Rrv. Hc. Ing., Univ.

Zulla
Vol. 1, N 1, 1978, W 33-43
Impreso en Venezuela

D. Zudl\evitch
Allied Cheroica!.

Engineering Technology Center. P.O. Box 2283 R.

MorrislOwn, New Jersey 07960.

U.S.A .

Phase Equilibrium Data and

Methods Implication
of Present State on Heavy
Petroleum Fractions and
Coal Processing
Part. l~- Review of Sorne Methods for Predict ing Vapor

Liquid Equilibri um.

(Recib ido et H de A bril, 1978)

RESUJ\.lEI\

SUMlltfARY

ta necesidad de prodftcir combustibles liqllidos y

productos quim icos (l partir de fracciones y residuos
pesados y altL/mente aromticos del petrleo y de car
bn plantea la pregun ta de si los datos y c()rrelaciot~es
termodinmicos existentes son aplicables y qu nuevos
datos debell ser medidos.

TIJe need to prod,ce liquid f llel and eh etnical fuel

stoclJks fro,." heauy atlcJ bighly aromatk petroleum
f ractions, residues, and coal poses tIJe questions whe
ther fhe existing thermodynamic dataorre/atiotts are
applicable and what new data should he measured.

La et.aluadn de las correlaciones exIstentes en

clJanto a s u aplicabilidad a las condiciones de proce
samiento de fluMas del carh, y aceite pesado se
presenta el: una serie de cuatro artculos. Tales et1a
luacirmes SOtl cotlSideradas importantes en la planifi
cacin de la medici,)" de ,metlo. dato e itlte~tgac,n.

Evaluatio,s of e.:dsting correlations as to their ap

plicabi/ity tn the conditions o/ processing coal fluids atl
d heut'y oil are presentad in '1 serIes of four articles.
Such el'aluatio7Js are c01lsidered important in planning
the measurement of7JeW data and(Itrther research.

111 the first article of the series, the methods based

1m the c/asslcal approach, utilizing tlapor presstJre and

E" este primer (/rlicl~ln de la serie, los mtodo

basados en el e1Jfoque clsico de utilizar JJresi1l de
,'apor, )' coeficiente de Jtgacidad SOIl di5mt,dos.

fugacity coefficient, are discussed.

Las partes 11, III Y rv de este artculo aparecern

en los proximos numero~ tic la revista.

-')3

1. INTRODUCTION

These are the Gibbs concept of cheDlcal potential

equ al ity , the Lewis concept of fugacity (1-46) as applied

to Raoult' Law, and the Van de.r Waals equation of

Phase equilibrium data are vital in eparation and

rreatment of liquid fuels. Tbe experience of more than ,
100 years oi processing crude oil and gas should aid in

tate approach, emprical correlatioos that have been

developed during the past century either relied on one,
or attempted to combine virtues o more chan one (1-57.

working with heavier crude oils and coal-derived Ji

1-60, 1-36, 1-75 I-l1, 1-38, 1-71, 1-72,1-13,1-15,1-27, I

quids. However, review o features of rhe processes for

producing fluid (gas and liquid) products from coa1 such
as liquefaction, example given in Figure 1, and gasi
fication, example given in Figure 2, would suggest that
compositions and types o chemicals that are found in
heavy oils are Jifferent {rom those o the oils that have
beco processed heretofore.

n).
In a multi-phase system thermodyoamic equili
brium XlSts when all phases are al {he same tempe
cature and pre sure, possess the sl:ffie total free energy
and for each component (1-75).

Correlations that are based 00 data and understan

ding o the behavior of pure chemicals and mixtures

(1)

have been developed for utilizing petroleum inspection

data for designing separatioos. Thus, based on available
correlations, (laboratory) true boiling poiot distillation
(TBP) curves of the gasolioe cuts (curves 1 and 2) in
Figure

"

{\

where f i V ane' f i L are the fugacity of component i o

lhe mixwre in rhe vapor phase and the liquid phase,
respectively.

3 Wilh additional density data can be considered

as sufficient information

for predicting separation,

blending aO(l product specifications, etc. However, the
same correlations would yield erroneous results if ap
plicu ro tbe carbolk oi!, wruch is a liquid derivative
{rom coaJ coking.

