CHAPTER 1

1.1 INTRODUCTION TO THE PROCESS

Ethyl acetate is a useful solvent for the production of lacquers, enamels, inks, adhesives
and pharmaceuticals. Recently, aromatic solvents have been replaced with ethyl acetate due to
its lower toxicity.
There are many available processes to produce ethyl acetate in industries. Ethyl acetate
is mainly produced by esterification of ethanol with acetic acid. In some industries, Tishchenko
reaction are used through the condensation of acetaldehyde with alkoxide. A new technology
to produce ethyl acetate was produce known as Advanced Acetates by Direct Addition
(AVADA) process. This process involves the usage of ethylene and acetic acid as a reactant.
In this processes, it used a heteropolyacid (HPA) which offers high activity and selectivity to
convey product at more than 99.97% purity (Flatley, 2001). All the processes has its advantages
and its appropriate services. The process selected in this case is Advanced Acetates by Direct
Addition process or known as Alkylation of acetic acid by ethylene.

According to Yamamoto, a direct addition of acetic acid to ethylene to produce ethyl

acetate has entice much concern because preferably this process will not produce by-product.
It is a generation path of high atom efficiency, if any of heterogeneous catalyst with high
selectivity and activity are used in the process. In this reaction, acetic acid is reacted with
ethylene to form ethyl acetate in the presence of heteropolyacid as a catalyst.

C2H4 + CH3COOH CH3COOCH2CH3

The ethylene and acetic gases are directly converted into ethyl acetate using a
heteropolyacid catalyst without usual intermediate stage of esterification. The catalyst used for
this process is silicotungstic acid. The vapor process involved passing a 4:1 ethylene to acetic
acid mixture over a catalyst bed made of zinc acetate-saaturated activated carbon at 180 C to
223.4C. The reaction is environmentally friendliness since no by product are produced.
However, problem arise from this reaction is that the catalyst lifetime where it is rapidly ageing
and cause loss of activity.

1
1.2 OVERALL PROCESS DESCRIPTION

The reactants in this process are ethylene and acetic acid. Fresh feed of ethylene (Stream
1) and acetic acid (Stream 2), along with makeup feed water (Stream 3) at 25 C and 101.32
kPa are fed into the mixer. The temperature of the vapour phase outlet of the mixer (Stream 4)
is decreased to 9.58 C and then the mixture is further to the compressor to increase the reaction
pressure from 101.3 kPa to 1000 kPa before being cooled to 180 C and the mixture flow into
the reactor. The reaction proceeds in the vapour phase in the reactor to attain a reaction
conversion of 72.56%. The main reaction involve in this process is the reaction between
ethylene and acetic acid to form ethyl acetate as stated below:

Silicotungstic Acid
C2H4 + CH3COOH CH3COOCH2CH3

Among the side reactions that occur in the reaction are the formation of ethanol and
diethyl ether according to the following equations:

CH3COOCH2CH3 + H2O C2H5OH + CH3COOH

2 C2H5OH (C2H5)2O + H2O

whereby ethanol and acetic acid is produced from the reaction of ethyl acetate and water while
diethyl ether and water are produced from 2 molecules of ethanol.

The outlet stream from the reactor (Steam 8) contains a mixture of ethylene, acetic acid,
water, ethyl acetate, ethanol and diethyl ether in vapour phase are cooled from 223.4C to 20
C then all these mixture enter a Phase Separator at temperature 20 C and pressure 989.7 kPa
where the two phase system is separated and removed as a vapour outlet stream (Stream 10)
and a liquid outlet stream (Stream 13). The vapour from the outlet of the phase separator mainly
containing ethylene with mole fraction 0.9861 is then recycle back to the mixer.

The pressure of the liquid outlet stream (Stream 13) is then reduced from 989.7 kPa to
500 kPa and sent to the Distillation Column (T-100) at 20 C as a cold liquid feed. The outlet
from the top of T-100 (Stream 18) at 127.2 C is fed to the Distillation Column (T-102) which
aims to removed diethyl ether and ethylene as a top product (Stream 19) which is discarded
after undergo treatment while the bottom product (Stream 20) is then fed to the Distillation
Column (T-102) at 70.4 C resulting in the separation of ethyl acetate (desired product) as the
top product (Stream 22) with the mass fraction of 0.8377.

