Chemical Engineering Journal xxx (2012) xxx–xxx

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Chemical Engineering Journal

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Esterification of fusel oil using reactive distillation – Part I: Reaction kinetics

Prafull Patidar, Sanjay M. Mahajani ⇑
Department of Chemical Engineering, Indian Institute of Technology, Powai, Mumbai 400 076, India

h i g h l i g h t s

" We present a process for value addition to fusel oil by esterification using RD.
" A unified LHHW kinetic model is presented for the different reactions involved.
" Applicability of the developed kinetic model to a feasible RD process is shown.

a r t i c l e i n f o a b s t r a c t

Article history: Fusel oil is a mixture of C2–C5 alcohols such as ethanol, n-propanol, iso-butanol and iso-amyl alcohol. It is
Available online xxxx expected that reactive distillation (RD), which is a proven intensification strategy for esterification of
individual alcohols can also be a promising option for simultaneous esterification of all the alcohols in
Keywords: fusel oil. To evaluate its feasibility and design a unit on large scale, kinetic and phase equilibrium models
Reactive distillation are necessary. In this work, we experimentally investigate reaction kinetics for all the esterification and
Esterification trans-esterification reactions of the different constituents of fusel oil with acetic acid. The reactions are
Fusel oil
performed in the presence of cation exchange resin, Amberlyst-15, in a batch reactor over a wide range
Reaction kinetics
Ion exchange resins
of parameters such as temperature, mole ratio and catalyst loading. A unified Langmuir–Hinshelwood–
Hougen–Watson (LHHW) model is proposed for the reacting system consisting of all the alcohols and
the experimental data is used to estimate the model parameters. The predictions are in line with the
experimental data for individual alcohols as well as their mixtures. A feasible process based on reactive
distillation is simulated in ASPEN PLUS using the kinetics developed in this work.
Ó 2012 Elsevier B.V. All rights reserved.

1. Introduction
The applicability of reactive distillation (RD) as a tool of
process intensification is well investigated in the past for esterifi-
cation of different alcohols [1]. The focus is on enhancing the per-
pass conversion and bringing cost-effectiveness and compactness
to the chemical plant through reduction in equipment cost and
energy consumption. In these studies, a pure alcohol or its aque-
ous solution is considered as a feedstock to make or recover a par-
ticular ester of interest [e.g. see 2,3]. To the best of our knowledge
there are no studies reported in literature, dealing with a mixture
of alcohols as a raw material. Fusel oil is one such feedstock com-
monly encountered in the industry as a byproduct of ethanol
manufacturing process through the fermentation route. Sugar-
containing substrates when fermented with yeast in the presence
of nitrogenous diet (e.g. proteins like albuminoids which promote
growth of yeast), yield ethanol associated with different
impurities collectively known as fusel oil. Major ones among these
impurities are aliphatic alcohols (see Table 1) higher in molecular
⇑ Corresponding author.
E-mail address: sanjaym@iitb.ac.in (S.M. Mahajani).
weight than ethanol, such as, n-propanol, iso-butanol and iso-amyl
alcohol [4–6]. All these alcohols and their esters are individually
valuable and hence after bulk separation of ethanol, one can ester-
ify and process the fusel oil for value addition [5]. Esterification of
such a mixture is more challenging, compared to that of an indi-
vidual alcohol, owing to the presence of a large number of azeo-
tropes and simultaneous trans-esterification reactions. There is
not much information available in the literature on the processing
of fusel oil to bring in value addition. Hence, the broad objective
of this work is to evaluate the applicability of RD for the esterifi-
cation of fusel oil and suggest the most cost-effective RD configu-
ration giving all the esters in pure form as products. As the first
step, in this article, we present the studies in kinetics of different
reactions involved in esterification of fusel oil with acetic acid (see
Eq. (1)) in the presence of ion exchange resin, Amberlyst-15, as a
catalyst. Ion exchange resins are highly versatile catalysts that
work well in both polar and non-polar media. They have been
successfully used in reactive distillation columns in a suitable
form, for the production of chemicals like fuel ethers such as
MTBE and TAME [1].
CH3 COOH þ ROH\¼¼¼¼¼¼[ CH3 COOR þ H2 O ð1Þ
Amberlyst-15

1385-8947/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2012.06.139

Please cite this article in press as: P. Patidar, S.M. Mahajani, Esterification of fusel oil using reactive distillation – Part I: Reaction kinetics, Chem. Eng. J.
(2012), http://dx.doi.org/10.1016/j.cej.2012.06.139
2 P. Patidar, S.M. Mahajani / Chemical Engineering Journal xxx (2012) xxx–xxx

