192 Ind. Eng. Chem. Process Des. Dev.

1982, 21, 192-195

product of selectivity and corresponding conversion, as Vo = volumetric flow rate, cm3/s

obtained from Figure 4, also corresponds to ether forma- W = mass of solids in bed, g
tion a t the bed exit. From the figure it is seen that a Greek Letters
catalyst dilution ratio of 3.67 is the optimum for formation
pa= bulk density of alumina, g/cm3
of intermediate product ether at the bed exit and a t this pg = bulk density of glass, g/cm3
dilution ratio ether formation is increased more than T = residence time in the bed, s
twofold (7% to 16%) over that obtained from the undi-
luted bed, with the advantage of lesser catalyst being em- Literature Cited
ployed. Caldwell, A. D.; Caklerbank, P . H. Br. Chem. Eng. 1969, 74, 1199.
Thus, when the intermediate is the desired product, as Ford, F. E.;Perlmutter, D. D. AIChE J . 1963,9 ,371.
Irani, R. K.; Kulkarni, B. D.; Doraiswamy, L. K. I n d . Eng. Chem. Process
is the case in most complex reactions, catalyst dilution of D e s . D e v . 1979, 18, 848.
the fluid bed can help to overcome the main drawback of Kunil, D.; Levenspiel, 0. Ind. Eng. Chem. Fundam. Ifi68a. 7, 446.
Kunll, D.: Levensplel, 0. Ind. Eng. Chem. Process Des. Dev. 1968b, 7,
a fluid bed, which is lower selectivity for a given level of 481.
conversion, without affecting the other useful features of Winter, O.,Eng, M. T. Hydrocarbon Process. 1976, 55, 125.
fluidized bed operation. National Chemical Laboratory R. K. Irani
Nomenclature Poona 411008, India B. D. Kulkarni
E = contacting efficiency in a fluid bed, dimensionless L. K. Doraiswamy*
FAo = molar feed rate of reactant A, g-mol/h Indian Institute of Technology S. Z. Hussain
P = partial pressure of component in the bulk phase, atm Bombay, India
d= partial pressure gradient of component between bulk
phase and catalyst fluid interface, atm Received for review September 4 , 1980
R = mass of catalyst in the undiluted fluid bed/mass of Revised manuscript received July 6, 1981
catalyst in the diluted bed, dimensionless Accepted July 24, 1981

Prediction of the Liquid Viscosity for Petroleum Fractions

The transport properties of petroleum fractions can be predicted via a modified corresponding state method
proposed by Ely and Hanley of the National Bureau of Standards. The basic idea behind the transport procedure
is that the properties of a mixture can be equated to those of a hypothetical pure substance, whose properties
are, in turn, determined via corresponding states from a reference fluid. The NBS model, after extensive com-
parisons with experimental data for pure hydrocarbons treated as undefined hydrocarbon mixtures, was extended
to the prediction of the viscosity of petroleum fractions. A large variety of experimental data for typical American
crude oils and various crude oils from the major oil-producing areas including Arabia, the Persian Gulf, and North
Africa were used to test the method. The agreement between the theory and experiment for the viscosity of the
fractions studied was less than 7 % .

Introduction
Very recently, Ely and Hanley of the National Bureau where
of Standards (1981) reported a corresponding states, con-
formal solution procedure to predict the transport coef-
ficients of nonpolar fluids and mixtures. The approach
has several attractive features; namely, it is predictive, it
can be applied to a wide variation of chemical types over with A4 the molecular weight. The viscosity thus involves
a wide range of thermodynamic states from the dilute gas scaling ratios f and h which are, in general
to the dense liquid, and the number of mixture compo-
nents is unrestricted, in principle. The only input data / Tx*,
fx,o = ( T X CTO)~,,O( vx*,%) (3)
required are the critical parameters, molecular weight,
Pitzers acentric factor, and (for thermal conductivity) the (4)
ideal gas specific heat. The purpose of this note is to point
out that the method seems very appropriate to estimate Here superscript c denotes the critical value and super-
the properties of petroleum fractions if we regard a fraction script * denotes reduction of the variable by the critical
as a hypothetical pure substance and estimate the neces- value: V is the volume (= l / p ) . The functions 0 and @
sary input parameters from the usual characteristics-the are the shape factors expressed in terms of the Pitzer
specific gravity a t 60 OF and an average boiling point. acentric factor, w , via functions of the form
The viscosity (7) of the fraction, designated by subscript ~x,o(~x,Vx,ux) = 1 + (ax- W O ) F ( T ~ , V , ) (5)
x a t a density ( p ) and temperature ( T ) is given in terms
of the viscosity of a reference fluid, designated by subscript ~ ) 1+
@ x , o ( T x , V x , ~= (ax- OO)G(T~,V,) (6)
0, evaluated at the correspondingdensity and temperature.
The equation is (Hanley, 1976; Mo and Gubbins, 1976) where F and G are universal functions reported, for ex-
0196-4305/82/1121-0192$01.25/0 0 1981 American Chemical Society
 Ind. Eng. Chem. Process Des. Dev., Vol. 21, No. 1, 1982 193