2
CHAPTER 2

2.1 THE CHOICE AND THE SEQUENCE OF THE EQUIPMENT

The equipment that involved in the production of Ethyl Acetate using alkylation process
are Mixer (MIX-100), Heater (E-100, E-103), Cooler (E-101, E-102, E-104), Compressor (K-
100), Conversion reactor (CRV-100), Phase separator (V-100), Expander (K-101) and
Distillation Column (T-100,T-101, T102). The major equipment in this process are Reactor
and Distillation Column. The operation involved are:

1. Mixer (MIX-100)

Mixer are used to combine Ethylene from Stream 1 (S1), Water from Stream 2 (S2),
and Acetic Acid from Stream 3 (S3). All the component entering the mixer at 25C and
101.32 kPa.

2. Heater (E-100 and E-103)

Heater are used in order to heat the mixture and to increase the temperature of the
mixture. In this process, heater is located after the mixer to increase the temperature of
the mixture from 25C to 50C and also after the expander.

3. Cooler (E-101, E-102 and E-104)

Cooler is used to cool down the mixture and to reduce the temperature of the stream. In
this process, coolers are situated both before and after the packed bed reactor and also
at the bottom stream of Distillation Column T-100 before entering the mixer.
4. Compressor (K-100)
Compressor is used to increase the pressure of the mixture to the reaction pressure
1000.078 kPa before sending the mixture to the reactor.

5. Reactor (CRV-100)

The reactant enter the reactor at the reaction temperature of 180C and 1000.078 kPa
and vapour phase direct addition process take place between ethylene and acetic acid.
The reactants are convert into the ethylene.

6. Phase Separator (V-100)

A vessel that separate the fluid mixture into the gas and liquid. In this process, ethylene
in the form of gas is separated from the fluid mixture.

3
7. Expander (K-101)

Expander is used to decrease the pressure of a vapor phase stream. In this process, the
pressure of the outlet from the phase separator is reduced from 1000.078 kPa to 101.32
kPa
8. Distillation column (T-100, T-101 and T-103)
In this process, Distillation Column T-100 are used to separate acetic acid as a bottom
product, Distillation Column T-102 are used to separate Diethyl Ether as the top product
while Distillation Column T-103 are used to separate Ethyl Acetate and water.

2.2 SEPARATION PROCESS EFFICIENCY USED IN THE PLANT

Conversion happened at reactor CRV-100 which the stream inlet is S7 and the stream outlet is
S8.

Conversion = x 100%

(0.0585)(8257)(0.0169)(7842)
= x 100%
(0.0585)(8257)

= 72.56%
For yield, it is the ratio of the amount of mole ethyl acetate formed at streams S22 and S23 to
the amount of ethyl acetate that could have been produced if the limiting reactant react with a
conversion of 100%. In this process, the limiting reactant is acetic acid since it is the lowest
amount of mole entering the feed streams.

Yield =

(0.8377)(155.1)+(0.1745)(24.74)
= 326.8

= 0.41
For selectivity, it is the ratio of the desired product which is the amount of mole ethyl acetate
formed at streams S22 and S23 to the amount of undesired product formed which is water at
stream S23.

Selectivity =

(0.8377)(155.1)+(0.1745)(24.74)
= (0.6537)(24.74)

= 8.3

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2.3 THE FLUID FLOW PRINCIPLES ADOPTED

Type of equipment: Reactor CRV-100

Pressure inlet: 1000kPa
Justification: The reaction is exothermic and higher product yields can be achieved at low
temperature and higher temperature.

Type of equipment: Distillation Column T-100, T-101, T-102

Pressure inlet: 500kPa, 500kPa, 100kPa
Justification: All the distillation columns are operated at high pressure to ensure that its
overhead vapour is not enough to cause boiling of those bottoms liquids.

2.4 THE CHOICE OF PROCESS CONDITIONS ADOPTED

An Equation of State (EOS) is a formula describing the interrelation between various

macroscopically measurable properties of a system. For physical states of matter, EOS usually
relates the thermodynamic variables of pressure, volume and number of moles of material. The
fluid package used for our process of Ethyl Acetate production is Lee-Kesler-Plcker (LKP)
equation of state. The reason why we decided to use LKP model is because it is considered to
be the most accurate general method for the calculation of non-polar substances and mixtures
and also it is highly recommended for Ethylene Towers. For our process, we do not have
ethylene towers but one of the major substances used is Ethylene thus it is relatable to use LKP
model for our process of Ethyl Acetate production. LKP model used the LKP method to
calculate Vapor-Liquid Equilibrium (VLE) and uses the Lee-Kessler method to calculate to
calculate enthalpy and entropy.

