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ASSIGNMENT 1:
PRODUCTION OF METHYL ACETATE VIA ESTERIFICATION
COURSE CODE:
CPE606
PROCESS MODELLING
PREPARED BY:
NAME STUDENT ID
NURUL SYAFIQAH BINIT MD SHAH 2021862162
WAN ARISSA BINTI WAN ZAID 2021862066
TENGKU SHAMIM AMELIN BINTI TENGKU ZAHIDI 2021497844
GROUP:
CEEH2206K
PREPARED FOR:
DR. MUHAMMAD SYAFIQ HAZWAN BIN RUSLAN
1
TABLE OF CONTENTS
1.0 PROCESS BACKGROUND................................................................................................................1
3.1 DESCRIPTION.................................................................................................................................4
3.2 PROCESS FLOW DIAGRAM........................................................................................................5
4.0 THE DESIGN OF THE REACTOR...................................................................................................6
1
1.0 PROCESS BACKGROUND
Methyl acetate also known as MeAc, acetic acid methyl ester or methyl ethanoate consists
of carboxylate esters. It is a volatile compound that has a low wall point (57 ℃) that is widely
used for resins and oils (Dionisio et al., 2018). Methyl acetate can be produced in many method
such as the process of air oxidation, carbonylation process and also the esterification process with
sulfuric acid as a catalysst. However, today's world is introducing new technology in its
manufacturing process by using reactive distillation (Methyl Acetate Plant, Methyl Acetate
Production Process and Technology Provider, n.d.). It is one of the new techniques that combines
both reaction and separation for a balanced reaction.
Synthesis and mechanism of kinetics of methyl acetate are also deliberated for
homogeneous and heterogeneous catalyzed reactions. The reactive distillation process also uses
the methyl acetate hydrolysis method. It has been developed since the laboratory scale as a
catalyst resin catalyst in the reaction. By using this acid catalyst, recovery of used acid is no
longer required which saves a lot of costs. Conventional methods are more complex and require
higher costs which causes, on average, the industry prefers reaction distillation (Pazmiño-
Mayorga et al., 2022). It is a balanced reaction, takes place in the liquid phase, and is cost
effective. This project is a conventional methyl acetate esterification process carried out in a
Continuously Stirred Tank Reactor (CSTR) which is more compliant with standards and
influences operating conditions like reactants flow rate, reaction temperature and conversion. A
number of constraints of physical properties must be analyzed before they design the reactor
including boiling point range, azeotrope behavior, temperature and so on.
In the esterification process, methanol must be added and water removed to achieve
balance in the process. Thermodynamically, the percentage of total conversion is low due to its
moist nature. Thermodynamically, the percentage of total conversion is low due to its moist
nature. Methyl acetate can achieved conversion up to 100% using the multi-stage reactive
distillation with ratio 1:1.7 of acetic acid to methanol but with reactor, it can archieved 83.8% of
methyl acetate with the same ratio which is of acetic acid to methanol (Ganesh et al., 2014).
Therefore, this process usually takes longer and requires more energy to maximize the conversion
of methyl acetate at a higher rate. This process is also an endothermic reaction that absorbs heat.
The jacketed reactor that surrounds the reactor needs heat to be absorbed to carry out the reaction.
The use of Low Pressure Steam (LPS) helps to provide energy to the hot utility in the
esterification rposes in the CSTR. After that, the liquid will go through a separation process
where liquid-liquid extraction (LLE) is used to remove all precipitates and get rich and pure
methyl acetate. So, dimethyl sulfoxide solvent is used to dissolve the solution in preseparation
1
(Yeh, n.d.).
2
2.0 CHEMICAL DESIGN
In the design of a product reactor, several factors must be studied first to analyze
complete information including chemical reactions, chemical kinetics information, product yield
of methyl acetate. The stoichiometry equation for the esterification of acetic acid with methanol is as
below:
Methanol (A) + Acetic Acid (𝐁) ↔ Methyl Acetate (C) + Water (D)
Based on the stoichiometry equation above, the reaction that occurs in the methyl acetate process
is a reversible reaction (Rohde et al., n.d.). The stoichiometry of each chemical is as stated:
Table 1: Table of stoichiometry of each chemical
Based on the study of the kinetics of acetic acid esterification with methanol that has
been studied, the overall reaction order for this process is a second order reaction (Kinetic
Behaviour of Esterification of Acetic Acid with Methanol over Solid Acid Catalysts, n.d.). In
this process, the forward and backward reaction rate constants and activation energies that
can be obtained from the Arrhenius plot. The rate of such a reaction can be written either as:
Forward Reaction:
−𝐫𝐟 = 𝐤𝐟𝐕𝐂𝐀𝐂𝐁 (2)
Reverse Reaction:
−𝐫𝐫 = 𝐤𝐫𝐕𝐂𝐂𝐂𝐃 (3)
3
respectively. In the rate of formation, k represents as the reaction rate constant. A reverse rate
reversible reaction is the same because it reaches equilibrium on both sides. Temperature is the
main factor in the dependence of reaction rates. It can be expressed in the Arrhenius Equation
according to different temperatures.
