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1000 Fluid Properties

Abstract
This section discusses the viscosity and gravity properties of Newtonian and non-
Newtonian fluids as they relate to the characterization of hydrocarbon liquids and
gases. It presents graphs and equations for estimating or calculating viscosity versus
temperature, gravity versus temperature, viscosity of blends and brine-in-oil emul-
sions, etc. Relationships of pressure and flow rate to viscosity are also discussed.
Conversion tables are included.
A general discussion of non-Newtonian waxy crude viscosity includes basic equa-
tions and analytical correlations. It covers practical aspects, principles, and equa-
tions related to the measurement of viscosity as well as the design and use of
viscometers. Laboratory measurement of non-Newtonian flow properties and gel
strength is discussed. An overview of computer program HOTOIL is included.

Contents Page
1010 Viscosity 1000-3
1011 Absolute Viscosity
1012 Kinematic Viscosity
1013 Temperature and Viscosity
1014 Viscosity Index
1015 Pressure and Viscosity
1016 Flow Rate and Viscosity
1017 Measurement of Viscosity
1018 Viscosity of Blends
1019 Viscosity of Brine-in-Oil Emulsions
1020 Gravity 1000-33
1021 Example
1030 Non-Newtonian Fluids 1000-37
1031 Laboratory Measurement of Flow Properties
1032 Laboratory Measurement of Gel Strength

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1033 Constitutive Relationships


1034 Calculation of Flow Parameters
1035 Hydraulics Equations
1036 Computer Program HOTOIL
1037 Estimating Pipeline Restart Pressure Gradient
1038 Wax Deposition
1040 References 1000-55
1041 Viscosity Conversion
1042 Viscosity Data
1043 Brine-in-Oil Emulsions

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1010 Viscosity
Viscosity is a measure of the internal friction or resistance of a fluid to the relative
motion of its parts. It may be regarded as the relationship between the force applied
to a fluid and the rate of deformation produced in the fluid.

1011 Absolute Viscosity


The force F required to move a fluid layer with surface area A located a distance D
from a stationary surface, at a velocity V, can be expressed by:

(Eq. 1000-1)
The coefficient is defined as the absolute, or dynamic, viscosity. Its metric system
dimensions are as follows:

(Eq. 1000-2)
where:
F = shearing force, dynes (dyne = gram cm/sec2)
V/D = velocity gradient, sec-1
A = area of shear, cm2
Since the poise is a relatively large number, absolute viscosity is normally expressed
in centipoise (0.01 poise).
The English system expression for absolute viscosity is as follows:

(Eq. 1000-3)

or
(Eq. 1000-4)
Conversion factors for absolute viscosities are included as Figures 1000-1 through
1000-5.

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Fig. 1000-1 Conversion Factors for Absolute Viscosity

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Fig. 1000-2 Viscosity ConversionFrom Various Terms to Saybolt Universal (1 of 2) Courtesy of Hydraulic Institute

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Fig. 1000-2 Viscosity ConversionFrom Various Terms to Saybolt Universal (2 of 2) Courtesy of Hydraulic Institute

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Fig. 1000-3 Viscosity of Common Liquids (1 of 4) Courtesy of Hydraulic Institute

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Fig. 1000-3 Viscosity of Common Liquids (2 of 4) Courtesy of Hydraulic Institute

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Fig. 1000-3 Viscosity of Common Liquids (3 of 4) Courtesy of Hydraulic Institute

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Fig. 1000-3 Viscosity of Common Liquids (4 of 4) Courtesy of Hydraulic Institute

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Fig. 1000-4 Viscosity Conversion Equations


Equation for Converting Kinematic Viscosity to Flow Times(1)
where:
1 + EV
T = DV + ------------------------------------------------------ T = flow time, seconds (or Engler degrees)
2 3
F + GV + HV + IV V = kinematic viscosity, centistokes (CS)
D,E,F,G,H,I = constants given below
Unit D E F G H I Range (CS)
(2)
Saybolt Universal 4.6324 0.03264 0.039302 0.02627 0.002397 0.00001646 >1.8
seconds at 100 F
Saybolt Universal2 4.6635 0.00677 0.039911 0.000938 0.000280 0.00000274 >1.8
seconds at 210 F
Saybolt Furol seconds 0.47170 0.0 0.4895 -0.005213 0.0000718 0.0 >48
at 122 F
Saybolt Furol seconds 0.47916 0.0 0.3797 0.0 0.0001783 0.0 >48
at 210 F
Redwood No. 1 4.0984 0.0 0.038014 0.001919 0.0000278 0.00000521 >40
seconds at 140 F
Redwood No. 2 0.40984 0.0 0.38014 0.01919 0.000278 0.000521 >73
seconds
Engler degrees 0.13158 0.0 1.1326 0.01040 0.00656 0.0 >1.0
Equation for Converting Flow Times to Kinematic Viscosity1
where:
BT
V = AT ------------------ V = kinematic viscosity, centistokes (CS)
3
T +C
T = flow time, seconds (or Engler degrees)
A,B,C = constants given below
Unit A B C Range
Saybolt Universal seconds at 0.21587 11,069 37,003 SUS >32
100 F
Saybolt Universal seconds at 0.21443 11,219 37,755 SUS >32
210 F
Saybolt Furol seconds at 122 F 2.120 8,920 27,100 SFS >25
Saybolt Furol seconds at 210 F 2.087 2,460 8,670 SFS >25
Redwood No. 1 seconds at 140 F 0.244 8,000 12,500 R1 >35
Redwood No. 2 seconds 2.44 3,410 9,550 R2 >31
Engler degrees 7.60 18.0 1.7273 E >1.000
(1) Figure 1000-5 is based on these equations and should provide equal accuracy.
(2) The following correction for Saybolt Universal seconds at other temperatures, is small and usually
unnecessary:

