Top Catal (2014) 57:14251429
DOI 10.1007/s11244-014-0314-4
Direct Synthesis of 1-Butanol from Ethanol in a Plug Flow
Reactor: Reactor and Reaction Kinetics Modeling
T. Riittonen T. Salmi J.-P. Mikkola
J. Warna
Published online: 3 September 2014
 Springer Science+Business Media New York 2014
Abstract Bio-ethanol is well known for its use as a gas-
oline additive. However, it can be blended in low portions to
traditional gasoline although it has a corrosive nature. By
taking advantage of modern continuous reactor technology
and heterogeneous alumina catalysts, ethanol can be
upgraded to 1-butanol in fixed beds. Butanol has more
feasible properties as fuel component in comparison to
ethanol. Mathematical modeling of reaction kinetics
revealed a simple kinetic model could be used to describe
the complex reaction process on a Cu/alumina catalyst. The
reaction kinetics model is based on five parallel reactions in
which ethanol reacts to 1-butanol, acetealdehyde, ethyl
acetate, diethyl ether and diethoxyethane, respectively.
Keywords Bio-ethanol  Bio-butanol  Heterogeneous
catalyst  Reaction kinetics  Fixed bed
List of symbols
c Concentration (mol/m3)
k Rate constant
k0 Frequency factor
Ea Activation energy (J/mol)
r Reaction rate
Q Sum of squares
R Component generation rate
R Gas constant in Arrhenius equation 8.314 (J/molK)
T Temperature (K)
T. Riittonen  T. Salmi  J. Warna (&)
Process Chemistry Centre, A bo Akademi University,
20500 Turku, Finland
e-mail: jwarna@abo.fi
J.-P. Mikkola  J. Warna
Chemical-Biological Center, Technical Chemistry, Umea
University, SE-901 87 Umea, Sweden
T Mean temperature of experiments (K)
qB Catalyst bulk density (cm3/gcat)
s Residence time (min)
Subscripts
i Component index
j Reaction index
1 Introduction
The catalytic transformation of bio-based ethanol to more
valuable products has been an issue for a long time. A
possible product candidate is 1-butanol that has mainly
been produced over metal oxide catalysts [13]. 1-Butanol
is also known to have higher energy content in comparison
to ethanol [1]. Furthermore, 1-butanol has other applica-
tions such as an industrial solvent and plasticizer [1].
Our previous work [4] concerned alumina-based catalyst
screening and investigation of the reaction mechanism in
the catalytic condensation of ethanol to 1-butanol in a
batch reactor. The information gathered has been used for
scale-up towards a continuous operating fixed bed reactor.
The results presented here are a straightforward continua-
tion of the work taking advantage of alumina.
It is well recognized [14] that the actual reaction
mechanism is based on the aldol condensation reaction. In
this reaction ethanol is first oxidized to acetaldehyde on the
catalyst surface followed by aldolisation with another
acetaldehyde molecule. Thereafter, the formed four-carbon
atom product is hydrogenated to 1-butanol. The aim of this
work is to demonstrate kinetics of the reaction, whereas the
actual catalyst preparation, characterization and evaluation
has been submitted to another journal as a full-scale
research paper covering the chemical part.
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2 Experimental
Experiments were performed in a liquid-phase catalytic
packed bed upflow reactor (Fig. 1) filled with a Cu/alumina
catalyst. The mass of the catalyst was 2 g and the bed
dimensions are listed in Fig. 1. The reactor system is dis-
played schematically in Fig. 1. Pure ethanol was fed to the
packed bed reactor with a HPLC pump. The product stream
was cooled down and samples were taken directly from the
product line and analyzed by gas chromatography (GC).
The pressure in the reactor was 70 bar in order to ensure
liquid-phase conditions and the pressure was controlled by
a flow controller at the output line (Fig. 2). The choice of
liquid-phase operation was due to the following reasons:
higher production capacity, easier separation of products
and better selectivity, compared to gas phase systems. For
Fig. 1 Reactor packing; 1 = quartz wool, 2 = quartz sand, 3 = cat-
alyst, 4 = silica beads. Reactor length 16 mm, reactor diameter
210 mm, catalyst bed length 7 mm
Fig. 2 Flowsheet of the
experimental equipment
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Top Catal (2014) 57:14251429
the kinetic modeling of the reaction, a series of experi-
ments were carried out over the investigated catalyst with
residence times of 92, 231, and 462 min and at tempera-
tures 200, 220, and 240 C. The catalyst bulk density was
qB = 1.42 g/cm3. The metal content of the catalyst was
4.5 wt%.
3 Reaction Kinetics and Reactor Modeling
The main reaction products were 1-butanol, acetaldehyde,
ethyl acetate, diethyl ether and diethoxyethane. Mathe-
matical modeling of the reaction kinetics revealed a simple
model could be used to describe the complex reaction
system. The kinetic model is based on five parallel reac-
tions in which ethanol reacts to 1-butanol, acetaldehyde,
ethyl acetate, diethyl ether and diethoxyethane. The packed
bed reactor was described with the ideal plug flow model.
Kinetic modelling of the experimental data was based on
the following overall reaction scheme.
A ! B H2 1
2A ! C W 2
2A ! D 2H2 3
B 2A ! E W 4
2A ! F W 5
where A = ethanol, B = acetaldehyde, C = 1-butanol,
D = ethyl acetate, E = 1,1-diethoxyethane, F = diethyl
ether H2 = hydrogen and W = water.
The second reaction in the scheme is the desired main
reaction, i.e. formation of 1-butanol from ethanol. It should
be emphasized that the reaction scheme (15) does not
represent the molecular mechanism on the catalyst surface,
but just the overall reactions. The scheme above is based
on the experimentally observed and identified chemical
species in the experimental data.
The simplest way to approach the reaction kinetics is to
use the law of mass action for reactions (15). This can be
justified for the case that the amounts of adsorbed species
Top Catal (2014) 57:14251429 1427

