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SECTION 25

Phase Equilibria
VAPOR-LIQUID EQUILIBRIA Availability of computers, coupled with the more refined K-
value correlations in modern process simulators, has made the
The equilibrium ratio (Ki) of a component i in a multicompo- previous GPA convergence pressure charts outdated. Complete
nent mixture of liquid and vapor phases is defined as the ratio sets of these charts are available from GPA as a Technical Pub-
of the mole fraction of that component in the vapor phase to lication, TP-22.
that in the liquid phase.
Data for N2-CH4 and N2-C2H6 show that the K-values in
yi these system have strong compositional dependence. The com-
­K
i=
xi Eq 25-1 ponent volatility sequence is N2-CH4-C2H6 and the K-values are
functions of the amount of methane in the liquid phase. For
For an ideal system (such as ideal gas and ideal solution), this example, at –123°C and 2070 kPa (abs), the K-values depend-
equilibrium ratio becomes the ratio of the vapor pressure of ing upon composition vary from:
component i to the total pressure of the system.
N2 CH4 C2H6
P*i
K
­ i= 10.2 0.824* 0.0118
P Eq 25-2
3.05 0.635  0.035*
This section presents an outline procedure to calculate the
liquid and vapor compositions of a two-phase mixture in equi- ­ here * indicates the limiting infinite dilution K-value. See ref-
w
librium using the concept of a pseudobinary system and the erence 5 for the data on this ternary.
convergence pressure equilibrium charts. Discussion of CO2 sep- ­ he charts retained in this edition represent roughly 12% of the
T
aration, alternate methods to obtain K values, and equations of charts included in previous editions. These charts are a compro-
state follow. mise set for gas processing as follows:
a. hydrocarbons — 3000 psia Pk [20 700 kPa (abs)]
­K-DATA CHARTS b. nitrogen — 2000 psia Pk [13 800 kPa (abs)]
These charts show the vapor-liquid equilibrium ratio, Ki, for c. hydrogen sulfide — 3000 psia Pk [20 700 kPa (abs)]
use in example and approximate flash calculations. The charts
do not give accurate answers, particularly in the case of nitro- The pressures in a. through c. above refer to convergence
gen. They are included only for illustrative purposes and to sup- pressure, Pk, of the charts from the Tenth Edition of this data
port example flash calculations and quick estimation of K-val- book. They should not be used for design work or related activi-
ues in other hand calculations. These charts should not be used ties. Again, they are in this edition for illustration and approxi-
in design calculations. mation purposes only; however, they can be very useful in such
a role. The critical locus chart used in the convergence pressure
Previous editions of this data book presented extensive sets method has also been retained (Fig. 25-8).
of K-data based upon the GPA Convergence Pressure, Pk, meth-
od. A component’s K-data is a strong function of temperature The GPA/GPSA sponsors investigations in hydrocarbon sys-
and pressure and a weaker function of composition. The conver- tems of interest to gas processors. Detailed results are given in
gence pressure method recognizes composition effects in pre- the annual proceedings and in various research reports and
dicting K-data. The convergence pressure technique can be technical publications, which are listed in Section 1.
used in hand calculations, and it is still available as computer
correlations for K-data prediction.

FIG. 25-1
Nomenclature

P* = vapor pressure, kPa (abs)


Ki = equilibrium ratio, yi R = universal gas constant, (kPa (abs) • m3) / (kmole • K)
xi T = temperature, K or °C
L = ratio of moles of liquid to moles of total mixture V = ratio of moles of vapor to moles of total mixture
N = mole fraction in the total mixture or feed xi = mole fraction of component i in the liquid phase
w = acentric factor yi = mole fraction of component i in the vapor phase
P = absolute pressure, kPa (abs) Subscripts
Pk = convergence pressure, kPa (abs), psia
i = component

25-1
­Example 25 -1  — Binary System Calculation Using the relationships
To illustrate the use of binary system K-value charts, as- ­ yi
i =
K
sume a mixture of 60 kmols of methane and 40 kmols of ethane xi Eq 25-3
at –87°C and 345 kPa (abs). From the chart on page 25-10, the ­L + V = 1.0 Eq 25-4
K-values for methane and ethane are 10 and 0.35 respectively.
By writing a material balance for each component in the
Solution Steps liquid, vapor, and total mixture, one may derive the flash equa-
­From the definition of K-value, Eq 25 -1: tion in various forms. A common one is,

yC1 Ni
­KC1 = = 10 xi = ∑
∑ = 1.0 Eq 25-5
xC1 L + VKi

yC2 Other useful versions may be written as


­ C2 =
K = 0.35
xC2 Ni
L = ∑ Eq 25-6
­Rewriting for this binary mixture: 1 + (V/L) Ki

1 – yC1 Ki Ni
yi =

= 0.35 L + VKi Eq 25-7
1 – xC1
­Solving the above equations simultaneously: ­At the phase boundary conditions of bubble point (L = 1.00) and
dew point (V = 1.00), these equations reduce to
xC1 = 0.0674
∑ Ki Ni = 1.0 (bubble point) Eq 25-8
yC1 = 0.674
and
­Also by solving in the same way:
∑ Ni/Ki =1.0 (dew point) Eq 25-9
xC2 = 0.9326
These are often helpful for preliminary calculations where
yC2 = 0.326 the phase condition of a system at a given pressure and tem-
To find the amount of vapor in the mixture, let v denote perature is in doubt. If ∑K­iN­i and ∑N­i/K­i are both greater than
kmols of vapor. Summing the kmols of methane in each phase 1.0, the system is in the two phase region. If ∑K­iN­i is less than
gives: 1.0, the system is all liquid. If ∑N­i/K­i is less than 1.0, the system
is all vapor.
­ kmols C1 + C2 = 100 kmols

