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Don T Gamble With Physical Properties For Simulation PDF
Don T Gamble With Physical Properties For Simulation PDF
ered, and no single method can han- Table 1. Thermodynamic property models
dle all systems. Table 1 lists some available in a simulator.
thermodynamic models available in
simulators. Equation-of-State Models Activity Coefficient Models
The four factors that you should
Benedict-Webb-Rubin(BWR)-Lee-Starling Electrolyte NRTL
consider when choosing property Hayden-O’Connell* Flory-Huggins
methods are: Hydrogen-fluoride equation of state for NRTL
• the nature of the properties of hexamerization* Scatchard-Hildebrand
interest; Ideal gas law* UNIQUAC
• the composition of the mixture; Lee-Kesler (LK) UNIFAC
• the pressure and temperature Lee-Kesler-Plocker Van Laar
range; and Peng-Robinson (PR) Wilson
Perturbed-Hard-Chain
• the availability of parameters.
Predictive SRK Special Models
To ease the selection of the right Redlich-Kwong (RK) API sour-water method
physical property methods, we sug- Redlich-Kwong-Soave (RKS) Braun K-10
gest using the decision trees shown in RKS or PR with Wong-Sandler mixing rule Chao-Seader
Figures 1–3. These trees are based on RKS or PR with modified-Huron-Vidal-2 mix- Grayson-Streed
the four factors for selecting property ing rule Kent-Eisenberg
methods, and can be used when the Sanchez-Lacombe for polymers Steam Tables
chemical components and approxi- .
* Not used for the liquid phase
mate temperature and pressure ranges
are known. While these diagrams are
simplifications, they do show the
Non-electolyte
basic steps of the decision-making See Figure 2
process, while the notes in the sidebar
amplify some of the key points.
The nature of the properties of in- Polar
terest. A question that you may ask E?
yourself when starting a simulation is
“Does the choice of physical property
Electolyte Electolyte NRTL
methods matter?” The answer is an or Pitzer
emphatic YES. The choice can ?
Real
strongly affect the prediction of the Peng-Robinson,
simulation. You should be selecting a Redlich-Kwong-Soave,
collection of methods that will best Lee-Kesler-Plocker
predict the properties or results of in- All Nonpolar
terest to you. R? Chao-Seader,
Grayson-Streed or
Because many chemical process Braun K-10
simulations include distillation, strip- Pseudo &
ping, or evaporation, one important Real
P?
potential consideration for the choice
of physical property models is
vapor/liquid equilibrium (VLE). This Vacuum
Braun K-10 or Ideal
is the area in which the most physical
property work is focused in chemical
engineering. Liquid/liquid equilibri- ? Polarity E? Electolytes
um (LLE) also becomes important in
processes such as solvent extraction Real or
and extractive distillation. R? Pseudocomponents P? Pressure
Another critical consideration is
pure-component and mixture en-
thalpy. Enthalpies and heat capacities
are important for unit operations such Source: (7)
as heat exchangers, condensers, dis-
tillation columns, and reactors. ■ Figure 1. The first steps for selecting physical property methods.
Polar P?
Non-electrolytes UNIFAC and its Table 3. UNIFAC revisions
No Extensions
Yes and extensions.
Schwartentruber-Renon,
PR or RKS with WS, Model Predicts
PR or RKS with MHV2
P > 10 bar Dortmund-modified VLE, LLE, HE, γ∞*
ij? UNIFAC (1993) (8)
■ Figure 2. Proceeding for polar and nonelectrolyte components. In addition, density, viscosity, pH,
and thermal conductivity may be es-
sential for other process calculations.
Hexamers Wilson, NRTL, UNIQUAC, Transport properties are important
or UNIFAC with special EOS
for hexamers
when doing equipment sizing calcula-
tions. Also, processes such as metallur-
Yes gy and mining will require calculations
DP?
for phase equilibria including solids.
The composition of the mixture.
Wilson Dimers Wilson, NRTL, UNIQUAC, Composition will influence all proper-
NRTL UNIFAC with Hayden O'Connell ties, due to the way mixture properties
VAP? or Nothnagel EOS
UNIQUAC are calculated. It will affect phase
UNIFAC
equilibria greatly because of the inter-
No Wilson, NRTL, UNIQUAC,
or UNIFAC* with Ideal Gas
action of the components in the mix-
or RK EOS ture. Usually, the interaction in the
liquid phase is the more important be-
cause of the close proximity of the
VAP? Vapor Phase Association molecules in that phase. The nature of
the vapor phase also can be significant
DP? Degrees of Polymerization if the components form complexes.
The important intermolecular forces
are electrostatic, induction, attraction,
*UNIFAC and its Extensions and repulsion between nonpolar com-
ponents, and chemical forces such as
Source: (7)
hydrogen bonding. A good overview
■ Figure 3. Options for vapor-phase calculations with activity-coefficient models. of these forces is given in Ref. 1.
