Int J Energy Environ Eng (2015) 6:21–30

DOI 10.1007/s40095-014-0146-9

ORIGINAL RESEARCH

The effects of combined catalysis of oxalic acid and seawater

on the kinetics of xylose and arabinose dehydration to furfural
Wijittra Hongsiri • Bart Danon • Wiebren de Jong

Received: 1 July 2014 / Accepted: 17 October 2014 / Published online: 12 November 2014
Ó The Author(s) 2014. This article is published with open access at Springerlink.com

Abstract It is known that both acids and salts have a Introduction

positive catalytic effect on the dehydration of pentoses to
form furfural, a potentially attractive platform chemical. In Sustainable biorefinery processes have a high potential for
this study the effects of the combined usage of an organic commercialisation; however, the processing costs need to
acid, instead of stronger mineral acids, and a saline catalyst be minimized further for the process to become economi-
is investigated. In order to assess these effects, the kinetics cally feasible. In view of sound sustainable biorefining
of pentose dehydration to furfural are studied using oxalic development, raw materials, reaction media and catalysts
acid as the primary catalyst and NaCl or seawater as the are preferably derived from sustainable resources. Also,
secondary saline catalyst. The interactions between these reactions are best performed under mild and environmen-
two types of catalysts are complex and are, therefore, also tally favourable conditions with minimal waste formation.
assessed thermodynamically. The addition of salts lowers Waste prevention is very much preferable over treating or
the activity coefficient of the hydronium ions, but simul- cleaning up [1]. Catalysts play a key role in the develop-
taneously favours the dissociation of the organic acid. It ment of sustainable biorefinery processes for the manu-
turned out that these two effects are of similar magnitude, facture of chemicals. The use of organic acids as catalyst
resulting in a fairly constant hydronium ion activity. for biopolysaccharide (both cellulose and hemicellulose)
Because nonetheless higher furfural yields are obtained hydrolysis and monosaccharide dehydration (both hexose
using the salts as a secondary catalyst, it is concluded that and pentose) offers a promising approach. Different
the salts influence the pentose dehydration mechanism organic acid catalysts (e.g. fumaric, oxalic or maleic acid)
directly. The final furfural yields obtained using oxalic acid have already been investigated as substitutes for the more
as the primary catalyst were only slightly lower than those widely applied mineral acids (mostly H2 SO4 or HCl) [19,
for similar experiments using HCl. The most distinctive 29, 33, 34]. Formic acid, a byproduct of furfural degrada-
difference between the two acids is the lower reaction rate tion, has been shown to be an effective catalyst for furfural
(and thus longer reaction times) when using oxalic acid. production [20]. Moreover, it can be shown to result in
Finally, it was observed that if no acidic catalyst is used, even slightly higher furfural yield and selectivity than
the salts tend to catalyse a loss reaction, which is sup- phosphoric acid and sulfuric acid [40]. In this context, it
pressed when an acid is present. has been shown that the use of an organic acid, such as
fumaric, maleic or formic acid, can effectively be used
Keywords Furfural  Pentose dehydration  Oxalic acid  instead of mineral acids [12, 19, 40].
Seawater  Biorefinery Oxalic acid is either manufactured by the nitric acid
oxidation of waste cellulosic materials or from carbon
monoxide under pressure in the presence of a catalyst. The
W. Hongsiri  B. Danon  W. de Jong (&) production technology has long been established [30, 31,
Process and Energy Department, Delft University
36]. All of the raw materials can be produced based on
of Technology, Leeghwaterstraat 44, 2628 CA Delft,
The Netherlands renewable, potentially sustainable biomass resources.
e-mail: [email protected] Thus, the use of oxalic acid as organic acid catalyst in

