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Carlson (1996)

Carlson (1996)

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hemical engineers use processsimulation to perform a varietyof important work. This work ranges from calculations of mass- and energy balances of large flow-sheets to prediction of the performance of process alternatives that can save millionsof dollars. An engineer very quickly candefine a complex flowsheet and all theprocess conditions. Desktop computersnow allow rating,sizing,optimization,and dynamic calculations that previouslyrequired large mainframe computers. Inthe past,these simulations were oftenbuilt by a group of experts,including aphysical property expert. Now,simulatorssuch as ASPEN PLUS,ChemCAD III,HYSIM,PRO II,and SPEEDUP are easi-er to use and more powerful than thestandalone programs of the past. Today,asingle engineer can set up the basic simu-lation specifications,including the physi-cal properties,in very little time.Missing or inadequate physical prop-erties,however,can undermine the accu-racy of a model or even prevent you fromperforming the simulation. That some re-quired information is missing is not anoversight in the simulator. After all,formost compounds,physical property pa-rameters are not known for every thermo-dynamic model or for all temperature orpressure ranges. Models have built-in as-sumptions and practical limits that shouldapply.In this article,we will provide practi-cal tips and techniques to help you accu-rately describe the physical propertiesneeded in a simulation. As an engineer,you always will have to make assump-tions in terms of physical properties,however. The goal of this article is to out-line the appropriate assumptions and toprovide techniques when properties aremissing.
The five important tasks
Successfully describing the physicalproperties to be used in a simulation in-volves five tasks:
selecting the appropriate physicalproperty methods;
validating the physical properties;
describing nondatabank compo-nents (chemical species or compound)and missing parameters;
obtaining and using physical prop-erty data; and
estimating any missing propertyparameters.It can be argued that these tasks arenot sequential and,to some degree,theyare concurrent. During simulation devel-opment,however,you will need to visiteach area to be confident that your simu-lation is as accurate as possible — sothat important decisions can be madebased on the results of your simulations.
Selecting the appropriatephysical property methods
This essential first step will affect allsubsequent tasks in developing accuratephysical properties in your simulation.Indeed,the choice of the physical proper-ty models for a simulation can be one of the most important decisions for an engi-neer. Several factors need to be consid-
Dont Gamble WithPhysical PropertiesFor Simulations
 Finding good values for inadequate or missing physical  property parametersis the key to a successful  simulation. And  this depends upon choosing the rightestimation methods.
Eric C. Carlson,
Aspen Technology, Inc.
ered,and no single method can han-dle all systems. Table 1 lists somethermodynamic models available insimulators.The four factors that you shouldconsider when choosing propertymethods are:the nature of the properties of interest;the composition of the mixture;the pressure and temperaturerange; and• the availability of parameters.To ease the selection of the rightphysical property methods,we sug-gest using the decision trees shown inFigures 1–3. These trees are based onthe four factors for selecting propertymethods,and can be used when thechemical components and approxi-mate temperature and pressure rangesare known. While these diagrams aresimplifications,they do show thebasic steps of the decision-makingprocess,while the notes in the sidebaramplify some of the key points.
The nature of the properties of in-terest.
A question that you may ask yourself when starting a simulation is“Does the choice of physical propertymethods matter?The answer is anemphatic YES. The choice canstrongly affect the prediction of thesimulation. You should be selecting acollection of methods that will bestpredict the properties or results of in-terest to you.Because many chemical processsimulations include distillation,strip-ping,or evaporation,one importantpotential consideration for the choiceof physical property models isvapor/liquid equilibrium (VLE). Thisis the area in which the most physicalproperty work is focused in chemicalengineering. Liquid/liquid equilibri-um (LLE) also becomes important inprocesses such as solvent extractionand extractive distillation.Another critical consideration ispure-component and mixture en-thalpy. Enthalpies and heat capacitiesare important for unit operations suchas heat exchangers,condensers,dis-tillation columns,and reactors.
Equation-of-State Models
Benedict-Webb-Rubin(BWR)-Lee-StarlingHayden-O’Connell*Hydrogen-fluoride equation of state forhexamerization*Ideal gas law*Lee-Kesler (LK)Lee-Kesler-PlockerPeng-Robinson (PR)Perturbed-Hard-ChainPredictive SRKRedlich-Kwong (RK)Redlich-Kwong-Soave (RKS)RKS or PR with Wong-Sandler mixing ruleRKS or PR with modified-Huron-Vidal-2 mix-ing ruleSanchez-Lacombe for polymers* Not used for the liquid phase.
Activity Coefficient Models
Electrolyte NRTLFlory-HugginsNRTLScatchard-HildebrandUNIQUACUNIFACVan LaarWilson
Special Models
API sour-water methodBraun K-10Chao-SeaderGrayson-StreedKent-EisenbergSteam Tables
Table 1. Thermodynamic property modelsavailable in a simulator.
All NonpolarPseudo &RealVacuumBraun K-10 or IdealChao-Seader,Grayson-Streed orBraun K-10PolarRealNon-electolyteElectolyteElectolytesElectolyte NRTLor Pitzer
See Figure 2 
?PolarityReal orPseudocomponentsPressureSource: (
 Figure 1. The first steps for selecting physical property methods.
Here are some pointers to help you navigate the decision trees that ap-pear as Figures 1–3.
What are pseudocomponents? 
In many applications where only non-polar molecules are present (such as in hydrocarbon processing and re-fining), the mixture is so complex that instead of representing it by all theknown constituents, it is easier to group the constituents by some usefulproperty such as boiling point. In this way, a mixture of hundreds of con-stituents can be reduced to 30 or fewer. The properties of these groupedconstituents, called pseudocomponents, are represented by an averageboiling point, specific gravity, and molecular weight. If you do not usepseudocomponents, the constituents should be described by a molecu-lar formula and are referred to as real components.
Why are electrolyte mixtures different? 