Table I. Kinematic Viscosity Prediction for Pure Hydrocarbons Treated as Nonstandards

visc. (pred,
visc. (exptl), this method),
compounds Ti,, O F APIgravity T, "F Mz/sX lo6 Mz/s x l o 6 dev, %
A. Paraffins
nonane 303.4 64.56 100.0 0.8087 0.7813 -3.7
210.0 0.4766 0.4363 -8.5
decane 345.4 61.23 100.0 1.0040 0.8728 -3.1
210.0 0.5591 0.5168 -7.5
undecane 384.6 58.61 100.0 1.2360 1.204 -2.5
210.0 0.6515 0.6085 -6.6
dodecane 421.3 56.51 100.0 1.512 1.482 -1.9
210.0 0.7563 0.7126 -5.8
tridecane 455.8 54.65 100.0 1.8280 1.815 -0.7
210.0 0.8686 0.8309 -4.3
tetradecane 488.3 53.06 100.0 2.1970 2.2124 0.7
210.0 0.9937 0.9649 -2.9
pentadecane 519.1 51.77 100.0 2.6120 2.6863 2.8
210.0 1.1260 1.1169 -0.8
hexadecane 548.2 50.54 100.0 3.081 3.2411 5.4
210.0 1.268 1.2886 1
.6
av abs dev 3.70
B. Naphthenes and Aromatics
ethylcyclopentane 218.2 52.03 100.0 0.619 0.536 -13.40
210.0 0.39 0.330 -15.31
propylcyclopentane 267.6 49.75 100.0 0.724 0.673 -7.00
210.0 0.46 0.394 -14.13
pentylcyclopentane 356.9 46.39 100.0 1.128 1.052 -6.73
210.0 0.62 0.560 -10.16
hexylcyclopentane 397.2 45.24 100.0 1.415 1.307 -7.5
210.0 0.13 0.657 -9.9
octy lcyclopentane 470.3 43.56 100.0 2.130 1.989 -6.6
210.0 0.98 0.903 -7.86
methylbenzene 251.1 30.81 100.0 0.5584 0.593 6.2
210.0 0.341 0.365 7.0
eth y 1benzene 277.1 30.81 100.0 0.6428 0.728 13.0
210.0 0.390 0.428 9.7
av abs dev 9.60

ample, by Leach et al. (1968) and by Ely and Hanley
(1981). Note that if fluids x and 0 are very similar, 8 and
4 tend to unity and the scaling ratios become those for
classical corresponding states. Methane was selected as
reference being the only fluid with enough reliable PVT
and transport property data correlated over a wide range
of experimental conditions.
The summary of the procedure is as follows. We are
given the equation of state, P, = P(po,To),of the reference
fluid and the viscosity, qo = q(po,To),of that fluid which
are incorporated in the routine of Ely and Hanley (1981).
We require the input pressure and temperature of the
petroleum fraction and the necessary critical parameters,
molecular weight, and Pitzer acentric factor. The transport
property routine then evaluates the density and hence the
viscosity by eq 1.
Estimation of Pseudo Properties of Petroleum
Fractions
In this study we decided to estimate the critical param-
eters and molecular weight of the fraction via the recent
method of Riazi and Daubert (1980). Hence, a property
X (critical value or molecular weight) is given by the simple
relation
x = ATbBSPGC (7)
where Tb is the average boiling point in OR of the fraction
and SPG is the specific gravity at 60 O F . A, B, and C are
constants appropriate for the property to be estimated.
Equation 7 is attractive in its simplicity and gives results
which are comparable with or superior to those obtained
from other methods.
As a first approximation, the pseudoacentric factor of
petroleum fractions was calculated by the Edmister
equation (1961), which is
w = (!) (L)
1 - 8' ln - 1.0 (8)
where 8' = Tb/Tc. The equation is not entirely satisfactory
in that it requires the pseudocritical pressure and tem-
perature, which have to be estimated, and the equation
becomes less reliable the further the ratio Tb/P deviates
from 0.7.
Test of the Method with Pure Hydrocarbons
Treated as Pseudo Components
Since viscosity data for petroleum fractions are often
unavailable, it seemed worthwhile to test the method by
estimating the viscosity of hydrocarbons with boiling points
which are close to the boiling points of the different pe-
troleum fraction cuts likely to be encountered. The hy-
drocarbons were thus treated as nonstandard (pseudo
components) in that they were characterized only by a
boiling point and a specific gravity; their molecular weights,
critical parameters, and acentric factors were estimated
by the methods of eq 7 and 8. Table I gives the results
of comparison for viscosity of selected substances taken
from API Research Project 44 (1975). Listed are the
boiling points, the specific gravity, and the viscosity ex-
perimental values at the temperatures 100 and 210 O F for
several paraffins, naphthenes, and aromatic hydrocarbons.
The percent deviations between prediction and experiment
are shown and it is observed that the agreement is ex-
cellent, overall, especially when we consider the approxi-
194 Ind. Eng. Chem. Process Des. Dev., Vol. 21, No. 1, 1982

