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chemical engineering research and design 9 0 ( 2 0 1 2 ) 696–703

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Chemical Engineering Research and Design
j our nal home page: www. el sevi er . com/ l ocat e/ cher d
Experimental study and model of reaction kinetics
of heterogeneously catalyzed methylal synthesis
Jan-Oliver Drunsel
a
, Mario Renner
b
, Hans Hasse
a,∗
a
Laboratory of Engineering Thermodynamics, University of Kaiserslautern, Erwin-Schrödinger-Straße 44, 67663 Kaiserslautern,
Germany
b
Ineos Paraform GmbH, Hauptstrasse 30, 55120 Mainz, Germany
a b s t r a c t
Reaction kinetics of the heterogeneously catalyzed formation of methylal from aqueous methanolic formaldehyde
solutions are studied in a plug flow reactor at 323, 333 and 343K using the acidic ion exchange resin Amberlyst
15 (Rohm and Haas) as catalyst. Parameters of an activity-based pseudo-homogeneous reaction kinetic model are
fitted to the experimental results. The model is based on the true speciation in the reacting solution and explicitly
includes the oligomerization reactions of formaldehyde in aqueous methanolic solutions. The reaction kinetic model
describes the experimental data well and is suited for process simulations in which both chemical reactions and
phase equilibria have to be described simultaneously.
© 2011 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords: Methylal; Reaction kinetics; Formaldehyde; Acetals
1. Introduction
Methylal is an important chemical which can be used as a sol-
vent or for producing concentrated formaldehyde-solutions
(Lojewska et al., 2008). Recent studies have shown that it
might also become an important resource in the production of
fuel additives (Burger et al., 2010). Methylal is produced from
methanolic formaldehyde solutions which typically also con-
tain water from the formaldehyde-production process. The
common process of methylal synthesis consists of a serial
arrangement of a reactor in which the feed is converted using
a heterogeneous acidic catalyst and a downstreamseparation
sequence which is needed to separate the product from the
unreacted educts and eventually from byproducts (see e.g.
Göring et al., 2004; Kaufhold and Müller, 1982). One major
disadvantage of that configuration results from the chemi-
cal equilibriumwhich limits the formaldehyde-conversion in
the reactor. Realizing chemical reaction and separation within
one apparatus using reactive distillation can overcome this
limitation. Therefore, producing methylal by reactive distilla-
tion has been focus of research of different groups over the

Corresponding author. Tel.: +49 631 205 3464; fax: +49 631 205 3835.
E-mail address: hans.hasse@mv.uni-kl.de (H. Hasse).
URL: http://thermo.mv.uni-kl.de (H. Hasse).
Received23 March2011; Receivedinrevisedform20 September 2011; Accepted23 September 2011
last years (Kolah et al., 1996; Masamoto and Matsuzaki, 1994;
Zhang et al., 2011).
The key to a successful design of such methylal processes
is the detailed knowledge of the reaction kinetics. In order
to keep thermodynamic consistency to phase equilibrium
model, also reaction kinetics must be described by an activity-
based model (Hasse, 2003). Moreover, it must be considered
that the educt of methylal synthesis, the methanolic, aqueous
formaldehyde solution, is itself a complex reacting solution
in which oligomerization reactions occur (Hahnenstein et al.,
1994). They have to be taken into account explicitly in devel-
oping predictive reaction kinetic models of reactions in which
formaldehyde solutions are used as educts (Maiwald et al.,
2006).
Masamoto and Matsuzaki (1994) carried out reac-
tion kinetics experiments of methylal synthesis in a
batch and tubular-fixed-bed-reactor at very low ini-
tial formaldehyde-concentrations (up to 0.051g/g, initial
methanol-concentrations between 0.2 and 0.6g/g). The model
these authors use to describe their experimental data is based
on overall concentrations rather than on true speciation, i.e.
0263-8762/$ – see front matter © 2011 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.cherd.2011.09.014
chemical engineering research and design 9 0 ( 2 0 1 2 ) 696–703 697
does not explicitly account for the chemistry in aqueous and
methanolic formaldehyde solutions, and is furthermore not
activity based. Moreover, no comparison between the model
and the experiments was carried out so that the quality of
the model remains unclear.