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sustainable biorefineries is very attractive and has not yet system. These results provide useful and sustainable syn-
been studied experimentally for the production of furfural. ergies for future biorefineries. However, the kinetics of the
Next, the use of co-catalysis, using different salts next to sugar dehydration have not been addressed. Knowledge on
the acidic catalyst, has been pointed out in previous the kinetics is required for better understanding of the
research work to improve the dehydration of lignocellu- reaction system and for improving the reactor design.
losic derivatives [15, 22, 27, 28]. Seawater offers a par- In this study, the effects of combined catalysis of oxalic
ticularly interesting and cheap catalytic reaction medium acid and seawater on the kinetics of pentose dehydration to
for biorefinery processes [14, 17, 21, 24, 33]. Thus non- furfural are investigated. The aim is to derive the kinetics
potable water sources can be used at large scale, mainly in of the formation of furfural from pentoses using oxalic acid
coastal localities, and for existing resources, such as macro as the primary acidic catalyst and in a natural saline
algae [13]. medium (seawater). Information on this is missing in the
Furfural, a hemicellulose derived platform chemical [3], literature. Therefore, first, the thermodynamic properties of
promises to be a very valuable product of the lignocellu- the resulting reaction solution are studied. Then, experi-
losic biomass-based biorefinery [8, 37]. It can easily be ments are presented using three different salt conditions: no
produced from biomass in a biorefinery system, and it is a salts, a 500 mM NaCl solution and seawater. The sub-
precursor for many different chemicals, used for the pro- sequent kinetic study comprises both the degradation of
duction of bio-plastics, bioblend solvents and biofuels. The furfural and the dehydration of two different pentoses
use of furfural presently is limited, which is contributed by (xylose and arabinose). Finally, the results are compared
some authors to the still inefficient production processes with results from a previous study using HCl as the acidic
and the relatively low oil prices [37]. catalyst. The approach followed in this study provides
Acidic saline aqueous solutions can minimize furfural important data for design of reactors to be integrated into
loss reactions [27, 28] as has been published previously. considerations of future furfural production processes.
Although some studies investigate xylose dehydration to
furfural in acidic and/or saline media, more research is
needed in this area to provide a clear picture on the syn- Methods and materials
ergistic effects of the two catalysts. Most of the previous
studies use either saline catalysts only, employ pure salts in A one-litre mechanically stirred stainless steel autoclave
contrast to real seawater or merely present yield studies. reactor was used for the experiments. The operating pres-
Recently, some papers concerning the sugar dehydration sure in the reactor was the saturation pressure of the mix-
with acid and seawater have been published. Grande et al. ture. An HPLC pump was used to introduce the reactant
investigated the combination of enzymes and bio-based into the reactor. Samples were taken from the liquid phase
acids for conversion of glucose into HMF in seawater [14]. by a sampling system making use of the pressure in the
Vom Stein et al. [35] used FeCl36H2 O, NaCl and seawater reactor. A schematic of the experimental setup is presented
as an additive for furfural production in a biobased biphasic in Fig. 1. The reagents used in the experiments, D-xylose,

Fig. 1 Schematic of the

experimental setup

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Int J Energy Environ Eng (2015) 6:21–30 23

Table 1 Thermodynamic Oxalic acid Salts Ionic strength (I) cH3 Oþ pKa1 pKa2 [H3O?] aH3 Oþ
properties of reaction media (mM) (–) (mol kg1 ) (–) (+) (+) (mM) (mM)
with different salt conditions
50 No salts 0.02 0.80 1.80 6.01 2:12  102 1:69  102
2
50 NaCl 0.48 0.51 1.35 5.20 2:74  10 1:40  102
50 Seawater 0.54 0.47 1.32 5.16 3:05  102 1:45  102
2
100 No salts 0.03 0.77 1.77 5.93 3:36  10 2:57  102
2
100 NaCl 0.50 0.51 1.35 5.20 4:80  10 2:44  102
100 Seawater 0.56 0.47 1.31 5.12 4:98  102 2:36  102