Example 25-2 — A typical high pressure separator gas is used
kmols C1 + kmols C1 for feed to a natural gas liquefaction plant, and a preliminary
= 60 kmols step in the process involves cooling to –30°C at 4140 kPa (abs)
in vapor in liquid
to liquefy heavier hydrocarbons prior to cooling to lower tem-
(yC1 × v) + (xC1 [100 – v]) = 60 kmols peratures where these components would freeze out as solids.
(0.674 × v) + (0.0674 [100 – v]) = 60 kmols Solution Steps
v = 87.8 kmols The feed gas composition is shown in Fig. 25-3. The flash
The mixture consists of 87.8 kmols of vapor and 12.2 kmols equation 25 -5 is solved for three estimated values of L as shown
of liquid. in columns 3, 4, and 5. By plotting estimated L versus calcu-
lated ∑x­i, the correct value of L where ∑x­i = 1.00 is L = 0.030,
whose solution is shown in columns 6 and 7. The gas composi-
­FLASH CALCULATION PROBLEM tion is then calculated using y­i = K­ix­i in column 8. This “correct”
The problem below illustrates the calculation of multicom- value is used for purposes of illustration. It is not a completely
ponent vapor-liquid equilibrium using the flash equations and converged solution, for x­i = 1.00049 and y­i = 0.99998, columns 7
the K-charts in detail. The variables are defined in Fig. 25-1. and 8 of Fig. 25-3. This error may be too large for some applica-
Note that the K-value is implied to be at thermodynamic equi- tions.
librium. ­Example 25-3 — Dew Point Calculation
A situation of reproducible steady state conditions in a piece A gas stream at 40°C and 5500 kPa (abs) is being cooled in a
of equipment does not necessarily imply that classical thermo- heat exchanger. Find the temperature at which the gas starts to
dynamic equilibrium exists. If the steady composition differs condense.
from that for equilibrium, the reason can be the result of time-
limited mass transfer and diffusion rates. This warning is made Solution Steps
because it is not at all unusual for flow rates through equip-
ment to be so high that equilibrium is not attained or even close- The approach to find the dew point of the gas stream is sim-
ly approached. In such cases, equilibrium flash calculations as ilar to the previous example. The equation for dew point condi-
described here fail to predict conditions in the system accurate- tion (∑N­i/K­i = 1.0) is solved for two estimated dew point tem-
ly, and the K-values are suspected for this failure—when in fact peratures as shown in Fig. 25-4. By interpolation, the
they are not at fault. temperature at which ∑N­i/K­i = 1.0 is estimated at –41.4°C.
Note that the heaviest component is quite important in dew
point calculations. For more complex mixtures, the character-

25-2
FIG. 25-2
Sources of K-Value Charts

Charts available from sources as indicated


Convergence pressures, kPa (abs) [psia]
Component
Binary
5500 6900 10 300 13 800 20 700 34 500 69 000
Data
[800] [1000] [1500] [2000] [3000] [5000] [10,000]
Nitrogen * □ □ □
Methane *      
Ethylene □ □ □
Ethane *      × ×
Propylene □ □ □
Propane *      ××
iso-Butane □ □ × × × × ×
n-Butane *† □ □ × × × × ×
iso-Pentane □ □ × × × × ×
n-Pentane *† □ □ × × × × ×
Hexane *† □ □ × × × × ×
Heptane *† × × × × ×
Octane □ □ × × × × ×
Nonane x × × × × ×
Decane □ □ × × × × ×
Hydrogen sulfide × ×
Carbon dioxide
** Use KCO2 = √ KC1 • KC2
* Binary data from Price & Kobayashi; Wichterle & Kobayashi; Stryjek, Chappelear, & Kobayashi; and Chen & Kobayashi
 Drawn for 1972 Edition based on available data Note: The charts shown in bold outline are published in
□ Reused from 1966 Edition this edition of the data book. The charts shown in the
× Reused from 1957 Edition shaded area are published in a separate GPA Technical
Publication (TP-22) as well as the 10th Edition.
† Prepared for Second Revisions 1972 Edition or revised
** Limited to CO2 concentration of 10 mole percent of feed or less

ization of the heavy fraction as a pseudocomponent such as hex- ­Separation of CO­2 and Methane
ane or octane will have a significant effect on dew point calcula-
tions. The relative volatility of CO­2 and methane at typical operat-
ing pressures is quite high, usually about 5 to 1. From this stand-
­Carbon Dioxide point, this separation should be quite easy. However, at process-
ing conditions, the CO­2 will form a solid phase if the distillation
Early data on CO­2 systems used to prepare K-data (P­k = ) is carried to the point of producing high purity methane.
charts for the 1966 Edition were not consistent. Later, experi-
ence showed that at low concentrations of CO­2, the rule of Fig. 25-5 depicts the phase diagram for the methane-CO­2
thumb binary system.21 The pure component lines for methane and
CO­2 vapor-liquid equilibrium form the left and right boundaries

­KCO2 = √ KC1 • KC2 Eq 25-10 of the phase envelope. Each curve terminates at its critical
point; methane at –83°C, 4604 kPa (abs) and CO­2 at 31°C, 7382
­could be used with a plus or minus 10% accuracy. Developments kPa (abs). The unshaded area is the vapor-liquid region. The
in the use of CO­2 for reservoir drive have led to extensive inves- shaded area represents the vapor-CO­2 solid region which ex-
tigations in CO­2 processing. See the GPA research reports (list- tends to a pressure of 4860 kPa (abs).
ed in Section 1) and the Proceedings of GPA conventions. The
reverse volatility at high concentration of propane and/or bu- Because the solid region extends to a pressure above the
tane has been used effectively in extractive distillation to effect methane critical pressure, it is not possible to fractionate pure
CO­2 separation from methane and ethane.­23 In general, CO­2 methane from a CO­2-methane system without entering the solid
lies between methane and ethane in relative volatility. formation region. It is possible to perform a limited separation

25-3
FIG. 25-3
Flash Calculation at 4140 kPa and –30°C

Column
1 2 3 4 5 6 7 8

Feed Gas 30°C Trial values of L Final L = 0.030


Component Composition 4140 kPa L = 0.020 L = 0.060 L = 0.040L Liquid Vapor
Ni Ni Ni L + Vki
xi = Ni
Ni Ki yi
L + V Ki L + V Ki L + V Ki L + V Ki
C1   0.9010 3.7 0.24712 0.25466 0.25084 3.61900 0.24896 0.92117
CO2**   0.0106 1.23 0.00865 0.00872 0.00868 1.22310 0.00867 0.01066
C2   0.0499 0.41 0.11830 0.11203 0.11508 0.42770 0.11667 0.04783
C3   0.0187 0.082 0.18633 0.13642 0.15751 0.10954 0.17071 0.01400
iC4   0.0065 0.034 0.12191 0.07068 0.08948 0.06298 0.10321 0.00351
nC4   0.0045 0.023 0.10578 0.05513 0.07249 0.05231 0.08603 0.00198
iC5   0.0017 0.0085 0.06001 0.02500 0.03530 0.03825 0.04445 0.00038
nC5   0.0019 0.0058 0.07398 0.02903 0.04170 0.03563 0.05333 0.00031
C6   0.0029 0.0014 0.13569 0.04730 0.07014 0.03136 0.09248 0.00013
C7+*   0.0023 0.00028 0.11334 0.03817 0.05712 0.03027 0.07598 0.00002
TOTALS   1.0000 1.17121 0.77714 0.89834 1.00049 0.99998
C7 0.00042
C8 0.00014
* Average of nC7 + nC8 properties

** √ KC1 • KC2

FIG. 25-4
Dew Point Calculation at 5500 kPa (abs)

Column
1 2 3 4 5
Feed Estimated T = –45°C Estimated T = –40°C
Ni Ni
Ni Ki Ki
Component Ki Ki
CH4 0.854 2.73 0.313 2.75 0.311
CO2 0.051   0.866 0.059   0.910 0.056
C2H6 0.063   0.275 0.229   0.300 0.210
C3H8 0.032   0.070 0.457   0.080 0.400
∑ 1.000 1.058 0.977

KCO2 calculated as √ KC1 • KC2

1.000 – 0.977 = –41.4°C


 1.058 – 0.977 
Linear interpolation: Tdew = –40 [–40 – (–45)]

