b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 3 6 3 6 e3 6 4 2

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Glycerol acetals, kinetic study of the reaction between glycerol

and formaldehyde

I. Agirre*, I. Garcı́a, J. Requies, V.L. Barrio, M.B. Güemez, J.F. Cambra, P.L. Arias
Chemical and Environmental Engineering Department, Engineering School of Bilbao Alameda Urquijo s/n, 48013 Bilbao, Spain

article info abstract

Article history: The acetalization reaction between glycerol and formaldehyde using Amberlyst 47 acidic
Received 17 August 2010 ion exchange resin was studied. These acetals can be obtained from renewable sources
Received in revised form (bioalcohols and bioalcohol derived aldehydes) and seem to be good candidates for
28 April 2011 different applications such as oxygenated diesel additives. A preliminary kinetic study was
Accepted 6 May 2011 performed in a batch stirred tank reactor studying the influence of different process
Available online 31 May 2011 parameters like temperature, feed composition and the stirring speed. A pseudo homog-
enous kinetic model able to explain the reaction mechanism was adjusted. Thus, the
Keywords: corresponding order of reaction was determined. Amberlyst 47 acidic ion exchange resin
Glycerol showed a fairly good behavior allowing 100% of selectivity towards acetals formation.
Formaldehyde However, the studied acetalization reaction showed high thermodynamic limitations
Acetal achieving glycerol conversions around 50% using a stoichiometric feed ratio at 353 K. The
Kinetics product is a mixture of two isomers (1,3-Dioxan-5-ol and 1,3-dioxolane-4-methanol) and
Amberlyst the conversion of 1,3-dioxolane-4-methanol into 1,3-Dioxan-5-ol was also observed.
ª 2011 Elsevier Ltd. All rights reserved.

1. Introduction reaction and apart of the methyl (ethyl) esters (biodiesel)

The development and commercial use of biodiesel have
expanded considerably in the last 10 years. Biodiesel is an
alternative fuel normally obtained from vegetable oils or
animal fats and it presents several technical advantages over
petro-diesel such as the reduction of exhaust emissions,
improved lubricity and biodegradability, higher flash point
and reduced toxicity. There are some other properties like
cetane number, gross heat of combustion and viscosity that
are very similar in biodiesels and in conventional diesels. But
biodiesels are worse than conventional ones in terms of
oxidation stability, nitrogen oxides emissions, energy content
and cold weather operability [1].
Biodiesel is obtained from the chemical reaction between
methanol (or ethanol) with vegetable oils in presence of basic
or acid catalyst. This reaction is called transesterification
glycerol is formed as a byproduct (10 wt %). Currently, small
amounts of this tri-alcohol are being used in pharmaceutical
and personal care areas, so, in order to avoid its incineration,
different alternatives are being investigated looking for high
added value products from glycerol: hydrogen gas production,
glycerin acetate and acetals formation as potential fuel addi-
tives, as composite additive, citric acid production, cosmetic
bonding agent for makeup including eye drops and conversion
to propylene glycol, acrolein, ethanol and epichlorhydrin [2,3].
A possible solution to the limitations that biodiesels
present is the use of adequate additives. Metal based additives
(manganese, iron, copper, barium.) were the most important
ones so far [4]. However, due to the harmful emissions that
this kind of additives implies, the use of renewable ashless
diesel combustion enhancer additives like acetals seems to
be the most suitable ones [5]. The acetals can be obtained

* Corresponding author. Tel.: þ34 946017297; fax: þ34 946014179.

