.

SPE/DOE
Socloty
of
Potroloum
Enghrows
U.S.
Dopartmosst
ofEnergy

SPE/DOE 14926

Prediction of Vapor and Liquid Viscosities From the

Lawal-Lake-Silberberg Equation of State
by AS. Lawal, Standard Alaska Production Co.
SPE Member

Copyright t986, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE/DOE Fifth Symposium on Enhanced Oil Recovery of the Society of Petroleum Engineera and the
Department of Energy held in Tulsa, OK, April 20-23, 1966.

This papar was selected for presentation by en SPE Program Committee following review of information contained in an abslracf submi!led by the
author(a). Contents of the peper, aa presented, have not bean reviewed by the Society of Pelroleum Engineera and ara subject to correction by fhe
author(a). The material, as presented, doea not necessarily raflect any position of the Society of Petroleum Engineers, ita officers, or membars. Papera
preaenfed at SPE maetings are subject to publication reviaw by Editorial Committees of the Society of Petrofeum Engineers. Permission to copy is
restricted to an abstract of not mora thafl 300 words. Illuetrafions may not be copied. The abstract should contain conspicuous acknowledgment of where
and by whom the papar is presented. Write Publications Manager, SPE, P.0, eox 833836, Richardson, TX 75063-3636. Talex, 730989, SPEDAL.

ABSTRACT
-— computed viscosities Eor several binary,
aulticomponents, natural gases and complex
systems resulted in an average absolute
A difficulty in mode1ing multicontact deviation of 3.5%. The extension of the
miscibility processes Is achievement of mixing rules to predictions of reservoir
consistent, stable convergence of gas and oil viscosity was generally within ~8’kof
oil phase compositions, densities, and the experimental values. Extensive
viscosities as the critical point is comparisons of the LLS viscosity equation
approached. The use of an equation of with other methods OE predicting reservoir
state offers the advantage of a single? oil viscosity are made and found to be
consistent source of calculating K-values generally superior in ease of use and in
and phase densities. The criterion of accuracy.
stable convergence viscosity in the
vicinity OE critical regions is not often The prediction of vapor and 1iquid
met without fine tuning with laboratory viscosities from the LLS equation of state
data as phase viscosity correlations are makes the present work very attractive for
usually developed independentof each other. compositional reservoir simulators and
other applicationswhich are repetitive in
The present study extends the van der Waals nature. The use of an equation of state to
model to viscosity by drawing an analogy predict phase viscosities offers an
between the graphs of PVT and PI,IT.Vapor opportunity to make calculations in the
and liquid viscosities based solely upon critical region without the computational
pure component critical data and acentric problems commonly associated with that
factor were derived from the effort. The internal consistency and the
Lawal-Lake-Silberberg (LLS) equation of convergence of vapor and liquid viscosities
state for methane through eicosane, at the critical point have heretofore been
i-butane, neo-pentane, carbon dioxide, and unattainable.
nitrogen. The 6718 experimental data used
cover a range of temperatures from -183*F
to 482°F and pressure up to 20,000 psia. INTRODUCTION,
FOr the twenty-four components, the average
absolute deviation of the predicted
viscosities from experimental is 5.9%. A The - possibility of correlating gas and
mixing rule which relates mixture liquid viscosities with the van der Waal!s
parameters to composition and pure equation of state was reported in 1912 by
component constants is proposed and Phillipsl, when he noted for the first
comparisonsof 9,000 experimentaldata with time that the graph of temperature versus
viscosity is similar to the graph of
Referencesand illustrationsat end of paper.
.

AQ
.“
 .

2 PREDICTIONOF VAPOR AND LIQUID VISCOSITIESFROM THE LAWAL-LAKE-SILBERBERGEQUATIONOF STATE SPE 14926

pressure against specific volume. But it (b) development OE the constants in the
was not until Little and Kennedy2 used Sakin equation for paraffin hydrocarbons
the van der Waals equation to predict heavier than n-butane15, (c) graphical
viscosity of reservoir oils that the idea approach similar in concept to Uyehara and
of Phillips was thoroughly tested. This Watson16~17$18, and (d) methods based on
initial attempt by Little,3 although equations of state.2~13 We set out to
useful and effective, cannot supply the construct viscosity models of Type (d)
needs of today’s petroleum industry because using the previously established technique
the regionally fitted functions of of Lawal.13 Therefore, the prime
temperature, pressure and composition have objective of this study was to usa the
no provision for reliable prediction of LaWal-Lake-Silberberg (LLS) equation of
vapor viscosity. Thus, like othar proposed state (EOS) to develop viscosity models
viscosity equations,4 the correlation of suitable for describing the dependence of
Little has no continuous transition from viscosity on temperature , pressure, and
liquid to gas state or vice versa and has composition for pure substances as well as
inevitably been limited to predicting their mixtures.
liquid viscosity.
In this work, using over 15,718
Beginning with the experimental studies experimental viscosity data points in the
reported by Phillips, investigatorsof the literature from pure components,
vapor-liquid viscosities behavior multicomponont, and ccmplex hydrocarbon
discovered the same tendency displayed by systems, vapor-liquid viscosities were
the plot of pressure versus spacific predicted with the LLS EOS. The
volume. The studies of Schroer and experimenti~lpure components data range in
Becker5 show the presence of a horizontal temperature from -1S3°F to 482’F and in
inflection on a temperature - viscosity pressure up to 20,000 psia. For
plot at the critical point of an inorganic twenty-four cc+nponentsof dilute viscosity
compound, ethyl ether. The experimental to dense gas consisting of normal paraffin
works reported in 1964 by Starling et hydrocarbons frcm methane through eicosane,
al.6 demonstrated the T-v graphs of i-butane, neo-pantane, nitrogen and carbon
saturated vapor-liquid viscosities of dioxide the average absolute percent
paraffin hydrocarbons consisting of ethane, deviation (AAPD) of the predicted
propane, and n butane displayed the same viscosities from experimental is 5.9%. A
phenomenon as orthobaric densities of these mixing rule which relates mixture
components. By using the Law of parameters to composition and - pure
Rectilinear Diameters, Starling7 component constants was found to give very
estimated critical viscosities of those good results for several binary, ternary,
components, thus suggesting the prasence of multicomponents,natural gases, and complex
horizontal inflection points on the SYSterns. The predicted mixture viscosities
critical isobar of the components. In were genarally within 3.5% of the
spite of the fact that the characteristic experimental values. The extension of the
behavior of vapor-liquid viscosities is mixing rules to predict viscosity of
analogous to the thermodynamicequations of reservoir oils was generally within ~8% of
state, the idea of Phillips has received the experimental. The application of this
less attention in the field of viscosity work was demonstrated by predicting
prediction than the method by Enskog. Ever viscosity of reservoir fluids at reservoir
since EnskogB showed the et~ocl. of temperatures and pressures, as affected by
density on viscosity in h~s 1917 the addition of miscible Enhanced Recovery
dissertation, nearly all empirical methods agents. Moreover, because numerical
developed to date and fitted to viscosity stability and reliability of compositional
data were tailored 9,10,11 to include studies conducted at pressures and
density as a correlating parameter. temperatures near tha critical point of
Consequently, correlations based upon tha hydrocarbon systems depends upon the use of
approach of Enskog warrant judicious a consistent set of correlations to
selection of density correlations. determine liquid and vapor properties, this
sl.udywas extended to predict vapor-liquid
Numerous attempts to develop a satisfactory viscosities of criticai composition fluids
mathematical description of the viscosity ranging from gas-condensate to black oil
phenomenon have been reported,12 but they systems.
have ❑et with only partial success. These
attempts which are revi@wed by Lawa113
have taken four approaches: (a)
development of the constants for the t pe
of equations similar to Thodos et al.14,