Nomenclature

ai liquid phase activity of species i Abbreviations

Ks,i adsorption constant of species i AcH acetic acid
Ef, Eb activation energy of forward and backward reaction, ER Eley–Rideal model
kJ/kmol EtAc ethyl acetate
0 0
kf ; kb Arrhenius pre-exponential factor for forward and EtOH ethanol
backward rate constant, kmol/kg s FID flame ionization detector
kf, kb forward and backward reaction rate constants, GC gas chromatograph
kmol/kg s iAmAc iso-amyl acetate
Mcat mass of catalyst, kg iAmOH iso-amyl alcohol
n initial molar holdup iBuAc iso-butyl acetate
Nfeed feed stage location in the distillation column iBuOH iso-butanol
Nreac reactive stage no. in the distillation column LHHW Langmuir–Hinshelwood–Hougen–Watson model
NT total number of stages in the distillation column nPrAc n-propyl acetate
QR reboiler duty nPrOH n-propanol
ri rate of the reaction of species i, kmol/s PH pseudo-homogeneous model
R ideal gas constant, kJ/kmol K RD reactive distillation
t time, s Sim simulation
T temperature, K SSE sum of squares of errors
xi mole fraction of species i in the liquid phase TCD thermal conductivity detector
VLE vapor–liquid equilibrium
Greek letter
mi stoichiometric coefficient for component i
/ objective function

Table 1
A typical composition of the distilled fusel oil on water-
free basis [5].
Component wt.%
Ethanol 12.4
n-Propanol 3.5
iso-Butanol 9.5
iso-Amyl alcohol 74.6
The major constituents of fusel oil are ethanol, n-propanol, iso-
butanol and iso-amyl alcohol and all are reactive under the condi-
tions of interest. Since we are dealing with the reaction mixture
consisting of alcohols and esters, trans-esterification reactions
(see Eq. (2)) are also likely to take place simultaneously and their
importance needs to be assessed.
CH3 COOR þ R0 OH\¼¼¼¼¼¼[ CH3 COOR0 þ ROH
Amberlyst-15
In all, four esterification and six trans-esterification reactions are
possible and are studied in the present work. The article is organized
as follows: First we review the information available in literature on
the kinetics of esterification of all the individual constituents of
fusel oil in the presence of ion exchange resin. The experimental
procedure for the reaction kinetics is described and the generated
data is presented. A unified activity based Langmuir–Hinshel-
wood–Hougen–Watson (LHHW) kinetic model is proposed and
the relevant parameters are estimated. The model is further used
to simulate a feasible RD configuration for the esterification of fusel
oil giving all the products in pure form. The experimental validation
of reaction in RD and further optimization is out of the scope of this
work and will be dealt with in the subsequent parts of this series.
2. Previous studies
The studies in esterification of acetic acid with different alco-
hols of interest, over ion exchange resins, are reported by several
investigators, and are summarized in Table 2. Kirbasßlar et al. [7]
and Hangx et al. [8] have studied esterification of acetic acid with
ethanol in the presence of Amberlyst-15 and Purolite CT179, and
proposed the kinetics models. However, their kinetic models do
not take into account the activities of components. Calvar et al.
[9] have studied the kinetics for this reaction, both when catalyzed
homogeneously by the acetic acid, and heterogeneously by Amber-
lyst-15. Pseudo-homogeneous activity based models have been
proposed and are used to assess the performance of reactive
distillation.
The kinetics of esterification of acetic acid with n-propyl alcohol
in the presence of ion exchange resins has also been reported [10–
13]. Rao and Bhagwat [10] used Dowex-50W cation exchange resin
for the reaction and interpreted the rate data using Langmuir–Hin-
shelwood model, whereas, Bart et al. [11] proposed an activity-
based Eley–Rideal (ER) model for this reaction catalyzed by cation
exchange resin Dowex Monosphere 650C. Brehelin et al. [12] have
investigated the reaction in the presence of homogeneous (sulfuric
ð2Þ acid) as well as heterogeneous (Amberlyst-15) catalyst and pro-
posed the pseudo-homogeneous activity based models, which is
further used in RD studies. Huang and Sundmacher [13] have mod-
eled the same reaction in the presence of Amberlyst-15 using
activity based ER and LHHW models. They have also provided
guidelines to overcome the convergence problem encountered in
the estimation of the LHHW model parameters.
Altiokka and Citak [14] have proposed a concentration based ki-
netic model to represent the esterification of acetic acid with iso-
butanol in the presence of Amberlite IR-120. The Eley–Rideal
model was found to be suitable for this reaction. Izci and Bodur
[15] examined the progress of this reaction in 1,4-dioxan as a sol-
vent using ion exchange resins Dowex 50Wx2 and Amberlite IR-
120. They have reported the catalytic activity of Dowex 50Wx2
to be higher than that of Amberlite IR-120. Korkmaz et al. [16] have
studied isobutyl acetate production by esterification in a pervapo-
ration membrane reactor using different membranes in the pres-
ence of Dowex 50W-X8 as catalyst. As regards to esterification of
acetic acid with isoamyl alcohol, only one systematic kinetic study
was found in the literature. Teo and Saha [17] used cation-ex-
change resin catalyst, Purolite CT-175, for this reaction and corre-
lated the kinetic data using activity-based LHHW model.