E-mail addresses: ion.agirre@ehu.es (I. Agirre), igarcia013@ehu.es (I. Garcı́a), jesus.requies@ehu.es (J. Requies), laura.barrio@ehu.es
(V.L. Barrio), belen.guemez@ehu.es (M.B. Güemez), jose.cambra@ehu.es (J.F. Cambra), pedroluis.arias@ehu.es (P.L. Arias).
0961-9534/$ e see front matter ª 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biombioe.2011.05.008
 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 3 6 3 6 e3 6 4 2 3637

from reactions between alcohols (bioalcohols) and aldehydes.
In the present study glycerol and formaldehyde were used as
reactants. As it is mentioned, large amounts of glycerol are
available as a sub-product of the transesterification reaction.
On the other hand, formaldehyde can also have a renewable
origin as it can be obtained from methanol. This alcohol can
be produced from syngas (CO and H2), which can be
obtained from biomass [6,7]. Thus, all the raw materials
required for this process can be obtained from a renewable
origin leading into a sustainable process.
However, not all the acetals can be used as diesel or bio-
diesel additive. Some acetals present low flash points and as
a result they are not suitable to use as diesel additives. Glyc-
erol acetals fulfill these diesel specifications while acetals of
ethanol require a big aldehyde in order to get an acceptable
flash point. Lower molecular weight acetals are being used as
surfactants, flavors, disinfectants [3,5], in cosmetics, food,
pharmaceutical area or in fragrances [2,8].
In terms of catalyst, acetals can be produced via homoge-
neous catalytic processes using strong mineral acids as cata-
lysts such as H2SO4, HF, HCl or p-toluensuphonic acid [9e11].
Kaufhold et al. proposed in a patent [10] an industrial process
for acetal production. In this process, apart from
a homogeneous strong acid catalyst an entrainer (hexane,
pentane) is used with a normal boiling point between 298 K
and 348 K. This entrainer must be water insoluble (<3%
soluble in water), thus the water is continuously removed
from the reacting phase shifting the acetalization reversible
reaction to the desired direction. However, these processes
entail corrosion problems, are uneconomical and they are
not environmentally friendly. The use of a heterogeneous
catalytic process would overcome most of the previously
indicated problems. Therefore, several solid acid catalysts
are being tested currently.
Capeletti et al. [5] reported the performance of several solid
acid catalysts, from commercial, natural and laboratory
sources. They concluded that exchange resins show enough
surface acidity to allow reaching equilibrium values much
faster than other less acid solid catalysts.
compound like NaOH which can deactivate the catalyst and
hinder the reaction. Therefore, in spite of containing high
water amounts and 10 wt% of methanol, cheaper and
commercially available formaldehyde was used as reagent.
2.2. Analysis
Both reactants (glycerol and formaldehyde) and reaction
products (1,3-Dioxan-5-ol, 1,3-dioxolane-4-methanol and
water) were analyzed by gas chromatography (Agilent 6890N)
using a flame ionization detector (FID) and a thermal conduc-
tivity detector (TCD). Agilent DB-1 60 m  0.53 mm  5 mm
capillary column was used with Helium as the carrier gas.
2.3. Batch stirred tank reactor (BSTR)
The experiments were carried out in a 1 L glass jacketed stir-
red reactor (Fig. 1). The reaction temperature was controlled
by an external thermostat (Lauda RE 304). This thermostat
contains an external thermocouple to be placed inside the
reacting mixture and allows the reaction temperature
control with an accuracy of 0.02 K. The reactor also is
connected to a condenser in order to condense and reflux all
the vapours keeping the reaction volume nearly constant
and avoiding emissions by evaporation.
The reactants were charged into the reactor (total initial
volume 0.5 L) and after stabilizing the system to the desired
temperature, the catalyst was added (starting time). At certain
specific time intervals different samples were withdrawn in
order to analyse them by GC. A bit of glass wool was placed in
the output sampling valve in order to keep the catalyst
amount constant in the reactor.

