Quantity Calculations of Liquefied Gases
Quantity Calculations of Liquefied Gases
Quantity Calculations of Liquefied Gases
1. INTRODUCTION
Accurate measurements and mass calculations are essential in the trade of Liquefied Gases. Due
to the physical properties of Liquefied gases, their quantity calculation is different from those used
for petroleum products or chemicals. Compared to other liquids the vapour existing in equilibrium
with liquid gas forms a significant quantity of the product. This vapour phase must, therefore, be
quantified if the necessary accuracy of the total mass assessed, is to be achieved.
This paper will deal with LPG (Propane, Butane and their mixtures) and commercial chemical
gases such as Propylene, Ethylene, Butylenes, 1,3-Butadiene, C4 mixtures, Vinyl Chloride
Monomer, Ammonia Anhydrous, LNG quantity calculations are somewhat different. Furthermore,
they are not shipped by our company, and will therefore not be discussed in this paper.
Page No. 1
The temperature which is required to sustain the single component system at a Saturated Vapour
Pressure equal to atmospheric pressure (760 mm Hg, 1.0132 Bar, 101.32 kPa) is termed the
Normal Boiling Point of the element or compound. Propane is thus described as having a Normal
Boiling point of -42.1 C, Chlorine -34.5 C and n-Butane -0.5 C.
Immediately after the loading operation there may be a period when equilibrium between vapour
and liquid phase has not been established in the ships cargo tanks. In other words, the actual
pressure in the cargo tanks may be below or above the saturated vapour pressure.
LPG and liquefied gases are frequently stored in bulk at temperatures which are close to their
Boiling Point or to those which equate to the Saturated Vapour Pressure. As a consequence, a
proportionately high amount of the total enclosed mass is able to exist in the vapour phase. This
means that the quantity held in both phases must be calculated in order to obtain the total quantity
of product present in the storage vessel.
Page No. 2
Page No. 3
It is now clear why it is necessary to specify so precisely the condition of the liquefied gas
under which it is assumed to be weighed. Although the mass of two cargoes may be
identical, if their volumes are not equal the upthrust caused by air displacement will be
different and hence their weights will be different. An extreme case could be conceived in
which two cargoes of equal mass were weighed, one entirely as a liquid, and the other
entirely as a vapour. The former would have a weight not greatly different in magnitude from
its mass; whilst the latter would have very little weight due to its very large air displacement.
The use of a precise standard avoids this ambiguity.
The derivation of cargo weight may be carried out in practice by two methods. The mass
may be calculated and this converted to weight by use of a conversion factor, which the
liquid density at 15C. The conversion factor used in this method is given by the short table
at the introduction to Table 56 of the ASTM/IP Petroleum Measurement Tables (see Table
below).
The second practical method of determining weight is directly from volume at 15C using a
volume to weight conversion factor. This weight conversion factor is the weight per unit
volume of the saturated liquid at 15C. This factor should not be confused with density,
although it is closely related. The factor has the units of weight per unit volume, whilst true
density has the units of mass per unit volume. The main Table 56 gives the relationship
between density at 15C and this volume to weight conversion factor.
The arithmetic derivations of both these factors are presented in Appendix 1.
As discussed earlier in this paper, liquefied gases always are handled in closed containers
from which air is totally excluded. Consequently air has no influence on neither the liquid
phase nor the vapour phase of the stored product.
Although from a purely scientific point of view, it is not correct to use apparent densities in
quantity calculations, they are applied in the commercial trade of liquefied gases. An
apparent density of a liquefied gas should be considered as a theoretical density. It may be
obtained from a True Density, converted to Apparent Density by applying ASTM Table 56.
Densities of the most common liquefied gases at their boiling point vary from 0.5680 Kg /
Litre (Ethylene) to 0.9714 Kg / Litre (Vinyl Chloride Monomer). When converting this true
density to a density in air (Apparent density), always a difference of 0.0011 Kg / Litre
appears. Note that conversion from density in air to density in vacuo has to be done by
introducing the conversion factors from ASTM Table 56 with a density at 15C. This
conversion is not always possible considering the critical temperature of some products
such as Ethylene, Methane, which are completely gaseous at 15 C.
