FACULTY OF CHEMICAL AND NATURAL RESOURCES ENGINEERING

BKC 4913
PROCESS SIMULATION PLANT DESIGN I

PROCESS SIMULATION REPORT

PRODUCTION OF 21,000 MTPA ETHYLENE OXIDE

Group Members:
JASMIN A/P TRAMARAJH

KA12006

MOHD HAFIZS BIN FIRDAUS

KA13137

NURUL ATIKA BINTI MOHD YATIM

KA12049

NURAMIRA FATEHA BT SUKOR

KA12068

AIIZAT IKHWAN BIN ABDUL JALIL

KA12078

Table of Contents
1.0 INTRODUCTION ............................................................................................................... 3
1.1 Overview ....................................................................................................................................... 3
1.2 Process Description ....................................................................................................................... 4

2.0 LITERATURE REVIEW .................................................................................................... 6

2.1 Air-based direct oxidation process ................................................................................................ 6

3.0 LIST OF CHEMICAL COMPONENTS DEFINITION ..................................................... 7

4.0 SELECTION OF THERMODYNAMIC MODEL OR FLUID PACKAGE MODEL ....... 9
5.0 PLANT CAPACITY DETERMINATION.......................................................................... 9
6.0 SUMMARY OF MAJOR UNIT OPERATIONS MODEL SPECIFICATION .................. 9
6.1 Reactor .......................................................................................................................................... 9
6.2 Separator ..................................................................................................................................... 11

7.0 CONCLUSION .................................................................................................................. 13

8.0 APPENDIX ........................................................................................................................ 14
Bibliography ............................................................................................................................ 18

1.0 INTRODUCTION
1.1 Overview
Ethylene Oxide (EO), in some cases alluded to as oxirane, is the most straightforward
cyclic ether. It is a colourless gas or fluid and has a sweet, etheric scent. The structure of an
EO particle is appeared in Figure 1.1 below.

Figure 1-1 The Ethylene Oxide Molecule

EO is formed by reacting ethylene with oxygen over an EO catalyst. The main
competing reaction is the combustion of ethylene to CO2 and water. There is also a
consecutive combustion reaction where EO further reacts to the combustion products. The
synthesis route chosen and the availability of raw materials for the process are tabulated in
Table 1-1.
Table 1- 1 Information of Synthesis Route and Raw Material
Synthesis Route

Direct Oxidation Process

Raw material used

1. ethylene
2. oxygen

Availability of raw material

1. Ethylene, the most important basic chemical product, is

produced by BASF
2. Oxygen obtained from the atmospheric air

The main objective of this project is to design a chemical plant, which produces
21,000 MTPA of ethylene oxide with a purity of higher than 99% from pure ethylene feed
through the partial oxidation process.

1.2 Process Description

Ethylene feed (stream 1) is mixed with compressed air with a pressure of 21 bar
(stream 3) which is initially compressed (Stream 1). Stream 1 and 2 are will then mix with the
recycled stream (Stream 32) from the membrane separator before being heated and fed into
the plug flow reactor at stream 5.
The reaction take place is shown below and consists of the catalytic oxidation of
ethylene to produce ethylene oxide. In addition to the desired reaction, combustion reaction
for ethylene and ethylene oxide occur. (Baiker, 1979).

C2 H 4 0.5 O2 C2 H 4O

(desired)

(1)

C2 H 4 3 O2 2CO2 2H 2O (undesired)

(2)

C2 H 4O 2.5 O2 2CO2 2H 2O (undesired)

(3)