Alternative iterate until ∑Ni/Ki = 1.0

of CO­2 and methane if the desired methane can contain signifi- One approach to solve the methane-CO­2 distillation problem
cant quantities of CO­2. is to use extractive distillation (See Section 16, Hydrocarbon
Recovery). The concept is to add a heavier hydrocarbon stream
At an operating pressure above 4860 kPa (abs), the methane to the condenser in a fractionation column. About 10 GPA re-
purity is limited by the CO­2-methane critical locus (Fig. 25-6). search reports present data on various CO­2 systems that are
For example, operating at 4930 kPa (abs), it is theoretically pertinent to the design of such a process.
possible to avoid solid CO­2 formation (Fig. 25-7 and 16-36). The
limit on methane purity is fixed by the approach to the mixture
critical. In this case, the critical binary contains 6% CO­2. A ­CO­2-Ethane Separation
practical operating limit might be 10-15% CO­2.
The separation of CO­2 and ethane by distillation is limited

25-4
FIG. 25-5 by the azeotrope formation between these components. An azeo-
21 tropic composition of approximately 67% CO­2, 33% ethane is
Phase Diagram CH4 -Ch2 Binary formed at virtually any pressure.24
Fig. 25-7 shows the CO­2-ethane system at two different
pressures. The binary is a minimum boiling azeotrope at both
pressures with a composition of about two-thirds CO­2 and one-
third ethane. Thus, an attempt to separate CO­2 and ethane to
nearly pure components by distillation cannot be achieved by
traditional methods, and extractive distillation is required.26
(See Section 16, Hydrocarbon Recovery)

­Separation of CO­2 and H­2S


The distillative separation of CO­2 and H­2S can be performed
with traditional methods. The relative volatility of CO­2 to H­2S
is quite small. While an azeotrope between H­2S and CO­2 does
not exist, vapor-liquid equilibrium behavior for this binary ap-
proaches azeotropic character at high CO­2 concentrations25(See
Section 16, Hydrocarbon Recovery).

FIG. 25-6
Isothermal Dew Point and Frost Point Data for Methane-Carbon Dioxide32

25-5
FIG. 25-7 ria for ideal or slightly non-ideal systems; they are not
suitable for representation of highly non-ideal systems
(e.g., methanol/water systems).
21
Vapor-Liquid Equilibria CO2-C2H6

They typically are applied only to hydrocarbon mix-


tures with relatively low concentrations of non-polar or
slightly polar fluids.
Recent advancements have made cubic EOS suit-
able for handling high concentrations of CO2, H2S, and
N2.
● Applicable for prediction of phase equilibria for pure com-
ponents (VLE) and mixtures (VLE and VLLE) and for
prediction of all thermodynamic properties for vapor and
liquid phases.
Originally developed for handling of pure compo-
nents, but inclusion and use of various mixing rules,
which incorporate binary interaction parameters, have
allowed the extension of use to binary and multicompo-
nent mixtures.
Useful over wide ranges of temperature and pres-
sure, including subcritical, supercritical, and retro-
grade regions.
● Require minimal pure component data. Experimental bi-
nary data can be used to “tune” binary interaction pa-
rameters, usually by regression of experimental data.
PHASE EQUILIBRIA METHODS ● Major EOS types include cubic, virial, corresponding
Numerous procedures have been devised to predict phase states, and multi-parameter. Descriptions of the more
equilibria (K-values) and the corresponding physical properties commonly used cubic and virial types are included below:
of the associated phases. These include:
Cubic EOS (e.g., van der Waal, Redlich-Kwong,
• Equations of state (EOS) Soave-Redlich-Kwong, Peng Robinson)
• Activity coefficient models Explicit in pressure (P) with respect to tempera-
ture (T) and volume (V). They have separate terms
• Electrolytic models to correct ideal gas predictions for attraction and
• Combinations of equations of state with liquid theory or repulsion forces between the molecules (correcting
with tabular data the real vapor pressure and volume predictions, re-
spectively). When considering the pressure and
• Corresponding states correlations. temperature fixed, the EOS can be algebraically re-
arranged to give a relationship for V that is a cubic
A number of methods can be used for the purpose of phase
(3rd order) polynomial.
equilibria and thermodynamic property prediction. In modern
times, calculations are not typically executed by hand, but in- These EOS will include other parameters, spe-
stead are solved by the use of thermodynamic simulation soft- cific to each chemical species that are generally de-
ware (commercial or proprietary). This section describes several termined from the critical properties, Pc and Tc, for
of the more popular procedures currently available. It does not the chemical species. Additional temperature-de-
purport to be all-inclusive or comparative. pendent functions can be added to more accurately
match pure component behavior (i.e., a tempera-
Equations of State (EOS) ture dependent function correlated to the accentric
Equations of state have appeal for predicting thermodynam- factor (ω) is normally used to better match a pure
ic properties because they provide internally consistent values component’s vapor pressure versus temperature be-
for all properties in convenient analytical form. The section be- havior).
low discusses the basic capabilities of EOS, historical develop- Multicomponent mixtures are treated with the
ment, and recent advances. same EOS parameters that are determined for the
EOS Capabilities — The following summarizes the basic pure components present in the mixture. The equa-
capabilities and describes the applicability for some of the more tions used to blend the pure component values are
commonly used EOS methods. referred to as “mixing rules”, which often include
“binary interaction parameters” to account for non-
● Although originally developed to describe simple gases, ideal interactions between pairs of unlike mole-
EOS have proven reliable for property prediction of most cules.
hydrocarbon-based fluids.
The EOSs are generally not “tuned” to pure
The simple cubic EOS are generally limited to pre- component liquid density data, so they give poor
diction of thermodynamic properties and phase equilib- representations of liquid molar volume/liquid den-

