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ISSN 2278-2540 | DOI: 10.51583/IJLTEMAS | Volume XIII, Issue X, October 2024
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Design of A PFR For the Production of 1,000,000 Tons Per Year of
Ethyl Acetate from Esterification of Acetic Acid and Ethyl Alcohol
Wosu Chimene Omeke
Department of Chemical Engineering, Federal University Otuoke, Bayelsa State, Nigeria.
DOI : https://doi.org/10.51583/IJLTEMAS.2024.131011
Received: 28 September 2024; Revised: 16 October 2024; Accepted: 19 October 2024; Published: 07 November 2024
Abstract: The research considered the design or size of a plug flow reactor for the production of 1,000,000 tons of ethyl acetate per
year from the esterification of acetic acid and ethyl alcohol in the presence of an acid catalyst. The PFR design models for volume,
height, diameter, space time, space velocity, quantity of heat generated, quantity of heat generated per unit volume of the reactor as
well as the temperature effect models were developed using the conservation principle of mass and energy at steady state operation
of the reactor. The developed models were simulated using MATLAB at initial feed and operating temperature of 299.830k and
343.15k respectively and fractional conversion variation between 0 to 0.95 at an interval of 0.05. At a maximum conversion of 0.95,
the PFR size specification for volume, height, diameter, space time, space velocity, quantity of heat generated and the quantity of
heat generated per unit volume of the reactor was 15.2774m
3
, 4.2691m, 2.1346m, 2.9956sec., 0.3338sec
-1
, 12821.5800j/s and
839.2536j/sm
3
respectively. The effect of the operating parameters on the performance or functional parameters of the reactor are
presented in profiles as shown in figure 2 to 12 and the profile behaviour or trend were in agreement with process behaviour of PFR
steady state operation in various literatures. The research have shown that in order to ensure sustainability and continuous production
of ethyl acetate to meet the global demand of the economic and viable product, the plug flow reactor have demonstrated a good
performance characteristics as a reacting media for the esterification process especially in the energy efficiency of the process as well
as the product yield.
Keywords: Esterification, ethyl acetate, plug flow reactor, design, MATLAB Simulation
I. Introduction
Ethyl acetate is an organic solvent and a chemical intermediate with the molecular formula C
4
H
8
O
2
and molecular weight of
88.10g/mol. It is a colorless liquid with a pungent smell and a non-toxic, non-hygroscopic volatile liquid and occurs moderately as a
polar solvent (Bijay & Hiren, 2011). It has a wide range of industrial applications such as production of pharmaceuticals, solvents,
inks, plastics, synthetic fruits and chemicals that can be applied domestically and industrially (Grodowska & Parzewki, 2010; Karan,
2017; Nagamalleswara, 2015). Traditionally, ethyl acetate production is via catalytic esterification of acetic acid and ethyl alcohol
(Calvar et al, 2007; Evelien et al, 2014; Sykes, 1986; Hasanoglu et al, 2009). Chemical reactions usually occur in chemical reactors
and esterification reaction can occur in reactors like the plug flow reactor (Ni & Meunier, 2007), continuous stirred tank reactor
(Tang et al, 2016), Microwave reactors (Umrigar et al, 2022; Baraka et al, 2023), Membrane reactors (Ghahremani et al, 2021) and
fixed bed reactors (Son et al, 2023). In this article, the plug flow reactor (PFR) also known as the tubular reactor (TR) or the packed
bed reactor (PBR) is considered as the reacting media for the esterification reaction. The PFR is characterized with uniform
composition, no mixing or back flow and the reactant species moves along at the same speed, unvarying product quality, cheap
maintenance, energy efficiency, high conversion rate and suitable for large capacity processes (Fogler, 2006). Generally, the design
of chemical engineering equipment involves the application of the fundamental principle of mass and energy for the reactor size
determination ( Wosu & Ezeh, 2024; Ojong et al, 2024; Wosu et al, 2024; Wosu et al, 2023).
The importance and applications of ethyl acetate have prompted several research in the field and thus; Hilmioglu (2022) stated that
ethyl acetate is produced in batch reactor using sulfo succinic acid as a catalyst and highlighted the advantage of this technology the
processes that obey the Le Chatelier principle which causes a shift or forward esterification reaction as a result of the excess reactant
involved in the process. Ding et al (2012) and Nurhayati et al (2017) also stated that sulphuric acid can be utilized as catalyst during
esterification process for ethyl acetate production while Ikhazuangbe & Oni in 2015 stated that ethyl acetate can also undergo
hydrolysis in the presence of sodium hydroxide and the experiment showed that the reaction rate depends on the feed concentration
while the rate constant is a function of the reaction time. Abdulaziz et al (2023) utilized the Aspen HYSYS as a tool for sensitivity
analysis of flow reactor performances during esterification process. Modern research have shown that ethyl acetate can be a
substitute for fuel (green premium) for vehicles and power generators (Heuser et al, 2019). This article delves into the design of a
PFR for ethyl acetate production as a tool to enhance sustainability and effective production to meet the ever growing global demand
of the economic and viable product.
