Fl

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,Yyhei

Thel,
2 that°"
Phase Behavior Fundamentals tem,y
TI-1.
conc
tenti al,
each é

Introduction

Tes:
The properties exhibited by anv substance depend upon its phase,
C (P41
namely, whether it is in the solid, liquid, or gaseous phase. Substances can
nen''e
be classified into two types-pure or single component. and multicompo-
mol-.
nent. Phase behavior relationships can be determined from laboratorv pVT
of tia
(pressure, volume. temperature) studies, or using theoretical/empirical
prescá
methods such as the equations of state. These relationships are frequently
1.no
shown graphically as "phase diagrams" to enhance qualitative understand- ,mí
ing. For design purposes, however, precise quantitative phase behavior data
are crucial. In Chis chapter, some fundamental concepts in phase equilib-
rium are introduced.

Qualitative Hydrocarbon Phase Behavior

A phase diagram for a single component system has three axes: p. V, and tem
T. Usually, p.T diagrams only are used for a single component system. For pressy-
multicomponent svstems, the mixture composition becomes an additional
variable. Generallr, three types of phase diagrams are used for mixtures: (a) 1
pressure versus temperature (p,T) diagrams, holding the composition fixed;
(b) composition-composition diagrams, keeping pressure and temperature
fixed; and (c) pressure-composition diagrams, keeping temperature fixed.

The Phase Rule

i
Gibbs' phase rule for the degrees of freedom of a system is written as:

N=C-P+2

18
 Phase Behaaior Fundamentals 19

where N = number of degrees of freedom of the system

C = number of distinct chemical components (or compounds) in the
system
P = number of phases in the system

The number of degrees of freedom of a system ís the number of variables

that must be defined to fix the physical state of the system. Usually, pressure,
temperature, and composition serve as the variables.
The phase rule can easily be verified. Consider a mixture consisting of C
components distributed in P phases. Then, at equilibrium, the chemical po-
tentials (see pages xx-,sc for thermodynamic criteria for equilibrium) for
each component are equal in each phase:

f¿il = /L,2 _ ... = F¿íp, for i = 1,2,...,C

Thus, we have (P - 1) equations for every component, or a total of

C(P - 1) equations. The unknowns are the mole fractions of each compo-
nent in each phase, which represent (C - 1)P unknowns, since lmowing the
mole fractions of (C - 1) components in any phase P fixes the mole fraction
of the last component (the sum of the mole fractions equals unity). Also, the
pressure p and temperature T are unknown. Thus, the total number o£ un-
knowns are (C - 1)P + 2. So, the number of degrees of freedom are:
11

N = number of unknowns - number of equations

=(C-1)P+2-C(P-1)
or,N=CP-P+2-CP+C=C-P+2

Single-Component Systems

Figure 2-1 shows a typical p,T phase diagram for a single-component sys-
tem. The equilibrium lines, AB, BC, and BD indicate the combinations of
pressure and temperature at which the adjacent phases shown on the dia-

f -------19
i C
VI III V1dl F/ VIIll

Compresse^d
iiquid 1 Su p erheated
Solid
-a---- b^^ - --- d I e- - hl vapor

Figure 2 -1. Pressure-temperature

diagram for a single component
Temperature ^ system.
 E
n
LJ
20 Gas Production Engineering
17,1
gram exist in equilibrium. Line AB represents the equilibrium between solid Tc,
and vapor. A solid aboye this line will sublime directly to the vapor phase, near 'R
without ever going through the liquid phase, on reduction of pressure to be- síon
low line AB. An example of this is "dry ice." Line BD indicates the solid disaj°i
liquid equilibrium. Line BC is the equilibrium between liquid and vapor syste)
phases. At the triple point, B, all three phases exist in equilibrium. Applying pror 1
the phase role, it can be seen that for a single-component system writh three corr,
phases, the degrees of freedom, N = 1 - 3 + 2 = 0. Hence, the triple point co
is a unique point that defines the whole system. The equilibrium lines, hoy;-- yon
ever, represent only two phases in equilibrium and the degrees of freedom tempé
N = 1. Therefore, specifying either the pressure or the temperature fixes the atd?c
other variables for the system. In the single phase regions, N = 2, and both phase
pressure and temperature must be known to determine the location (or state) T
of the system in the phase diagram. repr
The liquid-vapor equilibrium line (BC) begins at the triple point, B, and pass
ends at the critical point, C. At the critical point, liquid and gaseous phases the
become indistinguishable and their intensive properties (that is,. properties regir]
independent of the amount of fluida for example: density, viscosity) become at p7=Y.
identical. The pressure and temperature corresponding to the critical point ble t1
are termed critical pressure, p, and critical temperature, T, respective f luigj
and are a uniquely defined numerical value for every pure substance. More
formal definitions are as follows: Mul e

1. Critical temperature: The temperature aboye which a substance can- p, T 'gis

not be liquefied by the application of pressure alone. 3
2. Critica¡ pressure: The pressure at which gas exists in equilibrium with F:
liquid phase at the critical temperature. Also defined as the saturation fluid
pressure corresponding to the critical temperature.
3
Consider a constant pressure (isobaric) process represented by the line 3
abcdeh of Figure 2-1. From a to b the system is completely solid, and the
energy requirements for achieving the increase in temperature are simply
proportional to the specífic heat of the solid phase. From b to c, pressure and
temperature remain constant, but an energy equal to the latent heat of fu-
513
sion is required to convert the solid phase to liquid. The energy supplied is
converted into internal energy. The temperature increase from c to d re- 1
quires energy proportional to the specific heat of the liquid phase. At d the
liquid is a saturated liquid- any further addition of energy will cause va-
porízation at constant pressure and temperature. Energy equal to the latent
heat of vaporization is required to accomplish the change of phase from d to
e. At e, the vapor is termed saturated. At higher temperatures, for example
at h, it is called superheated. The energy spent for going from saturated va-
por state at e to a superheated state at h requires an amount of energy pro-
portional to the specific heat of the vapor.
 Phase Behavior Fundamentals 21

