Vol. 13 | No.

2 |920 - 933| April - June | 2020

ISSN: 0974-1496 | e-ISSN: 0976-0083 | CODEN: RJCABP
http://www.rasayanjournal.com
http://www.rasayanjournal.co.in

A REVIEW ON PROCESS PARAMETERS OF VARIOUS

PROCESS INTENSIFICATION TECHNIQUES FOR ETHYL
ACETATE PRODUCTION
Ganesh N. Patil1, 2,* and Nirmala Gnanasundaram1
1
School of Chemical Engineering, VIT University, Vellore, Tamilnadu 632014, India.
2
Mechanical and Industrial Engineering Department, College of Engineering, National
University of Science and Technology, Muscat, Oman.
*E-mail: ganeshpatil.nsk@gmail.com

ABSTRACT
Ethyl acetate is intensively used as a solvent for paints, coatings, resins, inks, main ingredient in different fragrances
and flavors for consumer products and decaffeination. An assessment of the ethyl acetate esterification process for
different process intensification techniques was studied to identify the several advantages over the traditional
process. Experimental and simulation details for individual ethyl acetate production process and coproduction
process with n-butyl acetate or isopropyl acetate are discussed. Simulation studies analysis shows the comparison of
various mathematical models and the identification of the most commonly used model for different process
simulators. This review focuses on ethyl acetate process intensification techniques including Reactive distillation,
pervaporation assisted reactive distillation, pressure-swing reactive distillation, reactive dividing wall columns,
reactive extractive distillation, microwave reactive distillation, reactive chromatography. The effect of various
process parameters i.e. ethanol flow rate, acetic acid flow rate, choice of a homogeneous and heterogeneous catalyst,
reflux ratio, feed tray position, the total number of trays, types of entrainer, condenser and reboiler duties on ethyl
acetate purity, overall production rate, energy consumption and total annual cost were discussed. Reactive
distillation overcomes chemical equilibrium limitations, saving energy and ensuring economic effectiveness by
reduced capital investment.
Keywords: Ethyl acetate, Reactive Distillation, Reactive Dividing Wall Column, Process Intensification
© RASĀYAN. All rights reserved

INTRODUCTION
Ethyl acetate (EA) is an important organic solvent widely used in various applications such as food and
beverage, pharmaceutical, cosmetics, textiles, paints and coatings, adhesives and sealants, and others. One
of the key issues in the production of acetates is the equilibrium limitation from the reversible reaction of
acetic acid and alcohol. This motivates the use of reactive distillation (RD) to achieve high conversion.
Ethyl acetate is the most common ester of ethanol and acetic acid. Ethyl acetate is produced by three
processes as given below:
1. Fischer Esterification Reaction process involves the reaction between ethanol and acetic acid, in the
presence of an acid catalyst i.e. sulfuric acid, hydrochloride acid, or toluene sulfonic acid. The main
drawbacks of this process include slow reaction rate and difficulty in separation of pure components
due to the presence of azeotropic groups like ethanol-ethyl acetate-water, ethanol-water, water-acetic
acid, ethyl acetate-ethanol, and ethyl acetate-water.1

CH3COOH + CH3CH2OH CH3COOHCH2CH3 + H2O + ∆H

2. Dehydrogenation of ethanol is the cost-effective method as compared to the Fischer esterification.

Dehydrogenation is carried out in a tubular reactor in the presence of copper or chromium catalyst.
The main drawback of the process includes excess ethanol requirement and difficult separation due to
hydrogen as a byproduct.
Rasayan J. Chem., 13(2), 920-933(2020)
http://dx.doi.org/10.31788/RJC.2020.1325640
 Vol. 13 | No. 2 |920 - 933| April - June | 2020