L-arabinose, furfural and anhydrous oxalic acid, were parameters which is applicable from room temperature to
obtained commercially, all with a 99 % purity (Sigma- 270  C [16]. The major ion concentrations of the different
Aldrich). Their concentrations in the experiments were salt solutions were included in the model which were
selected to be in-line with previous studies [5, 17, 26, 28] determined using ICP-OES elemental analysis as described
and indicate attractive economic potential [25]. The sea- above. The details of this thermodynamic property model
water was sampled from the North Sea near Scheveningen can be found in literature [2, 4, 16, 23]. The two-step
(The Netherlands) in June 2012. More details regarding the dissociation of oxalic acid can be represented as follows:
experimental procedure have been presented previously H2 C2 O4 þ H2 OHC2 O þ
4 þ H3 O ð1Þ
[17].
2;
The samples were analysed using an HPLC apparatus HC2 O
4 þ H2 OC2 O4 þ H3 O
þ
ð2Þ
with a Rezex RHM-Monosaccharide column, 8 % cross
linked Hþ , 300  7:80 mm (Phenomenex). A 0.005 N Next, using the following equation, the ionic strength is
H2 SO4 solution in demineralized water was used as the also calculated:
mobile phase at a flow rate of 0.6 ml/min with a column 1X n

temperature of 80  C. A Marathon XT auto-sampler I¼ mi z2i ; ð3Þ

2 i¼0
(Separations) was used to improve the reproducibility. The
C5-sugars were quantified by means of a Refractive Index where n is the number of ions, mi is the molality of the ion i
detector (Varian Model 350), while the other products, and zi is the charge of ion i.
mainly furfural, were analysed using both the Refractive The results are presented in Table 1 and Fig. 2. It is
Index detector and UV detector (Varian Model 310 Pro observed that the ionic strength of the solutions increases
Star). with the salts added, as expected. However, this increase in
ionic strength results in a decrease of the values of the ion
activity coefficients (only the hydronium ion activity
Results and discussion coefficient is shown). This lowers the activity of the
hydronium ions and, therefore, decreases the catalytic
Thermodynamics effect of the acid. However, the results also show that the
increase in ionic strength simultaneously results in an
In this section the thermodynamic properties of the reaction increase in the dissociation constants of the oxalic acid.
media employing the two different catalysts are presented. This latter effect results in higher hydronium ion concen-
In order to perform these calculations, the concentrations of trations. In short, the addition of the salts (or the increase in
the ions in the NaCl solution and in seawater were deter- the ionic strenght of the reaction solution) results in two
mined using ICP-OES elemental analysis. These results opposite effects. In Fig. 2 it is observed that these two
have been published previously [17]. effects are of similar magnitude. When the hydronium ion
Some works have made use of the electrolytes NRTL activity is calculated (see also Fig. 2) it is observed that
(eNRTL) [16, 39] and Pitzer model [10] for calculating the this variable remains fairly constant for all salt conditions.
thermodynamic properties of the aqueous electrolyte sys- In Fig. 3 the different effects that the addition of salts
tems. In this work, by applying the eNRTL model imple- can have on the catalysis of the dehydration of pentoses are
mented in the commercial software Aspen Plus (V-7.2), the summarized. Because the above-mentioned results indicate
ion activity coefficients, dissociation constants and hydro- that effect 2 and 3 in Fig. 3 cancel, it is concluded that if
nium ion concentrations have been calculated for the dif- the salts will have any effect on the dehydration reactions,
ferent reaction solutions. An advantage of the eNRTL this will be through direct influences on the mechanism
model is the temperature dependence of ion interaction (effect 1 in Fig. 3). This seems to be in accordance with the

