Exercise 2

Professor Terry A. Ring Department of Chemical Engineering The University of Utah

How to chose the best property prediction method for simulation ?

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054402 Design & Analysis II

Importance of Selecting the Appropriate Prediction Method

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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.).
054402 Design & Analysis II 2

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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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054402 Design & Analysis II

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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054402 Design & Analysis II

Issues in Selection of the Appropriate Thermodynamics Package

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Nature of mixture (e.g., hydrocarbon, polar, electrolyte, etc.) Pressure and temperature range Availability of data.

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054402 Design & Analysis II

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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054402 Design & Analysis II

Eric Carlson s Recommendations

Figure 1
Polar Non-electrolyte See Figure 2

E?
Electrolyte Real Electrolyte NRTL Or Pizer Peng-Robinson, Redlich-Kwong-Soave, Lee-Kesler-Plocker Chao-Seader, Grayson-Streed or Braun K-10

All Non-polar
Polarity
R? P? E?

R?
Pseudo & Real

Real or pseudocomponents Pressure Electrolytes

P?
Vacuum

Braun K-10 or ideal

7

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054402 Design & Analysis II

Yes

Figure 2
P < 10 bar (See also Figure 3)

NRTL, UNIQUAC and their variances WILSON, NRTL, UNIQUAC and their variances UNIFAC LLE

Yes

LL?
No Yes

ij?
No

Polar Non-electrolytes

P?

LL?
No Yes UNIFAC and its extensions

LL? Liquid/Liquid P? ij?

Pressure

P > 10 bar

ij?

Schwartentruber-Renon PR or SRK with WS PR or SRK with MHV2 PSRK PR or SRK with MHV2
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Interaction Parameters Available

No

054402 Design & Analysis II

Figure 3
Yes

Hexamers

Wilson, NRTL, UNIQUAC, or UNIFAC with special EOS for Hexamers

DP?
Dimers

Wilson NRTL UNIQUAC UNIFAC

VAP? DP?

VAP? No

Wilson, NRTL, UNIQUAC, UNIFAC with Hayden O Connell or Northnagel EOS Wilson, NRTL, UNIQUAC, or UNIFAC* with ideal Gas or RK EOS

Vapor Phase Association Degrees of Polymerizatiom

UNIFAC* and its Extensions

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054402 Design & Analysis II

Bob Seader s Recommendations

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054402 Design & Analysis II

10

Bob Seader s Recommendations

Figure 4
Yes Yes Yes PSRK
HC? LG?

Hydrocarbons Light gases Electrolyte Organic Polar Compound

PC?
No See Figure 5 See Figure 6 Yes

E? PC?

LG?
No

HC?

PC?
No See Figure 5

Yes No

Modified NRTL

E?
No
Special: e.g., Sour Water (NH3, CO2, H2S, H2O) Aqueous amine solution with CO2 and H2S
054402 Design & Analysis II 11

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Figure 5
Critical Cryogenic Narrow or wide HC and/ or LG PR

P?
Non-Critical PR, BWRS

T?
Non- Cryogenic SRK, PR

BP?

Very wide

LKP

BP? T? P?

Boiling point range of compound Temperature region Pressure region

12

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054402 Design & Analysis II

Figure 6
Yes NRTL, UNIQUAC

Available

PPS?
No Wilson

PC with HC

BIP?

Not Available

UNIFAC

BIP? PPS?

Binary Interaction Parameters Possible Phase Splitting

13

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054402 Design & Analysis II

Hyprotech Recommendations

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054402 Design & Analysis II

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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

1/3/13

054402 Design & Analysis II

15

Eric Carlson s Recommendations

Figure 1
for 1-Propanol ,H2O mixture Non-electrolyte Polar

See Figure 2

E?

Polarity
R? P? E?

Real or pseudocomponents Pressure Electrolytes

054402 Design & Analysis II 16

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Figure 2
P < 10 bar (See also Figure 3)

Yes

LL?
No

ij?
No

WILSON, NRTL, UNIQUAC and their variances

Polar Non-electrolytes

P?

LL?
No UNIFAC and its extensions

LL? Liquid/Liquid P? ij?

Pressure Interaction Parameters Available

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054402 Design & Analysis II

17

Bob Seader s Recommendations

Figure 4
for 1-Propanol ,H2O mixture
HC? LG? E?

Hydrocarbons Light gases Electrolyte Organic Polar Compound

Yes

LG?
No

Yes

See Figure 6

PC?

HC?

PC?

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054402 Design & Analysis II

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Figure 6
Yes NRTL, UNIQUAC

Available

PPS?

PC with HC

BIP?

Not Available

UNIFAC

BIP? PPS?

Binary Interaction Parameters Possible Phase Splitting

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054402 Design & Analysis II

1-Propanol, H2O
100 98 96 94 92 90 88 86 84 82 Perry NRTL PRSV UNIQUAC Van-Laar (Built-in Van-Laar(Perry)

TXY diagram for 1-Propanol, H 2O

T [oC]

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1-Propanol mol. frac.

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TXY macro for HYSYS

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