)lid To better understand vapor-liquid phase behavior, consider the region

b ase, near the critical point in greater detail. If one proceeds from d by a compres-
n be- sion process at constant temperature to f, liquid will at some point begin to
solid disappear into a seemingly gaseous phase. Aboye the critical point at f, the
vapor system is in a "fourth" phase that exhibits properties different from gas. T he
,,Ing properties of this fluid are in between those of gas and liquid, though not
._.ree correlatable to either. Jor example, it is denser than regular gas, and is more
jint comprensible than a regular liquid. By going further from f to a poínt g be-
)w- yond the critical temperature at constant pressure, from g to h at constant
'om temperature, and finally, back to e, a phase transition from the liquid state
the at d to a vapor state at e can be achieved without any abrupt change of
',oth phase.
,`ate) This shows that liquid and vapor phases are in reality quite similar: They
represent separate forms of the same condition of matter, and it is possible to
and pass from one state to the other without an abrupt change of phase. Thus,
)mases the terms liquid and vapor have a definite meaning only in the two phase
ierties region. For conditions far removed from the two-phase region, particularly
;. eme at pressure and temperature conditions aboye the critical point, it is impossi-
)int ble to define the state of the system, and is best referred to as being in the
t .ely, fluid state.
lore
Multicomponent Systems

b can-
p,T Diagrams for a Fixed Composition

i vith
Figures 2-2a and 2-2b show typical p,T phase diagrams for a reservoir
tion
fluid. The system has three regions: ( a) single phase oil, in the region aboye

Al line
:ate the
;..iply
and Single phose

E fu- ni¡ Criconden bar

--d is Ir
re- 1 Tro phase,
(GAS' +
CIL) 1 single phase
dthe r í r^ r1 Gas 2
1,9 va-
' atent
mdto
ample Temperature - Temperature -

:t.,1 va- Figure 2 - 2a. Pressure-temperature dia- Figure 2-2b. Phase diagram show-
;, pro- gram for a multicomponent reservoir ing two retrograde regions.
fluid.
22 Gas Production Engineering

the bubble point (BP) curve ; (b) single phase gas, in the region towards the
right of the dew point (DP) curve , and (e) the two phase region, which is the
portion bounded by the BP and DP curves . The BP and DP curves intersect
and terminate at the critical point, C.
Point A represents the maximum pressure at which liquid and vapor may
exist in equilibrium . This pressure is known as the cricondenbar. Similarly,
the cricondentherm is defined as the maximum temperature at which liquid
and vapor can exist in equilibrium . This is indicated as point B in Figure
2-2a. Along tvith the critical point , these serve as valuable tools for recon-
structing appro imate phase envelopes and to enhance their understanding.
The shaded region CAB , called the retrograde region , exhibits quite an
interesting behavior. Usually, on lowering the pressure . a liquid phase va-
porizes to gas. But in this region, on lowering the pressure , the gas at a be-
gins to generate liquid at b (see Figure 2-2a). On further reduction in pres-
sure , more and more liquid is condensed (refer to the quality unes ), until
point c is reached . Outside the retrograde region from c to d . liquid begins to
vaporize until the 100 % gas quality line (or the dew-point curve ) is reached
at d. It is evident that the retrograde region results from the chape of the
phase envelope and the quality lines. The inflection points of the quality
lines govern the retrograde area , which is bounded by the critical point, C,
the cricondenbar at A. and the cricondentherm at B.
For naturally occurring hydrocarbon mixtures , the critical point has al-
wavs been found to occur to the left of the cricondenbar ( Campbell , 1984).
If the critical point is to the right of the cricondenbar, t\vo retrograde re-
gions will occur as shown in Figure 2-2b.

p,T Diagrams for Variable Composition

The case discussed earlier concernéd studving the phase diagram at a

given fluid composition . VVhen fluid is produced from a reservoir, pressure
decreases over time . If we started off with an oil reservoir for example, a
two-phase region will eventually be encountered at pressures below the bub-
ble-point curve. The heavier components in the reservoir fluid will begin to
vaporize , leading to altered reservoir f luid compositions. WWrhenever the res-
ervoir fluid is in the two-phase region , compositions also change due to the
selective removal of components in the mobile phase. Therefore, the phase
equilibrium relationships change with time for a tv_ pical reservoir svstem,
and the shifts in the phase envelopes as a function of composition must be
studied careful1v.
Figure 2-3 shows a p,T diagram for a binare mixture of ethane (C2H6)
and normal-heptane (n-C7H16). It can be seen that with a shift in the mix-
ture composition from 100 ro ethane to 100 % n-heptane, the phase envelope
shifts towards the right. This shows that the shape and location of the phase
 Phase Behavior Fundamental 23

the 1,400
CO1.IPOSTflON
the cZ NO . w T, % ETHANE
c 10000
sect ct 9022
c2 5025
1 M0 9.78
c, n- EPTANE