II. Materials and Methods
2.1 Materials
The materials utilized in the research are computer set, data obtained from journals, textbooks and the simulation tool used is
MATLAB.
2.2 Methods
The methodology adopted in this research is quantitative and the data used were obtained from thermodynamic properties of the
reactant species and products, literature data, and calculated/derived data and the following procedures were sequentially adopted;
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2.2.1 Development of the Reaction Kinetic Models
The Kinetic model of the esterification reaction is obtained from the reaction chemistry of the process in equation (1)
Acetic acid + Ethyl alcohol
Ethyl acetate + Water (1)
Equation (1) can be expressed molecularly as;
(2)
Symbolically, equation (2) can be expressed as;
(3)
where A represents acetic acid, B is ethyl alcohol, C is ethyl acetate, D is water and
represents kinetic rate constant which is an
indication that the reaction process is temperature dependent and the process condition is exothermal. The depleting rate of the
reactant species is related to the rate constant, fractional conversion, initial concentration of the limiting reactant, temperature,
activation energy as shown in equation (4)
(4)
2.2.2 Development of the PFR Design/Sizing Model
Consider the schematic representation of a plug flow reactor with mass and heat effect
Figure 1: PFR Schematic with Mass and Heat Effect
The design and temperature effect model of the PFR is developed the application of the conservation principle of mass and energy
thus;
(4)
The terms in equation (4) can be defined, substituted and simplified at steady state to yield the PFR performance model for volume,
height, diameter, space time, space velocity, quantity of heat generated as well as the quantity of heat generated per unit volume of
the reactor thus;
(5)
(6)
(7)
(8)
(9)
(10)
(11)
The temperature effect model of the PFR in Figure 1 developed using the conservation principle of energy balance in equation (12)
z
z z
H = VCpT
H
o
= V
o
o
Cp
o
T
o
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(12)
The terms in equation (12) can be defined, substituted and simplified to yield the temperature effect model thus;
(13)
Data for Evaluation
The data for evaluation in this research are the properties/thermodynamic data and data obtained from literatures as presented in table
1 and 2 respectively.
Table 1: Properties/ Thermodynamic Data
Data/Parameter
Values
Description
1050Kg/m
3
Density of acetic acid
789Kg/m
3
Density of ethyl alcohol
902Kg/m
3
Density of ethyl acetate
997Kg/m
3
Density of water
101325Kg/m
3
Initial pressure
R
8314Nmmol
-1
K
-1
Gas constant
Table 2 Data Obtained from Literature
Data
Values
Description
References
343.15K
Operating temperature of the reactor
Nagamalleswaraet al., 2015
mol/m
3
Reaction rate
Nagamalleswara et al, 2015
59.403kJ/mol
Activation energy
Nagamalleswara et al, 2015
III. Results and Discussion
The results and discussion of the PFR design for the production of ethyl acetate from the esterification of acetic acid and ethyl
alcohol is presented in Table 3 and Figure 2 to 10.