3. Tishchenko reaction process which is commonly used in Germany and Japan involves an organic
chemical reaction that works on the principle of dismutation or disproportionation of an aldehyde. It
is performed in the presence of a sodium or aluminium alkoxide catalyst, typically aluminium
triethoxide. A disadvantage of this process includes the insufficient supply of acetaldehyde outside
the petrochemical industries.
To overcome various inefficiencies of listed methods, many new technologies like improving production
rate through process intensification process, switching to automation with artificial intelligence,
enhancing plant performance through the internet of things (IoT) and assembling, maintaining and
training with augmented reality are incorporated into the ethyl acetate industry.
In the Reactive Distillation (RD) process the reaction and separation processes take place in a single unit
instead of two separate units. Thus production cost is reduced for RD compared to the traditional reactor-
separator systems. Few advantages of the RD process include lower energy consumption, higher reactant
conversion, low capital and operation cost. This article aims to study the effect of various reactive
distillation process parameters on ethyl acetate production.

Reactive Distillation
Reactive Distillation (RD) is a process that combines chemical reaction with distillation in a single unit.
In the reactive distillation unit, the reaction products are removed in time resulting in high reaction
conversion. The heat released from the reaction can be used in the distillation process. RD has various
advantages like higher conversion of the reactant for reversible reactions, improvement in the selectivity
of the desired product, avoiding azeotropic conditions, and preventing the formation of undesired
products and hot spots 2,3. The major problems of the RD system are the removal of water formed during
the esterification and separation of various azeotropes formed by ethyl acetate(EA), acetic acid (AA) and
water.
Tang et al. proposed a process flow sheet for EA esterification reaction as shown in Fig.-1. In the
proposed configuration a decanter was placed above the RD column to remove the water and the organic
phase is passed through the stripper to remove the pure ethyl acetate. Top from the stripper recycled to the
decanter. The dominant design variables identified for this process were feed ratio and number of trays in
the rectifying section.4

Fig.-1: Process Flow Sheet for EA Production4

Reddy et al. compared the energy requirement of reactive distillation and reactive chromatography (RC)
for EA production. RC required less energy due to the complete conversion of ethanol but RD required
more energy due to the high reflux ratio. A high reflux ratio was used to avoid the loss of acetic acid.5

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Table-1: List of Azeotropes present in the Ethyl Acetate System5

Components T (0C) Type of Azeotrope Composition
Ethyl Alcohol Ethyl Acetate Water
EtOH–EA 71.77 Homogeneous 0.448 0.552 0
EtOH–water 78.14 Homogeneous 0.892 0 0.108
EA–water 71.24 Heterogeneous 0 0.676 0.324
EtOH–EA–water 70.45 Homogeneous 0.151 0.558 0.291

S. Hu et al. presented the relationship between reflux ratio and the number of theoretical stages for
conventional and reactive distillation as shown in Fig.-2. The reflux ratio in the RD column was divided
into two parts R1 and R2 as follows: (1) R1 was used for regular operation and can be reduced to R1minby
increasing the theoretical stage number of RD column; (2) R2 was only used as an entrainer to carry the
accumulated H2O out of the column. The value of R2 was constant and does not alter due to a change in
the number of theoretical stages. The author suggested that reduction in R2 through process innovation
and optimization can help to improve the process efficiency.6