Kolah et al. (1996) accomplished experimental and model-
based investigations on methylal production by batch and
continuous reactive distillation. The authors developed an
activity-based model based on the true speciation, but only
considered the formation of the first hemiacetal in methano-
lic and the first glycol in aqueous formaldehyde solutions.
Dedicated reaction kinetic experiments were carried out and
results are graphically shown, but not used in the description
of the reactive distillation simulations as chemical equi-
librium was assumed for the methylal formation reaction.
Unfortunately, no comparison between the reactive distil-
lation experiments and the model is shown, so that it is
neither possible to validate the author’s assumptions nor their
data.
In the present work, reaction kinetic experiments of
methylal-formation were carried out in a tubular fixed-bed
reactor. The conditions are chosen so that also data on the
chemical equilibrium are obtained. The acidic ion exchange
resin Amberlyst 15 of Rohm and Haas is used as a catalyst.
Ternary mixtures of formaldehyde, water and methanol are
used as a feed. The concentration of formaldehyde in the
feed is varied in the range between 0.05 and 0.15g/g, the
methanol concentration is about 0.8g/g. The studied temper-
ature range is 323–343K. These choices are made according
to process development considerations. At higher tempera-
tures side products such as dimethyl ether, formic acid and
methyl formate, whichwere not observedinthe present study,
may become important (Kuhnert, 2004), at lower tempera-
tures reaction rates are unnecessarily low. Parameters of an
activity-based pseudo homogeneous model are fitted to the
results of the experiments based on their true speciation,
i.e. accounting for the oligomerization reactions of formalde-
hyde in aqueous methanolic solutions. Under the conditions
of the experiments carried out in the present work, i.e. in
the presence of the strong acidic catalyst, the methylal for-
mation reaction is the kinetically limiting step whereas the
oligomerization reactions in aqueous methanolic formalde-
hyde solutions are so fast that it can be assumed that they
are always in chemical equilibrium. The equilibrium con-
stants of these reactions as well as the UNIFAC model for
the activity coefficients were taken from previous work from
our group (Kuhnert, 2004; Kuhnert et al., 2006). The UNI-
FAC group assignment, the volume- and surface parameters
Table 1 – UNIFAC group assignment (Kuhnert, 2004).
Component Group
Formaldehyde 1CH
2
O
Water 1H
2
O
Methanol 1CH
3
O
Methylal 1C
3
H
8
O
2
Methylene glycol 1HO(CH
2
O)H
Hemiformal 1CH
3
O, 1CH
2
OH
Poly(oxymethylene)glycol (n−1)CH
2
O, 2OH, 1CH
2
Poly(oxymethylene)hemiformal (n−1)CH
2
O, 1CH
3
O, 1CH
2
OH
Table 2 – UNIFAC size (r
i
) and surface (q
i
) parameters of
pure components/groups (Kuhnert, 2004).
Group Group number r
i
q
i
CH
2
O 1 0.9183 0.780
H
2
O 2 0.9200 1.400
C
3
H
8
O
2
3 2.9644 2.716
HO(CH
2
O)H 4 2.6744 2.940
OH 5 1.0000 1.200
CH
2
6 0.6744 0.540
CH
3
O 7 1.1459 1.088
CH
2
OH 8 1.2044 1.124
CH
3
OH 9 1.4311 1.432
as well as the group interaction parameters are given in
Tables 1–3.
2. Chemical system
Formaldehyde is a gas at ambient conditions and com-
monly used in liquid aqueous or methanolic solutions.
These solutions are highly reactive multicomponent
mixtures (Walker, 1963). In methanolic and aqueous
solutions, poly(oxymethylene)hemiformals HF
n
s and
poly(oxymethylene)glycols MG
n
s are formed:
CH
3
OH+CH
2
O HO(CH
2
O)CH
3
. ¸¸ .
HF
1
(I)
HO(CH
2
O)
n−1
CH
3
+CH
2
O HO(CH
2
O)
n
CH
3
. ¸¸ .
HFn
(n ≥ 2) (II)
H
2
O+CH
2
O HO(CH
2
O)H
. ¸¸ .
MG
1
(III)
Table 3 – UNIFAC interaction parameters a
i,j
/K (Kuhnert, 2004).