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Fig. 2 Hydronium ion

concentration ([H3 Oþ ]), activity
coefficient (cH3 Oþ ) and activity
(aH3 Oþ ) for solutions with oxalic
acid concentration of 50 mM
(a) and 100 mM (b) for all three
salt conditions at 200  C

literature. Marcotullio et al. [27] propounded that anions, in both the furfural degradation [5, 15, 22, 26, 33, 37] and
particular Cl , favor the formation of the 1,2-enediol, the pentose dehydration reactions [6, 9, 28, 38]. Moreover, the
first intermediate in the rate limiting reaction towards reaction scheme for arabinose dehydration is assumed to be
furfural, in an acidic medium. At the same time, the more analogous to that of xylose. A similar approach is
polarizable halides stabilize the transitional states during employed in this study.
subsequent dehydration steps [28]. Also the cations are All reaction rate constants (k, min1 ) are estimated by
reported to catalyse the pentose dehydration proportionally least square fitting of the concentration expressions on the
to their ionization potential, which increases for Kþ , Naþ , experimental data. All these model equations were imple-
Ca2þ , Mg2þ and Fe3þ [15]; however, it is reported that this mented using MATLAB. The differential equations were
effect plays only a minor role [27]. solved using the ode45 function and the lsqcurvefit func-
tion was used for the fitting of the experimental data.
Kinetics The molar furfural yield Y (%) is calculated using the
following equation:
The kinetics of furfural formation from xylose have been Cf
extensively studied employing different temperatures, cat- Y¼  100; ð4Þ
Cp;0
alysts, reactant and catalyst concentrations [7]. Generally a
simple reaction scheme is assumed, as presented in Fig. 4 where Cf represents the maximum furfural concentration
[11, 18, 28, 37, 41]. Most studies use first-order kinetics for (mM) within the experiment and the initial pentose

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Int J Energy Environ Eng (2015) 6:21–30 25

 
Ea
k ¼ A exp ð5Þ
RT
where R = 8.314 J/(mol K) and the temperature T is in K.
In order to be able to correctly calculate the reaction rate
constants for the pentose dehydration, first the rate con-
stants for furfural degradation need to be determined.
Therefore, in the following subsection, these furfural deg-
radation rates are presented. In the subsequent subsection
the kinetics of pentose dehydration using oxalic acid and
different salt conditions are presented.

Furfural degradation
Fig. 3 Possible effects of salts on the dehydration of a pentose
The kinetics of pure furfural degradation are investigated
first. Experiments were performed with an initial furfural
concentration of 50 mM using 50 mM oxalic acid at three
different temperatures (160, 180 and 200  C). These
experiments were all without any salt added. The results
are presented in Fig. 5 and in Table 2. Also the results of
comparable studies on furfural degradation (using mineral
acids [17, 32, 38] and without any acidic catalyst [18]) are
Fig. 4 The simplified reaction pathway for the dehydration of xylose included for comparison purposes.
to furfural The results indicate that furfural degradation in oxalic acid
is relatively slow compared to its degradation using mineral
concentration Cp;0 (mM) is calculated from the weight of acids. It is interesting to note that the values of the activation
the inserted reactant. All experiments ran for 60 min with energy decrease following an increase in the strength of the
around 15 data points per experiment. acid, as expected. However, the activation energy in water
For the degradation of furfural the activation energy Ea alone is close to that obtained in HCl (while the resulting
(kJ/mol) and pre-exponential factor A (min1 ) have been reaction rates are the smallest). This can be explained by the
calculated from the values of the reaction rate constants at fact that the degradation of furfural in water alone cannot be
three different temperatures, using the Arrhenius equation considered as an acid catalysed reaction, as pKw values are
for the kinetic rate constant k: relatively low at high temperatures [19].

