Documente Academic
Documente Profesional
Documente Cultură
h i g h l i g h t s
Synthesis of 1,1-diethoxybutane was studied in a batch reactor.
Thermodynamic equilibrium constant was determined in the temperature range of 293.15323.15 K.
The standard formation properties of 1,1-diethoxybutane have been determined.
Two-parameter kinetic model based on a LangmuirHinshelwood indicates good agreement with the experimental data.
a r t i c l e
i n f o
Article history:
Received 5 June 2014
Received in revised form 14 November 2014
Accepted 15 November 2014
Available online 25 November 2014
Keywords:
Synthesis of 1,1-diethoxybutane
Batch reactor
Amberlyst 47 catalyst
Kinetics
Thermodynamics
a b s t r a c t
The synthesis of 1,1-diethoxybutane was carried out in a batch reactor from a liquid phase reaction
between ethanol and butyraldehyde using Amberlyst 47 as the solid acid catalyst to obtain thermodynamic, kinetic and adsorption parameters. The reaction equilibrium constant was experimentally determined in the temperature range 293.15323.15 K. The standard properties of the reaction at 298.15 K
were also estimated. The effects of temperature, molar ratio of ethanol to butyraldehyde, stirrer speed,
and catalyst loading on the reaction rate were investigated. Kinetic experiments were performed in
the same temperature range at 6 bar. A two-parameter kinetic law based on a LangmuirHinshelwoodHougenWatson rate expression, using activity coefcients from the UNIFAC method, was used
to predict the experimental data of the heterogeneous liquid-phase reaction. The kinetic parameters were
determined based on the kinetic model. The model predicts the kinetic data very well and it will be useful
for design and optimization of integrated reactionseparation processes.
2014 Elsevier B.V. All rights reserved.
1. Introduction
In recent years, there has been a growing trend in the development of sustainable technology for production of environment
friendly gasoline and diesel fuels. Biodiesels or fatty acid alkyl
esters are an alternative fuel which is obtained from vegetable oils
or animal fats. Biodiesels have various technical advantages over
conventional gasoline or diesel fuels such as the reduction of emissions, enhanced lubricity and biodegradability, higher ash point
and lower toxicity [1]. They also show properties such as cetane
number, heat of combustion and viscosity that are similar to the
conventional diesels. However, they are inferior to conventional
diesel in terms of oxidation stability, nitrogen oxides emissions,
energy content and cold weather operability [2]. Employment of
additives is one of the approaches that can improve the quality
Corresponding author. Tel.: +351 225 081 671; fax: +351 225 081 674.
E-mail address: arodrig@fe.up.pt (A.E. Rodrigues).
http://dx.doi.org/10.1016/j.cej.2014.11.077
1385-8947/ 2014 Elsevier B.V. All rights reserved.
Nomenclature
a
ap
Ap
C
Ca
Cb
C b0
Cp
C p0
C ps
De,j
Dj;m
liquid-phase activity
specic particle surface area (cm1)
total external area of particles (cm2)
concentration (mol cm3)
Carberry number
bulk concentration (mol cm3)
initial bulk concentration (mol cm3)
concentration inside the particle (mol cm3)
initial concentration inside the particle (mol cm3)
concentration on the particle surface (mol cm3)
effective diffusivity (cm2 min1)
molecular diffusivity in the mixture (cm2 min1)
D0j;i
Ea
DG0
DG0f
DHs
DH0
DH0f
k0;c
kc
K 0;s
Keq
kL
Kc
Ks
KX
MRD
N
NE
NMi
S0
DS0
r
r A=B
r obs
rp
R
Rc
R
Rp
t
T
V
V liq
Vp
x
X exp
X model
zik
~zik
259
Greek letters
c
activity coefcients
eb
bulk porosity
ep
porosity of catalyst particle
h
set of model parameters to be estimated
l
viscosity (cp)
m
stoichiometric coefcient
q
dimensionless radial coordinate
qp
catalyst/particle density (g cm3)
s
tortuosity factor
/wp
WeiszPrater parameter
U
parameter in Eq. (26)
Subscripts
A
ethanol
B
butyraldehyde
C
DEB
D
water
exp
experimental
i
relative to component i
j
relative to component j
liq
liquid phase
m
mixture
model
predicted from model
p
particle
s
relative to the surface of the particle
260
Ethanol (99.5% purity) was obtained from Panreac. Butyraldehyde and 1,1-diethoxybutane (97% purity) were obtained from
Acros Organics. Acetone (99.98% purity) was obtained from Fisher
Chemical and used as the internal standard in gas chromatograph.
