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Chemical Engineering Communications
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Production of Isoamyl Propionate: Use of Amberlyst - 15
in batch reactor and packed bed reactor
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Journal: Chemical Engineering Communications
Manuscript ID Draft
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Manuscript Type: Research Paper
Date Submitted by the

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Author:
Complete List of Authors: Mahajan, Yogesh; Dr. B. A. Technological University, Lonere, Chemical
Engineering
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Katariya, Amit; Praj Matrix, Pune, Chemical Engineering

Bhandare, Rajendra; Dr. B. A. Technological University, Lonere,
Chemical Engineering
Esterification, propionic acid, isoamyl alcohol, Amberlyst 15, kinetic

Keywords:
model, regression
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URL: http://mc.manuscriptcentral.com/ Email: wngill@sfo.com

Page 1 of 38 Chemical Engineering Communications
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3 Production of Isoamyl Propionate: Use of Amberlyst - 15
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6 in batch reactor and packed bed reactor
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8 Yogesh. S. Mahajan a*, R. B. Bhandare a, and A. Katariya b
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11 a Chemical Engineering Department, Dr. B. A. Technological University,
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Lonere, Tal. Mangaon, Dist. Raigad, Maharashtra, India, 402103.
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b Amusavi MTC Private Limited, Chinchwad, Pune, Maharashtra, India 411019
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21 * e- mail: ysmahajan@dbatu.ac.in
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26 Abstract
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29 Esterification of isoamyl alcohol and propionic acid is presented in this work. Batch
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31 experiments were performed initially to obtain the kinetics. Regression was then done to
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obtain a kinetic model. Langmuir Hinshelwood Houghen Watson model with activities was
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36 found to represent the data well. Packed bed experiments were performed further in order to
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38 assess the possibility of continuous operation.
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Keywords: Esterification, propionic acid, isoamyl alcohol, Amberlyst 15, kinetic model,
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47 regression.
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Chemical Engineering Communications Page 2 of 38
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3 INTRODUCTION
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Exploring alternative catalysts, routes and processes for important chemicals have
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9 always been an area of active research for the chemical engineering fraternity. In addition,
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11 replacement of the fossil fuel based chemicals by bio-alternatives is also gaining importance,
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13 of late. Fusel oil is one such alternative, which is a mixture of isoamyl alcohol and amyl
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16 alcohol (Leyva et al. 2013, 2015) Isoamyl alcohol is produced by fermentation. Though
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18 isoamyl alcohol can be used in fusel oil compositions, it can be effectively used to produce
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20 important chemicals, thus adding value to the products and / or processes. Isoamyl propionate
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23 (IP), an ester, is produced by reacting isoamyl alcohol with propionic acid. IP has several
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applications like use in flavor industry, due to its pineapple aroma. The simplest route to
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27 produce isoamyl propionate is the direct esterification of alcohol and acid in the presence of
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acid catalyst (scheme 1):
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33 Scheme 1
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36 This reaction is reversible in nature and hence the conversion is equilibrium
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38 limited. Naturally, in order to improve conversion, one has to adopt means like increasing
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temperature, use of catalyst or separation of components. Reactive separations (RS) which