Group i Group j
1 2 3 4 5 6 7 8 9
1 – 867.8 0.0 189.2 237.7 83.36 0.0 238.4 238.4
2 −254.5 – a
2,3
(T) 189.5 −229.1 300.0 −219.3 a
2,8
(T) 289.6
3 0.0 a
3,2
(T) – a
3,2
(T) 237.7 83.4 0.0 0.0 410.0
4 59.2 −191.8 a
2,3
(T) – −229.1 300.0 −142.4 289.6 289.6
5 28.06 353.5 28.06 353.5 – 156.4 112.8 −137.1 −137.1
6 251.5 1318.0 251.5 1318.0 986.5 – 447.8 697.2 697.2
7 0.0 423.8 0.0 774.8 1164.8 273.0 – 238.4 238.4
8 −128.6 a
8,2
(T) 0.0 −181.0 249.1 16.5 −128.6 – 0.0
9 −128.6 −181.0 −71.2 −181.0 249.1 16.5 −128.6 0.0 –
a
2,3
(T)/K=−225.5+0.7205(T/K), a
3,2
(T)/K=1031.0−1.749(T/K), a
2,8
(T)/K=451.64−114, 100/(T/K), a
8,2
(T)/K=−1018.57+329, 900/(T/K) .
698 chemical engineering research and design 9 0 ( 2 0 1 2 ) 696–703
HO(CH
2
O)
n−1
H+CH
2
O HO(CH
2
O)
n
H
. ¸¸ .
MGn
(n ≥ 2) (IV)
As formaldehyde is an important chemical, these reac-
tions have intensively been studied, see e.g. Hahnenstein et
al. (1994), Maiwald et al. (2003), Ott et al. (2005) and references
therein. The reaction rates are very high at low pH-values so
that under the conditions of the present study the chemical
equilibriumof the Reactions (I)–(IV) is attained on a time scale
which is much faster than that of the formation of methy-
lal. It can therefore be assumed that equilibrium is attained
instantaneously. The equilibriumdistributionof the oligomers
mainly depends on the overall formaldehyde concentration
and the methanol/water ratio. At the conditions studied in
the present work, HF
1
and MG
1
are the predominant species.
Even though monomeric formaldehyde plays the central role
in the reaction network, its concentration is always very low.
Typical numbers are of the order of 5×10
−5
mol/mol (calcu-
lated by the use of the model and parameters published by
Kuhnert (2004)) for the conditions studied in the present work.
Whereas Reactions (I)–(IV) occur in all methanolic, aqueous
formaldehyde solutions and, hence, no catalyst is needed,
the formation of acetals which is discussed now only occurs
in the presence of acidic catalysts. In the presence of such
catalysts, the hemiacetals HF
n
react with methanol forming
acetals:
HO(CH
2
O)
n
CH
3
+CH
3
OH
H
+
H
3
CO(CH
2
O)
n
CH
3
+H
2
O (V)
The first acetal (n=1) is methylal. A more detailed scheme of
the reaction mechanism of methylal formation is discussed
by Kolah et al. (1996). The formation of the longer-chained
acetals withmore thanone CH
2
Ogroup (n>1) is not important
at the conditions studied in the present work. They were not
detected in the experiments and are therefore not included in
the model.
3. Experimental
3.1. Chemicals and analysis
The feedstock that was used for the experiments was pre-
pared by dissolving paraformaldehyde in methanol and water.
Paraformaldehyde was purchased from Merck, methanol
(purity 99.9%) was purchased from Sigma Aldrich and water
was bidistilled. Gas chromatography with the internal stan-
dard method was applied to determine the fractions of
methanol, water and methylal. An Agilent 6980N gas chro-
matograph equipped with a heat conductivity detector and an
Agilent J&P HPINNOWax column (diameter 0.32mm, length
30m, film thickness 0.32␮m) was used. The sodium sulfite
method was applied to determine the fraction of formalde-
hyde in the mixtures (Walker, 1963). Upon the analysis, the
formaldehyde oligomers are split up, hence, overall concen-
trations of methanol, water, methylal and formaldehyde are
measured. Each sample was analyzed several times, the max-
imumrelative deviations were 3% for methanol, 6% for water,
4%for formaldehyde and 5%for methylal. These numbers are
considered also as estimated error of the analysis. The high
error for methylal is due to the difficult handling of that low-
boiling substance.
