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LHHW Kinetics Sterification Acetic Acid PDF
LHHW Kinetics Sterification Acetic Acid PDF
LHHW Kinetics Sterification Acetic Acid PDF
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Abstract
Kinetics of heterogeneous catalysed esterification of acetic acid with isoamyl alcohol was studied with a cation-exchange resin catalyst,
Purolite CT-175, in a stirred batch reactor to synthesise a value added ester, isoamyl acetate. Physical and chemical characterisation of
the catalyst in the form of scanning electron micrographs, Brunauer–Emmett–Teller (BET) surface area measurement, sodium capacity
determination, particle size distribution, and pore size distribution was conducted to assess its performance as a catalyst for esterification
reaction. The density functional theory (DFT) model was used to analyse the pore size distribution data of the catalyst. Effects of various
parameters such as speed of agitation, catalyst particle size, mole ratio of reactants, reaction temperature, catalyst loading, and reusability
of the catalyst were studied to optimise the reaction condition. The equilibrium conversion of acetic acid was found to increase slightly
with an increase in temperature from 333 to 363 K and also it increased appreciably with an excess of isoamyl alcohol in the reacting
system. CT-175 catalyst can be reused without any loss of catalytic performance. The nonideality of each species in the reacting mixture was
accounted for by using the activity coefficient via the use of the UNIFAC group contribution method. The kinetic data were correlated with
the Langmuir–Hinshelwood–Hougen–Watson model. The surface reaction is the rate-limiting step.
2004 Elsevier Inc. All rights reserved.
Keywords: Esterification; Ion-exchange resins; Heterogeneous kinetics; Kinetic modeling; Isoamyl acetate; Reactive distillation; Acetic acid recovery
makes the esterification process difficult to operate econom- processes by combination of reactive distillation and perva-
ically. The presence of azeotropes also poses difficulty in poration for the production of n-butyl acetate by transesteri-
subsequent purification processes. Reactive distillation is an fication of methyl acetate with n-butanol. Pervaporation (us-
effective method that has considerable potential for carry- ing Pervap 2255 membranes) was incorporated with reactive
ing out equilibrium-limited liquid-phase reactions. It is a distillation for further separation of the methanol–methyl ac-
unit operation that combines chemical reaction and distil- etate binary mixture that exists in the distillate stream of
lation within a single vessel, thereby reducing equipment an RDC. This combination of reactive distillation and per-
and recycle costs. Other advantages offered by reactive dis- vaporation shifts the equilibrium towards the desired ester
tillation include high selectivity, reduced energy uses, and product which leads to conversion close to 100% [27].
reduction or elimination of solvents [3]. The production of The ester of isoamyl alcohol, namely, isoamyl acetate,
methyl acetate is a classic example of successful reactive finds wide industrial applications. It is used in large quanti-
distillation [4,5]. This method has also been used for the es- ties as artificial flavouring (preservative in sodas, soft drinks,
terification of a fatty acid [6], as well as being devised as etc., banana-flavoured food items, artificially pear-flavoured
a new method to clean industrial water [7]. However, the food articles), as an additive in cigarettes, and as a solvent for
major disadvantage is that chemical reaction has to show sig- tannins, nitrocellulose, lacquers, celluloid, and camphor. It is
nificant conversion at distillation temperature [8]. also used to manufacture celluloid cements, waterproof var-
To accelerate the reaction rate, catalysts are always em- nishes, artificial silk, leather, or pearls, photographic films,
ployed in a liquid-phase esterification. Despite a strong cat- bronzing liquids and metallic paints, perfuming shoe pol-
alytic effect, the use of homogeneous catalyst, e.g., sulphuric ish and dyeing, and finishing textiles. In the present study,
acid, suffers from drawbacks [3], such as the existence of which is part of a wider project with the aim of designing
side reactions with reactants/products, equipment corrosion, RDC, the kinetic behaviour of the heterogeneously catal-
and having to deal with acid-containing waste. Many solid ysed esterification of acetic acid with isoamyl alcohol is
catalysts, e.g., new solid acids and bases [9], ion-exchange studied in a stirred batch reactor using Purolite CT-175 (an
resins [10,11], zeolites [12–14], and acidic clay catalysts acidic cation-exchange resin) as a catalyst. The experimen-