However, the selectivity of the third reaction can be greatly suppressed by introducing
chlorine compounds to the reaction gases in small amounts. These compounds suppress the
third reaction by ensuring the silver surface of the catalyst is covered evenly with a supply of
chlorine.
The compound used in our process would be vinyl chloride. As the amount is in parts
per million, its composition would not result in an obvious deviation in material and energy
balances. Thus, since the amount is not really significant, this will be neglected in our
material and energy balance calculations and only the first two reactions will be considered.
The reaction is exothermic and takes places at a temperature of 280C and a pressure
of 21 bar. The reaction occurs adiabatically. The conversion of the whole process involved is
kept low to enhance the selectivity of the desired product as the selectivity deceases with
increasing conversion. The optimum single-pass conversion of ethylene has been determined
to be approximately 41%. The molar ratio of air to ethylene at the reactor is 6:1.
The process stream leaving the reactor is cooled and this stream is sent to the
separation unit, ethylene oxide absorber, where ethylene oxide is separated to the desired
purity of 99%. Here, pure water enters into the ethylene oxide absorber and acts as the
4

absorbent. The pure water absorbs ethylene oxide and leaves at the bottom of the unit. The
bottom product from the ethylene oxide absorber is cooled to 70C temperature and fed into
the distillation column to obtain the desired product which is ethylene oxide. Another
distillation column is added to obtained ethylene oxide with >98% purity and at the same
time to make a pure water recovery from the bottom product of the distillation column and
fed into the ethylene oxide absorber.
The distillate product from the ethylene oxide absorber are compressed and fed into
the separation unit, membrane separator. Distillate product from membrane separator will be
the recycle stream whereas the bottom product will be the purge stream. The components
involved in recycling are ethylene, oxygen and nitrogen while the other component will be
purged.
Figure 1-3 shows the process flow diagram for simulation process in Aspen Plus.

Figure1-3 Process flow diagram for simulation process.

2.0 LITERATURE REVIEW

2.1 Air-based direct oxidation process

The direct oxidation process is chosen as the synthesis route in ethylene oxide
production. The direct oxidation process utilizes the catalytic oxidation of ethylene with
oxygen over a silver based catalyst to yield ethylene oxide. There are two types of processes
that can be used for direct oxidation and it depends on the source of oxidizing agent. They are
the air-based process and the oxygen-based process. The air-based process, oxygen enriched
air is fed directly into the system; meanwhile the latter uses a high purity oxygen stream
which more than 98% mol of oxygen that is from an air separation unit.
Air-based direct oxidation is chosen as the main process for ethylene oxide
production. The advantages are:
1. Low ethylene concentration (feed) converted with air to ethylene oxide.
2. Low ethylene conversion, the reactor operates at low conversion degree, but higher
selectivity.
3. Lower cost compare to other synthesis route.

2.2 Reaction Kinetics

The reaction kinetics involved in ethylene oxide production is as follow (Ahmed, 2013)
k1

k2

Where;
*
*

+
+

(4)
(5)

These equation, (4) and (5) are use as the reaction kinetics in the reactor. The reactor
used in the simulation is RPlug. The decision make to choose this reactor is based on the
reaction kinetics obtained from the report entitled Production of Ethylene Oxide. The reaction
kinetics satisfies the requirement to use Langmuir-Hinshelwood-Hougen-Watson kinetics
(LHHW). The kinetic equation which consist of driving force expression and adsorption
expression is inserted into the reaction part in the Aspen Plus simulation. The example of the
LHHW expression equation is as follow.
(

(6)

where;
(7)

The equation (6) and (7) shows how the value of kinetic reactions is determined from
the given information.
(8)

(9)
The values in Equation in (8) and (9) above are used in the reaction in Aspen Plus
simulation.

3.0 LIST OF CHEMICAL COMPONENTS DEFINITION

Ethylene oxide (EO) is a flammable and colourless gas at temperatures above 51.3 F
(10.7 C). There are many synthesis routes in the production of EO such as chlorohydrin
process, direct conversion of ethanol, direct oxidation process and many more. Direct
oxidation process can be divided into two types which are the air-based process and the
oxygen-based process. In this report, we will focus on the air-based direct oxidation
process.
7

Based on the research, there are two reaction we are taking into consideration which
are:
k1

k2

In this model, we are using seven components in order to produce our assigned product
which is the Ethylene Oxide (EO).

