Engineering Practice

Selecting the Right Thermodynamic Models

for Process Simulation
Software that enables complex processes to be simulated continues to evolve for a
wide range of thermodynamic conditions. Selection of the most appropriate models
plays a crucial role in adequately representing real-life conditions
Atul B. Choudhari
Tata Consulting Engineers Ltd.

ne of the first and most

O
important decisions to
be made when model­ Select an
equation of
Are there polar

ling a chemical process state (EOS) model

*-©- components present?

system using a computer simulation

package is the selection of an ap­
propriate method for simulating ther­ Are the operating
modynamic properties. Thermody­ Select a modified
EOS model
conditions near the
critical region?
namic-property methods enable the
mathematical calculation of pres­
sure, temperature, composition and
specific volume for multi-component Are there any light gases
or supercritical components present
and multi-phase chemical systems. (such as H , CO2, N2)?
2
These calculation methods are also
used as a basis for determining the
state functions of a system, such as Select an activity coefficient model with Select an activity coefficient model
Henry's law (if available) for the liquid for the liquid phase and an EOS for
enthalpy and entropy and hence, phase, and an EOS for the vapor phase the vapor phase
Gibbs free energy. This article pro­
FIGURE 1. This decision tree can aid in the selection of the most appropriate thermodynamic method
vides an overview of the primary
thermodynamic-property meth­
ods, and discusses the basis that junction with either the ideal gas the following:
underlies each one, the strengths equation or an EOS, to accurately • Steam tables
and weaknesses of each, and appli­ incorporate vapor-phase behavior. • API Sour-Water Method
cability of each to various chemical This is sometimes referred to as a • Glycol
systems, to assist in the selection dual-model approach. • Amines
decision. 3. Henry’s Law. Henry’s Law is gen­ Commercial simulation pack­
In general, thermodynamic-prop­ erally employed for environmental ages often use terminology such
erty methods can be categorized applications. It is applied along with as ‘‘thermodynamic system” or
according to the following four op­ liquid-activity-coefficient methods, “thermodynamic package" in the
tions (each of which is discussed in such as non-random two-liquid input data section. Selection of the
greater detail below): (NRTL) methods. Henry’s Law deter­ most appropriate thermodynamic
1. Equations of state (EOS). These mines the amount of a supercritical method is not just a decision on the
are primarily suited to describing va­ component (non-condensable) gas thermodynamic-property method.
por-phase behavior and predicting in the liquid phase. Instead, it involves selection of all
the vapor-liquid equilibrium (VLE) be­ 4. Special models. For specific appli­ the relevant equations and methods
tween the vapor phase and an ideal, cations, a specially developed ther­ that the simulation will use to predict
saturated liquid phase. modynamic package (for instance, vapor-liquid equilibrium (VLE), vapor-
2. Liquid-activity-coefficient meth­ having binary interaction param­ liquid-liquid equilibrium (VLLE), state
ods. These have been developed eters that are specially developed functions (such as enthalpy and
specifically to model non-ideal liquid- for the components associated with entropy), physical properties and
phase behavior. These methods are these systems) is generally transport properties.
more empirical in nature than EOS available in most of the commer­
and therefore require more data cial simulation packages. The types Equations of state (EOS)
about the system and its compo­ of systems that are often included Any equation that attempts to re­
nents. They must be used in con­ in these special models include late the pressure, temperature and

50 CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM DECEMBER 2019

 TABLE 1. EQUATION OF STATE (EOS) APPLICABILITY GUIDE
Classification Low High Liquid Polar Comments
pressure pressure phase molecules
Ideal gas equation Yes No No No Strictly applicable to ideal gas systems