AA
SPS 14926 AKANNI S. LAWAL 3

RRVIEW OF PREVIOUSLYDEVRLOPED CORRELATIONS In 1966, Little and Kennedy2 correlated

viscosity of reservoir oils by drawing an
analogy with the van der Waals (VOW)
Methods Eor predicting viscosities of vapor equation of state. They fitted the
and liquid range from rnathematicall constants in the.VDW SOS to the viscosity
rigorous12 to completely empirica12i data of methane through n-hexane and
with all methods having some degree of nitrogen for the paraffin hydrocarbons and
success. Attention will be focused here nitrogen; an AAPD of 1.9% on 1006 data
only on those correlationswhich have been points was reported. But, contrary to the
applied to predict reservoir fluids theoretical understanding of cubiC
viscosities; an extensive discussion of equations of state, the minimum real root
other methods are provided elsewhere.13 always gave them the best results for
mixture liquid viscosities. One drawback
A major graphical correlation of viscosity of their work is that the coefficients of
based on the tabulations prepared in 1940 the equation are not continuous with
by K. M. Watson appeared in the 1944 respect to pressure. It is therefore not
National Petroleum News.16 viscosity surprising that a completely different
charts were presented for reduced pressure function was reported for complex
up to 30 and reduced temperature of 5. mixtures. Nonetheless, their approach
Similar charts were later developed by Carr shows that some form of VDW model can be
et al.17 Dempsey25 Eitted polynomial adapted to representviscosity behavior.
functions to data points read from these
charts, but the functions have some Ely and Hanley24 presented an extended
disadvantages.21 Nevertheless, the corresponding state for viscosity and
functions provided a computerized source thermal conductivity of. non-polar pure
for predictingviscosityof reservoirgases. fluids and their mixtures. Their model,
which covers a large range o! PVT states,
The Thodos type of equations14 which requires critical parameters, Pitzer’s
relate viscosity to a fourth degree acentric factor and shape factor of pure
polynomial in the reduced densit
al,l{ form the component as input. By using improved
basis of Lohrenz et liquid methods of obtaining mixture properties for
viscosity correlation that has been the pure canponents, a better accuracy was
enjoying great acceptance and application achieved for viscosity (AAPD of 7% was
by engineers. Because this ❑ethod is reported for the pure components and
rather fast (using a digital computer) and mixtures). Pedersen et al.22 has studied
scnnewhatmore easily tuned to experimental Ely and Hanley method and reported
data in comparison to the other methods non-convergence of shape factor for
available, it received a rapid and multicaaponent systems. However, the
widespread acceptance. However, certain tedious way of predicting viscosities
limitations were required in using Lohrenz through a rather complicated function was
et al. correlation. HacDonald13 reported unchanged, although some improvements were
inconsistent vapor-liquid viscosities from made at the expense of the range OF
the correlations as the critical state of applications.
multicomponent mixtures is approached.
Saeedi and Rcwe4 showed unreliable Probably the first attempt at a general
prediction of vapcx viscosity and correlation of vapor-liquid viscosities as
non-convergence of viscosity at the functions of pressure, temperature, and
crl.tical temperature and pressure of composition for pure substances as well as
mixtures for reservoir fluids ranging frcm their mixtures was made by., Lawal.13
gas-condensate to black-oil systerns. Although, in this exploratory study, no
Pedersen et al.~2 recently reported that popularly known equation of state was used
the accuracy of viscosity predicted frcm to derive the viscosity equation, the
Lohrenz et al. correlation depends on the attempt established the characteristics of
density correlations employed. Lawal13 an equation of state which are necessary
showed that the lack of continuous and sufficient to explore any BOB for the
transition from liquid to gas state or vice prediction of viscosity behavior. The work
versa leads to non-convergence of liquid reported In this present study was
and gas viscosities at the critical point essentially based on the success of the
of pure ccsaponents as well as their previous approach of Lawal. Thus, after
mixtures. Therefore, the Lohrenz et al. the LLS EOS is presented, the design of the
correlation has generall been recommended LLS viscosity equation will be discussed.
for liquid viscosity4~2 I and the method
by Carr et al.l_f or Lee et al.zs has

received much attention for gas

viscosity.4

Vil
 4 PREDICTIONOF VAPOR AND LIQUID vIsc~ITI~ FR~ THE ~wAL-~KE-s~LB~B~G EQUATION OF STATE SPE 14926

Q . Zc% - 1)3 + 2Q2ZC+ Q(1 -3ZC) (lo)

THE LAWAL-ME-SILB~B~ EOUATION OF STATE d Zc
.,
A summary of the Lawal-Lake-Silberberg
(LLS) e,quationof state’”ispiesented here
for convenience. The details of the Y(TR,u) = [1 + K (1 - TR1/2)]2 (11)
development and the application in
reservoir fluid systems are given
elsewhere.13~26 Where

The LLS equation has the form

. 0.14443 + 1.066240 + 0.0275602 - 0.180;4w3 (12)

p=wb--v@&f#qjp (1)

The mixture parameters used in Equations 1

Equation 1 can be rewritten as and 2 are defined by the mixing ruIes

23 - [1 + (1 -@)B]Z2+ [A-aB- (f3+m)B2]Z

- [AB- B(B2 + B3)] = O (2)

Where
(15)
A=z (3)
R2T2
am = ~ \xixj(l -kij) ail/2aj1/2 (16)
(4)

Applying Equation 1 at any temperature we The expressions for the Eugacity of pure
have components and for a component in a mixture
are given elsewhere.26 The
distinguishing feature of the LLB S0S is
the limiting critical volume Q which was
a(T) = Qa R21’c2 Y(TR,w) optimized for the individual component by
(5) using the established experimental values
Pc
of Tc, Pc, and Zc. Consequently, the
LLS S0S yields the correct Zc at the
(6) critical temperaturesand pressures of pure
substances and gave significantly better
results in the critical regions than any
S0s which has an assigned (fixed) Zc for
all substances or extrinsic Zc
Where correl?iew .13 The optimized values of
Q and the two coefficients in the
attractive pressure term of Equation 1 for
some hydrocarbon, non-hydrocarbonand polar
components are given in Table 1. The
Qa=[l+(s2- 1)ZC]3 critical properties and acentric factor are
(7) obtained from the tabulation of Reid et
al.27 Note that Rquetion 1 through
Q= b/Vc Equation 10 reduce to the PR EOS for = =
2, 8 = 1. It can also be deduced for this
case that Zc = 0.3074 and Q = 0.2531.
Qb=Qzc (8) Similarly for BRK sos we find e =1, 8 =
O, Zc = 1/3, Q = 0.25991 and for VW
a= 1+($2- 3)ZC Eos a = o, 6 = o, Zc = 3/8, Q = 1/3
(9) end a = a(T).
QZc
SPE 14926 AKANNI S. LAWAL 5