𝐤 = 𝐀𝐞 𝐑𝐓 (4)
According to the Arrhenius Equation, A represents the pre-exponential factor, Ea is the
activation energy, T is the absolute temperature, and R is the universal gas constant. The values
of the pre-exponential, A and the activation energy, Ea of this reaction are obtained from
experiments. The values are as stated in Table 2 (Kinetic Behaviour of Esterification of Acetic
Acid with Methanol over Solid Acid Catalysts, n.d.)
The product yield for this esterification of methanol and acetic acid with simple unit
reactive distillation can achieved to 90% of conversion but the conversion can increase up to
100% with the using of multi-stage reactive distillation (Ganesh et al., 2014). The higher value of
yield is because of the reactive extraction that immediate separation of the ester from the reaction
mixture. But, if the process without using the reactive extractive distillation which only with
reactor, the yield and conversion will be low which is can be only achieved to 83.8% (Ganesh et
al., 2014).
4
3.0 PROCESS DESCRIPTION
3.1 DESCRIPTION
As shown in Figure 4.2 below is the process flow diagram for the esterification of acetic
acid and methanol to produce methyl acetate and water. This process started with the reactant
which is acetic acid is fed to the reactor which operating condition of 25◦C at 101.3 kPa and then
being pumped and preheated to 39◦C and 131.7225 kPa before enter the reactor. Same goes to the
other reactant which is methanol that also is being fed to the reactor which is methanol that first
being mixed with the recycle stream from the separator. Both reactants are fed to the Continuous
Stirred Tank Reactor (CSTR) (T-100) with heterogenous catalyst used was sulfuric acid. The
methanol and acetic acid are preheated to avoid a premature reaction (Luyben & Tramper, 1982)
This process of esterification is an endothermic reaction which required a heating jacket to supply
heat to the reactor. It also convinces that this rection is endothermic reaction as it has been proved
and evaluate with the thermodynamics properties which are reaction entropy (ΔS°) and heat of
reaction (ΔH°) (Jagadeeshbabu et al., 2011). In this reactor, the temperature for the operating will
be in the range of 21°C to 65.6°C at 1.01300 bar. If the temperature if more than 65.6°C, there
will be a vapour appear in this process.
After the reaction is carried out in the reactor, the product is fed to the reactive extractive
distillation column. This equipment is a technique used to separate components that have close
boiling point or azeotropes, which by the presence of additional liquid that have the higher
boiling point compare to the component that being separated (United States Patent (19) Berg et al.
54 SEPARATION OF METHYL ACETATE, n.d.). As in this esterification reaction, it is
impossible to produce pure methyl acetate from the mixture of methanol-methyl acetate because
of the boiling azeotrope as both of these components will go to the overhead as the initial
product(Yeh, n.d.). In this production of methyl acetate, dimethyl sulfoxide is used to be the
extractive agent which is used to improve separation by breaking the azeotrope of methyl acetate
and methanol. (Methyl acetate, (b.p. =56.3 C.) and methanol, (b.p. = 64.5° C). Dimethyl sulfoxide
at stream 6 enters the extractive column with temperature of 60◦C at 101.3kPa. Methyl acetate
and water that comes from the rector also feed to the extractive column but heated first from 20◦C
to 53.5◦C (Graczová et al., 2018). At the top product which is stream 9, methyl acetate is
produced while at the bottom, the product is heated from 123.7◦C to 160.0◦C and send to the
separator to separate the dimethyl sulfoxide and methanol. Methanol will be separate as a top
product meanwhile dimethyl sulfoxide will separate as a bottom product and being recycled back
to the methyl acetate column at stream 14 with 20 kPa and 176.6◦C.