Table 1- 2 Chemicals Components in the Production of Ethylene Oxide

Component ID

Component Name

Boiling Point

Ethylene

-103.74

Oxygen

-182.962

Nitrogen

-195.806

Carbon Dioxide

-78.45

Water

100

Ethylene Oxide

10.45

Potassium Carbonate

*decomposes

As shown above, both Nitrogen and Oxygen are obtained from the atmospheric air as
we are using the air-based direct oxidation process. Other components are mentioned in
reaction (1) and (2) above. On the other hand, Potassium Carbonate is used as the
absorbent in the Carbon Dioxide Absorber in the simulation model.

4.0 SELECTION OF THERMODYNAMIC MODEL OR FLUID PACKAGE MODEL

There are two types of fugacity models, equation of state and liquid-state activity coefficient
models. In this simulation, liquid-state activity coefficient is recommended since a polar
component is involved in the simulation. In production of ethylene oxide, ethylene and
oxygen are both hydrocarbon without pseudo-component. In choosing a thermodynamic
model also need to consider all the component boiling point (Tb), critical temperature (Tc),
critical pressure (Pc) and acentric factor () (Carlson, 1996).
NRTL fluid package was chosen as the main thermodynamic model for the unit
operation in the simulation. Most of the component properties are already in the simulation
system in the Aspen Plus.

5.0 PLANT CAPACITY DETERMINATION

Plant capacity: 21,000 MT/annum

Operating hour: 8000 hours

Raw material feed:

-

Ethylene: 951.33 kmol/hr

Air: 22344.2 kmol/hr

Product rate: 122.568 kmol/hr

Product purity: 97-99 % purity of ethylene oxide

6.0 SUMMARY OF MAJOR UNIT OPERATIONS MODEL SPECIFICATION

6.1 Reactor
In our simulation process, RPlug is chosen as the reactor used. RPlug is a rigorous
model for plug flow reactors. The type of reactor is adiabatic reactor. The chosen reaction
type is Langmuir-Hinshelwood-Hougen-Watson kinetics (LHHW). LHHW reaction is used
since the reaction provided in Aspen Plus is compatible with our chosen reaction kinetics.
The reaction stoichiometry is;

10

k2

Where;
*
*

+
+

(4)
(5)

(8)

(9)
Table 1-3: Summary of parameter inserted for ractor (RPlug) in simulation
Parameters
Reactor type

Value
Adiabatic

Pressure (bar)

21

Number of tube

500

Length of tube (m)

10

Diameter of tube (m)

0.03

Temperature (K)

164

Activation energy, Ea1 (kJ/kmol)

43585.7

Activation energy, Ea2 (kJ/mol)

77763.2

k1

0.0168

k2

33.215

Bed voidage
Particle density (kg/m3)

0.4
1250

10

11

6.2 Separator
The type of separator used in the simulation is RadFrac for absorber and distillation
column whereas separator for membrane separator with method NRTL.

Ethylene oxide absorber

Table 1-4: Summary of parameters used in ethylene oxide absorber
Parameters
Number of stages

Value
17
- Stream 7 = 17

Feed stages

- Stream 8 = 10
- Stream 9 = 1
Pressure (bar)

22

Temperature (K)

172

Enthalpy (cal/sec)

-2.0315e09

Distillation column 1
Table 1-5: Summary of parameters used in distillation column 1
Parameters
Number of stages
Feed stages

Value
30
- Stream 12 = 21

Pressure (bar)

22

Temperature (K)

197

Enthalpy (cal/sec)

-1.9784e09

Distillate rate (kmol/hr)

Reflux ratio

1000
4

11

12

Distillation column 2
Table 1-6: Summary of parameters used in distillation column 2
Parameters

Value
25

Number of stages

- Stream 14 = 20

Feed stages
Pressure (bar)

15

Temperature (K)

168

Enthalpy (cal/sec)

-1.3043e07
2000

Distillate rate (kmol/hr)

Reflux ratio

Membrane separator
Table 1-7: Summary of parameters used in membrane separator
Parameters

Value

Pressure (bar)

23

Temperature (K)

179

Enthalpy (cal/sec)

6.95826e06

Split fraction (Recycle stream)

