FUNDAMENTALS OF LIQUID MEASUREMENT – PART 1
Class Number 2160
Ralph S. Papesh
BP Pipelines (North America) Inc.
28100 Torch Parkway
Warrenville, IL 60555
Accurate liquid measurement is an important aspect
of the petroleum industry. With regard to commerce,
it is the basis of custody transfer between producers,
pipelines, refineries, petrochemical plants, utility
plants, products marketing and the transportation
industry. As it pertains to process control, it is
needed to maintain specific flow rates, pressures
and levels to ensure precise quality and
environmental control.
In either custody transfer or process control, daily
small percentage volumetric measurement errors
can accumulate to large volumetric errors over a
long period of time. These errors can have an
adverse impact on the profitability of a company.
In order to help minimize liquid petroleum
measurement inaccuracies, a fundamental
understanding of the physical laws that affect
measurement are necessary. Therefore, while
knowledge of measurement equipment principles
and applications are necessary to design or
maintain an accurate system, it is equally important
to understand the hydrocarbon physical properties
that affect volume, oil quality, the method of
measurement, and consequently, the price of oil.
These physical properties include: Temperature,
Density (or relative density, or API gravity),
Compressibility, Sediment and water (S&W), Vapor
Pressure (RVP or TVP), and Viscosity.
Temperature
Temperature measurement normally plays a
relatively significant role in volumetric measurement,
compared to the other physical properties, since
petroleum liquids expand readily when heated and
contract when cooled. The amount it expands or
contracts not only depends on the temperature, but
also on the density of the liquid. For example, crude
oil does not expand or contract the same amount as
gasoline, given the same deviation in temperature,
because crude oil has a higher density. So when a
barrel of oil is bought or sold by either meter or tank
measurement, the temperature and density must
also be measured simultaneously.
The petroleum industry has adopted standards of
volume to correct for the effects of thermal
expansion/contraction. The standard volume in the
United States is the barrel, which contains 42 US
gallons measured at the standard temperature of
60°F. In Europe, and many other parts of the world,
the standard volume is the liter, which is measured
at the standard temperature of 15°C. Tables of
Volume Correction Factors (VCF) for correcting
volumes, measured at any temperature, to the
equivalent volume at standard temperature are
available from the American Petroleum Institute
(API) and the International Standards Organization
(ISO).
Tank temperature measurements are obtained with
a mercury thermometer, a new environmentally safe
glass thermometer, or with an electronic
thermometer. While a mid-level temperature reading
is necessary on small tanks, readings are normally
taken at the upper, middle, and lower levels on large
tanks to determine the average temperature.
Custody transfer metering system temperatures are
measured dynamically with in-line thermometers
and/or electronic transmitters. These devices
should be located immediately downstream of the
meter tube to obtain a temperature representative of
flow measurement conditions. Batch temperature
measurements should be flow weight averaged.
Density or Gravity
Density is defined as the mass of fluid per unit
volume at a given temperature. Examples are
grams per cubic centimeter (gm/cc), pounds per
cubic foot (lb./cu. ft.) and kilograms per cubic meter
(kg/cu. m.).
Relative Density is the ratio of the density of a liquid
at a given temperature to the density of pure water
at a standard temperature, which is either 60°F or
15°C. The temperature of the liquid and the
temperature of water are shown as 70°F/60°F, for
example, and must be included with the density
statement.
Density and relative density are most commonly
used for light liquid hydrocarbons (e.g., LPG, NGL,
etc.), petrochemicals and, sometimes, refined
products. Relative density is also used for
determining VCF for crude oils and other
hydrocarbon mixtures when API correction Tables 5
and 6 cannot be used.
API Gravity is a special gravity scale commonly
used in the petroleum industry. API gravity is most
often measured with a hydrometer, which is a sealed
graduated cylinder with a weight in the bottom. The
hydrometer scale can be graduated in relative
density (specific gravity) or API gravity. API gravity is
related to relative density and the density of water
(which is defined as 10°API) by the following
formula:
°API @ 60°F = ______141.5_______ - 131 5
Rel. Den. 60°F/ 60°F
API gravity is inversely related to relative density.