5
3.2 PROCESS FLOW DIAGRAM
Figure 3.2: Process Flow Diagram (PFD) of acetic acid and methanol via esterification
4.0 THE DESIGN OF THE REACTOR
Stream 1 Stream 2
F1 (m3/min) F2 (m3/min)
CA1 (mol/m3) CB2 (mol/m3)
T1 (C) T2 (C)
ρ1 (kg/m3) ρ2 (kg/m3)
V1 (m3) V2 (m3)
ASSUMPTION
1. It is a perfectly mixed, thus
concentration inside = concentration output,
CA = CA3; CB = CB3; CC = CC3; CD = CD3
2. Only liquid is present in this reactor, thus
constant densities for all streams, ρ = ρ1 = ρ2 = ρ3
3. The capacity of the methyl acetate is 30,000 tonnes/year which is 3762.3942 kg/hr
4. The feed mole ratio between methanol and acetic acid is 1:1.7
5. The molar feed flowrate of methanol is 97.8029 kmol/hr and acetic acid is 57.5311 kmol/hr
as 83.8% conversion of methyl acetate.
6. Mass flowrate for each feed is 3003.6122 kg/hr for methanol and for acetic acid is
3311.5375 kg/hr
Methanol =
kmo kmo
100% x 46.2111 l = 57.5311 l
83.8% hr hr
7
4.2 TOTAL CONTINUITY EQUATION (TCE)
[mass flow into the - [mass flow out of the = [time rate of change of
system] system] mass inside the system]
dm
ṁ¿ −ṁout =
dt
ṁ ¿ =F1 ρ1+ F 2 ρ2
ṁout =F 3 ρ3
dρV
F 1 ρ1 + F 2 ρ2−F 3 ρ3=
dt
Where ρ1= ρ 2=ρ3
dv
(F 1+ F 2−F 3) ρ= ρ
dt
dv
F 1+ F 2−F 3=
dt
dv
Where =0
dt
F 1+ F 2=F 3
Component A
d (VCa)
= F1CA1 − F3CA3 − k1VCA3CB3 + k2VCC3CD3
dt
When V = constant, CA3 = CA ; CB3 = CB ; CC3 = CC ; CD3 = CD
(d Ca)
Thus, V = F1CA1 − F3CA − k1VCACB + k2VCCC
dt
Final equation:
8
dCA F 1C A 1−F 3 C CA
= −k 1 VC A C B+k 2VC C C D
dt V
Component B
d (VCb)
=¿F2CB2 − F3CB3 − k1VCA3CB3 + k2VCC3CD3
dt
dCB
Thus, V =¿F2CB2 − F3CB − k1VCACB + k2VCCCD
dt
Final equation:
dCB F 2C B 2−F 3 C B 3
= −k 1 VC A C B+ k 2VC C C D
dt V
Component C
d (VCc )
=¿−F3CC3 + k1VCA3CB3 − k2VCC3CD3
dt
When V = constant, CA3 = CA ; CB3 = CB ; CC3 = CC ; CD3 = CD
dCc
Thus, V =¿−F3CC + k1VCACB − k2VCCCD
dt
Final equation:
dCc −F 3 C 3
= +k 1 VC A C B−k 2 VC C C D
dt V
Component D
d (VCD)
=¿−F3CD3 + k1VCA3CB3 − k2VCC3CD3
dt
When V = constant, CA3 = CA ; CB3 = CB ; CC3 = CC ; CD3 = CD
dCD
Thus, V =¿ −F3CD + k1VCACB − k2VCCCD
dt
Final equation:
dCD −F 3 C 3
= + k 1 VC A C B−k 2 VC C C
dt V
9
1
0
4.4 ENERGY BALANCE FOR PROCESS
To find the ideal operating temperature for the reactor and temperature jacket to deliver the
necessary heat to the reactor temperature, the energy balance equations for the reactor and heating
jacket are derived. The energy balance equation must be derived under some assumptions.
