Exercise 2

How to chose the best

property prediction
method for simulation ?

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 Importance of Selecting the Appropriate
Prediction Method
 Correct predictions of the physical
properties of the mixture as a 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
operations (distillation, LL extraction, etc.).

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Principle Steps in Selecting the
Appropriate Thermodynamics Package
1. Choosing the most suitable
model/thermo method.
2. Comparing the obtained predictions
with data from the literature.
3. Adding estimates for components
that not available in the chosen
thermo package. Can they be
neglected?
4. Generation of lab data if necessary
to check the thermo model.

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 Sources of Information

1. Publications and professional

literature that deal with the process
in question or with the components
that participate in the process.
2. Simulator reference manual (HELP).
3. DATABANKS
4. Rules of thumb.

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 Issues in Selection of the Appropriate
Thermodynamics Package

 Nature of mixture (e.g.,

hydrocarbon, polar,
electrolyte, etc.)
 Pressure and temperature
range
 Availability of data.

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 Recommendations for the Selection of
the Appropriate Thermodynamics Package

Eric Carlson, “Don’t gamble with physical

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

Prof J.D. (Bob) Seader,

University of Utah
Hyprotech Recommendations

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 Eric Carlson’s Recommendations
Figure 1 Non-electrolyte
See Figure 2

Polar
E?

Electrolyte Electrolyte NRTL

Or Pizer

Real Peng-Robinson,
All Redlich-Kwong-Soave
Non-polar Lee-Kesler-Plocker
R?
Chao-Seader,
Polarity Grayson-Streed or
Real or Pseudo & Real Braun K-10
R?
pseudocomponents P?
P? Pressure
Vacuum
E? Braun K-10 or ideal
Electrolytes
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 Yes NRTL, UNIQUAC
and their variances
Figure 2 Yes
LL?
WILSON, NRTL,
P < 10 bar No UNIQUAC and
ij? their variances
(See also
Figure 3) Yes
UNIFAC LLE

P? No
LL?
Polar
Non-electrolytes
No UNIFAC and its
extensions
Schwartentruber-Renon
LL? Liquid/Liquid Yes
PR or SRK with WS
PR or SRK with MHV2
P? Pressure P > 10 bar
ij?
ij? No PSRK
Interaction Parameters
Available PR or SRK with MHV2
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 Wilson, NRTL, UNIQUAC,
Hexamers
Figure 3 or UNIFAC with special EOS
for Hexamers
Yes
DP?
Wilson, NRTL, UNIQUAC,
Dimers
UNIFAC with Hayden O’Connell
or Northnagel EOS
VAP?
Wilson
NRTL Wilson, NRTL,
No
UNIQUAC UNIQUAC, or UNIFAC*
UNIFAC with ideal Gas or RK EOS

VAP? Vapor Phase Association

UNIFAC* and its Extensions
DP? Degrees of Polymerizatiom

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 Bob Seader’s Recommendations

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 Bob Seader’s Recommendations
Yes PSRK
Hydrocarbons
Figure 4 Yes
HC?

PC? LG? Light gases

No E? Electrolyte
See Figure 5
Yes
LG? Yes See Figure 6 PC? Organic Polar
Compound

No
PC?
HC?
No
See Figure 5
Yes
Modified NRTL
No
E?
No Special: e.g., Sour Water (NH3, CO2, H2S, H2O)
Aqueous amine solution with CO2 and H2S
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 Figure 5
Critical
PR
Cryogenic
P?
Narrow or Non-Critical
PR, BWRS
wide
T?
HC and/ Non- Cryogenic
or LG SRK, PR
BP?

Very wide BP? Boiling point range

LKP
of compound
T? Temperature region

P? Pressure region
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 Figure 6

Yes
NRTL, UNIQUAC

Available
PPS?

No
PC with HC Wilson
BIP?

BIP? Binary Interaction

Not Available Parameters
UNIFAC
PPS? Possible Phase
Splitting

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 Hyprotech Recommendations

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

Eric Carlson, “Don’t gamble with physical

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

Prof J.D. (Bob) Seader,

University of Utah

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 Eric Carlson’s Recommendations
for 1-Propanol ,H2O mixture
Figure 1
Non-electrolyte
See Figure 2

Polar
E?

Polarity
Real or
R?
pseudocomponents
P? Pressure

E? Electrolytes
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 Figure 2 Yes
LL?
WILSON, NRTL,
P < 10 bar No UNIQUAC and
ij? their variances
(See also
Figure 3)

P? No
LL?
Polar
Non-electrolytes
No UNIFAC and its
extensions

LL? Liquid/Liquid

P? Pressure

ij? Interaction Parameters

Available
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 Bob Seader’s Recommendations
for 1-Propanol ,H2O mixture
Figure 4 HC? Hydrocarbons

LG? Light gases

E? Electrolyte
Yes
LG? Yes See Figure 6 PC? Organic Polar
Compound

No
PC?
HC?

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 Figure 6

Yes
NRTL, UNIQUAC

Available
PPS?

PC with HC
BIP?

BIP? Binary Interaction

Not Available Parameters
UNIFAC
PPS? Possible Phase
Splitting

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 1-Propanol, H2O
TXY diagram for 1-Propanol, H2O
100
Perry
98 NRTL
PRSV
UNIQUAC
96
Van-Laar (Built-in
Van-Laar(Perry)
94

92
T [oC]

90

88

86

84

82
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
1-Propanol mol. frac.
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 TXY macro for HYSYS

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