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43 involve reaction and separation occurring in a single vessel have been proven to be
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45 advantageous for such reactions (Tayler and Krishna 2000, Hiwale et al. 2003).Reactive
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47 distillation (RD), reactive extraction (RE) and reactive chromatography (RC) are possible
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alternate processes to achieve this. Out of these, RD is applicable but it is highly heat
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52 intensive and hence can sometimes be economically unattractive (Mahajan et al 2008a,
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54 Mahajan et al 2008b, Talnikar and Mahajan 2014, Shinde et al. 2015, Talnikar et al. 2017,
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Talnokar et al.2018). Reactive extraction, although not heat intensive, may bring in
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59 difficulties in choosing the correct entertainer and in the separation of entertainer - rich and
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3 entertainer - lean (extract and raffinate) phases. RC can be an attractive alternative since it
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6 employs differences in adsorption-desorption of chemical reagents on external solid phase,
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8 which can also act as catalyst.
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11 Many researchers have studied reactions of amyl alcohol in the past. For example,
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13 amyl alcohol was reacted with acetic acid using Dowex - 50W (Lee et al. 2000, Pang et al.
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16 2008, Qi and Malone et al. 2011). Similarly, amyl alcohol was esterified with propionic acid
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18 in the presence of several ion exchange resins (IER, Amberlyst - 15, Dowex - 50W and
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20 Amberlyst IR 120) (Erdem et al 2006).Amyl alcohol was esterified with hexanol using RD
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23 wherein design and control study was performed (Wu et al 2013). RE of propionic acid was
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done using tri-n-octylamine (Keshav et al. 2010) and Tri-n-butyl phosphate (Kumar et al.
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27 2011).
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30 The presently selected reaction scheme of producing isoamyl propionate by
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33 reacting propionic acid with isoamyl alcohol was studied by Levya et al. (2013) using
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35 Amberlyst 70 as the catalyst. A heterogeneous kinetic model based on NRTL using activities
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37 was used for regression. Effect of catalyst loading, reaction temperature and change in mole
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ratio were taken into account and a good match of the model and experiments was achieved.
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42 Further, Leyva et al. (2015) performed this reaction using RD environment. Equilibrium
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44 stage model (EQ) was used to predict the experimental data and an excellent match was
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observed. Large conversion and purity were obtained using RD. It is thus evident that use of
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49 IERs is established for this important synthesis, especially using RD.
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52 The literature, however, does not have a mention of the enhancement of the
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54 reaction performance by the use of reactive chromatography (RC) or packed bed reactor. As
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stated, with a RC or a packed bed process, the heat requirement will be much lesser compared
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59 to RD. This may bring in the much needed economic advantages. Hence, this work has used
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3 packed bed for this system. Amberlyst - 15 (A - 15) is shown to be an effective catalyst for
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6 many esterification reactions (Sharma et al. 1993, Hiwale et al. 2004) and the present work
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8 uses A - 15 as the catalyst. This work has undertaken to explore this reaction in batch reactor
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10 followed by the packed bed runs. The purpose of the work on packed bed is only to explore
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the possibility of application to this important synthesis.
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16 Materials and Methods
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19 Propionic acid and isoamyl alcohol (99% each) were supplied by Thomas Baker.
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21 Isoamyl propionate (IP, > 98%) was provided by Tokyo Chemical Industries, Japan. Ion
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exchange resin A - 15 was purchased from Rohm and Haas Co. and its physical properties are
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26 follows: moisture holding capacity 48 to 52 %, particle size 0.6 to 0.85 mm, average pore
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28 diameter: 300 Ao, total pore volume 0.40 mL / g, maximum operating temperature 120° C.
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30 T - 63 and T - 66 were purchased from Thermax Ltd., whereas Indion - 190 was obtained
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33 from Ion Exchange India Ltd. Properties of all the catalysts are available elsewhere (Mahajan
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35 et al. 2008a, Shinde et al. 2015).

