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Department of Chemical Engineering and Materials Science, Michigan State University, 2527 Engineering Building, East Lansing,
Michigan 48824-1226, United States
ABSTRACT: Esterication of butyric acid with ethanol, n-butanol, and ethanol/n-butanol mixtures was studied using Amberlyst
70 cation-exchange resin and homogeneous p-toluene sulfonic acid as catalysts. The kinetics of individual alcohol esterication
were rst examined in batch reactions at dierent temperatures and catalyst loadings, and then esterication in ethanol/n-butanol
mixtures of varying concentration ratios was characterized. Both nonideal solution and ideal solution kinetic models were
developed. These models accurately predict the esterication of butyric acid by the individual alcohols; a simple additive
combination of the individual alcohol esterication kinetics properly describes mixed alcohol esterication, indicating that the
alcohols do not compete with each other or inhibit esterication when present together. When solution density is included in the
kinetic rate expression to account for the actual concentration of OH groups in ethanol and n-butanol, butyric acid
esterication kinetics with the two alcohols are described by a common rate constant. This rate constant also predicts butyric acid
esterication kinetics with other alcohol combinations, suggesting a generalized esterication rate constant for simple alcohol
esterication of butyric acid over Amberlyst 70 catalyst. These results provide signicant predictive capabilities for simulating
processes such as reactive distillation processes for mixed alcohol esterication.
1. INTRODUCTION
The growing need to reduce dependence on fossil sources for
fuels and chemicals has led to exploration of pathways for their
manufacture from renewable sources. Esters of higher alcohols
(alcohols with more than two carbons) are one such
industrially important class of compounds, and economically
viable processes for making them need to be designed. Blends
of esters are being considered as attractive solvents or additives
to biofuels because of their high energy density and favorable
fuel properties. The most common route for producing esters is
direct esterication of carboxylic acids with alcohols1 using
either homogeneous acid catalysts such as sulfuric acid or ptoluene sulfonic acid (p-TSA) or solid heterogeneous acid
catalysts such as cationic exchange resins.
Mixed alcohol streams from biomass can be obtained in
several ways: from condensation of lower alcohols to higher
alcohols via the Guerbet reaction,24 via FischerTropsch
synthesis of alcohols from synthesis gas,58 or from fusel
alcohols9 produced in ethanol fermentation. Esterication for
biofuel or solvent applications is an attractive use of these
mixed alcohol streams, as it would lead to value-added products
without the need for separation into individual components.
Simultaneous esterication with multiple alcohols is described
in the patent literature.1013
Since esterication reactions are thermodynamically limited,
reactive distillation is a viable option for mixed alcohol
processing.14,15 In simulations of reactive distillation, esterication of a mixture of amyl alcohol and n-butanol with acetic
acid has been examined to compare separation-rst and
reaction-rst schemes.16 Reaction-rst schemes were determined to be more economical. Design of such reactive
distillation schemes for mixed alcohols requires a good
understanding of the kinetics of the reaction system, as it is
generally not known whether the presence of one alcohol
2012 American Chemical Society
Article
temp. (C)
catalyst
ethanol:acid
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
60
80
100
120
60
80
100
120
60
60
60
80
80
80
80
80
80
60
80
100
120
60
80
100
120
60
60
60
80
80
80
A-70
A-70
A-70
A-70
A-70
A-70
A-70
A-70
A-70
A-70
A-70
A-70
A-70
A-70
A-70
A-70
A-70
p-TSA
p-TSA
p-TSA
p-TSA
p-TSA
p-TSA
p-TSA
p-TSA
p-TSA
p-TSA
p-TSA
p-TSA
p-TSA
p-TSA
4.3
2.8
8.7
6.6
0.5
2.6
0.9
1.5
4.5
2.0
0.8
1.9
0.6
2.9
2.8
3.7
3.7
0.4
3.6
5.0
0.5
1.9
3.7
n-butanol:acid
3.7
4.4
4.5
3.3
4.7
2.6
4.2
1.7
3.9
1.9
3.8
2.2
3.0
2.0
3.0
2.8
3.7
1.8
3.3
1.0
2.7
1.9
0.9
14.9
15.0
15.0
14.9
10.9
10.9
10.9
10.9
14.9
12.8
11.5
12.6
12.9
12.6
11.5
12.6
11.5
14.8
14.9
15.0
15.0
10.9
10.9
10.9
10.9
11.4
13.0
14.4
11.4
12.6
14.0
0.0100
0.0101
0.0075
0.0099
0.0096
0.0101
0.0101
0.0115
0.0109
0.0085
0.0099
0.005
0.0105
0.0077
0.0093
0.0196
0.0097
0.0012
0.0013
0.0012
0.0013
0.0013
0.0013
0.0014
0.0013
0.0012
0.0013
0.0013
0.0013
0.0014
0.0014
Article
study. This is because low loadings of catalyst (0.1 wt % pTSA and 1 wt % A-70), low ratios of alcohol to acid (3:1
6:1), and relatively low temperatures were used in the
experiments.
