Ind. Eng. Chem. Res.

1989,28, 213-221 213

GENERAL RESEARCH

The Effect of Temperature and Pressure on the Viscosities of Crude

Oils and Their Mixtures
Jasem M. Al-Besharah,* Saed A. Akashah, and Clive J. Mumford+
Petroleum, Petrochemicals and Materials Division, Kuwait Institute For Scientific Research, P.O. Box 24885,
13109 Safat, Kuwait

The kinematic viscosities of light, medium, and heavy crude oils, and their binary and ternary
mixtures, were measured over a temperature range of 10-50 “C and a pressure range of 14.7-8000
psi. These data were used to develop a new method to predict the viscosity of crude oils and their
blends a t high pressure, based upon the densities of the components and the kinematic viscosity
at atmospheric pressure. This prediction method gave excellent agreement with the measured values,
the absolute average deviations being 6 2 % and <6.0% for the binary and ternary crude oil mixtures,
respectively. This was significantly better than the current equation adopted by the American
Petroleum Institute which resulted in deviations of <34.7% and <27.7% for the same binary and
ternary mixtures.

Accurate data on oil viscosity as a function of temper-
ature, pressure, and composition are required for reservoir
studies, process design, or the solution of oil transportation
problems. Numerous investigators have reported viscosity
measurements for different types of pure hydrocarbons,
oils, and petroleum products and developed empirical or
semiempirical correlations to describe the viscosity-tem-
perature-pressure behavior of liquids (especially for hy-
drocarbon mixtures or petroleum products).
The theory of the free volume or activation energy of
viscous flow has been discussed thoroughly by several re-
searchers such as Eyring and Hirschfelder (1937), Ewe11
and Eyring (1937), Frisch et al. (1940),Powell et al. (19411,
McAllister (1960), Irving (1977), Heric and Brewer (1967,
1969,1970),Macedo and Litovitz (1965) and Gubbins and
Tham (1969). The liquid is assumed to exist as a regular
lattice, with momentum transfer resulting from molecules
vibrating within the lattice structure, moving into nearby
holes, or combinations of these two events; the movement
from a lattice site to a hole is considered analogous to an
activated chemical reaction. Numerous methods are also
available for the prediction of the viscosity of hydrocarbons
and petroleum products based on the principle of corre-
sponding states. However, no theory is yet available upon
which to base a simple and reliable method to calculate
the viscosity of liquids with high accuracy, and empirical
estimation techniques must be used. These techniques do
not conflict with theory and usually allow some of the
unknown or incalculable theoretical constants to be ap-
proximated empirically from structure or other physical
properties.
Block (1951) reviewed the different approaches used to
describe the viscosity-temperature-pressure relationship
of lubricating oils in terms of empirical formulae and their
prediction from correlations based on properties that are
easily accessible at atmospheric pressure. The aim was to
study the effect of any increase or decrease in viscosity of
Present address: Department of Chemical Engineering and
Applied Chemistry, Aston University, Birmingham, U.K.
08S8-5885/89/2628-0213$01.50/0
lubricating oils on the hydrodynamic load-carrying capacity
of machine parts. An approach was proposed in which the
viscosity-temperature-pressure relationship is fiit studied
individually for “similar groups” of natural lubricating oils
originating from a similar source and refined in a similar
way. Data on Pennsylvania oils as a typical “similar group”
were used to examine several correlations, such as the
Hersey and Lowdenslager (1950) formula,
where n and K are constants, qa is the viscosity at at-
mospheric pressure, q p ) is the viscosity at the required
pressure, and P is the required pressure.
It was proposed that viscosity could be a function of
specific volume only. This implies that, given knowledge
of the effects of temperature and pressure on density
(equation of state), an equivalence could be established
between their effects on viscosity. While this may serve
as a reasonable approximation for simple liquids, lubri-
cating oils and crude oils comprise complex mixtures of
heterogeneous compounds.
Sanderson (1949) presented a formula to calculate the
kinematic viscosity, v,
log log [ ~ ( p+
) 0.61 = CP1I2+ D (2)
where C and D are constants, P is the pressure, and v(p)
is the kinematic viscosity at the required pressure.
Mehrotra and Svrcek (1984) observed that the viscosity
of Marguerite Lake bitumen decreased with an increase
in temperature, but the reduction in viscosity was less steep
in the high-temperature region. Similar behavior was
observed for Athabasca bitumen (Mehrotra and Svrcek,
1985).
Mehrotra and Svrcek (1986) subsequentlypresented new
data for the effect of pressure and temperature on a gas-
free Athabasca bitumen viscosity covering a temperature
range of 43-120 “C and pressure up to 10 MPa (1450 psi).
The compression of bitumen was found to result in a
significant increase in viscosity but only a small increase
in density. Two correlations were developed to describe
0 1989 American Chemical Society
214 Ind. Eng. Chem. Res., Vol. 28, No. 2, 1989
the effect of pressure and temperature on the viscosity of Table I. Inspection Data for Light, Medium, and Heavy
the bitumen: Crude Oils
model 1 crude oil
In p = exp[u, + u2 In T ] + a# (3) test units light medium heavy
density at 15 OC g/mL 0.8445 0.9059 0.9667
model 2 API gravity OAPI 35.96 24.62 14.79
In In P = [al + u2 In T ] + u3P (4) kinematic viscosity
a t 10 "C cSt 14.22 163.40 2193.10
where T is in K and P is in MPa. a t 20 "C cSt 9.512 81.46 887.90
The average absolute deviation was 1.8% with model a t 30 "C cSt 7.141 51.81 426.40
2 compared to 2.8% with model 1. An increase in pressure a t 40 OC cSt 5.960 34.63 223.50
to 10 MPa (1450 psi) resulted in a 49% increase in the a t 50 OC cSt 4.850 24.98 130.00
bitumen viscosity a t 43 "C compared with a 33% at 120 pour pt "C -18 -14 -23