Fig.-2: Relationship between the Reflux Ratio and the Number of Theoretical Stages6
C. Li et al. discussed entrainer enhanced reactive distillation in esterification reaction to increase the
relative volatility of water by forming a minimum heterogeneous azeotrope with water. The
heterogeneous azeotrope distilled from the top of the column separates the product and water. Entrainer
shifts chemical equilibrium, keeps the reaction section temperature below the thermal stability limit of the
catalyst. Entrainer removes the water from the reaction section, improve the conversion, and increase the
selectivity of the product. Entrainer volume and its volatility determine the temperature of the reaction
section. [7-8]
Entrainer improves the conversion rate of the feedstock, increases the selectivity of the products in the
reversible reaction, efficiently uses the raw materials and increases the process efficiency, provides more
energy savings.6
S. Hu et al. studied various entrainers and presented experimental properties of entrainer liquids for EA
production as shown in Table-2. After comparing the characteristics of all listed entrainers, the author
suggested the NBA as the most appropriate entrainer. The advantages of using the NBA as an entrainer
over others are discussed as follows. (1) the highest percentage of NBA was present in the five
component system of the NBA–EA–EtOH–AA–H2O(126.01 oC), whereas the azeotropic temperatures for
NBA–H2O and EA–H2O was 91.01 oC and 70.37 oC, respectively; (2) moles of water entrained by NBA
was 5.18 times more than that by EA, and the solubility of NBA in water is less than that of EA in water;
(3) the temperature gradient is about 108–112 0C (1atm), existed within the column makes the separation
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easier. The author developed the novel new process flow sheet with a side draw to the RD column. The
stage number of the rectifying section and reactive section, side draw location and flow rate, side draw
aqueous phase reflux flow rate, and the overhead organic reflux flow rate was investigated to determine
an optimal flowsheet design. For similar capital investment, the new process shows 32% lower energy
consumption.6
Table-2: Experimental Properties of the Entrainer Liquids6
Component Normal Azeotropic Azeotropic Aqueous Phase Organic Phase
Boiling Temperature Composition (H2O) (H2O) at 40oC (H2O) at 40oC
Point (with H2O)
Cyclohexane 80.78 69.44 29.9 99.98% 0.17%
Benzene 90.13 69.24 29.76 99.95% 0.38%
n-BA 26.2 91 70.10 99.7% 9.5%
Isobutyl 117.2 87.40 56.02 99.87% 9.53%
Acetate
Sec butyl 112.4 87 62.56 99.92% 11.49%
Acetate
Amyl Acetate 146 95.2 83.4 -
Lai et al. studied reactive distillation for the coproduction of ethyl acetate and isopropyl acetate. The
effect of impure feed containing more water and excess cost to boil up water increased the total annual
cost. Thus the TAC was less if the pure ethyl acetate feed is used. Control strategies for reactive
distillation were studied with two control structures, dual-temperature control and one-temperature-one-
composition control. Three disturbances, feed flow, acid feed purity, and alcohol feed composition, were
introduced to assess control performance using dual-temperature control and one-temperature-one-
composition control. The results showed that the TAC increase by a factor of 5% for EA production
using reactive distillation. Simulation results show good control performance for reactive distillation with
azeotropic feeds.8
Tavan et al. studied hydration of ethylene oxide for ethyl acetate production. For minimum energy
demand suggested optimum ethylene oxide and ethanol flow rate were 0.45 mol/. Optimum reflux ratio
for pure EA was identified as 3.5. Simulation results of RD show less energy requirement for the ethanol
rate, the ethylene oxide rate and reflux ratio optimum values as compared to the conventional process.
The proposed ethyl acetate RD process showed high esterification conversion, pure products, reduction in
the equipment costs and required energy.9
Tian et al. proposed a co-production process for ethyl acetate and n-butyl acetate using Reactive
Distillation Column. The effect of feed molar ratio of ethanol to n-butanol on energy saving was studied.
Total annual costs of individual and coproduction processes were compared and the result shows that the
coproduction process cost for a similar capacity of ethyl acetate was less. When the feed molar ratio of
ethanol to n-butanol was less than 1.0, similar product purities were obtained as that with the individual
technologies. The energy-savings increases slightly as the feed molar ratio of ethanol to n-butanol
decreases. Compared with the individual technologies, the coproduction technology can save 20.40%
energy when the feed molar ratio of ethanol to n-butanol was 0.5.10
He et al. proposed green catalyst 1-sulfobutyl-3-methylimidazolium hydrogen sulfate ([HSO3-
bmim][HSO4]) for ethyl acetate production. Optimum catalyst dose of 0.203 mol/L was selected based on
simulation results and equipment cost. It was found that a higher number of theoretical plates in the
rectifying section give high purity ethyl acetate and hence 7 plates in the rectifying section were selected.
When the reflux ratio was high, distillate composition was close to azeotrope result in the increase of
unreacted ethanol content. For the high purity of ethyl acetate, optimum reflux suggested value was 2.
Reactant reacts faster for small tray hold up, for the increase of holdup purity of product increases and
thus 0.04 L tray holdup was identified. Fed tray location was suggested as the first plate over reboiler at
the bottom. It was found that ethanol being the lightest component added at the lower feed tray increases
the reactive section length. Simulation results provide 98.94 wt % of ethyl acetate and 91.51% of ethanol
conversion. Used Green catalyst was superior to Amberlyst 15 for similar conversion and reaction rate.11
Fernandez et al. did a series of experiments ethyl acetate production in a reactive distillation pilot column.
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The effect of excess ethanol feed and stoichiometric feed configuration was studied in the presence of an
acidic Ion-exchange resin heterogeneous catalyst. The authors developed a new dynamic model based on
experimental results. The increase of reflux ratio increased the distillate flow rate and decrease of water
content. The increase of ethanol flow rate resulted in higher ethanol conversion and reduction is acetic
acid.12