3.1. Mass Transfer Considerations. Accurate characterization of reaction kinetics requires that experiments be
conducted in the kinetic regime, i.e., at conditions where
external and internal mass transfer resistances do not aect the
reaction rate. Preliminary experiments at varying stirring speeds
showed that conversion rates were unaected above 600 rpm,
implying that the external mass transfer resistances are
negligible at a stirring speed of 800 rpm. To estimate the
inuence of intraparticular mass transfer resistance in the
heterogeneous catalyst reaction, the WeiszPrater criterion was
used.21 The observable modulus was rst calculated by eq 1
w =
* ) d p
(robs
CAT
Deff C BA 6
(1)
Vp,swollen
3
Vp,dry
(2)
(3)
3. RESULTS
A list of all experiments conducted along with their conditions
(temperature, initial reactant molar ratio, weight fraction of
catalyst) is given in Table 1. Control experiments to investigate
autocatalysis of the reaction showed negligible rates over the
temperature range studied. Although etherication side
reactions have been observed in other studies involving the
esterication of n-butanol7,13 and ethanol8 at temperatures
above 386 K, no ethers (di-n-butyl ether, diethyl ether, or ethyl
n-butyl ether) were observed in the reaction samples in this
1847
run
temp. (C)
ethanol:acid
1
2
3
4
5
6
7
8
60
80
100
120
60
80
100
120
4.3
2.8
8.7
6.6
n-butanol:acid
3.7
4.4
4.5
3.3
0.99
0.99
0.99
0.98
0.99
0.98
0.98
0.98
Article
Figure 1. vant Ho plots for equilibrium constants of ethanol and n-butanol esterication of butyric acid: () ethanol ideal solution; () ethanol
activity based; () n-butanol ideal solution; () n-butanol activity based. Error bars for each temperature represent one standard deviation.
NC
K a, m = Kx , mK , m =
(xii)EQ
i ,m
i=1
(4)
dxi
1
= ( i , mrm)
dt
1
dNi
dx
= NT i = ( i , mrm)V
dt
dt
1
(6)
(5)
x BEBEx W W
K a, m
(7)
Article
Table 3. Optimized Kinetic Parameters with 95% Condence Limits and Equilibrium Constants from Experimental Data (T in
Kelvin)
n-butanol
ethanol
parameter
ideal
activity
ideal
activity
Ka
Amberlyst 70
ko ((kg solnm3)/ (kg cat.skmol))
Ea (kJ/kmol)
p-toluenesulfonic acid
ko ((kg solnm3)/(kg cat.skmol))
Ea (kJ/kmol)
exp(8.182654/T)
exp(8.852207/T)
exp(7.502339/T)
exp(6.881365/T)
1
n
NC
(8)
fABS =
1
Ncn
NC
(9)
Article
with p-TSA was 0.015. For n-butanolbutyric acid esterication, the average deviation per data point over all experiments
with A-70 was 0.016 and p-TSA was 0.020. These values
indicate that the experimental data are indeed reasonably
represented by the kinetic models. For the mixed alcohol
esterication, the average deviation of the predicted values from
experimental data was 0.011 for A-70 and 0.013 for p-TSA. The
similarity of these deviations with those from the tted
individual alcohol experiments is verication that the combined
model is a good representation of mixed alcohol esterication.
These deviations thus represent the scatter in the experimental
data collection and analysis procedure, the largest contributor
to which was measurement of water concentration using Karl
Fischer analysis.
The uncertainty in the rate constants at the 95% condence
level (Table 3) are quite reasonable, given the relatively small
number of data points (ranging from 32 to 60 depending on
the data set) used in each regression and the relatively low
Article
Article
alcohol
i, kmolm3
methanol
ethanol
ethanol
propanol
n-butanol
n-butanol
isobutanol
2-EHA
4-heptanol
1-heptanol
1-octanol
23.5
16.4
16.4
12.8
10.4
10.4
10.4
6.2
6.8
6.8
6.1
5.0b
2.3a
3.0b
2.2b
3.0a
3.0b
1.9b
2.8b
2.5b
0.9b
0.9b
Greek
4. CONCLUSIONS
The kinetics of ethanol and n-butanol esterication of butyric
acid in the presence of homogeneous p-toluene sulfonic acid
and heterogeneous ion-exchange resin catalyst Amberlyst 70
have been accurately described by an activity-based kinetic
model with solution density included. Mixed alcohol
esterication kinetics are accurately predicted by an additive
combination of esterication rates of the individual alcohols,
indicating that alcohols do not compete with each other or
inhibit each other in simultaneous esterication reactions. By
including solution density to describe actual concentrations of
OH and COOH in solutions of neat reactants, butyric acid
esterication kinetics with simple C2C8 alcohols are
described by a single rate constant, which serves as a
generalized rate constant for butyric acid esterication over
Amberlyst 70. The additivity of rates and existence of a
generalized rate constant greatly simplies the simulation of
actual biorenery esterication processes with single or multiple
alcohols.
Abbreviations
AUTHOR INFORMATION
Corresponding Author
Notes
A-70 = Amberlyst 70
BA = butyric acid
BE = butyrate ester
BB = n-butyl butyrate
But = n-butanol
EB = ethyl butyrate
EQ = equilibrium
Eth = ethanol
OH = alcohol
p-TSA = p-toluene sulfonic acid
UNIFAC = universal functional activity coecient
W = water
REFERENCES
Article