7-1

CHAPTER 7

HYSYS SIMULATION

7.1

Introduction

HYSYS is a powerful engineering simulation tool, it has been uniquely created with
respect to the program architecture, interface design, engineering capabilities and
interactive operation. The integrated steady state and dynamic modeling capabilities,
where the same model can be evaluated from either perspective with full sharing of
processes information, represent a significant advancement in the engineering software
industry. However, polymerization process cannot be simulated by using HYSYS
(Krishnan, 2011). HYSYS is widely used in universities and colleges in introductory and
advanced courses especially in chemical engineering. In industry the software is used in
research, development, modeling and design.

7.2

Component

Component that involved in this process is ethylene oxide (C2Oxide) and water (H2O)
as raw material and Ethylene Glycol (EGlycol), Di-ethylene Glycol (DEGlycol) and Triethylene Glycol (TEGlycol) as a product and side product.

7.3

Thermodynamic Fluid Package

When choosing a thermodynamic model, it is compulsory to follow a procedure for

deciding which model to adapt to the simulation. As state in Clarkson University
website, there is decision tree to be followed to choose a suitable fluid package. The
summary of fluid package and its procedure is shown below:

7-2

7.3.1

Summary of Aspen Property Methods

Table 7.1: Summary of Aspen Property Methods

Ideal Property Methods
Ideal Property Method

K-Value Method

IDEAL

Ideal Gas/Raoult's law/Henry's law

SYSOP0

Release 8 version of Ideal Gas/Raoult's law

Equations of State
Abbreviation

Equation of State
Lee-based Methods

BWR-LS

BWR Lee-Starling

LK-PLOCK

Lee-Kesler-Plcker
Peng-Robinson-based Methods

PENG-ROB

Peng-Robinson

PR-BM

Peng-Robinson with Boston-Mathias alpha function

PRWS

Peng-Robinson with Wong-Sandler mixing rules

PRMHV2

Peng-Robinson with modified Huron-Vidal mixing rules

Redlich-Kwong-based Methods

PSRK

Predictive Redlich-Kwong-Soave

RKSWS

Redlich-Kwong-Soave with Wong-Sandler mixing rules

RKSMHV2

Redlich-Kwong-Soave with modified Huron-Vidal mixing rules

RK-ASPEN

Redlich-Kwong-ASPEN

RK-SOAVE

Redlich-Kwong-Soave

RKS-BM

Redlich-Kwong-Soave with Boston-Mathias alpha function

Other Methods

SR-POLAR

Schwartzentruber-Renon

Activity Coefficient Methods

Abbreviation

Liquid Activity Coefficient

Pitzer-based Methods

Vapor Fugacity Coefficient

7-3

PITZER

Pitzer

Redlich-Kwong-Soave

PITZ-HG

Pitzer

Redlich-Kwong-Soave

B-PITZER

Bromley-Pitzer

Redlich-Kwong-Soave
NRTL-based Methods

ELECNRTL

Electrolyte NRTL

Redlich-Kwong

ENRTL-HF

Electrolyte NRTL

HF Hexamerization model

ENRTL-HG

Electrolyte NRTL

Redlich-Kwong

NRTL

NRTL

Ideal gas

NRTL-HOC

NRTL

Hayden-O'Connell

NRTL-NTH

NRTL

Nothnagel

NRTL-RK

NRTL

Redlich-Kwong

NRTL-2

NRTL (using dataset 2)

Ideal gas

UNIFAC-based Methods
UNIFAC

UNIFAC

Redlich-Kwong

UNIF-DMD

Dortmund-modified UNIFAC

Redlich-Kwong-Soave

UNIF-HOC

UNIFAC

Hayden-O'Connell

UNIF-LBY

Lyngby-modified UNIFAC

Ideal gas

UNIF-LL

UNIFAC for liquid-liquid systems

Redlich-Kwong

UNIQUAC-based Methods
UNIQUAC

UNIQUAC

Ideal gas

UNIQ-HOC

UNIQUAC

Hayden-O'Connell

UNIQ-NTH

UNIQUAC

Nothnagel

UNIQ-RK

UNIQUAC

Redlich-Kwong

UNIQ-2

UNIQUAC (using dataset 2)

Ideal gas

VANLAAR-based Methods
VANLAAR

Van Laar

Ideal gas

VANL-HOC

Van Laar

Hayden-O'Connell

VANL-NTH

Van Laar

Nothnagel

VANL-RK

Van Laar

Redlich-Kwong

VANL-2

Van Laar (using dataset 2)

Ideal gas

7-4

WILSON-based Methods
WILSON

Wilson

Ideal gas

WILS-HOC

Wilson

Hayden-O'Connell

WILS-NTH

Wilson

Nothnagel

WILS-RK

Wilson

Redlich-Kwong

WILS-2

Wilson (using dataset 2)

Ideal gas

WILS-HF

Wilson

HF Hexamerization model

WILS-GLR

Wilson (ideal gas and liquid enthalpy

Ideal gas

reference state)
WILS-LR

Wilson (liquid enthalpy reference

Ideal gas

state)
WILS-VOL

Wilson with volume term

Redlich-Kwong

7-5

Property Methods Decision Diagram

Yes

Yes

WILSON
NRTL
UNIQAC
etc.