asphaltenes content % wt 0.89 4.4 6.75
"C. Thus, the effect of pressure was more significant at sulfur content % wt 2.15 3.75 4.66
lower temperatures where the viscosity of bitumen was Conradson carbon residue % wt 4.74 7.84 11.37
high. Graphical representation of the increase of viscosity metals on ash by
with pressure demonstrated a nonlinear relationship but ASTM-D3327
a linear relationship of In p with pressure over the whole Ni jtg/g 3.4 20.0 26.7
range of temperatures. V jtg/g 13.8 44.3 100.9
Kouzel (1965) presented an equation to calculate the Corning dc and Brookfield standard fluids covering the
effect of pressure on the viscosity of high molecular weight range 5-5000 cSt at 25 "C and three different balls with
hydrocarbons densities of 7.6781,7.7095, and 7.7641 g/cm3, respectively.
P P The reservoir and the viscometer were evacuated and
log - = -[0.0239
PO 1000
+ 0 . 0 1 6 3 8 ~ 0 ~ . ~ ' ~ ] (5) then filled with the crude oil such that no air bubbles could
enter the system. The appropriate ball was then allowed
where p is the viscosity at T and P in cP, h0 is the viscosity to fall freely in the barrel inside the viscometer at the
at T and 1 atm in cP, and P is the pressure in psi. This required temperature and pressure. The falling time (in
equation has been adopted by the American Petroleum s) was recorded for each combination of temperature and
Institute (API Technical Data Book, 1970). The devia- pressure at the three roll angles (23", 45", and 70"). The
tions between calculated and experimental viscosities of viscosity (in cP) was subsequently calculated and converted
high molecular weight hydrocarbon were reported as ap- to the kinematic viscosity. The repeatability of the vis-
proximately 5% for pressures < 5000 psi and approxi- cosity measurement did not deviate more than 0.1% about
mately 8% for pressures up to 10000 psi. the mean value.
Recently, Ahrabi et al. (1987) measured the viscosities A glass capillary Type BS/IP-RF-U tube-calibrated
for a crude oil and natural gas liquid (NGL), from a North viscometer supplied by Scientific Glassware, U.K., was
Sea Oil reservoir, within the temperature range 303-375 used for the determination of the kinematic viscosity at
K and pressure range 14.5 to ~ 6 4 5 0psi. Measured vis- atmospheric pressure over a range of temperatures. The
cosities for liquid-phase crude oil increased with an in- viscometer was placed in an oil bath supplied by Townson
crease in pressure, with a pronounced break at the bubble & Mercer Ltd., U.K., and was capable of maintaining the
point at all temperatures. temperature within fO.O1 "C (k0.02O F ) of the selected
Ahrabi et al. also reported that the viscosity of the North temperature. As in a previous study of crude oil blends
Sea crude oil decreased with an increase in pressure until (Al-Besharah, 1988), the kinematic viscosity was deter-
about 940 psi; it then increased linearly with an increase mined by the standard method of test, ASTM D445/IP71
in pressure at four different temperatures. This behavior (1983), for the measurement of kinematic viscosity of
is unusual, since pressure generally exhibits a linear rela- transparent and opaque liquids. The kinematic viscosity,
tionship with log viscosity of liquids. u, was calculated from the measured flow time, t , and the
The present work provides a better description of the viscometer calibration constant by using
behavior of the viscosity of crude oils at various temper-
u = Ct (6)
atures and pressures. The effect of temperature and
pressure on the kinematic viscosity of Kuwait crude oil and where v is the kinematic viscosity in cSt, C is the cali-
their blends was studied and a method developed to pre- bration constant of the viscometer in cSt/s, and t is the
dict the viscosity of the crude oil as a function of tem- flow time in s. Duplicate measurements did not deviate
perature and pressure. more than 0.35% about their mean. Reproducible mea-
surements should not deviate more than 0.7% about their
Experimental Section mean.
Viscosity measurements at high pressure were performed Crude Oil Samples. Three types of Kuwait crude oils
by using the Ruska rolling ball viscometer (Type 1602) (light, medium, and heavy) were used in this study. The
which is part of the Ruska PVT system. The viscometer inspection data on the three crude oils are shown in Table
was heated electrically by a jacket control system which I. All mixtures were prepared on weight percentage basis.
facilitated temperature control up to 150 "C and was The compositions of the binary and ternary mixtures are
connected to a digital time clock for measurements with shown in Tables I1 and 111, respectively.
a repeatability of 0.1 70.
This apparatus consisted of a manually operated mer- Results and Discussion
cury pump connected to a stainless steel reservoir cell of The kinematic viscosities of the three crude oils and
about 600-cm3 capacity. The cell was connected to the their binary mixtures at atmospheric pressure (14.7 psi)
viscometer, which contained a bleed valve, and could be and temperatures in the range 10-50 "C are shown in
adjusted at angles of 23", 45", or 70" to promote free fall Table IV and are represented graphically in Figures 1and
of a stainless steel ball of specific diameter. The instru- 2. Clearly an increase in the temperature of the crude oil
ment was calibrated a t each temperature using Dow results in a significant decrease in its viscosity. The rate
 Ind. Eng. Chem. Res., Vol. 28, No. 2, 1989 215

1
0
0
1
- loo(
800. 801
600 - 60C

400 - 40(

200 - 20c

100 - 1 oc
m i x 12

80 - 80 mix 8
60 -
medium c r u d e .
d
- 60 m ~ 11
x

-
L
40-
v)
40 m i x 10
v)

-0
-21
.- mix 9

-21
.-
ln
20-
ln
0

.-ln
20 mix 7
mix 4

0 >
0 mix 6
.-ln mix 3
> IO- .E 10
mix 2

-
.-
m
8 -

6 -
E
m
.t
8
6 mix 5
E Y mlx 1
m
,E 4 - 4
Y

2 - 2

1 L I I I I I 1
0 10 20 30 40 50 f 10 20 30 40 50 60
Temperature ('c ) Temperature ('c)
Figure 1. Effect of temperature on the kinematic viscosity of light, Figure 2. Effect of temperature on the kinematic viscosity of crude
medium, and heavy crude oils at atmospheric pressure. oil binary mixtures at atmospheric pressure.