-nay
-irly, i \
;quid
1
;ure c,
—con-
aoo
uing.
C ` C3
an
va-
be-
sres- w
1^

:ntil 4w 05
A 0J
Sto
-hed
Figure 2-3. Pressure-
the temperature diagram
'glity for the ethane/n-hep-
T* C. A3 BZ
tane system. (After
B Stalkup, 1978, 1983;
0
0 100 200 roo 500 courtesy of SPE of
as al-
TEMPERATURE. ¶ AIME.)
o3 4).
1 . re-
envelope are composition dependent. The dashed line dra^vn tangent to all
the phase envelopes at their critical points is called the critical locus. The
critical point for a mixture is thus a function of its composition. Mixtures
-,vith more than tuvo components have more than one critical locus, and the
'.t a problem becomes quite complex. Simple mixina rules have been devised (to
°sure be discussed later) to represent this shift in terms of "pseudocritical" proper-
J£1 a ties for correlation purposes. The only reliable method at this point ¡sí labo-
nub- ratorv measurement, since none of the correlations are verv exact.
:in to
res- Composition- Composition Diagrams (Fixed p,T)
the
..pase According to the Gibbs phase rule, N = C - P + 2 degrees of freedom
-m must be specified for completely defining the phase behavior of a mixture
. be with C componente distributed in P phases. Such a rigorous description,
however, is neither practically feasible nor usually necessary. Ternary dia-
lis) grams are used as an approximate method for representing the phase behav-
iix- ior of multicomponent mixtures. These diagrams represent the phase behav-
19pe ior of a ternarv (three-component) mixture exactly; mixtures with more
`case componente are approximated by three pseudocomponents. For hvdrocar-
 9
1*
24 Gas Production Engineering
E
100% Cj Figure 2-4. A typical ternary
phase diagram for a reservoir
Huid. w^
7

d
'° J
Plait point
N

0
100% 100 %,
C7'
c 2 - C6
13
3

bon systems, the three pseudocomponents generally used are methane (C1), adding tII
ethane through hexane (C2-C6), and C, T , which represents all hydrocarbon The appi)
fractions w-ith molecular weight greater than hexane. sured as
Figure 2-4 shows a t-, ¡cal ternary phase diagram for a reservoir fluid. that resul«>
Each corner of the triangle represents 100 % of the component indicated, diagrams'11
whereas the side opposite to this corner representa 0%, of that component. taining er)
The distance in between a corner and the opposite side is divided into equal ited since*
parts to represent fractions between 100 Tú and 0%, of the component. Thus, shows a p
the point A in Figure 2-4 represents a mixture containing 67 % Cl, 18.57c mole ro n
C2-C6, and 15 9o C7, , lving in the two-phase region. Such a mixture, under
equilibrium conditions. would result in a gas phase of composition y in equi-
librium v,rith a liquid phase of composition x. The dashed fine connecting
these equilibrium gas and liquid compositions, occurring on the dew-point Q .i
and bubble-point curves, respectively, is called a tie-line. Clearly, there can
be an infinite number of such tie-lines. The tie-lines disappear at the critical In mo!'"
point, also called the plait point, where the liquid and gas phases become phases pr'1
identical. Outside the phase envelope, single-phase gas occurs aboye the productic
dew-point curve, whereas single-phase liquid occurs below the bubble-point the opera]
curve. The size of the two-phase region depends upon the pressure and tem- The singl
perature. With increasing pressure, the two-phase region collapses to gionism
smaller sizes, u^hereas x ith increasing temperature it expands in sine. the vapor
Lever's rule can be applied to determine the relative amounts of gas and tionofpr.
liquid in equilibrium. For example, the mixture at A wwould split into a gas-
liquid ratio equal to the ratio of the distance of A, along the applicable tie- Thermod-)
line, from the bubble-point and dew-point curves, that is, Ax/Av.
Phase i
Pressure- Composition Diagrams (Fixed T) from one 3
energy of j
Pressure-composition diagrams also serve as a useful method for display- ergy,G,
ing phase behavior data. These diagrams are obtained for reservoir oils by can be ma$

3
•
 Phase Behavior Fundamentals 25

ternary Figure 2 -5. Pressure-composition

- ervoir diagram for a reservoir huid.

-- Cricondenbar

ioo
Concentration of Ci , %

mne (Cj), adding the desired injection fluid to the oil in a high-pressure visual cell.
iicarbon The appropriate (bubble-point or dew-point) saturation pressures are mea-
sured as a function of the injection fluid mole fraction in the total mixture
fluid. that results from the mLdng of the injection fluid with the reservoir oil. Such
.icated, diagrams are easier to obtain than the ternary diagrams, which require ob-
áonent. taining equilibrium samples and compositions, but their applicability is lim-
o equal ited since thev do not offer information of a general nature. Figure 2-5
• `. Thus, shows a pressure-composition diagram for a reservoir oil as a function of the
18.5% mole% methane in the mixture.
Tes, under
si in equi-
)nnecting
.ew-point Quantitative Phase Behavior and Vapor-Liquid Equilibrium
L.iere can
critical In most petroleum production operations, it is important to know the
become phases present in order to design the system. In processing and other post-
ove the production operations, it is desirable to control these phases by controlling
le-point the operating conditions, or condensing or vaporizing selected components.
nd tem- The single-phase regions are relatively easier to define. The tuvo-phase re-
' ipses to gion is more difficult, lince we need to know additional parameters such as
-=ze. the vapor-liquid ratio, and the compositions of both the phases, as a func-
gas and tion of pressure and temperature.
'to a gas-
cable tie- Thermodvnamic Criteria for Equilibrium