Table 4: Design Results showing Fractional Conversion, Temperature, Reactor Volume, Height, Diameter, Space Time, Space
Velocity, Quantity of Heat Generated and the Quantity of Heat Generated per unit Volume of the Reactor
X
A
T(K)
V
R
(m3)
H
R
(m)
DR(m)
(s)
S
V
(S
-1
)
Q(J/s)
q(J/sm3)
0.05
299.830
0.042
0.599
0.299
0.008
120.512
674.820
15945.818
0.15
299.830
0.142
0.897
0.449
0.028
35.942
2024.460
14267.311
0.25
299.830
0.268
1.109
0.555
0.053
19.028
3374.100
12588.804
0.35
299.830
0.433
1.302
0.651
0.085
11.779
4723.740
10910.297
0.45
299.830
0.658
1.496
0.748
0.129
7.752
6073.380
9231.789
0.55
299.830
0.983
1.711
0.855
0.193
5.190
7423.020
7553.282
0.65
299.830
1.493
1.967
0.983
0.293
3.415
8772.660
5874.775
0.75
299.830
2.412
2.307
1.154
0.473
2.114
10122.300
4196.268
0.85
299.830
4.556
2.852
1.426
0.893
1.119
11471.940
2517.761
0.95
299.830
15.277
4.269
2.135
2.996
0.334
12821.580
839.253
Table 4 shows the design result of the PFR for esterification process. Here, the MATLAB simulation was performed at initial feed
and operating temperature of 299.830k and 343.15k and varying fractional conversion from 0 to 0.95 at an interval of 0.05 and the
process behaviour showed that the reactor volume, height, diameter, space time and quantity of heat generated increases with an
increase in the fractional conversion while the space velocity and the quantity of heat generated per unit volume of the reactor
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decreases as the fractional conversion increases. At a maximum conversion of 0.95, the reactor volume, height, diameter, space time,
space velocity, quantity of heat generated and the quantity of heat generated per unit volume of the reactor are 15.277m
3
, 4.269m,
2.135m, 2.996seconds 0.334sec
-1
, 12821.580j/s, 839.254j/sm
3
respectively.
3.1 Results of PFR Design Parameters Process Behaviour
The effect or variation of fractional conversion and temperature on the performance parameters of the PFR is presented below.
Profile of PFR Volume (V
R
) and Fractional Conversion (X
A
)
Figure 2: Profile of PFR Volume (V
R
) and Fractional Conversion (X
A
)
Figure 2 is a profile or relationship between the PFR volume and fractional conversion during esterification process obtained from
the MATLAB simulation. The result showed that at initial feed and operating temperature of 299.830k and 343.15k respectively with
changes in fractional conversion from 0 to 0.95 at an interval of 0.05, the reactor volume increases exponentially as the fractional
conversion increases. At a maximum conversion of 0.95, the PFR maximum volume for yearly production of ethyl acetate was
15.2774m
3
. The exponential relationship between the PFR volume and fractional conversion is dependent on the reaction kinetic
scheme of the esterification process, mass transfer effect, design assumptions made, the effect of temperature, pressure and
concentration of the reactant species.
Profile of PFR Height (H
R
) and Fractional Conversion (X
A
)
Figure 3: Profile of PFR Height (H
R
) and Fractional Conversion (X
A
)
Figure 3 is a relationship between the PFR height and fractional conversion during the esterification process for ethyl acetate
production. According to the plot, an initial linear increase of the reactor height was observed at fractional conversion change from 0
to 0.05, this increase became exponential at fractional conversion above this range. At maximum conversion of 0.95, the maximum
height of the reactor at maximum volume was 4.2691m, the profile behaviour between the PFR height and fractional conversion as
obtained from the MATLAB simulation depends on certain factors such as the reaction kinetic scheme or rate law of the
esterification process, mass transfer effect,design assumptions and effect of temperature, concentration and pressure of the reactant
species.
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Profile of PFR Diameter (D
R
) and Fractional Conversion (X
A
)
Figure 4: Profile of PFR Diameter (D
R
) and Fractional Conversion (X
A
)
Figure 4 is the behavioural relationship between the PFR diameter and fractional conversion gotten from the MATLAB simulation of
the esterification process for ethyl acetate production. Just like the PFR height, an initial linear increase of the reactor diameter was
observed at fractional conversion change from 0 to 0.05, this change became exponential at higher conversion above this range. At a
maximum conversion of 0.95, the PFR diameter was 2.1346m. it is important to note that this profile behaviour is influenced by
certain factors such as the rate law of the esterification reaction, mass transfer effect, feed parameters and design assumptions made
during the process.
Profile of PFR Space Time () and Fractional Conversion (X
A
)
Figure 5: Profile of PFR Space Time () and Fractional Conversion (X
A
)
Figure 5 is the profile relationship of the PFR space time also known as the residence time and fractional conversion during the
esterification process for ethyl acetate production. The MATLAB simulation profile showed that there is an exponential increase in
space time as the fractional conversion increases. At a maximum conversion of 0.95, the space time recorded was 2.9956sec. this is
the maximum time spent by the reactant species in the reactor during the esterification process and this time is greatly influenced by
the rate constant or the pre-exponential factor of the reaction kinetic scheme.
Profile of Space Velocity (S
V
) and Fractional Conversion (X
A
)
Figure 6: Profile of PFR Space Velocity (S
V
) and Fractional Conversion (X
A
)
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Figure 6 is the MATLAB simulation result showing the profile behaviour of PFR space velocity and fractional conversion during
esterification process for ethyl acetate production. The space velocity is mathematically defined as the reciprocal of space time and
this mathematical relationship is demonstrated in the profile as the space velocity exhibited an exponential decrease as the fractional
conversion increases. At maximum fractional conversion of 0.95, the space velocity recorded was 0.3338sec
-1
. This profile behaviour
is greatly influenced by the rate constant or frequency factor from the esterification reaction kinetics.