C2H4 = 0.98

O2 = 0.023

N2 = 0.02

C2H4O = 0

CO2 = 0

H2O = 0

12

13

7.0 CONCLUSION

Modelling and simulation are two vital tools which are extensively used by engineers
in various industries. By completing this project using simulation software, we have
enhanced our knowledge and skills in using simulation software, particularly in the use of
Aspen PLUS. Aspen PLUS is used to simulate a production of ethylene oxide for 21000
tonnes per annum in this project. In our process of synthesizing ethylene oxide from raw
material to final product, several major unit operations are used and simulated accordingly
which includes mixer, heaters, coolers, absorbers, strippers, membrane separator, reactor and
distillation column with the skills that we have acquired in our Process Simulation and
Computer Aided Design (PSCAD) class and the special simulation class for the plant design
project. The simulation for the production of ethylene oxide is successfully run and the data
obtained from the simulation is attached in Appendix.
One of the major difficulties we faced throughout this project is to match the material
and energy balance obtained from the simulation with the manual calculation. The
differences might be due to some minor errors in the kinetic values inserted in the simulation
software, which would lead to an overall variation in the material and energy balances. The
units for the kinetic model inserted must be made sure to be correct and tally with the other
information inserted. Apart from that, the selection of the operating temperature and pressure
should also be done precisely.
Last but not least, we would like to express our gratitude to Dr. Mohammad Rizza Bin
Othman in assisting and teaching us patiently about the knowledge of using the ASPEN
PLUS software. We are glad to complete this project successfully.