Electrolyte mixtures includecomponents that are charged molecules (ions) or that form salts. Somesimulators allow calculation of electrolyte reaction equilibrium withphase equilibrium. This is a very powerful method and its usage coversmany applications such as caustic scrubbing, neutralization, acid pro-duction, and salt precipitation. The nonideality of electrolyte solutions,usually containing water, can be observed in boiling point elevation, salt-ing out of gases (that is, adding salts to the solution to change the solubil-ity of gases), and salt precipitation. The most common electrolyte meth-ods are the Pitzer model, and the modified-NRTL activity coefficientmodel of Chen and coworkers. Some electrolytes, like formic acid andacetic acid, are very weak and an electrolyte method is not required.
Which type of method should be chosen for mixtures containing polar components but no electrolytes? 
There are two groups of methods — based on activity coefficients or equations of state. Use activity-coef-ficient-based methods when pressures are low to medium (typically lessthan 10 bar or 150 psia) and if no components are near critical point. Ac-tivity coefficient models also often are used to accurately predict non-ideal liquid behavior such as for VLE and for LLE. In contrast, equation-of-state methods excel in their ability to represent data and extrapolatewith temperature and pressure up to and above the mixture criticalpoint. Now, however, methods relying on cubic equations of state withpredictive mixing rules effectively combine the strengths of the twomethods. (See Table 2.) For higher pressures (and temperatures), thesespecial equations of state are better as they were developed to apply toa wider range of temperatures. These methods incorporate activity coef-ficients in the calculation of component interactions represented by ex-cess Gibbs free energy. Most of the latter use a UNIFAC-based activitycoefficient model as the default, but you can use any activity coefficient.At simulation pressures less than 10 atm and where there are nonear critical components, for the best results use the Wilson, NRTL, orUNIQUAC binary parameters that may be available in built-in databanks,or fit binary parameters to experimental data (if available) using activitycoefficient models. These parameters may have been determined at dif-ferent temperatures, pressures, and compositions than you are simulating,though, so you may not obtain the best possible accuracy. If interactionparameters are not available, however, you can use the UNIFAC method.
When should UNIFAC be used? 
UNIFAC and other UNIFAC-based ac-tivity coefficient models are predictive approaches that use structuralgroups to estimate component interactions. From structural informationabout organic components usually available in the built-in databank,UNIFAC is able to predict the activity coefficients as a function of com-position and temperature. You can make use of UNIFAC when you do nothave experimental data or binary parameters or when an approximatevalue is acceptable (for instance, for a component with low priority). Inrecent years, there have been improvements to UNIFAC (see Table 3)that can better predict VLE, heat of mixing, and LLE over a wider temper-ature range. Recent extensions to UNIFAC proposed for molecules suchas refrigerants and sugars may be useful, and you can add the groupsand parameters to your simulation. Simulators may have the ability togenerate binary interaction parameters for Wilson, UNIQUAC, or NRTLfrom UNIFAC.Not all components can be described using UNIFAC, however, andnot all group interactions are available. Examples of components that donot have UNIFAC groups include metals, organometals, and phosphates.So, we highly recommend always doing a search for available data onbinary or ternary systems of interest.
How should the vapor phase be treated? 
The choice of the VLEmethod using an activity coefficient model also requires a choice ofmodel for the vapor phase properties. If vapor phase association is ob-served (as in the case of acetic acid), then the vapor phase modelshould be Hayden-O’Connell or Nothnagel. A system containing hydro-gen fluoride may require a special model to represent the high degree ofassociation due to hydrogen bonding. Association in the vapor phasecan have a strong effect on phase equilibria and enthalpy.
When should defaults be overridden for other physical property methods? 
Prediction of density, enthalpy, and viscosity also are impor-tant in simulators, and you shouldn’t automatically accept the defaultmethods. Check the simulator documentation for the default method andmixing rules.Vapor density is calculated by an equation of state or the ideal gaslaw. Mixture liquid densities can be calculated by an equation of state, atemperature-dependent model such as that of Rackett, or by a tempera-ture- and pressure-dependent model such as the COSTALD. For psuedo-components, an American Petroleum Institute (API) method typically isemployed. The Rackett model is recommended for general use.Vapor enthalpy usually is calculated via an ideal gas assumption oran equation of state. The equation-of-state methods calculate a depar-ture from ideality called the vapor enthalpy departure. For componentssuch as acetic acid, the Hayden-O’Connell model is best, and will calcu-late a larger-than-normal vapor enthalpy departure.Liquid enthalpies are calculated by a variety of methods. If the simu-lator uses the ideal gas as the reference state, then the pure-componentliquid enthalpy is calculated from the ideal gas enthalpy and a liquid en-thalpy departure. This can be written as
+ (
is the pure-component liquid enthalpy,
is the ideal gas en-thalpy, and (
) is the liquid enthalpy departure. This departure in-cludes the heat of vaporization, the vapor enthalpy departure from theideal pressure to the saturation pressure, and the liquid pressure cor-rection from the saturation pressure to the real pressure. Simulatorsalso allow separate calculations for a liquid enthalpy directly from theliquid-heat-capacity polynomial. For some components, the method inEq. 1 will not be accurate enough for liquid-heat-capacity predictions.This can be very important if you are exporting your property informationto another program such as one for rigorous heat-exchanger design. Youcan use the latter liquid-heat-capacity (CpL) method to improve the ac-curacy of liquid heat capacities.Viscosity is another important property for sizing of piping, pumps,heat exchangers, and distillation columns. There are various vapor andliquid methods for calculating viscosity and, generally, the parameter re-quirements for these methods are substantial.
Navigating the decision trees

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