Figures 1 through 8 show comparisons of where a, b, a, 13 are constants and b(T)

predicted orthobaric densities and vapor and C(X) are functions of temperature.
pressure with experimental data 28’29 of Equation 17 takes the same form as the LLS
polar and non-polar substances. It can be S0S with the exception that the positions
seen from these figures that the equations of T and P have been reversed and C(A)
of state yield acceptable values of vapor has replaced the universal gas constant R.
pressure and saturated vapor densities; the For large values of viscosities, Equation
LLS Eos gave the best orthobaric densities 17 reduces to the family of rectangular
which are internally consistent with the hyperbolas each of which approaches the
critical behavior of the pure substances. line w = b(T) as an asymptote.
The experimental data of Figure 2 was used Consequently, two constraints are
as implicitlybuilt into the repulsive term of
COM#&%r:% S:: E~;?iRob~~;3fhou$ Equation 17, namely, the prediction of
liquid density values predicted from the liquid vlscoslty and gas viscosity which
SRK EOS are generally lower than increases with temperature at. low
experimental data except for small pressures. In contrast to the LLS EOS,
molecules26 like nitrogen, hydrogen the co-volume b is a constant at all
sulfide, and methane, both SRK and PR temperatures and pressures. Equation 17
equations generally predict lower liquid can be rewritten in the reduced coordinates
density for polar substances. The poor giving rise to the functional form
predictions of liquid density from PR and
SRK equations is a consequence of the
f(PR, UR, TR) = O (18)
prescribed number for $2 and the
assignment of a convenient value for
critical compressibility factor Zc which which forms the basis of the Law of
inevitably result in large deviations corres onding states for Viscosity
between 1iquid density data and the charts!6*17 and correlations.27*33
equations of state at temperatures and Therefore, the hypothesis implied by
pressures near the critical state. Equation 17 may have sane theoretical
However, the prediction results of the LLS reasoning attributed to it. As of now,
EOS in Figures 4 through 8 suggest that the there is still a discrepancy between the
co-volume should be a function of theoretical understanding and practical
temperature instead of being independent of behavior of vapor-liquid viscosities. The
temperature as in most van der Waals type discrepancy in the theoretical
of model. understanding of gas-liquid viscosities has
been summarized by Brush12 who also
Based on its general applicability to any reviewed 584 references on liquid
component with its high-pressure Vistmsity. He concluded that there is no
density26 and saturated liquid density general agreement on whether viscosity is
predictions which are more satisfactory essentially due to attractive and repulsive
than those of other equations of state, the forceslz although the experimental data
LLS EoS was chosen to design a correlation, reported for pure substances32~33 as well
suitable for describing the dependence of as for mixtures of components34~35 do not
viscosity on temperature, pressure, and preclude this possibility. Evidently, sane
ccinposltion. The success of acccxnplishing theoretical basis exists for this
this task will be described In the next possibility.
section.
We determined the parameters of Equation 17
by comparing the expansion of
DESIGN OF THE LLS VISCOSITY EQUATION
(v - )1~)3 (19)
The objective is to design a functional
form of equation for vapor-liquid viscosity with the expansion of Equation 17 at the
behavior based on the similarity in the critical pOlnt where P = PC. T = Tc,
graphs of PVT and TMP. In an effort to . c(h) = c; the
P Mc and
make the viscosity relationships simple, relationship between a and B is thereby
only third order equations were considered established for any desired @ frcm
and the parameters of the equation were Equation 20.
llmited to the critical and physical
properties of pure substances. We propose
a cubic equation of the form

*-3 - 3*-2+ 3(B -a)@-l - (az + 8 - a~) = O (20)

T = C(A)P .- a (17)
P - b(T) p2 + abp - i3b2

-.,
A7
 6 PREDICTIONOF VAPOR AND LIQUID VISCOSITIESFROM THE LAWAL-LAKE-SILB~BmG EQUATION OF STATE SPE 14926

where $ = b/pc The temperature Eunctions OE Equation 17

were determined by the previously used
techniques13as
The dimensionless viscosity * OE a
component can be selected to establish the
best values of a and 13 OE Equation 17 b(T) = b(Tc) EXP[S(mR - 1)1 (25)
which minimize the sum of the absolute
deviations in the predicted vapor-liquid c(k) = C(TC)[l + q(~R - 1)]-2
viscosities and experimental data. But (26)
because OE the similarity in the graphs or
PVT and TIIP, it is easily shown that the
dl.mensionless volume Q is a good In Equations 25 and 26 s and q are
approximation Eor @. Nevertheless, the characteristic constants of each pure
values of o OE Equation 20 that component examined. These constants have
minimized the errors in the gas-liquid been correlated against molecular weights
viscosities of ethane, propane and n-butane (%) and acentric factors (u). The
were close to the values established in resultingequations are
Table 1 for Q of the same components.
Therefore, e and 13 were obtained from
Equations”9 and 10 respectively and the S = 2.29405 + 0.01939 ~ - 6.0198-4 %2 (27)
other parameters established at the
critical point for Equation 17 are given as + 6.21868u - 0.17323w ~
follows
I
q = 0.89739 + 0.00726~+ 7.277E-4~ 2
PCTC (28)
C(TC) =— (21)
4.21440 + 60.8445u2 - 0.4025w~
z&c

~C(Tc) Pc (22) A good approximation for the function b(Tl

b(Tc) =
Tc is the dilute gas viscosity of pure
components. Figure 9 shows a great success
in predicting the effect of temperatureon
QaC(Tc)2 PC2 gas viscosity of some components which are
a(Tc) = (23)
not used in the regression of Equation 27.
Tc
The corrector factor C(A) is a
monotonically decreasing function of
temperature and pressure that was
backed-out of Equation 17 using
The coefficients % and $la in experimental viscosity of pure components
Equations 22 and 23 are derived from frcm dilute to dense gas reported at
Equations 7 and 8 of the LLS Eos. Notice various temperatut.?s
and pressures.
that the positions OE the critical
properties have been reversed from those of The mixture viscosity equation is
Equations 5 and 6 and the universal gas representedby Equation 29.
constant R has been replaced by the
parameter C(TC). The critical viscosity
in lieu of experimental values is given by T_ ~P Am (29)
-— -
— the empirical correlation reported by P - b(T)m 112+ ~bmv - ~bm2
Uyehara and Watson16 as

Where ~ bm, ~, ~, and 8M are

7.7 #-F$#P#3 mixture parameters. The mixing rules for
Mc = (24) use with these parameters were established
Tel/6 by <he trial-and-error techniques
previously used to develop characteristic
viscosity equation.13 The mixing KUleS
where ~ is the molecular weight of a are defined by
component, Pc Is critical pressure in
atmospheres and T= is in degrees K. The
prediction of critical viscosities Erom (30)
Equation 24 is within about 2% of the
experimentalvalues.13 i

(31)

4a
 SPE 14926 AKANNI S. LAWAL 7

xi -n (c) For all temperatures greater than the

z~
b(T)m =
[ b(T)i
l/n 1 n=9 (32) critical regardless of the prevailing
pressure, choose the maximum real rod
if three unequal roots are obtained.

cm = : ; xixjeij (d) Complex roots and roots less than

(33) function b(T), including negative
roots, obtained from Equations 17 and
29 have no significant meaning and
should be discarded.
eij= (1 - 41j) a(Tc)i1/2 a(Tc)jl/2 (34)
(e) For any ❑ixture of components, the
composition of vapor will correspond
to the smallest root (greater than
The mixing rules for ~ and ~ are b(T)m) being selected while the
the same as those of Equations 13 and 14 of liquid composition results fnxn the
the LLS EOS. In Equation 34, dij is an maximum real root from Equation 29.
empirically determined binary interaction Any condition of temperature,
coefficient characterizing the binary pressure, and composition which
formed by components i and j. In this results in only one real and two
study, &ij is calculated from ccxaplex roots automatically
detet~i.nes that the real root be
chosen.
6ij = Iwj -Qil (35)
VAPOR AND LIQUID VISCOSITIES PREDICTIONS