SUS = CS [ 1 + 0.000061 ( t 100F ) ] ------------------------------


SUS100F
CS100F

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Fig. 1000-5 Viscosity ConversionCentistokes to Saybolt Universal or Saybolt Furol

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1012 Kinematic Viscosity


Kinematic viscosity, , is defined as the absolute viscosity of a fluid divided by its
density. In the metric system, the unit of kinematic viscosity is the stoke and is
expressed as follows:

=/
(Eq. 1000-5)
where:
= kinematic viscosity, stokes
= absolute viscosity, poises
= density, grams/cm3
The most commonly used unit of kinematic viscosity is the centistoke (cs = 0.01
stoke). The corresponding unit in English units is ft2/sec. To convert centistokes to
English units, multiply by 1.08 x 10-5 to obtain ft2/sec.

1013 Temperature and Viscosity


In liquids, an increase in temperature increases the kinetic energy of molecules and
thus reduces viscosity. In gases, on the other hand, an increase in temperature
increases interaction between molecules, which increases viscosity.
Viscosity versus temperature curves for a number of petroleum products and crude
oils are included as Figures 1000-6 through 1000-12. These curves are plotted on
a special graph paper which, for most oils, produces a straight line. This graph paper
is described in American Society for Testing Materials (ASTM) Standard D341-43
and may be obtained from ASTM. If the viscosity of an oil is known at a given
temperature, its viscosity at other temperatures may be estimated by plotting the
known point on this graph paper and drawing a line parallel to one for a similar oil.
The viscosity versus temperature curves for a number of gases are given in
Figure 1000-18. Under most flow conditions, the viscosity of gases is so low that,
for fluid flow problems, it may be assumed to be constant at all ordinary tempera-
tures and pressures. This assumption has been made in plotting the curves for gas
and steam flow. The error attributable to assuming constant viscosity in flow calcu-
lations will usually be smaller than experimental errors.
For most flow problems, the data plotted in the viscosity-temperature charts is suffi-
ciently accurate. This is particularly true in the turbulent flow region. However,
when pumping high viscosity liquids under laminar flow conditions the pressure
drop is directly proportional to viscosity, and viscosity data must be as accurate as
possible. Under these conditions, there is no substitute for a test of the actual mate-
rial to be pumped.

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Fig. 1000-6 Viscosity DataAverage San Joaquin Valley Crudes

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Fig. 1000-7 Viscosity DataLos Angeles Basin Crudes

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Fig. 1000-8 Viscosity DataSan Joaquin Valley and Coastal Crudes

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Fig. 1000-9 Viscosity DataMiscellaneous Crudes

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Fig. 1000-10 Viscosity vs. Temperature, Refined ProductsLight Products

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Fig. 1000-11 Viscosity vs. Temperature, Refined ProductsAsphalts & Fuel Oils

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Fig. 1000-12 Viscosity vs. Temperature, Refined ProductsLubricating Oils

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Fig. 1000-13 Viscosity of Liquid Ethane, Propane, and N-Butane

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1014 Viscosity Index


The viscosity index is an empirical number indicating the effect of a change of
temperature on the viscosity of an oil. A low viscosity index signifies a relatively
large change of viscosity. The viscosity index is calculated by comparing the
viscosity-temperature relationship of the oil under test with those of two standard
oils, one of which is assumed to have a 0 viscosity index and the other a 100
viscosity index. The procedure for calculating the viscosity index is given in ASTM
Standard D2270-64.

1015 Pressure and Viscosity


Below the critical pressure the viscosity of liquids is essentially constant with
respect to changes in pressure. Above the critical pressure, however, viscosity may
increase substantially with an increase in pressure. Variation of liquid and gaseous
viscosity at high pressures is covered in the American Petroleum Institute (API)
Technical Data Book - Petroleum Refining, Chapter 11, Viscosity.

1016 Flow Rate and Viscosity


At constant temperature and pressure, the viscosity of most fluids is independent of
flow rate. These fluids are called Newtonian fluids. Most petroleum crude oils and
products can be considered Newtonian fluids at temperatures above their pour
points. For some non-Newtonian fluids, viscosity is a function of flow rate or time.
These fluids are further categorized as pseudoplastic, semiplastic or thixotropic. See
also Section 1030.
At constant temperature, the viscosity of a pseudoplastic fluid decreases as the rate
of shear increases. Asphalts, glues, and molasses are pseudoplastic fluids.
A semiplastic fluid is a material that will sustain a certain shear stress without
flowing. Once this shear stress has been exceeded, the material will behave like a
normal fluid, and may have a relatively low viscosity. An example of such a mate-
rial is a clay slurry such as drilling mud.
At constant temperature and shear rate, the viscosity of a thixotropic fluid
decreases with time to a minimum value. When the shearing stress is removed, the
viscosity increases with time to the value at zero shear. Examples include paints,
ketchup, crude oil emulsions and oils near or below their pour points.
Finally, the viscosity of a dilatant fluid increases as the rate of shear increases.
Certain colloidal solutions are dilatant.

1017 Measurement of Viscosity


Liquid viscosity is usually determined by timing the efflux of a given volume of
liquid through a standard aperture or capillary tube under specified conditions. The
aperture or capillary, together with a heating bath and other necessary parts, forms a
viscometer.

