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Aspen Plus Simulation of Saponification of Ethyl Acetate
Aspen Plus Simulation of Saponification of Ethyl Acetate
Aspen Plus Simulation of Saponification of Ethyl Acetate
Journal of
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DOI: 10.4172/2157-7048.1000205
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ISSN: 2157-7048
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Research Article
Research Article Open
OpenAccess
Access
Abstract
This work presents the modelling and simulation of saponification of ethyl acetate in the presence of sodium
hydroxide in a plug flow reactor using Aspen Plus simulation software. Plug flow reactors are widely used in the
industry due to the non-mixing property. The use of plug flow reactors becomes significant when there is a need for
continuous large scale reaction or fast reaction. Plug flow reactors have a high volumetric unit conversion as the
occurrence for side reactions is minimum. In this research Aspen Plus V8.0 has been successfully used to simulate
the plug flow reactor. In order to simulate the process as accurately as possible HYSYS Peng-Robinson EOS package
was used as the property method. The results obtained from the simulation were verified by the experiment carried
out in the EDIBON plug flow reactor module. The correlation coefficient (r2) was 0.98 and it proved that simulation
results satisfactorily fit for the experimental model. The developed model can be used as a guide for understanding
the reaction kinetics of a plug flow reactor.
Keywords: Aspen Plus; Modelling; plug flow reactor; Simulation such issues, modelling and simulation of reactors has become useful
when it comes to process optimization and to investigate the effect of
Nomenclature various operating parameters towards the process.
T - Absolute Temperature; C - Concentration; x - Fractional Practice of process simulation has evolved over last two decades in
Conversion; k0 - Frequency Factor; λm - Molar Conductivity of an ion; the field of engineering. When it comes to process engineering, there
k - Rate Constant; r - Rate of Reaction; V - Reactor Volume; Treference - is a wide range of process simulation packages which are specifically
Reference Temperature; κT - Solution Conductivity; κTreference - Solution developed for particular process areas namely, Aspen Plus, Chemcad
Conductivity at Treference; θ - Temperature Coefficient; R - Universal Gas and Petro-SIM. All these simulators follow the sequential modular
Constant; F - Volumetric Flow Rate approach where the user is able develop a process by combining
standard modules in a logical manner. Aspen Plus is one of the
Introduction industry’s leading process simulation software which has the ability to
Plug flow reactors (PFRs) also known as Continuous Tubular design and simulate a chemical process comprehensively.
Reactors (CTRs) play a key role in chemical manufacturing facilities
Aspen Plus has been used by investigators to simulate and optimize
where a transformation of chemical substances takes place. In a plug
various kinds of process plants and unit operations. Sohail Rasool Lone
flow reactor, feed is introduced from one end of a cylindrical tube
et al. [2] developed a model to simulate ethyl acetate reactive distillation
and flows continuously through the length of the reactor as a series
column using a RADFRAC model Harjeet Nath et al. [3] developed
of plugs. The product is then collected from the other end of the
a model to simulate the abatement of fluorine inside a fluidized bed
reactor. In modelling it is assumed that Inside a PFR, the fluids flow
reactor using RCSTR and RGIBBS models. Rajul Nayak et al. [4]
consistently and there is no radial variation in velocity, concentration,
developed a model to simulate coal gasification using RYIELD, RGIBBS
and temperature or reaction rate [1]. The main advantages of PFRs are
and RSTOIC models.
that they have a high volumetric unit conversion and the capability
of running for longer periods without maintenance. For isothermal The primary objective of this study is to develop a model for a Plug
reactions greater than zeroth order, the PFR volume will usually be Flow Reactor and to simulate the saponification of ethyl acetate in
lower than the Continuously Stirred Tank Reactor (CSTR) volume for the presence of sodium hydroxide by varying the reactor temperature
the same conversion and reaction conditions (temperature, flow rate, and reactant flow rates using Aspen Plus. In order to validate the
etc.) [1]. applicability of the developed model, simulation results were compared
with the experimental results collected using EDIBON PFR module
For the industry, PFR can be configured as a single long tube or a
bunch of short tubes depending on the application. The diameter of
the cylindrical reactor varies from a few centimeters to several meters.