Phase equilibrium is reached when there is no net transfer of material

from one phase to another. Such transfers involve a decrease in the total free
energy of the system. Thus, when equilibrium is attained, the total free en-
display- ergy, G, also called Gibbs free energy, will be at its minimum value. This
.r oils by can be mathematically expressed, at a given p and T as:
 Fi
26 Gas Production Engineering

dG = 0 (2-1)

Note that "no net transfer" does not imply that the svstem is static. There is
still a continuous exchange or transfer of material bet-,veen the phases. But dG:
the rate of transfer of each component from one phase to another is just bal-
anced by the same transfer occurring in the opposite direction from the lat- To pres
ter to the former phase. Thus, there is no net transfer of and- molecular spe- ,,vhere tpE
cies from one phase to another, and no net change in composition occurs in fugacit\;,
anv of the phases.
An equivalent idea is expressed using the condition that dE = 0. where E
is the total enero v content of the svstem. Note that the derívative in Equa-
tion 2-1 is with respect to all possible variations, except those of p and T.
Gibbs defined chemical potential, µ, to express these ideas. The chemical
potential of anv component i in a phase is the rate at which the total free
enero v of that phase changes as one changes the amount of the component i.
keeping p. T. and amounts of all other components of the phase constant:
Fug-
equal t)
v".s.ni ac
ani V.S.ni be eacila
units
where ni represents the moles of any component i, V is the svstem volume, purely,
and S is the svstem entropv. Chemical potentials are intensive properties and gas-
depend upon the composition of the mixture, but not on the total mass. For at cons a
a single-component ideal gas, the chemical potential is given by: reduc r
Fugac3-
µ = µ* + RT In (p/p*) (2-J) Fuga
the ch).
u-here R is the gas constant, and the superscript * refers to anv arbitrarv 3
standard state. For a perfect gas mixture. the chemical potential for anv
component i, is given by:

µi = gi* + RT In (pi/pi* ) Using

can, 2
= µ* + RT In (pi/p*) - RT In vi , (2-4) when

where vi is the mole fraction of component i in the mixture. It is not possible The E,.
to ascribe absolute numeric values to quantities such as free energv and O
chemical potential. The ratio between tino isothermal states as previously The
defined suffices for application purposes. liquida
Equation 2-2 can be manipulated to vield the result that the necessarv poner$
condition for equilibrium is that the chemical potentials of a given compo- (xi) pF.
nent are equal in all the phases. Thus, the chemical potential can be consid-
ered as a k-ind of driving force for mass transfer bet-,veen phases.
 Phase Behavior Fundamentals 27

The change in free energy, dG, for any substance is given by dG = v dp.
For an ideal gas (pv = RT; see Chapter 3 for further detail), this becomes:

dG = RT d In p (2-5)

To preserve this simple mathematical form of this equation for other cases
where the system is not an ideal gas, Lewis defined a special function called
fugacity, f, as follows:

dG = RT d In f (2-6)

Integrating Equation 2-6, we can obtain:

G - G* = RT ln(f/f*) _ P vdp
p,

Fugacity can, therefore, be defined as a quantity whose numeric value is

equal to the pressure when the substance is in the state of an ideal gas. It can
be easily seen on comparing Equations 2-5 and 2-6 that fugacity has the
units of pressure, and is proportional to pressure for an ideal gas. From a
purely theoretical standpoint, any substance in any phase-solid, liquid, or
gas 'can be brought into an ideal gas state bv sufficient pressure reduction
at constant temperature. It can be seen also in the equations of state, which
reduce to the ideal gas form, pv = RT, at the limit when p = 0 or v = oo.
Fugacity thus serves a very valuable purpose in equilibria studies.
Fugacity for a component i in a mixture can now be defined in terms of
the chemical potential as follows:

+RTin( f;I£;*)
= µ* + RT In (f;lf*) - RT in y; (2-8)

Using these relationships, it can be seen that the condition for equilibrium
can, alternatively, be stated in terms of fugacity. A system is in equilibrium
when the fugacities of a given component are equal in all the phases.

The Equilibrium Ratio

The vapor-liquid distribution coefficient. commonly known as the vapor-

liquid equilibrium ratio or the equilibrium vaporization ratio, K;, for a com-
ponent i, is simply the ratio of its mole fractions in the vapor (y;) and liquid
(x;) phases at equilibrium conditions:

K; = y; /x; (2-9)
28 Gas Production Engineering

Equilibrium ratio values can therefore be determined by laboratory equilib- for ap4:
rium flash experiments by analvzing the mole fractions of the different com-
ponente in the vapor and liquid phases. In 4°)_

The Partial Pressure Approach

K-values can be expressed in terms of partial pressures of the components.

The assumption, of course, is that the gas obevs ideal gas laves and behaves A^
forac:.
as an ideal mixture. Therefore, such a concept is only applicable at low pres- total r
sures, up to about 400 psi.
At equilibrium, the partial pressure of component i in the vapor phase K;
(= pvj) must be equal to the vapor pressure exerted by its presente in the
liquid phase (= p-;x;). Thus, at equilibrium: ,,i•here
and v2p
py; = p,,x; implving that v; /x; = Pj/p This c,

So, K; = P•i/p (2-10)

where pi is the vapor pressure of component i at the equilibrium pressure

and temperature conditions.
This approach is verv useful as a practical method for determining the
equilibrium constants , but has limited applicability.