Table 11. Compositions of C r u d e Oil Binary Mixtures Table IV. Measured Kinematic Viscosities (cSt) of Light,
ComDrising Light. Medium. a n d Heavy Crude Oils Medium, and Heavy Crude Oils a n d t h e Binary Mixtures at
weight % of crude oil Atmomheric P r e s s u r e
mixture light medium heavy kinematic viscosity (cSt) at
1 90 10 mixture 10 OC 20 O C 30 O C 40 "C 50 "C
2 60 40 light crude 14.22 9.512 7.141 5.960 4.850
3 40 60 medium crude 163.40 81.46 51.81 34.63 24.98
4 10 90 heavy crude 2193.10 887.90 426.60 223.50 130.00
5 90 10 1 16.44 10.71 9.171 6.519 5.625
6 60 40 2 31.71 19.35 14.79 10.79 8.192
7 40 60 3 49.86 29.96 21.83 14.57 11.95
8 10 90 4 116.0 64.23 42.18 26.10 17.80
9 90 10 5 19.02 11.76 10.55 6.952 5.909
10 60 40 6 54.63 33.17 26.60 15.43 11.98
11 40 60 7 146.12 78.80 52.10 32.02 20.70
12 10 90 8 1022.60 442.50 230.05 129.60 75.02
9 200.87 101.20 62.65 37.56 25.10
Table 111. ComDositions of T e r n a r y Crude Oil Mixtures 10 381.55 186.04 109.57 64.41 38.06
weight % of crude oil 11 643.14 298.60 180.65 97.45 60.81
12 1675.70 729.30 372.32 188.61 109.02
mixture light medium heavy
1 30 30 40 reported previously for other hydrocarbon and petroleum
2 30 50 20 products by Mehrotra and Svrcek (1984, 1985, 1986).
3 55 40 5
4 20 30 50 The measured kinematic viscosities of the three indi-
5 10 70 20 vidual crude oils and their binary mixtures in the tem-
perature range 25-50 "C and pressure range from atmos-
of decrease in the viscosity of the heavy crude is greater pheric to 8000 psi are shown in Tables V and VI and are
than the rate for the lighter crudes. This behavior has been represented graphically in Figures 3-5. The crude oils
216 Ind. Eng. Chem. Res., Vol. 28, No. 2, 1989

Table V. Measured Kinematic Viscosities of Light, Medium, and Heavy Crude Oils at High Pressure
kinematic viscosity (cSt) at
crude oil temp, "C 14.7 psi 2000 psi 4000 psi 6000 psi 8000 psi
light 25 8.251 9.801 12.32 15.03 17.81
30 7.141 8.420 10.49 12.89 15.56
40 5.960 7.084 8.361 9.905 11.88
50 4.850 5.671 6.690 7.742 9.011
medium 25 65.13 84.03 110.80 147.00 189.10
30 51.81 67.33 88.58 114.10 141.50
40 34.63 44.25 58.59 74.92 92.55
50 24.98 31.67 39.69 49.05 60.41
heavy 25 620.00 842.10 1281.00 1802.OO 2470.00
30 426.60 580.10 870.60 1202.00 1670.00
40 223.50 299.50 428.05 618.30 867.70
50 130.00 184.90 249.20 351.20 490.40

0.0; I

-
7.0

1.ot
I -
- _- -
light c r u d e
medium c r u d e
heavy crude

Oi 1
2000 4000 6000 8000
pressure I ps, )

Figure 3. Effect of pressure on the kinematic viscosity (u) of light,

medium, and heavy crude oils.

used in this study were stabilized crudes (dead crudes); -B 25°C

i.e., the concentration of the dissolved gases was very low ----e 30'c

(<1.0% wt). Therefore, the effect of the dissolved gases 2 01

on the viscosity of the crudes is negligible. Consequently,
as expected, the viscosities of the liquid-phase crude oils
increased as the pressure increased. Straight lines were
obtained when In v of the crudes were plotted against the
pressure. It is clear from Figures 3-5 that the rate of
increase in the viscosity (the slope of a straight line), at
a constant temperature, increased as the density of the
crude increased. As expected, the slopes of the straight
lines decreased as the temperature increased, the behavior
of which is similar to that for dead Athabasca bitumen
reported by Mehrotra and Svrcek (1985) and Khan et al.
(1984).
In the present work, a method has been developed to
predict the viscosity of crude oils at high pressure and
different temperatures. This method considers the change
in density ( p ) of the crude oils due to change in temper-
ature. The densities at the required temperature ( p T ) of
the three individual crude oils (light, medium, and heavy)
were calculated using the ASTM standard conversion ta-
bles for the volumetric measurements of crude oils,
knowing at least one density measurement at any tem-
perature. The slopes (R)of the (In v)-pressure straight
lines shown in Figure 3 at each temperature for each of
the three crudes were calculated by
A In v
slope = R = - (7)
AP
2000 4000 6000 8000
Pressure ( psi1
Figure 4. Effect of pressure on the kinematic viscosity ( u ) of crude
oil binary mixtures at 25 and 30 "C.
where v is the kinematic viscosity in cSt and AP is the
change in pressure in psi.
Table VI1 shows p T and R data for the three crudes at
different temperatures. The calculated ~ T ' s are, then,
plotted against the corresponding slopes (R),where a linear
relationship was obtained (Figure 6). By linear regression,
the following equation was obtained:
R = -4.65521 X + (6.66906 X l O - * p ~ ) (8)
where R is the slope of the (In v)-pressure straight line and
pT is the density of crudes at the required temperature in
g/mL. After rearrangement, eq 7 can be written as
"p-
- 0eR(P-14.7) (9)
where up is the kinematic viscosity at the required pressure
in cSt, v, is the kinematic viscosity at atmospheric pressure
in cSt, P is the pressure in psi, and R is the slope of the
(In v)-pressure straight line and is calculated from eq 8.
The measured kinematic viscosity data for crude oil
binary mixtures, shown in Table VI, were used to test the
proposed method. The percent deviations of the calculated
viscosities from the experimental measurements are shown
in Table VIII.
 Ind. Eng. Chem. Res., Vol. 28, No. 2, 1989 217

