Article

pubs.acs.org/IECR

Esterication Kinetics of Tributyl Citrate Production Using

Homogeneous and Heterogeneous Catalysts
Oscar M. Osorio-Pascuas, Miguel A. Santaella, Gerardo Rodriguez, and Alvaro Orjuela*
Department of Chemical and Environmental Engineering, Grupo de Investigacion en Procesos Qumicos y Bioqumicos, Universidad
Nacional de Colombia, 111321 Bogota D.C., Colombia
S Supporting Information
*

ABSTRACT: In this work, the production of tributyl citrate via catalytic and self-catalyzed esterication of citric acid with 1butanol was studied. Both, methanesulfonic acid (MSA) and Amberlyst 70 ion-exchange resin were evaluated as catalysts in the
reaction. The kinetic eects of the temperature (353393 K), the feed molar ratio of alcohol to acid (8:1 to 16:1), and catalyst
loadings (0.51.5 wt % of MSA, and the equivalent amount of Amberlyst 70) were evaluated. Experiments were carried out using
stirred batch reactors under isothermal operation. A BoxBehnken design was used to optimize the number of experiments
required to obtain a valid kinetic model. Chemical equilibrium conditions were evaluated independently from kinetic
experiments, reducing the number of parameters to adjust during data regression. Self-catalytic rate of reaction was also
evaluated, and it was included within the overall kinetic model. The obtained models show good agreement with experiments,
and they can be used for process analysis and simulation.

1. INTRODUCTION

Among the variety of citrate esters, tri-1-butyl citrate (TBC)

stands out as a widely used ingredient in cosmetic products and
as a raw material to produce acetyl tri-1-butyl citrate (ATBC).
The acetylated tributyl citrate provides even better results as a
plasticizing agent for polyvinyl chloride (PVC).10
TBC is manly produced by direct esterication of citric acid
(CA) (a major fermentation-derived commodity), with 1butanol (also available from fermentation) in a sequential
parallel reaction scheme, as shown in Figure 1. At the industrial
scale, TBC is produced in batch or batch fed stirred tank
reactors using a homogeneous acid catalyst.1214 Some reports
also indicate the benet of using of heterogeneous catalyst as
ion exchange resins to avoid the need for corrosion-resistant
materials.15 Although homogeneous catalysts can become very
corrosive to equipment and could be dicult to remove, they
are preferred because they are more active and ecient in
reaching high conversions to the trialkyl ester below the
decomposition temperature of citric acid (448 K).16
Each esterication step described in Figure 1 is strongly
limited by chemical equilibrium. Therefore, the continuous
removal of the water generated in the process and the use of
alcohol excess are common practices to achieve high
conversion. For that same reason, energy-intensive alcohol
recovery and recycling steps are required, involving higher
processing costs.
To reduce energy consumption and processing costs during
citrates production, intensication by reactive distillation (RD)
has been proposed for citrates production, specically for
triethyl citrate.11,15 In this case, removal of ethanol excess and
water was accomplished by distillation, while reaction was

Production and consumption of biobased chemicals have

gained pace in recent years because of the global trend for
moderating dependence on petrochemicals, the need for
reducing the environmental impacts of using fossil resources,
and also as a result of the public scrutiny over the potential
negative eects of being exposed to harmful chemicals. In
contrast to most petroleum-based chemicals, biobased products
are commonly renewable, biocompatible, and suitable for
biodegradation. In this regard, the substitution of petrochemicals with biobased alternatives in the formulation of consumer
goods is particularly important in the plasticizers sector. These
components are widely used in the fabrication and transformation of polymers, providing the exibility and plasticity
required in the nal products. The current world plasticizer
market amounts to c.a. 7 million tons per year, and it is
extensively dominated (86%) by phthalic acid esters of long
chain alcohols (e.g., 2-ethyl hexanol, nonanol). The remaining
nonphthalate plasticizers are used mainly in niche applications.1
Although phthalates are well-known as general-purpose
plasticizing agents and have been used in a variety of polymeric
materials,2,3 some studies indicate that they may represent
certain risks to human health and that they are not easily
biodegraded.48 Furthermore, in the traditional phthalic
anhydride synthesis processes (gas-phase oxidation of naphthalene or o-xylene3) some aromatic trace impurities may
remain in the plasticizer, preventing its use in products
designed for direct contact with humans. In contrast, even if
biobased plasticizers such as citric acid esters (with or without
acetylation) are not for general purpose, they are generally
recognized as safe (GRAS) by dierent international regulatory
agencies. This characteristic makes citrates suitable plasticizers
for pharmaceutical and cosmetic applications, medical devices,
food packaging, and toys.2,3,911
XXXX American Chemical Society

Received: September 26, 2015

Revised: November 22, 2015
Accepted: November 30, 2015

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Figure 1. Esterication of citric acid with 1-butanol.

