples
are summarized in Table 1.
D()-fructose (Fluka), D()-Sucrose (Fluka) and
inulin from Dahlia Tubers (Fluka), (20 D 37.0
(c6.5 g/dl, H2O) and Mn5,000), were used as
received.
4-Methyl-pentan-2-one (MIBK) from Fluka was
reuxed on KMnO4 and then distilled. The distillate
was subsequently washed with 5% NaHCO3 aqueous
solution, dried on CaSO4 and distilled again. The so-
obtained MIBK was eluted through a column packed
with activated alumina, just before the use.
Table 1
Niobium-based catalytic systems used for carbohydrates dehydration
Sample Type
NA Nb2O5
xH2O
P/N1 H3PO4-treated niobic acid
P/N2 H3PO4-treated niobic acid
NP1 Niobium phosphate
NP2a Niobium phosphate
NP3b Niobium phosphate
NP4 Niobium phosphate
NP5c Niobium phosphate
a
Prepared from NP1 by treatment under vacuum at 528 K for 6 h.
b
Prepared from NP1 by treatment under vacuum at 423 K for 6 h.
c
Prepared from NP4 by treatment under vacuum at 423 K for 6 h.
297
2.2. Catalytic experiments and analyses
Batch catalytic experiments (A method) in aqueous
solution were carried out under nitrogen atmosphere
in a 100 ml magnetically stirred glass ask, equipped
with a reux condenser and heated with a thermo-
stated oil bath at 1108C. The proper amount of catalyst
was added to the aqueous solution of the carbohydrate
substrate and the reaction was allowed to proceed for a
prexed time. The duration was evaluated considering
the incipient reuxing of the reaction medium as the
initial time. Intermediate samplings of the reaction
mixture were accomplished and analysed.
Flow experiments (B method) were performed in a
jacked column glass reactor, packed with pressed
catalyst pellets and thermostated at 858C by circulat-
ing water heated at 908C. 1020% fructose aqueous
solutions were used. The whole reaction mixture was
continuously recycled to the catalytic bed, samplings
(very small portions) being accomplished at xed
times.
Another series of catalytic experiments (C method)
was performed on 6 and 10 wt% aqueous solutions of
the carbohydrate substrate with the same procedure as
that reported for batch experiments. However, after a
suitable time, the reaction mixture was quickly cooled
and the heterogeneous catalyst separated from the
liquid by centrifugation. The catalyst was subse-
quently treated with a small amount of acetone to
completely remove the adsorbed solution of the reac-
tion products, whereas the liquid phase and its wash-
ings were treated with a known amount of MIBK, in
order to extract HMF and 2-furaldehyde (2FA). The
P/Nb (g-at/g-at) Surface area (m2/g) Nb (wt%)
0.0 n.d. 55.9
0.61 170 55.7
1.92 170 36.1
0.45 180 46.6
0.45 150 n.d.
0.45 n.d. n.d.
0.53 n.d. 43.4
0.53 277 n.d.
298 C. Carlini et al. / Applied Catalysis A: General 183 (1999) 295302
aqueous layer, and the recovered solid catalyst were
submitted to a subsequent catalytic cycle. A small
amount of both aqueous and MIBK layers were nally
analysed.
HMF and 2FA, identied by GCMS, were directly
analysed in the presence of an internal standard (THF),
by GC on a Perkin-Elmer Sigma 3B gaschromato-
graph, equipped with a Tenax packed column (2 m), a
ame ionization detector and a Carlo Erba DP 700
integrator. When fructose was applied as substrate for
the catalytic dehydration experiments, the residual
carbohydrate was determined as silyl-derivative by
GC analysis in the presence of n
hexadecane as inter-
nal standard, according to the literature procedure
[35]. The same chromatograph, equipped with a
OV-17 packed column (2 m, 50% methyl-phenyl-sili-
cone on Chromosorb W HP), a thermoconductivity
detector and a Carlo Erba DP 700 integrator, was used.
When inulin was used as substrate, HMF and 2FA
were determined as above described, whereas the