The Fugacity Approach

Flash 3
Non-ideal behavior can be accounted for bv using the fugacity coeffi-
Th
cients. The fugacity (or activity) coefficient, *;, for a component í is defined
multi
as the ratio of its fugacity, f;, to its partial pressure, p;:
amou
have a
*; = f;/p; with Ii rrb *; = 1 (2-11)
P^ liquid'
presen)e
For a gas phase, the partial pressure, p; = y;p. To enable definition of a liq- C012,
uid fugacity coefficient, an equivalent hvpothetical partial pressure concept separa)r
is used, and liquid phase partial pressures are expressed as p; = x;p. moles >
Fugacity coefficients are commonly written as: {}., } ).

F =ti
3
In * = In f/p = J [(v/RT) - (1/p)]dp
0 11
P. J

= Z - 1 - In Z - (1/RT) S CO [p - (RT /v)]dv (2-12)

 Pitase Behavior FundamentaLs 29

for a pure component, and

In *i = In fi/pxi

_ -In Z + [(1 /v) - (1/RT)(ap/ani );dv (2-13)

JV

for a component i in a mixture , where ni is the moles of component i in the

total mixture . K can be expressed in terms of fugacity coefficients as follows:

K; (2-14)

where ^L and *Y;' are the fugacity coefficients of component i in the liquid
and vapor phases, respectively, coexisting under equilibrium conditions.
This can be verified, by expanding the right-hand side term of Equation
2-14:

[fL
'ili-¡*y = /(x iP)]/[fy/(yiP)]

= (yip)/ (xip) since fL = f;' at equilibrium

= yi/xi = Ki

Flash Calculations

These calculations involve solving simple material balance equations for

multiphase systems in order to establish the phase compositions as well as
amounts upon equilibrium separation. In oil and gas systems, we generally
have a two-phase oil-gas phase breakup. Water is assumed immiscible in the
liquid oil (oleic) phase, and miscible only in the gaseous phase where its
presence can be quantified by Dalton's law of partial pressures.
Consider F moles of a hydrocarbon mixture of composition {zi} enters a
separation unit. At the operating conditions of the separator, it splits into L
moles of liquid of composition {x}, and V moles of vapor of composition
{ yi } . Then, by the law of conservation of mass:

F=L+V

and

Fzi = Lxi + Vyi for each component i

30 Gas Production Engineering 3
1
Changing to a unit mole basis, F = 1, for simplicity: howev.
is vervW,
L+V=1 (2-15a) to acc i
tem.
and verv ri
and thl
z;=Lx;+VV;=Vx,(L/V+K) (2-15b) Equatl
111
Thus, ave get

Vx; = z;l(L.'V K) V
Reserv.jr
and

Figt
Vv;=VKx =z;í(LIKV+1)
carbone
with tI
The following additional relationships must also be satisfied:
3;. ana
consta)
n n
ture ca:
x;=7 v. z;=1
=1=i=1 thew€ :
produ.
and condit'
Resé
h; = v;/x; saturati
dissolvf
Thus. the amount of vapor, V. can be calculated as follows:

n n
1
[z/(L/KV+ l)]
3
(2-16)
=1 ;=1
3
If liquid. L. is desired, it can be calculated as follows: 3
n 3
L=L x; _ [z,/(KVIL + 1)] (2-17) 3

Equations 2-16 and 2-17 requíre a trial and error tupe of solution scheme.
3
Both these equations are equivalent, and one has the choice of using either 3
one; knowing either L or V is sufficient, since L + V = 1 (Equation 2-15a).
From the standpoint of obtaining an accurate solution, these equations, Figure)
 Phase Behavior Fundamentais 31

however, are different. It is easy to envision that for a stream F for wbich V
is very small, any error in the calculation of V will be far more detrimental
to accuracy as compared to an error in the calculation of L. For such a sys-
tem. it will therefore be necessary to solve for V using Equation 2-16 using
very rigorous convergente criteria (that is, use a very low error tolerance),
and then obtain L by difference. Similarly, for predominantly gas systems,
Equation 2-17 would provide better accuracy.

Applications

Reservoir Behavior

Figure 2-6 shows a p,T phase diagram for a naturally occurring hvdro-
carbon fluid of a known composition. Consider four different reservoirs,
with this same fluid, but with different initial conditions denoted bv li, 217
3i, and 4.. The vertical lines represent the pressure decline in the reservoir at
constant temperature. The curved lines represent the pressure and tempera-
ture changes imposed upon the reservoir fluid as it flows upward through
the wellbore, and both pressure and temperature decline to the wellhead ri
producing conditions. The subscripta s and r denote surface and reservoir j
conditions, respectively.
Reservoir 1, occurring aboye the bubble-point curve, is called an under-
saturated oil reservoir. It is also called a black oil reservoir, depletion drive,
dissolved gas drive, solution gas drive, or internal gas drive reservoir. Gas is

Condensote
Re se r yo ir s
Oil Reservoirs Gas Reservoirs
R4i
ri
i

Temperature -

Figure 2 -6. A typical pressure-temperature phase diagram for a reservoir fluid.