2.2. Analysis. The analytic technique described here was

adapted from a previous report on citrates esterication.11 CA,
mono-1-butyl citrate (MBC), di-1-butyl citrate (DBC), and
TBC were analyzed by using a Dionex-Ultimate 3000 HPLCSystem, using a reversed phase C18 column (Acclaim 120, 3
150 mm, 3 m). The oven temperature was set at 373 K, and
the mobile phase ow rate was maintained as 1 mL/min using a
programmed gradient of acetonitrile (ACN)/water (pH 2.1) as
follows: 0% ACN (t = 0 min), 60% ACN (t = 20 min), 90%
ACN (t = 25 min), and 0% ACN (t = 28 min). Samples were
diluted in acetonitrile (3/100 v/v) before injection, and the
species were quantied by ultraviolet (UV) detection at a
wavelength of 210 nm. CA and TBC were identied by
comparison of the retention times of standards. Quantication
was carried out by previous calibration and response factor
determination. Solutions of known composition were prepared
and analyzed by triplicate, ensuring a detector linear response.
The maximum error of HPLC analysis in these components
was 0.5%.
For the MBC and DBC, there were no commercial
chromatography standards available. Moreover, according to
the chemical structure, the occurrence of two isomers was
expected for both intermediate esters (dicult to resolve by
standard HPLC), because esterication can occur in the
terminal or middle carboxylic group of the CA. In all reaction
samples, two peaks were observed in the chromatography plots
for each intermediate ester. For quantication purposes, the
two unresolved peaks of each intermediate ester were
considered as a single component. Because similar detector
responses for CA and TBC were obtained, the response factors
of the missing citrates were calculated based upon the degree of
substitution. Those were obtained by interpolating a linear
relationship between the molecular weight of CA and TBC and
their corresponding response factors. Adequacy of this
assumption was veried by keeping track of the total amount
of moles of citric species that had to be constant in each
experiment. Finally, the concentrations of water (H2O) and 1butanol (BtOH) were determined by reaction stoichiometry
and by mole balance. By using the considerations described
above, and because the response factors for some citric species
were assumed, it was observed that the maximum relative error
close to the total mass balance was 5% in the sum of the
experimental mass fractions of all components. This was
considered acceptable taking into account the lack of
commercial chromatography standards for calibration of
intermediate citrates.
2.3. Heterogeneous Catalyst Pretreatment and Preliminary Tests. As-received Amberlyst 70 was washed in
ethanol under agitation for 2 h using a stirred glass container.

promoted by Amberlyst 15 as catalyst. According to these

reports, it is recommended that operation occur at high
temperatures to benet the reaction rate, but the temperature
should be maintained below 393 K to avoid thermal damage of
the catalyst.17
Despite RD having been also proposed for the production of
other CA esters,12 there is a lack of kinetic and thermodynamic
information in the open literature allowing process modeling
and design, particularly when using commercial homogeneous
or heterogeneous catalysts such as methanesulfonic acid and
Amberlyst 70. Methanesulfonic acid (MSA) is widely used as a
liquid catalyst in esterication processes because of its good
activity, lower corrosiveness compared with stronger acids
(sulfuric or hydrochloric), and less degradation of the product
(color darkening). On the other hand, Amberlyst 70 ionexchange resin can operate at higher temperatures than most
commercial ion exchange resins (maximum operating temperature of 463 K18), and similarly to other solid catalysts, it can be
easily recovered and regenerated in continuous process
systems. Although reports indicate Amberlyst 70 has lower
acid sites concentration in the polymeric matrix (>2.55 eq/
kg18) than other ion exchange catalysts, it has shown good
performance in dierent etherications and also in esterications of poly(carboxylic acid)s operating in RD units.1927
In this regard, this work describes a study on the
esterication of CA with 1-butanol using MSA and Amberlyst
70 as homogeneous and heterogeneous catalyst, respectively.
The eect of the catalyst concentration, reactants molar ratio,
and temperature over the rate of reaction was evaluated for
each catalyst. Because the autocatalytic eect was considered
important based on preliminary experiments, it was also studied
and incorporated within the complete kinetic models. The
obtained models are intended to be used in the modeling of
reactive distillation processes.

