Jens Ahlers*, Jrgen Rarey*, Jrgen Gmehling* Todd Willman**

Chair of Industrial Chemistry University of Oldenburg, Germany * DDBST GmbH * EPCON international**

Improving your separation

process simulation with
accurate binary parameters
AIChE Regional
Process Technology Conference
Galveston, TX October 2009

Problems of fitting gE model parameters only to isobaric VLE data

H. C. Van Ness (Rossini Lecture 1994)

Pure & Appl. Chem. 67, 859 (1995)

In the early unsophisticated days of chemical engineering VLE data were

taken at constant pressure for direct application in the design of distillation
columns, which were treated as though they operated at uniform pressure.
There is no longer any excuse for taking isobaric data, but regrettably the
practice persists, and we have examined two such data sets. Rigorous
thermodynamic treatment of isobaric data present problems that do not
arise with isothermal data. Their origin is the need to take into account not
only the composition dependence of the excess Gibbs energy but also its
temperature dependence.

Results for the system ethanol (1) n-decane (2) using Wilson
parameters fitted to isobaric VLE only and recommended values
VLE only
450

(ij f(T))

recommended values (ij

= f(T))

T/K

T [K]

450

400

400

350

350

0.5

x1, y1

ln hE
i = i

1
R

0.5

x1, y1

3,200

hhE E[J/mol]
[J/mol]

hE

[J/mol]

2,400

1,600

800

0
0

0.5

x1

Results for the system ethanol (1) n-decane (2) using Wilson
parameters fitted to isobaric VLE only and recommended values

VLE only (ij f(T))

12

recommended values (ij

1, 2

1 , 2

= f(T))

12

0
0

0.5

x1

0.25

0.5

2.00

1.6

x1

0.75

log

log

1.75

1.2

1.50

0.8

1.25

0.4

2.75

3.25
1000/T [K]

3.5

1.00
2.8

3.0

3.2

1000/T [K]

3.4

VLE at 101.3 kPa of Acetone (1) + Water (2) using

NRTL parameters taken from process simulator
376

372

T [K]

y1

0.9
0.8

356

0.5

352
348

vapor composition
vs. liquid composition

0.4
0.3

344
340

0.2

336

0.1

332
328

0
0.1

0.2

0.3

Activity coefficient i

13

0.4
0.5
0.6
x(C4) [mol/mol]

0.7

0.8

x1

0.9

activity coefficient
vs. liquid composition

10
9

0.1

0.2

0.3

0.4
0.5
0.6
x(C4),y(C4) [mol/mol]

0.7

52

12
11

separation
factor 12
alpha12 []

Act.Coeff.(C4),Act.Coeff.(C174) []

364
360

0.6
T [K]

y(C4) [mol/mol]

0.7

Temperature
vs. composition

368

8
7
6
5
4
3
2

0.8

0.9

x1,y1

48
44

separation factor
vs. liquid composition

40
36
32
28
24
20
16
12
8
4

0
0

0.1

0.2

0.3

0.4
0.5
0.6
x(C4) [mol/mol]

0.7

0.8

0.9

x1

0.1

0.2

0.3

0.4
0.5
0.6
x(C4) [mol/mol]

0.7

0.8

0.9

x1

VLE of Acetone (1) + Water (2) at 101.3 kPa

using simulator parameters

VLESepFac/x-Chart

separation factor 12

1.9

separation
factor vs.
liquid
composition
separation
factor
vs.
liquid composition

1.8

1.8

1.7

1.6

1.3
UNIQUAC

12
UNIQUAC 1.2

1.5

12

SepFac []

1.4

1.3

1.2

1.1

NRTL 12 1

12=1

0.8

0.9

0.8

Wilson Azeotrope at 94.5 mol%

12 0.7

0.7

0.6
0.9

0.9

0.91

0.92

0.93

0.94

0.95
x(C4) [mol/mol]

0.96

0.97

liquid mole fraction xacetone

0.98

0.99

1.0

Activity coefficients at infinite dilution

of Acetone + Water using NRTL

15

15

Acetone in Water
10

10

Water in Acetone
0

0
280

320

360

T [K]

NRTL using simulator parameters

400

280

320

360

400

T [K]

NRTL parameters from simultaneous

regression to VLE, hE, and azeotropic
data

Excess enthalpies of Acetone + Water using NRTL

hE [J/mol]

hE [J/mol]