Table VI. Measured Kinematic Viscosities of Crude Oil Binary Mixtures at High Pressure
kinematic viscosity (cSt) a t
mixture temp, O C 14.7 psi 2000 psi 4000 psi 6000 psi 8000 psi
1 25 9.788 11.58 14.13 17.54 21.14
30 9.171 11.42 13.50 17.04 19.64
40 6.519 7.756 9.314 11.78 14.34
50 5.625 6.625 7.713 9.266 10.90
2 25 16.97 19.90 25.30 32.21 38.92
30 14.79 17.41 22.69 27.33 33.07
40 10.79 13.05 15.74 19.61 22.55
50 8.192 9.721 12.21 14.54 17.43
3 25 25.53 33.01 42.15 53.67 66.68
30 21.83 27.81 34.81 45.05 53.03
40 14.57 18.29 23.18 27.55 33.86
50 11.95 14.89 18.51 22.40 27.52
4 25 51.04 68.79 83.62 105.90 139.21
30 42.18 51.02 64.04 82.71 105.85
40 26.10 35.06 46.55 59.89 77.09
50 17.80 21.82 28.99 35.01 43.31
5 25 11.42 13.38 16.33 20.21 24.44
30 10.55 12.90 15.28 18.52 22.22
50 5.909 7.146 8.622 10.48 12.61
6 25 28.15 35.75 45.32 55.62 71.81
30 26.60 34.37 42.89 52.90 65.91
40 15.43 20.22 24.06 30.95 37.72
50 11.98 15.33 18.67 23.01 28.62
7 25 63.67 83.02 110.04 143.22 190.29
30 52.10 70.47 89.20 111.75 145.30
40 32.02 40.16 54.29 67.86 86.62
50 20.70 27.06 34.46 42.65 54.63
8 25 302.50 416.00 561.51 796.12 1110.60
40 129.60 182.12 246.10 316.48 435.72
50 75.02 105.50 141.03 187.41 248.40
9 25 78.58 102.21 130.56 172.86 226.70
30 62.65 82.22 105.50 141.70 177.90
40 37.56 48.79 65.05 78.12 100.70
50 25.10 32.58 41.36 50.51 63.25
10 25 140.16 184.67 250.33 336.85 448.21
40 64.41 87.90 116.30 149.70 186.60
50 38.06 50.06 67.21 85.27 110.28
11 25 234.02 312.77 431.01 585.32 795.50
30 180.65 252.10 347.80 480.60 605.20
40 97.45 138.30 188.50 255.10 353.50
50 60.81 83.52 110.14 143.15 190.09
12 25 493.58 701.23 986.91 1345.80 1880.60
30 372.30 513.40 715.70 989.50 1375.00
40 188.60 258.40 361.20 495.60 710.30
50 109.02 150.10 207.20 288.50 396.30

Table VII. Measured Densities at Different Temperatures ( p T ) and the Slopes of (In v)-Pressure Straight Lines ( R ) for
Light, Medium, and Heavy Crude Oils
light crude oil medium crude oil heavy crude oil
temp, OC or 104R PT 10-4~ or 10-lR
25 0.8376 0.9988 0.8992 1.3475 0.9601 1.7652
30 0.8341 0.9932 0.8958 1.2703 0.9568 1.7315
40 0.8272 0.8583 0.8890 1.2513 0.9502 1.7215
50 0.8201 0.7762 0.8822 1.1034 0.9436 1.6512

The pT's of the mixtures, P ~ , were

~ ~ easily
~ , measured
or calculated by the simple mixing rule
Pmix = CxtPi (10)
where pmix is the density of the mixture, pi is the density
of component i, and xi is the weight fraction. The percent
deviations of the calculated mixtures densities by this
equation were very low, Le., <0.6% in most cases, and it
can be used with confidence (Al-Besharah, 1988).
It is clear from Table VI11 that the deviations of the
calculated viscosities a t high pressure from the experi-
mental measurements are very low and less than 8.5% in
most cases, with absolute average percent deviations of 2.1,
2.4, 3.9, and 5.2 a t 2000, 4000, 6000, and 8000 psi, re-
spectively. In general, the deviation increases as the
pressure increases, the highest deviation (10.5%) being
obtained a t 8000 psi and 30 "C for mixture.
The three crude oils (light, medium, and heavy) were,
also, used to prepare five ternary mixtures with the com-
positions shown in Table I11 in order to test the proposed
method. The measured and calculated viscosities by the
proposed method are shown in Tables IX and X, respec-
tively, where the absolute average percent deviations are
3.6, 3.0, 4.4,and 6.0 a t 2000, 4000, 6000, and 8000 psi,
respectively.
The densities of the blends could be measured or cal-
culated in a similar manner to the binary mixtures.
For comparitive purposes, Kouzel (1965) method, eq 5,
was used to calculate the viscosities of the binary and
ternary crude oil mixtures over the same range of tem-
peratures and pressures. The results are summarized in
Tables XI and XII. The absolute average deviations from
the measured values were 6.8%, 14.5%, 23.9%, and 34.7 %
at 2000, 4000, 6000, and 8000 psi, respectively, for the
218 Ind. Eng. Chem. Res., Vol. 28, No. 2, 1989