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37 Analysis was done by titration as well as with gas chromatography (GC). Acid
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content of the reaction mass was calculated by titration with NaOH using phenolphthalein
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42 indicator. NaOH solution was standardized using oxalic acid. The accuracy of titration was
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44 determined to be ~ 98%. Gas chromatograph (GC) was used to identify compositions of
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alcohol, ester and water. Nucon GC (model 5765) with TCD was used with Porapack - Q
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49 column (length 1.82 m, O.D. 1/8 inch, made up of SS). Accuracy of the results obtained with
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51 actual weights of components taken initially was seen to be > 99%. The GC program
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53 consisted of the following: oven temperature 2300C, injector and detector temperatures
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56 1600C. Separate peaks were obtained for different components. Mass of all components in the
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58 sample was obtained by conversion of the area obtained through calibration using isopropyl
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3 alcohol as internal standard as well as by titration. The amounts obtained by GC and by
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6 titration were matched and the accuracy of match was observed to be ≥ 97%.
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10 Batch kinetics
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Batch kinetic experiments were performed in a glass batch reactor
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15 (500 ml) fitted with stirrer, sample collector, inlet ports, thermocouples and constant
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17 temperature oil bath (± 10 C). Catalyst was dried overnight at 1050 C under vacuum. In a
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typical experiment, calculated quantity of the acid was placed in the reactor. Simultaneously,
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22 required quantity of alcohol and computed quantity of catalyst were kept in two separate
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24 containers in the same oil bath which was set to the desired temperature. As soon as the
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26 desired temperature was reached, the alcohol and the catalyst were quickly poured in the
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29 reaction vessel, while assigning this instant of time as ‘zero time’. At this time and after
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31 regular intervals of time, samples were collected and analyzed as previously described. Care
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33 was taken to make sure that the total sample quantity withdrawn for analysis is small enough
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so as not to affect the mass balance.
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38 A blank run was conducted (without catalyst) and it was observed that almost no
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40 reaction occurs. Generally, batch kinetics involves evaluation of the effect of parameters on
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the rate of reaction and reaction performance. Typically, mass transfer limitations (speed of
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45 agitation and size of catalyst) and the effect of various parameters (temperature, catalyst
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47 amount and type, mole ratio of reactants etc.) are evaluated. In IER catalyzed reactions, it
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49 becomes further necessary to determine the effect of initial water present on the course of
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52 reaction. Additionally, repeatability runs and reuse runs are also performed.
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54 The present work follows the same sequence of experiments.
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3 Effectiveness of different catalysts
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6 Four different catalysts (IERs) were used with a catalyst loading of 5% w/w (catalyst /
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8 propionic acid), mole ratio (1: 3 :: acid: alcohol) at 700C and stirrer speed of 900 rpm. Figure
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10 1 shows that T - 66 shows slightly better performance over other catalysts. Catalysts T - 66
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and T - 63 are not easily available in local market specially in smaller quantities and their
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15 supply is not thus guaranteed. It can be seen from figure 1 that conversion obtained using
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17 T - 66 and A -15 is almost similar. A - 15 is a well-known catalyst for several reactions
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including esterification (Shinde et al. 2015, Talnikar et al. 2018). Also, A-15 is known to be
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22 used in several RD, RE and RC applications (Kiss et al 2006, Popken et al. 2006, Gyani et al
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24 2008, Reddy et al. 2014) and hence this work has used A-15. It may be noted that A - 70 and
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26 A - 15 have different properties. Also the cost of A - 70 is much higher than A - 15.
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31 Assessing mass transfer limitations
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33 In order to make sure that the reaction does not have mass transfer limitations,
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generally two types of runs are performed: effect of speed of agitation and effect of size of
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38 catalyst on the course of reaction. For the reaction to be intrinsically kinetically controlled,
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45 a) Effect of speed of agitation

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47 Figure 2a shows the effect of speed of agitation on conversion. For these runs, the
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49 following reaction conditions were used: 343 K, catalyst loading 5%, mole ratio of 1: 3 with
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52 A-15 as the catalyst. It is seen from the Figure 2a that for a wide range of agitation
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54 (300 - 1100 rpm), there is very negligible change in conversion. Hence all the further runs
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3 b) Effect of catalyst size
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6 The dried catalyst was crushed and was screened to obtain different sizes by passing
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8 through various sieves. Figure 2b shows the result of the runs conducted under the condition
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10 stated. It is seen that almost negligible change in conversion is observed. Thus mass transfer
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limitations are absent and the reaction can be said to be intrinsically kinetically controlled.
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15 Weisz - Prater Criterion (CWP) was also calculated for present synthesis. The value of CWP
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17 was found to be 0.02 (0.019). Since CWP << 1.0, mass transfer effects can be assumed to be
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negligible (Yadav et al. 2001, Fogler, 2006).
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24 Effect of different parameters
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26 Kinetic experiments using ion exchange resins (IER) are generally studied by
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29 evaluating the effect of different parameters on the course of reaction. These parameters are
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31 temperature, catalyst loading, mole ratio and initial water content.
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a) Temperature
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38 As temperature increases, movement of the molecules increases, thereby
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40 increasing interactions and hence usually conversion increases. Temperature was changed
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from 333 - 373 K. Figure 3a shows that as the temperature increases, the conversion also
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47 temperature needs to be limited. IERs have upper temperature limit (Shinde et al. 2015,
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49 Talnikar et al.2018). It is seen that at 343K, @ 55% conversion is achieved. Hence further
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52 runs were conducted at this temperature.
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3 b) Mole ratio
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6 Increasing mole ratio of reactants generally favours the conversion of the limiting
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8 reactant. Mole ratio was changed from 1: 1 to 1: 5. It is seen from Figure 3b that as the mole
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10 ratio of acid to alcohol increases, the conversion also increases. However, after the mole ratio
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of 1: 3, this effect is not significant. Hence, further runs were carried out with 1: 3 mole ratio.
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Since catalyst favours a reaction, it is natural that more the catalyst loading, more
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22 will be the conversion. Figure 3c shows that as the catalyst loading increases, conversion also
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24 increases. However, due to economic view point, it is beneficial to use smaller quantity of
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26 catalyst and hence further runs were carried out with 5% catalyst loading, where @ 55%
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29 conversion was obtained in 5 h.