IlI. THE CLASSICAL APPROACH

Expanding Equation 1 in eitbe.r phase, one can
develop the fugacity of i independently trom the
properties o the compound and system condirioDs.
Here, me Lewis and RandalJ appcoach (1-45) departs
from [he rigorous Gibbs and (he Van der Waals
(equalion of state) approaches, which sta tes that the
fugacity of the compound in either phase depends on
the concentrations and propenies of the orber com
pound.

'1 he uistillation curve foc the carbolc oil is shown

as Curve 3 in Figure 3. Its composition is roughly re
pe sented by the heart cut components comprising [he
creosote lil d cribed in Table L Review of Table 1 im
mediately suggests that the creosote and carbolic oils
that are typical coal liquid product ' are grossly diffe
rent from ther pure hydrocarbon petroleum equi
val~nt prouuct . Therefore, tbere is danger o serious
desigll errors if p >troleum engineering correlatons are
usco "ti, ithotl[ raking accouat of lhese majar differences.

In tbe pre ent paper, Raoult's and Henry's law and

the concept o activity coefficients for (he components
in the liquid phase will be used. The compound's fu
gacity, in the vapor phase, ~ , at system temperature
and pressure is calculated from l v

i'.cverthelcss, c1assical thermodynamics provides

all lhe nccessary relatiol1ships to describe (be equilibria
and di<;lribulions cncountered. If kinetics and heat and
mas<; transfer are excluded, the phase equilibria and
olher properties can be developed. There is no neeu to
mea~urc all propcrties al all conditioos. Obtaining su
ficicOl J ata lO permit modelliog will allow calculaton
of other dara poinsts,

"fV

"

(2)

= ~iV Y i P

11

where ~ v is the fugacity coefficient for component i

in the mixture, y i is its mole tracton and P 1S the
total pressure. Until 1938, the value of
i was cal
culated as if compound i existed alone at system con
ditions. Several geoeralized charts were developed (1
47) where the Lewis simplificaron was worked back
wards to provide values a( hpothetical conditioDS to ex
pand the range o applicability beyond valid conditions
for the compouod. lo may cases, the assumptions were
su fficieot as long as the designers applied tbem consis
tentIy.

Parts 1 and II of this series describes the correla

rioos rhat ha e been developed for predicting phase
bch a vior and other properties o mixtures o'{ petroleum
fractions and discusses the limitations of these metbods.
Part 111 will cover (he methods developed by the pe
rro leum imlustry for obtaining the data ponts to be in
serteJ in these correlations.

n. CE ERAL CONSIDERATIONS
Rc\'iew o lhe bases of all (VLE) vapor-liquid
cquilibr ium corrdations iodicates three approaches
that can nOl be brought together at a11 conditions.

The fugacity of (he compound in the liquid phase is

usual1y ca1culated rom Gibbs concept o the standard
state and the activity coefficient. In practce, some of

- 'M

Raoult's simplifications are carded over and tbe vapor

pressure of the componnd at
temperature Is taken
as the standard state. The rigorous equation is

me

iL

yI

(8)

(3)

IL

where fi is the fugadty in the standard state and T is

Prausnitz has introduced terms that are widely

the activity oeffjcieot o the compound in tbe liquid

used in dcscribing the application o Equations 6 amI 7

to compounds at supercritical coodition . In 1960, he
introduced the "hypotherical standard tate fugadty",

f~L

phase. If the calculations o

involve the use o

tbe vapor pressure, pO,

one should be careful in setI
ting the variables o the P ynting correction, destrip

tion 01 which follows.

me

tem tcmperature.

JP V. d P

G. :

as a function of reduced properties and the third

p:trameter, W , the 'acentric factor". Later he Dlro

duced (he terro "asymmetrical correlation", where H j
of Equations 7 and 8 reptaces fiL for supercritical
compounds, while Equation 6 is used for the
com
xlunds that are liquids with real vapor pressures at the sys

Whcn cornbiuing Equations 2 and 3, the equality

must be at the ame pressure and the integraton of
free energy dillere.nce, the "Poynting eHect" (Equation

y
4) must be done correetl ."

f?