Therefore, liquids that are commonly called “heavier”
have low API gravities and high densities or relative
densities. Also, liquids that are commonly called
“lighter” have high API gravities and low densities or
relative densities.
The following table shows some typical density
ranges for various types of petroleum liquids. Crude
oils are almost always priced at a given API gravity
or for an API gravity range.
Petroleum Relative API Gravity
Liquid Density Range
Crude Oils 1.000 - 0.780
10° - 50°
Fuel Oils, Jet Fuel 0.875 - 0.780 30° - 50°
Gasolines 0.780 - 0.685 50° - 75°
Butanes, Propane 0.685 - 0.505 75° - 115°
The procedure for measuring density, relative
density or API gravity by hydrometer is described is
API MPMS Chapter 9.1 (ASTM D 1298). This
method requires a separate thermometer to
measure the temperature of the liquid at the time of
the density measurement. Alternatively, a
thermohydrometer may be used, which is similar to
a conventional hydrometer, but has a small glass
thermometer built into it, making it possible to read
both measurements with one device. Volatile liquids
that evaporate readily at ambient temperature must
use a pressure hydrometer device as described in
API MPMS Chapter 9.2. This is a clear glass or
plastic cylinder with sealable end caps with a
hydrometer and thermometer inside the tube. The
tube is filled with liquid, carefully bled down to
atmospheric pressure, and placed in a constant
temperature bath maintained at standard
temperature. The hydrometer is read after the
contents of the tube have stabilized at the bath
temperature.
For liquids that are so volatile that they would boil at
atmospheric pressure, such as LPG or LNG, density
is measured with a pycnometer. This device is a
glass or stainless steel container with an accurately
known internal volume. The pycnometer is totally
filled with liquid at the same pressure as the system
that custody transfer measurement or meter proving
is conducted. The filled pycnometer is then weighed
and the density calculated from the weight and
volume. This is done after correcting for the
pycnometer tare weight and the buoyancy effect of
air during weighing.
Density can affect equipment performance. The
length of time that a thermometer must be
suspended in a tank to determine the temperature of
the tank contents increases relative to an increase in
density of the contents. Also, the rangibility of a
turbine meter is affected by changes in density.
API gravity or relative density is also essential to the
conversion of a volume measured at operating or
ambient temperature to equivalent standard volume
at standard temperature. The equivalent volume at
standard temperature is obtained by multiplying the
volume measured at operating temperature by a
Volume Correction Factor (VCF) that may be
obtained for most crude oils and refined products
from API Table 6. The operating temperature and
API gravity are required for this. Table 6A is for
crude oils, and Table 6B is for refined products. A
portion of Table 6A is shown below:
TABLE 6A, GENERALIZED CRUDE OILS
VOLUME CORRECTION TO 6O F
TEMP API GRAVITY AT 60 F
F 45.0 45.5 46.0 46.5 47.0
75.0 0.9920 0.9920 0.9919 0.9919 0.9918
75.5 0.9917 0.9917 0.9916 0.9916 0.9915
76.0 0.9915 0.9914 0.9914 0.9913 0.9913
To use Table 6, round both temperature and API
gravity to the nearest 0.5° and enter the table. This
table is not to be interpolated for intermediate
values. Therefore, the VCF for a 45.8°API crude at
75.6°F would be 0.9916.
In some applications, notably meter proving, VCF is
called CTL or the Correction for Temperature of the
Liquid.
While the above tables are convenient to use, the
preferred method for obtaining VCF is with an
algorithm. An algorithm was developed by API from
data on refined products and a large variety of crude
oils from around the world. The API algorithm,
which relates densities, VCF, and temperatures is:
VCF = ρt/ρ60 = EXP[-α60∆t(1+0.8α60∆t)]
In which:
VCF = Volume Correction Factor
ρt = density at temperature t
ρ60 = density at 60°F
α60 = thermal coefficient of expansion for
that type of liquid at 60°F
∆t = t - 60.0
As previously stated, liquids expand and contract
with temperature changes. Likewise, liquid volume
change occurs because of variations in density or
API gravity. These changes are relatively small,
compared to temperature changes, but are not
negligible. Therefore, the API gravity of crude oil
measured at some temperature, other than standard
temperature, must be corrected to the equivalent
API gravity at 60°F by using API Table 5. Table 5A
is for crude oils and Table 5B is for refined products.