1 200

-1 200

800

400

T = 5 C
T = 25 C
T = 35 C
T = 90 C

-2 400

T = 15 C
T = 25 C
T = 35 C
T = 45 C
T = 90 C

-400

-800

-3 600
0

0.5

x1

NRTL using simulator parameters

0.5

x1

NRTL parameters from simultaneous

regression to VLE, hE, and azeotropic
data

Azeotropic data at infinite dilution

of Acetone + Water using NRTL

6,000

6 000

P [kPa]

P [kPa]

6 000

4 000

4 000

2 000

2 000

P [k Pa ]

4,000

2,000

0.5

0.75

y1,az
NRTL using simulator parameters

0
0.5

0.5

0.75
y(C4) [mol/mol]

0.75

y1,az
NRTL parameters from simultaneous
regression to VLE, hE, and azeotropic
data

13

13

12

12

11

Activity
coefficient
i
Act.Coeff.(C4),Act.Coeff.(C174)
[]

Activity
coefficient
i
Act.Coeff.(C4),Act.Coeff.(C174)
[]

VLE at 101.3 kPa of Acetone (1) + Water (2) using NRTL

comparison simulator revised regression

activity coefficient
activity
coefficient
vs. liquid
composition
vs. liquid composition

10
9
8
7
6
5
4
3

11

9
8
7
6
5
4
3

0.1

0.2

0.3

52

0.4
0.5
0.6
x(C4) [mol/mol]

0.7

0.8

48

0.9

x1

0.1

0.2

0.3

52

0.4
0.5
0.6
x(C4) [mol/mol]

0.7

0.8

0.9

x1

48

44

separation
alpha12 []factor 12

separation
factor 12
alpha12 []

activity coefficient
vs. liquid composition

10

44

separation factor
vs. liquid composition

40
36
32

separation factor
vs. liquid composition

40
36
32

28

28

24

24

20

20

16

16

12

12

8
4

8
4

0
0

0.1

0.2

0.3

0.4
0.5
0.6
x(C4) [mol/mol]

0.7

0.8

0.9

x1

0
0

0.1

0.2

0.3

0.4
0.5
0.6
x(C4) [mol/mol]

0.7

0.8

0.9

x1

DDB: An Ideal Tool for the Critical Examination of Model Parameters

Prior to Process Simulation (Acetone (1) + Cyclohexane (2) (Wilson))

h E / Jmol-1

50oC

P / mmHg

VLE
o
25 C

140oC
35oC
25oC

hE

o
0 C

x1

ln i

azeotropic
data

Temperature / C

i
8

Temperature / C

x1, y1

SLE

cyclohexane in acetone
acetone in cyclohexane

x1

y1,az

wilson.cdr, 18.05.99

1000T-1 /K

The GPA Data Bank Joint DDBST & EPCON Project for GPA

The new GPA Data Bank, Fifth Edition, provides 100% of all published GPA
experimental thermophysical property data in electronic format including
searchable text copies of all GPA Research Reports and Technical Publications.
A joint project undertaken by DDBST GmbH (Oldenburg, Germany) and EPCON
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The result is a comprehensive compilation of all GPA experimental data
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GPA Data Bank Main Applications

Main
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-- Data
Book
Data Book Explorer
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-- GPA
Data
GPA Data Bank
Bank
-- Data
Data Bank
Bank Configuration
Configuration
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Data Bank
Bank Literature
Literature Search
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Pure Component
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Flash/Mixture Calculations
Calculations
-- Unit
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Unit Conversions

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Main Applications
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The navigation bar on the left side of the screen is used to access programs in the GPA Data Bank. The Main Applications are the
primary software tools developed by DDBST and EPCON to view, graph, and fit data for determination of phase equilibrium for any gas
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GPA Data Bank Utility Programs

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-- Edit
Components
Edit Components
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Data Editor
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Contribution Parameters
Parameters
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Component List
List Editor
Editor

Click
Click on
on the
the Utility
Utility Programs
Programs tab
tab

The Utility Programs in the GPA Data Bank provide the ability to edit component and mixture data. The Parameter Editor is used to
store the binary parameters generated from the GPA Data Bank for direct use in process simulation software.

GPA Data Bank Data Bank Explorer

Click
Click on
on any
any one
one of
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the 195
195 GPA
GPA Research
Research Reports
Reports or
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Technical
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GPA Data
Data Bank
Bank Explorer
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Data
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Toolbar full
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forward/back commands
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In
In recent
recent reports,
reports, search
search by
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all
occurrences
display all occurrences
The GPA Data Bank provides all of the GPA Research Reports and Technical Publications in electronic, searchable format using the
Data Bank Explorer interface. This provides quick access to over 30 years of GPA research work with all experimental data converted
into electronic data format - providing full value from your companys GPA research investments.