Please cite this article in press as: P. Patidar, S.M. Mahajani, Esterification of fusel oil using reactive distillation – Part I: Reaction kinetics, Chem. Eng. J.
(2012), http://dx.doi.org/10.1016/j.cej.2012.06.139
 P. Patidar, S.M. Mahajani / Chemical Engineering Journal xxx (2012) xxx–xxx 3

Table 2
Summary of the work reported on ion exchange resin catalyzed esterification of alcohols considered in the present work.

S. no. Ion exchange resin Temperature and Kinetic model Reference Remarks
used as catalyst pressure range
Esterification of ethanol
1 Amberlyst-15 323–353 K; 1 atm Concentration-based ER Kirbasßlar et al. [7] Used kinetics for RD studies
2 Purolite CT179 328–338 K; 1 atm Concentration-based PH Hangx et al. [8] The order with respect to acetic acid is 1.5
3 Amberlyst-15 303–353 K; 1 atm Activity-based PH Calvar et al. [9] Used kinetics for RD studies
Esterification of n-propanol
4 Dowex 50W 323–343 K; 1 atm LHHW Rao and Bhagwat [10]
5. Dowex Monosphere 303–343 K; 1 atm Activity-based ER Bart et al. [11]
650C
6. Amberlyst-15 Not provided Activity-based PH Brehelin et al. [12] Used kinetics for RD studies
7 Amberlyst-15 338–368 K; 1 atm Activity-based PH, ER Huang and LHHW model was most suitable
and LHHW Sundmacher [13]
Esterification of iso-butanol
8 Amberlite IR-120 318–348 K; 1 atm Concentration-based ER Altiokka and Citak
[14]
9 Dowex 50Wx2, 318–348 K; 1 atm Concentration-based PH Izci and Bodur [15] Reactions are performed in the presence of 1,4-
Amberlite IR-120 dioxane as solvent
10 Dowex 50W-X8 333–343 K; 1 atm – Korkmaz et al. [16] Reaction is studied in pervaporation membrane
reactor
Esterification of iso-amyl alcohol
11 Purolite CT-175 333–363 K; 1 atm Activity-based LHHW Teo and Saha [17]