Table VIII. Calculated Kinematic Viscosities of Crude Oil Binary Mixtures at High Pressure Using Equations 8 and 9
kinematic viscosity (cSt) a t
2000 psi 4000 psi 6000 psi 8000 psi
mixture temp, "C calcd '70 dev. calcd % dev. calcd % dev. calcd % dev.
1 25 11.87 2.5 14.42 2.0 17.51 -0.2 21.27 0.6
30 11.08 -3.0 13.39 -0.8 16.18 -5.0 19.55 -0.4
40 7.795 0.5 9.332 0.2 11.17 -5.1 13.38 -6.7
50 6.651 0.4 7.892 2.3 9.364 1.1 11.11 2.0
2 25 21.09 6.0 26.26 3.8 32.68 1.5 40.68 4.5
30 18.29 5.0 22.66 -0.1 28.07 -2.6 34.77 5.1
40 13.22 1.3 16.23 3.1 19.92 1.6 24.45 8.4
50 9.950 2.4 12.10 -0.9 14.72 1.3 17.91 2.7
3 25 32.25 -2.3 40.81 -3.2 51.64 -3.8 65.34 -2.0
30 27.45 -1.3 34.57 -0.7 43.54 -3.4 54.83 3.4
40 18.15 -0.7 22.65 -2.3 28.27 2.6 35.28 4.2
50 14.76 -0.9 18.26 -1.4 22.58 0.8 27.93 1.5
4 25 66.07 -3.9 85.70 2.5 111.15 4.9 144.16 4.9
30 54.36 6.6 70.18 9.6 90.61 9.5 116.99 10.5
40 33.33 4.9 42.64 -8.4 54.55 -8.9 69.82 -9.4
50 22.54 3.3 28.57 -1.4 39.23 3.5 45.93 6.0
5 25 13.96 4.4 17.10 4.7 20.94 3.6 25.64 4.9
30 12.83 -0.5 15.64 2.3 19.05 2.9 23.21 4.4
50 7.060 -1.2 8.445 -2.1 10.10 -3.6 12.09 -4.2
6 25 36.14 1.0 46.45 2.5 59.76 7.4 76.85 7.0
30 33.99 -1.1 43.51 1.4 55.69 -5.2 71.28 8.1
40 19.54 -3.4 24.78 3.0 31.43 1.5 39.86 5.7
50 15.04 -1.9 18.90 1.2 23.76 3.3 29.86 4.3
7 25 84.42 1.7 112.17 1.9 149.04 4.1 198.03 4.1
30 68.77 -2.4 90.97 2.0 120.33 7.7 159.18 9.5
40 41.89 4.3 54.92 1.1 71.99 6.1 94.38 8.9
50 26.84 -0.8 34.86 1.2 45.28 6.2 58.82 7.7
8 25 421.12 1.2 587.69 4.7 820.14 3.0 1144.54 2.8
40 178.10 -2.2 245.32 -0.3 337.91 6.8 465.45 6.8
50 103.06 -2.6 141.97 0.7 195.55 4.3 269.36 8.4
9 25 103.37 1.1 136.28 4.4 179.65 3.9 236.83 4.5
30 82.07 -0.2 107.72 2.1 141.38 -0.2 185.56 4.3
40 48.76 -0.1 63.42 -2.5 82.49 5.6 107.28 6.5
50 32.30 0.9 41.62 0.6 53.65 6.2 69.15 9.3
10 25 188.91 2.3 255.19 1.9 344.72 2.3 465.67 3.9
40 85.68 -2.5 114.22 -1.8 152.26 1.7 202.97 8.8
50 50.17 0.2 66.27 -1.4 87.54 2.7 115.64 4.9
11 25 320.56 2.5 440.14 2.1 604.31 3.2 829.73 4.3
30 246.44 -2.2 336.96 -3.1 460.73 -4.1 629.97 -5.3
40 131.76 -4.7 178.55 -5.3 241.96 -5.2 327.89 -7.2
50 81.48 -2.4 109.41 -0.7 146.91 2.6 197.27 3.8
12 25 692.70 -1.2 974.58 -1.2 1371.17 1.9 1929.15 2.6
30 520.41 1.4 729.24 1.9 1021.90 3.2 1431.96 4.1
40 261.31 1.1 362.94 0.5 504.09 1.7 700.14 -1.4
50 149.69 -0.3 206.05 -0.6 283.63 -1.7 390.42 -1.5
abs av YO dev. 2.1 2.4 3.9 5.2
mean av YO dev. 0.3 0.6 1.7 3.5