Deionized water was used for calibration purpose in gas chromatograph. A commercial strong acid ion-exchange resin named
Amberlyst 47 was used as the catalyst. The catalyst was provided
by Rohm and Haas (USA) in an opaque spherical bead-form.
Amberlyst 47 has a macroporous cross-linked polystyrene polymer
matrix with sulfonic groups according to the datasheet provided by
the manufacture. No information was available for the crosslinking
degree; however, it has a less to moderate swelling property in
methanol and water which means higher cross-linking degree
and rigid polymer structures. It has a surface area of 50 m2/g with
an average pore diameter of 240 .
2.2. Reactor setup
The experiments of reaction between ethanol and butyraldehyde
were carried out in a closed glass-jacketed1 dm3 autoclave reactor
(Bchi, Switzerland). The reactor was mechanically stirred and it is
equipped with pressure and temperature sensors, and with a
blow-off valve. The reactor was operated in a batch mode and its
temperature was controlled by thermostated silicon oil (Lauda, Germany) that ows through the jacket. The reactor was pressurized
with helium to maintain the reaction mixture in liquid phase over
the entire temperature range. The reactants were charged into the
reactor and heated to achieve the desired reaction temperature.
The dry catalyst was placed in a basket at the top of the stirrer shaft.
The basket falls down in the reaction solution as soon as the agitation
starts. In this way, the starting time of the reaction was accurately
dened. Samples were collected through one of the outlets of the
reactor in denite time interval and then analyzed.
2.3. Analytical method
All the samples were analyzed in a gas chromatograph (GC2010 Plus, Shimadzu) using a fused silica capillary column (CPWax 57 CB, 25 m 0.53 mm ID, df = 22.0 lm) to separate the compounds. The column was connected with a ame ionization detector (FID) and a thermal conductivity detector (TCD) to identify and
quantify the compounds present in the sample. Water was
detected in the TCD whereas the other compounds were identied
in FID. Helium N50 was used as the carrier gas. The injector and
detector temperature was maintained at 250 C. The column temperature program of gas chromatographic analysis was given as
follows: 7.5 min initial hold at 50 C; heating from 50 to 100 C
at a rate of 50 C/min and holding for 2 min. The reproducibility
of peaks was found to be good for all of the compounds in gas
chromatograph.
3. Thermodynamic analysis for the synthesis of 1,1diethoxybutane
The acetal, 1,1-diethoxybutane (DEB), is produced from the
homogeneous liquid phase reaction of ethanol and butyraldehyde
in a batch reactor described in the previous section. The reaction
is catalyzed by sulfonic acid ion exchange resin (Amberlyst 47)
according to the following stoichiometry.
H
2 Ethanol A Butyraldehyde B
DEB C Water D
K eq
aC aD xC xD cC cD
KXKc
a2A aB x2A xB c2A cB
where, a are respective activity of the compounds, x are molar fractions of the compounds and c are the activity coefcients of the
compounds at the equilibrium. KX and Kc are the equilibrium constants based on the molar fractions and activity coefcients, respectively. Due to strong non-ideality of the reaction mixture, activity
coefcients of compounds in the liquid phase were used to calculate
the equilibrium constant. The activity coefcients of compounds
were computed by the UNIFAC method [29,30]. The parameters
needed for UNIFAC method were taken from literature [31] and
they are presented in Appendix A. The average experimentally measured equilibrium compositions and the corresponding equilibrium
constant at each temperature are shown in Table 1.
The temperature dependence of equilibrium constant, Keq, is
given by,
ln K eq
D S0 DH 0 1
R
R T
where, DS0 and DH0 are the standard entropy and standard enthalpy
of the reaction, respectively, and R is the universal gas constant.