[15,16], used in heterogeneous reactions have been reported tal reaction rates obtained in this work were correlated by
in the literature. Among them, cation-exchange resins are the heterogeneous kinetic models based on single- and dual-site
most commonly used solid acid catalysts in organic reac- mechanisms. The behaviour of liquid mixtures in the liquid-
tions [10,11]. The heterogeneous macromolecular network phase reactions may deviate markedly from that of the ideal
has thus become a crucial and integral part of industrial solution. The activity coefficients are used in the model to
acid catalysis. Ion-exchange catalysis involves the use of account for the nonideal mixing behaviour of the bulk liquid
ion-exchange resins (IERs) to promote reactions that are phase, and the activity coefficients were predicted using the
normally catalysed by mineral acids and bases. In many UNIFAC group contribution method [28]. Moreover, the ba-
reactions ion exchangers have been found to offer better sic investigation of intrinsic reaction kinetics in the presence
selectivities towards the desired product(s) compared to ho- of an emerging heterogeneous catalyst is very limited for the
mogeneous catalysts. The use of IERs as catalysts holds present system. Hence, we thought that it would be worth-
distinct advantages [17] over catalysis effected by homoge- while to develop a reliable rate expression, which would
neous catalysts: (a) the purity of the products is higher, as be applicable over a wide range of operating conditions,
the side reactions can be completely eliminated or are sig- and could be conveniently used for the design of an RDC.
nificantly less; (b) the catalyst can be easily removed from The emphasis was placed to optimise the reaction condition.
the reaction mixture by filtration; (c) the corrosive envi- The kinetic data were correlated with heterogeneous kinetic
ronment caused by the discharge of acid-containing waste models. The present work is directed towards understanding
is eliminated. IERs also find good applications in reactive the chemistry of the reaction and obtaining a suitable rate
distillation columns (RDCs), wherein they play a dual role expression and checking its validity under different experi-
of catalyst and a form of tower packing [1]. IERs have mental conditions.
been used in esterification [18] as well as the hydrolysis of
methyl acetate in a catalytic distillation column [19]. Fur-
thermore, they have also been used for the esterification of 2. Experimental methods
acetic acid with methanol [20], liquid-phase esterification
of propionic acid with n-butanol [21,22], esterification of 2.1. Materials and catalysts
acetic acid with amyl alcohol [23], esterification of lactic
acid with methanol [24], and esterification of acetic acid Acetic acid (99.8%) and isoamyl alcohol (99%) were
with butanol [25]. Esterification of formic acid, acrylic acid, purchased from Aldrich Chemical Company, Inc. Isoamyl
and methacrylic acid with cyclohexene in batch and distil- acetate (> 99% purity) was purchased from Fisher Scien-
lation column reactors using ion-exchange resins as cata- tific, UK. The purity of the chemicals was verified by gas
lysts was studied by Saha and Sharma [26]. Very recently, chromatographic analysis, and they were used without fur-
Steinigeweg and Gmehling [27] reported transesterification ther purification. The cation-exchange resin used in this
176 H.T.R. Teo, B. Saha / Journal of Catalysis 228 (2004) 174–182
of acetic acid was observed. Hence, we can infer that CT- Table 2
175 resin can be used repeatedly for this reaction without UNIFAC activity coefficient parameters
sacrificing catalytic activity. According to the manufactur- Component Liquid mole fraction, x Activity coefficient, γ
er’s specification, the lifetime of ion-exchange resin catalyst Acetic acid 0.147 0.872
is normally about 6000–10,000 operating hours when used Isoamyl alcohol 0.476 1.060
at elevated temperatures. Isoamyl acetate 0.189 1.836
Water 0.189 3.259
4.2.6. Kinetic modelling
The kinetics of esterification reaction can be expressed the experimental and calculated reaction rates using the
using a simple pseudohomogeneous model or more com- equation [24]
plex models based on the Langmuir–Hinshelwood–Hougen–
Watson mechanism (LHHW) or the Eley–Rideal (ER) mech- SRS = (rexp − rcalc )2 , (4)
anism [23,25,38,39] in the absence of any intraparticle dif- samples
fusional limitation. Pseudohomogeneous first- and second-
where SRS is the minimum sum of residual squares result-
order models are applicable to many ion-exchange resin-
ing in the fitting procedure, and r is the reaction rate. The
catalysed reactions. These models are applicable for highly
subscripts exp and calc denote experimental and calculated
polar reaction medium. As all the experiments were con-
values, respectively.