Generalized correla­ Yes Yes No Yes The compressibility factor and accentnc factor attempt to account for non-ideality. These
tions (such as Lee- correlations are of a graphical form and are easy to use. The basic premise is that all gas­
Kesler-Plocker) eous components with similar accentricity behave similarly at the same reduced tempera­
ture (TJ and reduced pressure (PJ
Virial equations Yes No No No Though these equations have reasonable accuracy for non-polar gas mixtures at low to
medium pressures, they have limited applicability, as they have not been developed to the
extent of the more popular cubic EOS
Cubic EOS (such as Yes <1,000 Yes No (unless Cubic EOS (cubic with respect to specific volume) are the most popular EOS used in the
Peng Robinson (PR), bar for specifically oil-and-gas and petrochemical industries. They are relatively simple to apply and are able
SRK, RK and others) PR,and modified) to predict the behavior of saturated liquid-phase components, in addition to vapor-phase
<350 bar behavior. They are all susceptible to errors in prediction at or very near the critical point,
for SRK but are considered to be more accurate than activity coefficient methods in that region.
However, by themselves they cannot predict within the two-phase (V-L) region of a pure
component
More complex EOS Yes Yes Yes Yes Such EOS contain many adjustable parameters, which can extend their applicability,
(such as Benedict- though often only for a limited range of components. Their applicability to describing
Webb-Rubin; BWRII liquid-phase behavior is equation-specific

specific (molar) volume of a compo­ are present at relatively low pressure contain binary interaction param­
nent (or mixture of components) in a and high temperature. eters, which have been determined
single phase can be termed an EOS. In order to extend the applicabil­ from experimental data and actual
The ideal gas law represents the ity of the ideal gas equation to real plant operating data. Descriptions
simplest EOS. gas systems and include liquid- of the applicability of various EOS
phase pressure-vapor-temperature to various chemical systems can be
PV = nRT (PVT) behavior, a number of pa­ found in online or in published oper­
rameters and modifications are ating manuals such as those found
Where: introduced below: in Refs. 1 and 2 that accompany
P = The pressure of the gas • The compressibility factor most commercial computer simula­
V = The volume of the gas • Acentric factor tion packages. The general applica­
n = The number of moles • Van der Waal a and b correction bility of EOS methods is summarized
T = The absolute temperature factor in Table 1.
R = The ideal gas constant • The binary interaction parameter However, EOS typically have a
Proprietary modifications to vari­ number of limitations, which re­
This equation makes no allowance ous EOS can help to extend their strict their application to relatively
for intermolecular forces, and as­ applicability to moderately non-ideal simple and primarily non-polar com­
sumes individual molecules do not mixtures of components commonly ponents, such as hydrocarbons
occupy any volume relative to the encountered in oil-and-gas and pet­ and light gases. The main
total volume. Due to these simplify­ rochemical processes. For example, limitations include the following:
ing assumptions, this EOS is only mixtures of glycol, alcohol, water • Complexities introduced by the
applicable to simple, spherical mole­ and hydrocarbons can be described mathematical methods that are
cules in the gas or vapor-phase that by some modified EOS. These EOS used to determine the fugacity co­

TABLE 2. LIQUID ACTIVITY COEFFICIENT METHOD APPLICABILITY GUIDE

Method Binary Different-sized Non-ideal/ Phase Comments
parameters molecules Polar binary splitting
mixtures
Ideal solution None No No No Only applicable to similarly sized molecules and components consisting of simi­
lar molecular species
Regular solution None Yes Yes Yes Allows pure component data to be used to predict activity coefficients. Non-ad-
justable parameters attempt to account for differences in polarity and molecular
size. Applicable to typical non-polar molecules such as hydrocarbons
Two-suffix Margules One No No Yes Simplistic. Assumes all molecules are of a similar size and only considers inter­
actions between two molecules (hence two-suffix) throughout a mixture
Two-constant Mar- Two No No Yes Assumes similarly sized molecules, but assumes that intermolecular interac­
gules tions between pairs ot molecules (ot different molecular species) are not equal
Three-suffix Mar­ Two No Yes Yes By extending the number ot molecules involved in interactions to three, the
gules range ot applicability is extended. Most widely used of the Margules methods
Van Laar Two Yes Yes Yes Does not assume similar sized molecular components, and has been extended
to non-ideal mixtures. Wide usage and simole to apply
Wilson Two Yes Yes No The main drawback is its inability to predict LLE (for instance, liquid-liquid im-
miscibility)
NRTL Three -Five Yes Yes Yes Widely applicable. Good forVLE. LLE and VILE
UNI-OUAC Two Yes Yes Yes Parameters not as dependent on temperature as NRTL parameters. Its form
makes it more applicable to solutions containing small or large molecules (such
as polymers)