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The viscosities of petroleum products are generally specified in terms of time, and
using one of the following viscometers:
Saybolt Universal for lubricating oils, gas oils, and crude oils. Saybolt
Universal viscosity is the time in seconds needed for the delivery of 60 cc of
liquid from the Saybolt viscometer. Temperatures usually employed are 70F,
130F, and 210F.
Saybolt Furol for crude residuum and heavy fuel oils. Saybolt Furol viscosity
is the time in seconds needed for the delivery of 60 cc of liquid from the
Saybolt viscometer equipped with a Furol outlet tube. The test is usually run at
a temperature of 122F. The outflow time of the Furol instrument is approxi-
mately one-tenth that of the Universal.
Although Saybolt viscometers are used in petroleum product specification, capil-
lary instruments are more widely used in making viscosity measurements. Capillary
instruments give more precise and reproducible results which can be converted to
centistokes or Saybolt seconds with the appropriate charts. Test procedures for kine-
matic viscosities and descriptions of several commercially available viscometers are
given in ASTM Standard D-445-65. Equations and tables for converting kinematic
viscosity to Saybolt Universal viscosity and Saybolt Furol viscosity are given in
Figures 1000-4 and 1000-5.

1018 Viscosity of Blends


Figure 1000-16 provides a convenient means of estimating the viscosity of blends of
petroleum liquids at a given temperature. Reasonably accurate results can be
expected if the two oils being blended are of the same or similar type. If more accu-
rate data are required the blend should be tested.

1019 Viscosity of Brine-in-Oil Emulsions


Flow from many producing wells consists of an emulsion in which globules of brine
are dispersed in crude oil. The viscosity of such an emulsion can have a direct influ-
ence on pumping pressures and line sizes. No theoretical means of estimating a
brine-in-oil emulsions viscosity over the range of possible brine content is avail-
able. However, experimental data compiled by William Woelfin (see Section 1040,
reference 9) allows approximation of emulsion viscosity if the clean oil viscosity is
known. Given the degree of emulsification (tight, medium, loose) and the percent
brine content, the viscosity of the emulsion can be calculated from the viscosity
ratio and clean oil viscosity (see Figure 1000-17).
Emulsions with higher brine contents (about 60 to 70%), develop a very high
viscosity and may show plastic-solid qualities. At an inversion point (usually 70 to
80%) the brine-in-oil emulsion inverts to oil-in-brine and the viscosity drops to
roughly that of the brine.

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1000 Fluid Properties


Fig. 1000-14 Viscosities of Hydrocarbon Liquids From Engineering Data Book, 9th ed., 1972. Courtesy of GPSA.
1997 Chevron USA Inc. All rights reserved.

Fluid Flow Manual


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Fig. 1000-15 Approximate Viscosity-Temperature Relations for Liquid Petroleum Fractions

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Fig. 1000-16 Viscosity Blending Chart (1 of 2)


VISCOSITY BLENDING CHART

1. This chart can be used to estimate the viscosity of a blend of two oils where their viscosities and volume frac-
tions for a given temperature are known.
2. Reasonably accurate answers can be expected only where the two oils being blended are of the same type.
3. Viscosity scales on the chart are based on Chevron Research Companys blending factor method in which the
viscosity scale is drawn proportional to:
ln [ l + ln (2)]
Where equals kinematic viscosity in centistokes.
Example:
Given: A blend is to be made with 80% consisting of an oil with a 10,000 centistoke viscosity and 20% of
an oil with a 100 centistoke viscosity.

Problem: Determine the viscosity of the blend.

Solution: 1. Connect the point for the higher viscosity oil (10,000 cs) on the left-hand scale with the point
for the lower viscosity oil (100 cs) on the right hand-scale with a straight edge.

2. Read the viscosity of the blend at the percentage composition of the blend.
For this example, the viscosity of the blend is 3,200 cs.

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Fig. 1000-16 Viscosity Blending Chart (2 of 2)

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Fig. 1000-17 Viscosity of Brine-In-Oil Emulsions (1 of 2)


VISCOSITY OF BRINE-IN-OIL EMULSIONS

1. This chart may be used to estimate the order of magnitude of the effective viscosity of a brine-in-oil emulsion at
a given temperature if the viscosity of the clean oil at that temperature and the percent brine in the emulsion are
known.
2. To estimate an emulsion viscosity:
Classify the emulsion as follows:
Tight. Small brine particle sizemight occur in a wet well where a high gas-oil ratio results in
extremely agitated flow.
Medium. Brine particle size between that of tight and loose emulsionsmight occur if a pump
is in poor condition or under moderate gas agitation.
Loose. Large brine particle sizemight occur in production from a pumping well in which
mechanical equipment is in good condition.
Find the point on the appropriate curve for percent brine in emulsion and read the corre-
sponding viscosity ratio.
Calculate the viscosity of the emulsion by multiplying the viscosity of the clean oil by the viscosity
ratio.
3. In general, emulsions are thixotropic fluids with appreciable shear strength. As the percent brine approaches the
inversion point (often about 79%) the shear strength of the emulsion may be very high and the emulsion may
take on a plastic-solid quality.
4. At the inversion point a brine-in-oil emulsion will invert to an oil-in-brine emulsion. Viscosity of the oil-in-brine
emulsion will be approximately that of the brine.
Example:
Given: A tight emulsion of 40% brine in 12.3 API Inglewood crude is flowing at 100F.
Problem: Determine the viscosity of the emulsion.
Solution: From Figure 1000-17, viscosity ratio = 5.

From chart on Figure 1000-8, viscosity of clean oil = 34 cs.


Viscosity of emulsion = (viscosity of clean) (viscosity ratio).
Viscosity of emulsion = (34 cs) (5) = 170 cs.