UNIF-LL

UNIFAC
UNIF-LBY
UNIF-DMD

Liq-Liq

ELECNRTL
No
Yes

Yes
Yes

NRTL
UNIQAC
etc.

Interaction
Parameters
Available?
Liq-Liq
No

Pr < 0.1 &

T < Tci

No

No
Yes

Electrolyte
Yes
Interaction
Parameters
Available?

No
Property Method
Choice

SR-POLAR
PRWS
RKSWS
PRMHV2
RKSMHV2

Polar or
T < Tci

Yes

No

PENG-ROB
PR-BM
LK-PLOCK
RK-SOAVE
RKS-BM

No

WILS-NTH, WILS-HOC,
NRTL-NTH, NRTL-HOC,
UNIQ-NTJ, UNIQ-HOC,
Dimers
UNIF-HOC

PSRK
RKSMHV2

Degree of
Polymerization

No Pseudo
Components
Yes

CHAO-SEA
GRAYSON
BK10

Yes

Hexamers
No

High Pressure?

No

WILS-HF

Vapor-phase
Association?

BK10
IDEAL
No

WILSON, WILS-RK, WILS-LR, WILSGLR, NRTL, NRTL-RK, NRTL-2,

UNIQUAC, UNIQ-RK, UNIQ-2, UNIFAC,
UNIF-LL, UNIF-LBY, UNIF-DMB

Figure 7.1: Property methods decision diagram (Source: http://people.clarkson.edu/~wwilcox/Design/thermodl.htm)

7-6

Thus since our process involve polar reaction, liquid-liquid reaction and also
ideal gas, thus the best is UNIQUAC fluid package. It is also had been proven since
several articles of simulating ethylene glycol is using the UNIQUAC as their fluid
package.

7.4

Process Description

Stream 1 contain pure water with initial pressure 1 atm and temperature 25 C is mixing
with Stream EO contain pure ethylene oxide with pressure 10 atm and temperature 30 C
in the mixer with molar ratio 22:1 or mass ratio 9:1 of water and ethylene oxide before
being preheated into 150 C by a heater and enter the reactor. The huge ratio different
between water and ethylene oxide is simply because this reaction is highly exothermic
and the temperature is control by the existence of the excess water itself.

Reaction takes place at 200 C and 20-30 atm as it is the optimized parameter to
the reaction to occur in the tubular reactor. Product from reactor then goes to cooler and
valve to lower the temperature to 75 C and the pressure into 10 atm before entering the
evaporator. This is purposely to ease the evaporation process in the evaporator.

The evaporator is mainly used to vaporize excess water in the product.

Multistage evaporator is used due to very huge amount of water in the stream and it
cannot be handled by single evaporator. The first evaporator operate at temperature 190
C and pressure 10 atm. Bottom product from evaporator 1 is goes to valve before
entering evaporator 2 to reduce its pressure into8 atm in order to lower the boiling point
of the mixture and thus it will ease the evaporation of water.

The second evaporator operate at same temperature as first evaporator (190 C)

but with different pressure (8 atm).The bottom product from evaporator 2 then goes to
distillation column 1 to purification process. There are 3 distillation column are applied.
First column is highest pressure, the second is lower than the first column and the last
column is in vacuum pressure. The first column is to completely remove the excess

7-7

water that not capable to be removed in evaporator, the second column is to purify
ethylene glycol and the last column is to separate di-ethylene as top product and triethylene glycol as bottom product.

The first distillation column condenser operate at temperature 170.9 C and

pressure 8 atm while the reboiler operate at 266.9 C and 8 atm. The stage of column is
set to be 20 stages since the compound in the mixture have a slightly different boiling
point. The parameter used is 1.00 reflux ratio and 2.00 boil-up ratio. The top product is
100% water in liquid phase.

The product from first column then feed into second distillation column. The
column condenser operates at 205.6 C and 2 atm while the reboiler is operating at 243.8
C and 2 atm pressure. The stage value in the second reactor is also 20 stages. The
parameter used in the column is 1.00 reflux ratio and 14 boil up ratio. The top product is
high purity Ethylene glycol with minor moisture.

The last column is mainly to separate the by-product of this process which is diethylene (DEG) and tri-ethylene glycol (TEG). The condenser operates at 218.2 C and
50 kPa while the reboiler operates at 254 C and also 50 kPa (vacuum pressure). The
stage used is also 20 stages and with parameter 0.5 reflux ratio and high boil up ratio.
The top product is high purity DEG and the bottom is highly purity TEG.

The monomer EG from stream 16 is stored in a storage tank. After the amount of
Eg is sufficient it will be pumped to the polymerization reactor which operates at 55C
and 500 kpa to produce exactly PEG400. Then the product stream is reduced the
pressure by valve into 1 atm before the product and the residue catalyst which is salt are
filtered in the filter to separate between salt solution and PEG400. The purified PEG400
then go to the storage.