chemical ENGINEERING WWW.CHEMENGONLINE.COM DECEMBER 2019

 TABLE 3. EOS VERSUS ACTIVITY COEFFICIENT METHODS relations, such as those by Chao-
EOS model Activity coefficient models Seader (CS) and Grayson-Streed
Suitable for ideal and non-polar liquids Suitable for defininq hiqhlv non-ideal liquids (GS), can also be used to better
Consistent property prediction in “critical" region Inconsistent in predicting behavior near the
predict the fugacity coefficient for a
"critical" region
range of components in the liquid
Applicable for vapor and liquid phase Represent the liquid phase only. Additionally, the gas
phase must still be defined using an EOS model phase. Thus, when used in con­
Parameters can be easily extrapolated with Binary interaction parameters depend on junction with an EOS to predict the
temperature temperature vapor-phase fugacity coefficient,
VLE data can be predicted for sys­
efficient from an EOS Using EOS to predict fugacity tems containing light hydrocarbons
• Mixing rules that are used to ex­ coefficients. EOS can be used to and hydrogen. In fact, it is gener­
tend the use of EOS to mixtures mathematically determine the va­ ally recommended [7] to use the GS
are somewhat arbitrary, and there­ por-phase fugacity coefficient and, method for systems involving heavy
fore reduce the validity of the though often with less accuracy, the hydrocarbons and hydrogen, such
results liquid-phase fugacity coefficient. This as hydrotreating processes. It is also
• EOS are best suited to describing is done by relating the fugacity coef­ recommended for use in the simula­
vapor-phase behavior. However, ficient to measurable properties of tion of topping units and vacuum ap­
in combination with the advanced pressure, temperature and specific plications handling heavy ends.
mixing rules, EOS can (sometimes) volume through the use of residual
be used to model the liquid-phase functions. Residual functions use the Liquid-activity coefficient
behavior for simple and non-po- thermodynamic properties of Gibbs methods
lar liquid mixtures. Examples for free energy, enthalpy and entropy to Non-ideal behavior in the liquid
sample systems are mixtures of mathematically describe deviations phase is evidenced by the following:
propane, ethane and butane and from ideal gas behavior, and can • Strong departures from Raoult's
mixtures of benzene and toluene therefore be used to evaluate the fu­ law (which relates ideal-gas phase
• EOS become inaccurate at higher gacity coefficient of a component in behavior and ideal-liquid phase
pressure and lower temperature, a phase. behavior), due to polarity or hydro­
and fail to predict condensation of For predicting liquid-phase fugac­ gen bond formation
a gas to a liquid ity coefficients, semi-empirical cor­ • The formation of azeotropes