Table 4 – Properties of the acidic ion exchange resin
Amberlyst 15.
Ion exchange capacity (mmol H
+
/g dry cat.) 4.88
a
Harmonic mean size water swollen (mm) 0.60–0.85
b
Finest content (<0.355mm) Max. 1%
b
Coarse beads (>1.180mm) Max. 5%
b
Catalyst internal porosity (mL pore volume/g cat. dry) 0.4
b
Swelling properties Water MeOH Mal
Specific volume (mL bulk swollen
cat./g bulk dry cat.)
2.8
a
2.9
a
2.5
a
a
This work.
b
Product data sheet.
3.2. Catalyst
In the present work, the acidic ion exchange resin Amberlyst
15 of Rohmand Haas was used to catalyze the reaction. Table 4
gives an overview of its properties. The determination of the
total capacity was carried out in the present work according
to DIN 54403. Additionally, the swelling of the catalyst in the
different pure solvents used in the present work was studied
experimentally at roomtemperature. The swelling is similar in
water andmethanol andlower inpure methylal. For numerical
values, see Table 4.
3.3. Experimental procedure
The experiments were carried out in a plug flow reactor. The
reactor set-up has been successfully used in many previous
reaction kinetic studies (Schmitt and Hasse, 2006; Parada,
2009; Ryll, 2009). A scheme of the reactor is shown in Fig. 1.
The feed mixture is prepared gravimetrically and stored in
the drum D1. As methylal is only produced upon contact
with the catalyst, a one feed arrangement is sufficient. A
pre-equilibration regarding the formation of the oligomers is
not required as that equilibriumis established extremely fast
in the reactor as explained above. A constant flow through
the reactor is provided by a piston pump (type Bischoff HPD
Multitherm 200). The mass flow was determined by weigh-
ing the reactor effluent. The desired pressure in the reactor
is adjusted by a back-pressure valve located at the outlet of
the reactor. It was set to about 5bar in the present work to
ensure a proper operation of the pump and avoid evaporiza-
tion. In order to adjust the desired reaction temperature and
to ensure isothermal conditions during the experiments, the
reactor is immersed in a thermostatted bath. Prior to entering
the reactor the feed passes a pre-heating section (coiled tube)
in the thermostatting bath in which it is heated up to reac-
tion temperature. The reactor consists of 9 tubes made of the
nickel-based steel 2.4605 with an inner diameter of 10.3mm.
The length of the tubes is 128mm for tubes 1–4, 257mm for
the tubes 5 and 6, and 385mm for the tubes 7–9. The tubes
were filled with catalyst swollen in methylal (smallest vol-
ume, cf. Table 4). In order to avoid destruction of the catalyst
by swelling during the experiments, an expansion space of a
length of about 5mmwas left in each tube. At the inlet of the
first tube and at the outlets of all other tubes, sample ports
are located (X1–X10 in Fig. 1) which allow collecting samples
for analysis and, hence, determining the concentration profile
along the reactor. The sample ports are equipped with a cool-
ing systemto avoid partial evaporation while taking samples
chemical engineering research and design 9 0 ( 2 0 1 2 ) 696–703 699
TI TI
TI TI TI TI TI TI
TI TI TI TI TI TI
PI PI
D1 D1
D2 D2
X1 X1
X2 X2
X4 X4
X5 X5 X7 X7 X9 X9
X3 X3 X6 X6 X8 X8
X10 X10
Fig. 1 – Scheme of the plug flow reactor (X sample port, T temperature measurement, P pressure measurement, D drum).
fromthe hot pressurized reactor. Seven calibrated Pt100 resis-
tance thermometers (accuracy 0.1K) are located in the tubes
to monitor the temperature during the experiment. The set
temperature was maintained constant within the accuracy of
the temperature measurement. After all settings were done,
the reactor was left undisturbedfor at least 120min before tak-
ing samples from all sample ports against the flow direction
proceeding from X10 to X1 in order not to disturb the steady
state mode of the reactor. Even though 120min were known
to be sufficient from preliminary experiments, the establish-
ment of the steady state was monitored by taking samples
fromthe reactor outlet.
