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Table of Contents
Technical Support..................................................... v
Online Technical Support Center ............................vi
Phone and E-mail ................................................ vii
1
2.2
2.3
Package............................ 3-1
3.1
3.2
4.2
4.3
5.2
5.3
5.4
References ...........................................................A-1
Index.................................................................... I-1
ix
Introduction
1-1
1 Introduction
1-1
1-2
1-2
Introduction
1-3
1-4
1-4
Gasoline Fractionation
2-1
2 Gasoline
Fractionation
2.1 Gasoline Sulphur Species Distribution............................................ 2
2.2 Light/Medium Gasoline Fractionation ............................................ 5
2.3 Improve Fractionator Design ......................................................... 8
2-1
2-2
HYSYS Sim
Name
NPB F
BPT Range
F
HYSYS Comp
ID
Formula
E-Mercaptan
95.09
70-90
354
C2H6S
Dimethyl Sulfide
diM-Sulphide
99.23
75-80
380
C2H6S
Iso-propyl Mercaptan
2C3Mercaptan
126.61
110-130
3162
C3H8S
Tert-butyl Mercaptan
t-B-Mercaptan
147.59
120-150
524
C4H10S
M-E-Sulfide
151.97
130-140
381
C3H8S
n-Propyl Mercpatan
nPMercaptan
150.89
115-130
389
C3H8S
Thiophene
Thiophene
183.29
140-200
384
C4H4S
Iso-Butyl Mercaptan
2-M-1C3Thiol
191.21
180-200
732
C4H10S
n-Butyl Mercaptan
nBMercaptan
209.23
185-200
390
C4H10S
Dimethyl disulfide
diMdiSulphid
229.53
190-200
385
C2H6S2
2-Methyl Thiophene
2MThiophene
234.59
200-250
733
C5H6S
3-Methyl Thiophene
3MThiophene
239.81
210-270
734
C5H6S
Tetrahydrothiophene
Thiolane
250.01
220-260
526
C4H8S
1-Pentyl Mercaptan
1Pentanthiol
259.95
245-255
525
C5H12S
Hexyl Mercaptan
1Hexanethiol
306.77
290-340
847
C6H14S
Benzothiopene
ThioNaphtene
427.81
400+
3116
C8H6S
Gasoline Fractionation
2-3
Component Name
DIPPR ID
HYSYS ID
CH4S
METHYL MERCAPTAN
1801
353
C2H6S
ETHYL MERCAPTAN
1802
354
C3H8S
n-PROPYL MERCAPTAN
1803
389
C4H10S
tert-BUTYL MERCAPTAN
1804
524
C4H10S
ISOBUTYL MERCAPTAN
1805
732
C4H10S
sec-BUTYL MERCAPTAN
1806
731
C6H14S
n-HEXYL MERCAPTAN
1807
847
C9H20S
n-NONYL MERCAPTAN
1808
3068
C8H18S
n-OCTYL MERCAPTAN
1809
871
C3H8S
ISOPROPYL MERCAPTAN
1810
3162
C3H8S
ISOPROPYL MERCAPTAN
1810
695
C6H12S
CYCLOHEXYL MERCAPTAN
1811
3280
C7H8S
BENZYL MERCAPTAN
1812
3319
C3H8S
1813
381
C4H10S
1814
730
C6H14S
DI-n-PROPYL SULFIDE
1817
846
C4H10S
DIETHYL SULFIDE
1818
382
C2H6S
DIMETHYL SULFIDE
1820
380
C4H4S
THIOPHENE
1821
384
C8H6S
BENZOTHIOPHENE
1822
3116
C4H10S2
DIETHYL DISULFIDE
1824
383
C11H24S
UNDECYL MERCAPTAN
1825
958
C10H22S
n-DECYL MERCAPTAN
1826
945
C5H12S
n-PENTYL MERCAPTAN
1827
525
C2H6S2
DIMETHYL DISULFIDE
1828
385
C6H14S2
DI-n-PROPYL DISULFIDE
1829
848
C12H26S
n-DODECYL MERCAPTAN
1837
3013
C8H18S
tert-OCTYL MERCAPTAN
1838
3373
C7H16S
n-HEPTYL MERCAPTAN
1839
865
C4H10S
n-BUTYL MERCAPTAN
1841
390
C6H6S
PHENYL MERCAPTAN