2. EXPERIMENTAL DETAILS
2.1. Material. For reaction experiments, anhydrous citric
acid (99.9%, FG) was obtained from Sucroal S.A. (Colombia)
and 1-butanol (99.5%, for analysis) was purchased from
Panreac (Spain). The concentration of all chemicals was
checked by gas chromatography or high-performance liquid
chromatography (HPLC), and the chemicals were used without
further purication. Tributyl citrate (98%, Aldrich, United
States) and citric acid (99.9%, Sigma-Aldrich) standards were
used for calibration purposes. Methanesulfonic acid (98%) was
obtained from Alfa Aesar (Germany) and Amberlyst 70 resin
was supplied by Dow Chemical Company (United States).
Acetonitrile (99.9% HPLC grade, Panreac, Spain) and
deionized water were used as HPLC solvents.
B

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below the desired temperature, the required amount of MSA

was loaded into reactor through the sampling port using a
syringe. After the mixture reached the reaction temperature (it
normally took 1015 min), the reaction time was started.
When operating with the self-catalytic system, the stirring
rate was maintained at 700 rpm from the beginning of the
operation. When using Amberlyst 70, reagents and catalyst
were charged to the reactor from the beginning. Then, the
reactor was closed and operated at room temperature and 700
rpm for about 10 min to allow CA dissolution. Later, the
heating was started, and after the mixture reached the required
temperature, the stirring rate was adjusted to 1100 rpm. At this
point, the time recording was initiated.
During all experiments, 0.20.3 cm3 samples were withdrawn
at specic time intervals through the sampling port by using a
syringe. The samples were transferred to an ice bath before
analysis. Eight to ten samples were obtained in each 8 h
reaction experiment.
2.5. Chemical Equilibrium Experiment. Reaction equilibrium experiments were carried out in sealed glass tubes of 10
mL, which were attached to a rotating rod within an isothermal
oven (Figure 3). The reactants together with the MSA were

An ethanol resin volumetric ratio of 1:4 was used during this

process, and it was repeated at least three times. The rinsing
process was repeated with deionized water until constant
conductivity of the supernatant solution was measured.
Afterward, the resin was ltered and dried under vacuum at
353 K until constant weight. The dried catalyst was maintained
in a hermetic container within a vacuum oven until the nal use
in kinetic experiments.
From preliminary experiments using Amberlyst 70 as
catalyst, it was found that external mass-transfer resistances
were negligible when operating at stirring rates above 800 rpm.
For this reason, further reactions were run above this agitation
rate. Additional experiments evaluating the eects of catalyst
particle sizes on the reaction rate allowed ensuring the absence
of internal mass-transfer limitations when working with particle
sizes below 300 m. Because the mean particle size of highly
monodisperse Amberlyst 70 beads is around 500 m,18 the
catalyst was subjected to grinding before use in the kinetic
experiments. This process was performed in a mortar using
liquid nitrogen to cool the solid, avoiding the temperature rise
caused by friction during the milling process. To ensure the
thermal stability of the acid sites, the ion exchange capacity of
the resin was measured before and after the grinding process.
Details of the standard method to evaluate ion exchange
capacity are described elsewhere.28 The concentration of acid
sites before and after this treatment was nearly constant, and it
was 4.01 0.12 eq/dry kg.
2.4. Batch Kinetic Experiment. The esterication
reactions were performed under batch conditions in a set of
three well-mixed 100 cm3 stainless steel jacketed reactors, each
one equipped with a circulating oil bath for isothermal
operation and a stirring plate (see Figure 2). Also, a sampling

Figure 3. Scheme of equipment used for chemical equilibrium

experiments.

previously added into tubes at the desired concentrations. The

stirring rate was adjusted between 90 and 100 rpm, and the
temperature was maintained constant within 0.1 K by using a
PID controller. The tubes where maintained at reaction
conditions for 2872 h, and at the end the equilibrium
conditions were obtained by HPLC analysis of the reactive
media.
Figure 2. Scheme of equipment used for batch kinetic experiments.

3. RESULTS AND DISCUSSION

A BoxBehnken experimental design was implemented to
reduce the required number of experiments to t the kinetic
model. BoxBehnken is a type of response surface design used
when each factor has only three levels, and it is recommended
when the region of interest and the region of operability are
nearly the same. Because it requires fewer evaluation points, it
is less computationally expensive than central composite
designs (such as the factorial design).29 In our case, three
dierent factors at three levels are considered: initial reactants
molar ratio (8:1 to 16:1), reaction temperature (363393 K),
and catalyst loading (0.51.5 wt %). In the case of Amberlyst
70, the required weight of catalyst was calculated using the

port and a temperature probe were located over the reactor

cover to follow the reaction conditions with time. Inside the
reactor, at the end of the sampling port, a stainless steel lter
was located to avoid catalyst removal during operation.
Initially, when using the homogeneous catalyst (MSA), the
desired amount of CA and BtOH were added into the reactor
at room temperature. After the reactor was closed, the magnetic
stirring was set at 500 rpm and maintained for 10 min to mix
reactants and dissolve the CA. Thereafter, heating was initiated
by allowing the bath uid to pass through the reactor jacket,
and the stirring rate was adjusted to 700 rpm. Around 5 K
C