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33 d) Initial water present
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IERs have strong affinity towards water (Aragon et al. 1994) and hence the
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38 conversion reduces due to inhibition. In order to assess this effect, water was initially added
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40 to reaction mass based on weight of catalyst (w/w). Figure 3d shows that as the initial water
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content increases, conversion decreases drastically (55% with no water to 30% when 100%
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45 w/w water based on catalyst was added). This implies that if water is separated from reaction
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47 mass, then the conversion will increase due to the reduced catalyst inhibition. RD, RE as well
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49 as RC can thus be effectively applied to this reaction scheme. RD has been shown to be
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52 beneficial for this process (Leyva et al 2013, 2015). No work on RC or packed bed is
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3 e) Catalyst reusability
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6 Ability of the catalyst to be reused several times is advantageous. Catalyst A - 15 was
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8 checked for the possibility of its reuse. Figure 4 (a) shows the conversion obtained after three
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10 reuses of the catalyst. For these runs, after the previous run, the catalyst was filtered, washed,
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dried and then used as previously discussed. It is seen that only negligible loss in the catalytic
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15 activity occurs. This proves that A - 15 possesses the unique ability of catalyzing the reaction
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22 f) Long run
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24 A system is said to reach a state of (pseudo -) equilibrium when there is no net change
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26 in the concentration. Figure 4b pertains to the run carried out for a sufficiently long time. At
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29 equilibrium, the conversion is seen to be ~ 75 (74.8) %. Use of reactive separation (RS) like
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31 RD or RC will help improve the conversion beyond equilibrium.
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34 Kinetic modeling
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36 For utilization of the kinetic data for design and scale-up, it is helpful to develop a
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39 kinetic model. This is also helpful in process intensification activity with processes like RD,
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41 RE or RC. Different models like pseudo - homogeneous (PH), Elay Rideal (ER) and
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43 Langmuir Hinshelwood Houghen Watson (LHHW) were attempted for the fit. PH model fit
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46 was inaccurate. ER model and LHHW model fits were better but that by LHHW model
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48 yielded a better fit. The model equation is represented in the form of activities of the
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50 components involved. The model expression is given by Equation 1.
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Equation 1,
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55 In the above equation, the constant kc is an Arrhenius type forward rate constant. Ec is the
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57 activation energy. Equation 2 represents the expression for rate constant.
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59 Equation 2,
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3 KM, is the temperature dependent reaction equilibrium constant, expressed as equation 3.
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6 Equation 3,
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8 Kd’s are the adsorption equilibrium constants for each component respectively.
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10 Generally, water is very strongly adsorbed on resin. Many researchers have proven that IER
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catalysed reactions are strongly influenced by adsorption desorption of water. Although other
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15 components may also adsorb - desorb, the magnitude is generally smaller and hence the
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17 adsorption coefficient of water is usually taken to be temperature dependent as an initial
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guess. If this does not help to fit the data, then temperature dependency of other components
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22 is also considered subsequently. In the present case, the adsorption of water was considered
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24 to be temperature dependent with the expression given by the equation 4. It is seen that with
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26 this assumption, the experimental data is predicated reasonably well by the model.
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29 Equation 4,
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31 Batch kinetic model was implemented in MATLABTM programming environment. The
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33 ordinary differential equations (ODEs) representing the batch kinetic model were solved
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using ODE15s solver option of MATLABTM. The calculated error between the predicted and
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38 experimental values was optimized using FMINSEARCH function of MATLABTM. Values
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40 of various parameters thus obtained are listed in Table 1. Respective binary interaction
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parameters for implementing the UNIQUAC activity model are given in
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45 Table 2.
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47 Table 1,
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49 Table 2,
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52 In Figure 5 (a) to 5 (d), the performance of the model predictions is compared with the
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54 obtained experimental data. Variation in temperature, catalyst loading, initial molar ratio of
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56 the reactants and the initial water in the catalyst were used in the model prediction and
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analysis. A good fit of the data is obtained, which can be seen from Figure 5 (e), the parity
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3 plot, showing the value of R2 as 0.993. This makes the model useful in various simulation
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6 experiments involving reaction and downstream processing. This model can also be used in
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8 RS environment because the kinetics will remain unaltered.
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Packed bed reactor studies are discussed next as the initial step towards process
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15 intensification for this important chemical. The purpose of these experiments is only to
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17 establish whether RC or packed bed reactor can help the reaction or not. It is seen through
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batch experiments that ion exchange resins and especially Amberlyst - 15 can be effectively
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22 used for the synthesis of isoamyl propionate. About 55% conversion was obtained with
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24 Amberlyst - 15 for a catalyst loading of 5 % with a mole ratio of 1: 3 of acid to alcohol at 70 o
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26 C (343 K) in 5 h. IER have strong affinity towards water. So when reaction occurs, the water
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29 formed would be preferentially adsorbed over the catalyst bed. Thus it is expected that in RC
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31 environment or packed bed reactor configuration, water will be separated from the reaction
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33 mass. This will help by improving the conversion by separating the water from reaction mass.
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In order to explore the possibility of making the process continuous, the reaction was carried
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Packed bed reactor experiments
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45 A column of glass (2 cm diameter and 50 cm height) was used for this purpose. The
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47 column was provided with a sintered plate to retain the catalyst and thermocouples. A
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49 peristaltic pump, calibrated for the mixture, was used for feeding the mixture of propionic
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52 acid and isoamyl alcohol in given proportion. The acid and alcohol were mixed in a separate
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54 feed tank. The column was filled with the desired quantity of catalyst. Hot oil was circulated
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56 through the jacket to provide necessary heat. Initially, only alcohol was circulated through
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pump. As soon as the desired temperature was reached, the mixture of alcohol and acid
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3 (i.e. feed mixture) was passed through column. The exit samples were collected at regular
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6 intervals of time and were analysed with GC as well as titration to find out the compositions.
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8 Temperature was also recorded. In the packed bed column, when the mixture passes through
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10 the catalyst, reaction occurs. As reaction proceeds, more and more water was formed but
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since ion exchange resins have strong affinity for water, the formed water is strongly
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15 adsorbed, whereas the unreacted acid, and alcohol and the formed product flow out.
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It is shown in this work that IERs and specially A - 15 can be effectively used for the
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22 important synthesis of isoamyl propionate. It is further shown through packed bed