NO attempt is made at this time to optimize

&ij for every binary system. Table 2 shows a s-ry of the prediction
results from paraffin hydrocarbons of
methane through eicosane. including
CRITERIA FOR VISCOSITY SELECTION FROM i-butane, neo-pentane as well as
EQUATIONS 17 AND 29 non-hydrocarboncomponents such as nitrogen
and carbon dioxide. The sources of
experimental data are provided
The viscosity Equations 17 and 29 are cubic elsewhere.13 The pure components
so that for any given temperature and critical properties are obtained from the
pressure there are three values of tabulations of Reid et al.27 and
viscosity which satisfy the equations. The Kudchadker et al.36 These critical data
first criterion in selecting gas viscosity are shown in Table 1 along with the
is to compare the roots of Equation 17 with previously establishedls~40 values of
the value of Eunction b(T), Equation 25. Q, the limiting critical volumes. Not ice
Any root smaller than b(T) is rejected that these limiting critical volumes also
since b(T) represents the asymptotic value suffice for the limiting critical viscosity
of viscosity. The Eollowing rules are used A in Equation 20.
with Equations 17 and 29 Eor pure
substancesand mixtures: Figures 9 through 14 show gas-liquid
viscosities prediction for dilute gas, pure
(a) In the gas region, as indicated by the components, and binary systems. The
fact that the pressure is less than prediction results shown in these figures
the vapor pressure at the prevailing are excellent but the estimated two phase
-. temperature, if three real unequal envelope shown as dashed lines in the
roots are obtained, choose the Eigures are not computed values. They
smallest root greater than function serve only as illustrations of the
b(T). saturatedvapor and liquid viscosities.

(b) In the liquid or dense gas region, as The sources of binary and multicomponent
indicated by the pressure being systems are reported elsewhere.13
greater than the vapor pressure at the
prevailing temperature, choose the
maximum of the roots when three real
unequal roots are obtained.

All
8 PREDICTIONOF VAPOR AND LIQUID VISCOSITIESFROM THE LAWAL-LAKE-SIL8ERSERGEQUATION OF STATE SPE 14926

RESERVOIR FLUIDS VISCOSITY PREDICTION Where w Is the acentric factor predicted

from the Lawal et al.38 correlations.
Equation 37 is also used to predict
The prediction OE reservoir oil viscosities pseudo-ccaponent Zc which is necessary to
presents a diEEerent problem from those of ccapute the parameters of Equation 29
binary and multiccmponent systems. The without imposing any restriction on the
problem 1s being able to characterize the nature of the heavy fraction in the complex
heptanes-plus pseudo-component fraction in mixtures. The limiting critical volume of
the ccmplex systems. Moreover, the the pseudo-components is estimated from
critical properties as well as acentric 13 Equation 38.
factor are required for this
pseudo-component. The pseudo-component
critical properties and acentric factor are f2f= 0.356473 - 0.0450320 - 0.195031w2 (38)
predicted from Lawal et al.38
+ 0.337453W3
correlations and the results are tabulated
along with the viscosity prediction shown
in Tables 3 through 5. The critical
properties and acentric factor predicted A total of 260 data
from the Lawal et al.38 correlations were complex systems sources3~~;in~ref;j’d ‘~
also used In the other viscosity an AAPD of.8.4% resulted. The worst errors
correlations, namely, Little and occurred with low molecular weight
Kennedy,2 Lohrenz et al.,lg Lee et fractions where the prediction results from
al.23 and the Quarter-Power Mixing Equation 29 are generally within 9-12% of
Rule13 method which is illustrated in the experimental values. The prediction
Equation 36. results for various types of reservoir
fluids are sununarizedin Tables 3 through
s. It is noteworthy that the prediction
results frm Equation 29 are far better
‘m ‘[~t“l-4 (36)
than those from the correlations of Little
and Kennedy, Lohrenz et al. and Quarter
Power Rule. The Quarter Power Rule
surprisingly predicted better results for
In Equation 36, xi represents the pure reservoir gases than the method by Lee et
component composition and pi and pm al.55, but gave worse results for
represent the viscosity of pure substance reservoir oils. For crude oil systems
and mixture respectively. shown in Table 5, the LLS viscosity
Equation 29 predicted higher value than the
The pure component viscosity required in experimental viscosities. The temperature
EqlJiJ1.iOIJ 36 iS derived from the LLS function b(T) is responsible for this type
viscosity Equation 17 using all the of behavior. At the present time, no
parameters specified by Equation 17. since attempt is made to derive new temperature
the heptanes-plus fraction is treated as a Eunctions for heptanes-plus fractions.
pseudo-component without splitting into However high viscosity values should be
macro components, we require adequate expected from Equation 29 for reservoir
method of predicting critical fluid systems having heptanes-plus
compressibility factor of the fraction. Fractions with molecular weights in excess
After testing the two methods commonly used of 350.
to
factor,!?$~$~ctthe ‘~ethodfr~u,gges~~ntr~
Rowlinson52 predicted the Zc of THE CONVERGENCE OF MHTURE VISCOSITY
hydrocarbons, non-hydrocarbons as well as !xx!?mQQ!
polar compounds within an error OF ~ 1.5%
and it is very consistent with the trend of
critical compressibility Eactor with the In this section we explore the consistency
molecular weights of pure substances. and the convergence of the viscosity
Therefore, the Equation 37 suggested by Equation 29 which is developed for mixture
Rowlinson was used to predict Zc of of components. In order to predict phase
heptanes-plusfraction. viscosity from Equation 29, the composition
of the vapor and liquid phases at
equilibrium temperature and pressure are
required. These phase compositions were
obtained from the LLS SOS by flashing the
Zc . 0.293 (37) overal1 critical composition at fixed
1 + o.375al critical temperature,but at several values
of pressures up to the critical pressure of
SPE 14926 AKANNI S. LAWAL 9

the system. The same equilibrium phase correlationswhich are usually subjected to
compositions obtained through the LLS EOS pressure and temperaturerestrictions.
were used to predict phase viscosity in all
the viscosity correlations presented for As a general rule, no restriction was
comparison with Equation 29. The COMpleX imposed, on the nature of the heavy
mixtures used in this study were selected fraction in the complex mixtures or pure
from Saeedl and Rowe4 which are based on substances, but whenever improvements are
the critical data tabulated by Fair.37 needed fcr any component or system, it is
‘the gas-condensate critical composition recommer,iedthat the parameter C(X) and
fluid reported by” Jacoby and Yarborouqh56 Functian b(T) of Squatione 25 and 26
was also used in this study. Thus, the respectively be recorrelated for the
ccmplex mixtures employed for the analysis purpcses of matching the viscosity equation
are critical at the indicated temperatures to experimentaldata.
and they also have critical pressures at
these temperatures. The prediction results The ~~lications of the internal
for all the viscosity correlations methods consistency and convergence of vapor-liquid
are presented in Figures 15 through 17 for viscosities at the critical point of pure
natural gas, gas-condensate and black oil substances and their mixtures go beyond the
systems. Although, these figures are results of this study and its
computed from hypothetical critical applications. This iS indeed only a
composition fluids because of lack of presentation of a new idea and a more
experimental saturated vapor and liquid accurate method to predict gas-liquid
viscosities data, they serve for viscosities for polar and non-polar
demonstrationpurposes only. substances. Furthermore, there is no
reason whatsoever that negates the
AS can be seen Ercm Figures 15 through 17, possibility of using the same method to
none of the published viscosity obtain correlations for thermal
correlations converge at the critical conductivities of gas and liquid. It ‘is
pressure of these systems. on the other noteworthy to mention that when the thermal
hand, Equation 29 predicts continuously conductivity equation is reported, the
smooth gas-liquid viscosities, and the dimensionless numbers which are often
phase viscosities converge continuously at necessary in the design OE pipelines and
the critical points cf these complex oil field separatorsare tractable.
systems. This achievement of a stable
convergence of viscosity is the ultimate
goal of the application of Equation 29 in NOMENCLATURE
reservoircompositionalsimulators.