1842
391
C4H8S
TETRAHYDROTHIOPHENE
1843
526
C2H6OS
DIMETHYL SULFOXIDE
1844
950
C3H6O2S
3-MERCAPTOPROPIONIC ACID
1873
3153
COS
CARBONYL SULFIDE
1893
355
2-3
2-4
Formula
Component Name
DIPPR ID
HYSYS ID
H2S
HYDROGEN SULFIDE
1922
15
CS2
CARBON DISULFIDE
1938
364
C12H8S
DIBENZOTHIOPHENE
2823
3441
C12H26S
tert-DODECYL MERCAPTAN
2838
3460
C5H6S
2-METHYLTHIOPHENE
2844
3216
C5H6S
2-METHYLTHIOPHENE
2844
733
C5H6S
3-METHYLTHIOPHENE
2845
3217
C5H6S
3-METHYLTHIOPHENE
2845
734
C2H4O2S
THIOGLYCOLIC ACID
2872
3134
C5H9NS
N-METHYLTHIOPYRROLIDONE
3888
3223
C4Cl4S
TETRACHLOROTHIOPHENE
4877
3169
C4H10O2S
THIODIGLYCOL
6855
3195
C2H6OS
2-MERCAPTOETHANOL
6858
3138
C4H10OS
ETHYLTHIOETHANOL
6859
3192
C2H6S2
1,2-ETHANEDITHIOL
6860
3139
2-4
Gasoline Fractionation
2-5
2-5
2-6
Light/Medium Gasoline
Temperature
F
Sulphur ppm
wt
20%
95.60
0.00
25%
117.15
0.00
30%
142.28
0.11
35%
151.77
10.9
40%
168.61
1354.0
45%
182.07
36.8
50%
196.67
0.00
55%
220.88
0.00
2-6
Gasoline Fractionation
2-7
2-7
2-8
2-8
Gasoline Fractionation
2-9
2-9
2-10
2-10
3-1
3-1
3-2
Introduction
3.1 Introduction
The Clean Fuels Property Package is a specially designed
property package for the accurate VLE representation of thiolhydrocarbon containing systems. The Clean Fuels Pkg contains
the latest advances made in the development of cubic equations
of state and mixing rules. A new vapour pressure alpha function
is available that is correlated against DIPPR vapour pressure
data as well as DIPPR pure component properties for 1454
HYSYS components. New databases are available containing
regressed coefficients for 101 thiol-hydrocarbon binary pairs,
and a new proprietary thiol-hydrocarbon estimation method is
able to predict the formation of azeotropes and calculate the
binary parameters from infinite dilution activity coefficient data.
The Clean Fuels Pkg allows User Data to be supplied for
azeotropes and infinite dilution activity coefficient data as well
as supporting 49 DIPPR thiol containing components listed in the
table of the sulphur species supported in HYSYS for the Clean
Fuels Property Package in Section 2.1 - Gasoline Sulphur
Species Distribution.
3-2
3-3
The Clean Fuels Property Package uses an optimal twoparameter cubic equation of state TST (Twu-Sim-Tassone)3 to
represent Clean Fuels Processes. The TST cubic equation is
represented as follows:
RT a
P = --------- -------------------------------------------v b v 2 + 2.5bv 1.5b 2
(3.1)
(3.2)
a ( T c ) = 0.427481R T c P c
(3.3)
b = 0.086641RT c P c
(3.4)
Z c = 0.296296
(3.5)
where:
c = critical point
The value of Zc from the SRK and PR equations are both larger
than 0.3 while Zc from the TST equation is slightly below it,
closest to the real one for many substances.
A prerequisite for the accurate VLE representation of thiolhydrocarbon systems in the entire composition range is the
accurate calculation of pure component vapour pressures.