Singh et al. did a simulation study on homogenously catalyzed esterification reaction for EA production.
EQ model and Aspen Plus model simulation results were compared for similar kinetic and process
parameter values. The reaction rates reported for EQ models were five times higher than the rate based
mode during the 34-37 reaction stage. The effect of the tray of product purity was studied and found that
the product purity remains the same if the trays reduced from 48 to 42 in the upper section of the column.
Shifting the feed stage location from 39 to 33 stages improved the ethanol conversion rate. The ethanol
reaction rate increased by an additional ethanol feed at the bottom stage.13
Giwa et al. did simulation and economic comparison study for conventional and reactive distillation
process based on higher purity of ethyl acetate, capital and operating cost. Simulation and economic
analysis were done by using Aspen plus. Simulation data were presented for similar input conditions and
the result shows benefits of the RD method over the conventional method for EA production.14
Wang et al. studied the effect of heat integration to reduce the production cost of EA. Alternative
configurations designs i.e. two configurations with three columns and one configuration with two
columns were studied for the heat integration/coupling process as follows. (1) Separation of ethanol/ethyl-
acetate mixtures by using pressure-swing distillation. (2) RD column followed by a conventional
distillation column operated at high pressure. (3) Reactive distillation and extractive distillation coupled
with Heat integration and thermal coupling technologies for energy reduction. It was identified that the
Reactive distillation and extractive distillation column coupled with heat integration provides high-purity
ethyl acetate for lower annual cost15.
Calvar et al. compare the results for ethyl acetate production in RD by using acetic acid as a
homogeneous catalyst and Amberlyst 15 as a heterogeneous catalyst. The esterification reactions were
carried out between 303.15 and 353.15K temperatures and different reactant compositions. T was seen
that the purity of ethyl acetate depends on the azeotrope composition. Two different setups were studied
as follows. (1) Feed was introduced into the column as a mixture of reactants: Ethanol feed introduced
into the upper part of the catalyst with excess acetic acid provides higher EA (2) Reactants Ethanol and
acetic acid added separately and found provides lower EA production than previous setup 16.
Giwa et al. investigated the effects of property models on the qualities of the desired products obtained
from reactive distillation processes in Aspen Plus. Packed type distillation column with 25 segments
including the condenser and the reboiler is used during the study for the coproduction of EA and NBA.
Fourteen different models were studied, the highest mole fractions of EA and NBA was obtained for the
Wilson model and Peng-Robinson equation of state model.17
Park et al. did experimental and simulation study for the production of EA by using reactive distillation.
The experimental setup consists of a distillation tower with 10 catalyst-packed plates, five separation
trays above the catalyst packed plates, and three separation trays below the catalyst packed plates. EA
purity obtained was 70% and further distillation gives 98% for optimum reflux ratio, feed flow rate of
acetic acid and ethanol.18
Andrew et al. did a simulation study for the production of EA by RD using chemcad simulator. Effects of
reflux ratio, distillate rate, feed tray location and activity model on the composition of ethyl were studied.
The optimum composition of ethyl acetate was obtained for when acetic acid fed to the second tray and
ethanol was added on the twelfth tray for a reflux ratio of 12. Ziegler-Nichols (ZN) tuning method was
used for pressure control. By manipulating the flow rate of steam, reboiler pressure control can be
adjusted. Manipulating Condenser heat duty was used to control of the purity of ethyl acetate.19
A summary of reactive distillation types of study with various catalysts, simulation models including
simulator details and process parameters studied by various researchers are presented In Table-3.
Reactive Distillation Pervaporation Hybrid Process
Lee et al. proposed reactive distillation pervaporation (RD-PV) hybrid configuration where a side stream
was removed from the rectifying section. Membrane pervaporation unit used to extract ethyl acetate from
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the side stream. The process had a 13% energy saving as compared to the conventional two-column (RD
and stripper) process. The author studied two temperature control strategies – single point and dual points
and proposed the dual temperature control strategy due to its advantages to handling throughput and feed
composition disturbances20.
Table 3: Summary of Reactive Distillation Simulation and Other Process Parameters for EA Production
S. No. Type of Study Catalyst Thermodynamic Process Parameters Ref.
Model Studied
1 Simulation Sulfuric acid NRTL Effect of ethanol low rate, 9
(Aspen Hysis) Ethylene oxide flow rate
and Reflux ratio on
temperature and
component compositions
in RD column.
2 Simulation Amberlyst 36 RADFRAC Effect of feed molar ratio 10
(Aspen Plus 11.1) (For VLE data) of ethanol to n-butanol on
NRTL (For n- product purities and
butyl acetate) energy consumption
UNIQUAC (For
ethyl acetate)
3 Experimental and 1-Sulfobutyl-3- RADFRAC 1. Comparison of 11
Simulation methylimidazolium Kinetic models and
(Aspen Plus V hydrogen sulfate catalysts.
8.4) 2. Effect of reaction
temperature, catalyst
concentration, initial
reactant molar ratio,
Feed tray location of
ethanol, theoretical
plate number of
rectifying and tray
holdup on product
purity.
4 Experimental and Amberlyst 36 RADFRAC Effect of ethanol feed 21
Simulation (For VLE data) location, acetic acid feed
(Aspen Plus 11.1) NRTL (For n- location, feed stage of the
butyl acetate) reaction mixture of acetic
UNIQUAC (For acid and n-butanol, reflux
ethyl acetate) ratio of ethyl acetate
reactive distillation
column, and distillate to
feed ratio of n-butyl
acetate column, on the
ethanol/n-butanol
conversions, ethyl
acetate/n-butyl acetate
purity, and energy
consumption.
5 Experimental and Acidic NRTL 1. Steady state 12
Simulation ion-exchange resin conditions for a feed
configuration with
excess ethanol
2. Stoichiometric feed
configuration effect
on catalyst activity
3. Effect of feed flow
rates, reflux flow rate
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and heat duty