25-6
sity (There are techniques to improve this, such as Examples include NBS Steam Tables, Span
introducing a volume translation term; see ‘Recent and Wagner EOS (CO2), Wagner and Pruss
EOS Advancement’ section below). EOS (Water), and heat transfer fluid models.
Not generally accurate for polar compounds or Historical Development of EOS for Phase Equilibria
long chain hydrocarbons (There are techniques to — Two popular state equations for K-value predictions are the
improve this, such as introduction of a higher order Benedict-Webb-Rubin (BWR) equation and the Redlich-Kwong
temperature dependency on the attraction param- equation.
eter or asymmetric mixing rules; see ‘Recent EOS
Advancement’ section below). The original BWR equation17 uses eight parameters for each
component in a mixture plus a tabular temperature dependence
Virial EOS (e.g., BWR, BWRS, Lee-Kessler-Plocker) for one of the parameters to improve the fit of vapor-pressure
data. This original equation is reasonably accurate for light
Explicit in pressure (P) with respect to tempera- paraffin mixtures at reduced temperatures of 0.6 and above.8
ture (T) and volume (V). Expanded in terms of vol- The equation has difficulty with low temperatures, non-hydro-
ume raised to powers much higher than 3rd order. carbons, non-paraffins, and heavy paraffins.
Because of the larger number of parameters Improvements to the BWR include additional terms for tem-
that can be tuned to pure component data, these perature dependence, parameters for additional compounds,
EOS can be more accurate than cubic EOS when and generalized forms of the parameters.
calculating liquid densities.
Starling20 has included explicit parameter temperature de-
For pure components, these EOS can give a pendence in a modified BWR equation that is capable of pre-
more accurate representation than cubic EOS for dicting light paraffin K-values at cryogenic temperatures.
all thermodynamic data. However, the determina-
tion of these parameters is more complex, requires The Redlich-Kwong equation has the advantage of a simple
more experimental data, and may require a compli- analytical form which permits direct solution for density at spec-
cated procedure for fitting that experimental data. ified pressure and temperature. The equation uses two parame-
ters for each mixture component, which in principle permits pa-
When applied to multicomponent mixtures, the rameter values to be determined from critical properties.
large number of pure component parameters must
be blended, perhaps each with their own mixing However, as with the BWR equation, the Redlich-Kwong
rules. Inaccuracies associated with the application equation has been made useful for K-value predictions by em-
of these mixing rules may make the mixture prop- pirical variation of the parameters with temperature and with
erties no more accurate than what one would get acentric factor11, 18, 19 and by modification of the parameter-com-
from a simpler cubic EOS. bination rules.15, 19 Considering the simplicity of the Redlich-
Kwong equation form, the various modified versions predict K-
Not usually applicable for polar systems. values remarkably well.
Computerized corresponding states methods Interaction parameters for non-hydrocarbons with hydro-
may be based on virial EOS for reference fluids. carbon components are necessary in the Redlich-Kwong equa-
The corresponding states methods then provide the tion to predict the K-values accurately when high concentra-
framework to blend the properties of the reference tions of non-hydrocarbon components are present. They are
fluids to give values for a multicomponent mixture. especially important in CO2 fractionation processes, and in con-
Other applicable EOS types ventional fractionation plants to predict sulfur compound dis-
tribution.
EOS for Associating Systems
The Chao-Seader correlation7 uses the Redlich-Kwong equa-
EOS that include terms for the physical tion for the vapor phase, the regular solution model for liquid-mix-
forces (attraction/repulsion) and an associating ture non-ideality, and a pure-liquid property correlation for effects
term that takes into account hydrogen bond- of component identity, pressure, and temperature in the liquid
ing; see Kontogeorgis and Folas34 for reviews of phase. The correlation has been applied to a broad spectrum of
associating EOS. compositions at temperatures from –50°F to 300°F and pressures
The SAFT (Statistical Associate Fluid The- to 2000 psia. The original (P,T) limitations have been reviewed.12
ory) family of EOS are based on Wertheims Prausnitz and Chueh have developed16 a procedure for high-
perturbation theory and can be applied to a pressure systems employing a modified Redlich-Kwong equa-
wide range of fluids including long chain com- tion for the vapor phase and for liquid-phase compressibility
ponents and hydrogen bonding (e.g., hydrocar- together with a modified Wohl-equation model for liquid phase
bon-alcohol-water systems). activity coefficients. Complete computer program listings are
CPA (Cubic-Plus-Association) EOS com- given in their book. Parameters are given for most natural gas
bines a cubic equation of state (e.g., SRK) for components. Adler et al. also use the Redlich-Kwong equation
describing physical interactions with an asso- for the vapor and the Wohl equation form for the liquid phase.6
ciation term similar to SAFT. The corresponding states principle10 is used in all the proce-
Highly Accurate Pure Component EOS dures discussed above. The principle assumes that the behavior
of all substances follows the same equation forms and equation
Typically apply only to utility systems parameters are correlated versus reduced properties and acen-
within a facility, not to the main processing tric factor. An alternate corresponding states approach is to re-
and separation trains. fer the behavior of all substances to the properties of a reference

25-7
substance, these properties being given by tabular data or a available experimental data; however, more experi-
highly accurate state equation developed specifically for the ref- mental data is required to allow for a proper fit of the
erence substance. The deviations of other substances from the mixing equation.
simple critical-parameter-ratio correspondence to the reference
substance are then correlated. Mixture rules and combination Application of more complex mixing rules can make
rules, as usual, extend the procedure to mixture calculations. EOS methods adequate for polar/non-ideal systems.
Leland and co-workers have developed9 this approach exten- Specifically, Activity Coefficient methods have
sively for hydrocarbon mixtures. been used directly in some mixing rules to more ac-
“Shape factors” are used to account for departure from simple curately predict binary interactions of mixtures
corresponding states relationships, with the usual reference sub- with polar and non-polar components at high pres-
stance being methane. The shape factors are developed from PVT sure, despite the Activity Coefficient method only
and fugacity data for pure components. The procedure has been being fit to available low pressure experimental
tested over a reduced temperature range of 0.4 to 3.3 and for pres- data (i.e., Wong-Sandler).
sures to 4000 psia. Sixty-two components have been correlated ● Enhanced binary interaction parameters
including olefinic, naphthenic, and aromatic hydrocarbons.
Group contribution methods have been developed to
The Soave Redlich-Kwong (SRK)13 is a modified version of estimate binary interactions (e.g. Predictive SRK) and
the Redlich-Kwong equation. One of the parameters in the orig- greatly improve predictions especially for mixtures
inal Redlich-Kwong equation, a, is modified to a more tempera- with polar and non-polar components.
ture dependent term. It is expressed as a function of the acen-
tric factor. The SRK correlation has improved accuracy in Interaction parameters are typically fitted to ex-
predicting the saturation conditions of both pure substances perimental data for each specific EOS and mixing rule
and mixtures. It can also predict phase behavior in the critical combination. In turn, more quality experimental data
region, although at times the calculations become unstable in the pressure, temperature, and compositional region
around the critical point. Less accuracy has been obtained when of a particular application of interest allows for en-
applying the correlation to hydrogen-containing mixtures. hanced binary interaction parameters and improved
EOS predictions. However, fitting interaction parame-
Peng and Robinson14 similarly developed a two-constant ters to different sets of data will result in inconsistent
equation of state in 1976. In this correlation, the attractive predictions from one tool to another.
pressure term of the semi-empirical van der Waals equation
has been modified. It predicts the vapor pressures of pure sub- Binary interaction parameters are often tempera-
stances and equilibrium ratios of mixtures. ture dependent, and may be fit by differing tempera-
ture dependency forms, for which proper choice can
In applying any of the above correlations, the original criti- impact EOS performance. The ability for a user to spec-
cal/physical properties used in the derivation should be inserted ify binary interaction parameters is included in many
into the appropriate equations. It is common for one to obtain of commercially available simulation products. A tool
slightly different solutions from different computer programs, that allows for non-constant specification (e.g., includes
even for the same correlation. This can be attributed to differ- temperature dependence) will result in improved re-
ent pure component and binary parameters, iteration tech- sults.
niques, convergence criteria, and initial estimation values,
among other items as described in the Recent EOS Advance- ● Additional equation terms
ments sub-section below. Determination and selection of a par- Addition of extended or advanced ‘alpha’ functions
ticular equation of state and interaction parameters must be (intermolecular attraction) to improve fitting of vapor
done carefully, considering the system components, the operat- pressure, which can improve the ability of the EOS to
ing conditions, etc. handle polar/non-ideal systems. Addition of volume
Recent EOS Advancements — While some of the funda- translation parameters allow for better prediction of
mental, basic equation of state forms are included at the end of liquid densities for the EOS.
this section, there have been many advancements in the predic- ● Liquid phase property handling
tion of phase equilibria and thermodynamic properties since
the last update of this section (pre-1990). As a result, and due to Modification of the handling of the term describing
the extensive use of commercial simulation tools, results which real volume of molecules/intermolecular repulsion al-
differ somewhat will likely be obtained for the same Equation of low for better prediction of liquid densities for the
State, depending on the software chosen, and even options se- EOS.
lected within the software. In addition to those items listed in
the “Historical development of EOS” section above, this is large- ● Solids handling (e.g., ice, hydrate, solid CO2, solid hydro-
ly due to the advancements made in application of EOS meth- carbon)
ods. The following is a brief summary of some basic reasons for While EOS are used to represent the fugacity of
these differences from one software package to another, along components in a fluid phase (vapor and liquid), they
with a general description of advanced applications of EOS can be combined with models representing the fugacity
methods. in the solid phase to model VSE and LSE. See the sec-
● Improved mixing rules
tion titled “Equations of State and the Solid Phase” be-
low for more detailed discussion.
A number of different mixing rules can be applied to
an EOS, some much more complex than others. In gen- There are a number of multi-parameter equations (i.e.,
eral, more complex mixing rules allow for the range of GERG35), that currently exist and are able to model systems to
applicability of an EOS extended further beyond the within experimental error. However, due to the complexity and
computing power required for these, they are not often used in