3.4. Experimental program
The studied three feed compositions (F1–F3) are given in
Table 5. The default feed mass flow was 10g/min. With that
feed flow experiments were carried out for all feeds at 323.15,
333.15 and 343.15K. In a mass flow study carried out for F2
Table 5 – Overall feed compositions.
Feed MeOH Water (g/g) Fa
F1 0.8 0.05 0.15
F2 0.8 0.1 0.1
F3 0.86 0.07 0.07
at 343.15K the feed was increased up to 30g/min in order to
check for an influence of external mass transfer.
3.5. Experimental results
Fig. 2 shows the result of the mass flowstudy ina plot inwhich
measured overall methylal concentrations are depicted as a
function of the pseudo retention time of the mixture at two
different liquid loads. The pseudo retention time is defined as
the ratio of the mass of catalyst between the reactor inlet and
the sample point and the mass flowof the reacting liquid. For
varying liquid mass flows but otherwise same conditions, it
should be expected that the reaction extent is the same for
the same pseudo retention time if there is no effect of mass
transfer between the liquid and the solid catalyst. The pro-
files are independent of the liquid load, thus external mass
transfer limitations canbe neglected. For the subsequent stud-
ies, a constant mass flow of 10g/min was chosen to keep the
consumption of reactants low.
Fig. 3 illustrates the influence of the temperature on the
reaction kinetics for the same feed. As expected, the reac-
tion rate increases with rising temperature. The chemical
equilibrium, however, is nearly independent of temperature.
Thus, the heat of reaction is small. The influence of feed
composition on the reaction is shown in Fig. 4. Results from
three experiments are depicted which were carried out at
the same temperature but with different molar ratios of
700 chemical engineering research and design 9 0 ( 2 0 1 2 ) 696–703
0 2 4 6 8
0
0.02
0.04
0.06
0.08
0.1
0.12
Fig. 2 – Results of reaction kinetic experiments carried out
to study the influence of the liquid flow rate on the
methylal formation: overall methylal mass fraction as a
function of the pseudo retention time (cf. text) for the flow
rates 9.5m
3
/(m
2
h) () and 28.5m
3
/(m
2
h) (). The feed is F2
(cf. Table 5), the temperature is 343.15K. The line is a guide
for the eye.
0 10 20 30 40 50 60 70 80
0
0.02
0.04
0.06
0.08
0.1
Fig. 3 – Results of reaction kinetic experiments: overall
methylal mass fraction as a function of the mass of dry
catalyst for the temperatures 323.15K (), 333.15K (), and
343.15K (). The feed is F3 (cf. Table 5). The lines are guides
for the eye.
methanol/formaldehyde in the feed. As expected, the equilib-
riumconcentration of methylal decreases upon an increase of
that ratio. The time that is needed to reach the equilibriumis
not significantly affected.
The complete data set for all experiments will be published
later in Drunsel (2011).
4. Reaction kinetic model
4.1. Overview
The experimental reactionkinetic results were correlatedwith
a pseudo homogeneous activity based model. The reaction
termfor a control volume is given by
dn
i
dt
=
i
c
H
+
cat,dry
m
cat
r, (1)
0 10 20 30 40 50 60 70 80
0
0.05
0.1
0.15
0.2
Fig. 4 – Results of reaction kinetic experiments: overall
methylal mass fraction as a function of the mass of dry
catalyst for different values of the number of the molar ratio
methanol/formaldehyde. Feed F1 (), Feed F2 (), and Feed
F3 (), cf. Table 5. The temperature is 343.15K. The lines are
guides for the eye.