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24 experiments that the process can be made continuous at much less conditions compared to
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26 RD. The conversion obtained in 3 hr in a packed bed experiments is much higher than that of
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29 batch experiments (@ 67% compared to @ 33%). This shows the applicability of this
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31 technique for possible process intensification with additional advantages. The future work
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33 would comprise of the scaled up continuous packed bed in the RC environment. This will be
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explored and will form the basis for further communication.
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38 Several runs were performed. Table 3 shows the details of these runs. Figure 7 and 8
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40 show the temperature and composition profile for run no. 2. The conversion obtained for this
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run was 53.10 % in three hours. For the same conditions, the conversion obtained in batch
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45 mode for three hours was less (32.55%). Thus, it is seen that the process can be made
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47 continuous and also that better conversion is obtained.
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49 Figure 6,
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52 Table 3,
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54 Figure 7,
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56 Figure 8,
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6 CONCLUSION
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8 Esterification of propionic acid was carried out with isoamyl alcohol using
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10 A - 15 as the catalyst. In three hours, in batch reactor the maximum conversion obtained was
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32.55% under the conditions studied therein. A kinetic model was obtained by regressing the
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15 data. Using activities, Langmuir Hinshelwood Houghen Watson (LHHW) model described
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17 the data well. Further, in order to make the process continuous, packed bed experiments were
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performed. It was observed that in packed bed reactor, in three hours of operation the
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22 conversion obtained was increased to 50 % whereas with batch reactor it was 32.55 %. Thus
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24 more than twice conversion was obtained using packed bed reactor, showing that this
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26 technique can prove to be a better option.
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3 NOMENCLATURE
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CWP - Weisz- Prater Criterion
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10 Ec - activation energy (kJ/mol)
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13 kc - Arrhenius type forward rate constant
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16 Kd - respective adsorption equilibrium constants for each component
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19 KM, - temperature dependent reaction equilibrium constant,