2. Materials and methods

2.1. Materials

Glycerol (99 wt% for synthesis) from Panreac and formaldehyde

(36.5wt % stabilized with 10 wt% of methanol) from Sigma Aldrich
were used as reagents. Glycerol formal (99 wt %) for GC calibration
was obtained from Acros Organics. The glycerol formal is a mixture
of two of the isomers that are formed reacting glycerol with form-
aldehyde: 1,3-Dioxan-5-ol (55 wt%) and 1,3-dioxolane-4-methanol
(45 wt%). Amberlyst 47 was the selected catalyst.
Before using commercially available formaldehyde (36 wt%)
different tests using paraformaldehyde (95 wt%) from Fluka
were performed. This polymer is insoluble in glycerol and
therefore the reaction between glycerol and paraformaldehyde
in the presence of heterogeneous catalyst was negligible. On
the other hand, low concentration of formaldehyde was
obtained depolymerizing paraformaldehyde in water, even at Fig. 1 e Schematic drawing of the stirred batch reaction
high temperatures (423 K) without adding any other external system.
3638 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 3 6 3 6 e3 6 4 2
Before adding the catalyst sample, it was previously dried
at room temperature due to its high moisture content. Thus,
the catalyst had only the equilibrium humidity with the air
and therefore the weighting could be controlled.
3. Results and discussion
3.1. Preliminary experiments
Before starting the experiments, some tests were performed
using H2SO4 as catalyst. The reaction behavior was completely
comparable to the behavior observed using Amberlyst 47
acidic ion exchange resins. Besides, no additional byproducts
were observed using the sulphuric acid. However, with the
exception of these initial ones, all the experiments were
carried out using Amberlyst 47 resin in order to avoid all the
problems associated with the use of corrosive homogeneous
catalyst: i.e. catalyst removal and reuse.
Repeating at least three times each experiment using the
same Amberlyst 47 sample very similar results were obtained
and, as a consequence, it was established that the catalyst did
not suffer significant deactivation.
Besides, additional experiments proved that the methanol
present in the formaldehyde solution did not influence the
acetalization reaction selectivity. On the other hand, the
presence of high amounts of water in this solution had some
influence on the equilibrium conversion.
3.2. Reaction mechanism
According to Sharma & Chopade [12] the reaction mechanism
for acetalization of ethylene glycol with formaldehyde
involves two reversible steps: the first one where the alcohol
Fig. 2 e Acetalization reaction mechanism using glycerol and formaldehyde as reactants.
reacts with the aldehyde molecule leading to the formation
of the corresponding hemiacetal and the second one, where
the two hydroxyl groups of the hemiacetal join to form the
corresponding dioxolane, releasing a water molecule. Some
other authors [13] explained a more detailed mechanism for
the reaction between glycerol and acetaldehyde, indicating
more in detail all the different steps of the reorganization of
the hemiacetal molecule. In the present case, the mechanism
proposed by Sharma & Chopade [12] was followed. However,
in this case, two acetal isomers can be formed. One glycerol
molecule has three different hydroxyl groups (OH) and
depends on which two OH groups join to each other 1,3
dioxan-5ol or 1,3-dioxolane-4-methanol can be formed.
The first step in the formaldehydeeethanol reaction system,
which does not require a catalyst, is much faster than the
second one [12]. There are also some evidences that indicate
a similar behavior when glycerol and formaldehyde are used
as reactants. Just after mixing these compounds at room
temperature the mixture temperature increases notably due