25-8
facility design simulations. One obvious use of an equation of R2 T2c
 Pc 
this nature is to generate pseudo-experimental data from which a = 0.45724 a

new binary interaction parameters can be regressed for a spe-
a ⁄2 = 1 + m (1 – Tr⁄2)
1 1
cific system (P, T, and composition), and in turn used in an EOS
to improve its reliability. m = 0.37464 + 1.54226 w – 0.26992 w2
R Tc
­BASIC EQUATION OF STATE FORMS
 Pc 
b = 0.0778

Refer to original papers for mixing rules for multicomponent
mixtures. ­Benedict-Webb-Rubin-Starling (BWRS)20, 29
­van der Waals30 R T Co Do Eo 1
 T T T  V
P = + Bo R T – Ao – 2 + 3 – 4 2
V
Z3 – (1 + B) Z2 + AZ – AB = 0
d 1 d 1
 T  V 
aP + bRT – a – 3 + a a + 6
A = 2 2 T  V
R T
bP c 1 γ ⁄v2
–γ

V  T   V 
B = + 3 2 1 + 2
RT
27 R2 T2c Note: w, the acentric factor is defined in Section 23.
a =
64 Pc
Other Phase Equilibria Methods
R Tc
b = Activity Coefficient Models — Another common method
8 Pc
used for the purpose of phase equilibria and thermodynamic
­Redlich-Kwong28 property prediction is the use of Activity Coefficient models.
The following is a brief summary of the basic capabilities and
Z3 – Z2 + ( A – B – B2) Z – AB = 0 describes the applicability for some of the more commonly used
aP Activity Coefficient methods.
A = 2 2.5
R T ● Activity coefficient models are the best method for repre-
bP sentation of highly non-ideal and/or polar systems (i.e.,
B = aqueous systems, amines, NH3, caustic, CO2, H2S) and
RT are therefore typically used in the chemicals industry.
R2 T2c.5
 Pc 
a = 0.42747 ● While these models are generally only applicable to pre-

diction of phase equilibria for binary and multicompo-
R Tc nent mixtures (VLE and LLE), they are not for phase
 Pc 
b = 0.0867
equilibria of pure components. However, they do require
high quality pure component property predictions (e.g.,
­Soave Redlich-Kwong (SRK)13 vapor pressure). Depending on the specific Activity Coef-
ficient method, it may not always allow for LLE predic-
Z3 – Z2 + (A – B – B2) Z – AB = 0
tion because tuning the models to VLE specific data or
aP LLE specific data may result in drastically different pa-
A = 2 2
R T rameters. For this reason, VLLE predictions must also be
used with caution.
bP
B = ● Applicable for prediction of thermodynamic properties
RT
for the liquid phase only. Vapor properties are unreliable
a = ac a
and must be calculated using another method; histori-
R2 T2c cally this has been done using ideal gas assumptions for
 Pc 
ac = 0.42747
the vapor phase, but commonly includes more advanced
EOS methods, as described in the ‘Mixed Models’ section
a ⁄2 = 1 + m ( 1 – Tr⁄2)
1 1
below.
m = 0.48 + 1.574 w – 0.176w2 ● Limited to systems within the pressure and temperature
R Tc ranges of the experimental data it is correlated against.
 Pc 
b = 0.08664

These models are only suitable for low to moderate
­­Peng Robinson31 pressure systems, typical in the chemicals industry, be-
cause activity coefficients depend on temperature, but
Z3 – (1 – B ) Z2 + (A – 3B2 – 2B ) Z – (AB – B2 – B3) = 0 are independent of pressure, while mutual solubilities
aP are in fact dependant on pressure in high pressure LLE
A = 2 2 systems.
R T
At typical operating pressures, the use of a vapor
bP
B = pressure is not appropriate for light gases above the
RT critical point and instead these light gases are treated
as Henry’s components, where Henry’s law coefficients
are derived from experimental gas solubility data.

25-9
Extrapolation outside the experimental data range Hydrogen bonding (i.e., methanol-water-hydrocar-
is not recommended. bon systems)
● Requires a separate model to determine liquid density. ● Natural Gas Dew Point Calculations
The Poynting correction is used to account for pressure
dependence of a components liquid phase activity. ● Other considerations that impact phase equilibria