The Chao and Seader Correlatioo (1-15) and tbat o

Gra son aoJ Streed (1-27) are further developmentl> of
the Smith and Watsoo (1-67) hypothesis rhat the term

PI

(4)

-, he choice {either PJ or P as the . tanuan] state

dicta tes lhe path o ntegralion am1 a!so \', hether \ Ti ,

(9)

lhe partial molal volume, or V. the pure compound's

motal volume in the liquid pbas~, is used in Equation 4.

follO\\s the tbeorem of corresponuing statel>. Tbese

rorreLations wiU be further discussed.

At equilibrium , rhe classical Lewis approach leadl>

h can be shown rhat if ideal gas behavior is as

sumeu fur lhe \'aporl> at a11 onditions anu if lhe lquiLl

to

o" I V Y I

Y,

P :

)t

if

o
I

(5)
()

Ifimplifying asumpliom. are maJ~, CiL

is al
culated from vapor pres~ur anu rhe correcrion oC
Equation 4 . 1111.L'i bquation 5 becOOle.
"

of V Y

P :

y xI

"" i

P
V

e)t p

L
RT

dP

is incompressible, Equation 5 degenerates into Raouit's

La\, ""ilh the actl"it~ coelficients. Ba ed on these a'i
sumptlOIls, \an Laar (1-35) anJ Margule (1-4<1), and
later HilJebraml (1-33), catchard amI mber\ (1-14, J
56, 1-1, 1. 12, 1-61, 1-78) aJJrcssed lhcmseh~s LO 1 h('
noniucality in lhe liquid phase e . pr<.'l>sed in ten\.lS of ae
tivity cueflicienls. The rcader may nole lhat althollgh
lhe aetivity eoefficienl r can be den'vcd al> the partial
mola! uerivativc o the exccs~ Gibbs Iree ent>rgy,
E

po

rhe

(6)

abov~

equation I
tcmiHd) lHed in the
ch~mical jndu~try, where lhe implifying assumptions
governing the transitiom from Equation 5 do not cau e
scrtouS errors. Born in mind is the idea that compound i
has a real vapor preSSllre at system temperature, i.~., it
is not a supercritical gas or solido
The emprica l approach named aLer 1 leney is:

P Y

"
PI:

(7)
H i )( i

Sublotituting Equarion 7 into Equation 5 ano 6

R T In

r, : G., : ( ~
a ni )n 2

(10)

the simple equatJUn meu by van 1 aar anJ others

(11 )

cannot ah\ ay" be r igofOu!.1 y Jeriyet! \', it h fe uatioll

rom the [O(al (,ibbs free energy.

tj

Of the widely used methoUs fm pretlicling VLF.

lhe method of Chueh anu Prausnirz is basJ on
Equations 8 amI ~, anu the hao-S ader amI Grayson
Strccd merhods are bascd on Eqllurion 9. '[ he variaton!.
are in the orrelatiolls for lhe slandaru state { u or JI i
and tbe rncthods by which thc aeliviry coeffidenl, '(i
ilo gen.eraleJ. In aU thr~e mNhoJs, th: H.eJlidl-K 'l~H1g
cquatJOn of slate (1-62) JS u ed for preuletmg tbe .l5 i \. ,

-'35

of Equation 2, though Chueh and Prausnitz used a

more refined form (1-16).

(Note that ~ i is not the fugadty coefficient).

For mixtures under low pressures, and for systems

where a1l compounds are subcritical, Equation 6 is used

Assurning the validity of the prediction o i and

.0'V (the fugacity coefficient), Chao and Seader used
many tbousands of experimental K values to deve10p an

direcuy with 0' iV calculatcd byan equation of state

or a generalized chart as is 0 i . The molar volurue Vi
is often used as Vi.

Data on the solubility of supercritical compounds,

e.g. Hz, N2, CH4, H2S, in solvents are sometimes ex
pressed by Henry's Law con tants Hi, although wirh so
many variables affecting it, Hi is not a constant. At

sorne conditions the variations cancel each other and a

semblance of constancy results.
Because o the relative insensitivity of the ratio K
y/xi to variations in composition, it is generally
adopted for use in flash and distillation cakulations.
Hence, Equation 5 is usually presented as a function of
Equanon 9.

y
f
= __ = i L yi

o
=

~i v P

)( I

IV. THE CHAO-SEADER

STREED CORRELA TIONS

vi

yl

(1],)

~j v

A D

GRAYSON

As a form of the dassical Equation 5, Chao and

Seader (E-3) presented a generalized approach for
predicting K values

=
KI

vi
0V

ri

I ( 6 - 6 )

(14)

RT

J;

being the solubilty parameter (1-34) and {he

average fo r the mixture,

[; =2

~i

6 i

expression for In y o as a function of the reduced

properties TRi and PRi of component i with the Pitzer
(1- 57) acentric factor V i as the third parameter.