AAPD = average aboslute per cent

CONCLUSIONSAND RECOMMENDATIONS deviation
A“ constant defined by Equation 3
B= constant defined by Equation 4
A state equation presented here for c= parameter defined in viscosity
viscosity as functions of pressure, Equation 17
temperature, and composition is K= absolute temperature scale,
sufficiently reliable for many engineering degrees Kelvin
purposes. It is applicable to heptanes-plus kij = interactioncoefficient
pseudo-canponents and any pure components Mw= molecular weight
and their mixtures. Its continuity with n= number of data points
respect to gas and liquid viscosities N= number of components
qualifies the LLS viscosity equation as a P= preseure
distinct improvement over previously q= parameter defined in Equation 26
developed correlations. The internal R= gas constant
consistency of the LLS viscosity equation s= parameter defined in Equation 25
and the convergence of phase viscosity have T= temperature
heretofore been unattainable. For v= specific volume
sensitive application, its validity should x= mole fraction
always be verified against experimental z= compressibilityfactor
data and adjustmentsmade as needed.

The LLS viscosity equation can be used with

the corresponding–states viscosity
correlations which require pure-cc+nponent
viscosity in their mixing rules without
resorting to the purely empirical

-.
51
10 PREDICTIONOF VAPOR AND LIQUID VISCOSITIESFROM THE LAWAL-LAKE-SILBERBERGEQUATIONOF STATE SPE 14926

s.ubscriDts 4. Eheedi, and

J., Rowe, A. M. :
“viscosity correlations Eor
compositional Reservoir Simulator,”
a,b = coefficients of attractive and paper SPE 9642 presented at the 1981
repulsive terms Middle East Oil Technical Conference,
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E . identification of dimensionless
volume 5. Schroer, E., and Becker, G.: “Studies
i,j,k= Indtces of the Critical State V. The Behavior
m= mixture of Viscosity in the critical State,”
R= reduced state Z. Physik. Chem. (1935) ~, 178.

6. Starling, K. E., Eakin, B. E., Dolan,

Greek Letters J. P., and Ellington, R. T.:
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pressure term
characteristic constant in 7. Starling,‘ K. E.: Critical Re9ion
Equation 11 viscosity Behavior of Ethane, Propane
u . acentric factor and n-Butane, U. S. Thesis Illinois
A= constant defined in Equation 26 Institute of Technology, Chicago
$= dimensionless viscosity defined (1960).
in Equation 20
v= viscosity 8. Chapman , S., and Cowling, T. G.: ~
6 . interaction coefficient Eor Mathematical TheorY of Non-Uniform
viscosity defined in Equation 25 Gases, First Sdition, Cambridge
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of Equations 22, 23, and 38
9. Eakin, B. E.: A State Eauation fox
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ACKNOWLEDGEMENT Institute of Gas Technology, ChiCa$’o
(1962).

The author gratefully acknowledges the
assistance OE Susan M. Brown, Lorraine M.
Culbert and Norma N. Ofiu. Support was
provided by the management of Standard Oil
Production Company and Standard Alaska
Production Company to publish this paper.
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.—
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 SPE 14926 AKANNI S. LWAL 11

16. Uyehara, O. A., and Watson, K. H.: “A 27. Reid, R. C., Prausnitz, d. H., and
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Transfer, Report No. UT 71-2, Texas Data (1963) Q, 396.
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15, i971). of Gases and -s Mixtures, State
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22. Pedersen, K. S., Christensen, P. L., ?lathematicalLiterature, Moscow, USSR
‘rhomassen,P., and Fredenslund,AA. : (1959).
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Instituttet Eor Kemiteknik Danmarks “viscositiesof The methane - Propane
Tekniske Hdjskole, Denmark (June system,” Ind. Eng. Chem. (1943) &
1983). 754.

23. Lee, A. L., Gonzalez, M. H., and 35. Lee, A. L.: Viscoeitv of Liaht
Eakin, B. E.: “The Viscosity of Hydrocarbons, Honograph on AMdKiCan
Methane-n-Decane Mixtures,*’J. Chem. Petroleum Institute Research Project
Brig.Data (July 1966) ~ (3), 281. 65“, Published by the American
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Ind. F~tc. Chem. Fundam. (1981) ~ Zwolinski, B. J.: “The Critical
(4), 323. Constants of organic Substances,”
Chem. Rev. (1968) ~, 659.
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Treats Gas Viscosity as a Variable,” 37. Fair, w. B., Jr.: “The Prediction of
oil and Gas J. (Aug. 16, 1965) 141. critical Temperatures of
Rulticom90nent, Predominantly
26. Lawal, A. S, van der Lean, E. T., and ~drocarbon Mixtures, Report No. UT
Thambynayagam, R. K. H .: 76-2, Texas Petroleum Research
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Lawal-Lake-Silberberg Equation of Austin (MOV. 1, 1976).
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Condensate Phase Equilibria,” paper 38. Lawal, A. S., Lake, L. W., and
SPE 14269 presented at the 1985 SPE Silberberg, I. H.: “COrKelati- of
Annual Technical Conference and Binary Interaction Parameters,
Exhibition, LaS Vegas, September critical Temperature and
22-25.
12 PREDICTIONOF VAPOR AND LIQUID VIScOsIT~ss FR~ THE LAWAL-LAKE-SILM=BERG EQUATION OF STATE SPE 14926

pressure/Acentric r’actor Eor Heavy Ethane,” J. Chem. Sng. Data (January

FrtKXiOnS,” Paper 7C prepared for
1984 Winter National Meeting of the
A. I. Ch. E., Atlanta, Georgia, March 49.
11-14.
39. starling, K. E., Eakin, B. E., and
Ellington, R. T.: “Liquid, Gas and
Dense - Fluid Viscosity of Propane,” 50.
A. I. Ch. E. (September 1960) Q (3),
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1962) ~ (l), 33.
Lee, A. L., and Ellington, R. T.:
“Viscosity of n-Pentane in the Liquid
Phase,” J. Chem. Brig.Data (October
1965) ~ (4), 246.
smith, A. S., and Brown, G. G.:
“Correlating Fluid Viscosity,” Ind.
Eng. Chem. (June 1943) ~ (6), 705.

40. Vargaftik, N. B.: Tables on the
ThermoPhYsical Properties of Liquids
and Gases in Normal and Dissoci&ted
gtate~, second Edition, John Wiley
and Sons, Inc., New York (1963).
51. Shelton, J. L., and Yarborough, L.:
“Multiple Phase Behavior in Porous
Media During C02 or Rich - Gas
Flooding,” J. Pet. Tech. (Sept.
1977), 1171.