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22 ABBREVIATIONS
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25 A - 15 - Amberlyst -15
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CW in - cold water inlet

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CW out - cold water outlet
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exp. - experimental
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38 IER - ion exchange resin
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41 RC - reactive chromatography
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44 RD - reactive distillation
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47 RE - reactive extraction
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50 RS - reactive separation
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T- temperature
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57 Simu - simulation
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References
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7 1. R. Taylor and R. Krishna, Modeling reactive distillation, Chem. Eng. Sci., 2000, 55, ,
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9 5183 – 5229, doi: 10.1016/S0009-2509(00)00120-2
10 2. V. Shinde, G. N. Patil, A. Katariya and, Y. S. Mahajan, Production of tetrahydrofuran by
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12 dehydration of 1, 4-butanediol using Amberlyst-15: Batch kinetics and batch reactive
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14 distillation, Chem.Eng. Proc.: Proc. Inten., 2015, 95, 241 - 248,
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doi:/10.1016/j.cep.2015.06.016
17 3. R. S. Hiwale, N. V. Bhate, Y. S. Mahajan and S. M. Mahajani, Industrial Applications of
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19 Reactive Distillation: Recent Trends, Ind. Jou. of Chem. Reac. Eng. 2004, 2, 1 – 52,
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21 doi:/10.2202/1542-6580.1109
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22 4. V. D. Talnikar, Y. S. Mahajan, Recovery of acids from dilute streams:A review of

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24 process technologies, Kor.Jour. of Chem.Eng., 2014, 31, , 1720 – 1731, doi:
ee
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26 /10.1007/s11814-014-0202-4
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28 5. V. D. Talnikar, O. A. Deorukhkar, A. Katariya, Y. S. Mahajan, Value-Added
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29 Esterification for the Recovery of Trifluoroacetic Acid: Batch Kinetics and Reactive
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31 Distillation studies, Chem. Eng. Comm. 2017, 204, 356 – 364, doi
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33 :/10.1080/00986445.2016.1271795
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6. W. Qi and M. F. Malone, Semibatch Reactive Distillation for Isopropyl Acetate Synthesis,
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36 Ind. Eng. Chem. Res., 2011, 50, 1272 – 127, doi:10.1021/ie1003 54x
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38 7. M. J. Lee, H. T. Wu , H. M. Lin, Kinetics of Catalytic Esterification of Acetic Acid and
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40 Amyl Alcohol over Dowex, Ind. Eng. Chem. Res., 2000, 39, 4094 - 4097,
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41 doi:10.1021/ie0000764
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43 8. X. Y. Pang, P. Lv, Y. Yang, H. Ren, and F. Gong, Esterification of Acetic Acid with
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45 Isoamyl Alcohol over Expandable Graphite Catalyst, E.J. Chem., 2008, 5, 149 – 154, doi
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:/10.1155/2008/941953
48 9. Y. Wu, H. Lee, C. Lee, H. Huang, I. Chien, Design and Control of Thermally-Coupled
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50 Reactive Distillation System for Esterification of an Alcohol Mixture Containing n-Amyl
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52 Alcohol and n-Hexanol, Ind. Eng. Chem. Res., 2013, 52, 17184 – 17197, doi:/10.1021/
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IE 4006035)
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55 10. F. Leyva, A. Orjuela, A. Kolah, C. Lira, D. Miller, G. Rodríguez, Isoamyl propionate
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57 production by reactive distillation, Sep. and Pur. Tech., 2015, 146, 199 – 212, doi:
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59 10.1016/j.seppur.2015.03.039
60
15
1
2
3 11. F. Leyva, L. Fernando, A. Orjuela, A. Lira, D. Miller, G. Rodríguez, Kinetics of
4
5 propionic Acid and Isoamyl Alcohol Liquid Esterification with Amberlyst 70 as Catalyst,
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7 Ind. Eng. Chem. Res., 2013, 52, 18153 - 18161, doi: 10.1021 / ie402349t/
8
9
12. A. Keshav , K. Wasewar, S. Chand, Reactive extraction of propionic acid using tri-n-
10 octylamine, Chem. Eng. Comm., 2009, 197, 606 - 626, doi: 10.10 80/
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12 09864400903249015
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14 13. S. Kumar, D. Datta, B. Babu, Differential Evolution Approach for Reactive Extraction of
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Propionic Acid Using Tri-n-Butyl Phosphate (TBP) in Kerosene and 1-Decanol, Mat.
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17 Man. Proc., 2011, 26, 1222 – 1228, doi 10.1080/042 6914. 2011. 55 1965
18
Fo
19 14.B. Erdem, M. Cebe, Kinetics of esterification propionic acid with n - amyl alcohol in the
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21 presence of cation exchange resins, Kor.J.Chem.Engg., 2006, 23, 896 - 901,doi:
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22 10.1007/s11814-006-0005-3
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24 15. T. Polpken, S. Steinigeweg and, J. Gmehling, Synthesis and Hydrolysis of Methyl
ee
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26 Acetate by Reactive Distillation Using Structured Catalytic Packings: Experiments and
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28
Simulation, Ind. Eng. Chem. Res., 2001, 40, 1566 – 1574, doi: 10.1021/ie0007419
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29 16. A. Kiss, F. Omota, A. Dimian, and G. Rothenberg, The heterogeneous advantage:

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31 biodiesel by catalytic reactive distillation, Top. in Catal., 2006, 40, 141 – 150, doi:/ 10.
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33 1007 /s11244-006-0116-4
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17. V. Gyani and S. M. Mahajani, Reactive Chromatography for the Synthesis of 2
iew
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36 Ethylhexyl Acetate, Sep. Sci. and Tech., 2008, 43, 2245 – 2268, doi:/10.1080/0149 6390
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38 802118871
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40 18. B. Reddy and S. M. Mahajani, Feasibility of Reactive Chromatography for the Synthesis
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41 of n-Propyl Acetate, Ind. Eng. Chem. Res.,2014, 53, 1395 – 1403,doi:/10.1021/ie403533t

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43 19. Y. S .Mahajan, R. S. Kamath, P. S .Kumbhar, S. M. Mahajani, Self-condensation of
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45 cyclohexanone over ion exchange resin catalyst: Kinetics and Selectivity aspects, Ind.
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Eng. Chem. Res., 2008, 47, 25 – 73, doi: 10.10 21/ie061275b
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48 20. G. D. Yadav, A. V. Joshi, Etherification of tert-amyl alcohol with methanol over ion
49
50 exchange catalyst, Org. Pro. Res. Dev., 2001, 5, 408 – 414, doi:10.1021/op010018
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52 21. J. Aragon, J. Vegas, and L. Jodra, Self-Condensation of Cyclohexanone Catalyzed by
53 Amberlyst-15. Study of Diffusional Resistances and Deactivation of the Catalyst, Ind.
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55 Eng. Chem. Res., 1994, 33, 592 – 599, doi: 10.1021/ie00027a016
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57 22. M. M. Sharma, A. Chakrabarti, Cation ion exchange resin as catalyst, Rea. Poly. , 1993,
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20, 1 – 45, doi:0923-1137/93/
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3 23. Y. S. Mahajan, A. K. Shah, R. S. Kamath, N. B. Salve, S. M. Mahajani, Recovery of tri-
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5 luoroacetic acid from dilute aqueous solutions by reactive distillation, Sep. Pur. Tech.,
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7 2008, 59, 58 - 66, doi/10.1016/j.seppur.2007.05.027
8
9
24. V. D. Talnikar, O. A. Deorukhar, A. Katariya, Y. S. Mahajan, Intensification of the
10 production of 2 ethylhexyl aceatate: Batch kinetics and reactive distillation, Int.J Chem.
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12 Rea. Eng., 2018, 16, 1- 15, doi.org/10.1515/ijcre-2017-0134
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14 25. H. S. Fogler, Elements of Chemical Reaction Engineering, Prentice –Hall, Inc. New
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Jersey, U.S.A., 2006.
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Fo
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4 Scheme
5 1
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11  a a 
12 Wcat  kC  a PAa IAA  IAP WATER 
13  KM  Equation 1
R 
14
15
1  K d , PAa PA  K d , IAAa IAA  K d , IAp a IAP  K d ,WATER aWATER 2
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17
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Fo
Ec
19  Equation 2
20
k c  kC , 0 e RT
21
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22 EM
 Equation 3
23 KM  KM, 0  e T
24
ee
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EdW
26  Equation 4
27 K d , Water  K d , W 0  e T
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25 Figure 1. Performance of different catalysts: conversion of limiting component (PA), catalyst as indicated;
26 temperature 343 K, catalyst loading 5 % (w/w of PA), mole ratio 1:3 (PA: IA)
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60 URL: http://mc.manuscriptcentral.com/ Email: wngill@sfo.com