Table IX. Measured Kinematic Viscosities of Ternary Crude Oil Mixtures at High Pressure
kinematic viscosity (cSt) a t
mixture temp, O C 14.7 psi 2000 psi 4000 psi 6000 psi 8000 psi
1 25 50.05 63.85 81.51 104.512 135.63
30 37.25 47.50 61.50 79.51 98.12
40 25.56 32.02 42.43 53.66 66.69
50 18.20 23.51 29.92 37.71 48.33
2 25 36.41 45.72 58.51 75.04 96.03
30 28.35 35.56 45.98 65.50 72.94
40 18.93 23.79 29.71 37.54 46.63
50 13.30 16.72 21.34 26.21 33.05
3 25 16.22 20.61 25.70 31.24 38.52
30 13.57 16.21 20.02 24.93 30.05
40 9.755 11.70 14.29 17.50 21.95
50 7.651 9.100 11.51 14.14 17.32
4 25 82.01 106.10 142.20 178.40 229.20
30 62.71 81.51 108.20 136.80 167.90
40 39.43 52.76 69.51 88.91 111.37
50 26.02 33.75 43.06 53.80 66.01
5 25 65.07 80.51 105.30 138.90 179.90
30 50.51 65.01 84.29 106.10 139.01
40 31.98 39.89 49.91 66.55 85.70
50 21.71 27.01 34.53 43.66 56.52
 Ind. Eng. Chem. Res., Vol. 28, No. 2, 1989 219
Table X. Calculated Kinematic Viscosities of Ternary Crude Oil Mixtures at High Pressure Using Equations 8 and 9
kinematic viscosity (cSt) at
2000 psi 4000 psi 6000 psi 8000 psi
mixture tems. "C calcd % dev. calcd % dev. calcd % dev. calcd % dev.
1 25 65.45 2.5 85.77 5.2 112.39 7.5 147.28 8.6
30 48.50 2.1 63.24 2.8 82.49 3.7 107.58 9.6
40 32.99 3.0 42.67 0.6 55.19 2.8 71.37 7.0
50 23.29 -0.9 29.86 -0.2 38.28 1.5 49.08 1.5
2 25 47.07 3.0 60.99 4.2 79.04 5.3 102.40 6.6
30 36.49 2.6 47.06 2.4 60.70 -7.3 78.28 7.3
40 24.15 1.5 30.87 3.9 39.45 5.1 50.43 8.1
50 16.82 0.6 21.31 -0.1 27.00 3.0 34.20 3.5
3 25 20.23 -1.8 25.27 -1.7 31.57 1.1 39.45 2.4
30 16.84 3.9 20.94 4.6 26.03 4.4 32.36 7.7
40 12.00 2.5 14.78 3.4 18.20 4.0 22.42 2.1
50 9.327 2.5 11.39 -1.1 13.90 1.7 16.97 -2.0
4 25 107.49 1.3 141.18 -0.7 185.42 3.9 243.52 6.2
30 81.85 0.4 107.04 -1.0 139.98 2.3 183.06 9.0
40 51.01 -3.3 66.11 -4.9 85.68 -3.6 111.05 -0.3
50 33.37 -1.1 42.87 -0.4 5.08 2.4 70.76 7.2
5 25 85.67 6.4 113.03 7.3 149.13 7.4 196.75 9.4
30 66.22 1.9 87.00 3.2 114.30 7.8 150.16 8.0
40 41.55 4.2 54.10 8.4 70.42 5.8 91.67 7.0
50 27.96 3.5 36.09 4.5 46.57 6.6 60.09 6.3
abs av % dev. 3.6 3.0 4.4 6.0
mean av % dev. 1.7 2.0 3.3 5.8