In their publication, Chao and Seader (1-15) pre

sented the functions v (o) and v (1) of Equation 17.

They also presented atable of Vi and 6' i for many
light hydrocarbons and bydrogen lor use with their
oorre1ation. Later, Chao and Erbar (1964) and Cavett (1
14) expanded the rabIes to include constants for H2S
and C02. and showed how the correlation couid be
used for petroLeum fractions, using standard petroleum
measurements. The method has become the workhorse
o the petroleum industry design routines.
The Chao-Seader corre1ation was deve10ped with
data 00 mixtures of light hydrocarbons and hydrogen at
temperatures up t 4000 F. Grayson and Streed (1-27)
expanded its use up to 700F and aboye 3000 psia. The
resultant Grayson-Streed corre1ation is of the sameform
115
the Chao-Seader, with different coefficients for !he
Chao-Seader, with difierent coefficient for (he func
tioos in Equation 17. They also added values for Vi and
i for petroleumfractions .

(13)

They proposed c.alculating ~ iV for eacb com

ponent in the vapor pha~e by the equation of Redlich
and Kwong (1-62); the activity coefficient '( j was as
sumed for that correlation to be exactly caJculated by
the Hildebrand Regular Solution Theory (1-34)
where

(L 5)

and
(16)

V. CORRELATION AN D PREDICTION OF

ACTIV1TY COEFFICIENT 't( i. V ALUES

Per Equation 3, the activity coefficient -( i is a

direct descriptioD of the component's partial molal ex
cess Gibbs free energy. By this definition, deviation
from ideal mixing is implied. For simplicity, we shall
refer to Equations 6 and 11 as a means for calculating
'( i for component i from experimental data, xi, y i, ~
and POi or COi which are functions o temperature. The
values for alI components are interrelated through
the Gibbs-Duhem equation.
Di the maDy availabLe integral forros of the Gibbs
Duhem equation only four are o direct interest to
modern designers.
- The Van Laar equatioD for binary mixrures (1-74)
and the Black modification for multiromponent
computations (1-12) .
- The Wohl (1-81) expansion of the Matgules type of
equation (1-49) as proposed by Adler et al (1-1).

- The Renoo, Wilsoo, Black and van Laar equations

require correlation equation coefficients to be es
tablished from experimental data. However, while
a curve fitting soludon can yield
unique coef6...
oents for a vart l..aar and Margule<> equations, the in
terdependence of the Wilson and &non energy pa
rameters leads to the possibility of multip1e roots, as
seeo in Figure 4 (1-59). This, however, does not greatl
Y diminish their usefulness.

Hildebrand-Scatchard (1-34) Regular Solution ap

proach, and the Flory-Huggins formulas for mix
tures of large and smaU molecules (1-23, 1-37,1-55,

1-73).
The Wilson (1-79) equation as expanded to multi
component solutioDS (1-54) and the NRTL, Renon
equation (J-65).

Each of me aboye procedures predict values of

'O utilizings empirica! eorrelation parameters. In prac

- For many hydrocarbon systems, the simple Regular

Solution approach of Hildebrand (1-34) is adequate.
That explains the usefuloess o the Chao-Seader aod
4the
GraysonStreed prediction techniques, (see
discussion o Equation 12). However, when nonhy
drocarbons, especially water and polar compoonds,
are present the standard procedures for predicting
d i and Vi would lead to erroneous answers.

tieally a1l cases, the predietion of the multicomponeot

system is done via sorne combination of the coefficients
for the binary pairs, although sorne attempts have been
made to develop coefficients for ternary interactions

I).
Activity coefficients are thoroughly discussed io
the literature (1-4 1-12 1-30 1-34 1-56 1-60 1-64 1
"
""
75). The correlation
parameters for the binary mix
ture have specific nomenclature tbat will be used in tbe
present diseussion. These are given in Tabie 2.