Fig. 5 Arrhenius plot for

furfural degradation using
different acidic catalysts

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26 Int J Energy Environ Eng (2015) 6:21–30

Table 2 Kinetic parameters for Catalyst Temperature Reactor Ea A References

furfural degradation using
 1
different acidic catalysts Type (mM) ( C) (kJ/mol) (min )

H2 SO4 100 150–210 Tube 83.6 1:4  107 Williams and Dunlop [38]
HCl 100 130–170 Autoclave 48.1 1:3  103 Rose et al. [32]
HCl 50 160–200 Autoclave 63.9 2:0  10 3 This studya
a 6
This calculation is based on H2 C2 O4 50 160–200 Autoclave 86.3 7:1  10 This study
the experimental results of our Water – 180–220 Autoclave 58.8 1:2  10 5 Jing and L€
u [18]
previous study [17]

It was shown before that the furfural degradation rates Pentose dehydration
(using HCl as the acidic catalyst) were lower when salts are
present [17]. However, since these rates using oxalic acid are The pentose degradation experiments were performed with
smaller by a factor of 10, it is chosen here to use the same an initial pentose concentration of 50 mM and oxalic acid
values for all different saline conditions. The value of kf that concentrations of 50 and 100 mM. Three different salt
will be used in the calculation of the pentose dehydration conditions were investigated: no salts, a 500 mM NaCl
kinetics at 200  C in the next section is 2:0  103 min1 . solution and seawater, all at 200  C.

Fig. 6 Xylose degradation (upper row) and furfural yields (lower row) in 50 mM (a) and 100 mM (b) oxalic acid at 200  C with three different
salt conditions. X xylose, Oxalic oxalic acid

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Int J Energy Environ Eng (2015) 6:21–30 27

Table 3 Estimated kinetic rate parameters for xylose dehydration at Table 4 Estimated kinetic rate parameters for arabinose dehydration
200  C at 200  C
Catalyst Salts Rate constant (103 ) Y Catalyst Salts Rate constant (103 ) Y
(%)
Type (mM) kx1 kx2 kx1 =kx2 (%) Type (mM) ka1 ka2 ka1 =ka2
(min1 ) (min1 ) (min1 ) (min1 )
Oxalic acid 50 No salts 34.0 21.3 1.60 50.5
Oxalic acid 50 No salts 16.7 33.9 0.49 24.5
Oxalic acid 50 NaCl 45.1 23.2 1.94 59.3
Oxalic acid 50 NaCl 31.8 39.0 0.82 44.7
Oxalic acid 50 Seawater 62.8 18.5 3.39 68.8
Oxalic acid 50 Seawater 45.7 44.3 1.03 48.2
Oxalic acid 100 No salts 51.0 57.0 0.89 47.2
Oxalic acid 100 No salts 29.3 46.7 0.63 29.4
Oxalic acid 100 NaCl 76.7 75.2 1.02 59.1
Oxalic acid 100 Seawater 150.1 74.3 2.02 66.6
Oxalic acid 100 NaCl 50.9 31.2 1.63 52.0
Formic acid [20] pH 1.53 No salts 150.0 30.0 5.00 60.0 Oxalic acid 100 Seawater 49.6 31.6 1.57 51.9
H2 SO4 [27] 50 No salts 195.6 81.6 2.40 61.4 HCl [17] 50 No salts 49.9 50.5 0.99 34.5
HCl [17] 50 No salts 123.1 73.7 1.67 52.8 HCl [17] 50 NaCl 106.6 90.1 1.18 49.1
HCl [17] 50 NaCl 226.3 111.3 2.03 64.3 HCl [17] 50 Seawater 115.0 88.8 1.30 53.9
HCl[17] 50 Seawater 268.8 97.4 2.76 71.7 Water [17] – No salts 11.2 27.1 0.41 24.1
HCl [27] 50 No salts 223.8 56.4 3.97 68.7 Water [17] – NaCl 23.4 22.1 1.06 27.0
HCl [27] 50 NaCl 317.0 70.2 4.51 72.8 Water [17] – Seawater 42.3 60.6 0.70 26.2
Water [18] – No salts 11.9 12.3 0.96 40.0
Water [17] – No salts 17.2 13.2 1.30 51.5
Water [17] – NaCl 25.0 21.3 1.17 46.1 In the upper row of Fig. 6 the symbols represent the
Water [17] – Seawater 47.6 61.7 0.77 44.8 experimental results while the lines represent the kinetic
model for the dehydration rate of xylose. This dehydration
rate is defined as (kx1 þ kx2 ). The molar furfural yields are
presented in the lower row of Fig. 6.
First, the xylose dehydration rate is discussed. It is
observed that the dehydration rate of xylose is dependent
on both catalysts; an increase in acid concentration and the
addition of salts result in increased dehydration rates.
However, the increase in the rate due to the increase in acid
concentration is larger than that due to the addition of the
salts.
Next, regarding the furfural yields, the effects of the two
catalysts are different. The addition of salts results in a
distinct increase of the furfural yield, for both acid con-
centrations. However, the maximum furfural yields are
comparable for the two different acid concentrations.
These observations are confirmed by the estimated
values for the kinetic rate parameters, see Table 3. Both the
values of kx1 and kx2 increase significantly due to the
doubling of the oxalic acid concentration (explaining the
relatively high increase in the dehydration rate), while for
the different salt conditions only such a distinct increase is
observed for kx1 . This can be observed more clearly in
Fig. 7 where the two reaction rates of xylose are presented
graphically for the different salt conditions. Comparing the
trend in the bars for any of the acid cases clearly shows that
where kx1 increases with the addition of the salts, kx2
remains fairly constant. The trends of 50 and 100 mM
oxalic acid, however, are similar in shape; the main dif-
ference is the fact that both k values are higher when using
Fig. 7 Kinetic rate constants of xylose dehydration under different 100 mM oxalic acid. In other words, the addition of the
acid and salt conditions at 200  C. a kx1 , b kx2 . OA oxalic acid salts selectively favours kx1 , the reaction towards furfural,