From the values of Keq at different temperatures, the standard
entropy and standard enthalpy of the reaction were determined
by plotting ln Keq vs. 1/T. The plot of ln Keq vs. 1/T is shown in
Fig. 1. The data was tted well by a straight line. The slope of this
straight line gives the value of the standard enthalpy of the reaction
while the standard entropy was calculated from the intercept of the
straight line. From the values of DS0 and DH0 , Eq. (3) can be
expressed as,
ln K eq
1036:80
2:56
T
Table 1
Experimental equilibrium compositions and equilibrium constants.
Temperature
293.15 K
303.15 K
313.15 K
323.15 K
xA
xB
xC
xD
0.3772
0.1966
0.2131
0.2131
0.3856
0.2016
0.2064
0.2064
0.3960
0.2030
0.2005
0.2005
0.4076
0.2054
0.1935
0.1935
KX
1.6235
1.4212
1.2628
1.0972
cA
cB
cC
cD
1.1106
1.2768
1.3652
1.8863
1.1156
1.2799
1.3687
1.9372
1.1186
1.2831
1.3755
1.9809
1.1198
1.2853
1.3830
2.0228
Kc
1.6352
1.6646
1.6970
1.7357
Keq = KXKc
2.6547
2.3657
2.1430
1.9044
261
1
From the Eq. (5), the value of standard free energy change was
1
obtained as DG0 2275:33 J mol . Based on the experimental
values of DH0 , DS0 and DG0 , the standard formation properties of
DEB were calculated and presented in Table 2 [32]. The value of
standard enthalpy of formation of DEB given in literature as
540.46 kJ mol1 [27].
4. Kinetic studies
The experimental results of the reaction kinetics of the production of DEB from the reaction of ethanol and butyraldehyde catalyzed by the Amberlyst 47 resin are presented in this section.
The effect of various conditions, such as catalyst loading, initial
molar ratio between ethanol and butyraldehyde, and reaction temperature, on the conversion of butyraldehyde as a function of time
was studied. These studies were performed varying the condition
under evaluation and keeping constant the remaining conditions.
Ca
r obs qp C b C ps
kL ap C b
Cb
/wp
r obs qP R2c
De;j C j
Table 2
Standard formation properties at 298.15 K.
Component
DH0f kJ mol1
DG0f kJ mol1
S0 J mol
Ethanol [17]
Butyraldehyde [17]
DEB*
Water [17]
277.6
239.2
517.2
285.8
174.8
119.5
234.3
237.1
160.7
246.6
476.7
70.0
1
K1
262
(=0.05 cm) is the particle radius [27], Cj is the concentration of limiting reactant in the mixture, and De,j is the effective diffusivity. The
value of qP is taken as 0.5508 g/cm3 [27]. The WeiszPrater criterion states that diffusion does not limit the reaction if the value of
/wp is less than 1. On the other hand, strong diffusion limitations
exist if /wp > 10. The expression for determination of effective diffusivity is given as,
De;j
ep Dj;m
s
Dj;m l0:8
m
n
X
xi D0j;i l0:8
i
"
1=3
iV j
3V i
Vj
2=3
#
10
dC b;j
Ap
@C p;j
De;j
j A D
dt
V liq
@r rrp
11
with
Ap
@C p;j
1 @
@C p;j
1 ep mj qp Rp
De;j r 2
2
r @r
@t
@r
3
Vp
rp
12
Temperature (K)
/wp
293.15
303.15
313.15
323.15
1.52
1.76
2.18
3.03
14
r rp
@C p;j
0
@t
15
C p;j C p;j rrp
16
dC b;j
3 1 eb
@C p;j
2
De;j
rp eb
dt
@ q q1
17
@C p;j De;j 1 @
@C
1 ep
2 2
mq R
q2 p;j
@t
rp q @ q
@q
ep j p p
18
q0
@C p;j
0
@t
19
20
A S B S
I1 S S
Table 3
WeiszPrater parameter for determination of internal
diffusion
(rA/B = 2.1,
catalyst = 1 wt.%,
stirring
speed = 500 rpm, P = 6 bar).