residual inulin was determined again as silyl-deriva-
tive of fructose because the acid component of the
silylating mixture (triuoroacetic acid) favours the
complete degradation of inulin to fructose (longer
times of silylation were therefore adopted).
When sucrose was used as substrate, due to its
complete hydrolysis under the adopted reaction con-
ditions to fructose and glucose, this last was deter-
mined by an automatic Beckman Astra TM analyser,
according to an enzymic method [36], HMF, 2FA and
fructose being determined as above described. In all
cases polymeric by-products were determined by
difference [35].
IR spectra for catalysts characterization were
recorded on a Nicolet Magna 750 Fourier transform
instrument, using pressed disks of pure catalysts
powders, eventually activated by outgassing at differ-
ent temperatures into the IR cell.
GC/MS spectra of the reaction products were per-
formed by a HewlettPackard 5995 A spectrometer.
3. Results and discussion
All niobium-based catalysts were employed in
batch experiments (entries A1A12, Table 2) for
dehydration to HMF of different substrates, such as
fructose, sucrose and inulin, in aqueous medium. A
substrate/catalyst weight ratio analogous to that pre-
viously employed in the same reaction by using other
heterogeneous catalyst, such as zeolites [19,20] zir-
conium phosphate [11] and cation exchange resins
[15] was adopted. All the above catalysts not only
show a high activity to HMF but also result unable to
rehydrate HMF to levulinic and formic acids, contra-
rily to what previously reported for homogeneous
protonic acids [1] as well as for heterogeneous cata-
lysts based on acid ion exchange resins [16] in aqu-
eous medium. In all cases 2-furaldehyde (2FA) was
formed, although at low extent, according to a recent
observation [37]. It is worth noting that relevant
amounts of polymeric by-products (soluble polymers
and insoluble humins) are also formed, particularly at
high substrate conversion. A more detailed examina-
tion of the above results shows the different perfor-
mances of the employed catalysts. In particular, when
6% aqueous fructose solutions were used as substrate,
P/N1 and P/N2 catalysts show (entries A1 and A2) for
conversion near 30% (at reaction time shorter than
1 h) a high selectivity to HMF (>93%) corresponding
to a turnover value (TN>5) much higher than those
previously reported for other heterogeneous catalysts
under similar conditions [2]. However, at longer reac-
tion times these good selectivities drop due to poly-
merization reactions. On the contrary, NP1NP5
catalysts offer excellent selectivities at low conver-
sion, but they still display good performances at higher
conversions (entries A3, A4 and A6A8). This beha-
viour could be related to the slightly higher strength of
Lewis and Brnsted acid sites on NP catalysts as
compared with P/N ones [33]. When a higher con-
centration of fructose (10 wt%) was used in the pre-
sence of NP2 catalyst, at short reaction time (0.5 h)
activity and selectivity were comparable to those
obtained with a less concentrated fructose solution
(6 wt%) (compare entries A5 and A4); however, at
longer reaction times (12 h) a higher substrate con-
centration favours polymerization reactions, thus
decreasing the selectivity to HMF. Although NP cat-
alysts seem more promising for application perspec-
tives, at longer reaction times they suffer from
progressive deactivation, probably assignable to an
interaction of the reaction products with the stronger
acid sites leading to a surface loading.
In order to check if cheaper and amply available
keto-hexoses sources could be used as alternative
 C. Carlini et al. / Applied Catalysis A: General 183 (1999) 295302 299