Some examples of common Activity Coefficient models in- Reactive (i.e., amine gas treating, caustic treating)
clude: Chien Null, NRTL, Margules, UNIFAC, UNIQUAC, van Mass transfer limited (i.e., tertiary and hindered
Laar, and Wilson. amines)
Electrolytic Models — Electrolytic models are a sub-set of Absorption (i.e., CO2 and H2S adsorption in physical
Activity Coefficient models. The general purpose of Electrolytic or chemical solvents)
models is to handle systems where dissociation of components
is important. In general, these components do not directly par- Overall, it is important to understand the capabilities and
ticipate in VLE (i.e., ions or solids that do not dissolve or vapor- limitation of each method of representing phase equilibria and
ize), but they often influence activity coefficients of other spe- prediction of thermodynamic properties, and each method’s
cies by reaction or interaction and in turn, indirectly participate specific applicability to the gas processing industry for proper
in impacting the phase equilibria of the system. These models choice and use. However, it should be noted that tuning of a
generally require high quality experiment data for the specific method to quality experimental data in the region of operation
application they are being applied to (e.g., amine gas treating or interest is perhaps more important than the method choice
systems). itself, specifically, the choice of mixing rules and quality of bi-
nary interaction parameters, which can typically be readily
Mixed Models — Mixed models are commonly used in or- modified in commercial software.
der to combine the strengths of the various methods described
above. These models commonly use an EOS method for phase More specific information relative to phase equilibria meth-
equilibria and prediction of vapor phase thermodynamic prop- ods can be found in Goodwin et al36 and Kontogeorgis and Fo-
erties, but use an Activity Coefficient or Electrolyte method for las.34
determination of thermodynamic properties and/or density of Dew Point Calculation — A thermodynamic dew point is
the liquid phase(s). However, because of the use of multiple defined as that point where liquid first appears from the gas
methods, these models do not always produce consistent predic- phase. An EOS model actually calculates this point with ex-
tions, especially at or near the critical point. actly zero liquid dropout. In reality, for natural gas this point
cannot directly be measured from experimental methods, but
Practical Application of Phase can be estimated from PVT data taken very near the dew point
Equilibria Methods envelope by extrapolating liquid dropout data to 0.0 volume
General Considerations — While phase equilibria of typ- percent liquid.
ical hydrocarbon systems is modeled very well with currently In pipeline operations, one can consider a practical dew
available commercial computer simulation tools, there are point that represents a small volume of liquid condensation
many areas where careful attention to method selection is need- which does not impact pipeline performance, usually represent-
ed. Some systems, due to the thermodynamic complexity, are ing a trace of liquid on the pipe wall. This practical dew point is
difficult to model using the basic methods described above, even what is actually measured by the Bureau of Mines chilled mir-
with more and/or better quality experimental data. Some ex- ror device.
amples of these complex systems in the gas processing industry
are shown below. The equilibria and thermodynamic property In recent work for the GPA by Bullin, et. al., (RR-213), the
results obtained using a specific method for these systems practical dew point was defined as 0.00027 m3 liquid per 1000
should be carefully evaluated and compared to commercial ex- m3 gas. As a natural gas gets leaner, the difference between the
perience when used in a process design: EOS predicted dew point of 0.0 volume percent liquid and the
practical dew point of 0.00027 m3 liquid per 1000 m3 gas can
Complex Systems to Model — increase to a much as 5.6°C. The practical dew point can be
● Operating conditions that cause divergence from ideal
represented by the temperature in a Bureau of Mines chilled
fluid behavior mirror device where droplets begin to form. Thus, when EOS
models are used, both the thermodynamic dew point of 0.0 vol-
Self associating/dimerizing (i.e., aqueous solutions) ume percent liquid and the practical dew point of 0.00027 m3
liquid per 1000 m3 gas should be considered when adjusting the
Dissociating (i.e., amine gas treating, sour water) EOS parameters to match the experimental values, and also to
Sterically hindered dissociating compounds (i.e., better determine the conditions that impact plant/pipeline per-
certain amines) formance. For lean gases where there is more than a 2.2 to 5°C
difference in the two values, it may be necessary to only fit to
Near critical and supercritical fluids (i.e., supercrit- the practical dew point value to evaluate plant/pipeline perfor-
ical natural gas compression, supercritical H2S/CO2 mance.
compression, hydrocarbon systems near critical)
This also points to the fact that when fitting an EOS model
Combinations of non-polar and polar compounds to an experimentally obtained dew point value, it should not be
(i.e., hydrocarbon systems with sour or produced water, assumed that the reported dew point (experimental) represents
dehydration or dew point depression with glycols or the thermodynamic dew point of 0.0 volume percent liquid, un-
methanol) less of course it has been confirmed to be extrapolated from
multiple experimental points within the two phase envelope.

25-10
It cannot be overemphasized that If the EOS is fit to the The Deshmukh and Mather, Li and Mather, and Austgen
wrong “dew point” condition for some natural gas compositions methods all use activity coefficient models for the liquid phase,
(thermodynamic versus practical), it can significantly affect the and EOS models for the vapor phase. Model parameters must
amount of liquids that are predicted to condense in plant opera- be found for each by regressing the models to experimental
tions or in pipelines, affecting overall designs. Also for these data. The primary limitation is not the models themselves, but
gases with a significant difference in the “dew point” value, the the highly variable, and sometimes unknown quality of the ex-
volume percent liquid data will display an upward curvature as perimental data. Because the experimental data is often the
the thermodynamic dew point is neared. This may result in a limitation and not the model, this may allow any of the activity
requirement for a more expanded composition to be used in the coefficient models to be just as reliable as the others for a given
EOS model, perhaps even above C12+. application.
Amine Treating — Amine treating is one of the most com- Sour Water — Stripping H2S, CO2, and ammonia, from sour
mon unit operations in the gas processing industry. There are a water is performed in many sour natural gas treating plants.
variety of amine solution types (i.e. primary, secondary tertiary, Common applications include condensed water (H2S and CO2),
sterically hindered, mixtures, with additives), and solution sulfur plant tail gas quench tower blowdown (H2S ,CO2, and
strengths, all of which possess characteristics that cause diver- caustic or ammonia) and to a more limited extent, stripping of
gence from ideal fluid behavior (self associating/dimerizing, dis- sour produced water (brine, including NaCl and many other
sociating and potentially sterically hindered, and combinations salts, with H2S, and CO2). Much of the literature describes de-
of polar and non-polar compounds). In addition they are also sign and operation of refinery sour water strippers, which handle
complicated systems to model being reactive, sometimes mass (H2S CO2, ammonia, cyanides, phenols, and organic acids).
transfer limited, absorption/desorption systems. This combina- Guidelines specific to gas treating are more limited.
tion of system attributes presents challenges for predicting
equilibrium and thermodynamic properties accurately. All Sour water serves as a good example of the strong effect of pH
thermodynamic phase equilibrium models depend on experi- on ionic dissociation, and of the smaller, though sometimes sig-
mental thermodynamic equilibria data. Many times technology nificant, effect of dissolved salt concentrations on gas solubility.
suppliers, and or/simulation support companies, will use real A principal ionization equilibrium for H2S in aqueous solu-
plant data to verify a model in area of interest. Some of the most tion,
common models used to describe the phase equilibria of amine
systems are described below.37 Choice of the appropriate model → H+ + HS–
H2S ← Eq 25-11
should be considered carefully.
● Kent-Eisenburg (1976)38 Model – Based on defining chemi- is greatly affected by pH. The un-dissociated fraction of the to-
cal reaction equilibria in the liquid phase. Assumes all ac- tal H2S is close to 1 for a pH of less than 5, about 0.33 at a pH of
tivity and fugacity coefficients are unity (i.e., ideal solutions 7.0, and less than 0.01 at a pH of 9.043. Since the vapor pressure
and ideal gases) and forces a fit between experimental and of H2S is produced by its un-dissociated fraction, pH in a strip-
predicted values by treating two of the reaction equilibrium ping tower has a great effect on the stripping efficiency. As H2S
constants as variables (e.g., the amine dissociation reaction gas is stripped from solution, the dissociated ions re-combine to
and the carbamate formation reation). This approach is provide more un-dissociated H2S —which revives the partial
typically only applicable to systems with single acid gases pressure above the solution. It should be noted that the pH of
(CO2 or H2S, but not both) and unless a modified approach the solution changes as CO2, is stripped from the water. In some
is used, to primary and secondary amines. The model services, with H2S, CO2, NH3, and low salts, the pH must be
should not be extrapolated as it’s thermodynamic basis is controlled to (typically to 7-8) to insure that both components
weak and does not support extrapolation. can be stripped. Stripping is, of course, enhanced by higher
temperatures.
● Deshmukh and Mather (1981)39 Method – Based on De-
bye-Huckel theory and is thermodynamically rigorous. Salt concentration of tens of thousands of ppm, as is com-
Similar to the Kent-Eisenburg Model in use of chemical mon in produced waters, reduces the solubility of H2S and thus
reactions, but activity coefficients are estimated on the enhances stripping — but this is a smaller influence than tem-
basis of ion-ion, ion-molecule, and molecule-molecule in- perature, and much smaller than pH. The pH of produced water
teraction parameters. Uses either the Suave-Redlich- is typically above neutral to start, even with the dissolved salts,
Kwong or Peng-Robinson EOS for the vapor phase. An because of the natural buffers in the water. The pH is further
activity coefficient description of Henry’s law is used to elevated, as the CO2 is stripped from the brine, sometimes re-
describe the physical solubility of acid gases in the amine sulting in fouling of the mass transfer medium within the strip-
solvents. Binary interaction parameters must be adjust- per. Therefore, acid is sometimes added in front of the stripper
ed in order to fit final VLE model to experimental data. to lower the pH and prevent fouling.