A portion of Table 5A is shown below.
TABLE 5A, GENERALIZED CRUDE OILS
TEMP API GRAVITY AT OBSERVED TEMPERATURE
F 35.0 35.5 36.0 36.5 37.0 37.5
51.5 35.7 36.2 36.7 37.2 37.7 38.2
52.0 35.6 36.1 36.6 37.1 37.6 38.1
52.5 35.6 36.1 36.6 37.1 37.6 38.1
This table is to be interpolated. Therefore, a crude
oil that measures 36.3°API at 52.0°F, the standard
gravity at 60°F would be 36.9°API. The calculation
for this is:
36.6+[(36.3-36.0)x(37.1-36.6)]/(36.5-36.0)=36.9
API/ASTM/GPA TP-25 – Tables 23E and 24E
should be used for Light Hydrocarbons. This
standard was published in 1998 and replaces
ASTM-IP Technical Publication Tables 23 and 24 –
1952, and GPA Technical Publication TP-16, which
were previously used for volumetric measurement of
LPG.
API Table 6C is used for individual and special
applications where the volume is corrected to 60º F
against thermal expansion coefficients at 60º F.
Compressibility
Compressibility is another factor that must be
considered. Liquids expand when pressure is
reduced and shrink in volume when pressure is
increased. The effects of compressibility are less
than those due to temperature, but are not
negligible. Correction factors for compressibility
(CPL) are given in API MPMS Chapter 11.2. The
equation is:
CPL = 1/ [1-(P-Pe)*F]
In which:
P = the operating pressure in psig
Pe = the equilibrium vapor pressure at
operating pressure (or zero for liquids with
vapor pressures less than atmospheric)
F = the compressibility factor determined in
accordance with API MPMS Chapter 11.2.1
or Chapter 11.2.2. A portion of API MPMS
11.2.1 is shown below.
COMPRESSIBILITY FACTORS PER POUNDS SQ. IN.
(DIVIDE ALL NUMBERS BY 100000)
TEMP API GRAVITY AT 60 DEG. F
Deg F 18.0 18.5 19.0 19.5 20.0
99.0 0.434 0.437 0.440 0.444 0.447
99.5 0.434 0.437 0.441 0.444 0.448
100.0 0.435 0.438 0.441 0.445 0.448
This table is not interpolated. Note that the numbers
in the table must be divided by 100000. The table
was made this way to save space by not including a
bunch of leading zeros for each value of “F”. By way
of example, calculate the volume of 1000 bbls of a
19.9°API (at 60°F) fuel oil metered at a pressure of
500 psi and a temperature of 100°F. The
compressibility factor (F) from the table is
0.00000448, and CPL is:
CPL=1/[1-(500-0)*0.00000448]=1.0023
The equivalent volume at atmospheric pressure is:
(1000 bbls)*(1.0023)=1002 bbls.
S&W
Sediment and Water (S&W) is a collective term for
non-hydrocarbon materials that are contained in
crude oil. Crude oils may contain large amounts of
S&W as they come from the oil wells, and are treated
on-site to reduce S&W to a concentration, typically
1.0% or less, which is set by the pipeline, marine
carrier, or other transportation service which
transports the crude oil from the field to a refinery.
S&W is usually in the form of tiny droplets which are
suspended in the oil, and generally will not separate
from the oil phase when undisturbed. This is different
from “Free Water” which is water that exists as a
separate phase from the oil phase. Samples to be
used for S&W measurement must not contain any
free water. Most petroleum oils and refined products
may contain very small amounts of water in solution in
the hydrocarbon phase. In most areas, the maximum
acceptable total S&W is 1.0%. The maximum
acceptable free water is 0.3%. In Texas, New Mexico,
and Louisiana, the total allowable S&W content is
1.0%. Also, you may have free water up to 1.0% if no
sediment is present.