Table 2
Fructose, sucrose and inulin dehydration to HMF carried out in aqueous medium by different heterogeneous niobium-based catalysts in batch
experiments (A method)a

Entry Catalyst Substrate Rb (w/w) Time (h) Conversion (%) Selectivity (%)c TNd

HMF 2FA

A1 P/N1 Fructose 6% wt 1.7 0.5 31.2 93.3 Traces 5.1

1.0 33.3 30.3 Traces 0.9
2.0 61.5 12.4 Traces 0.3
A2 P/N2 Fructose 6% wt 1.6 0.5 28.5 97.8 2.2 5.1
1.0 55.0 39.6 2.5 1.9
2.0 61.4 35.1 2.7 1.0
A3 NP1 Fructose 6% wt 1.4 1.0 25.1 91.8 0.5 1.8
2.0 39.0 71.2 0.9 1.2
3.0 48.0 67.4 1.4 0.7
A4 NP2 Fructose 6% wt 1.4 0.5 28.8 100.0 0.0 4.6
1.0 29.3 85.2 0.9 1.9
2.0 33.3 71.9 Traces 0.9
A5 NP2 Fructose 10% wt 1.5 0.5 29.2 98.8 1.2 4.4
1.0 35.4 60.2 2.5 1.6
2.0 65.5 29.2 3.7 0.7
A6 NP3 Fructose 6% wt 1.4 1.0 24.7 100.0 Traces 1.6
2.0 26.5 94.7 0.8 1.0
3.0 33.8 89.2 3.2 0.8
A7 NP4 Fructose 6% wt 1.6 1.0 30.6 78.7 6.2 2.1
2.0 45.2 61.1 7.2 1.2
3.0 51.2 59.4 7.5 0.9
A8 NP5 Fructose 6% wt 1.7 1.0 15.4 95.9 1.0 1.4
2.0 22.0 89.8 2.7 1.0
3.0 27.4 79.1 2.8 0.7
A9 NP4 Sucrosee 12.7% wt 1.9 4.0 30.0 91.3 8.7 0.5
A10 NP2 Inulin 6% wt 1.5 0.5 29.5 87.2 4.5 5.1
1.0 41.2 72.2 5.8 2.7
2.0 49.9 47.7 5.9 1.0
A11 NP3 Inulin 6% wt 1.5 1.0 33.8 67.8 7.0 2.1
2.0 42.4 48.1 7.5 0.9
3.0 49.4 47.5 7.8 0.7
A12 NP4 Inulin 6% wt 1.6 1.0 31.6 82.1 4.2 2.3
2.0 40.8 70.8 4.7 1.4
3.0 46.9 65.8 6.2 1.1
a
Reation conditions; T1008C; amount of catalyst is in the 0.71.7 g range.
b
Substrate to catalyst weight ratio.
c
When HMF2FA<100 polymeric by-products are also present.
d
Turnover number expressed as (mmol of HMF/g of catalysth).
e
This concentration is equivalent to 6% wt of fructose moieties, to which conversion and selectivities are referred.

substrates, sucrose and inulin, were tested. As reported
in entry A9, the fructose moiety of sucrose can be
selectively converted (>90%) into HMF, quite analo-
gously to fructose itself, while the glucose residue is
recovered unchanged. An analogous trend is observed
for the fructose units of inulin in the presence of
different NP catalysts (entries A10A12), thus con-
rming that in aqueous medium the hydrolysis of
sucrose and inulin is faster then their dehydration
[38]. Therefore, it may be concluded that sucrose
and particularly inulin can be fruitfully proposed as
raw materials for HMF production.
In order to approach a reactor design more similar to
pilot plant requirements, fructose dehydration was
300 C. Carlini et al. / Applied Catalysis A: General 183 (1999) 295302

Table 3
Fructose dehydration to HMF carried out in flow experiments on NP4 niobium catalyst pellets (B method)a

Entry Substrate Rb (w/w) Time (h) Conversion (%) Selectivity (%)c TNd

HMF 2FA

B1 Fructose 10 wt% 0.8 0.3 26.5 81.9 6.8 2.9

1.0 33.5 73.4 6.9 1.1
1.5 38.4 67.7 6.9 0.7
3.0 45.5 58.0 7.0 0.4
B2e Fructose 20 wt% 1.6 1.0 27.0 79.6 14.8 1.9
2.0 30.2 73.5 14.2 1.0
4.0 39.6 56.6 11.9 0.5
a
Reaction conditions: T858C; weight of catalyst is 5 g.
b
Substrate to catalyst weight ratio.
c
Selectivity: when HMF2FA<100 polymeric by-products are also present.
d
Turnover number expressed as (mmol of HMF/g of catalysth).
e
The same catalytic bed employed in entry B1 was used.