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Table 1. Evaluation of Internal Mass-Transfer Resistances at
Initial Reaction Conditions Using the WeiszPrater
Criterion
cat (kg/m3) (swollen)
dp (m) (swollen)
CCAo (mole fraction) (solution)
wcat (kgcat/kgsol)
BtOH association factor WilkeChang
CA molar volume at TB (cm3/mol)a
19
experimental run
T (K)
robs (mol CA/mol.s)
sol (kg/m3)
liquid (cp)36
DCA (m2/s)
De (m2/s)
w

1000
378
0.058
0.0264
1.0
223.14
0.57
3b
363.15
9.68 106
818
0.633
1.43 109
4.63 1010
0.0662
0.258
0.996

4b
393.15
4.35 105
794
0.389
2.51 109
8.16 1010
0.173
0.419
0.988

Figure 5. Self-catalyzed esterication of CA with BtOH. Conditions of

run 22. Molar ratio 12:1 (alcohol:acid), 393 K. (, CA; , MBC; ,
DBC; , TBC; , BtOH; , H2O).

Aspen Plus v. 7.3, Database.

Figure 4. Initial reaction rate of CA with BtOH for various catalyst

concentrations: () MSA and () Amberlyst 70. Experiments
performed with a reactant molar ratio, 8:1 (alcohol:acid) and 378 K.
(*Mass concentration of catalyst corresponding to MSA acid
equivalents. Datum at 0 wt %, cat corresponds to the self-catalytic
experiment.)

Figure 6. Mole fraction-based equilibrium constants (KEQ) for

esterication of CA with BtOH catalyzed with MSA at dierent
temperatures. , Keq 1; , Keq 2; , Keq 3.

Table 2. Kinetic Parameters Adjusted for Self-Catalyzed

Reactions

same acid equivalents of MSA in the reactive phase. Some

additional experiments were carried out to analyze the eect of
temperature, concentration of catalyst, and the self-catalytic
reaction. Conditions of kinetic experiments are summarized in
Table S1 in the Supporting Information, and the full set of
kinetic plots (Figures S2S41) are also available there.
3.1. Mass-Transfer Considerations on the Heterogeneous System of Reaction. In preliminary CABtOH
esterication experiments using Amberlyst 70 as catalyst,
negligible external liquidsolid mass-transfer limitations were
observed when operating with agitation rates above 800 rpm.
On the other hand, intraparticle mass-transfer eects were
analyzed by taking into consideration the WeiszPrater module
(w). As a general criterion, absence of intraparticle masstransfer limitations can be assumed when w is much less than

parameter
ko self,1
ko self,2
ko self,3
Eaself,1
Eaself,2
Eaself,3
Keq 1
Keq 2
Keq 3

units

values

condence interval

1/s
1/s
1/s
J/mol
J/mol
J/mol

3.207 10
8.873 106
1.166 107
71 433
77 346
80 894
8.68
3.56
1.04
6

1.183 105
4.517 105
1.776 106
237
1099
3693

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Table 3. Kinetic Parameters Adjusted for Catalyzed Reaction of Homogeneous and Heterogeneous System
parameter

units

MSA

condence interval

Amberlyst 70

condence interval

ko cat,1
ko cat,2
ko cat,3
Ea1
Ea2
Ea3
Keq 1
Keq 2
Keq 3

1/(%wt cat)*s
1/(%wt cat)*s
1/(%wt cat)*s
J/mol
J/mol
J/mol

2.678 105
3.103 105
4.247 105
57 917
60 065
66 406
8.68
3.56
1.04

4.877 104
3.333 104
2.342 104
1850
1114
585

1.543 105
1.275 105
8.255 104
65 582
67 529
70 561
8.68
3.56
1.04

8.573 103
6.755 103
6.037 103
872
263
1140

= robs/(wcat
sol )
robs

(2)