Table 11. Experimental and Predicted Viscosities for Crude Oils

visc. visc .
bred, (Pred?
visc. this visc . this
(exptl), method), (exptl), method),
Tb > API T, MZ/sX MZ/sX Tb 7 API T, M2/s x MZ/sx
F gravity F 1 0 6 lo6 dev,% F gravity F lo6 106 dev, %
Oklahoma Crude Oil Minas (Sumatra) Crude Oil
279.5 55.2 32 1.130 1.124 -1.44 182.0 71.5 100.0 0.464 0.441 -4.95
68 0.879 0.864 -1.65 130.0 0.404 0.384 -4.95
104 0.708 0.688 -2.75 4.95
140 0.592 0.564 -4.67 301.0 56.39 100.0 0.782 0.781 -1.39
212 0.448 0.404 -9.88 130.0 0.653 0.654 0.15
3.75 0.77
369.5 46.3 32 2.050 1.969 -4.19 412.0 48.59 100.0 1.380 1.415 2.53
68 1.440 1.436 -0.26 130.0 1.090 1.132 3.85
104 1.090 1.093 0.25 210.0 0.668 0.694 3.89
140 0.877 0.861 -1.83 3.42
212 0.611 0.580 -5.04
2.31 511.0 41.2 100.0 2.350 2.46 4.68
130.0 1.750 1.89 8.00
459.5 39.4 32 4.680 3.609 -22.86 210.0 0.992 1.06
68 2.840 2.495 -12.15 - 6.85
104 1.930 1.807 -6.33 - 6.51
140 1.430 1.364 -4.62 av abs dev for crude 4.12
212 0.900 0.856 -4.85 Iranian Export Crude Oil
10.12
194.0 65.3 100.0 0.5054 0.470 -7.00
av abs dev for crude 5.51 210.0 0.4480 0.408 -8.93
Pennsylvania Crude Oil 7.96
279.5 58.2 32 1.130 1.121 0.77 275.0 55.45 100.0 0.670 0.690 2.98
68 0.871 0.861 -1.16 130.0 0.573 0.582 1.57
104 0.702 0.685 -2.41 210.0 0.423 0.400 -5.44
140 0.591 0.561 -5.04 3.33
212 0.448 0.401 -10.47 353.0 49.79 100.0 0.945 1.026 8.57
3.97 130.0 0.783 0.842 7.53
369.5 51.6 32 2.030 1.96 -3.12 210.0 0.530 0.544 2.64
68 1.420 1.43 0.72 6.25
104 1.090 1.086 -0.38 434.0 45.11 100.0 1.470 1.607 9.31
140 0.857 0.854 -0.30 130.0 1.170 1.274 8.88
212 0.618 0.574 -7.09 210.1 0.728 0.767 5.35
2.32 7
-.85
3.620 -22.12 av abs dev for crude 6.2
459.5 46.0 32 4.660
68 2.780 2.495 -10.25 Stabilized Arabian Crude
104 1.900 1.800 -5.23 245.0 61.91 100.0 0.593 0.593 0.00
140 1.400 1.354 -3.24 -1.55
130.0 0.514 0.506
212 0.92 0.847 -7.96 1.55
9.76
av abs dev for crude 5.35 319.0 52.89 100.0 0.801 0.858 7.11
130.0 0.674 0.714 5.93
210.0 0.471 0.474 0.63
4.56
385.0 47.91 100.0 1.160 1.219 5.08
130.0 0.945 0.987 4.44
210.0 0.615 0.622 1.13
3.55
-
av abs dev for crude 3.23
Safanya (Saudi Arabia) Crude Oil
291.0 58.3 100.0 0.860 0.742 -13.72
130.0 0.720 0.662 -13.60
13.66
394.0 48.8 100.0 1.250 1.279 2.32
130.0 1.020 1.032 1.18
210.0 0.648 0.644 -0.61
1.37
av abs dev for crude 6.28

mations introduced by eq 7 and 8, and appreciate that the
data themselves can only be considered reliable to within
about 5 and 15%.
Application to Petroleum Fractions
The agreement shown in Table I indicates that the
method can be applied to petroleum fractions with con-
fidence. Accordingly, experimental viscosity data for
typical American Crude Oils (Dean, 1921; Lane, 1924)
regarded as paraffin base (Pennsylvania Crude),
naphthene base (California Crude) or intermediate base
oils; (Oklahoma and Wyoming Crude) and various foreign
crude oils (Maddox, 1979) were used to test the method.
Table I1 shows comparisons between the experimentaland
 Ind. Eng. Chem. Process Des. Dev., Vol. 21, No. 1, 1982 195