13
r0
D0j;i
8:2 108 T
ep
i1
ij
D0j;i
where C b;j is the bulk concentration of component j, C p;j is the concentration of component j inside the particle pore, V liq is the volume
of liquid inside the reactor, r p is the particle radius, Ap is the total
external area of particles, V p is the total volume of particles, r is
the radial position and t is the time coordinate.
Similarly, mass balance inside the catalyst particle at constant
temperature is given by,
21
I1 S S
I 2 S D S
22
I2 S A S
C S S
23
263
R kc
aA aB aaACKaeqD
1 K s;A aA K s;B aB K s;C aC K s;D aD K I1 aA aB K I2 aC =aA 2
24
R kc
aA aB aaACKaeqD
1 K s;D aD 2
25
According to the above kinetic model, there were two parameters to be estimated, the kinetic constant kc and the adsorption
constant of water K s;D ; at each temperature.
4.2.1. Parameter estimation from experimental data
The model equations were solved numerically using the software gPROMS (general PROcess Modeling System), version 3.3.1
which is commercial package from Process System Enterprise.
The particle radial domain in batch reactor model was discretized
using the second-order orthogonal collocation in the nite
element method (OCFEM). The system of ordinary differential
equation was integrated over time using DASOLV integrator
implemented in gPROMS. For radial discretization, 10 nite
elements with two collocation points were used in each element.
For all simulations, tolerance equal to 105 was xed. The
unknown parameters kc ; K s;D proposed in the kinetic model were
estimated using Parameter Estimation tool in gPROMS providing the best t of measured and predicted conversion data using
the maximum likelihood method. The objective function associated with the parameter estimation is described by the following
equation:
( NM "
#)
2
NE Xi
X
N
1
~zik zik
U ln2p min
lnr2ik
2
2 h
r2ik
i1 k1
Ea
kc k0;c
RT
28
DH s
K s;D K 0;s
RT
29
where Ea is the reaction activation energy, k0;c is the pre-exponential constant, R is the universal gas constant, K 0;s is a constant,
DHs is the enthalpy of adsorption of water and T is the temperature.
The plot of kc and K s;D tted in Arrhenius and Vant Hoff equation, respectively, are shown in Fig. 3. The data were tted well
by the straight lines. The slopes of these lines give the values of
the activation energy Ea and enthalpy of adsorption DHs . The
corresponding values were obtained as Ea 37:92 2:58 kJ=mol
and DHs 24:28 1:8 kJ=mol, respectively. A value of
Ea = 35.50 kJ/mol was obtained by Arisketa and co-workers
[27,28]. This may be due to consideration of a non-ideal mixture
and a simple kinetic model to describe the acetalization reaction.
A summary of the proposed kinetic model and their parameters
is presented in Table 5. In order to validate the existence of internal
diffusion resistance; by simulation it is possible to observe the concentration gradient inside the catalyst particle. Fig. 4 shows the
internal concentration prole of butyraldehyde at different temperatures after 10 min. The presence of concentration gradient
between the surface and the center of the catalyst indicates the
presence of internal mass transfer resistance.
Table 4
Estimated model parameters at different temperatures.
Temperature (K)
293.15
1
kc mol g
K s;D
min
1
303.15
313.15
323.15
0.06196
0.08603
0.15584
0.25050
2.9385
2.2377
1.6991
1.1566
26
MRD%
1 X X model X exp
100
N
X exp
27
Fig. 3. Arrhenius and Vant Hoff plots for kc and Ks,D, respectively, at different
temperatures.
264
Table 5
Kinetic law and parameters from proposed kinetic model.