3-3
3-4
Thermodynamic Model
N ( M 1 ) L ( 1 Tr )
= Tr
(3.6)
(0)
+ (
(1)
(0)
(3.7)
where:
(0) is for =0
(1) is for =1
b vdw
A 0 A 0vdw
*
* a vdw
1 - -----a = b ---------- + ------- - -------------- ln -----------
*
b
RT
b vdw C v0 RT
b =
xi xj
i
1--( b + bj )
2 i
(3.8)
(3.9)
3-4
3-5
v 0 + w
1
-
C v0 = ----------------- ln -------------( w u ) v* + u
0
vdw
(3.10)
ai
A vdw
A 0vdw
a vdw
-------------= --------------= C v0 ---------- x i ----**
RT
RT
b vdw i b i
(3.11)
G
------- =
RT
xj ji Gji
xi -----------------------n
i
xk Gki
j
(3.12)
(3.13)
3-5
3-6
Thermodynamic Model
G ji = exp ( ji ji )
(3.14)
(3.15)
b
G ji = ----j
bi
(3.16)
where:
2
ai aj
a
C v0 a i
- -------- --------j + 2k ij -------- ------- ij = -------b
RT b i
bj
i bj
(3.17)
v 0vdw = r
(3.18)
(3.19)
3-6
3-7
3-7
3-8
Thermodynamic Model
3-8
4-1
4-1
4-2
You can add a Clean Fuels Pkg Extension only if it exists as part
of a HYSYS case. A Property Package Extension that is part of an
existing case can be accessed in the HYSYS Basis Environment.
In the Basis Environment, you can view and adjust the
extension variables as you would any HYSYS Property Package.
Before creating a new Clean Fuels Pkg, the user is required to be
working within a HYSYS case that has a Fluid Package installed.
The Fluid Package must consist of a property package and
associated flowsheet components.
4-2
4-3
4-3
4-4
The Clean Fuels Pkg property view has two tabs (NRTLTST and
TST CEOS), and on each tab are groups of related parameters.
4-5
methods.
User Data
The User Data button allows the user to provide either infinite
dilution activity coefficient data or azeotrope data per binary in
the calculation of interaction parameters for azeotrope
prediction of thiol-hydrocarbon binaries.
4-5
4-6
The Twu Alpha Params button allows the user access to the Twu
vapor pressure alpha function parameters L, M and N, as well as
access to the DIPPR pure component properties Tc and Pc.
Figure 4.4
4-6
5-1
5-1
5-2
Introduction
5.1 Introduction
The following example demonstrates how to use the Clean Fuels
Pkg to model a gasoline fractionator. In this example, a light/
medium gasoline is fractionated in a gas plant column. The
amount of sulphur is calculated in the light gasoline and the
gasoline endpoint is set to 150F for design. The case will
consist of a FCC Gasoline feed stream to the tower and two
outlet streams, a light gasoline product stream and an
intermediate naphtha which is sent to an upstream hydrotreater
for further treating. The design objective is to maximize the
yield of light gasoline since hydrotreating of gasoline results in
severe octane loss.
Figure 5.1
5-2
5-3
Components
5-3
5-4
Flowsheet Setup
5-4
5-5
7. In the Input Data group, click on the Edit Assay button. The
Assay Input Table property view appears.
Figure 5.4
Temperature [F]
0.0
108.6
5.0
167.3
15.0
190.2
20.0
201.4
25.0
213.6
30.0
226.3
35.0
239.3
40.0
252.7
45.0
266.2
50.0
279.5
55.0
292.4
60.0
305.5
75.0
348.3
90.0
407.9
95.0
425.5
98.0
458.3
100.0
490.2
5-5
5-6
Flowsheet Setup
9. After you have entered the assay input data, click the OK
button to return to the Assay property view.
Figure 5.5
10. Close the Assay property view to return to the Oil Manager
property view.
11. Click on the Cut/Blend tab to create a Blend object.
12. Click the Add button. The Blend property view appears.
Figure 5.6
5-6
5-7
14. From the Cut Option Selection drop-down list of the Data
tab, select Auto Cut.
15. Click the Add button to select the assay.
Figure 5.7
Flow Rate
Mass
364008 lb/hr
The default Flow Unit is Liquid Volume ensure that you have
selected Mass from the drop-down list before specifying the
flow rate.
17. Close the Blend property view to return to the Oil Manager
property view.
18. Click on the Install Oil tab, and in the Stream Name
column type FCC Gas Oil as shown in the figure below.
Figure 5.8
5-7
5-8
Flowsheet Setup
19. Click the Calculate All button to calculate the all the assays
and blends. Then click the Return to Basis Environment
button. The Simulation Basis Manager appears.
20. Click on the Fluid Pkgs tab, and then click the View button.
Ensure that you have selected the Clean Fuels Pkg in the
Current Fluid Packages list.
21. From Fluid Package property view, click the View Property
Package button. The Clean Fuels Pkg property view
appears.