13
6 Simulation Para-toluene- NRTL 1. Comparison of EQ
(Aspen Plus) sulfonic acid and rate-based models
in Aspen Plus
2. Effect of number of
stages on product
purity
3. Effect of feed stage
location on ethanol
conversion
4. The combined effect
of feed location and
the addition of
fresh ethanol on heat
duty
22
7 Experimental and Amberlyst 35 - 1. Experimental
Simulation runs for Type II
(Aspen Plus) RD Process
2. Study the
initial charges to
the column
holdups and a
start-up
procedure for
continuous
production
23
8 Simulation Sulfuric Acid RADFRAC Comparison of catalyst
(Aspen Plus) Purolite CT179 NRTL cost, capital investment
cost and energy cost,
reaction rate, number of
trays for homogeneous
and heterogeneous
catalytic processes.
14
9 Simulation NA UNIQUAC Comparison of
(Aspen Plus) conventional and RD
processes based on
product purity, total
annual cost, operating
cost, equipment and utility
cost and installed cost.
15
10 Simulation Potassium NRTL 1. RD column top
(ChemCad) butanolate mixture (Ethanol +
Ethyl acetate)
separation by
Extractive
Distillation, Pressure
Swing Distillation
and Convectional
distillation and to
calculate annual cost
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for each method.