where c
H
+
cat,dry
m
cat
is the number of active catalyst sites within
the control volume. The overall reaction rate r is the differ-
ence between forward and backward reaction rate which is
described here using a second order activity based approach:
r = k
f
(T)a
HF
1
a
MeOH
−k
b
(T)a
Mal
a
H
2
O
. (2)
The application of Eqs. (1) and (2) to a stationary plug flow
reactor yields
dx
(n)
i
dm
cat
=
1
˙ n

i
c
H
+
cat,dry
(k
f
(T)a
HF
1
a
MeOH
−k
b
(T)a
Mal
a
H
2
O
), (3)
where dx
(n)
i
/dm
cat
is the differential change of the mole frac-
tion of component i in a differential section of the reactor that
contains agivendifferential mass of catalyst. Inthe derivation,
it is assumed that the overall molar density of the reacting
solution does not change. Note that this assumption is not
evenstrictly needed, as also Eq. (3) canbe postulatedas a start-
ing point for the correlation. The temperature dependency of
the reaction rate constants is described using the Arrhenius
approach
k
f,b
(T) = k
f,b
(T
0
)exp
_

E
f,b
R
_
1
T

1
T
0
__
, (4)
where T
0
denotes a reference temperature which can be arbi-
trarily chosen and k
f,b
(T
0
) the reaction rate constants for the
forward and backward reaction, respectively, at the reference
temperature. The reaction rate constants and the activity
based thermodynamic equilibrium constant K(T) are related
by
K(T) =
k
f
(T)
k
b
(T)
. (5)
Only the reaction kinetics of the methylal formation (Reaction
V) were explicitly considered. For the reasons given above, it
was assumed that for all other reactions the (activity based)
chemical engineering research and design 9 0 ( 2 0 1 2 ) 696–703 701
Table 6 – Parameters for calculating the activity based chemical equilibriumconstants of Reactions (I)–(IV) using the
correlation given in Eq. (6).
A B C D
MG
1
−30.946 4.819 ×10
3
3.741 −4.534 ×10
−3
MG
2
−30.941 5.653 ×10
3
3.741 −4.534 ×10
−3
MG
n
, n≥3 −30.933 5.361 ×10
3
3.741 −4.534 ×10
−3
HF
1
1.130 ×10
3
−2.510 ×10
4
−1.984 ×10
2
0.316
HF
2
1.129 ×10
3
−2.551 ×10
4
−1.984 ×10
2
0.316
HF
n
, n≥3 1.129 ×10
3
−2.563 ×10
4
−1.984 ×10
2
0.316
2.9 2.95 3 3.05 3.1
−6
−5
−4
−3
−2
−1
0
backward
forward
Fig. 5 – Reaction rate constants fromindividual fits of
forward and backward reaction (Feed F1 (), Feed F2 ()
and Feed F3 (), cf. Table 5) and trend line fits (–).
chemical equilibrium conditions are fulfilled. The following
correlation for the equilibriumconstants was used:
ln(K
i
(T)) = A+
B
(T/K)
+Cln(T/K) +D(T/K). (6)
The equilibrium constants of the Reactions (I)–(IV) as well as
the activity coefficient model, which is of the UNIFAC type
(with some individually adjusted parameters) were adopted
from Kuhnert (2004), who studied mixtures of formaldehyde,
water, methanol, and methylal, but treated methylal as an
inert component as no catalyst was used in their study. Note
that Kuhnert (2004) assumed a reaction scheme that differs
fromthe one presented here so that the equilibriumconstants
had to be converted. The result is presented in Table 6. The
parameters describing the methylal formation (Reaction V)
were fitted to the data from the present work. From these,
the equilibrium constant of Reaction (V) can be found using
Eq. (5). It is consistent with the form presented in Eq. (6), but
as a consequence of Eqs. (4) and (5) the parameters C and
D are zero. The differential-algebraic-equation (DAE) system
describing the reaction system was implemented and solved
in Matlab.
0 10 20 30 40 50
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
Fig. 6 – Comparison of overall concentration between
model (lines) and experimental data (symbols) for feed F2
at T=343.15K: methanol (), water (), methylal (×) and
formaldehyde ().
4.2. Fitting procedure and results
The reaction kinetic model described in the previous section
has four adjustable parameters k
f,b
(T
0
) and E
f,b
which were
fitted to the present experimental data. Since only overall
concentrations were obtained as results of the experiments,
true concentrations had to be calculated first. Therefore, the
model from Kuhnert (2004) was applied and chemical equi-
librium for the methylene glycol and hemiformal formation
reactions was assumed to determine the species distribution.
Subsequently, reaction rate constants k
f,b
were fitted for each
experiment individually using a least square method with the
sum of the deviations of concentrations between model and
experiment for methylal, methanol and water as objective
function. Only the first eight data points of each experiment
were taken into account, as the remaining ones were always
equilibrium data and including them would have led to an
overweight of the equilibrium part of the experiment com-
pared to the kinetic part. HF
1
and MG
1
are the predominant
oligomers at the conditions studied here. Thus, the maxi-
mum chain length of oligomers that was considered is n=5.