100
Molefraction
90 0.6
85
0.4
80
NRTL-RK
Ideal Liquid
0 0.2 0.4 0.6 0.8 1 0.2
Molefraction Acetonitrile
Source: (14)
The magnitude of the electrostatic simulator to report the dipole mo- water, at 1 atm. The azeotrope is ac-
and induction forces is related to the ments of databank components as one curately predicted at approximately
polarity of the components. Compo- measurement of polarity. In general, 0.7 mole fraction of acetonitrile. Fig-
nents such as water, acetone, mixtures of nonpolar components ure 5 presents VLE for a mixture of
formaldehyde, and methyl chloride will exhibit less nonideal behavior. two slightly polar compounds,
are strong dipoles. Many polar com- Figures 4–7 illustrate the effect of toluene and phenol, at 1 atm. The de-
pounds are associative, and form polarity on binary vapor/liquid equi- viation from ideality is shown by
complexes or dissociate into ions. libria. Figure 4 shows the predicted comparing the predicted curve from
Components like ethane and n-hep- and experimental VLE of two highly an ideal liquid assumption to that
tane are nonpolar. You can use your polar components, acetonitrile and from a method predicting nonideality
81 16
Vapor Molefraction C2H6
80.5 Vapor Molefraction C6H6 Liquid Molefraction C2H6
Liquid Molefraction C6H6 14
Total Temperature, ˚C
80
79.5
12
Total Pressure, Atm
79
78.5 10
78
8
77.5
6
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Molefraction 4
Source: (15)
0 0.2 0.4 0.6 0.8 1
■ Figure 6 (above). VLE of cyclohexane/benzene system at 1 atm.
■ Figure 7 (right). VLE of ethane/propylene system at 40°F. Molefraction
100
1
80 0.0006
0.996 0.00055
60
0.994
0.0005
40 0.992
Liquid 2 Molefraction C6H12O
Liquid 1 Molefraction C6H12O 0.00045
0.99
20
0.988
0 10 20 30 40 50 60 70
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 Temperature, ˚C
(the nonrandom two-liquid activity sets based upon methods that fre- Validating
coefficient model (NRTL) and quently are used for certain types of the physical properties
Redlich-Kwong equation of state for mixtures. Usually the sets are identi- A necessary step in any simulation
the vapor phase). Figure 6 depicts the fied by the method used for phase project is validation of the physical
VLE of a mixture of cyclohexane and equilibria. When these sets use an properties. This involves reporting, tab-
benzene at 1 atm. Here, the interac- equation-of-state model, the same ulating, or plotting pure-component and
tion of seemingly similar molecules model is used for many properties, in- mixture properties and comparing the
with a difference in boiling point of cluding those for phase equilibria. results to known data or expected be-
less than 1°C causes an azeotrope at a The pressure and temperature havior. This is an important step in any
composition of about 0.54 mole frac- range. This is especially important in simulation and should be performed for
tion of benzene. A mixture such as choosing the method to perform databank as well as nondatabank com-
ethane and propylene (Figure 7) is an phase equilibria calculations. Meth- ponents. Simulators can provide these
almost ideal one, and does not deviate ods that are based on Raoult’s law or calculated properties in tabular and plot
much from Raoult’s law. that use activity coefficients are not format. This is a useful tool for under-
Mixtures of nonpolar and polar accurate at high pressure or when the standing how pure-component and mix-
compounds, such as water and hydro- temperature is above the critical tem- ture properties, such as density, heat ca-
carbons, often will form two liquid perature of a component. You can use pacity, and excess properties, vary with
phases that are very immiscible. Fig- Henry’s law when you have light temperature, pressure, and composition,
ures 8 and 9 show examples of misci- gases in subcritical solvents, but it and how they behave when extrapolat-
ble and immiscible systems of liq- generally is not recommended for ed. Similarly, such results can be used to
uid/liquid equilibria, respectively, at 1 concentrations of solute greater than generate plots of VLE and LLE to com-
atm. In Figure 8, cyclohexanol is im- 5%. In general, equations of state are pare to diagrams in the literature and ac-
miscible in the water phase but the better suited to predict VLE over a tual field data. Some simulators have
organic phase contains up to 0.50 wide temperature or pressure range, the capability to generate residue curves
mole fraction water (0.10 mass frac- especially at high temperature and for distillation of ternary mixtures. The
tion water). Figure 9 shows the high pressure. residue plot capability also is a powerful
degree of immiscibility in both the The availability of parameters. tool for distillation analysis.
organic and water phases for a mix- Without sufficient pure-component Use the tabulation and plotting
ture of benzene and water where and binary parameters, you will be tools to determine the cause of dis-
there is less than 0.06% by mole ben- unable to calculate pure-component or crepancies in properties. If a mixture
zene (0.3% by mass). Because of this mixture properties. You must choose property is incorrect, investigate if a
behavior, some simulators have a spe- among obtaining and using experi- single component is the cause by re-
cial property method to treat the mental or literature data, estimating porting pure-component properties.
water phase as organic-free (also parameters, or choosing a less rigor- Another useful technique is to com-
called Free-Water). ous method. This should be investigat- pare the same flowsheet or property-
Most simulators offer collections ed for all physical property methods in- table results while using different
of property methods in predefined cluding those shown in Figures 1–3. physical property methods.