also carried out in ow experiments by using a column
reactor packed with NP4 catalyst pellets (entries B1
and B2, Table 3). Despite the higher substrate con-
centrations adopted in these experiments, due to the
lower contact surface of catalyst pellets with respect to
powdered material, similar performances to those
obtained in batch experiments (see B1 and A7 entries)
were found. In order to verify if the catalyst retains its
activity in subsequent cycles the catalytic bed pre-
viously employed was reused in a new experiment
(entry B2) with a fresh 20 wt% aqueous fructose
solution. The results conrm that the catalyst is still
active and selectivity data are promising, at least at
short contact time.
The drop of selectivity to HMF at higher conver-
sions, observed in all the above experiments, may be
mainly addressed to the high residence time of HMF in
the reactor and hence on the catalyst surface. There-
fore, in order to overcome this detrimental effect,
batch experiments characterized by short reaction
cycles (0.5 h each), followed by an extraction step
of the reaction products with MIBK and subsequent
recycle of both the residual aqueous substrate solution
and the solid catalyst, were performed on fructose and
inulin substrates (entries C1C3, Table 4). Indeed,
when 6 wt% fructose aqueous solution was used,
selectivity to HMF near 98% after two cycles was
obtained for a conversion higher than 75% (entry C1).
If these results are compared with those obtained in the
corresponding batch experiment (entry A4, Table 2) it
may be concluded that the separated extraction step
not only enhances the selectivity to HMF but also
prevents the catalyst surface loading, thus improving
its productivity. Moreover, the catalyst showed the
highest activity never reached before (TN>6). Slightly
lower selectivity and conversion (near 90% and 60%,
respectively) were achieved after four cycles when a
higher concentration of fructose was used (entry C2).
Finally, when inulin was employed as substrate in
aqueous medium (entry C3), again relevant selectivity
(>72%) and conversion (>75%) were obtained after
three cycles, thus indicating that this substrate repre-
sents a very promising candidate as cheap raw mate-
rial for the catalytic dehydration to HMF.
4. Conclusions
On the basis of the obtained results the following
concluding remarks can be drawn:
1. Batch experiments carried out on aqueous fructose
solutions for the dehydration to HMF show that P/
N catalysts display a lower selectivity at high
substrate conversion than NP ones. The above
behaviour may be probably ascribed to a slightly
higher strength of Lewis and Brnsted acid sites in
the latter systems. Moreover, all the examined
niobium catalysts display an activity, in terms of
TN values, which is higher with respect to those
found up to now in the presence of other
heterogeneous systems when applied under simi-
lar conditions.
 C. Carlini et al. / Applied Catalysis A: General 183 (1999) 295302 301

Table 4
Fructose and inulin dehydration to HMF carried out in aqueous medium with heterogeneous NP2 catalyst in batch experiments (C method)a

Entry Substrate Rb (w/w) Cycle Time (h) Conversion (%) Selectivity (%)c TNd

C1 Fructose 6 wt% 1.6 1 0.5 33.6 98.3 5.9

2 1.0 75.8 97.8 6.7
C2 Fructose 10 wt% 1.6 1 0.5 37.7 90.2 6.1
2 1.0 45.3 89.7 3.6
3 1.5 51.8 89.3 2.7
4 2.0 60.3 89.3 2.4
C3 Inulin 6 wt% 1.6 1 0.5 25.2 77.5 3.5
2 1.0 48.7 74.0 3.3
3 1.5 76.3 72.0 3.2
a
Reaction conditions: T1008C; amount of catalyst is in the 0.71.7 g range; subsequent cycles were performed by extraction of reaction
products with MIBK, followed by recycle of catalyst and residual substrate aqueous solution.
b
Substrate to catalyst weight ratio.
c
Selectivity after every cycle; 2-furaldehyde and polymeric by-products are also present.
d
Turnover number expressed as (mmol of HMF/g of catalysth).