Kinetic law
Equilibrium constant
(dimensionless)
Kinetic constant
(mol g1 min1)
Adsorption constant of water
(dimensionless)
265
where k1 and k1 are the forward and backward rate constant,
respectively. The adsorption coefcient can be written as
q
a2
K 0s;A kk11 a2ASa2 with K s;A K 0s;A aaAASaS :
where k2 and k2 are the forward and backward rate constant,
respectively. The adsorption coefcient can be written as
5. Conclusion
A S
BS BS
B2
k2
Step 3 surface reaction between the adsorbed species of ethanol and aldehyde to give adsorbed hemi-acetal:
k3
A S B S I1 S S
B3
k3
where k3 and k3 are the forward and backward rate constant,
respectively. The adsorption coefcient can be written as
aI
S aS
D S : I1 S S I2 S D S
k4
where k4 and k4 are the forward and backward rate constant,
respectively. The adsorption coefcient can be written as
K 4 kk44
aI
a
2 S DS
aI
a
1 S S
C S : I2 S A S C S S
k5
aS
K 5 kk55 aaI CS
:
S aAS
2
B6
k6
Appendix A.
Tables A.1 and A.2 present the UNIFAC method parameters used
in this work to calculate the activity coefcients.
Appendix B.
B5
where k5 and k5 are the forward and backward rate constant,
respectively. The adsorption coefcient can be written as
CS CS
Acknowledgments
B4
where k6 and k6 are the forward and backward rate constant,
respectively. The adsorption coefcient can be written as
K s;C kk66 aaCCSaS :
Step 7 desorption of water:
k7
DS DS
B7
k7
where k7 and k7 are the forward and backward rate constant,
respectively. The adsorption coefcient can be written as
K s;D kk77 aaDDSaS :
Assuming the surface reaction (i.e., Step 4) is the rate
determining step, the rate expression for LangmuirHinshelwoodHaugenWatson (LHHW) kinetic model is:
k4
hI2 S hDS
R k4 hI1 S hS k4 hI2 S hDS k4 hI1 S hS
k4
1
k4 hI1 S hS
hI S hDS
K4 2
B8
where hI1 S ; hI2 S and hDS are the fractions of catalyst sites occupied
by I1 S, I2 S and D S, respectively, hS is the fraction of vacant sites
and K 4 is the adsorption coefcient for step 4.
The total activity composed of vacant and the adsorbed species
on the catalyst surface can be expressed as:
2A 2S 2A S
k1
B1
a a
s;C C S
K s;A K s;B K 3 aA aB aS K s;A
K 5 aA
h
i
K a
aS 1 K s;A aA K s;B aB K s;C aC K s;D aD K s;A K s;B K 3 aA aB K s;As;CK 5CaA
B9
266
Table A.1
Relative molecular volume and surface parameters of the pure species.
Molecule (i)
Group identication
No. of main group
v i
k
Rk
Qk
Ethanol
CH3
CH2
OH
1
1
5
1
2
15
1
1
1
0.9011
0.6744
1.0000
0.848
0.540
1.200
Butyraldehyde
CH3
CH2
CHO
1
1
10
1
2
21
1
2
1
0.9011
0.6744
0.9980
0.848
0.540
0.948
DEB
CH3
CH2
CH
CH2O
1
1
1
13
1
2
3
26
3
2
1
2
0.9011
0.6744
0.4469
0.9183
0.848
0.540
0.228
0.780
Water
H2O
17
0.9200
1.400
where K 0I1
Table A.2
Interaction parameters for UNIFAC method.
am,n
Taking K I1
am,n
1
5
7
10
13
10
13
0
156.4
300
505.7
83.36
986.5
0
229.1
529
237.7
1318
353.5
0
480.8
-314.7
677
203.6
116
0
7.838
251.5
28.06
540.5
304.1
0
hj
aI1 S aAS
a2A aB a2S
ajS
a0
K 0I1
K s;A
a2AS
a2A a2S
aI1 S aS
aAS aBS
K 2s;A K s;B K 3
B15
I2 S 2A AS C
where
K 0I2
aCS aS
B16
a2AS
K 5 K 2s;A
aI S aAS a2 a2
aAS aC
2 aCS A S
2
K s;C
aI2 S aA
aC aS
Taking K I2
B10
K s;A
K s;C
K 5 K s;A
K 0I2
B17
aI S aS
1 aI2 S aDS
R k4 1
K 4 a0 a0
a0 a0
K 3 aAS aBS aS
1
aCS aS aDS
k4
K 4 K 5 a0 aAS a0
a0 aS a0
K 3 K s;A K s;B aA aB a2S
1 K s;C K s;D aC aD a2S
k4
2
2
K4
K s;A K 5 aA a0
a0
1 K s;C K s;D aC aD aS 2
k4 K s;A K s;B K 3 aA aB
a0
K4
K s;A K 5 aA
1 K s;C K s;D aC aD
K s;A K s;B K 3 aA aB
K4
K s;A K 5 aA
k4
2
K s;C aC
1 K s;A aA K s;B aB K s;C aC K s;D aD K s;A K s;B K 3 aA aB
K s;A K 5 aA
!