6.0
t
-

1.5 -

*
'0
a

1.0 -

0.5
0.70 0.74 0.78 0.82 0.86 0.90 0.94 0.BB

dT( g / m l 1

-0 40:
Figure 6. Relationship between the slopes (R)of (In u)-P straight
----- w so'c lines, obtained from Figure 3, and crude oil density at the required
temperature ( p T ) . R = d In u / d P , with u in cSt and P in psi.
1.0
2000
pressure
4000
( PSI)
6000 8000 ature ( p T ) or its estimation from standard tables, knowing
the density at any temperature; simple mixing rules can
Figure 5. Effect of pressure on the kinematic viscosity of crude oil be used to estimate the density of mixtures; (11) calculation
binary mixtures at 40 and 50 O C .
of R from eq 8; and (111) calculation of the viscosity at the
required pressure (v,) from eq 9, providing the viscosity
binary mixtures and 6.7%, 12.1%, 18.870,and 27.7% at of the crude at atmospheric pressure ( y o ) , is known or can
2000,4000,6000, and 8000 psi, respectively, for the ternary be determined.
mixtures. The deviations of the calculated viscosities were found
to be low (absolute average deviations 15.2% and 16.0%
Conclusion for the binary and ternary mixtures, respectively). The
The effect of temperature and pressure on the viscosities proposed method will be of value for heavy crude oils
of stabilized (dead) Kuwait crude oils and their binary and reservoir simulation studies.
ternary mixtures was studied. A general method was de- Kinematic viscosities predicted by the proposed method
veloped to predict the kinematic viscosity of crude oils in showed significantly better agreement with the experi-
the range "API 14.79-35.96 and their mixutres a t high mental values than the method currently used, eq 5.
pressure. The proposed method comprises (I) measure- A similar approach can be followed to predict the
ment of the density of the crude a t the required temper- kinematic viscosity of live crudes, provided an allowance
220 Ind. Eng. Chem. Res., Vol. 28, No. 2, 1989
Table XI. Calculated Kinematic Viscosities of Crude Oil Binary Mixtures at High Pressure Using Equation 5
kinematic viscosity (cSt) a t
2000 psi 4000 psi 6000 psi 8000 psi
mixture temp, O C calcd 70dev. calcd o/c dev. calcd % dev. calcd % dev.
1 25 12.52 8.1 16.01 13.3 20.48 16.7 26.19 23.9
30 11.70 2.5 14.93 10.6 19.05 11.8 24.30 23.7
40 8.217 5.9 10.36 11.2 13.06 10.8 16.46 14.8
50 7.039 6.2 8.829 14.5 11.07 19.5 13.89 27.4
2 25 22.22 11.6 29.09 15.0 38.08 18.2 49.86 28.1
30 19.25 10.6 25.05 10.4 32.60 19.3 42.42 28.3
40 13.86 6.2 17.81 13.1 22.88 16.7 29.40 30.3
50 10.42 7.1 13.24 8.4 16.84 15.9 21.41 22.8
3 25 34.09 3.3 45.53 8.0 60.80 13.3 81.19 21.8
30 28.93 4.0 38.34 10.1 50.81 12.8 67.34 27.0
40 18.96 3.7 24.67 6.4 32.11 16.5 41.78 23.4
50 15.43 3.6 19.91 7.6 25.70 14.7 33.17 20.5
4 25 70.90 3.1 98.48 17.8 136.80 29.2 190.03 36.5
30 57.93 13.6 79.57 24.3 109.29 32.1 150.11 41.8
40 34.93 0 46.75 0 62.57 4.5 83.75 8.6
50 23.40 6.0 30.75 6.0 40.40 15.4 53.10 22.6
5 25 14.70 9.8 18.91 15.8 24.34 20.4 31.32 28.1
30 13.53 4.9 17.36 13.6 22.27 20.3 28.57 28.6
50 7.425 3.9 9.330 8.2 11.72 11.9 14.73 16.8
6 25 37.80 5.7 50.77 12.0 68.17 22.6 91.55 27.5
30 35.62 3.7 47.70 11.2 63.87 20.7 85.52 29.8
40 20.14 0 26.29 9.2 34.31 10.8 44.78 18.7
50 15.48 0.01 19.99 7.0 25.81 12.2 33.33 16.5
n
25 89.78 8.1 126.59 15.0 178.49 24.6 251.67 32.2
30 72.53 2.9 100.98 13.2 140.59 25.8 195.74 34.7
40 43.35 7.9 58.69 8.1 79.46 17.1 107.58 24.2
50 27.41 1.3 36.31 5.4 48.08 12.7 63.68 16.6
8 25 486.09 16.8 781.10 39.1 1255.15 57.7 2016.90 81.6
40 192.92 5.9 287.19 16.7 427.51 35.1 636.39 46.1
50 107.23 1.6 153.28 8.7 219.10 16.9 313.19 26.1
9 25 112.33 9.9 160.60 23.0 229.60 32.8 328.24 44.8
30 88.23 7.3 124.25 17.8 174.97 23.5 246.40 38.5
40 51.29 5.1 70.04 n -
1.1 95.64 22.4 130.60 29.7
50 33.55 3.0 44.85 8.4 59.95 18.7 80.14 26.7
10 25 209.51 13.4 313.18 25.1 468.15 39.0 699.81 56.1
40 90.97 3.5 128.49 10.5 181.47 21.2 256.30 37.3
50 52.06 4.0 71.22 6.0 97.42 14.2 133.25 20.8
11 25 366.28 17.1 573.30 33.0 897.33 53.3 1404.49 76.5
30 276.19 9.6 422.27 21.4 645.61 34.3 987.06 63.1
40 141.78 2.5 206.28 9.4 300.13 17.7 436.67 23.5
50 85.64 2.5 120.62 9.5 169.87 18.7 239.23 25.9
12 25 837.17 19.4 1419.93 43.9 2408.35 78.9 4084.82 117.2
30 611.86 19.2 1005.56 40.5 1652.59 67.0 2715.95 97.5
40 289.98 12.2 445.85 23.4 685.51 38.3 1054.00 48.4
50 160.21 6.7 235.43 13.6 345.97 19.9 508.41 28.3
abs av 70dev. 6.8 14.5 23.9 34.7
Table XII. Calculated Kinematic Viscosities of Crude Oil Ternary Mixtures at High Pressure Using Equation 5
kinematic viscosity (cSt) at
2000 psi 4000 psi 6000 psi 8000 psi
mixture temp, "C calcd % dev. calcd 9~dev. calcd % dev. calcd 70dev.
1 25 69.48 8.8 96.44 18.3 133.88 28.1 185.84 37.0
30 50.83 7.0 69.35 12.8 94.63 19.0 129.13 31.6
40 34.19 6.8 45.73 7.8 61.16 14.0 81.81 22.7
50 23.95 1.9 31.52 5.3 41.47 10.0 54.58 12.9
2 25 49.59 8.5 67.55 15.4 92.00 22.6 125.31 30.5
30 38.10 7.1 51.21 11.4 68.82 5.1 92.49 26.8
40 24.95 4.9 32.87 10.6 43.32 15.4 57.08 22.4
50 17.26 3.2 22.39 4.9 29.05 10.8 37.69 14.0
3 25 21.20 2.8 27.70 7.8 36.20 15.9 47.31 22.8
30 17.60 8.6 22.82 14.0 29.60 18.7 38.39 27.8
40 12.47 6.7 15.98 11.8 20.46 16.9 26.18 19.3
50 9.706 6.7 12.31 7.0 15.62 10.5 19.82 14.4
4 25 117.57 10.8 168.54 18.5 241.60 35.4 346.35 51.1
30 88.30 8.3 124.32 14.9 175.05 28.0 246.47 46.8
40 53.98 2.3 73.90 6.3 101.17 13.8 138.50 24.4
50 34.84 3.2 46.64 8.3 62.45 16.1 83.61 26.7
5 25 91.86 14.1 129.68 23.1 183.07 31.8 258.44 43.6
30 70.18 7.9 97.50 15.7 135.46 27.7 188.21 35.4
40 43.29 8.5 58.59 17.4 79.31 19.2 107.35 25.3
50 28.81 6.7 38.24 10.7 50.75 16.2 67.36 19.2
abs av % dev. 6.7 12.1 18.8 27.7
 I n d . E n g . Chem. Res. 1989, 28, 221-224 22 1