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Fig. 1000-17 Viscosity of Brine-In-Oil Emulsions (2 of 2)


VISCOSITY OF BRINE-IN-OIL EMULSIONS

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Fig. 1000-18 Viscosity of Gases

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Fig. 1000-19 Weights of Petroleum Products

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1020 Gravity
In the petroleum industry the mass-volume relationship most commonly used for
gases and liquids is gravity. Gravity can be expressed in several ways, for instance,
specific gravity and degrees API.
The density of a fluid, , is defined as its mass per unit volume.

=m/v
(Eq. 1000-6)
The density of water at standard conditions of 14.7 psia and 39.4F (4C) is 62.43
1bm/cu ft or 1000 kg/m3. The standard conditions for defining water are not equiva-
lent to the more commonly used, which are 14.696 psia and 60F.
The specific weight, , of a unit volume of a material depends on its location in the
earths gravity field. Thus:

=g
(Eq. 1000-7)
Specific gravity (SG) is the ratio of the weight of a substance to the weight of an
equal volume of water (or air, density 0.0763 lbm/cu ft) at standard conditions. Since
specific gravity is related to standard conditions it does not change with location.
Specific gravity may also be expressed as a ratio of density.
API gravity is expressed in degrees and is related to specific gravity by the equa-
tion shown in Figure 1000-23. Other gravity scales exist and conversion tables are
available. Since specific gravity is based on water at a standard temperature,
substances which change volume with temperature have varying specific gravities.
Figure 1000-20 shows the temperature relationship for oils. In Figure 1000-20:
Specific gravities are referred to water at 60F
The temperature correction to specific gravity is based on the ASTM-IP Petro-
leum Measurement Tables, Table 24
Figure 1000-19 gives API gravities and corresponding volume measurements for
various refined petroleum products. Figures 1000-21 and 1000-22 show the thermal
expansion of petroleum fractions. Figure 1000-21 provides a fast means of solving
for resultant gravity after blending two oils of different gravities. The graph repro-
duces the equation on Figure 1000-23. Values obtained from Figure 1000-21 are
approximate since no allowance has been made for shrinkage of the blend. Where
more accurate data is required, a test should be made of the stocks in question.
Specific gravities in Figure 1000-21 are referred to water at 60F. For use of the
chart all gravity data should be at the same temperature.

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Fig. 1000-20 Gravity Conversion Chart

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Fig. 1000-21 Gravity Blending Chart

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Fig. 1000-22 Thermal Expansion of Petroleum Fractions (1 of 2)

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Fig. 1000-22 Thermal Expansion of Petroleum Fractions (2 of 2)

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Fig. 1000-23 API and Baum Gravity Tables Courtesy of Goulds Pumps

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1021 Example
Find the gravity of a blend consisting of 21-1/2% 42API gravity oil and 78-1/2%
23.50API gravity oil. On Figure 1000-21, lay a straightedge connecting the specific
gravity of the heavier oil at the top of the page (0.913) with the specific gravity of
the lighter oil at the bottom (0.815). The intersection of this line with the composi-
tion of the blend gives the gravity of the blend: 0.892 specific gravity, or 27.1API
gravity.

1030 Non-Newtonian Fluids


It is normal for waxy crude oils to flow from producing wells at elevated tempera-
tures. At these temperatures, the properties of waxy crudes are much like those of
normal crude oils. However, when the temperature of a waxy crude approaches the
pour point, its consistency and behavior deviate significantly from those of normal
crude oils.
Waxy crudes anomalous characteristics impose special design considerations on
facilities that handle them. This section describes the equipment and techniques
Chevron Research has developed to measure the properties of waxy crudes, and the
procedures and computer programs that the Chevron Research and Technology
Company has used to design facilities for handling waxy crudes.

The Sources of Anomalous Behavior


Deviations from normal crude oil behavior are caused by precipitation or crystalli-
zation of wax from the crude oil as it cools. The wax forms a structure within the oil
that changes the consistency, and can develop into a gel resembling shoe polish
that sets up a solid plug requiring significant pressures to move.
An added complication with waxy crudes is their history-dependence. The rates at
which the wax components crystallize and the nature of the structure that is devel-
oped depend on the cooling rate and the amount of stirring or shearing of the oil as
it cools. Therefore, the properties measured in the laboratory specifically near or
below the pour pointdepend on the temperature profile (thermal history) and
shearing profile (mechanical history) of the oil sample before the test. This history-
dependence is not observed in normal crude oils.

The Importance of Sample Collection and Handling


Since the measured properties depend on the concentration and distribution of wax
components in the sample and the blend of other non-waxy components, the sample
collection procedure must ensure that the sample is truly representative of the oil
that will be produced. Sample distortion during drill stem tests may result from
deposition of wax in the tubing (and its loss from the sample), dilution by the diesel
cushion, wax deposition on cold surfaces in the separator or storage tank, and
contamination by other oils left over in the test separator.
These sources of error cannot be eliminated, but their effects can be minimized by
running a longer drill stem test to increase the wellhead temperature, filling and
emptying the separator and storage tanks with the produced crude several times

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during the drill stem test, keeping the separator and storage facilities hot, and taking
the samples as late in the drill stem test as possible.
Sample drums should be clean, preferably epoxy-coated, and (if possible) filled
from flowing lines rather than from storage tanks. After the residual gas has been
allowed to boil off, the drums should be sealed tightly for shipment to prevent loss
of light ends and intrusion of water.
In the Chevron Research laboratory the drums are heated and stirred to melt any
wax that may have precipitated and deposited on the drum surfaces. This is done in
a way that minimizes the loss of light ends. The crude is then put in smaller
containers for ease of handling.
The collection and handling process imposes a different history on the crude sample
than would the production process. Before any testing is done, this history is
erased, usually just before the test, by heating the sample enough to ensure that all
the wax is back in solution. This temperature is often close to the reservoir tempera-
ture.