Table 111. Comparison between Actual Experimental and Calculated Kinemetic Viscosities
deviations
no. of temp range, AAD max
compounds points "F bias," % dev, % dev, %
pure hydrocarbonsC 49 32-464 2.97 5.71 -15.31
California crude oil 27 32-212 7.19 7.89 -18.75
Oklahoma crude oil 35 32-212 5.03 5.48 -22.86
Pennsylvania crude oil 62 32-212 5.75 6.34 -32.69
Wyoming crude oil 23 32-212 6.61 6.61 -11.32
undefined hydrocarbon mixtures 10 100-210 6.68 6.68 -11.30
foreign crude oilsd -42 100-210 4.44 5.96 -30.20
248 5.52 6.38
Bias= (100/n)&" {[q(calcd) - q(exptl)]/q(exptl)}. AAD = (lOO/n)Z:i"[lq(calcd) - q(exptl)(/q(exptl)]. Paraffins,
naphthenes, and aromatics. Arabia, Persian Gulf, North Africa, etc.

the calculated values of the liquid viscosities for these
fractions via eq 1, and a summary of the results of this
work is given in Table 111. It is seen that the method
presented in this study produces an overall average ab-
solute deviation of 6.14% for all different boiling point
fractions (248 points) tested.
Conclusions
We have applied the extended corresponding states
technique of Hanley (1976) and of Ely and Hanley (1981)
to estimated the viscosity of petroleum fractions. The
results of Tables I1 and I11 indicate that the overall
agreement between the theory and data is excellent. It
should be stressed that the procedure is predictive in that
no transport data are required, and in fact, the only input
is the boiling point and the specific gravity. The experi-
mental range of the method is, in principle, unrestricted.
It should further be noted that the method will yield a
density and thermal conductivity, and work is in progress
to assess the prediction of this latter property for petro-
leum fractions.
Acknowledgment
We are grateful to the Management of Fluor Engineers
and Constructors, Inc., for permission to present these
results and to the Methods and Data group for helpful
discussion.
Nomenclature
T = temperature
P = pressure
p = density
V = volume
7 = viscosity
F7 = viscosity equation parameter
h, f = scaling ratios
(J = acentric factor
8, 4 = shape factors
F, G = shape factor functions
8' = Edmister equation parameter
A , B, C = parameters for the Riazi-Daubert equation
Superscripts
c = critical point value
* = value reduced by critical value
Subscripts
x = denotes petroleum fraction
0 = denotes reference substance
b = boiling point of the fraction
Literature Cited
API Research Project 44, "Selected Values of Properties of Hydrocarbons
and Related Compounds", Tables of Physlcal and Thermodynamic Proper-
ties of Hydrocarbons, A and M Press: College Station, Texas (extant
1975).
Dean, E. W.; Lane, F. W. Ind. Eng. Chem. 1021, 13(9), 779.
Edmister. W. C. "Applied Hydrocarbons Thermodynamics"; 1961, Gulf Pub-
lishing Co.: Houston, TX, 1961; p 27.
Ely, F. J.; Hanley, H. J. M. Paper presented at the 60th GPA Annual Meeting,
San Antonio, TX, Mar 1981; Ind. Eng. Chem. Fundam. 1981, 20, 323.
Eiy, F. J.; Hanley, H. J. M. U.S. Department of Commerce, Natlonai Bureau of
Standards, Technical Note 1039, 1961.
Hanley, H. J. M. Cryogenics 1076, 16, 731.
Lane, F. W.; Dean, E. W. Ind. Eng. Chem. 1024, 76(9), 905.
Leach, J. W.; Chappelear, R. S.; Leland, T. W. AIChf J . 1968, 14, 568.
Maddox, R. N.; Amin, M. 6. Paper presented at the AIChE Meeting, San
Francisco. CA, Nov 1979.
Mo, K. C.; Gubbins, K. E. Mol. phys. 1078, 37, 825.
Riazl, M. R.; Daubert, T. E. wdrocarbon Process. 1080, 175.
Fluor Engineers and Monica E. Baltatu
Constructors, Znc.
Zrvine, California 92730
Received for review April 3, 1981
Revised manuscript received September 3, 1981
Accepted September 14, 1981