Here, robs is the rate of reaction per unit volume of reacting

liquid phase. In this study, this is evaluated as the consumption
rate of CA with time. In eq 2, wcat
is the catalyst loading
(kilogram of catalyst per kilogram of reacting phase), and sol is
the density of reacting phase.
In preliminary tests, it was found that dry Amberlyst 70
particles could swell up to double their volume when contacted
with BtOH. Therefore, the particle diameter at reacting
conditions (dp) can be calculated as
d p/d pdry =

(VPswollen/VPdry )

Taking into account that after the catalyst was grinded before
use, obtained particle size distribution was in-between 150 and
300 m. The higher value of this interval (300 m) was used to
estimate the swollen particle diameter with eq 3, obtained a dp
value of 378 m. The particle diameter used in this calculation
was conservative taking into account that WeiszPrater module
increase with the particle size.
Alcohol adsorption within the macroreticular structure of
Amberlyst 70 modies its density because of the swelling eect.
The catalyst density under reaction conditions has been
previously reported as 1000 kg/m3 in similar reactive
media,19,32,33 so this value was used for WeiszPrater module
evaluation. The eective diusivity (De) was calculated based
upon the liquid-phase diusion coecient (DCA) estimated
from the WilkeChang model,34 using eq 4.

Figure 7. Calculated data versus experimental data for esterication

between citric acid and 1-butanol catalyzed with methanesulfonic acid
(, CA; , MBC; , DBC; , TBC; , BtOH; , H2O).

De = (/ )DCA = 2DCA

(4)

As observed, eective diusivity was computed as the

quotient of particle porosity () and pore tortuosity (), or
assuming that is the inverse of .32,33 Then, the observed
WeiszPrater modulus can be used to calculate the
eectiveness factor of the reaction () taking into consideration
the Thiele modulus () for spherical particles using the
following expression:

Figure 8. Calculated data versus experimental data for esterication

between citric acid and 1-butanol catalyzed with Amberlyst 70 resin
(, CA; , MBC; , DBC; , TBC; , BtOH; , H2O).

W = 2 = 3( coth 1)

the unity. For a spherical particle the WeiszPrater module can

be calculated as30,31
)cat (d p/6)2 /(DeCCAo)
W = (robs

(3)

(5)

Equation 5 represents the WeiszPrater modulus for a

spherical pellet assuming a rst-order reaction in CA, which
is considered to be a valid assumption in this case because of
the large excess of alcohol used in experiments.
The calculated values of w for an initial molar ratio of 16:1
(BtOH:CA) and at 363.15 and 393.15 K are shown in Table 1.
Results indicate that the main eect in the reaction is the
kinetic one because w 1 (internal mass-transfer resistance
can be negligible30) and the eectiveness factor is nearly
unity.30,35 As observed, this analysis was performed in the

(1)

where robs
is the observed rate of reaction per mass of catalyst
and cat and dp are the catalyst density and particle diameter,
respectively. De is the eective diusivity of CA within the
catalyst particle, and CCAo is the concentration of CA in the
bulk liquid at the beginning of the reaction. For the calculation
of the observed reaction rate (robs
) the following equation can
be used:
E

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temperature limits of the kinetic study, ensuring that observed

reaction rates during experiments corresponded to intrinsic
kinetics. This was also experimentally conrmed by performing
kinetics runs using dierent catalyst particle sizes. As shown in
Figure S1 of the Supporting Information, there are no
dierences when working with particles below 250 m.
3.2. Eect of Catalyst Loading. The eect of varying the
catalyst concentration (MSA and Amberlyst 70) in the reaction
is presented in Figure 4. In this case, only the reaction rate at
time zero for the rst step of esterication (CA consumption)
was considered. As observed, for both homogeneous and
heterogeneous catalysts, reaction rate is directly proportional to
catalyst loading. Additionally, the slope of the trend line for
Amberlyst 70 is smaller than that for MSA. This indicates that
for an equivalent amount of active sites, MSA is more eective
as catalyst than Amberlyst 70 resin. This was expected because
of the mobility of the homogeneous catalyst. Another
important nding of these preliminary experiments is that
reaction occurs even without catalyst. This indicates that is
important to consider the self-catalytic reaction, which is
expected to be more signicant at high temperatures.
Another important nding of these preliminary experiments
is that reaction occurs even without catalyst. This indicates that
is important to consider self-catalytic reaction, which will be
more signicant at high temperatures.
3.3. Self-Catalytic Reaction. Self-catalytic reaction was
evaluated according to conditions reported in Table S1 (runs
1725). The temperature and molar ratio ranges correspond to
those evaluated for the catalytic systems. In this case, the
reaction is promoted by the acidic groups of the citric species
(CA, MBC, and DBC). A typical reaction prole of selfcatalytic reaction is observed in Figure 5. All the kinetic proles
obtained in the self-catalytic experiments are also available in
the Supporting Information.
3.4. Kinetic Model Description. In a batch reactor, the
change in the composition of the chemical species can be
expressed as follows:
dNi /dt = NT(dxi /dt ) = irv , iV