Characterization of Crude
Standard laboratory tests are normally used to characterize a crude sample. These
tests usually include gravity, pour point, viscosity (in a capillary viscometer at
higher temperatures), and water content. If the water content is higher than that
expected from the production separators it is removed before the testing begins,
because water can have a significant effect on the crude properties.
Additional testing includes wax content, microscopic cloud point, specific heat
capacity, distillation, and toluene and pentane insolubles. These tests are only done
if required for a specific purpose.

1031 Laboratory Measurement of Flow Properties


The primary tests for waxy crudes include consistency measurements with a
concentric cylinder viscometer, and gel yield strength measurements with a long
1/4-inch diameter tube. This equipment will now be discussed in more detail.
For any given project the laboratory testing program must suit the planned or
existing facilities. The thermal and mechanical histories of the oil flowing through
the producing facilities must be estimated and these estimates used to design the test
program. The program design includes a definition of the initial oil temperature
(history erasing temperature), temperature profile in time, and shearing profile in
time.
The temperature profile, T(t), is usually defined by the initial temperature, Ti,
ambient temperature, Ta, and cooling parameter, , where

T(t) = Ta + (Ti - Ta) e-t


(Eq. 1000-8)
If the time, t, is in hours then the parameter, , is in hours-1.

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As oil flowing in a pipeline cools, the shearing profile changes, increasing from the
inlet to the outlet. This shearing (or turbulence) can be characterized by the power
dissipation density (in horsepower/cubic foot). Although this change can be simu-
lated in the laboratory, fluid properties are usually not very dependent on the
amount of turbulence, and this parameter usually remains fixed in a test.
In a typical test of consistency, an oil sample heated to Ti is placed in a device that
simulates the shear. This device is immersed in a temperature-controlled bath and
cooled according to the predefined temperature profile (Eq.1000-8) while being
subjected to shear at a specified rate. When the oil temperature reaches the range of
interest, the oil sample is transferred to a concentric cylinder viscometer that is
also immersed in the temperature-controlled bath. Cooling continues while the
sample is sheared in the viscometer. The temperature in the bath is controlled to
within a fraction of a degree. This is an important feature of the laboratory proce-
dure.
Concentric cylinder viscometers come in various styles. The Ferranti model favored
by Chevron Research is shown in Figure 1000-24. The oil sample is contained in the
annular gap between the two cylinders. The outer cylinder is rotated at a controlled
speed and the inner one is fixed to a torsion balance. The cylinder diameters, the
annular gap between the cylinders, and the rotation speed of the outer cylinder
define the shear strain rate imposed on the oil in the gap. The cylindrical area of the
inner cylinder and the torque on the torsion balance define the resulting shear stress
on the oil. The air bubble under the inner cylinder eliminates end effects.

Fig. 1000-24 Ferranti Viscometer

At various temperatures along the cooling profile, the rotational speed of the outer
cup is varied to measure shear stress/shear strain rate pairs over a range of shear
strain rates. In the Ferranti viscometer this is done at three shear strain rates. In other
viscometers pairs can be measured at up to eight shear strain rates.

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During these shear scans the shear strain rate is held constant long enough to let
transient or thixotropic effects decay. The resulting pairs are called equilibrium
values. Chevron has found that these measurements can be quite misleading if the
thixotropic effects often associated with waxy crude oils are not permitted to decay
before the test values are recorded.
The temperature range for these consistency tests is usually from the neighborhood
of the pour point down to the lowest temperature of interest or to the point where
the viscometer goes off scale. The use of the shear stress, shear strain rate pairs
produced by these tests is discussed in the section on calculation of flow parameters.

1032 Laboratory Measurement of Gel Strength


In many pipelines the crude oil temperature at the inlet is higher than the ambient
temperature. In these cases there is a temperature distribution in the oil along the
pipeline. If the pipeline is long enough, the oil cools to the ambient temperature. If
the flow is stopped, all of the oil in the pipeline will eventually cool to the ambient
temperature. The oil near the inlet will cool the most. The oil near the outlet may
already have cooled to the ambient temperature under dynamic (flowing) condi-
tions. This oil will have a different cooling history than the oil cooled under static
conditions; that is, without shear. The measurement of gel strength must simulate
these dynamic and static cooling histories.
To test gel strength, the oil sample is heated, placed in the (dynamic) shearing
device, immersed in a temperature-controlled bath, and cooled to a transfer tempera-
ture, Tt (the oil temperature at a given point in the pipeline when flow stops). The
oil is then transferred to a coiled tube (Figure 1000-25) and cooled statically to the
test temperature (usually the pipeline ambient temperature) along the defined
profile. The coil is carefully crafted to prevent formation of unvented gas pockets
during filling.
After several hours at the test temperature, the oil is subjected to a pressure differ-
ence which is slowly increased until the oil yields or starts to flow. The pressure
difference at yielding is used to calculate the breakaway yield strength (BAYS), b,
as follows:

tb = Dp/4L
(Eq. 1000-9)
where:
D = inside diameter of coil
p = pressure difference across the coil
L = length of the coil
In general, the BAYS at any temperature Ta depends on the amount of static cooling
T = Tt - Ta. A test program usually includes measuring the BAYS as a function of
T. For many crudes, there is a value for T that gives a maximum value for BAYS.