Profile of the PFR Quantity of Heat Generated (Q) and Fractional Conversion (X
A
)
Figure 7: Profile of the PFR Quantity of Heat Generated (Q) and Fractional Conversion (X
A
)
Figure 7 shows that there is a linear increase relationship of the quantity of heat generated as the fractional conversion increases
during the esterification process in the PFR. The relationship simply means that the quantity of heat generated during the reaction
process is directly proportional to the fractional conversion of the reactant species. At a maximum conversion of 0.95, the quantity of
heat generated was 12821.5800j/s. This relationship was as a result of the effect of reaction rate, feed rate, heat transfer and the
process operating condition.
Profile of the Quantity of Heat Generated per unit Volume of the PFR (q) and Fractional Conversion (X
A
)
Figure 8: Profile of the Quantity of Heat Generated per unit Volume of the PFR (q) and Fractional Conversion (X
A
)
Figure 8 shows that the quantity of heat generated per unit volume of the PFR decreases linearly as the fractional conversion
increases during the esterification process for ethyl acetate production. According to the plot, at a maximum fractional conversion of
0.95, the quantity of heat generated per unit volume of the PFR decreases to 839.2536j/sm
3
. This profile behaviour is greatly
influenced by heat transfer effect and operating condition of the process.
Profile of PFR Temperature (T) and the Fractional Conversion (X
A
)
Figure 9: Profile of PFR Temperature (T) and the Fractional Conversion (X
A
)
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Figure 9 that at initial feed and operating temperature of 299.830k and 343.15k respectively with varying fractional conversion from
0 to 0.95 at an interval of 0.05, the PFR operates effectively during the esterification reaction for ethyl acetate production. This is an
indication that when the initial feed and operating temperature is within its specific range for esterification reaction, the process will
be greatly favoured and this will enhance optimum yield of the target product as well as the energy efficiency of the process.
IV. Conclusion
1,000,000 tons of ethyl acetate was produced from the esterification of acetic acid and ethyl alcohol in a Plug flow reactor (PFR).
The reaction media (PFR) was designed by applying the conservation principle of mass and energy over the reactor during the steady
state process. The performance model of the PFR mass and energy balance were simulated using MATLAB at initial feed and
operating temperature of 299.830k and 343.15k varying fractional conversion from 0 to 0.95 at 0.05 intervals to give the reactor
functional parameters. At a maximum conversion of 0.95, the PFR design or size specification for volume, height, diameter, space
time, space velocity, quantity of heat generated and the quantity of heat generated per unit volume of the reactor was 15.2774m
3
,
4.2691m, 2.1346m, 2.9956sec., 0.3338sec
-1
, 12821.5800j/s and 839.2536j/sm
3
respectively. The resultant effect of the fractional
conversion and temperature on the PFR functional parameters were presented in figure 2 to figure 9. The researched showed that the
PFR is a suitable reaction media for esterification process and its design will enhance the optimum production of ethyl acetate and its
sustainability to meet its global demand.
Nomenclature
Symbol
Definition
Unit
H
R
Change in enthalpy of reactants
J/mol
A
Acetic acid
-
B
Ethyl alcohol
-
C
Ethyl acetate
-
C
i
Initial concentration of species
mol/m
3
Cp
Specific heat capacity
J/mol
D
Process water
-
D
R
Diameter of the reactor
M
E
Activation Energy
J/mol
F
A
Initial molar flow rate
mol/S
H
i
Enthalpy of species
J/mol
H
R
Height of the Reactor
M
K
o
Pre-exponential factor
S
-1
Q
Quantity of Heat generated
J/S
Q
Quantity of heat generated per reactor volume
J/Sm
3
R
Gas constant
Nmmol
-1
k
-1
r
A
Reaction rate of species
mol/m
3
/s
S
V
Space velocity
Sec
-1
T
Operating Temperature
Kelvin
T
c
Temperature of coolant
K
T
o
Initial or fed temperature
K
UAc
Heat transfer coefficient
Kg/m
2
SK
V
i
Fractional conversion
Dimensionless
V
o
Volumetric flow rate
m
3
/S
V
R
Volume of the Reactor
m
3
i
Density of species
Kg/m
3
Space time
Seconds
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