(6)

where Ni is number of moles of component i, NT the total

number of moles in the reactor, xi the mole fraction of
component i in the liquid reactive media, i the stoichiometric
coecients of component i, and rv,i the volumetric reaction rate
for component i. Because of the large excess of alcohol required
to dissolve CA, the mixture density can be considered nearly
constant with time. For this reason, and taking into account
that the total number of moles is conservative, eq 6 can be
simplied to eq 7.
dxi /dt = ri

(7)

According with literature, the esterication reaction can be

described by using a power law kinetic model assuming an
Arrhenius-type temperature dependence and a rst order with
respect to each reactant.11 Therefore, for a typical esterication,
the kinetic model can be expressed in a pseudohomogeneous
model as
rj = Ccatk w, j(xAcidxAlcohol x Esterx Water /KEQ, j)

(8)

where CCat is the catalyst or active sites concentration and kw

and KEQ are the reaction rate constant and the equilibrium
constant of reaction j, respectively. Here, an approximate mole
fraction-based model is used when a thermodynamic model is

Figure 9. Esterication of CA with BtOH. Molar ratio 8:1

(alcohol:acid), 393 K, and 1 wt % of catalyst loading. (a) MSA, (b)
Amberlyst 70, and (c) Self-catalytic (, CA; , MBC; , DBC; ,
TBC; , BtOH; H2O).
F

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not available to describe phase equilibria of the reactive media

(otherwise, an activity-based model is preferred). For a catalytic
esterication, the rate constant of reaction j is termed kCatj, and
it can be expressed as
k Catj = ko,Catj exp[ Ea Cat, j/(RT )]

KEQj = xi , ij,j

Here, i,j is the stoichiometric coecient of component i in the

reaction step j. The values of the equilibrium constants were
determined by measuring the nal concentration of reaction
(after 3 days or more) at temperatures between 342 and 373 K.
MSA was used as catalyst during these experiments because its
activity is higher than that of Amberlyst 70, and no solidliquid
equilibria might aect results. In addition, the higher activity of
MSA helps to ensure a real chemical equilibrium condition in
the time frame of the experiments. The temperature dependence of the chemical equilibrium constants are presented in
Figure 6 as the linear form of a vant Ho-type relationship.
The equilibrium constant for the formation of MBC (Keq 1)
was measured only at 373 K adding 5 wt % of water to the
reactive mixture. This was done because after several attempts
to determinate the chemical equilibrium constant, the nal
concentration of CA was well below the uncertainty of the
chromatographic technique. The addition of water helped to
shift the chemical equilibrium to the reactants, allowing
measurable concentrations of CA, and to obtain a reproducible
experiment. The other equilibrium constants, Keq 2 and Keq 3,
were evaluated with initial mixture of CA and BtOH only, at all
temperatures. As observed, molar-based equilibrium constants
are nearly independent of temperature, indicating that reactions
are virtually thermoneutral (i.e., negligible heat of reaction).
The averaged Keq 1, Keq 2, and Keq 3 values obtained were 8.68,
3.56, and 1.04, respectively.
3.6. Determination of Kinetic Parameters. The kinetic
parameters (pre-exponential factors and energies of activation)
were calculated from the numerical integration of the kinetic
rate expressions. The model was integrated using a commercial
software (Matlab), solving eqs 1214 (without catalyst) and eq
1517 (with catalyst) via an ODE23 function (fourth-order
RungeKutta), using the initial mole fraction concentration of
components (t = 0) as the initial condition in the solution of
the set of ordinary dierential equations. The molar balance
was calculated to determine the concentration proles of
species in the batch reactor, as described in eqs 1924.