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1033 Constitutive Relationships


The relationship between the load exerted on and deformation of a material is called
a constitutive relationship. The familiar relationship between load and deformation
(or stress and strain) for steels is linear over a range of stress called the elastic
range. The slope of the stress-strain curve is the modulus of elasticity. Beyond the
elastic limit (above the yield strength) the curve is not straight. For liquids, there is a
similar constitutive relationship. However, instead of stress and strain, the relation-
ship is between shear stress and shear strain rate. Several relationships, or flow
models, for different liquids are shown in Figure 1000-26.

Fig. 1000-25 BAYS Pipe Rig Fig. 1000-26 Flow Models

Newtonian liquids have a certain constitutive relationship: the shear stress is propor-
tional to the shear strain rate. The proportionality constant (or slope) of the Newto-
nian relationship is the absolute viscosity , a function of temperaturethe lower
the temperature, the higher the slope. For Newtonian liquids we can express the
relationship between shear stress, , and shear strain rate, s, as

= s
(Eq. 1000-10)
If the shear strain rate and the corresponding shear stress are known, then the abso-
lute viscosity is

= /s
(Eq. 1000-11)
The absolute viscosity of Newtonian fluids is a function of temperature only.
Furthermore, Newtonian liquids will flow even when a very small shear stress is
applied.

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In general, there is no reason for the constitutive relationship for liquids to be


straight and to go through the origin. There are many such non-Newtonian relation-
ships or flow models. In Figure 1000-26 the Power Law (or Pseudoplastic) Model
goes through the origin but is curved. The Bingham Model is straight but does not
go through the origin. The Herschel-Bulkley Model is neither straight nor does it
go through the origin. The equations describing the relationship between shear
stress, , and shear strain rate, s, for these models are as follows:
Power Law Model:

= sn
(Eq. 1000-12)
Bingham Model:

= y + s
(Eq. 1000-13)
Herschel-Bulkley Model:

= y + sn
(Eq. 1000-14)
For Equations 1000-13 and 1000-14 the parameter y is the intercept of the curve
with the vertical axis. This intercept yield strength is not the same as the BAYS,
and one cannot be estimated from the other. Often the BAYS, b, is larger than y. In
addition, power law liquids have no intercept yield strength but can have a BAYS.
Equations 1000-12 and 1000-13 are two-parameter models; to define the flow
model one needs either (, n) or (, y). Equation 1000-14 requires three parame-
ters to define the flow, (, n, and y). The Herschel-Bulkley model becomes the
power law model when y = 0 and the Bingham model when n = 1. All three
become the Newtonian model when y = 0 and n = 1. Heat loss and pressure drop
can be calculated for any of these models.
All of the flow parameters just discussed depend upon temperature. With non-
Newtonian liquids one can also talk about the apparent viscosity,

a = /s
(Eq. 1000-15)
Apparent viscosity is a function both of temperature and shear strain rate; as the
shear strain rate increases, the apparent viscosity decreases. This leads to the notion
of shear thinning liquids. In contrast to the Newtonian and power law models,
Bingham and Herschel-Bulkley liquids will not flow when a small shear stress is
applied, but only when the applied shear stress exceeds the intercept value y. The
study of flow models and the measurement of flow properties is the science of
rheology. Often the flow properties and flow model for a liquid are called the
rheology of the liquid.

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As we shall see, the selection of the flow model comes from an analysis of the labo-
ratory data. When plotted as shear stress versus shear strain rate, the laboratory data
suggest a model that gives the best fit of the data.

1034 Calculation of Flow Parameters


As discussed earlier, the laboratory work measures the equilibrium shear stresses
associated with shear rates, s, at a uniform temperature. The equipment used dictates
the number of (,s) pairs measured at each temperature. Some devices, such as the
Ferranti viscometer, measure three; others measure up to eight.
At higher temperatures, crude oils demonstrate Newtonian behavior. At these
temperatures, conventional capillary viscometers can be used to measure the
viscosity. The task at this stage of the analysis is to develop a set of curves that
shows the variation in flow properties as a function of temperature. There should be
a continuous relationship from the Newtonian behavior at higher temperatures to the
non-Newtonian behavior at lower temperatures. The viscosity term will be the
continuous thread. At higher temperatures, where the liquid is Newtonian, y will be
zero and n will be unity.
There are many ways to accomplish this data reduction; we will discuss the method,
employing hand calculations and the computer program HOTOIL (see following
and Appendix D), that the Company has found most useful. The first step is to
generate a plot of shear stress versus temperature with shear strain rate as a param-
eter as shown in Figure 1000-27. On the right side of the figure the curves are devel-
oped from the Newtonian viscosity measurements.
Such measurements can normally be represented as a straight line using special
graph paper (discussed in Section 1010) that plots kinematic viscosity versus
temperature (see Figures 1000-6 through 1000-12). Lower temperature data that
deviate from a straight line may indicate the onset of non-Newtonian behavior.
At any temperature T, the kinematic viscosity, , can be read from this plot and
converted to absolute viscosity, , with the following equation:

(T) = (T) SG(T)


(Eq. 1000-16)
where:
SG(T) = specific gravity of the liquid at T
The Newtonian curves on the right side of Figure 1000-27 are calculated with
Equation 1000-10, s being the parameter of each curve. The circled points are
typical data from a laboratory viscometer. The task is to draw smooth curves for
each shear strain rate through these circled points, blending into the Newtonian
curves on the right. These curves are also shown.
Using the curves in Figure 1000-27, (,s) pairs can be read for any temperature.
These pairs can be plotted on either linear or log-log graph paper. On linear graph
paper, Bingham liquids will appear as a straight line. On log-log graph paper, Power