41. Carr, N. L.: “Viscositiesof Natural 52. Rowlinson, J. S.: “Prediction of

Gas Components and Mixtures”, Thermodynamic Properties,*’ Phase
Institute Technology,” Rauilibria and Fluid ProPerties in
Research Bull~~in N~s23 (June 1953). the chemical Industry, Sstimetion and
Correlation - Storvick, T. S., and
42. Cullick, A. S., and Mathis, M. L.: Sandier, S. 1. (Editors). ACS
“Densities and Viscosities of Sympositm’Series 60, Washington, D.
mixtures of Carbon Dioxide and c. (1977).
n-Decane from 31OK to 403K and 7 MPA
to 30 MPA,” J. Chem. Eng. Data (1984) 53. smith, J. M., and Van Ness H. C.:
~ (4), 393. Introduction to chemical Engineering
Thermodynamics, McGraw-Hill Book
43. Comings, E. W., Mayland, B. J., and Company, New York City (1975) 272.
Egly, R. S.: “The Viscosity of Gases
at High Pressures,: University of 54. Bhagia, N. S, An ECIUatiOn of State
Illinois Engineering Experiment for Condensate Fluids, Ph.D.
station Bulletin, No. 354, Urbana, Dissertation,Texas A & H UIIiVt?R5itY,
The University (1944). College Station (1967).

44. Giddings, J. G., Kao, J. Y., and 55. Lee, a. L., Starlin9, K. E., DOlaI’1,
Kobayashi, R.: “The Viscosity of J. P., and EllingtOn, R. T.:
Light Hydrocarbon Mixtures at High “viscosity Correlation for Light
Pressures: The Methane Propane Hydrocarbon systems,” A.I.Ch.E.J.
System,” J. Chem. Phys. (1966) 45, (1964) JQ (5), 694-
598.
56. Jacoby, R. H. and Yarborough, L.:
45. KUSS, z.:
E. “High Pressure “PVT Measurements on Petroleum
Research: 11. viscosity of Reservoir Fluids and Their Uses,”
Compressed Gases,” Z. Agnew Phys. Ind. Eng. Chem. (mtober 1967) X!
(1952) 4, 203. (10), 49.

46. Baron, J. D., R~f, J. G., and Wells,

F. W.: “viscosity of Nitrogen,
Methane, Ethane and Propane at
Elevated Temperature and Pressure,”
J. Chem. Sng. Data (July 1959) ~ (3),
283.

47. Carmichael, L. T., and Sage, B. H.:

“viscosity of Ethane at High
Pressures,” J. Chem. Eng. Data
(January 1963) f!(l), 94.

48. Eekin, B. E., Starling, K. E., Dolan,

J. P., and Ellington, R. T.: “Liquid,
Gas and Dense Fluid viscosity of

,——
.5A
-.
 SK 14926
TABLE 1
PARAMETERS USED IN THE LAWAL-LAKE-SILBERBERG EQUATION OF STATE
Component Tc(”R) Pc(Psia) @ Zc !2 F a 6’
Methane 343.0 667.8 .008 .289 .350 .0164 2.3149 2.6670
Ethane 549,8 707.8 .098 .285 .330 .0215 2.5417 2.7546
Propane 665.7 616.3 .152 .281 .0230 2.6195 2.9560
Isobutane 734.6 529.1 .176 .283 ::!: .0235 2.6169 2.8353
n-Butane 765.3 550.7 .193 .274 350 .0240 2.8561 3.2418
Neopentane 780.8 464.0 .203 .276 :370 .0237 2.6914 3.1876
n-Pentane 845.4 488.6 .251 .269 .345 .0243 3.0796 3.4445
n-tiexane 913.2 436.9 .296 .265 .335 .0243 3.3092 3.6148
n-Heptane 972.3 396.8 .351 .263 .315 .0243 3.5469 3.6950
n-octane 1023.8 360.6 .394 .259 .325 .0241 3.6492 3.8951
n-Nonane 1070.2 335.0 .444 .260 .315 .0242 3.6862 3.8440
n-Decane 1111.5 304.5 .490 .247 .325 .0237 4.2264 4.5072
Undecane 1149.7 290.0 .535 .244 .328 .0240 4.3466 4.6583
Dodecane 1184.9 272.0 .562 .242 330 .0238 4.4311 4.7627
Tridecane 1216.7 250.0 .623 .238 :334 .0233 4.6237 4.9948
Tetradecane 1249.7 209.0 .679 ,234 .342 .0214 4.7485 5.1797
Pentadecane 1274.7 232.0 706 .232 346 .0237 4.8051 5.2638
Hexadecane 1299.7 206.0 :742 .229 :354 .0225 4.8492 5.3561
Heptdecane 1323.7 211.0 .770 .227 .360 .0235 4.8846 5.4248
Octadecane 1341.7 202.0 .790 .226 366 .0234 4.8909 5.4609
Nonadecane 1363.7 194,0 .827 .224 :377 .0233 4.9030 5.5225
Eicosane 1379.7 186.0 .907 .219 .407 .0232 4.8668 5.5916

Nitrogen 229.2 492.3 .040 .291 .355 .0189 2.2294 2.6098

Carbon dioxide 547.5 1070.6 .225 .275 .360 .0344 2.7677 3.2114
Benzene 1011.8 709.8 .212 .274 .0314 2.8830 3.2361
Ammonia 730.1 1635.7 .250 .242 :% .0270 4.3798 4.7456
Methanol 922.7 1174.2 .559 .224 360 .0286 5.0675 5.6144
Ethanol 929.2 925.8 .635 .248 :365 .0292 3.8281 4.3515
Acetic acid 1069.9 839.1 .454 .200 .385 .0305 6.1948 6.8809
Acetone 914.6 681.9 .309 .263 .300 .0268 3.6743 3.6719

TABLE 2
PTJRE COMPONENT VISCOSITY CORRELATION RESULTS
COMPONENT NO. OF TEMPERATURE XAXIMUM
DATA RANGE(”F) P(PSIA)
METHANE 1203 -118 TO 482 11760
ETHANE 957 5 TO 482 11760
PROPANE 979 70 TO 482 20000
ISOBUTANE 419 100 TO 460 80tif)
N-BUTANE 555 40 TO 460 10000
NEOPENTANE 101 100 TO 482 8000
N-PENTANE 515 77 TO 482 8000
N-HEXANE 120 70 TO 280 100GO
N-HEPTANE 60 50 TO 250 2000
N-OCTANE 40 50 TO 250 2000
N-NONANE 50 TO 250 2000
N-DECANE 2:! 40 TO 460 8000
UNDECANE 70 TO 400 500
DODECANE ;: 70 TO 400 450
TRIDECANE 70 70 TCI 400 400
TETRADECANE 70 TO 400 500
PENTADECANE H 70 TO 400 300
REXADECANE 61 70 TO 350 400
HEPTDECANE 62 70 TO 400 500
OCTADECANE 63 70 TO 400 500
NONADECANE 57 70 TO 400 450
EICOSANE 58 70 TO 400 500
NITROGEN 290 - 57 TO 482 15000
CARBON DIOXIDE 521 - 58 TO 482 11760

.“
 .