*Corresponding author: Wasalathilake KC, Department of Chemical and Process
Construction cost, pumping cost, residence time and heat transfer Engineering, University of Moratuwa, Sri Lanka, Tel: 94775804882; E-mail:
requirements are the main factors which affects the choice of diameter. 090544c@uom.lk
PFRs are widely used in the industry for gas and liquid phase systems. Received June 27, 2014; Accepted August 28, 2014; Published September 01,
Gasoline Production, Oil cracking, oxidation of sulfur dioxide to sulfur 2014
trioxide, synthesis of ammonia, polymer manufacturing are some the
Citation: Wijayarathne UPL, Wasalathilake KC (2014) Aspen Plus® Simulation of
industries where PFRs are being used broadly. Saponification of Ethyl Acetate in the Presence of Sodium Hydroxide in a Plug Flow
Reactor. J Chem Eng Process Technol 5: 205. doi: 10.4172/2157-7048.1000205
Though they are a number of applications, the controlling of PFR has
become a challenging task when it comes to chemical manufacturing. Copyright: © 2014 Wijayarathne UPL, et al. This is an open-access article
distributed under the terms of the Creative Commons Attribution License, which
Time varying characteristics of the process have made the operation of permits unrestricted use, distribution, and reproduction in any medium, provided
the reactor difficult and it needs extensive monitoring. For overcome the original author and source are credited.
Page 2 of 8
[5]. During the laboratory experiment, fractional conversions of the Furthermore, online conductivity meter displays the conductivity
reaction are determined using the conductivity values of the reactants value for the solution as at 25°C. Therefore, it should be corrected to the
and products under different temperatures. operating temperature using the expression,
100
Theory =κTreference × κT (6) [9]
100 + θ(T − Treference )
Saponification
Hydrolysis reaction of ethyl acetate with sodium hydroxide is in
Saponification is the hydrolysis of a carboxylic acid ester in a the form of A+B→C+D. Moreover, the concentration of both the NaOH
basic medium (equation 1). Saponification is essentially a soap- and CH3COOC2H5 are similar, the concentration of components at
manufacturing process that takes place by reacting the fatty acid with initially and any time t, can be expressed as follows (Table 1).
alkali, especially triglycerides producing glycerol and carboxylate salts
(soap). By replacing the concentration terms in above equations (4) and
(5),
NaOH+ CH3COOR → CH3COO-Na+ + ROH (1)
κfeed = [λ Na+ × CA0] + [λOH- × CA0] and
In this experiment, saponification of ethyl acetate in the presence of
sodium hydroxide is used to demonstrate the saponification reaction. C A (1 − x A ) C A0 x A
The saponification of ethyl acetate reaction is as follows. κ product = λ Na+ × C A0 + λ OH − × 0 + λ CH3COO− ×
2 2
NaOH+ CH3COOC2H5 → CH3COO- Na+ + C2H5OH (2) Fractional conversion could be determined by solving for x.
When it comes to chemical kinetics, this reaction is a prominent PFR theory
second order reaction identified in literature [6,7].
Since the saponification of ethyl acetate with presence of sodium
In a PFR, reactant fluids are pumped through a tubular section
hydroxide is a second order reaction [6], rate of the reaction can be
where the reaction is carried out. At the inlet of the PFR, reactant
expressed as follows.
concentration is very high; hence the rate of reaction is also high.
But, when it passes through the reactor, reactants get consumed and r = kCNaOHCCH3COOC2H5 (7)
products are formed. Therefore rate of reaction drops through the PFR
According to the Arrhenius equation
with respect to reactor length.