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Fluid Flow Manual 1000 Fluid Properties

Law liquids will appear as a straight line. The flow model selected should give the
best representation of the data over the shear strain rate range of interest.
Pairs from Figure 1000-27 at T = T1 are plotted in Figure 1000-28. Using least
squares regression techniques, the parameters for Bingham and Power Law equa-
tions can be calculated. The resulting equations are
Power Law:
= 14.09s0.355
r2 = 0.998
Bingham:
= 20.49 + .837s
r2 = 0.973
The term r2 is a measure of how well the curve fits the data; the closer the value is
to unity, the better the fit. For these points, the Power Law is a better fit.
The same process can be applied at several temperatures. Using Figure 1000-27,
three data pairs can be selected at any temperature and the parameters calculated for
the selected flow model. These parameters can then be plotted against temperature
as shown in Figure 1000-29. For this plot, the absolute viscosity-like term, , is
converted to a kinematic viscosity-like term, , using the inversion of
Equation 1000-16:

(T) = (T)/SG(T)
(Eq. 1000-17)
Equation 1000-17 relates the data more easily to the higher temperature Newtonian
measurements and is easier to use with HOTOIL. The term viscosity-like is used
because, in the non-Newtonian range, the factor is not always given in units of
viscosity. For the same reason the units of in Figure 1000-29 are stokes. The vari-
able n in Figure 1000-29 is the second parameter for the selected flow model. See
also Figure 1000-31.
The curves in Figure 1000-29 characterize the constitutive relationship for the liquid
over the temperature range of interest. These curves, in tabular form, will be used as
input data for HOTOIL. Before discussing this program, we must discuss the equa-
tions needed for the hydraulics calculations.

1035 Hydraulics Equations


The equations for relating flow rate, Q, to pressure drop, p, in circular pipes for the
four flow models discussed above are known explicitly only for the laminar flow
range. These equations can be found in any text on non-Newtonian fluid mechanics.
To permit the calculation of Q(p) or p(Q) for any flow regime and for any flow
model, the generalized non-Newtonian equations can be used. In the laminar range,
the generalized equations yield the same results as the model-specific equations.

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Fig. 1000-27 Laboratory Data

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Fluid Flow Manual 1000 Fluid Properties

Fig. 1000-28 Flow Curve at T1

The generalized non-Newtonian hydraulics equations are shown with the corre-
sponding Newtonian equations in Figure 1000-30. Instead of the flow rate, Q, the
equations are expressed in terms of the flow velocity, where

(Eq. 1000-18)
In Figure 1000-30, the two p(V) equations are identical, using the Fanning friction
factor, f, to relate the p term to the V term. For the laminar flow range, the relation-
ship between f and the Reynolds number is also identical for Newtonian and Non-
Newtonian. The only difference is in the definition of the generalized Reynolds
number which, for non-Newtonian, is expressed in terms of the generalized flow
parameters, K and n.
For the turbulent flow range, Figure 1000-30 shows the relationship between the
friction factor and the Reynolds number. Note that the generalized non-Newtonian
equation collapses to the Newtonian equation when n = 1 (When n = 1, K = ).

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1000 Fluid Properties Fluid Flow Manual

Fig. 1000-29 Flow Parameters

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Fig. 1000-30 Hydraulics Equations


Newtonian Generalized Non-Newtonian

p - V:

Laminar f:

Turbulent f:
(smooth tube)

Reynolds No.:

p = pressure drop d = liquid density


L = pipeline length gc = gravity conversion factor
D = pipeline inside diameter = liquid viscosity
V = liquid velocity K, n = generalized flow parameters (see
Figure 1000-31)
f = friction factor

Similarly, the generalized Reynolds number collapses to the Newtonian Reynolds


number when n = 1.
The equations in Figure 1000-30 for the turbulent flow range friction factor are for
smooth tubes. A correlation relating f to Reg for rough tubes has not been
published. To estimate the non-Newtonian rough tube turbulent friction factor,
HOTOIL uses an approximation:

(Eq. 1000-19)
where:
fr = rough-tube friction factor at Reg
fs = smooth-tube friction factor at Reg from equation in
Figure 1000-30
fnr = rough-tube friction factor for Newtonian liquids at Re = Reg
fns = smooth-tube friction factor for Newtonian liquids at Re

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Newtonian friction factors are calculated with the Colebrook equation.


The final element needed to make Figure 1000-30 complete is a criterion for estab-
lishing the transition from laminar to turbulent flow. This is provided in a paper by
Dodge and Metzner and is reproduced in texts on non-Newtonian flow. The
minimum Reynolds number for the turbulent flow regime can be approximated as
follows:

Ret = 4000 (1 - 0.25 n)


(Eq. 1000-20)
In the computer program the friction factor in the critical range between laminar and
turbulent flow is assumed to be constant at fcr, where fcr is the turbulent friction
factor at Ret. The laminar range is assumed to stop at Rel where

(Eq. 1000-21)
This is the Reynolds number at the intersection of the laminar friction factor curve
and the horizontal line f = fcr.
The equations in Figure 1000-30 are valid for any liquid model. The liquid proper-
ties enter the equations through the terms K and n. For each of the models
discussed above, the relationships between the generalized parameters K and n
and the model-specific flow parameters , n, and y are shown in Figure 1000-31.
The equations for the Herschel-Bulkley Model become the equations for the Power
Law Model when y = 0 and for the Bingham Model when n = 1.
Finally, the equations in Figure 1000-31 for the Bingham and Herschel-Bulkley
models involve the term

(Eq. 1000-22)
where:
tw = Dp/4L, the shear stress at the wall
This presents some computational difficulties in that p is needed to calculate p. In
the computer program this is done in iterative fashion, a value for w is assumed and
then w is calculated. This process is repeated until the assumed value equals the
calculated value.