(9)

As for the self-catalyzed reaction kSelf j, it can be expressed as

k Selfj = ko,Selfj exp[ EaSelf, j/(RT )]

(10)

Herein, R is the ideal gas constant and T is the absolute

temperature; koi and Eai are the pre-exponential factor and the
activation energy of reaction i, respectively. Regarding the CCat
parameter in eq 8, for the catalytic reaction, it can be assumed
as the catalyst loading in weight percent (wcat, kilograms of
catalyst/100 kilograms of reactive phase). In the case of the
self-catalytic system, CCat can be expressed as the molar
concentration of acid equivalents from citric species (xacid):11
xacid = 3xCA + 2xMBC + xDBC

(11)

Here, we assumed that the self-catalytic activity is proportional

to the total concentration of hydrogen ions present in CA
(three hydronium ions), MBC (two hydronium ions), and
DBC (one hydronium ion). Dierently from the catalytic
reaction, in the self-catalytic system the concentration of active
sites (xacid) changes with time; having its maximum at time zero
and gradually decreasing over time until reaching a value near
to zero.
Taking into account the above, the kinetic models for the
self-catalytic reactions during CA esterication can be dened
as follows:
rSelf,1 = xacidk Self,1(xCAxBtOH xMBCx H 2O/KEQ1)

(12)

rSelf,2 = xacidk Self,2(xMBCxBtOH xDBCx H 2O/KEQ2)

(13)

rSelf,3 = xacidk Self,3(xDBCxBtOH xTBCx H 2O/KEQ3)

(14)

(18)

In this case of the catalytic reaction, there is a synergic eect

of the self-catalytic reaction. For this reason, the kinetic model
is described as the linear combination of both eects as follows:
r1 = (xacidk Self,1 + wCatk Cat,1)(xCAx BtOH xMBCx H2O/KEQ1)
(15)

r2 = (xacidk Self,2 + wCatk Cat,2)(xMBCxBtOH xDBCx H 2O/KEQ2)

(16)

r3 = (xacidk Self,3 + wCatk Cat,3)(xDBCxBtOH x TBCx H 2O/KEQ3)

(17)

Equations 1517 are the complete kinetic models that describe

CA esterication with BtOH using either homogeneous or
heterogeneous catalyst. Because the number of parameters is
large (15 in total) to t with few kinetic experiments, and there
is lack of thermodynamic models to calculate the phase and
chemical equilibrium of the system, the kinetic equations were
mole fraction-based as a simplication, and the equilibrium
constants were experimentally obtained. Additionally, the
kinetic parameters of self-catalytic reaction were obtained by
tting data from noncatalytic experiments only (runs 1725).
3.5. Reaction Equilibrium Constants. The chemical
equilibrium constants for the three reaction steps can be
estimated in a mole fraction-basis as follows:

dxCA /dt = r1

(19)

dxMBC/dt = r1 r2

(20)

dx DBC/dt = r2 r3

(21)

dx TBC/dt = r3

(22)

dx BtOH/dt = r1 r2 r3

(23)

dx H2O/dt = r1 + r2 + r3

(24)

The kinetic parameters were determined by the minimization

of the objective function described in eq 25, using a genetic
algorithm method from Matlab libraries.
NC

Fmin = [ (xi ,exptl xi ,calcd)2 ]/NC

i=1

(25)

Here, NC is the number of citric species; xi,exptl and xi,calcd are

the experimental and calculated mole fractions, respectively,
obtained from the concentration proles with time. Initially, the
kinetic parameters for self-catalytic system were calculated.
Later, the same optimization function was used to t the
catalytic parameters including the self-catalytic parameters
G

DOI: 10.1021/acs.iecr.5b03608
Ind. Eng. Chem. Res. XXXX, XXX, XXXXXX

Industrial & Engineering Chemistry Research

previously calculated. The nal values of the kinetic parameters

are presented in the Tables 2 and 3. Fmin values obtained in
each optimization were 1.19 105, 2.68 105, and 1.97
105 for self-catalytic, homogeneous, and heterogeneous
systems, respectively.
As expected, the MSA catalyst showed lower energies of
activation and higher pre-exponential factors in each reactions
step than the heterogeneous catalyst. This agrees with the
higher turnover frequency (6 times higher) for the same
amount of acid equivalents, as observed in the slopes of the
trend lines of Figure 4. The kinetic parameters here obtained
agree with similar reports on esterication reaction of
poly(carboxylic acid).11,19
Figures 7 and 8 are parity plots of the whole set of
experiments compared with calculations from the developed
models. Also, Figure 9 presents the good agreement between
experimental and calculated kinetic proles under dierent
catalysts and operating conditions. The whole set of experiments and plots are included in the Supporting Information. As
observed, there is good agreement between the obtained kinetic
expressions and the experimental observations. This indicates
that the obtained models can be used with condence for
process design and up-scaling purposes.
Figure 9 presents the agreement of the experimental and
calculated kinetic proles under dierent catalysts and
conditions. The whole set of experiments and plots are
included in the Supporting Information.

ACKNOWLEDGMENTS
This work was supported by Departamento de Administrativo
de Ciencia, Tecnologia e Innovacion Colciencias, under the
Project named Produccion de plastif icantes a partir de acido

citrico
usando procesos hibridos
de reaccion y separacion
simultanea, code: 1101-569-33201. M.A.S. thanks Jardin
Botanico de Bogota Jose Celestino Mutis for partial support
of his research.