EFFECTS OF PRESSURE AND THE LIMITA

TIONS OF THE ClASSICAl vu: AND THE HIP().
1HETICAL STANDARD STATES APROACHFS
a

Experimental results indicate tbat no single

equation fits all conditioos. The van Laar equation for
pinary mixtures is best for one type of deviatioo and
fail.. bad1y on other systems. It canoot be utilized for
multicomponent systems. The choice between me
Black equation and me form oI the Wohl equation
proposed by the M. W. Kellogg group (1-1) depends on
avaiLability o a data analysis program for establishing
the coefficients. This can be also said for the Wilson and
the Renon equations.

Since the time o van der Waals, it has been obser

ved that, in any binary and multicomponent system, for
every composition there is, alleast theoretically, a true
critical point. At this point, me vapor is indistingui
shable from the liquid, hence VLE separatioos are im
possible. Thermodynamically, me partial derivatives
indicating stability for a single component system at
the criticaL point do not apply to me true critica1 point
o a mixture. Therefore, other re1ations involving
fugacity and composition are USed (166). Furthermore,
corre1ations of the volumetric and other properties of
~ mixture, \Vim application o me theorem oi the
corresponding states, do not reIy on the true criticaL
temperature and pressure, but 00 their pseudo equi
valents. Tbe pseudo critica1 teD:lpeIatUre and the pseudo
critica! pressure are also used, directly or indirect1y, by
combining tbe eorretarion parameters, whenever
equations o state are applied.

lo severallarge scale evaluations (1-25, 1-35, 1-36, 1

54), the Wilson equation 00 the average yie1ded more
reliab1e results than the van Laar or the Margules tfP
equations. However, that equatioo canoot be applied to
mixtures where separation to two liquid phases is pos
sible. This observation led to development of the
Renoo equatioo, where the additional parameter
al10ws flexibility in the shape of the calculated free
energy curves, and the Reooo equation is preferred .
The following observations should be noted.
-

The High Pressure-Critical Region Phenomena

Wheo VLE o a mixture is_ coosidered, me high

pressure regioo at temperatures aboye the critica1 o
the ght key componeat, or the critical azeotrope, is
ca1led the critica! region. The shaded atea in Figure 5
roughIy describes such a region in a simple binary sys..
tem with a dome-shaped critica11ocus. IsothermaI cur
ves o K-values within the critical region tend to con
verge at the critical point. As illustrated in Figure 3, all
the K . value<> equal unity at the crit.ical pressure,' p cm.

The Black and Renoo equatioos are appliaW1e to

both binary and multicomponent mixtures. Al
tbough the Reooo equation is very hard to use in
hand calculations, it is quite suitable to machine
computation. Also, the equation has been wide1y
used and the parameter oC ,when DOt known, can
be approximated.

- Although the Wilson equation has been shown to fit

experimeotal data well, it is less widely applicable,
due to limitatioDs meotiooed aboye. Where it fails,
tbe Renon equation, which is equally good, can be
used.

Such convergence canoot occur at all tempera

tures. If prediction o Kvalues o componen.. in an
ideal mixture al low pressures is carried out by the
method of Lewis and Randall (1-45) or a simple venion

-31

of Equation 6 as described by the dotted curve in Figure

6, the critical region may be, paradoxic:a1Jy, defined by
its correspondence to the largest deviations between

prediction o the fugacity of a component in one phase

rloes not have much in common wth the correJaton of
the behavior of tbe other phase. Thus, as illustrated in
Figures 6 and 7, tbe Kvalue predicted by tbis rnemod
may oot converge at tbe critica! point.

predicted and actual K-values.

The behavior of mixtures within the shaded area of
Figure 6, above that corresponding to the minimum in
the curve of K-against P for me heavy component also
represents critical region phenomena. In essence, this
sudden curving upwards of the K-value curves for the
heavy compounds 1s tota1Jy consistent with the rigo

rous EquatioD 5. As the pressure is increased, two fac

tors that are dormant at low pressures become signl

ficant. These are the fugacity coeHicient oi the como

pound in the misture, ;1 i , and the Poynting effect,

their method within the critical regon.

b. Methods Based on the Concept of Convergence Pres

sute.

on the observatioo that, in mixtures of ght paraffins,

K ratios of individual components appear to converge

dlt

RT

pO

.0i

Prausnitt (1-16)