7-8

190
1013

7
190
810.6
25
101.3

Waste Water

180.5
810.6

25
1013
75
1013

10
170.9

2
Water

810.6

181.8
1013

12

P-101

25
101.3

205.6
202.6

24

E-102

Waste salt

55
500

25
303.9
9

R-101 4
30
1013

200
3040

18

V-101

14
8

22

21
11

T-104

30
500

190
810.6

25

R-102

T-101

13
218.2
50

170.9
810.6
30
1013

16

T-102
3

20
V-7

15

EO Storage Tank

23
55
101.3

P-102
V-102

190
1013

19

Storage Tank

243.8
101.3

254.4
50

T-103
17

Figure 7.2: PFD and table of ethylene glycol production

PEG to storage

7-9

7.5 Comparison between HYSYS and manual calculation

Component

EO
Water

EO
Water
EG
DEG
TEG

HYSYS

MANUAL
mass flowrate
Inlet
Outlet
Inlet
Mixer
1600
14226.26
1402.918
12626.26
12626.26
Component:
Reactor
1600
12.80363
1402.918
12626.26 13550.51
12626.26
0
603.1934
0
0
59.75029
0
0
14.22626
0

Percentage
Outlet

Inlet

Outlet

14029.18 12.31764 1.385341

0

0
12.31764
100
12626.26
0
6.820795
1262.626
0
109.3236
126.2626
0
111.3171
14.02918
0
1.385341

Component:
Evaporator
1

EO
Water
EG
DEG
TEG

HYSYS
Inlet
Out Top
12.807
12.727
13554.075 11345.54
603.352
196.69
59.766
16.198
1.423
0

Out Btm
0.2654
2019.429
572.7332
61.042
7.962

Percentage error(%)
Inlet
0
12626.26
1262.626
126.2626
14.02918

MANUAL
Out Top
0
11994.95
0
0
0

Out Btm
0
631.313
1262.626
126.2626
14.02918

Inlet
Out Top Out Btm
100
100
100
6.820795 5.723878 68.73804
109.3236
100
120.4562
111.3171
100
106.8455
1.385341
0
76.20168

7-10

Component:
Evaporator
2

EO
Water
EG
DEG
TEG

HYSYS
Inlet
Out Top
0.2654
0.08568
2019.4286 823.7275
572.7332 31.35888
61.042
1.54224
0.7962
0

Out Btm
0
1031.872
688.2744
76.7746
1.0788

Percentage error
MANUAL
Inlet
Out Top
0
0
631.313
599.7473
1262.626
0
126.2626
0
14.02918
0

Component:
Separator 1

EO
Water
EG
DEG
TEG

HYSYS
Inlet
Out Top
0
0
1031.8722
466.2
688.2744
0
76.7746
0
1.0788
0

Out Btm
0
49.6836
1151.914
128.538
1.8648

Out Btm
0
31.56565
1262.626
126.2626
14.02918

Inlet
Out Top Out Btm
100
100
0
68.73804 27.19105 96.94093
120.4562
100 83.44806
106.8455
100 64.45882
1662.017
0 1200.443

Percentage error
Inlet
0
31.56565
1262.626
126.2626
14.02918

MANUAL
Out Top
Out Btm
Inlet
Out Top Out Btm
0
0
0
0
0
31.56565
0
96.94093 93.22916
100
0
1262.626 83.44806
0 9.611172
0
126.2626 64.45882
0 1.770216
0
14.02918 1200.443
0 652.3154

7-11

Component:
Separator 2

EO
Water
EG
DEG
TEG

HYSYS
Inlet
Out Top
0
0
49.6836
46.2725
1151.9136 1068.728
128.538
0
1.8648
0

Out Btm
0
0
3.57555
210.1123
3.01213

Percentage error
MANUAL
Inlet
Out Top
Out Btm
Inlet
Out Top Out Btm
0
0
0
0
0
0
0
0
0
100
100
0
1262.626 1262.626
0
9.611172 18.14293
100
126.2626
0
126.2626 1.770216
0 39.90709
14.02918
0
14.02918 652.3154
0 365.7561

Component:
Separator 3

EO
Water
EG
DEG
TEG

HYSYS
Inlet
Out Top
0
0
0
0
3.57555
3.56044
210.11232 209.0213
3.01213
0.61828

Out Btm
0
0
0
0.071552
3.368448

Percentage error
Inlet
0
0
0
126.2626
14.02918

MANUAL
Out Top
0
0
126.2626
0

Out Btm
Inlet
Out Top Out Btm
0
0
0
0
0
0
100
0
0
100
100
0
0
39.90709 39.59342
100
14.02918 365.7561
100 316.4879

7-12

7.6

Conclusion Remark

As the objective of this chapter is to compare between HYSYS simulation and manual
calculation, it can be seen that there some calculation having a percentage error. It may
be come from the different way of calculation between fluid package used and manual
theory of calculation. However, estimation of real usage of flow rate still can be relied
on the HYSYS simulation.