Choosing Property Models

CHEN 4460 Process Synthesis,

Simulation and Optimization
Dr. Mario Richard Eden
Department of Chemical Engineering
Auburn University
Lab Lecture No. 4 Selection of Property Models
October 2, 2012
Contains Material Developed by Dr. Daniel R. Lewin, Technion,
Israel

Importance of Selection

Correct predictions of physical properties of

the mixture as function of temperature and
pressure.

Each method is suitable only for particular

types of components and limited to certain
operating conditions.

Choosing the wrong method may lead to

incorrect simulation results.

Particularly
important
for
reliable
computations associated with separation

Principal Selection Steps

Choosing the most suitable model/thermo
method.
Comparing the obtained predictions with
data from the literature.
Adding estimates for components not
available in the chosen thermo package.
Can they be neglected?
Generation of lab data if necessary to check
the thermo model.

Sources of Information

Publications and professional literature that

deal with the process in question or with the
components that participate in the process.

Simulator reference manual (HELP).

DATABANKS

Rules of thumb.

Types of Models
EOS Models

Activity Coefficient Models

Limited ability to represent non-ideal liquids

Can represent highly non-ideal liquids

Consistent in critical region

Inconsistent in critical region

Can represent both vapor and liquid phases

Can represent liquid phase only. Gas phase

must still be described by an EOS model

Parameters extrapolate well with temperature

Binary parameters are highly dependent on

temperature

NO

Do you have any POLAR

components in your system?
YES

Use EOS Model

YES

Are the operating conditions

near the CRITICAL region of the
mixture?
NO

NO

Do you have LIGHT gases or

SUPERCRITICAL components
in your system?

Use Activity Coefficient

Model

YES

Use Activity Coefficient

Model with Henrys law

Recommendations

Eric Carlson, Dont gamble with physical

properties for simulations, Chem. Eng.
Prog. October 1996, 35-46.

Prof J.D. (Bob) Seader, University of Utah

Aspentech Recommendations

Eric Carlson
Non-electrolyte

Figure 1
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E?
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Or Pizer

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Real
All
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Peng-Robinson,
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Lee-Kesler-Plocker

R?

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R?

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pseudocomponents

P?

Pressure

E?

Electrolytes

See Figure 2

Pseudo & Real

P?
Vacuum

Chao-Seader,
Grayson-Streed or
Braun K-10

Braun K-10 or ideal

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S
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Aspentech

Example: 1-Propanol/Water

Find the best thermodynamic package for 1Propanol , H2O mixture.

Eric Carlson, Dont gamble with physical

properties for simulations, Chem. Eng.
Prog. October 1996, 35-46.

Prof J.D. (Bob) Seader, University of Utah

Carlson: 1-Propanol/Water
Non-electrolyte

Figure 1
Polar

Polarity
R?

Real or
pseudocomponents

P?

Pressure

E?

Electrolytes

E?

See Figure 2

Carlson: 1-Propanol/Water
Figure 2

Yes
P < 10 bar
(See also
Figure 3)

P?

LL?

WILSON, NRTL,
UNIQUAC and
their variances

No

ij?

No

Polar
Non-electrolytes

LL? Liquid/Liquid
P?

Pressure

ij?

Interaction Parameters Available

LL?
No

UNIFAC and
its extensions

Seader: 1-Propanol/Water
Figure 4

Yes

HC?

LG?

Yes
No

PC?

See Figure 6

HC?

Hydrocarbons

LG?

Light gases

E?

Electrolyte

PC?

Organic Polar
Compound

Seader: 1-Propanol/Water
Figure 6

Yes

Available

PC with HC

NRTL, UNIQUAC

PPS?

BIP?

Not Available

UNIFAC

BIP?

Binary Interaction
Parameters

PPS?

Possible Phase
Splitting

Solution: 1-Propanol/Water
TXY diagram for 1-Propanol, H 2O

100

Perry
NRTL
PRSV
UNIQUAC
Van-Laar (Built-in
Van-Laar(Perry)

98
96

92

T [ C]

94

90
88
86
84
82

0.1

0.2

0.3

0.4

0.5

0.6

1-Propanol mol. frac.

0.7

0.8

0.9