● Li and Mather (1994)40 Method – Based on Pitzer’s Gibbs A common method to calculate equilibrium of sour water
excess energy equations41 and accounts for the various ionic systems is the Wilson-API-Sour method, and variants, which
and molecular species in the liquid phase when acid gas is use a modification of Van Krevelen’s approach to account for
dissolved into a mixed amine solution. This is a more mod- the ionization of H2S, CO2 and NH3 in the aqueous water phase
ern rendition of an activity coefficient approach. (See API Publication 95544 and GPA RR-5245). This type of mod-
el is valid up to about 50 psig, with limited other ionic (salt)
● Austgen et al. (1991)42 Electrolytic NRTL based model – species present. To extend the range of the sour equilibrium
This is also an activity coefficient model in the vein of prediction, mixed models using a combination of the API-Sour
those discussed in the ‘Elecrolytic’ and ‘Mixed’ model sec- model, and an EOS (e.g., Peng Robinson) have been developed.
tions above. It is one of the most thermodynamically rig- Alternate approaches which account for the influence of other
orous models, but requires use of binary and ternary in- ionic salts present in the solution are electrolytic and mixed
teraction parameters in regressing the model to electrolytic/EOS models.
experimental data.

25-11
A discussion on design of sour water stripper systems is pre-
sented in Section 19. Stevens and Mosher46 provide a broad re-
view of variations and options, and potential problems areas in
design and operation of sour water systems. Bechok47 is an old 500
but traditional reference for sour water equilibria and stripper 450
design. 400

P re s s u re , kP a (a b s )
350
EQUATIONS OF STATE 300

AND THE SOLID PHASE 250


200
As will be discussed in some detail later, equations of state 150
are limited in their ability to predict equilibria involving solid
100
phases. That makes it desirable to have a way of checking such
50
predictions made in simulations. Good experimental data, if
available, is the best check. Some ways of checking and/or cor- 0
-10 0 -90 -80 -70 -60 -50
recting simulated results are discussed below, after an intro-
duction to the general topic of solid phases. Te m p e ra tu re ,°C
Triple P oint locus line 44% H 2S , 56% CO 2 Tem p erature C orrectio n
The “Phase Rule”, developed by Gibbs back in the 1870s,
still serves as a trusty background to multi-phase equilibria.
For non-reactive compounds, the equation is:
In the above diagram, the continuous line marked with tri-
F = C + 2 – P Eq 25-12 angles is the triple point line for solids deposition in the pres-
where C is the number of components or species in the mixture, ence of both liquid and vapor phases from Sobocinski and Ku-
P is the number of phases present, and F is the number of de- rata25 with the data for the line given in the reference document.
grees of freedom of the system. In situations where solids may For the range of pressures and temperatures shown here, the
be of concern in gas processing, there are usually both liquid solid phase is CO2 “ice”. At much lower pressures and tempera-
and vapor phases also present. Three numerical examples for tures (< 28 kPa (abs) and < –96°C) it is possible for solid H2S to
the Phase Rule are shown in the table below, followed by dis- precipitate; that region, being of less industrial importance, will
cussion of their consequences when all three phases co-exist. not be discussed here. Sobocinski and Kurata25 cover this scien-
tifically interesting region (including a eutectic at 87.5 mol %
“C”, Number of “P”, number
Degrees H2S) in detail.
of Consequence
Components of Phases
Freedom The other two lines coming in from top right are lines for
isenthalpic blowdowns. The dotted line marked with X’s is the
1, single component 3, V, L, and S 0 Unique “Triple Point” result of a simulation without the benefit of any program exten-
2, two components 3, V, L, and S 1 Triple point locus line sion to allow solids prediction (see later discussion of such ex-
No locus line; much tensions). This simulation predicted the blowdown would inter-
3, three components 3, V, L, and S 2
more complex equilibria cept the triple point locus but then go straight through (since
the simulator had no knowledge of the locus) into a region to the
left, which is thermodynamically impossible. Thus, the simula-
tor predicted (a) no solids and (b) falsely low temperatures.
Single-Component Triple Points Knowledge of the triple point locus allows a simple manual cor-
The first example, for a single component, is best known. A rection to the simulated path, by forcing the blowdown to follow
unique triple point can be found, for example, on the P-H chart the triple point locus – as it must, so long as the three phases
for CO2 in this Section. This unique point on such a chart is co-exist.
useful to better understand the presence of various mixtures of
The dashed line marked with circles shows a second, and
phases in that area of the chart. However, the numerical values
smaller, correction that is discussed by Walter et al48 and mer-
of the triple point pressure and temperature are not very rele-
its only brief mention here; very accurate vapor-liquid equilib-
vant to process operations. It is highly unlikely that any ther-
rium data allowed a manual correction of the simulator’s isen-
modynamic path for a fluid (say, in blowdown) would pass
thalpic predictions, by adjustment of the vapor/liquid
through the triple point (see two such lines on the examples of
percentages along the path ahead of the interception of the tri-
uses for P-H charts, also in this Section). Thus, quantifying a
ple point locus line.
unique triple point is rarely of help in checking a simulated
prediction. As pressure reduction and cooling takes place along the lo-
cus line, precipitation of solid CO2 progressively enriches the
Two-Component Triple Point Locus Lines L/V two-phase mixture with H2S. It is not intuitively obvious
In contrast, in a few industrially important cases, knowl- that a single triple point locus line correctly shows all such P/T
edge of the triple point locus line for a two-component system pairs on the graph, regardless of the starting mixture composi-
can provide a very useful check on simulator predictions. The tion, but that is the case. For clarification of this point, refer to
example below is from a recently published study by Walter et Sobocinski and Kurata25.
al48 that checked, and made corrections to, simulations of blow- This method of using the triple point locus line to check on a
down of a high pressure acid gas line containing (essentially) process simulation could be applied to a few other industrially-
only CO2 and H2S. important two-component systems, e.g., methane/CO2, and
methane/benzene. However, any significant presence of a third
component negates the use of this tool, as discussed next.