32 Gas Production Engineering

produced at the surface conditions (1, is in the two-phase region), but no gas
is formed in the reservoir until the pressure reaches the bubble-point pres-
sure. Typically, higher API gravite oils release greater amounts of gas since
thev contain larger amounts of lighter componente. Below the bubble point,
the composition of the reservoir fluid starts changing. The free gas liberated
in-situ eventually begins te flow toward the wellbore in increasing quanti- The e
ties wvith reduction in pressure. The producing gas-oil ratio (GOR) therefore nature
goes up. given G J;
Reservoir 2, occurring in the t«.wo-phase region, is an oil reservoir with an are oftcl
initial gas cap. With declining pressure. GOR increases and the reservoir them tc " Vil-
fluid composition changes. hvdroc;''
Reservoir 3. occurring in the retrograde region, is a gas condensate reser- relevan-'T!
voir. On pressure reduction, liquid begins te condense at and beyond the Since e—1
dew-point curve. Since it clings te the pore spaces in the reservoir, a critical duced fi
saturation has te be built up before it can flomw toward the wellbore. Thus, all cona
the producing GOR (at the surface) increases. The intermediates that con- expecte .
dense out of the gas are verv valuable and their loss is a serious affair. How- where 5
ever, as pressure is reduced further, the liquid begins te revaporize into the
gaseous phase, This revaporization aids liquid recovery and, assuming that
the reservoir fluid composition is constant. may lead te a decline in the pro- Gas Prly'
ducing GOR at the surface. The reservoir fluid composition, however,
changes as retrograde condensation occurs: the p-T phase envelope shifts te It ma,
the right, increasing retrograde liquid condensation into gas. This retro- does no1 c
grade "loss" is greater for a greater shift of the p-T phase envelope te the the traiir
right, lower reservoir temperature, and higher abandonment pressure. tions, al
Reservoir 4, occurring in the single-phase gas region, is a true gas reser- cumula )
voir. It is generally known as a wet gas reservoir if 4, is inside the tino-phase and ar(
region, or as a dry gas reservoir if 4, is in the single-phase gas region. In this change c.
reservoir tepe, the reservoir (point 4r) is alwavs in the single-phase gas re- equiprr }.
gion, regardless of the pressure. So, the reservoir fluid maintains a constant where
composition lince there is no change of phase in the reservoir. propor í
The producing GOR for a reservoir is an excellent indication of the reser- i)
voir type. Generally, a reservoir is classified as a gas reservoir if the Reserve
GOR > 100,000 scf/stb, as an oil reservoir if the GOR < 5,000, and as a gas
condensate reservoir if the GOA; is between 5,000 te 100,000 scflstb. Resero
The relationship between the critical temperature, T,, and the reservoir predicb;
temperature, Tfi, determines whether retrograde condensation occurs or ior dat
not. For retrograde condensation te occur, the reservoir temperature must techniq d
be in between the critical temperature and the cricondentherm. Reservoir ships nl
systems in single phase mrith a surface GOR > 10,000 scflstb are likely te these n
have a high C1 fraction, and consequently, a low T,. Expect retrograde con- orbe .'

densation for such reservoirs. Reservoir systems in single phase that exhibit a fluid rris

3
 Phase Behavior Fundamentals 33

no gas GOR < 2,000 scflstb are likely to have T, > TR, implying a dissolved gas
.t pres- drive reservoir.
.s since
point,
Hydrocarbon Production and Separation
')erated
iuanti-
The design of the producing well and surface facilities depends upon the
aerefore
nature of the fluid being produced : gas, oil, or tuvo-phase gas and oil -,vith a
given GOR, and the presence of water. Since the intermediate hvdrocarbons
with an
are often the most valuable components , it is highly desirable not to lose
Cservoir
them to the gas, and to recover as much liquid as possible from the produced
hydrocarbons . For the design and operational optimization of these systems,
reser-
relevant phase behavior and gas-oil equilibrium parameters must be lcnowvn.
id the
Since the phase relationships are a function of the composition of the pro-
:ritical
duced fluid , we can never really design equipment that is optimum under
Thus,
all conditions. The only recourse is to design it for the —average " condition
t con-
expected over the life of the field , or to change the installation at some point
How-
where it mav become economically attractive to do so.
nto the
ing that
tne pro- Gas Processing and Transport
owever,
,áiifts to It may be necessary to remove heavier ends from the gas so that the gas 1
retro- does not condense liquids upon anticipated pressure-temperature changes in
to the the transport, processing, and handling systems. To enable such calcula-
e. tions, at least the dew-point curve for the fluid must be known. Liquids ac-
reser- cumulate in the piping systems, cause additional pressure drops in the lines,
phase and are generally undesirable because of the instability caused by phase
Tn this changes occurring as a function of pressure and temperature. Processing
Vas re- equipment must never be operated near the phase envelope boundaries
-instant \vhere small changes in pressure, temperature, or composition can cause dis-
proportionately large changes in vapor-liquid ratio.
reser-
if the Reservoir Engineering and Enhanced Oil Recovery
amagas
Reservoir engineering calculations, such as reservoir reserve estimates,
2rvoir predictions, and simulations using computers, require reliable phase behav-
irs or ior data. Nowhere is it more critical than in miscible enhanced recoverv
must techniques, where highly detailed and accurate phase equilibrium relation-
'rvoir ships must be known over a wide range of conditions. The performance of
-ly to these methods depends upon the ability of the injected fluid to be miscible,
' con- or be able to generate miscibility, with the reservoir fluid. The injection
k ibit a f luid must be tailored to requirements dictated solely by phase equilibrium.
34 Gas Production Engineering