2. Study of Heat
integration and
thermal coupling
between two columns.

24
11 Simulation Sulfuric acid NRTL Comparison of two basic
(Aspen Plus) control schemes and
development of a new
control scheme
25
12 Simulation Sulfuric acid NRTL Design of an ethyl acetate
(Aspen Plus) system to find optimum
operating conditions to
minimize the total
operating cost.
8
13 Simulation Purolite CT179 NRTL Effects of reactant purity
(Aspen Plus) (For EA) on the design and control
Amberlyst 15 (For of reactive distillation
IPAc)
16
14 Experimental and Amberlyst 15 UNIQUAC Effect of feed composition
Simulation and reflux ratio
17
15 Simulation NA 14 Different Comparison of 14
(Aspen Plus) models property models for
highest EA and NBA
production
4
16 Simulation Sulfuric Acid RADFRAC Comparison of three
(Aspen Plus) Purolite CT179 process flowsheets to
optimize the quantitative
design based on Total
annual cost
18
17 Experimental and Amberlyst-15 NRTL Experimental study for a
Simulation fixed number of catalyst
packed trays on ethyl
acetate concentration
19
18 Simulation Sulfuric acid NRTL Effect of reflux ratio,
(Chemcad) distillate rate, feed tray
location and activity
model on ethyl acetate
composition
26
19 Simulation Sulfuric acid NRTL Effect of pressure, reflux
(Chemcad) ratio, feed stage location,
excess reactants on the
reactants conversion and
the ethyl
acetate production

Hasanoglu et al. did the experimental study for esterification of ethyl acetate by using a batch
pervaporation membrane reactor. Molar ratios of reactants and change of temperature with
Polydimethylsiloxane membrane give higher conversion27. Vapor-liquid equilibrium calculations using
the Wilson equation and data obtained by pervaporation were compared. The degree of swelling increases
with ethyl acetate composition. An increase in temperature increases affinity between solve and polymer
which in turn increases the degree of swelling in the membrane. The optimum temperature of 30-40 C
was used for pervaporation separations by using Polydimethylsiloxane (PDMS) membranes.28
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He et al. studied a membrane reactor with sulfonated polyethersulfone, polyethersulfone, non H woven
fabrics composite catalytic coupled with a polyvinyl alcohol pervaporation membrane for ethyl acetate
production in a flow-through mode. Single flow-through mode and closed-loop flow through methods
were studied for the effect of temperature, ethanol to acetic acid molar ratio and residence time on ethanol
to ethyl acetate conversion. Results show that pervaporation-assisted esterification in the closed-loop
mode gives 95.4% conversion.29
Rathod et al. did a simulation study on esterification of acetic acid and ethanol using hydrophobic
membranes and proposed a mathematical model. Experimental and model results for acetic acid
conversion at 50 oC,60 oC and 70 oC were compared. Simulation results were in good agreement with the
experimental data.30
Zhang et al. did an experimental study on pervaporation of ethyl acetate by preparing the chitosan and
polyvinyl pyrrolidine (PVP) blend membranes crosslinked with glutaraldehyde (GA). The pervaporation
properties of the membranes were studied through dehydration of the ethyl acetate/ethanol/water
azeotrope. An increase in GA content increases the separation factor and decreases the permeation flux.
The addition of a certain amount of PVP enhances the hydrophilicity of the membranes. An increase in
feed temperature increases permeation flux and reduces separation factor.31
Das et al. did the experimental investigation to increase ethyl acetate conversion by 2 types of cross-
linked PVA membranes using maleic acid and citric acid as crosslinking agents. The water separation
ability of the cross-linked membranes from aqueous acetic acid and ethanol solutions were tested by
pervaporation. Separation factor and flux for PVAMA and PVACA membranes were studied for acetic
acid-water and ethanol-water separation. Both membranes show high selectivity and permeating ability.
Compare to conventional esterification 38% higher conversion of ethanol and acetic acid was obtained.32
Lv et al. did experimental studies and proposed a new energy-saving RD-PV process for ethyl acetate
production as shown in Fig.-3. The composite membrane was prepared by coupling the PVA/ceramic
with the RD reboiler. The effects of PV operating temperature and AA to ethanol molar ratio on the RD
performance were studied. PVA/ceramic composite membrane shows good PV performance and stability
with a given total flux and a separation factor of AA-water solution. Ethanol conversion and EA purity
were increased from 82.4 to 85.6 weight % and from 81.3 to 84.8% respectively.33