25-12
Multi-Component (3 or More) Triple Points 4. G
 rayson, H. G., and Streed, C. W., “Vapor-Liquid Equilibria for
High Temperature, High Pressure Hydrogen-Hydrocarbon Sys-
Once a third component is added in significant quantity, the tems,” Proc. 6th World Petroleum Cong., Frankfort Main, III,
number of degrees of freedom increases to 2 or more. That Paper 20-DP7, p. 223 (1963).
means there are no locus lines that can be drawn on a P-T 5. C
 happelear, Patsy, GPA Technical Publication TP-4, “Low Tem-
graph, but rather a multi-dimensional mass of data that does perature Data from Rice University for Vapor-Liquid and P-V-T
not lend itself to simple analysis. Addition of a few percent of Behavior,” April (1974).
H2S or ethane, to a methane/CO2 mixture, makes for such com-
plexity in many real separation cases. 6. A
 dler, S. B., Ozkardesh, H., Schreiner, W. C., Hydrocarbon Proc.,
47 (4) 145 (1968).
Simulation Tools for Predicting Solids 7. Chao, K. C., Seader, J. D., AIChEJ, 7, 598 (1961).
Many commercially available process simulators have spe- 8. B
 arner, H. E., Schreiner, W. C., Hydrocarbon Proc., 45 (6) 161
cial program extensions that will in some cases give precise pre- (1966).
diction of solids formation, or at least a warning that solids-for-
9. L
 each, J. W., Chappelear, P. S., and Leland, T. W., “Use of Mo-
mation threatens in the proposed working region. However, lecular Shape Factors in Vapor-Liquid Equilibrium Calculations
most predictions are limited to the existence of clathrate hy- with the Corresponding States Principle,” AIChEJ. 14, 568-576
drates. A commercially available extension has recently been (1968).
developed, and incorporated into at least one simulator, to pro-
vide a warning of potential CO2 solids formation. At the time of 10. L
 eland, T. W., Jr., and Chappelear, P. S., “The Corresponding
States Principle — A Review of Current Theory and Practice,”
writing, one simulator includes solid CO2 ice formation quanti-
Ind. Eng. Chem. 60, 15-43 (July 1968); K. C. Chao (Chairman),
tatively within its normal simulation calculations. Work is on- “Applied Thermodynamics,” ACS Publications, Washington, D.
going to cover solid species other than CO2, but has not yet been C., 1968, p. 83.
published or commercialized.
11. B
 arner, H. E., Pigford, R. L., Schreiner, W. C., Proc. Am. Pet.
Like most equations of state, the Peng-Robinson EOS in its Inst. (Div. Ref.) 46 244 (1966).
basic form is intended solely for vapor-liquid-equilibrium calcu-
12. Lenoir, J. M., Koppany, C. R., Hydrocarbon Proc. 46, 249 (1967).
lations, and is not capable of modeling solids. Program exten-
sions are available for the simulators which, based on the condi- 13. S
 oave, Giorgio, “Equilibrium constants from a modified Redlich-
tions predicted by the simulator EOS, can be used to inform the Kwong equation of state,” Chem. Eng. Sci. 27, 1197-1203 (1972).
engineer whether they are within solids forming conditions.
14. P
 eng, D. Y., Robinson, D. B., Ind. Eng. Chem. Fundamentals 15
Such predictions are usually reported by indicating at what (1976).
temperature the current stream will form solids – if the tem-
perature is colder than the simulator temperature, the process 15. Spear, R. R., Robinson, R. L., Chao, K. C., IEC Fund., 8 (1) 2 (1969).
is outside solids forming conditions, and conversely if the tem- 16. P
 rausnitz, J. M., Cheuh, P. L., Computer Calculations for High-
perature is warmer than the simulator temperature. The engi- Pressure Vapor-Liquid Equilibrium, Prentice-Hall (1968).
neer can then design to keep a safe margin away from solids
forming conditions. It is important to remember that these cal- 17. Benedict, Webb, and Rubin, Chem. Eng. Prog. 47, 419 (1951).
culations rely on the base thermodynamics of the EOS utilized 18. Wilson, G. M., Adv. Cryro. Eng., Vol. II, 392 (1966).
within the process simulator to give accurate temperatures and
compositions, in order for the calculation predictions to be ac- 19. Zudkevitch, D., Joffe, J., AIChE J., 16 (1) 112 (1970).
curate. 20. Starling, K. E., Powers, J. E., IEC Fund., 9 (4) 531 (1970).
Walter et al report that, when the solids-prediction capabil- 21. H
 olmes, A. S., Ryan, J. M., Price, B. C., and Stying, R. E., Pro-
ity of one simulator was utilized, it then accurately predicted ceedings of G.P.A., page 75 (1982).
the point of formation of the CO2 solids, and quantified them48.
22. H
 wang, S. C., Lin, H. M., Chappelear, P. S., and Kobayashi, R.,
But even without such simulator capacity, the triple point locus
“Dew Point Values for the Methane Carbon Dioxide System,”
line from Sobocinski and Kurata25 had already been used by G.P.A. Research Report RR-21 (1976).
hand to make the primary correction (as described by Walter et
al48). This could be done for other two-component systems by 23. P
 rice, B. C., “Looking at CO2 recovery,” Oil & Gas J., p. 48-53
the same method, if sufficient triple point data were available. (Dec. 24, 1984).
Systems with three or more components would require much 24. N
 agahana, K., Kobishi, H., Hoshino, D., and Hirata, M., “Binary
more complex analysis. Vapor-Liquid Equilibria of Carbon Dioxide-Light Hydrocarbons
at Low Temperature,” J. Chem. Eng. Japan 7, No. 5, p. 323 (1974).
­REFERENCES AND BIBLIOGRAPHY 25. S
 obocinski, D. P., Kurata, F., “Heterogeneous Phase Equilibria of
1. W
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FIG. 25-8
Critical Locus as Developed for Convergence Pressure
(Formerly used for Convergence Pressure for Hydrocarbons)

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