2. Batch experiments performed on sucrose and inu- Acknowledgements

lin in aqueous medium and in the presence of NP
catalysts indicate that the above substrates have
similar reactivity as fructose and hence they repre-
sent, particularly inulin, suitable raw materials for
the production of HMF.
3. Preliminary flow experiments, performed on aqu-
eous solutions of fructose by using a column
reactor packed with NP catalyst pellets, suggest
that also this approach offers good catalytic per-
formances, the same catalyst bed being success-
fully applied in subsequent cycles.
4. A significant improvement of both activity and
selectivity can be achieved combining reaction
with separated extraction steps for removing
HMF, thus allowing to reach excellent process
performances, in terms of activity, selectivity,
cheapness and stability of the heterogeneous cat-
alyst.
Taking into account that the better performances of
NP catalysts seem to be mainly related to the slightly
higher acidity of their active sites on the surface, new
heterogeneous catalytic systems, characterized by
even higher acid sites and by a more quantitative
knowledge of their nature, should be tested for car-
bohydrates dehydration to HMF. Indeed, this approach
would allow to better discriminate the effective role
played by Brnsted against Lewis centers on activity
and selectivity of the catalytic process. Work in this
direction is in progress.
The authors wish to express their gratitude to
Companhia Brasileira de Metalurgia e Minerac,ao
for supplying niobic acid and niobium phosphate
samples. Financial support from C.N.R. (Rome) is
also gratefully acknowledged.
References
[1] B.F.M. Kuster, Starch/Starke 42 (1990) 314.
[2] L. Cottier, G. Descotes, Trends in Heterocyclic Chem. 2
(1991) 233.
[3] M. Kunz, in: A. Fuchs (Ed.), Inulin and Inulin-containing
Crops, Elsevier, Amsterdam, 1993, p. 149.
[4] A. Gandini, in: Encycl. Polym. Sci. Eng., 2nd ed., vol. 7,
Interscience, New York, 1987, p. 454.
[5] B.F. M Kuster, H.S. van der Baan, Carbohydr. Res. 54 (1977)
165.
[6] B.F.M. Kuster, Carbohydr. Res. 54 (1977) 177.
[7] B.F.M. Kuster, H.M.G. Temmink, Carbohydr. Res. 54 (1977)
185.
[8] C.J. Moye, Z.S. Krzeminski, Aust. J. Chem. 16 (1963) 258.
[9] K. Hamada, H. Yoshihara, G. Suzukamo, Chem. Lett. (1982)
617.
[10] C. Fayet, J. Gelas, Carbohydr. Res. 122 (1983) 59.
[11] Y. Nakamura, Jpn. Kokai Tokyo Koho 8 013 243 (1980), to
Noguchi Research Foundation; Chem. Abstr. 93 (1980)
26260e.
[12] R.A. Schraufnagel, H.F. Rase, Ind. Eng. Chem. Prod. Res.
Dev. 14 (1975) 40.
[13] T. El Hajj, A. Masroua, J.-C. Martin, G. Descotes, Bull. Soc.
Chim. Fr. (1987) 855.
302 C. Carlini et al. / Applied Catalysis A: General 183 (1999) 295302
[14] A. Masroua, A. Revillon, J.-C. Martin, A. Guyot, G.
Descotes, Bull. Soc. Chim. Fr. (1988) 561.
[15] P. Vinke, H. van Bekkum, Starch/ Starke 44 (1992) 90.
[16] L. Rigal, A. Gaset, J.-P. Gorrichon, Ind. Eng. Chem. Prod.
Res. Dev. 20 (1981) 719.
[17] L. Rigal, J.-P. Gorrichon, A. Gaset, J.-C. Heughebaert,
Biomass 7 (1985) 27.
[18] L. Rigal, A. Gaset, Biomass 7 (1985) 267.
[19] J. Jow, G.L. Rorrer, M.C. Hawley, Biomass 14 (1987)
185.
[20] C. Moreau, R. Durand, C. Pourcheron, S. Razigade, Ind.
Crops Prod. 3 (1994) 85.
[21] P. Rivalier, J. Duhamet, C. Moreau, R. Durand, Catal. Today
24 (1995) 165.
[22] M.A. Schwegler, P. Vinke, M. van der Eijk, H. van Bekkum,
Appl. Catal. A: General 80 (1992) 41.
[23] T.G. Bonner, E.J. Bourne, M. Ruszkiewicz, J. Chem. Soc.
(1960) 787.
[24] D.W. Brown, A.J. Floyd, R.G. Kinsmann, Y. Roshan-Ali, J.
Chem. Technol. Biotechnol. 32 (1982) 920.
[25] R.M. Musau, R.M. Munavu, Biomass 13 (1987) 67.
[26] Q.P. Peniston, US Patent 2 750 394 (1956), Food Chemical
and Research Laboratories; Chem. Abstr. 51 (1957) 1284b.
[27] R.A. Hales, J.W. Le Maistre, G.O. Orth, US Patent 3 071 599
(1963), Atlas Chemical Industries; Chem. Abstr. 59 (1963) 576a.
[28] B.F.M. Kuster, H.J.C. van der Steen, Starke 3 (1977) 99.
[29] G. Braca, A.M. Raspolli Galletti, A. Criscuolo, G. Sbrana, It.
Pat. Appl. 0 023 63 (1992) C.N.R. (Rome).
[30] G. Busca, Catal. Today 41 (1998) 191.
[31] S. Okazaki, A. Kurosaki, Catal. Today 8 (1990) 113.
[32] R.T.L. Martins, W.J. Schitine, F.R. Castro, Catal. Today 5
(1989) 483.
[33] T. Armaroli, G. Busca, C. Carlini, M. Giuttari, A.M. Raspolli
Galletti, G. Sbrana, J. Mol. Catal. A: Chem., in press.
[34] D.C. Harris, in: Quantitative Chemical Analysis, 4th ed.,
Freeman, New York, 1996.
[35] B.F.M. Kuster, H.S. van der Baan, L.M. Tebbens, Carbohydr.
Res. 54 (1977) 159.
[36] R.R. Burton, Anal. Biochem. 14 (1966) 258.
[37] M.J. Antal Jr., W.S.L. Mok, G.N. Richards, Carbohydr. Res.
199 (1990) 91.
[38] W.N. Haworth, W.G.M. Joness, J. Chem. Soc. (1944) 667.