are minor on the catalyst surface. Since the amount of Table 1 Estimated frequency factors and activity energies
experimental data is limited, the use of a more sophisti- Parameter Value Est. relative SE (%)
cated model is unrealistic. The rate expressions are listed
below: k0,1 0.0218 min-1 (gcat/cm3) 25.5
-3
k0,2 2.55 9 10 m3 mol-1 min-1 27.3
R1 k1 cA 6 (gcat/cm3)
R2 k2 c2A 7 k0,3 3.71 9 10-3 m3 mol-1 min-1 25.5
(gcat/cm3)
R3 k3 c2A 8 k0,4 0.95 9 10-7 M6 mol-2 min-1 77.8
(gcat/cm3)
R4 k4 c2A cB 9
EA,1 76,800 J/mol 40.0
R5 k5 c2A 10 EA,2 127,000 J/mol 27.3
EA,3 183,000 J/mol 18.3
For describing of the laboratory-scale fixed bed reactor,
EA,4 0.19 J/mol Large
the pseudo-homogeneous plug flow model was used. Since
the catalyst particles were small (150250 lm) and the T = 220 C
reaction rates relatively slow, the internal diffusion resis-
tance in the porous catalyst particles was neglected. Cal-
where i denotes the values of the organic components A, B,
culation of the Thiele modulus gave a value of 0.07 or less,
C, D, E, F. The concentrations predicted from the model
this also confirms that the reaction conditions are clearly in
were obtained from numerical solutions of Eq. (11).
the kinetic regime.
The temperature dependence of the rate constants (k) are
The feed to the reactor consisted of pure ethanol (A),
taken into account with the Arrhenius equation.
which diminishes the role of external mass transfer resis-
Aj 1 1 E
tance at the outer surfaces of the catalyst particles. Thus, kj k0j e R T T 22
the use of the pseudo-homogeneous reactor model is jus-
tified. The model is written as follows, The backward difference method was used to solve the
mass balances (system of ordinary differential equations
dci =ds qB ri 11
ODE) and a hybrid method involving Simplex and
where s = the liquid residence time in the reactor, qB is the LevenbergMarquardt methods was used for estimation of
catalyst bulk density (=mass of catalyst/reactor volume) the kinetic parameters, i.e. in the minimization of the
and ri is the component generation rate calculated from the objective function, Eq. (21). The distribution and sensi-
stoichiometry: tivity of the parameters were controlled with the Markov-
X Chain Monte Carlo (MCMC) method [5].
ri mij Rj 12

where the index j refers to the reaction (R1R5). Appli-

cation of the stoichiometric relations (15) on Eq. (12) 700
gives the component generation rates as follows:
predicted concentration (mol/m3 )

600
rA R1  2R2  2R3  2R4  2R5 13
rB R1  R4 14 500

rC R2 15 400
rD R3 16
300
rE R 4 17
200
rF R 5 18
rH R1 2R3 19 100

rW R2 R4 R5 20 0
0 100 200 300 400 500 600 700
The model thus consists of eight ordinary differential
measured concentration (mol/m 3 )
equations for AW. The objective function for parameter
estimation was the sum of squares equation. Fig. 3 Parity plot model prediction versus experimental data, con-
X 2 centration in mol/m3 (white circle acetaldehyde, white square
Q ci;exp  ci;model 21 butanol, lozenge ethyl acetate, asterisk 1,1-diethoxy ethane)