It can be seen that only a few investigators have reported the
data on esterification kinetics in the form of suitable activity based
models. Moreover, kinetic data on simultaneous esterification of
mixture of alcohols along with trans-esterification of different es-
ters in the presence of ion exchange resins, has not been studied till
date, to the best of our knowledge. Though all the esterfications
have been studied in the presence of ion exchange resins, there
is no single resin that has been investigated for all the reactions
of interest. Hence, the models presented in the literature cannot
be applied in any form for the esterification of fusel oil. With this
background, the present work is undertaken to systematically
study and model the different esterification and trans-esterifica-
tion reactions involved in esterification of fusel oil with acetic acid
in the presence of a commonly used strong cation exchange resin,
Amberlyst-15. The kinetic data is correlated with the best suited
kinetic model that works for the mixture of alcohols in any propor-
tion over a reasonably wide range of reaction conditions.
3. Experimental studies
3.1. Materials and catalyst
Ethanol, n-propanol, iso-butanol, iso-amyl alcohol, 2-ethylhexa-
nol, n-propyl acetate (each >99 wt.%), and acetic acid (99.9 wt.%)
are obtained from s.d. Fine Chem Ltd., India. iso-Butyl acetate and
iso-amyl acetate (98% wt.%) are supplied by Loba Chemie Pvt.
Ltd., whereas, iso-propyl alcohol (AR grade, moisture <0.02%) and
ethyl acetate (99 wt.%) are supplied by Merck Ltd., India. The cata-
lyst used in the experiments is commercial strong-acid ion-ex-
change resin, Amberlyst-15, obtained from Rohm and Hass, India.
The fresh catalyst is sequentially washed with distilled water, iso-
propyl alcohol, dilute hydrochloric acid, and again with distilled
water before its use. This is followed by drying under vacuum at
70 °C for about 14 h to remove the moisture present in it.
3.2. Analysis
The reaction mixture is analyzed using a gas chromatograph
(Chemito, GC 8610) equipped with flame ionization detector
(FID) and a 30 m long BP-5 column (ID = 0.53 mm). Nitrogen is
used as a carrier gas with a flow rate of 0.5 ml/min. 2-Ethylhexanol
is used as an external standard. Water is analyzed separately using
a gas chromatograph (GC-911; MakAnalytica India, Ltd.) equipped
with a thermal conductivity detector (TCD). In this analysis, Pora-
pack-Q column is used with hydrogen as a carrier gas at a flow rate
of 30 ml/min. The oven temperature is varied from 70 °C to 190 °C.
The results obtained by GC are confirmed by independent titra-
tions with standard alcoholic 0.25 N sodium hydroxide (NaOH)
solution using phenolphthalein as an indicator.
3.3. Apparatus and procedure
The experiments are carried out in a bench-top stirred reactor
(autoclave, model no. 4561, Parr Instrument Company) coupled
with modular temperature controller to maintain the desired tem-
perature and the stirring speed. Reactor has inside diameter of 2.500
and a depth of 400 with a capacity of 300 ml. It is provided with a
four-blade stirrer of 1.3800 diameter. Reactor is filled to roughly
two-thirds of its volume during the experiments and the reaction
is carried out at a desired constant temperature and stirrer speed.
Sufficient stirring speed is maintained to ensure uniform mixing
even at high catalyst loading. The samples are withdrawn after
specific time intervals and immediately cooled down to below
10 °C, in order to avoid any evaporation losses and further reaction.
The parameters like temperature, mole ratio of reactants, and cat-
alyst loading are varied in different experiments to generate ki-
netic data over a wide range. The reactions are performed with
both single alcohol and the mixture of alcohols. Reproducibility
of the experiments was ensured by repeating some of the experi-
ments under identical conditions and the error involved was with-
in ±5% conversion of the limiting reactant.
3.4. Elimination of mass transfer resistance
It has been shown in the previous studies [18–20], performed
under the conditions similar to ones used in the present work, that
the effect of catalyst particle size and hence the intra-particle dif-
fusion resistance is unimportant for esterification reactions in the
presence of ion exchange resins (particle size used is 0.60–
0.85 mm, obtained through sieving). Moreover, external mass
transfer resistance has negligible effect on the reaction rate when
speed of agitation is sufficiently high (>900 rpm). We confirmed

Please cite this article in press as: P. Patidar, S.M. Mahajani, Esterification of fusel oil using reactive distillation – Part I: Reaction kinetics, Chem. Eng. J.
(2012), http://dx.doi.org/10.1016/j.cej.2012.06.139
4 P. Patidar, S.M. Mahajani / Chemical Engineering Journal xxx (2012) xxx–xxx

Table 3
Kinetic rate expressions for different product esters, in the reaction of acetic acid with quaternary mixture of ethanol, n-propanol, iso-butanol and iso-amyl alcohol.

ðkf 1 aAcH aEtOH  kb1 aEtAc aH2 O Þ þ ðkf 5 aEtOH anPrAc  kb5 aEtAc anPrOH Þ þ ðkf 6 aEtOH aiBuAc  kb6 aiBuOH aEtAc Þ
1 dnEtAc þðkf 7 aEtOH aiAmAc  kb7 aiAmOH aEtAc Þ ð3Þ
r EtAc ¼ ¼  2
M cat dt P
1 þ all components K s;i ai

ðkf 2 aAcH anPrOH  kb2 anPrAc aH2 O Þ  ðkf 5 aEtOH anPrAc  kb5 aEtAc anPrOH Þ þ ðkf 8 anPrOH aiBuAc  kb8 aiBuOH anPrAc Þ
1 dnnPrAc þðkf 9 anPrOH aiAmAc  kb9 aiAmOH anPrAc Þ ð4Þ
r nPrAc ¼ ¼  2
Mcat dt P
1 þ all components K s;i ai

ðkf 3 aAcH aiBuOH  kb3 aiBuAc aH2 O Þ  ðkf 6 aEtOH aiBuAc  kb6 aEtAc aiBuOH Þ  ðkf 8 anPrOH aiBuAc  kb8 aiBuOH anPrAc Þ
1 dniBuAc þðkf 10 aiBuOH aiAmAc  kb10 aiAmOH aiBuAc Þ ð5Þ
r iBuAc ¼ ¼  2
Mcat dt P
1 þ all components K s;i ai

ðkf 4 aAcH aiAmOH  kb4 aiAmAc aH2 O Þ  ðkf 7 aEtOH aiAmAc  kb7 aEtAc aiAmOH Þ  ðkf 9 anPrOH aiAmAc  kb9 aiAmOH anPrAc Þ
1 dniAmAc ðkf 10 aiBuOH aiAmAc  kb10 aiAmOH aiBuAc Þ ð6Þ
r iAmAc ¼ ¼  2
Mcat dt P
1 þ all components K s;i ai