Fig.-3: Experimental Setup of RD-PV Process.33

Pressure Swing Reactive Distillation

Homogeneous azeotropic mixtures are separated by using pressure swing distillation (PSD). The PSD
process uses the pressure sensitivity of the binary azeotropic point. An increase in pressure shifts
azeotropic point to lower concentrations of the low boiling component. Thus at different pressures
azeotropic mixture can be separated.
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Klein A. et al. discussed the advantages of the PSD process over the entrainer enhanced distillation
process. PSD process required less number of stages for the recycling of the entrainer. For effective heat
integration, the low-pressure column was heated by the heat of the condenser of the high-pressure
column. Process control strategies development was found to be difficult due to more complex
automation which makes PSD process more complex.34

Reactive Dividing Wall Column (RDWC)

H. Li et al. studied the experiment and simulation of ethyl acetate and butyl acetate coproduction for two
reactive dividing wall column structures. BA was used as an entrainer to remove the water generated by
the two esterification reactions. It was found that the experimental results were in good agreement with
the simulation results. Two types of RDWC structures RDWC-FC and RDWC-RS were proposed as
shown in Fig.-4 and Fig.-5. The co-production process operating parameters such as the reflux ratio of the
aqueous phase, reflux ratio of the vapor split, reflux ratio of liquid spilt of RDWC were optimized by
using Aspen Plus. Optimal operating parameters for both types of RDWC were calculated. Energy-saving
and TAC of RDWC were studied by comparing the RDWC-FC and RDWC-RS with traditional RD
column.35

Fig.-4: The Process of RDWC-RS for Co-producing Ethyl Acetate and n-Butyl Acetate35

Fig.-5: The Process of RDWC-FC for Co-producing Ethyl Acetate and n-Butyl Acetate35
Xie et al. studied the experiments and simulations of the RDWC for the production of ethyl acetate. To
avoid corrosion of the equipment caused by the acidity of the catalyst, heterogeneous catalysts Amberlyst
15 was added with a novel catalyst loading method. The reliability of the proposed simulation model was
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verified by the experimental study on the change of liquid split ratio and reflux ratio. The structural
parameter height (H) has an optimal value to achieve the optimal contact between the gas and liquid
phase reactive section of the column. A comparison of economic analysis was conducted between the
traditional RD column and RDWC. The results showed that RDWC can save 34.7% of total operating
costs and 18.5% of TAC.36
Santaella et al. proposed three RDWC configurations. In the first configuration (Fig.-6a), due to
continuous removal of water reduced the remixing effect into the reactive section resulted in higher
conversions and energy savings. In the second configuration (Fig 6b) water was removed as a side stream,
reduces ethyl acetate losses with an increase in the acetic acid losses results in lower conversions.
Modified configuration (Fig. 6c) suggested removing water by using additional reboiler and additional
bottoms stream, shown improved performance among the three configurations.37