The most common method for measuring S&W is the
centrifuge method, in which a measured (typically 50
ml) sample of crude oil is placed in a cone-shaped
glass centrifuge tube, mixed with an equal amount of
solvent to reduce the density and viscosity of the oil,
and then heated to 140°F (160°F for waxy crudes).
Several heated tubes and their contents are spun at
high speed in a centrifuge for a specified amount of
time during which centrifugal force drives sediment,
water and anything else heavier than the diluted oil to
the bottom of the tubes. After centrifuging, the relative
amount of S&W in the bottom of each tube is read
from a scale (usually calibrated in milliliters) that is
etched on the side of the tube. This quantity of S&W
is related to the original quantity of oil sample before
dilution and reported as percent S&W. The centrifuge
method measures suspended S&W, but does not
measure solution water.
There are two methods for determining S&W by
centrifuge, the “Laboratory Method” described in API
MPMS Chapter 10.3 (ASTM D 4007) and the “Field
Method” described in API MPMS Chapter 10.4. The
two methods use similar equipment, but differ
somewhat in detail. The laboratory equipment and
procedures are suitable only for a laboratory
environment and are generally considered to be
slightly more accurate. The equipment and
procedures for the Field Method are suitable for use
by gaugers or operators who work out of the back of a
pickup truck, and are accepted for custody transfer.
Water content may be determined in the laboratory by
distillation as described in API MPMS Chapter 10.2
(ASTM D 4006). This method is considered by API to
be the “Referee Method” which is to be used when
parties cannot agree on water content measurement
by other methods. The distillation method measures
solution water as well as suspended water. It does not
determine sediment content.
An oil sample, measured either by volume (typically
100 ml ±) or by weight, is placed in a glass
distillation flask, mixed with a large quantity of
solvent, and heated to the boiling point. The vapors
that emanate from the flask contain water vapor and
vapors of the lighter hydrocarbon components from
the oil sample. The vapors are cooled and
condensed back to liquid in a water-cooled glass
condenser, from which the condensate drips into a
slender glass receiver that has a cone-shaped
bottom. Liquid water, being heavier than the
condensed liquid hydrocarbons, collects in the
bottom of the receiver where the quantity can be
read from a milliliter scale etched on the side of the
glass receiver. This quantity of water is compared to
the original oil sample quantity and reported as
volume percent. The distillation method, even
though very accurate, requires several hours to
perform in a laboratory environment.
Another method that measures both suspended and
solution water is the Coulometric Karl Fischer
Titration, as described in API MPMS Chapter 10.9
(ASTM D 4928). An oil sample, typically 1 gm ±, is
placed in a glass vessel that contains a specific set
of chemicals called Karl Fischer Reagent. The
amount of sample injected into the analyzer can be
determined by weight or measured volumetrically
with a syringe.
A chemical reaction between the water in the
sample and the Karl Fischer Reagent causes an
electric current to flow between two electrodes
inserted into the solution. This electric current is
measured and correlated to the amount of water that
was consumed and reported directly to a readout. It
can be read in either milliliters or grams, which can
be converted to volume percent water or weight
percent water, depending on whether the original
sample was measured by volume or weight.
The Coulometric Karl Fischer Titration is relatively
fast and simple to use and is considered in the
industry to be as accurate as the distillation method.
The analyzer is available in units designed for
laboratory use, or those that are portable and
suitable for field use.
The Coulometric Karl Fischer Titration is a
modernized version of an older laboratory method
known as The Standard Test Method for Water in
Crude Oils by Karl Fischer Titration (API MPMS
Chapter 10.7, ASTM D 4377). This is a
conventional titration in which water is reacted with
excess Karl Fischer Reagent, and the excess
reagent is back titrated volumetrically. This
procedure can be performed only in a laboratory by
a trained technician, and has been largely replaced
by the coulometric method.