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21 Figure 2. (a) Effect of agitation speed on conversion (A - 15; 343 K; catalyst loading 5 %; mole ratio 1: 3)
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21 Figure 2. (b) Effect of catalyst size on conversion (A - 15; 343 K; catalyst loading 5 %; mole ratio 1: 3)
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21 Figure 3. (a). Effect of temperature on conversion (A - 15; catalyst loading 5 %, mole ratio 1:3)
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21 Figure 3. (b). Effect of mole ratio on conversion (A - 15; 343 K; catalyst loading 5 %)
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22 Figure 3. (C). Effect of catalyst loading on conversion (A - 15; 343 K; mole ratio 1:3)
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21 1:3)
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21 Figure 4. (a). Reusability of catalyst (A - 15; 343 K; catalyst loading 5%; mole ratio 1: 3)
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21 Figure 4. (b). Long run (A - 15; 343 K; catalyst loading 5%; 343 K; mole ratio 1: 3)
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22 Figure 5. (C). Kinetic model performance for change in the initial mole ratio of reactants (propionic acid:
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22 Figure 7. Temperature profile for run no 2 (Table 3) (343 K, mole ratio1:1, catalyst 30 gm, flow rate 4ml/
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22 Figure 8. Concentration profile for run no 2 (Table 3 ) (343 K, mole ratio 1:1, catalyst 30 gm, 4 ml / min)
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3 Table 1. Values of kinetic parameters obtained by regression. (PA: Propionic acid, IAA: iso -
4
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6 amyl alcohol, IAP: iso - amyl Propionate)
7
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9 kC,0 4.29E+12 mol/g.C/hr Ec 75.392 kJ/mol
10
11 KM0 3.32E+03 EM 242.11 K
12
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Kd,PA 7.53
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16 Kd,IAA 6.33E-05
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18 Kd,IAP 8 × 10- 4
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3 Table 2. UNIQUAC activity coefficient parameters
4
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6 Component i PA IAA PA PA IAA IAP
7
8 Component j Water Water IAA IAP IAP Water
9
10 BIJ [K] -295.53 -102.01 -271.97 131.34 72.24 -543.53
11
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13 BJI [K] 140.02 --173.95 193.16 -295.50 -175.09 -187.38
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10 Table 3: Details of runs (* Conversion after 3 hrs, ** Max conversion @ 67 % whereas in
11
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15 Run no. Temperature Flow rate, Catalyst loading Conversion
16
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18 (K) (ml / min) (g) % (*, **)
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Chemical Engineering Communications

Journal: Chemical Engineering Communications

Manuscript Type: Research Paper

Date Submitted by the

Katariya, Amit; Praj Matrix, Pune, Chemical Engineering

Esterification, propionic acid, isoamyl alcohol, Amberlyst 15, kinetic

URL: http://mc.manuscriptcentral.com/ Email: wngill@sfo.com

temperature, use of catalyst or separation of components. Reactive separations (RS) which

35 et al. 2008a, Shinde et al. 2015).

45 a) Effect of speed of agitation

29 conversion was obtained in 5 h.

22 important synthesis of isoamyl propionate. It is further shown through packed bed

19 KM, - temperature dependent reaction equilibrium constant,

CW in - cold water inlet

22 4. V. D. Talnikar, Y. S. Mahajan, Recovery of acids from dilute streams:A review of

29 16. A. Kiss, F. Omota, A. Dimian, and G. Rothenberg, The heterogeneous advantage:

41 of n-Propyl Acetate, Ind. Eng. Chem. Res.,2014, 53, 1395 – 1403,doi:/10.1021/ie403533t

24 24x19mm (300 x 300 DPI)

24 23x20mm (300 x 300 DPI)

24 24x19mm (300 x 300 DPI)

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