3
Prediction of the Phase Envelope

To accurately predict the phase envelope for a multicomponent hydrocar- The

bon svstem such as oil or gas is almost impossible . Experimental means must pure cc
be used, since imprecise results can be quite dangerous to use in the innu- quired.'j
merable planning , design. and operational problems. However. it becomes from la',y
verv necessarv to use correlations and predictive methods in mane- instantes ponent')
where such studies cannot be readily performed. time arlo
As a bare minimum . an accurate compositional analysis of the reservoir componS-
fluid is essential . Estimates of the critical point, the cricondentherm, and mum er,
cricondenbar can then be used in conjunction with vapor-liquid equílibrium rors up x
calculations for bubble -point and dew-point curves to generate reasonable to use.
phase equilibrium curves. Sometimes . only a portion of the phase curves
mal- be required.
Critica 1
Cricondentherm and Cricondenbar
Mane
Grieves and Thodos (1963) presented the following equations for the pre- drocarh
diction of cricondentherm temperatures: (1933)
^
troleurrI,)
Tt/T' = (Tb/Tb - 1)(e° 40x, -3.35 + 1.01 for 0 < x; < 0.55 (2-18) the ati

and
2
Tt/T' = (Tb/Tb - 1) (e6. 35xr- ;.38) - 0.418x, + 1.256 If SI'2
for 0.55 < x, < 0.925 (2-19) tion 2-C
paraffi j>-
For estimating cricondenbar temperatures , Grieves and Thodos (1963) sug (highly,
gest the following equations: have b,
Watson,
Tp/T' = (Te/ Tb - 1) (e4.33x ,- 3.62) + 1.008 for 0 < x, < 0.7 (2-20) Riazi a
Thus'
and specif le
reliable.
t
Tp/T' = (Tb/ Tb - 1)(e6.33xc -5.14) - 0.165xí + 1.116 can b ¿L.
for0. << x,<0.925 (2-21) 11

where Tt = cricondentherm temperature of the mixture, °R

Tp = cricondenbar temperature of the mixture, °R
T' = pseudocritical, pseudocricondenbar, or pseudocriconden-
therm temperature, whichever applicable, of the mixture, °R
Tb = normal (atmospheric) boiling point of the mixture. °R
 Phase Behavior Fundamentals 35

Th = molar average boiling point of mixture, "R

x¿ = mole fraction of low-boiling component

The calculation procedure is quite tedious. The mixture composition,

pure component critical temperatures , and normal boiling points are re-
quired . Values for Tb can be calculated using a mixing rule, or obtained
from laboratory measurements . One proceeds by taking two successive com-
ponente , calculating their Tt and Tp values , then adding one component at a
time and calculating the Tt and Tp values for this new mixture until all the
components have been included. Crieves and Thodos ( 1963 ) repon maxi-
mum errors of less than 5 % in cricondentherm , but significantly larger er-
rors up to 13 `,ro for cricondenbar temperatures . Such a correlation is difficult
to use , and the results are not very reliable.

Critical Point

\iany different studies have focused on the problem of characterizing hy-

drocarbons for predictions of their physical properties . Watson and Nelson
:,193:3) and Watson et al. (1935 ) characterized the chemical makeup of pe-
troleum mixtures using the boiling point and specific gravite. Thev defined
the Watson characterization factor, K, as follo vs:

K = TI?-31 1 -í

If SI units are used , with Tb in K (Kelvin ), the right-hand side of Equa-

tion 2-6 should be multiplied by 1.21644 (= 1.81 '). K defines the relative
paraffinicity of a hydrocarbon fraction. A typical range would be from 10.0
highly aromatic ) to 13 . 0 (highly paraffiníc). Several useful relationships
^^ave been found using the Watson characterization factor (for exarnple,
Watson et al ., 1935; Smith and Watson, 1937; Simon and Yarborough, 1963:
Riazi and Daubert , 1980; Whitson, 1983).
Thus , physical property correlations based upon the boiling point and
specific gravite have been used for a long time. and have proven to be very
reliable. Different correlation parameters have been proponed . iost of these
can be expressed using the follow-ing generalized equation:

9 = aTg y° (2-23)

where 8 = the property

Tb = normal or cubic-average boiling point, °R
-y = specific gravity at 14 .7 psia and 60°F
 O
O
36 Gas Production Engineering

For critical pressures and temperatures, the constants a, b, and e, deter-

mined bv Riazi and Daubert (1980) and Whitson (1983), are as follows:
If b `
B a b c gion.
Te5 O R 24.2787 0.58848 0.3596
pc, psia 3.12281 x 109 - 2.3125 2.3201 for Tb < 850°R Botl-^f,
p, psia 2.41490 x 1014 - 3.86618 4.2448 for Tb > 850°R
'An effi -
The maximum deviations viere found to be 10.6c7(, 9.3%, and 13.2%, re- alterna1-
spectively, for these three cases (Whitson, 1983). ture (off,
point c,
Bubble-Point and Dew-Point Curves curve.