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acetaldehyde b Fig. 4 a Fit of model prediction (solid line) to experimental data

(a) 200
(white square) at 200 C, concentration (mol/m3) versus residence
100 time (min). The grey area shows the 95 % confidence interval for the
model. b Fit of model prediction (solid line) to experimental data
0
0 50 100 150 200 250 300 350 400 450 500 (white square) at 220 C, concentration (mol/m3) versus residence
butanol time (min). The grey area shows the 95 % confidence interval for the
400
model. c Fit of model prediction (solid line) to experimental data
200 (white square) at 240 C, concentration (mol/m3) versus residence
time (min). The grey area shows the 95 % confidence interval for the
c (mol/m )
3

0 model
0 50 100 150 200 250 300 350 400 450 500
etylacetate
500

4 Parameter Estimation Results

0
0 50 100 150 200 250 300 350 400 450 500
1,1-dietoxyethane In the evaluation of the kinetic parameters, the frequency
400
factors k01k04 and activation energies EA1EA4 were
200 estimated. Reaction 5 was omitted, since diethyl ether
0 (F) was formed in small amounts in the experiments.
0 50 100 150 200 250 300 350 400 450 500
(min) The estimated parameter values, based on rate Eqs.(6
acetaldehyde
10) are listed in Table 1 and the fit of the model to the
(b) 400
experimental data is shown in Fig. 3 as a parity plot, model
200
predicted concentrations (mol/m3) versus experiment con-
0
0 50 100 150 200 250 300 350 400 450 500 centrations (mol/m3). The Fig. 4ac show the fit of the
butanol
400 model to experimental data as function of residence time,
200
Fig. 4ac also show the confidence interval (95 %, grey
area in the figures) for the model. For the calculation of the
0
c (mol/m )
3

0 50 100 150 200 250 300 350 400 450 500

ethylacetate
probability regions of the model the MCMC method is
500 used (Modest software). The errors of the estimated
parameters (Table 1) are a bit high, since the quality of the
0
0 50 100 150 200 250 300 350 400 450 500
experimental data was not as good as expected. In this case
200
1,1-diethoxyethane the MCMC method is helpful in identifying the optimal
values for the parameters.
100
The formation of 1,1-diethoxyethane (E) is low, and
0
0 50 100 150 200 250 300 350 400 450 500 therefore, it is difficult to estimate the frequency factor and
(min)
activation energy for reaction (4). The frequency factor k04
(c) 400
ethylacetate was identified with Simplex and LevenbergMarquardt
200 methods, but with a high error (77 %), but the activation
0
0 100 200 300 400 500
energy (EA4) was estimated to be close to zero (Table 1)
butanol with very large error. The reason for this is probably the
400

200
low concentration of 1,1-diethoxyethane and/or larger
experimental data error for this compound. When using the
c (mol/m3)

0
0 100 200 300 400 500 MCMC method for testing the distribution and sensitivity
acetaldehyde
1000 of the parameters (Fig. 5) we can see that the frequency
500
factors k0,13 and the activation energies EA,13 are iden-
0 tified with rather clear optimums. The activation energy
0 100 200 300 400 500

100 1,1-diethoxyethane EA,4 for reaction (4) predicted with the MCMC method is
50 not as well identified as EA,13 but has a broader optimum
0 range = 1025 kJ/mole. By using the MCMC method it is
0 100 200 300 400 500
(min) possible to get some information of in which range an

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Top Catal (2014) 57:14251429
Fig. 5 Parameter sensitivity plots showing the distributions of the estimated parameters, calculated with MCMC method
estimated parameter is in, whereas the Simplex and
LevenbergMarquardt methods gave no results. In order to
more reliable identify the activation energy of reaction 4
more experimental data would be needed.
5 Conclusions
The production of 1-butanol from ethanol was studied in a
continuous packed bed reactor. It was shown that the
reaction could be modelled with a rather simple kinetic
model and the reaction kinetics parameters were rather well
identified. The parameter identification was improved by
using the MCMC method which calculates the model
distributions.
Acknowledgments The work is a part of the activities of Process
Chemistry Centre (PCC), a centre of excellence financed by Abo
Akademi University, Finland. The Academy of Finland is
1429
acknowledged for financial support. In Sweden Bio4Energy and
Kempe foundation are acknowledged for financial support.
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