Fig.-6: Three Different Configurations of RDWC37

Safe et al. did the simulation study of EA production by RDWC shows the higher production by
removing the water produced in the reaction from the system. The reaction-separation efficiency
increased because the side stream extracts the water produced and the chemical equilibrium was
displaced. By extracting water can achieve a higher amount of ethyl acetate compound produced as
observed by the favorable modification of the equilibrium thermodynamic constant Simulation results
show 27.6 % improving in ethyl acetate purity comparing to reactive distillation in the same startup
condition.38
Zhang et al. studied the simulation of extractive dividing wall column (EDWC) in a three-column system.
EDWC was used to separate ethyl acetate and isopropyl alcohol using ethylene glycol as an entrainer. The
objective of the study was to estimate total annual cost, study the effect of control variables i.e. entrainer
flow rate and vapor split ratio on product purity, identification and comparison of various control
structures. Best control temperatures locations were identified using sensitivity criterion and basic control
structure was prepared. Based on control structure and sensitivity analysis two control structures were
prepared which shows a smaller deviation and less settling time. Entrainer flow rate and vapor split ratio
were adjusted to control the purity specifications.39
Xie et al. studied the coproduction of EA and NBA in RDWC. Effect of NBA as a entrainer was studied.
The effects of Catalyst loading per stage, reflux ratio, liquid split ratio and molar feed ratio, ethyl
acetate/n-butyl acetate purity, pressure drop and total energy consumption were investigated and the
optimum result was presented.40
Microwave Reactive Distillation (MRD)
Ding et al. developed a laboratory-scale microwave reactive distillation setup as shown in Fig.-7. The
acetic acid flow rate was kept at 2.5 ml/min for optimum EA production. With an increase in the reflux
ratio up to 4 the EA content was increased drastically. An increase in Reboiler heating power initially
increases the EA conversion but later it reduced the residence time of ethanol and reduces the EA

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conversion. Optimum heating power of 200W was estimated for higher EA production. The operation
time required for MRD process was less than RD process for similar energy requirements. Also, MRD
process gives higher EA production than RD for the similar reflux ratio.41

Fig.-7: Experiment Setup for MRD Process

(1:Microwave Generator, 2:Annular Water Load, 3: Rectangular Waveguide, 4: Microwave Cavity, 5:Rectification
Section, 6:Reaction Section, 7:Stripping Section, 8:Infrared Thermometer Probe)41
Reactive Chromatography
Reddy et al. did a comparative simulation study of reactive chromatography (RC) and reactive distillation
for the production of ethyl acetate. A simulated moving bed reactor (SMBR) was used for reactive
chromatography experimental setup as shown in Fig.-8. RC can completely convert ethanol to EA and
thus raffinate and extract phase were free from methanol. This reduces the energy requirement for the RC
process. For RD, volatility differences are less and thus a high reflux ratio was required to avoid the loss
of acetic acid from distillate which increases the energy requirement. There was a scope for suggested
detailed cost estimation and pilot-scale studies for the production of ethyl acetate by RC.5

Fig.-8: Schematic of SMBR for the Equilibrium Reaction (Acetic acid (AA) + Alcohol = Ester + Water); Solvent is
chosen as AA; D represents the Distillation Column.5

CONCLUSION
A review of various process intensification techniques used for ethyl acetate production has been carried
out. Techniques including Reactive distillation, pervaporation coupled reactive distillation, pressure-
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swing reactive distillation, reactive dividing-wall columns, reactive extractive distillation, microwave
reactive distillation, reactive chromatography, bubble-mediated reactive separation were studied for
various configurations. Researchers discussed the effect of various process parameters i.e. ethanol flow
rate, acetic acid flow rate, choice of a homogeneous and heterogeneous catalyst, reflux ratio, Feed tray
position, the total number of trays, types of entrainer, condenser and reboiler duties on ethyl acetate
purity, overall production rate, energy consumption and total annual cost were discussed in each process
intensification method. The review shows that there are two most commonly used catalysts (sulfuric acid
and Amberlyst 15) and NRTL thermodynamic model for simulation. There is sufficient data available for
experimentation and simulation of Reactive distillation as compare to other methods. Lower annual cost
and high energy saving will be possible in Reactive dividing wall column configuration as compared to
other process intensification techniques.
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