The amounts of longer oligomers are negligible. Fig. 5 shows
kinetic constants obtained from the individual fits. In order
to obtain a single set of parameters that describes the entity
of all accomplished experiments, the reaction rate constants
Table 7 – Parameters of the reaction kinetic model (cf. Eq. (5)) and equilibriumconstants (cf. Eq. (6)) of the methylal
formation. The reference temperature is T
0
=333.15K.
k
f
(T
0
) (mol/(mol
H
+ s)) k
b
(T
0
) (mol/(mol
H
+ s)) E
f
(kJ/mol) E
b
(kJ/mol) A (–) B (–)
0.322 0.0125 54.65 54.74 3.22 11.0
702 chemical engineering research and design 9 0 ( 2 0 1 2 ) 696–703
determined in the individual fits were correlated by a trend
line fit from which both activation energies E
f,b
and reaction
rate constants k
f,b
(T
0
) were determined. The results are sum-
marized in Table 7. From this also the chemical equilibrium
constant of the methylal formation can be determined using
Eq. (5). The resulting parameters A and B of Eq. (6) are also
included in Table 7. The B parameter corresponds to an almost
negligible enthalpy of reaction of −0.09kJ/mol. The resulting
number for K is about 25.9 in the temperature range stud-
ied here. From this, for concentrations typically encountered
from the experiments in the present work, the mole fraction
based(thermodynamically inconsistent) equilibriumconstant
K
x
can be found. The resulting numbers are about 5.1. Fig. 6
shows an example of the comparison between the correlation
of the experimental reaction data taken in the present work
and the overall correlation in terms of overall concentrations.
The agreement is excellent. The average overall relative devia-
tions betweenmodel andexperiments are 0.57%for methanol,
1.79% for water, 5.77% for methylal and 8.77% for formalde-
hyde. The high relative deviations for formaldehyde result
fromthe low concentrations.
5. Conclusion
Knowledge of reaction kinetics and chemical equilibrium is
essential for the design of reactors and reactive distillation
columns. In the present work, experimental studies on het-
erogeneous catalyzed formation of methylal from aqueous,
methanolic formaldehyde solutions were carried out in a plug
flow reactor. As a catalyst, Amberlyst 15 was used. Both the
influence of temperature and initial concentrations on kinet-
ics and chemical equilibrium were studied in a range that is
interesting for process design. Parameters of a pseudo homo-
geneous activity based model were fitted to the experimental
results. The model explicitly accounts for the oligomerization
reactions in the system formaldehyde, water, and methanol,
and is, hence, based on the true concentrations rather than on
the overall ones. In the resulting complex system of coupled
reactions, the formation of methylal is the rate determining
step. Only the parameters describing the methylal formation
were fittedtothe experimental data, all other parameters were
taken fromthe literature. The newmodel described the exper-
imental results well. It is thermodynamically consistent and
can also be used in models of reactive distillation processes
in which chemical reaction and phase equilibriumhave to be
described simultaneously.
Abbreviations
Fa formaldehyde
HF hemiformal
Mal methylal
MeOH methanol
MG methylene glycol
List of symbols
c total catalyst capacity
a activity
a
i,j
UNIFAC group interaction parameter
E activation energy
i, j UNIFAC groups
k reaction rate constant
K reaction equilibriumconstant
m mass
n mole number
n number of formaldehyde segments in formaldehyde
oligomer
stoichiometric coefficient
q
i
UNIFAC surface parameter
r reaction rate
r
i
UNIFAC volume parameter
T temperature
T
0
reference temperature
x
(n)
mole fraction
¯x
(n)
overall mole fraction
Indices
b backward reaction
cat catalyst
f forward reaction
i component index
References
Burger, J., Siegert, M., Ströfer, E., Hasse, H., 2010.
Poly(oxymethylene) dimethyl ethers as components of
tailored diesel fuel: properties, synthesis and purification
concepts. Fuel 89 (11), 3315–3319.
Drunsel, J.-O., 2011. Entwicklung von reaktions-
destillationsprozessen zur herstellung von
formaldehyd-vollacetalen. Ph.D. Thesis. University of
Kaiserslautern.
Göring, M., Hoffmockel, M., Lingnau, J., Mueck, K.-F., 2004.