ACN = Acetonitrile
ATBC = Acetyl Tri-n-butyl citrate or Acetyl Tri-1-butyl
citrate
BtOH = 1-butanol
CCat = Catalyst or active sites concentration
CCAo = Concentration of CA in the bulk liquid at beginning
of the reaction
CA = Citric acid
Cat = Catalyst/catalytic
dp = Catalyst particle diameter swollen
dp dry = Catalyst particle diameter dry
DBC = Di-n-butyl citrate or Di-1-butyl citrate
De = Eective diusivity of CA in the catalyst particle
Ea = Energy activation (J/mol)
Fmin = Minimization function
H2O = Water
HPLC = High performance liquid chromatography
kj = Reaction rate constant of forward of j (1/s)
koj = Pre-exponential factor of forward reaction j (1/s)
kw,j = Reaction rate global constant of j (1/s)
Keq = Equilibrium constant
MBC = Mono-n-butyl citrate or mono-1-butyl citrate
MSA = Methanesulfonic acid
NC = Number of citric component evaluated
Ni = Number of moles of component i
NT = Total number of moles in the reactor o in the reaction
mixture
PID = Proportionalintegralderivative (control system)
PVC = Polyvinyl chloride
R = Ideal gas constant
RD = Reactive distillation
Rf = Initial molar ratio (alcohol:acid)
r1 = Reaction rate for MBC production or AC consumption
r 2 = Reaction rate for DBC production or MBC
consumption
r3 = Reaction rate for TBC production or DBC consumption
ri = Reaction rate of component i (1/s)
robs = Observed rate of reaction
robs = Observed rate of reaction per mass of catalyst (mol/
kgcat.s)
rv,i = Volumetric reaction rate of component i (1/cm3.s)
Self = Self-catalysis
t = Time
T = Temperature (K)
TBC = Tri-n-butyl citrate or tri-1-butyl citrate
UV = Ultraviolet
V = Volume (cm3)
VP = Catalytic particle volume
wcat = Catalyst loading (% wt)
wcat
= Catalyst loading, kg of catalyst per kg of reacting phase
xacid = Mole fraction of acid species in self-catalytic reaction

ASSOCIATED CONTENT

S Supporting Information
*

The Supporting Information is available free of charge on the

ACS Publications website at DOI: 10.1021/acs.iecr.5b03608.
List of kinetic experiments performed for citric acid
(CA)/1-butanol (BtOH) esterication, kinetic proles
obtained with Amberlyst 70 using dierent particle
diameters, and kinetic proles obtained in experiments
(PDF)

NOMENCLATURE

List of Symbols and Abbreviations

4. CONCLUSIONS
A kinetic study of the esterication of citric acid with 1-butanol
using methanesulfonic acid and Amberlyst 70 resin as a catalyst
was performed. Experimental runs were carried out at dierent
temperatures (353393 K), feed molar ratios (8:1 to 16:1),
and catalyst loadings (0.51.5 wt % equivalent to MSA).
Independent experiments allowed obtaining the chemical
equilibrium constant for the three steps of reaction, and they
were found to be nearly temperature-independent. A
preliminary analysis indicated that self-catalytic reactions had
to be considered during the catalytic process, and the
parameters of a mole fraction-based were obtained for selfcatalytic and catalytic reactions. As expected, the homogeneous
catalyst demonstrated higher activity in the esterication
reaction. After comparison with the whole set of experiments,
the models show good agreement and can be used for process
design and up-scaling purposes.

Article

AUTHOR INFORMATION

Corresponding Author

*Phone: (+57) 1 3165000, ext. 14303. E-mail: aorjuelal@unal.

edu.co.
Notes

The authors declare no competing nancial interest.

H

DOI: 10.1021/acs.iecr.5b03608
Ind. Eng. Chem. Res. XXXX, XXX, XXXXXX

Article

Industrial & Engineering Chemistry Research

xi = Mole fraction of component i

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Greek Letters

= Particle porosity
= Eectiveness factor of reaction
i = Ratio of stoichiometric coecients of component i
cat = Catalyst particle density
sol = Density of reacting phase
= Pore tortuosity
= Thiele modulus
w = WeiszPrater modulus
Subscripts and Superscripts

calcd = Calculate data

exptl = Experimental data
i = component identication
j = reaction step identication (1, 2, or 3)

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DOI: 10.1021/acs.iecr.5b03608
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