0
where; kf ;j ¼ kf ;j expðEf ;j =RTÞ ð7Þ

0
kb;j ¼ kb;j expðEb;j =RTÞ; j indicates the reaction no: as arranged in Table 4 ð8Þ

these findings through few preliminary runs before systematically
generating the data on intrinsic kinetics.
3.5. Development of kinetic model and parameter estimation
The literature suggests that the activity based heterogeneous ki-
netic models such as LHHW, are best suited for the reactions with
ion exchange resin as catalyst and hence the LHHW model is chosen
to explain the kinetic data generated in the present work. In this
model, all the reactants and products are assumed to be adsorbed
on the catalyst surface. Based on this assumption, rate expression
for various species involved in the reaction can be developed [21]
to give kinetic rate expressions (Eqs. (3)-(6); Table 3) for different
product esters, in the reaction of acetic acid with quaternary mix-
ture of ethanol, n-propanol, iso-butanol and iso-amyl alcohol. Since
it is a liquid phase reaction, adsorption constants can be assumed to
be constant with respect to temperature. Reaction is assumed to
take place only in the liquid phase owing to the fact that very small
amount of reactants are present in the vapor phase, which do not
react owing to the absence of catalyst there.
The rate expressions with respect to other components, i.e.
reactants and water, can also be derived on similar lines. The

°
°
°
°
°
°

(a) (b) (c)

Fig. 1. Esterification of n-propyl alcohol with acetic acid. (a) Effect of temperature on the conversion of acetic acid (catalyst loading = 3% (w/w), AcH:nPrOH = 1:1); (b) effect of
catalyst loading (w/w) on the conversion of acetic acid (temperature = 343 K, AcH:nPrOH = 1:1); (c) effect of mole ratio, AcH:nPrOH, on the conversion of limiting reactant
(temperature = 343 K, catalyst loading = 3%).

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 P. Patidar, S.M. Mahajani / Chemical Engineering Journal xxx (2012) xxx–xxx 5

developed kinetics can be used to predict concentration profile kinetic parameters of the model, such as rate and adsorption con-
between any time interval t1 to t2 starting with the initial concen- stants with activation energy, are estimated by minimizing the
tration at time t1. The activities of different components are calcu- sum of squares of error between the calculated values of mole
lated using UNIQUAC thermodynamic model. It is observed in the fractions of different components and that observed through
experiments that the system is highly non-ideal as the values of experiments.
activity coefficient differ significantly from unity for many compo- X
nents, although the variation in the values during the course of min / ¼ ðxi;cal  xi;exp Þ2 ð9Þ
reaction is not much for most of the components. For example, samples
in most of the esterification experiments the values of activity
coefficient for acetic acid is below 1, for alcohols and esters be- MATLAB function ‘nlinfit’, which is based on Levenberg–Marquardt
tween 0.5 and 2, while that for water is between 2 and 3.5. The algorithm, is used to perform the regression analysis.

°
°
°
°
°
°

(a) (b) (c)

Fig. 2. Esterification of ethanol with acetic acid. (a) Effect of temperature on the conversion of acetic acid (catalyst loading = 3% (w/w), AcH:EtOH = 1:1); (b) effect of catalyst
loading (w/w) on the conversion of acetic acid (temperature = 343 K, AcH:EtOH = 1:1); (c) effect of mole ratio, AcH:EtOH, on the conversion of limiting reactant
(temperature = 343 K, catalyst loading = 3%).

°
°
°
°
°
°

(a) (b) (c)

Fig. 3. Esterification of iso-butyl alcohol with acetic acid. (a) Effect of temperature on the conversion of acetic acid (catalyst loading = 3% (w/w), AcH:iBuOH = 1:1); (b) effect of
catalyst loading (w/w) on the conversion of acetic acid (temperature = 373 K, AcH:iBuOH = 1:1); (c) effect of mole ratio, AcH:iBuOH, on the conversion of limiting reactant
(temperature = 373 K, catalyst loading = 3%).

°
°
°
°
°
°

(a) (b) (c)

Fig. 4. Esterification of iso-amyl alcohol with acetic acid. (a) Effect of temperature on the conversion of acetic acid (catalyst loading = 3% (w/w), AcH:iAmOH = 1:1); (b) effect
of catalyst loading (w/w) on the conversion of acetic acid (temperature = 373 K, AcH:iAmOH = 1:1); (c) effect of mole ratio, AcH:iAmOH, on the conversion of limiting reactant
(temperature = 373 K, catalyst loading = 3%).