13

14

8.0 APPENDIX
Heat and Material Balance Table
Stream ID

From

COMPP1

MIXER

HEAT1

To

MIXER

COMPP1

MIXER

HEAT1

REACTOR

Phase

VAPOR

VAPOR

VAPOR

VAPOR

VAPOR

Substream: MIXED
Mole Flow

kmol/hr

C2H4

951.3300

0.0

0.0

2656.798

2656.798

O2

0.0

4692.288

4692.288

4794.414

4794.414

N2

0.0

17651.94

17651.94

17993.89

17993.89

C2H4O

0.0

0.0

0.0

0.0

0.0

CO2

0.0

0.0

0.0

0.0

0.0

H2O

0.0

0.0

0.0

0.0

0.0

K2CO3

0.0

0.0

0.0

0.0

0.0

22344.23

22344.23

25445.10

25445.10

Total Flow

kmol/hr

951.3300

Total Flow

kg/hr

26688.38 6.44640E+5 6.44640E+5 7.32020E+5 7.32020E+5

Total Flow

l/min

18716.42 4.39599E+5 4.27395E+5 5.41217E+5 6.93695E+5

Temperature

25.00000

25.00000

30.52614

49.18735

140.0000

Pressure

bar

21.00000

21.00000

22.00000

21.00000

21.00000

Vapor Frac

1.000000

1.000000

1.000000

1.000000

1.000000

Liquid Frac

0.0

0.0

0.0

0.0

0.0

Solid Frac

0.0

0.0

0.0

0.0

0.0

Enthalpy

cal/mol

12541.80

-1.869E-13

38.50962

1487.185

2170.001

Enthalpy

cal/gm

447.0630

-6.477E-15

1.334804

51.69473

75.42948

Enthalpy

cal/sec

3.31428E+6

Entropy

cal/mol-K

-18.78122

-4.999168

-4.963570

-5.199771

-3.334933

Entropy

cal/gm-K

-.6694724

-.1732790

-.1720451

-.1807446

-.1159226

Density

mol/cc

8.47144E-4

8.47144E-4

8.71334E-4 7.83577E-4

6.11342E-4

Density

gm/cc

.0237655

.0244404

.0251383

.0225424

.0175874

28.05376

28.85040

28.85040

28.76861

28.76861

1343.145

19945.13

19945.13

24092.55

24092.55

Average MW
Liq Vol 60F

l/min

-1.1597E-9 2.39019E+5 1.05116E+7 1.53378E+7

14

15

Heat and Material Balance Table

Stream ID

10

From

REACTOR

COOL1

PUMP1

PUMP2

EOABS

To

COOL1

EOABS

EOABS

EOABS

COMPP2

Phase

VAPOR

VAPOR

LIQUID

LIQUID

VAPOR

Substream: MIXED
Mole Flow

kmol/hr

C2H4

2468.204

2468.204

.3237592

0.0

1740.274

O2

4700.108

4700.108 5.26148E-6

0.0

4440.253

N2

17993.89

17993.89 2.40192E-6

0.0

17097.24

C2H4O

188.5911

188.5911

0.0

66.02321

1.807154

CO2

7.03632E-3 7.03632E-3 9.39319E-8

H2O

7.03632E-3 7.03632E-3 1.09172E+5

K2CO3

0.0
25350.80

0.0 5.31879E-3
15000.00

14007.11

0.0

0.0

0.0

25350.80 1.09174E+5

15000.00

37350.90

0.0

Total Flow

kmol/hr

Total Flow

kg/hr

7.32020E+5 7.32020E+5 1.96684E+6 2.70229E+5 9.25108E+5

Total Flow

l/min

7.31916E+5 4.76080E+5

Temperature

164.3852

Pressure

bar

40747.08

4534.082 1.04756E+6

25.00000

198.5405

25.65433

172.1227

21.00000

22.00000

22.00000

22.00000

22.00000

Vapor Frac

1.000000

1.000000

0.0

0.0

1.000000

Liquid Frac

0.0

0.0

1.000000

1.000000

0.0

Solid Frac

0.0

0.0

0.0

0.0

0.0

Enthalpy

cal/mol

2178.073

1127.537

-64703.52

-68250.59

-19968.19

Enthalpy

cal/gm

75.42948

39.04807

-3591.499

-3788.484

-806.2086

Enthalpy

cal/sec

Entropy

cal/mol-K

-2.985256

-5.963060

-29.96221

-38.92646

-5.417724

Entropy

cal/gm-K

-.1033833

-.2065085

-1.663113

-2.160747

-.2187387

Density

mol/cc

5.77270E-4 8.87484E-4

.0446549

.0551379 5.94250E-4

Density

gm/cc

Average MW
Liq Vol 60F

l/min

1.53378E+7 7.93999E+6 -1.9622E+9 -2.8438E+8 -2.0718E+8

.0166690

.0256266

.8044927

.9933256

.0147184

28.87562

28.87562

18.01574

18.01528

24.76802

23901.88

23901.88

32844.42

4512.500

25951.78
15

16

Heat and Material Balance Table

Stream ID

11

12

13

14

15

From

EOABS

COOL2

DISTCOL1

DISTCOL1

DISTCOL2

To

COOL2

DISTCOL1

Phase

LIQUID

LIQUID

DISTCOL2
VAPOR

LIQUID

VAPOR

Substream: MIXED
Mole Flow

kmol/hr

C2H4

728.2538

728.2538 8.6444E-51

728.2538