WE 1492(j

TABLE 3

PREDICTION RESULTS OF VISCOSITY OF RESERVOIR FLUIDS

CO14PONENT MOLE FRACTIONS

CARBON DIOXY. DE .0037 .0013 .0000 .001!3 .0003 00s5 .0110 .0164 .0022
NITROGEN .0000 .0000 .0104 .0147 .0004 .0076 .0039 003s .0009
NETt4ANE .CS?S9 .221s .1303 .s54s .3f)ls .4413 .6709 .7257 ,510s
ETHANE .0059 .0045 0s34 .036s .0264 .1011 .0453 .0541 .0345
PROPANE .0141 .0061 ,0s99 .0356 .0123 ,0706 0s34 .0307 .0139
ISOBUTANE .0077 .0067 .0118 .0098 00s5 .0137 .0056 .0066 .0053
BUTANE .0071 00s8 .059s .0345 .0064 .0333 .0094 .0134 .0067
ISOPENTANE .0004 .0091 .01ss .0242 .0060 .0103 00s9 .0062 .0041
PENTANE .0012 .0067 .0332 .02ss .0046 .0193 .0046 .0054 .0023
HEXANE .0241 .0429 .0539 .0735 .0Z99 02ss .011s .010s ,021s
HEPTANE+ .6979 .6921 50s5 ,4920 .6034 .2715 20S5 .1269 397s

PRoPERTIES OF C74
GRAVITY (API ) 31.9 3?.4 32.5 32.3 37,7 39. s 30. s 29.7 31.3

tloL. UT 167.0 162,0 274.0 230.0 16S.0 223.0 267.0 273.0 246.0

PREDICTED C7’+ PROPERTIES

CRITICAL TEMP. (OR) Sls. s 803.2 954. s 004.7 S47.4 S96,0 947.4 953. !3 923, S

CRITICAL PSIESS. (PSIA) 43s .1 445.5 29S.5 3e4.6 304,3 3s5.3 276,4 e6.9. e 302.5

ACENTRIc FACTOR .4076 .3967 6393 .5451 .4536 .5299 .6244 .6371 .5796

ZXPT. VISCOSITY (CP) .6600 .5500 2.6200 1.6200 .6600 .1220 .1200 .1100
,,
TEMPERATURE (‘F ) 145.0 146.0 94.0 86.0 156.0 272.0 262.0 282,0 21B. O

PRESSURE ( PSIA) 1297.0 1162.0 696.0 1275.0 1650.0 34s7.0 7065.0 S590. O 4040.0

PREDICTED VISCOSITY (CP )

LOHRENZ-BRAY-CLARX .0364 .0300 .14s1 .0932 .0496 .09S7 .1835 1032 .0670

LITTLE AND KENNEDY .4393 S63S 1.9799 1.5770 .5035 17?.2 .33s7 2361 .6455

4TH POWER RULE .5103 .4403 .4741 .4597 .4756 .1064 .0673 .04’75 1774

PRESENT WORX ( EQ .29) 7s70 6S36 3.s915 1.3293 .S499 .1259 .1115 .0650 49s5

TABLE 4

PREDICTION RESULTS OF VISCOSITY OF NATURAL GASEs

I COHPONENT HOLE FRAcTIONS

CARBON DI OX IDE .0135 005s 00s9 .005s .0211 .0046 .0007 .0278 .0053
NITROGEN .0000 .0000 .0000 0$?06 .0000 000s .0028 .0030 00ss
METHANE .914s 92S5 .s415 775s .7840 .4267 .9441 6796
ETHANE : L%’ 02ss .0318 .0641 .0762 0861 .3251 .0144 :0621
PROPANE .0172 .0134 .0120 02s7 0342 044s 1s03 .0034 02S7
ISOBUTANE .0045 003s .0024 .0024 0112 .0116 .0020 .0007 .0056
BUTANE .005s .0043 .0040 .0113 .012s .0166 .0061 .0010 .0151
IsOPENTANE .0035 .0024 .0014 .0021 00s3 .0077 002s .0004 .0067
PEtlTANE .0037 .0020 .0017 .0047 .0060 0069 .0046 .0004 .0054
HEXANE .0071 .004s .0034 .004’4 .0116 .0103 .0102 .0004 .0147
HEPTANE+ .0316 .0202 .0119 .0137 .0426 .0206 03S7 .0044 070s

PItOPERT lES OF C7 t
GRAVITY (API 1 47.0 50.7 47.4 S4,5 49 5 60.4 40.4 41.3 45.4

tSOL. UT 155.0 142.0 15s.0 134.0 157.0 126.0 1’??.0 160.0 135.0

PREDICTED C7 * PROPERTIES
CRITICAL TEKP. (“R) 790.7 763.9 796.5 745.7 794.6 725,9 8S0.0 800.2 74s,0

CRITICAL PRESS (PSIA) 460.3 4s9.0 453.9 507.3 456.0 526,2 415,2 449,7 505.0

ACENTRIC FACTOR .3814 .3533 3s79 .3363 3s5s .3194 .4205 .3923 .3384

EXPT VISCOSITY (CP) .0350 .0360 .0300 .0300 .0460 .0360 .0490 .0230 .0700

TEMPERATURE (‘F ) 244.0 199.0 213.0 127.0 262.0 144.0 110.0 2s8.0 217.0

PRESSURE ( PSIA ) 5387.0 4561.0 4559.0 361s.0 4931.0 2606.0 Sooo .0 5750.0 4415.0

PREDICTED VISCOSITY (CP)

LoHREN Z -BRAY -cLARK .0707 .0708 .0926 .1527 .2,642 .2358 6.4340 .1261 ,3076

LITTLE AND XENNEDY ,0932 .1387 .1764 .2250 1784 ,2239 .1933 .1713 .1723

LEF, -GONZALEZ -EAKIN .0211 0195 .0131 .0151 .0311 ,0243 .0215 .0146 .0303

4TH POWER RULE .0260 .0226 .0226 .021s .0299 .0247 .0425 .0236 .0447

PRESENT WORK ( EQ .29 ) .0204 .0256 .0243 02B0 .0350 .0357 0s2s .0246 .0727
 TABLE 5

PREDICTION RESULTS OF RSSERVOIR OILS VISCOSITY

COHPONENT HOLE FRACTIONS

PIITRDOEN ,0010 .00s0 .0010 .0170 .0560 Ooeo .0060 .01s0 .0000
ffETHANE 02s0 .0600 1780 .0900 .1350 .1480 .2400 .3510 .6070
CARSON DIOXIDE .0170 ,0150 :0000 .0000 .0040 .0060 Ooao .0160 .0010
ETHANE .0000 ,0770 .0410 .0460 oe70 .0610 .0140 .0110 .0550
PROPANE .0030 .0s20 .0340 ,0710 .0630 .0920 .02s0 00s0 .0!520
ISOBUTANE .0020 .0200 .0090 .0100 .0150 .0190 00s0 .0000 .0100
BUTANE .0040 .0630 .0310 .0470 .0340 .0850 .0240 .0140 .01!s0
IS OPENTANE .0040 .0210 .0220 .0140 .0230 .0320 .0120 .0130 .0070
PZNTANE .0040 .0200 .0410 .0210 .0230 .03s0 .0160 .0170 00?0
HEXANE 02s0 0.9s0 0s30 .0350 .0870 .0650 .0790 05s0 .0200
HEPTANE+ .9020 .5410 .5910 0500 .5130 47’s0 .5700 .4920 .3470

PROPERTIES OF C7*
GRAVITY (API ) 25,0 29.5 47,0 28.7 27,9 31.7 33.0 40.1 3s.1

140L UT 22s.6 200.4 170.0 S96. O 231.0 218.0 231.0 219,0 2s2.0

PREDICTED c7+ PROPERTIES

CRITICAL TEHP. (“R) 94s.4 020.2 .958.6 111!5.6 948.4 929.2 94’9.4 933.1 Q73.2

CRITICAL PRESS (PSXA) 348.3 3s1.7 4s0 .1 177.5 544.4 369.9 344.4 304.0 312.0

ACENTRIC FACTOR 5205 4S04 .39$0 .s56s .5255 .4942 ,5255 .5005 .5692

EXPT VISCOSITY (CP) 1.4000 1.1300 .6700 3,4000 1.9300 .7500 1.3700 .4400

TEMPERATURE ( ‘F) 250.0 112.0 72.0 226.0 110.0 164.0 194.0 274.0 223,0

PRESSURE (PSIA) So. o 3s5.0 350.0 620,0 900.0 945.0 1090.0 21s0.0 36e5. o

PREDIcTED VISCOSITY (CP)

LOHRENZ-BRAY-CLARX .0209 .lle4 .0090 .0716 .2104 .1257 .1378 .0677 .0903

LITTLE AND XENNEDY 66s9 1,ss61 1.3124 4.6407 .7254 1.0747 .5457 .6611 .7341

4TH PoWER RULE 37,7370 .3691 .5073 2,2301 .7906 .5329 S966 .1437

PRESENT WORK (EQ.’29) 232.086S 1.1107 .7217 125,23S9 1.8834 7s361 2,5416 e344 ,3223

0 A Experimental Data (27)

Calculated: Equation of State
—Lawai=Lake=Siiberberg
--- PengRobinson
--Soave=Rediich=Kwong
1200

TEMPERATURE (OF)
Fig. l-0rtf!oE4rlc dersslty and vapor pressure predictions of catin dloxldc.
 .