Neither the distillation nor the Karl Fischer method
measures sediment content. In some crude oils
sediment is negligible and may be ignored. In
others, though, sediment content is significant. In
such cases, the water measurement must be
supplemented by a separate determination for
sediment.
Sediment can be measured by several methods.
One method for measuring sediment only is the
Sediment by Extraction Method (API MPMS Chapter
10.1, ASTM D 473) in which a sample of crude oil is
weighed into a special porous extraction thimble,
continuously bathed with hot solvent until all soluble
hydrocarbons are washed out, then dried and
weighed to determine the amount of residual
insoluble sediment.
A second method for measuring sediment is the
Sediment by Membrane Filtration Method (API
MPMS Chapter 10.8, ASTM D 4807) in which a
weighed sample of crude oil is placed on a micro-
pore membrane filter in a vacuum filtration device
and continuously washed with heated toluene until
all soluble hydrocarbon in washed out. The
insoluble sediment remaining on the filter membrane
is dried and weighed, and reported as percent
sediment.
A third method is “Determination of Water and/or
Sediment in Crude Oil by the Centrifuge Method
(Field Procedure)” API MPMS draft standard
Chapter 10.4. This method permits the use of field
centrifuges to measure sediment as an adjunct to
the portable Karl Fischer method for water
determination with the notation that “This method
does not always produce the most accurate results,
but it is considered the most practical method for
field determination of water and/or sediment.”
Sediment content and water content may be
reported separately, but many run tickets and oil
accounting systems are designed to handle
combined S&W quantities. In such cases,
separately measured water and sediment quantities
must be combined into one value of volume percent.
The centrifuge method measures sediment directly
in volume percent, but the extraction and membrane
filtration methods measure sediment on a weight
basis, and must be converted to volume percent.
For this purpose, the weights of the dried sediment
and of the oil in the sample are corrected to
equivalent volumes by their respective relative
densities. The relative density of the solid material
is always assumed to be 2.0 (which is a
compromise value between that of dry sand and
lighter sedimentary materials), and the relative
density of the oil is either determined directly by
density measurement or calculated from the
measured API gravity. Oil volumes are corrected for
S&W to give “net dry clean oil” which is the custody
transfer quantity.
Calculating Net Oil Volumes
Some important terms are:
GOV = Gross Observed Volume = the quantity as
measured at operating temperature and pressure in
a meter or in a tank. Gross volume includes the
S&W contained in the oil.
GSV = Gross Standard Volume = GOV corrected to
standard volume at 60°F with VCF or CTL and/or
CPL, as appropriate.
NSV = Net Standard Volume = net dry clean oil at
60°F = GSV minus S&W.
S&W may be calculated as bbls of S&W, then
subtracted from GSV bbls to arrive at NSV bbls, or
percent S&W may be converted to a correction
factor and multiplied times GSV to arrive at NSV.
S&W correction factor (CSW) is [1 – (S&W %/100)],
and NSV = (GSV) x (CSW).
Vapor Pressure
Standard volume is defined as being at a standard
temperature of either 60°F or 15°C. There is also a
pressure component of standard volume. For liquids
with vapor pressures less than normal atmospheric
pressure at the measurement or proving
temperature, the standard pressure is called one
standard atmosphere. For liquids that have vapor
pressures greater than normal atmospheric
pressure, the definition of standard pressure is the
equilibrium vapor pressure of that liquid at the
temperature of measurement or proving.
The pressure referred to in this context is called the
True Vapor Pressure (TVP). The technical definition
of TVP is the pressure at which the first bubble of
vapor forms in a liquid at a given temperature.
There are a variety of laboratory methods that
measure vapor pressures that very nearly fit the
technical definition. TVP is often calculated from
laboratory distillation data, such as the ASTM D 86
distillation method. For some hydrocarbon mixtures,
such as LPG, NGL, and EP mix, the TVP can be
calculated from a gas chromatograph compositional
analysis.