dE
E¿ −E out +Q added −W done =
dt
Energy Balance for CSTR:
E¿ =F 1 ρ1 (u1 + KE 1 + PE 1)+ F 2 ρ2 (u 2+ KE 2 + PE 2)
Eout =F3 ρ 3 ( u3 + KE 3+ PE 3 )
Qadded =QJacketed +Q G
QJacketed =λ f k f V f C A C B −λr k r V r C c C D
QG =U A H (T j −T )
W =W shaft + W flow
W shaft=0
W flow =F3 P3−F 1 P1−F 2 P 2
1
1
F 1 ρ1 ( u1 + KE 1+ PE 1 ) + F 2 ρ 2 ( u2 + KE 2 + PE 2 )−F 3 ρ 3 ( u3 + KE 3 + PE 3 ) + λ f k f V f C A C B −λ r k r V r C c C D +U A H ( T j−T )−
d ( ρ3 V 3 u3 )
F 1 ρ1 u1+ F 2 ρ2 u2 −F3 ρ3 u 3+ λf k f V f C A C B− λr k r V r C c C D +U A H ( T j−T ) −F 3 P 3+ F 1 P 1+ F 2 P2=
dt
1 ^ 1 ^ 1 ^
Where =V 1 , = V 2 , = V 3
ρ1 ρ2 ρ3
ρ3 ρ ρ d (ρ3 V 3
F 1 ρ1 u1+ F 2 ρ2 u2 −F3 ρ3 u 3+ λf k f V f C A C B− λr k r V r C c C D +U A H ( T j−T ) −F 3 P 3 + F 1 P1 1 + F 2 P 2 2 =
ρ3 ρ1 ρ2 dt
^ 3 + F1 P 1 ρ 1 V
F 1 ρ1 u1+ F 2 ρ2 u2 −F3 ρ3 u 3+ λf k f V f C A C B− λr k r V r C c C D +U A H ( T j−T ) −F 3 P 3 ρ3 V ^ 1 + F2 P2 ρ 2 V
^ 2=
d ( ρ3 V 3 u3 )
F 1 ρ1 ( u1 + P1 V^ 1 ) + F 2 ρ 2 ( u2+ P 2 V
^ ) −F ρ ( u + P V^ ) + λ k V C C −λ k V C C +U A ( T −T ) =
2 3 3 3 3 3 f f f A B r r r c D H j
dt
Where ( u 1+ P1 V
^ 1 )=h1 , ( u 2+ P2 V
^ 2 )=h2 , ( u3+ P3 V^ 3 ) =h3
In tank, ρu ≪≪ u
∴ u=h
d ( ρ3 V 3 h3 )
F 1 ρ1 h1 + F2 ρ2 h2−F 3 ρ3 h3 + λ f k f V f C A C B −λ r k r V r C c C D +U A H ( T j −T ) =
dt
Where h=C p T
d ( ρ3 V 3 ❑3 )
F 1 ρ1 Cp1 T 1+ F 2 ρ2 Cp2 T 2−F 3 ρ 3 Cp3 T 3 + λ f k f V f C A C B −λ r k r V r C c C D +U A H ( T j−T )=
dt
d( VT )
ρCp ( F1 T 1+ F 2 T 2−F 3 T 3)+V ( λf k f C A C B−λ r k r C c C D )+U A H ( T j−T ) =
dt
−Ea
The Arrhenius Equation is substituted in the equation K= A e RT because the rate constant is
temperature dependent. Thus,
dT F 1 T 1+ F 2 T 2−F 3 T 3
= + λf ¿ ¿
dt V
1
2
4.5 ENERGY BALANCE FOR JACKET
1. Considering that it is a liquid system, enthalpy, h J and internal energy, u J are expressed as
u J =h J and h J =heat capacity × temperature , Cp J T J (liquid phase).
2. The jacket's interior temperature, T J and outlet stream temperatures, T J outlet are same because
the fluid inside the jacket is perfectly mixed, T J =T J outlet.
3. Very few heat losses to the surroundings so it can be neglected.
4. The system does nothing because there is no shaft existed, hence W shaft=0.
5. The kinetic energy is negligible because the flow velocities at the inlet and outflow are not
particularly high. (KE=0)
6. Since it is assumed that the inlet and outlet flows have elevations that are nearly identical,
the potential energy is zero. (PE=0)