WE 14Q26

500
45
i 7?
/
, 450
-400 ~
. -350 g
g 30- -300 k
d s
& 25- N, -250 w
~ 20- -200 1!
s 15- -150 ;
0
lo- -100 ~
5- -50

0 # 80 120 160 200 240 280 320°

TEMPERATURE
(OF)
Fig, 2-OrthobWo density and vapor pressure prudlctlons cd n.butmw

o A Experimental Data
Calculated: Equation of State
—Lawal-Lake-Sllberberg
—-Pang-Robinson
-c--Soave=Redlich.Kwong

60- -600

E 50- -500
5 -.-,- “-%+
g
“%.~.%
IzJ 40- .-.+.%-, -400
u %..
-
E 30- -300
Cn
z
~ 20- -200

lo- -100

0 1
160200 240 280 320 360400440 480 52056060:
TEMPERATURE (OF)

denslly ●nd vapor pressure predktlons

Fig. 3-O fthobmk 01 Ia8nzem.
.
 WE 14926

o A Experimental Dab (29)

Calculated: Equation of State
—Lawa14.ake-Silberberg
--- PengRobineon
‘o---SoavRedlichcKwongng
!000

UJ

600 ~
w
a
n
400g
n
s
200

TEMPERATURE (W)
Fig, 4-0tIh0b8dc demlt y md VWIW pressure predictions of ethenol.

o A Experimental Data (29)

Calculated: Equation of State
— Lawa144ke$ilberbetg
--- PangRobinson
--- Soave-Redlich-Kwong
1200

1000

----
-’-. ‘-< w
--. -.-.-,
--.-.X.-.Z, +\\
-+. -. -\\
%%.
600 ~
%-.
w
E
400
;
200 ~

TEMPERATURE
(OF)
Fb. s–ofifwIuti dmalty ●nd vaporPreswreprcdctlonsof methanol.
 o a Experimental Data (29)
Calculated: Equation of State
— Lewalme”silbarberg
--- Peng-Robfnaon
-,--Soave-Redlich.Kwong
50]-

1
40{
OO. .

E 20-
U)
~
n
lo-

0“‘
-120-80 -40 0 40 80 120 160200240 2803
TEMPERATURE(OF)
Fig. @-Orihobark density and wOr pmssw predltiions of smmonk.

=
901 900

80- 800

Q
q 50-
------- - -----
g 40- -“------- “------- ---
--
“---------, -.-O
G “300g
~ 30-
n 20“ -2003

10-
0
240 280 320 360 40G 440 480 520 560 600 I
TEMPERATURE (°F)
F@ 7-O#ObDrk dondty and vcpc.r pressure ptodietlans of wetk std.
 S% 14926

0 A Exoerimentai Data (29)

Caicula~ed: Equation of S~te
— iawal=Lake-Siiberberg
—- Peng=Robinson
--’-Soave=Redlich-Kwon9
r“
700

60 600

~50_I
--- -----
--------- - ---~
-.-, ---- ---%

200 E
s
lo-
1
‘loo

‘$
120 160 200 240 280 320 360 400 440 L
TEMPERATURE (OF)
Fig. 8-otthObadc densw ●nd wwr prewure pr~lCtlOns Of =etOn*.

Experimental Data

liu’7’/ 1
o N, (33)
● C02 (33)
❑ c1 (33)
m C2 (48)
v C5 (49)

100
1 pressure: 1 atm.

“,-––
10 15 20 25 3’ 35
ViSCOSiTY (micropoise)
Fig, tI-Puts companuIt8 dilute gas VIUOSIIV pmdlctl’ans.
 SE 14926

VISCOSITY (micmpoise)
Fig. !O-Pmdlcllon of pure carbon dkwlde .I$COSW.

500,

VISCOSITY (micmpoise)
Fig. 11—Predktk.n of pure prop.ne V18CWIW,

I
 s!% 14926

460-
(1
(1
380- ,,

220- ‘~
1

140-
/
I
60 I I I [ I I I I I I I I I
0200600 1OOO14OO16OO 2200 2600
VISCOSITY (micmpoiae)
FIs. 12-Prediollon of Pura n.bukne vlscoslty,

● Experimental Data (35)

Component Mole %
Methane 20.0
Propane 80.0
500 — Calculated Eauation 29

O“ti’do’t i”tltk)’lobo’lim ‘1400

VISCOSITY (micmpoiae)
Fb. 13-Predkllm el tha rmthmqwop,m system.
 500 ● Experimental Data (35)
1
Component Mole %
Methane 70.0
30.0
n-Butane
— Calculated: Eauation 29

VISCOSITY
(micropoise)
Fig. 44-Prediction of the methane. n.butane system.

COMPONENT MOLE % (W)

Nitrogen 1130
Carbon Oioxide 0.30
Methane 85,80
Ethane 1.50
Propane 0.60
i - Butane 0.10
n - Butane 0.18
i- PWane 0.84)
n - Pentane 040
n - Hexane 0.04
Heptanes + 008
T = -IIWF
‘- b
----

, ‘k &

1 1 1 1 t
10 I 1 t I
~
1P”
PRESSURE (WA)
 COMPONENT MOLE % (56)
Nitrogen 0!66
Methane 59.66
Carbon Dioxide 1.80
Ethane 12,89
Propane 6.53
i . Butane 1.73
n - Butane 2.79
i - Pentane 1.00
n - Pentane 0.96
___ n - Hexanes
-%-- d
1,32
-.+. 6 Heptanes +
& 11.36
-\-
---+8 4 T = 2WF
--6-
-.. _
---

c
a
— Equation 29 \
-- Lohrenz et al, (19)
a Little and Kennedy (2)
o Lee et al. (55)
. Quarter-Power Rule (13)

---
---
----

PRESSURE (PSIA)
Fig, 16-Phase vlscodly predktlons In a Gas wrdenwe system.

1
COMPONENT MOLE % (13)
Nitrcgen 1.04
Methane 13.03
Ethane 8.34
Propane 8.99
i - Butane 1.18
n - Butane 5,98
i . Pentane 1.88
6 n - Pentane 3,32
n - Hexane 5.39
Heptanes + 50.85

— Equation 29
–– Lohrenz et al, (19)
A Little end Kennedy (2)
o Lee et, al. (55)

. Quarter-Power Rule (13)

.s

-/’”
●
00

104
1(Y
+5:---- I , I ,

PRESSURE (PSIA)
r I , I r , 1

Fig. 17-Phsw viscoalty pM@ctlans In o black oil sywom.