Please cite this article in press as: P. Patidar, S.M. Mahajani, Esterification of fusel oil using reactive distillation – Part I: Reaction kinetics, Chem. Eng. J.
(2012), http://dx.doi.org/10.1016/j.cej.2012.06.139
6 P. Patidar, S.M. Mahajani / Chemical Engineering Journal xxx (2012) xxx–xxx

4. Results and discussion
4.1. Esterification reactions with acetic acid
As mentioned before, first the experiments for the esterification
of individual alcohols are carried out over the wide ranges of
temperature, catalyst loading and reactant mole ratio. As expected,
the trends observed in the case of each alcohol are similar.
Fig. 1 shows the results obtained for n-propyl alcohol. The effect
of temperature on the rate of the reaction is investigated over a
temperature range of 343–363 K under otherwise similar condi-
tions. As shown in Fig. 1a, the fractional conversion of acetic acid
increases with an increase in temperature. Fig. 1b shows the effect
of catalyst loading on the rate of formation of n-propyl acetate,
over a range of 3–25% w/w (wt. of catalyst/wt. of reactants). The
rate increases linearly with an increase in catalyst loading over
the range studied. This can be attributed to a proportional increase
in the number of active sites provided by the catalyst. Further, the
mole ratio of n-propyl alcohol to acetic acid is varied from 0.5:1 to
2:1. As shown in Fig. 1c, the fractional conversion of the limiting
reactant increases when either of the reactants is used in excess
of the stoichiometric amount. As depicted in Figs. 2–4, similar

(a) (b) (c)

Fig. 5. Trans-esterification of n-propyl acetate with iso-butanol. (a) Effect of temperature on the conversion of iso-butanol (catalyst loading = 5% (w/w), nPrAc:iBuOH = 1:1);
(b) effect of catalyst loading (w/w) on the conversion of iso-butanol (temperature = 348 K, nPrAc:iBuOH = 1:1); (c) effect of mole ratio, nPrAc:iBuOH, on the conversion of
limiting reactant (temperature = 358 K, catalyst loading = 5%w/w).

(a) (b) (c)

Fig. 6. Trans-esterification of ethyl acetate with n-propanol. (a) Effect of temperature on the conversion of n-propanol (catalyst loading = 5% (w/w), EtAc:nPrOH = 1:1); (b)
effect of catalyst loading (w/w) on the conversion of n-propanol (temperature = 343 K, EtAc:nPrOH = 1:1); (c) effect of mole ratio, EtAc:nPrOH, on the conversion of limiting
reactant (temperature = 343 K, catalyst loading = 5%w/w).

(a) (b) (c)

Fig. 7. Trans-esterification of isobutyl acetate with ethanol. (a) Effect of temperature on the conversion of ethanol (catalyst loading = 5% (w/w), EtOH:iBuAc = 1:1); (b) effect of
catalyst loading (w/w) on the conversion of ethanol (temperature = 348 K, EtOH:iBuAc = 1:1); (c) effect of mole ratio, EtOH:iBuAc, on the conversion of limiting reactant
(temperature = 348 K, catalyst loading = 5%w/w).

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 P. Patidar, S.M. Mahajani / Chemical Engineering Journal xxx (2012) xxx–xxx 7

trends in the kinetics are realized in the case of esterification of
acetic acid with other alcohols.
4.2. Trans-esterification reactions
The experiments are carried out to study the possible individual
trans-esterification reactions of different alcohol-ester pairs. Again
the parameters like temperature, catalyst loading and reactant
mole ratios are varied to generate sufficient data. The results are
shown in Figs. 5–10 for the individual trans-esterification
reactions. The trends are similar to esterification reactions, how-
ever, these reactions are in general slower than the esterification
reactions under otherwise similar conditions.
4.3. Reactions of mixture of alcohols with acetic acid
Some selective experiments are performed with binary, ternary
and quaternary mixtures of different alcohols and the data is also
used for parameter estimation. Fig. 11a and b shows the results
of esterification of binary mixture of ethanol–iso-butanol and eth-
anol–iso-amyl alcohol pairs, while, Fig. 12a and b presents the data
for esterification of ternary mixtures of ethanol–n-propanol–iso-
butanol, and ethanol–iso-butanol–iso-amyl alcohol with stoichi-
ometric amounts of acetic acid. It is observed that in the mixture,
ethanol has the highest reaction rate followed by n-propanol, iso-
butanol and iso-amyl alcohol.
Table 4 gives the results of parameter estimation for LHHW
kinetic model involving all the possible reactions. The values of

(a) (b) (c)

Fig. 8. Trans-esterification of isoamyl acetate with ethanol. (a) Effect of temperature on the conversion of ethanol (catalyst loading = 5% (w/w), EtOH:iAmAc = 1:1); (b) effect
of catalyst loading (w/w) on the conversion of ethanol (temperature = 348 K, EtOH:iAmAc = 1:1); (c) effect of mole ratio, EtOH:iAmAc, on the conversion of limiting reactant
(temperature = 348 K, catalyst loading = 5%w/w).