The empirical methods based on the convergence

pressure (1-28, 1-29, 1-42. 1-44.153, -SO) are founded

'.p

The method of Chueh and

like that of Chao and Seader does not lead to conver

gence. In sorne cases it may fare better than the former.
Chueh and Prausnitz suggested caution when applying

to unity when plotted against pressure at constant

temperarure. The pressure at which convergen ce to
unity talees place is known as me convergence pres
sure o the system. In binar systems, convergen ce
corresponds to a true critical point oi the mixture.
Since, as yet, there is no rigorous method ior predic
ting real 01' quasi convergence points in multicom
ponent systeDlJ;, the onvergeoce pressure method is
based on purel}' empirical procedures. The techniques,
bom for finding m nvergence pr ures and using these
to predict K rat ios have been described by Hadden (1
28), Winn, (1-80) Lenoir and his coworker (1-42 1-43:
1-44), and the GPA (formerly GSMA) Data Book (1
53). The API Data Book preseats the Hadden-GraysoD
(1-29) modificaton o Winn method.

Tbe
coefficient decreases with pres5ure mote
significantly for high molecular weight hydrocarbons
than for ligbt ones. Similarly, the integral o VdP for
beavy compounds is positive and spans a wider range
due to the low vapor pressure, or P~ o the heavy
compound When Ibis efect, compounded wilh the lar
gc pa rtial molar voJume V; of the heavy molecule,
ta.keo e ponentially we have quite an effect. Similar
va ria tions, but with oppo~ite slgn, affeet the K-values
of Ihe light compounds. Since a11 component contri
bute toward all pbeoomena, the net effect is lbat, if the
tempcratur L" within the range of me continum of t.he
critical loco!>, convergence at K
1 an occur for all
compounds.

(I-l5, 1-27) fall into the same category as the abov . as

Since the converg nce pressure methods .have

been developed primarily from data for the light
paraffinic compounds, they are largely limited to
paraffinic and sorne oIefioic !>y tems. Convergence
pre sure correlaons employ assumptions based on
domeshaped critical loo, which are characteristic 01
light paraffin - paraffin hydrocarbon binaries. 1Ia
wever, sorne binaries, particularly those io which car
bon dioxide or hydrogen sulphidc i a component, pos
sess an S-shaped rather than a domeshaped critica!
locos (1-67, 1-38). Also, the critica! locu curves of
many systems (1-67) are neither continuous oor dome
shaped. A ccordingIy, applic.ation o the convergence
pressure methods o systems contammg oon
hydrocarbon constituents may lead to large errors.

they depend 00 generaLi.zed predictions of hypothetical

standard states. Although generally useful over a wide
range o conditions the correlatioo becomes increasio
gly inaccurate as the tme critical point is approached.
The failure o tbe Chao-Seader method in the critica1
region is largely due to lack of ioter-re1ationship bet
'W~~n th~ corr~taons avplied to the two phases; me

The utilization of any o the convergence pressure

methlXls requires experience, as judgemeot is needed
in selecting the appropriate convergeoce pressure and
in d ciding when to abide by many of the arbitrary
rules. Nevertheless, tbe convergence pressure methods

It is dear from the above that a good correlaton

for the VLE withio the critical region should be ca
pabl o predicting the convergence at the criticaJ x>int.,
For
lhis purpo e, expressions of alI variables in

Equation S should b symmetric.al in nature, l.e. tbe ex

pressions on botb sides of the eqnation
houJd contain all oeeded eJemeots for b ing identica1
al three important milestone where K
1. The e are
the saturated pure componnd, any azeotropic mixture,
and the critica! point, the latter i. po sible at the tem
perature in question.

The Chao-Seader and Graysoo-Streed mcthods

-3&

offer quick first estimates of K valueli. for hand cal

rulauons (I-2h, 129, 142, 1-53), Programming for

ACKNOWLEDGEMENT

romputer use is quite a task, which, ID view oi the

limited accuracy and field 01 applicatioo, may not be

The author wishes to express gratitude for the as

sistance of Norrnan J, Weinstein oi Recon Systems, In c.
and hving Zarember o the American Petroleum
In titute lor their advice and assistance in preparatton
o this manuscript.

worth undertaking,

J 0-

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