Figure 5.9
5-8
5-9
24. Create two streams named Sulphur Spike and Light Ends
in the Simulation Environment with the following stream
conditions and composition.
Conditions
Stream Name
Sulphur Spike
Temperature [F]
100
Pressure [psia]
114.6
219.6
60.1
nPMercaptan
53.5
Thiophene
106.0
Conditions
Stream Name
Light Ends
Temperature [F]
100
Pressure [psia]
114.6
1.705E+005
392.2
i-Butene
13543.9
n-Butane
2318.5
i-Pentane
40094.1
1-Pentene
49783.6
2M-13-C4==
1475.2
Cyclopentene
2345.5
3M1C5=
2162.2
Cyclopentane
1138.2
23-Mbutane
5138.8
2-Mpentane
30575.8
2M1C5=
3221.3
5-9
5-10
Conditions
1-Hexene
12306.8
n-Hexane
6004.2
25. Define the FCC Gas Oil stream conditions as shown in the
table below.
Conditions
Temperature [F]
100
Pressure [psia]
114.6
364008.7
32784.7
26. Add a Mixer with the outlet stream named FCC Gasoline,
and feed streams Sulphur Spike, Light Ends and FCC Gas
Oil.
27. Add a shell and tube Heat Exchanger with a 10 psi pressure
drop on both shell and tube sides.
The Shell side of the heat exchanger will heat the feed to the
column while the tube side cools the column bottoms
product.
28. In the Heat Exchanger property view, name the tube side
feed Medium Gasoline and the outlet tube side to
Hydrotreater.
29. Specify the shell side feed FCC Gasoline, and name the
outlet shell side Feed to Fractionator.
30. Specify a stream temperature of 223F for Feed to
Fractionator.
31. In the Parameters page of the Heat Exchanger property
view, change the Heat Exchanger Model to Exchanger
Design (Weighted).
5-10
5-11
5-11
5-12
The figure below shows the Monitor page after adding a TBP
End Point Volume Percent column.
Figure 5.12
5-12
5-13
Figure 5.14
5-13
5-14
5.3.1 Exercises
1. Add a HYSYS Spreadsheet (Sulphur Calculations) to
calculate the total sulphur content in ppm wt of light
gasoline.
Spreadsheet Connections
Cell
Object
Variable
D2
Light Gasoline
D3
Light Gasoline
D4
Light Gasoline
B6
Light Gasoline
Mass Flow
B7
Fractionator
Figure 5.15
5-14
5-15
Figure 5.16
5-15
5-16
Plot Utility
Figure 5.17
5-16
References
A-1
A References
1
Twu, C.H., Sim, W.D. and Tassone, V., A versatile liquid activity
model for SRK, PR and a new cubic equation-of-state TST, Fluid
Phase Equilibria 194-197, 2002, pp. 385-399.
Twu, C.H., Bluck, D., Cunningham, J.R. and Coon, J.E., Fluid Phase
Equilibria, 69, 1991, pp. 33-50.
Wong, S.H. and Sandler,S.I., 1992, AIChE J., 38, 1992, pp. 671-680.
Twu, C.H., Wayne, D., and Tassone, V., Liquid Activity Coefficient
Model for CEOS/AE Mixing Rules Fluid Phase Equilibria, 183-184,
2001, pp. 65-74.
Twu, C.H., Coon, J.E. and Bluck, D., Fluid Phase Equilibria, 150-151,
1998, pp. 181-189.
A-1
A-2
A-2
Index
C
Clean Fuels Pkg
adding 4-2
NRTLTST tab 4-4
property view 4-4
TST CEOS tab 4-5
tutorial 5-15-15
Clean Fuels Pkg Extension
user interface 4-3
using 4-2
E
Estimation Methods 3-7
F
Fractionator design
through accurate VLE models 2-82-10
G
Gasoline Sulphur species distribution 2-22-4
L
Light/Medium Gasoline fractionation 2-52-7
M
Modeling the Gasoline Fractionator 5-10
N
NRTLTST tab 4-4
User Data 4-5
P
Plot Utility 5-15
R
Requirements
system 4-2
T
Thermodynamic Model 3-23-7
estimation methods 3-7
TST CEOS tab 4-5
U
User Data 4-5
User Interface
Clean Fuels Pkg Extension 4-3
I-1
I-2