−E
Conductivity theory k = k0 exp (8)
RT
Conductivity of a solution is given by, κ=λmC (3) [8]. Where, is
Tubular reactors falls under the category of flow reactors where the
the molar conductivity of an ion and is the ion concentration in the
key assumption is that the fluid is perfectly mixed in the radial direction
solution. Feed stream for the PFR consists with equal volumetric flow
but not in the axial direction (zero back mix). Each plug of differential
rates of NaOH(aq) and CH3COOC2H5(aq). Since the conductivity value for
volume is considered as a batch reactor where the volume tends to be
CH3COOC2H5(aq) is negligible with reference to NaOH(aq), conductivity
zero.
of the feed solution can be estimated as,
κfeed =[λ Na+×CNa+] + [λOH-×COH-] (4) [8] The PFR model is well applied for many fluids. Ideal PFR consist
with a constant residence time which is same as the space time if other
Similarly for the product stream, since it consists with both the conditions such as pressure and temperature are same throughout the
products CH3COO-Na+ + C2H5OH as well as the unreacted, conductivity reactor [10-12].
NaoH of the product stream could be expressed as,
Plug flow reactor design equation (Figure 1)
κproduct = [λNa+×CNa+] + [λOH-×COH-] + [λCH3COO-×CCH3COO-] (5) [8]
General assumptions made for mathematically model an ideal plug
flow reactor,
• There is no mixing in the axial direction (direction of flow)
F F • Complete mixing in the radial direction
dv
Cᴧ0 ( 1- x) Cᴧ0 ( 1- x -dx) • Uniform velocity profile across the radius
Applying material balance for component A (NaOH) over small
elemental volume dv under the steady state operation results,
Figure 1: Elemental material balance for a PFR.
C A0 (1-x)F-(-rA dv) = C A0 (1-x-dx)F+0
q −rA dv =
C A0 F(dx)
A B C D x
V dx
0 0 = CA0 ∫ (9)
t=0
C A0 C A0 F 0
−rA
Residence time is same as the space time and given by
V
t=t C A0 ( 1 − x A ) C A0 ( 1 − x A ) C A0 x A C A0 x A τ= (10)
2
F x
2 2 2 dx
Therefore, τ =CA0∫ 2 2
(11)
Table 1: Concentration of streams with time. 0
kC A0 ( 1 − x)
Page 3 of 8
Page 4 of 8
Reactor Temperature (oC) 30 35 40 45 energy (Ea) and frequency factor (k0) were found to be 41400 kJ/kmol
Experimental results 0.73 0.76 0.80 0.83 and 2194760 respectively [8] and those values were fed to the Aspen
Simulated results 0.72 0.77 0.81 0.84 model (Figure 5). The results that were obtained upon the simulation of
the model are given in Table 3.
Table 2: Fractional conversion at different reactor temperatures.
Results and Discussion
PFR model in the aspen simulation represent the tubular reactor
in the experimental module and the parameters were set accordingly. Conductivity vs. Temperature
Length of the reactor was 16.5 m and the diameter of the tube was 5.8 Conductivity values of both NaOH stream and product stream
mm. Phase of operation for the experimental model was only liquid were adjusted to the operating temperature of the reactor according to
and therefore valid phase the PFR model in the Aspen was selected as equation (6) and were plotted against the reactor temperature (Figure
liquid- only (Figure 4). Operating condition for the PFR was set as 30oC 6). The conductivity values of the solution show linear dependence on
and 1atm. the reactor temperature.
After setting up the physical parameters, reaction kinetic parameters Comparison of simulated results and experimental results
were introduced to the Aspen model. According to the literature [8], the
Table 2 shows the calculated results for the fractional conversion of
saponification reaction follows the power law (equation 7) and hence it
the saponification reaction at different reactor temperatures for both
was selected as the reaction class in the Aspen model. Driving force was
the experiment and the simulation. It is clear from the results that
also set as ‘exponent’ of one for both the reactants since the reaction rate in both the cases, the fractional conversion increases as the reactor
is proportional to the concentration of each of the reactant. Activation temperature increases.
Page 5 of 8
35
30
Conductivity (mS/cm)
25
20
k0 (mS/cm)
15
kt (mS/cm)
10
5
0
30 35 40 45
Temperature (oC)
0.86
0.84
0.82
Fractional Conversion
0.80
0.78
0.76 Experimental Results
0.74 Simulated Results
0.72
0.70
30 35 40 45
Reactor Temperature (oC)
Figure 7: Fractional conversion vs reaction temperature.