1036 Computer Program HOTOIL


The equations presented in this section are used in the HOTOIL computer program.
This program can be used to calculate the non-isothermal pressure drop in a pipe-

1000-50 1997 Chevron USA Inc. All rights reserved. March 1997
Fluid Flow Manual 1000 Fluid Properties

line containing non-Newtonian liquids. HOTOIL makes this calculation by breaking


the pipeline into shorter segments, each with a temperature drop of no more than
2F. Each segment is treated as isothermal. The total pressure drop equals the sum
of the pressure drops in individual segments.
The program also calculates the internal film heat transfer coefficient used in the
temperature drop calculations. Correlations are included for the laminar and turbu-
lent heat transfer coefficients for both Newtonian and generalized non-Newtonian
liquids. The effects of friction heating and of pressure on viscosity are optional.
HOTOIL assumes that pressure affects only the viscosity-like parameter of
nonNewtonian liquids.

1037 Estimating Pipeline Restart Pressure Gradient


The BAYS (breakaway yield strength) can be used to estimate the pressure gradient
required to restart a gelled pipeline. The estimate is made by inverting
Equation 1000-9:

(Eq. 1000-23)
where:
b = BAYS
Designs usually include a safety factor over this estimate.
This model assumes that all of the gelled oil in the section will yield instanta-
neously at the pipe wall as a rigid body. This is rarely so. For instance, thermal
shrinkage may result in autodestruction of the gel. Voids may be present that permit
some flow before general yielding. Temperature gradients across the pipe radius
may leave a slower cooling, liquid core in large diameter pipelines. Finally, pres-
sure waves may generate much higher local pressure gradients as the wave moves
down the pipeline.
None of several attempts to model these mitigating effects has been successful.
Fortunately, Equation 1000-23 usually overpredicts the pressure gradient needed.
The peak value mentioned above may be used for the BAYS. If the design is
capable of generating shear stresses significantly larger than this peak value, then
the pipeline can be considered restartable. If more accurate estimates are needed, the
plot of b versus T, along with the estimated temperature distribution along the
pipeline, can be used to calculate the required pressure gradient distribution.
After the initial yielding, the waxy structure continues to break down and, for a
constant applied pressure gradient, the flow rate continues to increase. Estimates can
be made of this breakdown process but the laboratory work needed to generate the
flow properties and the engineering work needed to do the calculations are very
time consuming. These estimates are not done routinely.

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Fig. 1000-31 Generalized Flow Parameters


Constitutive Equation Generalized Flow Parameters
Power law
= sn

Bingham
= y + s

Herschel-Bulkley
= y + sn

1038 Wax Deposition


Several attempts have been made to measure wax deposition tendencies in the labo-
ratory. There are, however, no widely accepted ways of measuring wax deposition
and no useful models for relating the measurements to field experience. If wax
deposition in pipelines is possible, the normal response is to install scraper
launchers and traps. Scraping frequency is decided from operating experience.

1000-52 1997 Chevron USA Inc. All rights reserved. March 1997
Fluid Flow Manual 1000 Fluid Properties

Mitigating Actions
There are several mitigating actions available if the handling of waxy crudes
becomes troublesome. Lines can be kept hot with insulation or heaters. Non-waxy
crudes, lighter oils (diluents or solvents), and flow-improving additives may be
added. Additives can be effective, but are very crude-specific.
One should not generalize about the behavior of waxy crudes. Each seems to be
different, if not idiosyncratic, and must be considered a unique material. The design
features selected and mitigating actions used will, consequently, be site specific.

1040 References

1041 Viscosity Conversion


1. ODonnell, R. J. Equations for Converting Different Viscosity Units. American
Society for Testing and Materials, Materials Research and Standards, Vol. 9,
No. 5. May, 1969.
2. Standard Method for Conversion of Kinematic Viscosity to Saybolt Universal
Viscosity or to Saybolt Furol Viscosity. American Society for Testing and Mate-
rials, ASTM Designation D2161-66, ASTM Standards, Vol. 17, 1969.

1042 Viscosity Data


3. API - Technical Data Book - Petroleum Refining. American Petroleum Insti-
tute, 1966.
4. Standards of Tubular Exchanger Manufacturers Association, Section 10, 1968.
5. Gallant, R. W. Physical Properties of Hydrocarbons. Houston: Gulf Publishing
Co., Houston, 1969.
6. Sage, B. H., W. D. Yale, and W. N. Lacey. Effect of Pressure on Viscosity of N
- Butane and Isobutane. Industrial and Engineering Chemistry, Vol. 31, 1939, p.
223.
7. Lipkin, M. R., J. A. Davison, and S. S. Kurtz. Viscosity of Propane, Butane and
Isobutane. Industrial and Engineering Chemistry, Vol. 34, 1942, p. 976.
8. Swift, G. W., J. Lorenz, and F. Kurata. Liquid Viscosities Above the Normal
Boiling Point for Methane, Ethane, Propane, and N-Butane. AIChE Journal,
Vol. 6, No. 3, 1960.

1043 Brine-in-Oil Emulsions


9. Woelfin, Wm. Viscosity of Crude Oil Emulsions. California Oil World and
Petroleum Industry, March, 1962.

March 1997 1997 Chevron USA Inc. All rights reserved. 1000-53
1000 Fluid Properties Fluid Flow Manual

1000-54 1997 Chevron USA Inc. All rights reserved. March 1997