GPA Data Bank Component Selection

Select
Select the
the Add/Search
Add/Search Component
Component Button
Button

Select
Select As
As Subsystem
Subsystem to
to
view
view all
all data
data sets
sets
containing
containing the
the selected
selected
components
components

Select
Select References
References to
to
view
all
data
sets
view all data sets
categorized
categorized by
by source
source and
and
reference
reference

Enter
Enter in
in the
the name
name to
to search
search and
and select
select
the
the component
component name
name

All GPA components can be searched in a number of ways for retrieval of pure and mixture data. Selection of System (Exact Match)
will display all systems where only the selected components appear while selection of As Subsystem will display all systems where
the selected components and all others appear. VLE data for these systems is then automatically selected and graphed for review.

GPA Data Bank Automated Displays and Graphs

All
All VLE
VLE Data
Data sets
sets are
are automatically
automatically
selected
and
graphed
selected and graphed as
as shown
shown

Select
Select the
the desired
desired view
view including
including
3D
3D rotational
rotational capabilities
capabilities

The Query Results window shows all data sets for each data type as shown on the property tabs (the default selection is VLE data).
The graphing of VLE data is done automatically and other data types can also be graphed. As the pointer is moved over a data point
on the graph, the numeric data is displayed in a floating window as shown. Data can be exported in a several file formats.

GPA Data Bank Fitting Binary Parameters

Select
Select the
the Fit
Fit button
button to
to display
display both
both gE
gE
and
EOS
binary
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fitting
and EOS binary parameter fitting
options.
options.

Automated fitting of binary parameters for either gE and EOS models is provided for selected data sets. View the fit graphically or
numerically and save parameters to the Parameter database for use in process simulation.

GPA Data Bank VLE Prediction using UNIFAC

Select
Select the
the Predict
Predict button
button to
to estimate
estimate
VLE
data
sets
using
UNIFAC
VLE data sets using UNIFAC

Prediction of VLE data sets using PSRK and UNIFAC can also be provided by the GPA Data Bank. The VLE data sets can then be
used for prediction of binary parameters.

GPA Data Bank Access to All Experimental Data

All
All experimental
experimental Data
Data from
from GPA
GPA RRs
RRs
and
and TPs
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is now
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for the
the first
first
time
time using
using the
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X data
data option
option in
in the
the
DDBSP
software
DDBSP software

The Dortmund Data Bank Software Package (DDBSP) basic software applications are included in the GPA Data Bank. The DDB data
types were extended with the X data type so that all GPA experimental data could be captured into the GPA Data Bank. Selection of
the X data type provides a secondary set of property tabs that may be chosen to view the data sets available.

GPA Data Bank Access to References and Data

Selection
Selection of
of the
the References
References button
button will
will
show
show all
all references
references and
and their
their respective
respective
data
data sets.
sets. Just
Just select
select the
the reference,
reference, click
click
on
the
checkmark
icon
and
all
data
on the checkmark icon and all data
from
from this
this reference
reference will
will be
be individually
individually
shown.
shown.

Selection of the References button in the GPA Data Bank main window will provide a list of all references with authors, dates, volumes,
etc. Selection of one of these references and clicking on the checkmark icon will display all the data sets in that reference for further
graphing, fitting, etc. in the Query Results window.

GPA Data Bank ARTIST Property Estimation

Pure
Pure component
component properties
properties for
for any
any chemical
chemical
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can be
be estimated
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the Calculate
Calculate
menu
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contribution
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Draw
Draw any
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The Artist graphical user interface allows for drawing of any chemical structure and estimation of pure component properties. Group
contribution methods are provided for basic estimation capabilities and extended methods are available separately.

GPA Data Bank Flash Mixture Calculations

Enter Feed
Conditions and
Flash Conditions

View Stream
Properties when
calculation is
completed

Select to run flash

calculations

Enter pure and

pseudo components

Phase flows and

compositions are
shown for 3-phases

The Flash/Mixture Calculations program provides phase equilibrium and physical properties for each phase. The prediction of the
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DDB Simulation Software Thermo Engine Options

Calculation using Aspen Property
Toolkit to verify physical property
issues prior to process simulation.
2008
2009

VLE, HPV
hE, cPE, vE

Aspen Plus completed

Pro/II-Interface mostly
finished.

DDBSP & GPA Data bundled in SYSTEM 7 Process Explorer

(For more information, DDBST is represented in the EPCON International booth)