The experimental values obtained for fractional conversion were with increment of length of the plug flow reactor. This is because the
correlated with the results obtained from the simulation (Figure 7). The residence time of reactants increases with the length of the reactor,
correlation coefficient (r2) was 0.98 and it proved that simulation results where it allows sufficient time for the reaction to take place (equation
show a good fit for the experimental model. 11).
Effect of temperature on the reaction Effect of reactant flow rates on the reaction
Figure 8-11 show the variation of molar fractions of ethyl acetate A sensitivity analysis was done in Aspen Plus model to investigate
and sodium acetate at the reactor temperatures of 30°C, 35°C, 40°C and the effect of reactant flow rates towards the reaction.
45°C respectively. It is clear from these figures that the molar fractions
Figure 12 shows how the mole fractions of sodium acetate vary for
of reactants decrease with the increment of reactor temperature. This
different flow rates of NaOH and ethyl acetate. It shows that in each
is due to the fact that the reaction rate increases with the reactor
case the highest mole fraction of sodium acetate can be achieved when
temperature and hence, the molar fractions of products increase
equal flow rates of NaOH and ethyl acetate are pumped to the plug flow
(equations 7 and 8).
reactor. According to the stoichiometry of the reaction (equation 2) it
Figure 13 shows the curve for molar flow of sodium acetate obtained is clear that equal amounts of reactants are needed to obtain the highest
under different reactor temperatures (From 25°C to 200°C). It can be yield.
seen that the sodium acetate molar flow rate increases with the reactor
When the flow rate of ethyl acetate exceeds the flow rate of NaOH
temperature and it reaches a maximum value of 0.24 mol/h when the
as there is no more NaOH left in the reactor to react with ethyl acetate,
reactor temperature is150°C.
the excess ethyl acetate remains in the product stream. Therefore
It is also evident that the molar fractions of products increase though same amount of sodium acetate is produced by the reaction,
Page 6 of 8
mole fraction of sodium acetate is decreased because of the presence of to achieve the same conversion for a reaction while maintaining the
unreacted ethyl acetate in the product stream. other parameters as constant [15]. This theory is well applied for the
saponification reaction of ethyl acetate with sodium hydroxide. During
Volume comparison of CSTR and PFR
this study it has also proven with using Aspen simulation that the
Volume required for a PFR is relatively less when compared to volume of CSTR to achieve the same conversion is about 3.5 times that
the volume required for a Continuous Stirred Tank Reactor (CSTR) of a PFR (Figure 14). Therefore, it is economically feasible to use a PFR
Page 7 of 8
Figure 12: Variation of ethyl acetate mole fraction with acetate and NaOH flow rates.
Conclusion
0.2
In this work, a simulation model was developed for the reaction
of saponification of ethyl acetate in the presence of sodium hydroxide
0.15
inside a plug flow reactor using Aspen Plus. The model was validated
by the experimental results obtained from EDIBON Plug Flow Reactor
0.1 module. The experimental results showed a good fit to the Aspen Plus
0 25 50 75 100 125 150 175 200
Reactor Temperature (oC)
model.
Figure 13: Variation of Sodium acetate flow rate with reactor temperature. Aspen Plus model proved that the rate of reaction increases as the
reactor temperature and the length of the plug flow reactor increase.
The highest yield of the reaction was obtained at a reactor temperature
0.0007
of 150°C.
0.0006 These results improve the understanding of reaction kinetics with
Ethyl acetate mole fraction
0.0005 reference to the saponification reaction and would be very useful in the
0.0004
design of plug flow reactors.
0.0003 PFR Acknowledgement
0.0002 CSTR The authors would like to acknowledge Dr. Ismail F. M., Dr. Gunasekera M. Y.
and Mr. Rathnayake H.H.M.P. for providing the space and all facilities needed in the
0.0001 research study at the Department of Chemical and Process Engineering, University
0.0000 of Moratuwa, Sri Lanka.
0 500 1000 1500 2000
Reactor volume (ml) References
Figure 14: Ethyl acetate mole fraction vs reactor volume. 1. Scott FH (2006) Elements of Chemical Reaction Engineering. Prentice Hall
International.
Page 8 of 8
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