to the exothermic reaction taking place as a non-catalyzed
process. However, some difficulties were found when
analyzing these samples. This fact could be explained by the
exothermicity of a non-catalyzed reaction. When the sample
is injected into the GC (which is at 473 K) the reverse reaction
occurs due to a high decrease of the equilibrium constant
with the increasing temperature and as a result most of the
hemiacetal disappears and thus, the sample analysis is not
representative. Similar problems were gathered when the
reaction between ethanol and butanal was studied [14]. In this
case HPLC/MS analyses of ethanol-butanal mixtures at room
temperature confirmed the presence of the hemiacetal in the
samples [15]. In addition to this, some authors [16] reported
the unstable behavior of hemi-acetals. As a result, this study
only took into consideration the overall reaction (see Fig. 2)
 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 3 6 3 6 e3 6 4 2
converting glycerol and formaldehyde into acetals. A more
detailed analysis including hemiacetal concentrations would
have been possible only if the reaction mixture could be
analyzed without modifying its temperature. The kinetic
analysis that follows fulfill the requirements of the objectives
established for this study: provide the kinetic information that
it is necessary to design industrial processes to produce these
acetals.
The overall conversion was determined measuring the two
acetal concentrations. Detailed kinetic modeling should take
into account the evolution of both reactant and product
concentrations. For this system, a precise measurement of the
reactant concentrations is extremely difficult: formaldehyde
is fed as a mixture where its dimers or higher polymers could
be also present and glycerol and formaldehyde could be
present not only as free molecules but also combined as
hemiacetal.
In order to study the kinetics of the reaction, a mixture of
both acetals, 1,3 dioxan-5ol or 1,3-dioxolane-4-methanol, was
taken into account (Fig. 2) without considering possible
isomerization reactions between both acetals. As it is
depicted in Fig. 3 both isomers are primary products but
then the dioxalane suffers an isomerization reaction
towards the dioxane formation. This effect was also
observed by Camara et al. (2003) and Da Silva Ferreira et al.
[13,17] in the evolution of the acetals from glycerol and
acetaldehyde appearing in Port and Madeira wines. Aksnes
et al. [18] also studied the acetalization reaction between
glycerol and acetaldehyde and they also observed that 1,3
dioxalane isomers were formed faster but then the reaction
mixture proceeded towards the isomerization equilibrium
generating more 1,3 dioxanes. On the contrary, Ruiz et al.
[19] observed the isomerization from dioxanes to dioxalanes.
As the hemiacetal formation and decomposition reaction
rates are so high at the operating temperatures, the hemi-
acetal (HA) can be considered to be continuously at equilib-
rium with glycerol and formaldehyde.
½HA ¼ K1 ½FHO½Gly
Fig. 3 e Evolution of 1,3 dioxan-5-ol and 1,3 dioxalane-4-
methanol in function of time.
3639
Where K1 is the equilibrium constant (Kc) in (mol/L)1.The
formation rate of acetal (AC) could be written as
d½AC
¼ wk3 ½HA  wk4 ½AC½W (2)
dt
Where w is (gcat)/(reacting volume in L)
k3 and k4 are the kinetic constants. k3in L/(gcat$min) and k4
in L2/(min$gcat), [ ] indicates concentration in mol/L
Substituting [HA] from Eq. (1),
d½AC
¼ wk½FHO½Gly  wk4 ½AC½W (3)
dt
Where k ¼ k3K1 in L2/(gcat$min$mol). At t ¼ 0, the initial
conditions are:
½FHO ¼ ½FHO0
½Gly ¼ ½Gly0
(4)
½AC ¼ ½AC0 ¼ 0
½W ¼ ½W0
As there are no side reactions when operating with
Amberlyst 47 resin as catalyst the concentration of other
compounds can be calculated by molar balances:


½FHO ¼ ½FHO0  ½AC  ½AC0 (5)
 

Gly ¼ ½Gly0  ½AC  ½AC0 (6)


½W ¼ ½W0  þ ½AC  ½AC0 (7)
In the global reaction, the forward reaction is 1st order with
respect to glycerol and 1st order with respect to formaldehyde.
The reverse reaction is also 1st order with respect to acetal
and water. These orders of reaction will be confirmed later. In
order to solve the differential equation (3) together with the
initial conditions (4) and the mass balances (5, 6 and 7)
a fourth order Runge-Kutta integration method was used.
(1) Thus, minimizing the sum of squares of the difference
between the experimental and the predicted concentrations,
the apparent kinetic constants (k and k4) were calculated.
3.3. Mass transfer resistance
In order to avoid mass transfer resistance a wide range of
stirring speeds (from 1250 rpm to 1750 rpm) was tested. No
effect of the agitation on the reaction rate was observed (Fig. 4)
proving the absence of any external mass transfer resistance
even at the lowest stirring speed (1250 rpm), so all further
experiments were carried out at 1250 rpm.
The experiments were performed with a stoichiometric
feed ratio (1:1 of glycerol to formaldehyde molar ratio) at 353 K
with 5.0 wt% of Amberlyst 47. The bubble point temperature of
the initial composition is 365 K and as a result the selected
temperature for these experiments was near the operating
limit. As the effect of the temperature is much higher over the
reaction rate than over the mass transfer coefficient, if there
were any external mass resistances, they would be observed
much more clearly at high temperatures.
3640 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 3 6 3 6 e3 6 4 2

Table 1 e Comparison among calculated experimental

k/k4 ratios.
Orderforglycerol Glycerol : Formaldehyde molar ratio

1:1 2:1 3:1

a a
k/k4 B k/k4 B k/k4 Ba

0.5 0.35 6.80 0.29 3.90 0.24 3.00

1 6.34 3.80 2.81
1.5 116.57 50.44 32.67
2 2256.97 674.51 380.66

a Where b ¼ ½Ac½W ½Gly½FHO at the end of each experiment.

reaction follows an elemental order of reaction (equation (9)

with a ¼ 1). Sharma and Chopade [12,21] and Agirre et al. [14]
Fig. 4 e Effect of the stirring speed. 1:1 glycerol to also concluded that the acetalization reactions studied follow
formaldehyde molar ratio, 353 K and 5.0 wt% of Amberlyst 47. an elemental kinetic law. k/k4 cannot be considered as an
estimation of the Kc (equilibrium constant) because the kinetic
model used for the adjustment does not represent the exact
reaction mechanism. This explains why parameter b is not
approximately constant for the same temperature at different
3.4. Effect of the feed composition initial feed ratios.
Moreover, it was checked, as it was expected, that
Three different feed mole ratios were tested (Glycerol to increasing the molar ratio of glycerol the equilibrium
formaldehyde molar ratios of 1:1, 2:1 and 3:1) in order to check conversion with respect to formaldehyde (Fig. 5) increases.
the order of reaction and estimate equilibrium conversions.
All the experiments were performed at 353 K, 1250 rpm and
3.5. Effect of the temperature
with 5.0 wt% of Amberlyst 47.
Based on the kinetic expression developed in section 3.1
Three different temperatures were tested: 353 K, 363 K and
different glycerol pseudo-orders of reactions were tested. In
373 K. For each temperature, at least four different experi-
principle, due to its molecular structure, glycerine molecule
ments were performed being the definitive kinetic parameters
is the one that can follow different reaction mechanisms
the arithmetic average value of the calculated parameters for
and thus have a different pseudo-order of reaction with
each experiment.
respect to the proposed one.
As in all the previous experiments, all the tests were per-
Different reaction orders for glycerol were tested: 0.5, 1, 1.5
formed with 5.0 wt% of Amberlyst 47 resin and at 1250 rpm.
and 2. The proposed mechanism suggests one as the most
However, in this case 3:1 glycerol to formaldehyde molar ratio
probable order for glycerol.
was used looking for less volatile mixtures and higher opera-
d½Ac tion temperatures leading to higher reaction rates. Using the
a
¼ wk½FHO½Gly wk4 ½AC½W (8)
dt
All the experiments were repeated at least three times in
order to get accurate enough parameter values within a pre-
determined tolerance range for a confidence interval of 95%
according to the t-student distribution.
For the tested reaction orders with respect to glycerol, the
algorithm was able to meet the integration requirements in all
the cases and the adjustment between the calculated and the
experimental data was too good in order to distinguish and
choose the appropriate kinetic law. For example, the sum of
squares of the differences between the experimental and pre-
dicted concentrations was in the order of 108 for all the orders
tested. This result can be associated with the analysis being
carried out: on an overall reaction and not on each of the reac-
tions of a complex mechanism [20]. Therefore, (k/k4) values were
compared. Depending on the a value of equation (8), the order of
magnitude of k/k4 changes considerably. Thus, it was observed
that assuming pseudo order one for glycerol (equation (9) with
a ¼ 1) the estimated k/k4 values are comparable to the Fig. 5 e Effect of the excess of one of the reactants (glycerol)
experimental results (Table 1). Thus, it is concluded that the in the conversion.
 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 3 6 3 6 e3 6 4 2 3641