7. Overall heat transfer coefficient, U and heat transfer area, AH is both constant.
dE
E¿ −E out +Q added −W done =
dt
E¿ =F Jo ρJo ( u Jo + KE Jo + PE Jo )
Eout =F J ρJ ( uJ + KE J + PE J )
Q j=U A H ( T j−T )
W =W shaft + W flow
W shaft =0
W flow=F J P J −F Jo PJo
d ( ρ J V J (u J + KE J + PE J ))
F Jo ρJo ( u Jo + KE Jo + PE Jo )−F J ρ J ( u J + KE J + PE J ) +U A H ( T j−T ) −(F ¿ ¿ J P J −F Jo PJo )= ¿
dt
1 ^ 1 ^
Where =V Jo , =V J , h=u+ P V^ =CpT ( liquid phase )
ρJo ρJ
ρ ρ d ( ρJ V J u J )
F Jo ρJo u Jo−F J ρJ u J + U A H ( T j−T )−F J PJ J + F Jo P Jo Jo =
ρJ ρ Jo dt
F Jo ρJo u Jo−F J ρJ u J + U A H ( T j−T )−F J PJ ρ J V^ J + F Jo P Jo ρJo V ^ Jo= d (ρ J V J u J )
dt
d (ρ V J J)
u
F Jo ρJo ( u Jo + P Jo V^ Jo ) −F J ρJ ( uJ + P J V
^ J ) +U A H ( T j−T )= J
dt
d ( ρJ V J h J )
F Jo ρJo h Jo−F J ρ J h J +U A H ( T j −T ) =
dt
1
3
Thus,
d ( ρ J V J CpJ T )
F Jo ρJo Cp Jo T Jo −F J ρJ CpJ T J + U A H ( T j−T )=
dt
d (ρ J V J Cp J T )
ρCp ( F Jo T Jo−F J T J )+U A H ( T j−T )=
dt
F J (T Jo−T J ) U A H ( T j −T ) d (T )
+ U A H ( T j−T )=
VJ V J ρJ CpJ dt
By using and simulate in the Aspen HYSYS Method, the final design reactor parameter for
Continuous Stirred Tank Reactor, (CSTR) were done to be determined. Table 3 below shows the
summarized of the parameters of the designed CTSR.
Table 3: Final design parameters for CSTR
Operating Temperature 65.5◦C
Operating Pressure 1.02300 bar
Volume of the Reactor 470m3
Diameter of the Reactor 7.326 m
Length of the Reactor 11.04 m
Conversion 83.88%
1
4
5.0 REFERENCES
Dionisio, K. L., Phillips, K., Price, P. S., Grulke, C. M., Williams, A., Biryol, D., Hong, T., & Isaacs, K. K.
(2018). Data Descriptor: The Chemical and Products Database, a resource for exposure-relevant data
on chemicals in consumer products. Scientific Data, 5. https://doi.org/10.1038/SDATA.2018.125
Ganesh, B., Rani, K. Y., Satyavathi, B., & Patnaik, K. S. K. R. (2014). Experimental analysis in different
batch operating units for process intensification: methyl acetate production case study. International
Journal of Industrial Chemistry, 5(3–4), 85–93. https://doi.org/10.1007/s40090-014-0023-7
Graczová, E., Šulgan, B., Barabas, S., & Steltenpohl, P. (2018). Methyl acetate–methanol mixture
separation by extractive distillation: Economic aspects. Frontiers of Chemical Science and
Engineering, 12(4), 670–682. https://doi.org/10.1007/s11705-018-1769-9
Jagadeeshbabu, P. E., Sandesh, K., & Saidutta, M. B. (2011). Kinetics of esterification of acetic acid with
methanol in the presence of ion exchange resin catalysts. Industrial and Engineering Chemistry
Research, 50(12), 7155–7160. https://doi.org/10.1021/ie101755r
Kinetic Behaviour of Esterification of Acetic Acid with Methanol over Solid Acid Catalysts. (n.d.).
Luyben, K. C. A. M., & Tramper, J. (1982). Optimal design for continuous stirred tank reactors in series
using Michaelis–Menten kinetics. Biotechnology and Bioengineering, 24(5), 1217–1220.
https://doi.org/10.1002/BIT.260240518/FULL
Methyl Acetate Plant, Methyl Acetate Production Process and Technology Provider. (n.d.). Retrieved May
5, 2023, from https://www.slchemtech.com/methyl-acetate-plant/
Pazmiño-Mayorga, I., Jobson, M., & Kiss, A. A. (2022). A Systematic Methodology for the Synthesis of
Advanced Reactive Distillation Technologies. Industrial and Engineering Chemistry Research.
https://doi.org/10.1021/acs.iecr.2c04540
Rohde, C., Marr, R., & Siebenhofer, M. (n.d.). Investigation of Methyl Acetate Production by Reactive
Extraction.
United States Patent (19) Berg et al. 54 SEPARATION OF METHYL ACETATE. (n.d.).
Yeh, A.-I. (n.d.). The separation of three azeotropes by extractive distillation.
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