K s;C K s;D
1
aC aD
aA aB
K 2s;A K s;B K 3 K 4 K 5 aA
k4 K s;A K s;B K 3
2
K s;C aC
1 K s;A aA K s;B aB K s;C aC K s;D aD K s;A K s;B K 3 aA aB
K s;A K 5 aA
B11
2A B C D
B12
aCS
aDS
2
aC aD aS K s;C aS K s;D K s;A K s;B aCS aDS
2 2
aS
K s;C K s;D a2AS aBS
aA aB
aAS
aBS
aK
a2S K 02
s;A S s;B
aBS
aB aS
K s;A K s;B K 3
K eq
K 2s;A K s;B
K3K4K5
K s;C K s;D
B13
2A B 2S I1 S A S
B14
R kc h
aA aB KaeqC aaDA
1 K s;A aA K s;B aB K s;C aC K s;D aD K I1 aA aB K I2 aaCA
i2
B18
267
[28] I. Agirre, V.L. Barrio, B. Gemez, J.F. Cambra, P.L. Arias, Bioenergy II: the
development of a reactive distillation process for the production of 1, 1
diethoxy butane from bioalcohol: kinetic study and simulation model, Int. J.
Chem. Reactor Eng. 8 (2010).
[29] A. Fredenslund, R.L. Jones, J.M. Prausnitz, Group-contribution estimation of
activity coefcients in nonideal liquid mixtures, AIChE J. 21 (1975) 10861099.
[30] A. Fredenslund, J. Gmehling, P. Rasmussen, Vapor-Liquid Equilibria Using
UNIFAC: A Group Contribution Method, Elsevier Scientic Pub. Co.,
Amsterdam and New York, 1977.
[31] B.E. Poling, J.M. Prausnitz, O.C. John Paul, R.C. Reid, The Properties of Gases and
Liquids, McGraw-Hill, New York, 2001.
[32] D.R. Lide, CRC Handbook of Chemistry and Physics, CRC press, 2004.
[33] J.J. Carberry, Chemical and Catalytic Reaction Engineering, McGraw-Hill, New
York, 1976.
[34] F. Dekker, A. Bliek, F. Kapteijn, J. Moulijn, Analysis of mass and heat transfer in
transient experiments over heterogeneous catalysts, Chem. Eng. Sci. 50 (1995)
35733580.
[35] P. Weisz, C. Prater, Interpretation of measurements in experimental catalysis,
Adv. Catal. 6 (1954) 143.
[36] N. Wakao, J. Smith, Diffusion in catalyst pellets, Chem. Eng. Sci. 17 (1962) 825
834.
[37] L. Perkins, C. Geankoplis, Molecular diffusion in a ternary liquid system with
the diffusing component dilute, Chem. Eng. Sci. 24 (1969) 10351042.
[38] L. Grunberg, A.H. Nissan, Mixture law for viscosity, Nature 164 (1949) 799
800.
[39] E.G. Scheibel, Correspondence. Liquid diffusivities. Viscosity of gases, Ind. Eng.
Chem. 46 (1954) 20072008.
[40] N.S. Graa, L.s.S. Pais, V.M. Silva, A.E. Rodrigues, Oxygenated biofuels from
butanol for diesel blends: synthesis of the acetal 1,1-dibutoxyethane catalyzed
by amberlyst-15 ion-exchange resin, Ind. Eng. Chem. Res. 49 (2010) 6763
6771.