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 TABLE 4. RECOMMENDED THERMODYNAMIC METHODS FOR VARIOUS APPLICATIONS tion parameters, or to verify the
Type of system Recommended property method predictions of the model?
Glycol dehydration Peng Robinson (PR), specialized package If these criteria cannot be satisfied
Refinery crude tower (low pressure) Barun K10 (BK10), Grayson-Streed (GSKGrayson- with the available experimental data,
Streed Erbar(GSE). SRK/PR then the list of recommendations for
Refinery crude tower (high pressure) GS/GSE, SRK/PR
selecting an appropriate thermody­
Reformers and hydrotreaters GS/SRK/PR
namic property method should be
Sour water PR, sour PR, or special packages
consulted to ascertain whether there
Cryoqenic qas-processinq. natural qas SRK/PR. Benedict-Webb-Rubm Sterlinq (BWRS)
Air separation SRK/PR
might be an appropriately modified
Light hydrocarbons, petrochemicals SRK/PR, Soave Redlich Kwong Kabadi Oanner
EOS to describe the system. Many
(SRKKD) for hiqli pressure modified EOS are available to de­
Aromatics Ideal for low pressure, SRK/PR for pressure greater scribe a variety of common ideal
than 2 atm and partially non-ideal systems. In
Ethylene towers Lee Kesler Plocker (LKP), BWRS general, EOS are less cumbersome
Reservoir systems PR/SRK to use because of their ability to de­
Steam systems Steam tables
scribe both vapor-phase and ideal
HF Alkylation NRTL
liquid-phase behavior (unless modi­
Aromatics plus non-aromatics NRTL/UNIQUAC
fied to account for non-ideal behav­
Hydrocarbon systems where water solubility in hy­ SRKKD
drocarbon is important
ior), and because they are less reli­
Non-ionic, chemical applications Wilson. NRTL, UNIQUAC ant on parameters that are fitted for
Amine system EOS-based special packages a specific range of conditions. In any
case, there is no substitute for ap­
• The formation of two liquid phases tion, and the Van Laar equation. propriate experimental data for tun­
(via liquid-liquid extraction, LLE) Local compositional models are ing and checking model predictions.
The liquid-activity coefficient is es­ semi-empirical models based on the
sentially a correction factor that at­ concept that intermolecular forces Group contribution methods
tempts to quantify deviations from will cause non-random arrangement When experimental data are not
ideal solution behavior. It is a strong of molecules in the liquid phase. available, various methods can be
function of composition and to a These models incorporate param­ used to predict activity coefficients
lesser extent, temperature (thus ac­ eters related to energies of interac­ based on the theory that functional
counting for interactions between tion and distribution tendencies of groups within a molecule of any
molecules), but a much weaker molecules, and this increases their component contribute uniquely to
function of pressure. Since the activ­ general application and reliability the activity coefficient for that com­
ity coefficients of the components in while also increasing the need for ponent. These methods are approxi­
a mixture are related to the compo­ binary interaction data and experi­ mate because they rely on the fol­
sition, they are not independent of mental data. Examples of activity lowing two simplifying assumptions:
each other. coefficient methods that use local • That the contribution of a func­
There are two principal ap­ compositional models include NRTL tional group within any molecule is
proaches for determining activity co­ methods, Wilson, universal quasi­ the same, and
efficients for liquid mixtures: chemical (UNIQUAC) methods • That the contribution of each func­
1. Excess Gibbs free energy and more. tional group is independent of the
methods A word of caution when applying contribution of any other group
2. Local compositional models liquid-activity-coefficient methods is within a molecule
By estimating activity coefficients warranted here: Due to their empiri­ Examples of these group contri­
using semi-empirical or semi-theo­ cal nature and reliance on fitted pa­ bution methods include UNIFAC
retical equations and fitting adjust­ rameters, liquid-activity-coefficient and ASOG. In order to apply the
able binary interaction parameters to methods should be applied with UNIFAC method, all components
experimental data, VLE behavior can caution, giving heed to the following must be condensable and electro­
be predicted. criteria: lyte solutions cannot be modeled.
Excess Gibbs free-energy meth­ • Are components in the system Given the assumptions associated
ods use excess Gibbs free energy common and well understood? with these methods, in the absence
functions, which are analogous to • Are operating conditions relatively of experimental data for both the fit­
residual Gibbs free-energy functions moderate (that is, is the system at ting of adjustable parameters and
in that they mathematically (and low pressure, since fitted param­ the comparison with model predic­
thermodynamically) relate devia­ eter data available in commercial tions, such methods should be used
tions from ideal solution behavior to software packages are usually with extreme caution. From the au­
functions involving the activity coef­ based on the assumption of ideal thor’s experience, however, it can be
ficients of the components in the liq­ gas conditions in equilibrium with stated that the data obtained from
uid phase. Examples of activity coef­ the liquid phase)? the use of UNIFAC model is not as
ficient methods that use the excess • Are experimental data available accurate as the standard fitted val­
Gibbs free-energy methodology, and valid for the applicable range ues obtained from the various simu­
include the regular solution model, of operating conditions, either for lation packages.
various forms of the Margules equa­ regression to tune binary interac­ A summary showing the general

CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM DECEMBER 2019

applicability of the liquid activity coefficient methods is
given in Table 2. Table 3 lists key parameters that dif­
FLOWROX
ferentiate EOS and activity coefficient models, allowing Proven Performance
for a comparison.

Selecting an applicable thermodynamic

property method
The thermodynamic property decision tree for selecting
Flowrox Filtration
the thermodynamic property route is shown in Figure 1.
Table 4 provides general recommendations for the
Solutions
selection of a thermodynamic system for modeling
and simulation. These recommendations are generic in Filter service:
nature and are based on the author’s experience and
• Original quality and performance
available literature [7,2]. Readers are cautioned to verify
the applicability based on the operating conditions in­ with lower costs
volved, and are strongly recommended to validate the
simulation model. The recommended selection is in­ Smart Filtration Digital Service:
tended to serve as initial guide to model the system. • Real-time insight into the filtration process
Further, the availability of binary interaction parameters
& troubleshooting
and applicable temperature and pressure range must
be verified before the selection. Readers shall note
that the developers of specific simulation packages Flowrox Filter Press:
have several times modified the typical thermodynamic • Fully automatic operation
methods and have presented customized solutions in • High quality
their software products. Readers should also take pre­ • Superb performance
caution to check the suitability of a particular thermody­
namic method with respect to the reference and user
manuals of respective simulation software.

Concluding remarks
Commercially available simulation packages contain
databases of both pure component and binary interac­
tion parameter data. Binary interaction data can also be ..
extended to multi-component systems. When used in
conjunction with the mathematical methods pressure,
temperature and phase composition can be predicted.
The predictive accuracy of the thermodynamic model­
ing methods is dependent on both (a) the suitability of
Flowrox Ceramic Disc Filter:
selected mathematical method(s) to describe behavior • Highly efficient filtration
in the chemical system, and (b) the quality of the com­ • Lowest energy consumption
ponent data (pure and binary interaction) available for • Reliable operation
use in the model. ■
Edited by Suzanne Shelley

References
1 PRO/ll with Provision Reference Manual - Thermodynamic Property Methods Applica­
tion Guidelines.
2. HYSYS User Manual: Thermodynamics: Appendix A - Property Methods and Calcula­
tions.
3. Reid. R.C. Prausnitz. J.M.. and Shenvood. T.K.. ‘Properties of Gases and Liquids; 3rd.
Ed.,McGraw-Hi, 1977.
4.Smith J.M., Van Ness H.C.. Abbott M. M.. "Introduction to Chemical Engineering Ther­
modynamics.* 7th Ed.. McGraw-Hill. 2005.
0 Complete filtration solutions to
• maximize production
Author • reduce downtime
Atul B. Choudhari is technology principal at Tata Consulting • lower total costs!
Engineers Ltd, (Empire Tower, Cloud City campus, Thane-Bela-
pur Road. Airoli, Navi Mumbai 400708, India; Phone:+91 -22-
61148620; Email: [email protected]). In his 26 years of
professional experience. Choudhari has been involved with CONTACT US!
flowsheet simulations, process optimization, basic and detailed www.flowrox.com
888-356-9797
engineering for petrochemicals, petroleum refinery and hydro­
carbon processes. He has authored various technical papers [email protected] ©oo
in the field ot process optimization. Choudhari holds a bache­
lor's degree in chemical engineering trom Marathwada
University (Aurangabad). For details visit adlinks.chemengonline.com/73861-17
55
CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM DECEMBER 2019