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28 Int J Energy Environ Eng (2015) 6:21–30

Fig. 8 Arabinose degradation (upper row) and furfural yields (lower row) in 50 mM (a) and 100 mM (b) oxalic acid at 200  C with three
different salt conditions. A arabinose, Oxalic oxalic acid

while an increase in the acid concentration favours both subsequent furfural formation. The trends for the two dif-
reactions more or less equally. ferent oxalic acid concentrations are similar, i.e., both k
These results are in accordance with previous observa- values are higher when using 100 mM oxalic acid. Ana-
tions for these reactions using HCl as the acidic catalyst logue trends observed for xylose are also observed for
[17]. Moreover, the final furfural yields are comparable for arabinose. However, the main difference between the two
using either a mineral acid or an organic acid combined pentoses is that the arabinose reactions are generally slower
with salts, see Table 3. Only the reaction rates were sig- and the furfural yields lower. Also, the increase in the
nificantly lower in the latter case. oxalic acid concentration has a distinct smaller effect on
Thus, it is concluded that oxalic acid catalyses both the the reaction rates of arabinose, compared to the increase in
reactions towards furfural and towards loss products the xylose reaction rates. However, it is observed again that
equally, while the presence of the salts (and especially the the furfural yields increase with the addition of the salts,
combined ions of seawater) catalyses the reaction towards especially in case of seawater.
furfural more selectively. These conclusions confirm the There is one final remarkable observation in Fig.7. This
hypothesis that the salts have a direct influence on the is the fact that, when no acid is present, the kx2 also
mechanism, without interfering significantly with the increases with the addition of the salts. In none of the
acidic catalysis. Moreover, if seawater is used as the experiments with an acidic catalyst this is the case. This
reaction medium, the mineral acids can be replaced by behaviour has been reported before; Liu et al. showed that
organic acids without a loss of final yield. the loss reactions during the dehydration of xylose and
In Fig. 8 and Table 4 the results for arabinose dehy- xylotriose increase with the addition of inorganic salts as
dration are presented. The results indicate that salts have a the sole catalyst [22]. It seems that the salts catalyse a
significant effect on arabinose dehydration and the specific loss reaction, which is suppressed in the presence

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Int J Energy Environ Eng (2015) 6:21–30 29

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