ducted with ion-exchange resin catalyst, heterogeneous ki-
The LHHW model is applicable whenever the rate-
netic models, e.g., LHHW and ER models were applied for
determining step is the surface reaction between adsorbed
correlating the kinetic data available at different tempera-
molecules. On the other hand, the ER model has been ap-
tures, catalyst loadings and mole ratios of acetic acid to
plied if in the rate-limiting step, surface reaction takes place
isoamyl alcohol.
between one adsorbed species and one nonadsorbed reac-
From a statistical standpoint, the model with the least sum
tant from the bulk liquid phase. Moreover, because of the
of squares and random residuals would be the most suitable.
strong affinity of resins for water, the activity of water in the
Moreover, it would be essential that the parameters of the
catalyst gel phase, where the reaction occurs, is distinctly
model had a physicochemical meaning and the activation en-
different from that in the liquid phase [23]. The rate expres-
ergy was positive.
sion for the ER model is
Reaction rates were calculated by the differential methods
0
as proposed by Cunill et al. [40]. In the case of this hetero- Af −ERT aA aB − A r
Af aC aD
geneously catalysed reaction, the equation −rA = , (5)
(1 + KB aB + KD aD )
dXA and that for the LHHW model is
(−rA )V = NAO (2)
dt 0
Af −E aA aB − Ar
Af aC aD
was used, where −rA is the reaction rate of acetic acid, V is −rA =
RT
, (6)
the reacting mixture volume, NAO is the initial number of (1 + KB aB + KD aD )2
moles of acetic acid, XA is the conversion of acetic acid, where Af and Ar are the Arrhenius preexponential factors
and t is the time of the reaction. for the forward and reverse reactions, respectively, E0 is the
To account for the nonideal mixing behaviour of the bulk activation energy of the reaction, R is the gas constant, and T
liquid phase, the activity of the components was taken into is the temperature of the reaction. Parameters KB and KD are
account instead of the concentration of the components. The the adsorption equilibrium constants for amyl alcohol and
UNIFAC group contribution method was used for estimation water, respectively.
of the activity coefficients [41]. Table 2 gives the UNIFAC It is to be noted that the affinities of CT-175 resin cata-
activity coefficient parameters for all four components at a lyst for water and isoamyl alcohol are stronger than those
particular composition. for acetic acid and isoamyl acetate and hence the adsorption
The equilibrium constant was calculated from the com- terms for acetic acid and isoamyl acetate are neglected in the
ponent concentrations at equilibrium through the equation LHHW and ER models. Similar models were also proposed
by Lee et al. [23] for the study of kinetics of catalytic ester-
aC aD xC xD γC γD
Keq = = , (3) ification of acetic acid and amyl alcohol over Dowex 50W
aA aB eq xA xB eq γA γB eq
catalyst without taking the adsorption terms for both acetic
where Keq is the equilibrium constant of the reaction, a is acid and ester into consideration.
the activity of the component, x is the mole fraction of the The adsorption equilibrium constant for species i, Ki can
component, and γ is the activity coefficient of the compo- be defined as the ratio of the adsorption rate constant ka,i to
nent. Subscripts A, B, C, and D denote acetic acid, isoamyl the desorption rate constant, kd,i :
alcohol, isoamyl acetate, and water, respectively.
ka,A
The parameters for the different models were estimated KA = , (7)
by minimising the sum of residual squares (SRS) between kd,A
H.T.R. Teo, B. Saha / Journal of Catalysis 228 (2004) 174–182 181
ka,A
A + S A∗
kd,A
ka,B
B + S B∗
kd,B
k1
A + B C∗ + D∗
∗ ∗
k2
kd,C
C∗ C + S
ka,C
kd,D Fig. 9. Comparison between experimental and calculated (with LHHW
∗
D D+S
ka,D model) concentration profiles. Feed mole ratio (alcohol to acid), 2:1; tem-
Asterisks indicate the adsorbed species perature, 343.15 K; catalyst, CT-175; catalyst loading, 5% (w/w); stirrer
S represents a vacant active catalyst site speed, 500 rpm.
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