The bubble point may be defined as the p,v.T condition at which an all-
liquid system releases the first (infinitesimally small) drop of gas, signaling
the entre into the two-phase region. Thus. at the bubble point, the total
mixture composition. {z;}, is just equal to the liquid composition, {x;}. Since
1. C iD
the sum of the mole fractions equals unity, it is clear that for the gas phase
b
released at the bubble point, gin= 1 v; is equal to 1.0. and in all regions where
2. N
gas is not present, this sum will be less than 1.0. Thus, at the bubble point:
(a

n n n
(
K ;x; =v K;z;=1.0 (2-24)
i=1 i =1 i =1
G:P
3. Vx
At the dew point, the appearance of a liquid phase just begins for an all- i' )c
vapor system. The system composition, {z;}, is equal to the vapor composi- 4. P y'
tion, {y¡}. Also, for the just released liquid phase, the sum of the component
mole fractions equals unity. Therefore:

n n
x; _ y;/K; _ z;/K; = 1.0 (2-25)
s=1 ^=1 ^=1

Equations 2-24 and 2-25 can thus be used to predict the bubble-point and
dew-point curves, provided K-values are known for all the components as a f
function of pressure and temperature. A tvpical procedure would involve
calculating the quantities 1 K;7, and 1 z;/K; at different pressures and
temperatures. The state of the system can be determined by applying the
following rules that are true for vapor-liquid systems:

Ti E°=1 K;z; < 1.0, the system is single-phase all-liquid.

 Phase Behavior Fundamentals 37

deter- If En, 1 zi/Ki < 1.0, the system is in the single phase all-vapor region.
:ows:
n
If both i= 1 Kizi and E;'= 1 z,iK¡ > 1.0, the system is in the two-phase re-
gion.

350°R Both EP'_ 1 Kiz, and E ;'=1 zi/Ki 1.0.

350°R
'An efficient procedure to predict a bubble point is to find the pressure (or,
% , re- alternatively, the temperatura) at which E;'= 1 Kizi = 1.0 at a gven tempera-
ture (or pressure). A series of such points would then constitute the bubble-
point curve. A similar procedure can be used to reconstruct the dew-point
curve.

á,anall-
á_gnaling Questions and Probiems. -
_-¡e total
. j . Since
1. Given the pressure and temperature, is it possible to specify the num-
s phase
ber of phases for: (a) water, and (b) a mixture of alcohol and water?
where
2. Mame the tupe of phase diagram required for the following cases:
point:
(a) a single-component fluid being used for heat transfer in a nuclear
reactor.
(b) a two-component gas being compressed for storage as liquid.
(2-24) (c) a multi-component gas to be transported in a pipeline.
(d) design of an oil-gas separator.
3. What is the state of a substance at: (a) its critical point, and (b) aboye
ranall-
its critical point?
:omposi- 4. Define fugacity. Show that the fugacity of a substance must be equal in
-Iponent all phases in which it may exist at equilibrium.
5. Construct a p,T phase diagram for the following mixture:

Component mole % Tb, °F

(2-25)
C1 65 -258.7
CI, 20 -127.5
-int and C3 + 15 96.9
ents as a
involve Assume the C3 + fraction to be identical to n-C.5. The required hydro-
ares and carbon equilibrium ratios (K-values) can be taken from Figures
ing the 4-25 through 4-51 in Chapter 4.
6. From the phase diagram constructed in problem 5, determine the cri-
condenbar and cricondentherm temperatures. Compare these with
the ones obtained using Grieves and Thodos' relationships.
38 Gas Produetíon Engineering
3

References

Campbell, J. M.. 1984. Gas Conditioning and Processing. Vol. 1. Campbell

Petroleum Series. Norman, Oklahoma. 326pp. po,
Grieves. R. B. and Thodos. G., 1963. "The Cricondentherm and Cricon- 0
denbar Temperatures of Multicomponent Hvdrocarbon M\Mixtures." Soc.
Pet. Eng. J. , 3(4. Dec.), 2877-292.
Riazi. M. R. and Daubert, T. E.. 1980. "Simplifv Property Predictions."
Hydr. Proc.. 59(3. March), 115-116.
Simon, R. and Yarborough. L., 1963. "A Critical Pressure Correlation for 3
Gas-Solvent-Reservoir Oil Systems," J. Pet. Tech., 15(5. Mav). 556-560. 1,

Smith, R. L. and Watson, K. M.. 1937. "Boiling Points and Critical Proper- 71
ties of Hvdrocarbon Mixtures," Ind. and Eng. Chem.. 29(12. Dec.),
1408-1414.
Stalkup, F. 1.. 1978. "Carbon Dioxide Miscible Flooding: Past, Present, and
In de
Outlook for the Future," J. Pet. Tech.. 30(8, Aug.). 1102-1112.
a compí
Stalkup, F. 1.. 1983. Miscible Displacement. Volume 8, SPE Monograph Se-
search A
ries. Societv of Petroleum Engineers, Richardson, Texas. 204pp.
fluid p,)
Watson. K. M. and Nelson, E. F., 1933. "Improved Methods for Approx-
cant at")
imating Critical and Thermal Properties of Petroleum Fractions," Ind,
gas anca
and Eng. Chem., 25(8, Aug.). 880-887.
for imj'b
Watson, K. M.. Nelson, E. F., and Murphv. G. B.. 1935. "Characterization
charts ,
of Petroleum Fractions," Ind. and Eng. Chem.. 27(12. Dec.). 1460-1464.
equatic
Whitson. C. H.. 1983. "Characterizing Hvdrocarbon Plus Fractions." Soc.
wherea
Pet. Eng. J., 23(4. Aug.), 683-694.
v

Allfl
conditiú:
are con)
tially c
mole b.)