Table 3 e Arrhenius’ correlation’s parameters for the

reaction between glycerol and formaldehyde.
Forward reaction Reverse reaction
a
Ea (J/mol) 59062 46301
7463.6 34.5
!
ðLÞ2
A$
mol min gcat

a Pseudo-activation energy (see equation (9)).

In order to apply the kinetics of the present reaction in

further process developments, the kinetic constants obtained
at different temperatures (Table 2) were fitted to the
Arrhenius’ Correlation. Thus, Table 3 shows the pre-
exponential factor (A) and pseudo-activation energies for
Fig. 6 e Effect of the temperature on conversion. 3:1 both forward and reverse reactions of the global reaction.
glycerol to formaldehyde molar ratio, 5wt% of Amberlyst
   0 

47 and at 1250 rpm. Ea;3 DG  Ea;3 þ DG0
k ¼ k3 k1 ¼ A,EXP ,EXP ¼ A,EXP (9)
RT RT RT

stoichiometric feed ratio the maximum possible liquid-phase

operation temperature would have been around 353 K since the
4. Conclusions
bubble point of the initial mixture is 363 K (calculated by Aspen
Plus). Therefore, temperatures lower than 353 K should have
As a result of the kinetic study, it is proved that the acetali-
been chosen and, as a consequence, the reaction rate would
zation reaction between glycerol and formaldehyde is carried
have been really low. As a result really long experiments might
out in two different steps: the first one where the hemiacetal is
have been carried out (using more catalyst would have not
formed, is quasi instantaneous and it does not need any
been realistic as 5.0 wt% is quite an important quantity).
catalyst while the second step, where the acetal isomers are
In the case of the acetalization reaction between glycerol
formed, is the controlling one and requires an acid catalyst. It
and formaldehyde, contrary to other acetalization reactions
is proved that the studied reaction can be described using an
reported in the open literature [12,21,22], it was observed that
elemental kinetic model. Moreover, despite being an
an increase of temperature does not imply any significant
exothermic reaction, it is checked that the effect of the
change of the equilibrium conversion. Moreover, it can be
temperature in the studied range does not affect significantly
observed that increasing the temperature the reaction rate
to the final equilibrium conversion. All this information can
also increases (Fig. 6) as it can be expected.
offer new insights for glycerol conversion to added-value
This observation of temperature having no influence on
products such as diesel additives.
the final equilibrium conversion in the studied temperature
range must be related to the heat effects associated with the
whole reaction process. Silva et Rodrigues [23] observed
a similar behavior in their acetalization study between
ethanol and acetaldehyde. This implies that the net heat
Acknowledgements
effect of the whole process must be quite low. Conventional
The authors gratefully acknowledge the financial support of
thermodynamic calculations indicate that acetalization
this work by the Spanish Ministry of Science and Innovation
reactions are exothermic when standard heat of formations
(ENE2009-12743-C04-04), the Basque Government and the
are considered, including the studied one. However, it was
University of the Basque Country (UPV/EHU). Besides, the
checked that the mixing heat between water, formaldehyde
authors want to mention the collaboration of Rohm & Haas for
and glycerol is positive (endothermic) as well as the mixing
kindly supplying different Amberlyst resins.
enthalpy between water and the formed acetals.

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