727.9300

O2

259.8550

259.8550

163.1405

96.71452

96.71452

N2

896.6475

896.6475

836.8595

59.78801

59.78801

C2H4O

124.3751

124.3751 2.383E-156

124.3751

122.5679

CO2

1.71762E-3 1.71762E-3 1.1323E-69 1.71762E-3 1.71753E-3

H2O

1.10165E+5 1.10165E+5 7.641E-260 1.10165E+5

K2CO3

0.0

0.0

0.0

992.9978

0.0

0.0

Total Flow

kmol/hr

1.12174E+5 1.12174E+5

1000.000 1.11174E+5

2000.000

Total Flow

kg/hr

2.04399E+6 2.04399E+6

28663.65 2.01532E+6

48479.51

Total Flow

l/min

38686.33

36406.95

7654.197

42257.75

81553.80

Temperature

120.3362

70.00000

-151.6304

197.2026

168.2471

Pressure

bar

22.00000

22.00000

22.00000

22.00000

15.00000

Vapor Frac

0.0

0.0

1.000000

0.0

1.000000

Liquid Frac

1.000000

1.000000

0.0

1.000000

0.0

0.0

0.0

0.0

0.0

0.0

Solid Frac
Enthalpy

cal/mol

-65195.98

-66167.91

-1228.367

-64063.22

-23478.25

Enthalpy

cal/gm

-3577.943

-3631.283

-42.85451

-3533.994

-968.5846

Enthalpy

cal/sec

Entropy

cal/mol-K

-33.30635

-35.88559

-11.46990

-29.82302

-11.11571

Entropy

cal/gm-K

-1.827846

-1.969394

-.4001549

-1.645162

-.4585735

Density

mol/cc

.0483261

.0513517 2.17746E-3

.0438474 4.08728E-4

Density

gm/cc

.8805812

.9357129

.0624137

.7948536 9.90747E-3

18.22164

18.22164

28.66365

18.12771

24.23975

35307.05

35307.05

892.6300

34414.42

1570.004

Average MW
Liq Vol 60F

l/min

-2.0315E+9 -2.0617E+9 -3.4121E+5 -1.9784E+9 -1.3043E+7

16

17

Heat and Material Balance Table

Stream ID

16

17

18

19

From

DISTCOL2

COMPP2

MEMSEP

MEMSEP

To

PUMP1

MEMSEP

Phase

LIQUID

VAPOR

VAPOR

20

MIXER

PUMP2

VAPOR

LIQUID

Substream: MIXED
Mole Flow

kmol/hr

C2H4

.3237592

1740.274

34.80547

1705.468

0.0

O2

5.26148E-6

4440.253

4338.127

102.1258

0.0

N2

2.40192E-6

17097.24

16755.29

341.9448

0.0

1.807154

66.02321

66.02321

0.0

0.0

CO2

9.39319E-8

5.31879E-3

5.31879E-3

0.0

0.0

H2O

1.09172E+5

14007.11

14007.11

0.0

15000.00

0.0

0.0

0.0

0.0

0.0

37350.90

35201.36

2149.539

15000.00

C2H4O

K2CO3
Total Flow

kmol/hr

1.09174E+5

Total Flow

kg/hr

1.96684E+6 9.25108E+5 8.64416E+5

Total Flow

l/min

40735.88 1.01773E+6 9.59162E+5

58570.37

4531.202

Temperature

198.3671

179.1060

179.1061

179.1061

25.00000

Pressure

bar

15.00000

23.00000

23.00000

23.00000

1.000000

Vapor Frac

0.0

1.000000

1.000000

1.000000

0.0

Liquid Frac

1.000000

0.0

0.0

0.0

1.000000

0.0

0.0

0.0

0.0

0.0

Solid Frac

60691.77 2.70229E+5

Enthalpy

cal/mol

-64707.87

-19913.29

-21840.89

11653.53

-68262.20

Enthalpy

cal/gm

-3591.741

-803.9921

-889.4202

412.7367

-3789.128

Enthalpy

cal/sec

Entropy

cal/mol-K

-29.97071

-5.383663

-5.401631

-10.53141

-38.96517

Entropy

cal/gm-K

-1.663585

-.2173635

-.2199690

-.3729943

-2.162896

Density

mol/cc

.0446672

6.11669E-4

6.11669E-4

6.11669E-4

.0551730

Density

gm/cc

.8047139

.0151498

.0150203

.0172703

.9939570

18.01574

24.76802

24.55633

28.23478

18.01528

32844.42

25951.78

23147.51

2804.273

4512.500

Average MW
Liq Vol 60F

l/min

-1.9623E+9 -2.0661E+8 -2.1356E+8 6.95826E+6 -2.8443E+8

17

18

Bibliography
Ahmed, F. M. (2013). PRODUCTION OF ETHYLENE OXIDE. University of Khartoum.
Baiker, A. (1979). Kinetics of Ethylene Oxidation on a Supported Silver Catalyst. HELVETICA CHIMICA
ACTA.
Carlson, E. C. (1996, October). Don't Gamble With Physical Properties For Simulation. Chemical
Engineering Progress, 36.
Rebsdat, S. (2012). Ethylene Oxide. ULLMANN'S ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY, 557.

18