(a) (b) (c)

Fig. 9. Trans-esterification of iso-amyl acetate with n-propanol. (a) Effect of temperature on the conversion of n-propanol (catalyst loading = 5% (w/w), nPrOH:iAmAc = 1:1);
(b) effect of catalyst loading (w/w) on the conversion of n-propanol (temperature = 348 K, nPrOH:iAmAc = 1:1); (c) effect of mole ratio, nPrOH:iAmAc, on the conversion of
limiting reactant (temperature = 348 K, catalyst loading = 5%w/w).

(a) (b) (c)

Fig. 10. Trans-esterification of iso-butyl acetate with iso-amyl alcohol. (a) Effect of temperature on the conversion of iso-amyl alcohol (catalyst loading = 5% (w/w),
iBuAc:iAmOH = 1:1); (b) effect of catalyst loading (w/w) on the conversion of iso-amyl alcohol (temperature = 348 K, iBuAc:iAmOH = 1:1); (c) effect of mole ratio,
iBuAc:iAmOH, on the conversion of limiting reactant (temperature = 358 K, catalyst loading = 5% w/w).

Please cite this article in press as: P. Patidar, S.M. Mahajani, Esterification of fusel oil using reactive distillation – Part I: Reaction kinetics, Chem. Eng. J.
(2012), http://dx.doi.org/10.1016/j.cej.2012.06.139
8 P. Patidar, S.M. Mahajani / Chemical Engineering Journal xxx (2012) xxx–xxx

Fig. 11. The variation in the compositions of various components with time during reaction of acetic acid with: (a) binary mixture of ethanol–iso-butanol
(AcH:EtOH:iBuOH = 2:1:1; temperature = 353 K; catalyst loading = 3 wt.%) (b) binary mixture of ethanol–iso-amyl alcohol (AcH:EtOH:iAmOH = 2:1:1; temperature = 353 K;
catalyst loading = 3 wt.%).

Fig. 12. The variation in the compositions of various components with time during reaction of acetic acid with: (a) ternary mixture of ethanol–iso-butanol–iso-amyl alcohol
(AcH:EtOH:iBuOH:AmOH = 3:1:1:1; temperature = 345 K; catalyst loading = 5 wt.%) (b) ternary mixture of n-propanol–iso-butanol–iso-amyl alcohol (AcH:nPrOH:iBuOH:A-
mOH = 3:1:1:1; temperature = 348 K; catalyst loading = 5 wt.%).

Table 4
Parameters of the proposed LHHW kinetic model obtained. The values reported are for 95% confidence interval.

S. no. Reaction kf0 kb0 Ef Eb Ks,i (SSE)  104

1 AcH þ EtOH ¡þ EtAc þ water 2.9047  106 ± 2.26  104 1.0967  106 ± 2.70  104 53047 ± 32 59055 ± 668 Ks,AA = 4.52 ± 0.002 0.91
H
6 4 5 4
2 AcH þ nPrOH ¡þ nPrAc þ water 2.9075  10 ± 5.73  10 6.7793  10 ± 9.32  10 54596 ± 12 59237 ± 336 Ks,EtOH = 6.42 ± 0.01 1.7
H
3 AcH þ iBuOH ¡þ iBuAc þ water 8.5577  105 ± 1.26  104 1.1927  105 ± 0.24  103 53016 ± 71 58661 ± 224 Ks,nPrOH = 6.05 ± 0.12 2.54
H
4 AcH þ iAmOH ¡þ iAmAc þ water 2.1835  105 ± 3.29  103 9400.7 ± 687.1 47341 ± 204 50739 ± 597 Ks,iBuOH = 4.48 ± 0.001 2.15
H
5 EtOH þ nPrAc ¡þ EtAc þ nPrOH 1497.6 ± 41.6 4320.8 ± 49.4 42962 ± 75 45921 ± 36 Ks,iAmOH = 2.56 ± 0.003 0.45
H
6 EtOH þ iBuAc ¡ EtAc þ iBuOH 5016.1 ± 217.8 1155.1 ± 679.5 49460 ± 160 44237 ± 1336 Ks,EtAc = 1.95 ± 0.02 0.97
Hþ
7 EtOH þ iAmAc ¡þ EtAc þ iAmOH 1426.7 ± 273.9 832.7 ± 76.7 45648 ± 529 42817 ± 389 Ks,nPrAc = 1.68 ± 0.12 1.02
H
8 nPrOH þ iBuAc ¡þ nPrAc þ iBuOH 2505.8 ± 84.0 1339.3 ± 26.0 47547 ± 65 45011 ± 57 Ks,iBuAc = 0.42 ± 0.002 0.58
H
9 nPrOH þ iAmAc ¡ nPrAc þ iAmOH 7251.2 ± 891.1 2511.5 ± 48.6 52420 ± 411 48105 ± 68 Ks,iAmAc = 0.29 ± 0.001 0.25
Hþ
10 iBuOH þ iAmAc ¡þ iBuAc þ iAmOH 966.9 ± 135.3 2006.0 ± 82.2 47229 ± 367 50321 ± 82 Ks,H2O = 9.03 ± 0.18 2.35
H