is included for the effects of dissolved gas concentration. Eyring, H.; Hirschfelder, J. “The Theory of The Liquid State”. J .
Phys. Chem. 1937,41, 249.
Acknowledgment Frisch, D.; Eyring, H.; Kincaid, J. F. “Pressure and Temperature
Effects on The Viscosity of Liquids”. J . Appl. Phys. 1940,11,75.
The authors express their gratitude to Kuwait Institute Gubbins, K. E.; Tham, M. J. “Free Volume Theory for Viscosity of
Simple Nonpolar Liquids”. AZChE J. 1969, 15(2), 264.
for Scientific Research for financial support during the Heric, E. L.; Brewer, J. G. “Viscosity of Some Binary Liquid None-
course of this project. lectrolyte Mixtures”. J . Chem. Eng. Data 1967, 12(4), 574.
Heric, E. L.; Brewer, J. G. “Viscosity of Some Ternary Liquid No-
Nomenclature nelectrolyte Mixtures”. J . Chem. Eng. Data 1969, 14(1), 55.
Heric, E. L.; Brewer, J. G. “Viscosity in Three Quaternary Liquid
A-D = constants Nonelectrolyte Systems”. J. Chem. Eng. Data 1970, 15(3), 379.
a ( l ) , a(2), b ( l ) , b(2) = constants Hersey, M. D.; Lowdenslager, D. B. “Film thickness between geer
ASTM = American Society for Testing and Materials teeth”. Trans. Am. SOC. Mech. Eng. 1950, 72, 1033.
P = pressure, psi Irving, J. B. “Viscosities of binary mixtures: a survey of mixture
T = temperature, “C equations”. NEL Report 630, 1977; East Kilbride, Glasgow, Na-
t = flow time, s tional Engineering Laboratory.
R = slope of (In v)-pressure straight line, calculated from eq Khan, M. A. B.; Mehrotra, A. K.; Svrcek, W. Y. “Viscosity Models
for Gas-Free Athabasca Bitumen”. J . Can. Pet. Technol. 1984,
8, cSt/psi 23(3), 47.
x = weight fraction Kouzel, B. “How Pressure Affects Liquid Viscosity“. Hydrocarbon
Greek Symbols Proc. Pet. Refin. 1965, 44(3), 120.
Macedo, P. B.; Litovitz, T. A. “On The Relative Roles of Free Vol-
v = kinematic viscosity, cSt ume and Activation Energy in The Viscosity of Liquids”. J .
7 = absolute viscosity, CP Chem. Phys. 1965, 42(1), 245.
p = density, g/mL McAllister, R. A. “The Viscosity of Liquid Mixtures”. AIChE J .
e = constant 1960, 6(3), 427.
Mehrotra, A. K.; Svrcek, W. Y. “Measurement and Correlation of
Literature Cited Viscosity, Density and Gas Solubility for Marguerite Lake Bitu-
men Saturated with Carbon Dioxide”. AOSTRA J . Res. 1984,1,
Ahrabi, F.; Ashcroft, S. J.; Shearn, R. B. “High Pressure Volumetric, 51.
Phase Composition and Viscosity Data for a North Sea Crude Oil Mehrotra, A. K.; Svrcek, W. Y. “Viscosity, Density and Gas Solu-
and NGL“. Chem. Eng. Res. Des. 1987,65, 63. bility Data for Oil Sand Bitumens. Part I: Athabasca Bitumen
Al-Besharah, J. M. Unpublished Results, Kuwait Institute For Sci- Saturated with Co and C2H,”. AOSTRA J. Res. 1985, 4, 263.
entific Research, 1988. Mehrotra, A. K.; Svrcek, W. Y. “Viscosity of Compressed Athabasca
APZ Technical Data Book; “Petroleum Refining”. API: Washing- Bitumen”. Can. J . Chem. Eng. 1986, 64, 844.
ton, DC, 1970. Powell, R. E.; Roseveare, W. E.; Eyring, H. “Diffusion, Thermal
ASTM D445/IP71, The American Society for Testing and Materials, Conductivity, and Viscous Flow of Liquids”. Ind. Eng. Chem.
1983. 1941, 33(4), 430.
Block, H. “Viscosity-Temperature-Pressure Relationships, Their Sanderson, R. T. “Viscosity, Temperature, and Pressure of Lubri-
Correlation and Significance for Lubrication”. World Pet. Cong., cating Oils”. Ind. Eng. Chem. 1949, 2059.
3rd 1951, Sec. VI1
Ewell, R. H.; Eyring, H. “Theory of The Viscosity of Liquids as a Received for review February 29, 1988
Function of Temperature and Pressure”. J. Chem. Phys. 1937,5, Revised manuscript received August 24, 1988
726. Accepted September 2, 1988

Isoquinoline Alkaloids. 1. An Efficient Preparation of

d,I-Laudanosoline Hydrobromide
Christian T. Goralski,* Richard C. Krauss, Billy M. Williams, Daniel R. Henton, and
Douglas T. Brown
Pharmaceuticals Process Research, Michigan Applied Science a n d Technology Laboratories,
The Dow Chemical Company, Midland, Michigan 48674

An efficient process for the preparation of laboratory and pilot-plant quantities of d,l-laudanosoline
hydrobromide ( 5 ) from papaverine hydrochloride (1) with no intermediate isolation is described.
The average 91% yield of 5, based on the amount of starting 1, obtained from this procedure is a
considerable improvement over the 69% yield of 5 , which is obtained when the intermediates
papaverine (2), papaverine methiodide (3), and d,l-laudanosine (4) are isolated and purified.

The isoquinoline alkaloid d,l-laudanosoline hydro- Treatment of d,l-glaucine with 85% phosphoric acid as
bromide (5) has been studied by both Schoepf and described by Wang (1982) and Goralski (1982) afforded
Thierfelder (1932) and Robinson and Sugasawa (1932) as
a potential starting material for the synthesis of morphine
and aporphine alkaloids. A large quantity of 5 was re-
quired for the preparation of laboratory and pilot-plant
quantities of the aporphine alkaloid d,l-glaucine by a
modification of the procedures of Tietze (1968) and Ma-
asboel and Sim (1981) as described by Henton et al. (in
CH3P
the 1.5 phosphate salt 6 which was shown by Schuster et

CH3

CH3
HI ’ 1 . 5 H,PO,

press) for the preparation of [6a-13C]-d,l-glaucine. c

08S8-5S85/S9/2628-0221$01.50/0 0 1989 American Chemical Society