Verfahren zur Herstellung von Acetalen. Patent EP 1824807.
Hahnenstein, I., Hasse, H., Kreiter, C.G., Maurer, G., 1994. 1H- and
13C-NMR-spectroscopic study of chemical equilibria in
solutions of formaldehyde in water, deuteriumoxide, and
methanol. Ind. Eng. Chem. Res. 33 (4), 1022–1029.
Hasse, H., 2003. Thermodynamics of reactive separations. In:
Sundmacher, K., Kienle, A. (Eds.), Reactive Distillation: Status
and Future Directions. Wiley-VCH Verlag GmbH & Co. KGaA,
Weinheim, pp. 63–96 (Chapter 4).
Kaufhold, M., Müller, W., 1982. Process for the recovery of pure
methylal frommethanol–methylal mixtures. Patent US
4385965.
Kolah, A.K., Mahajani, S.M., Sharma, M.M., 1996. Acetalization of
formaldehyde with methanol in batch and continuous
reactive distillation columns. Ind. Eng. Chem. Res. 35,
3707–3720.
Kuhnert, C., 2004. Dampf-flüssigkeits-gleichgewichte in
mehrkomponentigen formaldehydhaltigen systemen. Ph.D.
Thesis. University of Kaiserslautern.
Kuhnert, C., Albert, M., Breyer, S., Hahnenstein, I., Hasse, H.,
Maurer, G., 2006. Phase equilibriumin formaldehyde
containing multicomponent mixtures: experimental results
for fluid phase equilibria of (formaldehyde+(water or
methanol) +methylal)) and
(formaldehyde+water +methanol +methylal) and comparison
with predictions. Ind. Eng. Chem. Res. 45, 5155–5164.
Lojewska, J., Wasilewski, J., Terelak, K., Lojewski, T., Kolodziej, A.,
2008. Selective oxidation of methylal as a new catalytic route
to concentrated formaldehyde: reaction kinetic profile in
gradientless flow reactor. Catal. Commun. 9, 1833–1837.
Maiwald, M., Fischer, H.H., Ott, M., Peschla, R., Kuhnert, C.,
Kreiter, C.G., Maurer, G., Hasse, H., 2003. Quantitative NMR
spectroscopy of complex liquid mixtures: methods and results
for chemical equilibria in formaldehyde–water–methanol at
temperatures up to 383K. Ind. Eng. Chem. Res. 42 (2), 259–266.
Maiwald, M., Grützner, T., Ströfer, E., Hasse, H., 2006. Quantitative
NMR spectroscopy of complex technical mixtures using a
virtual reference: chemical equilibria and reaction kinetics of
formaldehyde–water–1,3,5-trioxane. Anal. Bioanal. Chem. 385,
910–917.
Masamoto, J., Matsuzaki, K., 1994. Development of methylal
synthesis by reactive distillation. J. Chem. Eng. Jpn. 97, 1–5.
chemical engineering research and design 9 0 ( 2 0 1 2 ) 696–703 703
Ott, M., Fischer, H.H., Maiwald, M., Albert, K., Hasse, H., 2005.
Kinetics of oligomerization reactions in formaldehyde
solutions: NMR experiments up to 373K and
thermodynamically consistent model. Chem. Eng. Process. 44
(6), 653–660.
Parada, S., 2009. Nebenreaktionen bei der heterogen katalysierten
Reaktivdestillation amBeispiel der Herstellung von
Butylacetat. Ph.D. Thesis. University of Stuttgart.
Ryll, O., 2009. Thermodynamische Analyse gekoppelter
Reaktions-Destillations-Prozesse: konzeptioneller Entwurf,
Modellierung, Simulation und experimentelle Validierung.
Ph.D. Thesis. Universität Stuttgart.
Schmitt, M., Hasse, H., 2006. Chemical equilibriumand reaction
kinetics of heterogeneously catalyzed n-hexyl acetate
esterification. Ind. Eng. Chem. Res. 45, 4123–4132.
Walker, F., 1963. Formaldehyde, third ed. London, Chapman &
Hall.
Zhang, X., Zhang, S., Jian, C., 2011. Synthesis of methylal by
catalytic distillation. Chem. Eng. Res. Des. 89 (6), 573–580.