kinetic parameters obtained by regressing smaller data set, which tions, results in different numerical values of kinetic parameters,
does not include the experimental data of individual alcohol reac- with the predictions being satisfactory over a reduced composition

Please cite this article in press as: P. Patidar, S.M. Mahajani, Esterification of fusel oil using reactive distillation – Part I: Reaction kinetics, Chem. Eng. J.
(2012), http://dx.doi.org/10.1016/j.cej.2012.06.139
 P. Patidar, S.M. Mahajani / Chemical Engineering Journal xxx (2012) xxx–xxx 9

space. Further the reactions with quaternary mixture are performed

and the data is used to examine the reliability of the proposed
model. Fig. 13a and b shows the comparison of the results of the
reaction of quaternary mixture of alcohols with stoichiometric
amount of acetic acid. Fig. 14 gives the parity plot comparing mole
fractions of limiting reactant, in all the different experiments per-
formed, with that predicted by the proposed kinetic model. The pre-
dicted compositions for the different components agree reasonably
well with the experimental data.

5. Application of the kinetic model for reactive distillation

The developed kinetics is intended to be used for simulating

esterification of fusel oil using RD. Some preliminary RD simula-
tions are performed using the developed kinetic models in RAD-
FRAC module (equilibrium stage model) of ASPEN PLUS
simulator, for feed containing alcohol mixtures and acetic acid.
The VLE model used is UNIQUAC-HOC with binary interaction
Fig. 14. Parity plot showing comparison of predicted and experimental values of
parameters taken from ASPEN Databank. Fig. 15 shows one of the mole fractions of limiting reactants in all the experiments.
the representative feasible configurations with stream composi-

Fig. 13. Comparison between calculated and experimental mole fractions of (a) acetic acid and (b) other reactants, for the reaction of acetic acid with a quaternary mixture of
ethanol–n-propanol–iso-butanol–iso-amyl alcohol (AcH:EtOH:nPrOH:iBuOH:AmOH = 4:1:1:1:1; temperature = 348 K; catalyst loading = 5 wt.%).

Please cite this article in press as: P. Patidar, S.M. Mahajani, Esterification of fusel oil using reactive distillation – Part I: Reaction kinetics, Chem. Eng. J.
(2012), http://dx.doi.org/10.1016/j.cej.2012.06.139
10 P. Patidar, S.M. Mahajani / Chemical Engineering Journal xxx (2012) xxx–xxx
Fig. 15. Schematic diagram showing simulation details of a feasible RD process for esterifying a mixture of alcohols.
tions and other results. In this configuration the first column rep-
resents the RD column with reaction taking place in the last two
stages including reboiler. The product mixture is removed in the
form of distillate and sent to other non-reactive distillation col-
umns for further separation. As no product is withdrawn from
the bottom, no stripping section is provided here. To check the
sensitivity towards RD simulation results, the kinetic rate con-
stants were varied by ±10%. The suggested process configuration
remains unaltered even in the changed conditions. A detailed
study of different alternative process configurations for esterifica-
tion of fusel oil using RD, is in progress and will be covered in the
subsequent part of this series.
6. Conclusion
The reaction kinetics of esterification of acetic acid with etha-
nol, n-propanol, iso-butanol and iso-amyl alcohol as well as their
mixtures over the cation-exchange resin, Amberlyst-15, are stud-
ied. The kinetic data obtained in a batch reactor under various con-
ditions are correlated using an activity-based LHHW model. The
model explains the data successfully over a wide range of catalyst
loading and temperature for different esterification and trans-
esterification reactions. The developed kinetic model is used for
process simulation of esterification of fusel oil using reactive distil-
lation and is shown that a process involving one reactive distilla-
tion column and four non reactive distillation columns can be
successfully used to obtain all the esters in pure form. The experi-
mental validation and optimization of design and operating
parameters is the subject of future work.
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Please cite this article in press as: P. Patidar, S.M. Mahajani, Esterification of fusel oil using reactive distillation – Part I: Reaction kinetics, Chem. Eng. J.
(2012), http://dx.doi.org/10.1016/j.cej.2012.06.139