Table 4. Examples and reliability of sources When fitting phase equilibria data, the
of pure component data. regression algorithm attempts to re-
duce the objective function while the
Source Evaluated Generally Reliable? physical property method is being used
to check that the components meet the
Critical Data of Pure Substances, DECHEMA* Critically Yes constraints of phase equilibria.
CRC Handbook of Chemistry and Physics (Beilstein)* Noncritically Yes The work of a successful regres-
DIPPR Data Compilation* Critically Yes sion involves selecting the right phys-
Encyclopedia of Chemicals, Drugs, and Biologicals Noncritically Yes ical property model and parameters,
Encyclopedia of Polymer Science and Engineering Noncritically Yes representing the data properly, choos-
ESDU Validated Engineering Data Index Noncritically Yes ing appropriate standard deviations of
Handbook of Thermophysical Properties of Gases Noncritically Yes the data, and starting with suitable
and Liquids initial estimates of the parameters.
JANAF Thermochemical Tables Critically Yes The following are general guidelines
Lange’s Handbook of Chemistry Noncritically Yes for data regression.
Perry’s Chemical Engineer’s Handbook Noncritically Yes • Make sure that you are regress-
Properties of Gases and Liquids Noncritically Yes ing the right parameters. Use the
Selected Values of Properties of Chemical Critically Yes same physical property method and
Compounds (TRC)* built-in databank that you will be
Vapor Pressure of Pure Substances Noncritically Yes using in the simulation. Choose pa-
rameters that have impact on the data
* Parts of these sources are available on-line from DIALOG Information Services, STN Interna- being used. For example, when using
tional, or Technical Databases Services, Inc. (TDS) an equation-of-state method such as
Peng-Robinson or Redlich-Kwong-
Soave, you should determine the
ters. First, divide the components Regressing data acentric factor, ω. But, if you are
into three groups: high, medium, and Data regression is a powerful tool using an activity coefficient method,
low priority. Base the priority on cri- for engineers not just to make the you should determine two or more
teria such as composition, and the best of available data, but also to ana- constants for the Antoine model.
purity specifications of the process lyze the goodness of fit of a physical • Estimate as few parameters as
— if a component purity is specified, property model to the data. Most sim- possible. There is a tendency to use a
that component is important even if it ulators include a data regression fea- large number of parameters when fit-
appears only in low concentrations. ture. Examples of commonly re- ting a model to data such as tempera-
Second, pair the components into gressed data include binary VLE and ture-dependent properties or binary
high/high, high/medium, high/low, LLE, vapor pressure, heat of vapor- phase equilibria. Try to regress the
medium/medium, medium/low, and ization, density, and heat capacity. data with as few parameters as possi-
low/low groups. Search the available Data regression finds the best fit of ble. If the regression results report
sources, including in-house ones, for parameter estimates to the experimen- that the standard deviation of the esti-
any data for all groups. If certain tal data. The best fit is represented by mated parameters is of the same order
component pairs are known to be- finding the lowest value of an objec- of magnitude as the values of the pa-
have ideally, they can be excluded tive function while matching the rameters, you may be estimating too
from the search. Next, use the UNI- phase equilibrium or other constraints. many parameters for your given data.
FAC method for the missing pairs in One common regression technique is The larger the temperature range of
the medium/medium, medium/low, called Maximum Likelihood Estima- your data, the more parameters that
and low/low categories. UNIFAC is tion. The objective function for this you can estimate.
not recommended, however, for any method is: • Watch out for incomplete data. A
pairs that include the components of Σj wj (Σi((Cim - Cie)/σi)2) (2) regression may yield poor results if
high priority. A secondary literature there are missing data points, particu-
search can be used to find binary data where j is a data group, Cim and Cie are larly composition data. For example,
for similar compounds and those pa- measured and estimated variables, re- some authors do not report all com-
rameters then substituted. Propose spectively, such as temperature, pres- positions in VLLE or immiscible
experimental work if any binary pa- sure, composition, or heat capacity, σi LLE. You may need to estimate the
rameter data are still missing or if is the standard deviation or the error in missing compositions so that phase
data regression exposes data as inad- the measurement of the variable, and equilibrium can be calculated for all
equate (3). wj is the weighting of the data group. components. Find out how your sim-
Table 7. Estimated properties for propyl phenyl ether (C9H12O). (189.9°C), density at 25°C (0.9474
g/cm3), and molecular structure:
Property Name Units Estimated Value Estimation Method OCH 2CH2CH3