5
 Condenser
S10 Reflux
20C, 989.7 kPa Drum

S9
20C, 989.7 kPa V- Diethyl
100 Ether
S19 Ethylene
44.47C, 500 kPa
K-101 E-102
T-101

S8 S13
223.4C, 1000 kPa 20C, 989.7 kPa
S11
-56.82C, 101.3 Reboiler
kPa

CRV-100

S18
VLV-100 127.2C, 500 kPa S20
125.1C, 500 kPa
E-103 S7
180C, 1000 kPa Condenser

E-101 S14
20C, 500 kPa Condenser Reflux
Drum
S6
213.5C, 1000 kPa

VLV-102 Ethyl
S11 K-100
Acetate
25C, 101.3 kPa
T-100 S22
S5 64.76C, 100 kPa
50C, 101.32 kPa S21
70.4C, 100 kPa

Acetic Acid E-100

25C, 101.32 kPa
S23 Water
S4 Reboiler
S2 MIX-100 82.28C, 100
Ethylene 9.58C,
25C, 101.32 kPa 101.32 kPa kPa
S1 Reboiler
Water
25C, 101.32 kPa S16
S3 82.06C, S15
S17
25C, 101.3 kPa 101.3 kPa 137.4C, 500 kPa

VLV-101
E-101

Complete Process Flow Diagram

6
Material streams and compositions

7
8
9
10
11
Compositions in mass fraction

Stream S4 to S7 S8 to S9 S10 to S12 S13 to S14 S15

Ethylene 0.710 0.668 0.960 0.003 0.000
Water 0.008 0.006 0.000 0.018 0.017
Acetic Acid 0.104 0.028 0.001 0.091 0.120
Ethyl Acetate 0.174 0.285 0.032 0.859 0.859
Diethyl Ether 0.004 0.011 0.007 0.022 0.000
Ethanol 0.000 0.002 0.000 0.007 0.004
Total mass flow (kg/h) 279800 279800 194700 85450 70850
Stream S18 S19 S20 to S21 S22 S23
Ethylene 0.047 0.460 0.000 0.000 0.000
Water 0.090 0.000 0.022 0.002 0.337
Acetic Acid 0.000 0.000 0.000 0.000 0.000
Ethyl Acetate 0.695 0.000 0.843 0.869 0.438
Diethyl Ether 0.131 0.540 0.112 0.120 0.000
Ethanol 0.037 0.000 0.023 0.009 0.225
Total mass flow (kg/h) 14590 558.5 14030 13170 867.7

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CHAPTER 3

CONCLUSION

As a conclusion, we have successfully achieved our target of 100000 tonnes/year

production of Ethyl Acetate with slightly higher annual production which is 100250
tonnes/year. The process to produce Ethyl Acetate which is the desired product, also produced
other by-product which is the mixture of ethylene and diethyl ether. This mixture by-product
can be further processed to separate these two components by using simple distillation. Simple
distillation of these two components would let us to export both products or at the least, we can
re-use the ethylene produced to our process by supplying it to the feed flow. This step not could
help us by gaining profits from the sale of the ethylene and diethyl ether to other companies,
but we also could save cost by re-use the ethylene to our feed flow.

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CHAPTER 4

REFERENCES

Ethyl Acetate by Direct Addition of Ethylene and Acetic Acid. Retrieved June 19, 2017 from
https://www.ihs.com/products/chemical-technology-pep-reviews-ethyl-acetate-by-direct-
addition-2007.html

Innovation in the Production of Ethyl Acetate and Acetic Acid. Retrieved June 19, 2017 from
http://www.eurochemengineering.com/Innovation-in-the-production-of-acetic-acid-and-
ethyl-acetate.aspx

Production using BPs Avada Ethyl Acetate Process Kicks Off. Retrieved June 19, 2017 from
https://www.icis.com/resources/news/2001/12/10/153003/production-using-bp-s-avada-ethyl-
acetate-process-kicks-off/

Yamamoto, Y., Hatanaka, S., & Tsuji, K. (2008). Applied Catalysis A: General. Direct
Addition of Acetic Acid to Ethylene to form Ethyl Acetate, , 60.

(n.d.). Property Package Descriptions Equations of State (EOS). Retrieved June 21, 2017, from
razifar.com/cariboost_files/Property_20Package_20Descriptions.pdf

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