Another form of vapor pressure is the Reid Vapor
Pressure (RVP). It is determined in accordance with
the ASTM D 323 method. A small chamber of fixed
dimensions is filled with the liquid to be tested, then
connected to an empty (but not evacuated) vapor
chamber of fixed dimensions. The assembled
apparatus is immersed in a constant temperature
bath at 100°F until the pressure in the apparatus
stabilizes at a constant pressure as indicated by a
calibrated pressure gauge on the top of the vapor
chamber. This pressure is recorded as the RVP,
psia at 100°F. For certain petroleum stocks, TVP
may be estimated from RVP by the use of charts.
RVP is used to set safe operating specifications for
the transportation of crude oil or petroleum products.
Normally, they may be accepted for transportation
only if their RVP is less than 10 psia. This helps to
prevent excessive losses due to evaporation,
damage to tanks or marine vessel compartments
due to excessive pressure or boiling, or inaccurate
measurement due to flashing in meters. Vapor
pressure, even when less than atmospheric, causes
evaporation loss of petroleum liquids from tanks and
vessels that are not fitted with evaporation loss
prevention and/or recovery systems.
Viscosity
Viscosity is the characteristic of a fluid that causes it
to resist flow. Viscosity is measured in several ways,
and is reported in a variety of units. The
fundamental unit of absolute viscosity is the poise,
which is the force in dynes to effect a tangential
displacement over one square centimeter in one
second. Kinematic viscosity is defined as absolute
viscosity divided by density in consistent units.
Kinematic viscosity is measured in Stokes and is
more useful in predicting the effect of viscosity on
meters, pumps, pipe friction loss, etc. Both poise
and Stokes are too large for most practical
applications, so the centipoise (cp), which is 0.01
poise, and the centistoke (cs), which is 0.01 Stoke,
are commonly used.
These viscosities are commonly measured either
with small glass capillary tubes of specified
dimensions and viscosity determined by the time for
a liquid sample to flow through the capillary, or with
mechanical viscometers which actually measure
shear forces in a liquid sample. The higher the
numerical value of viscosity, the greater the
resistance the fluid offers to flow. The viscosity of
many common petroleum products range from about
0.5 cp to about 2 cp, whereas viscosity of crude oils
range from a few hundred cp to thousands of cp.
Other viscosity units are used for specific
applications. Saybolt Universal Seconds (SSU) and
Saybolt Furol Seconds (SSF) are examples that are
reported as the number of seconds required for 60
cc of liquid sample to flow through orifices of
specified dimensions at specified temperatures.
These viscosity units are commonly used for
industrial oils, lubricating oils and fuel oils, because
the tests are relatively quick and easy to run.
Viscosity is very sensitive to temperature. For
example, a product with a normally high viscosity,
such as gas oil, will have difficulty flowing through a
pipeline at cold temperatures, but will flow readily
when heated. Pressure normally has little effect on
viscosity, but may become significant at pressures
greater than 1,000 psig. where an increase in
pressure will increase viscosity noticeably.
The effect of viscosity is well known in the operation
of pumps and pipelines. Increases in viscosity
increase horsepower required to operate pumps and
to overcome friction loss as liquids flow through
pipes. As it pertains to measurement equipment, the
viscosity of oil has an effect on slippage in both
positive displacement and turbine meters, thereby,
affecting the meter factor. High viscosity oil reduces
slippage in positive displacement meters, which
results in lower meter factors. Turbine meters are
particularly susceptible to the effects of viscosity.
Higher viscosity tends to reduce the linearity of
turbine meters and may significantly increase the
minimum flow rate rating. Since viscosity changes
noticeably with temperature, relatively small
changes in temperature may markedly affect the
performance of a turbine meter in high viscosity
liquid service.
Conclusion
Accurate liquid measurement is necessary in order
to economically compete in the petroleum industry
today. Therefore, it is essential to obtain an
understanding of hydrocarbon physical properties
and how they affect measurement equipment and
methods.
Reference
Poynter, Wesley G., “Fundamentals of Liquid
Measurement – Part 1”, International School Of
Hydrocarbon Measurement –2002