Page No. 4
to
to
to
to
to
Factor for
converting
Weight in Vacuo
to Weight in Air
Density at 15C
(Kg/L)
Factor for
converting
Weight in Air to
Weight in Vacuo
0.5191
0.5421
0.5673
0.5950
0.6255
0.99775
0.99785
0.99795
0.99805
0.99815
0.5000
0.5202
0.5433
0.5685
0.5961
to
to
to
to
to
0.5201
0.5432
0.5684
0.5960
0.6265
1.00225
1.00215
1.00205
1.00195
1.00185
0.6256 to 0.6593
0.6594 to 0.6970
0.6971 to 0.7392
0.7393 to 0.7869
0.7870.to 0.8411
0.99825
0.99835
0.99845
0.99855
0.99865
0.6266 to
0.6604 to
0.6981 to
0.7403 to
0.7880.to
0.6603
0.6980
0.7402
0.7879
0.8421
1.00175
1.00165
1.00155
1.00145
1.00135
0.8412
0.9035
0.9757
1.0605
0.99875
0.99885
0.99895
0.99905
0.8422
0.9045
0.9767
1.0615
0.9044
0.9766
1.0614
1.1000
1.00125
1.00115
1.00105
1.00095
to
to
to
to
0.9034
0.9756
1.0604
1.1000
to
to
to
to
4. VAPOUR DENSITY
4.1. General
The density of a vapour depends on the following factors: Temperature, Pressure and nature
of the product. The relation between these parameters is given by the perfect gas law:
PV nRT
or
PV
Where: P
V
n
m
MM
R
T
=
=
=
=
=
=
=
m
RT
MM
pressure (absolute)
volume
number of moles
mass
mole mass (which is function of the nature of the product)
universal gas constant
temperature, degrees Kelvin ()
()
T( K ) 27315
. T( C )
Page No. 5
28815
.
1.01325 P( bar )
MM
X
X
27315
. T ( C )
1.01325
23.6451
28815
.
101325
.
P( bar )
MM
1
X
X
X
27315
. T ( C )
101325
.
23.6451 z
Compressibility factors are more important at higher temperatures and especially at high
pressure (dense vapour condition). Under the conditions in a gas tanker or in a storage tank
ashore, the compressibility factor is near to 1. The differences resulting by applying this
compressibility factors are negligible.
Page No. 6
5. LIQUID DENSITY
5.1. Introduction
The density of a liquid as a function of temperature is usually given by a power series
equation. For relative small temperature ranges, the density temperature relation ship can
be regarded as linear. In the oil industry, the general practice is to correct observed
measurements to volumes and/or densities to a reference temperature of 15 C. Liquefied
gases have a boiling point varying from 0C for n-Butane to -162 C for Methane (LNG).
Temperature ranges are considerable greater when compared to the those found in the
petroleum and chemical trades. This will reflect in other methods and quantity calculation
routines for liquefied gases.
In the next paragraphs, methods are described for the density determination of commercial
liquefied gases.
5.2. Practical density test method : The Pressure Hydrometer (ASTM D1657)
This test method, last revised in 1989, covers the determination of relative density or
density of light hydrocarbons including Liquefied Petroleum gases (LPG). The test method is
not applicable for products having vapour pressures higher than 1.4 MPa at 15 C.
figure 5.1
Pressure hydrometer cylinder
Page No. 7
i=1
Where :
Ci = Concentration of compound i, in liquid volume percent.
The relative density of different compounds are listed in Table 5.A (1) here below:
Table 5.A.
Relative density of compounds
(1)
Compound
Relative Density at
60/60 F (15.56 C)
Ethane
0.35619
Propane
0.50699
Propylene
0.52095
n - Butane
0.58401
i- Butane
0.56287
Ref : ASTM D 2598-91, 1996 Annual Book of ASTM standards, Volume 05.02
Page No. 8
5.3.2.
The liquid density of mixtures of hydrocarbon liquids at their boiling point as a function of
temperature as calculated by the Francis Formula is based on an extension of the
correlation of the liquid density of pure hydrocarbon liquids, at their boiling point, as a
function of the temperature. This correlation is achieved by neglecting the effect of
volumetric shrinkage.
The Francis Formula is applicable only to LPG mixtures at their boiling point, within the
temperature range -60C to +30C.
Appendix 2 gives the procedure for liquid density calculation of LPG by using the Francis
Formula.
Specific calculation methods are introduced for the density calculation of single and pure
compounds. These methods are frequently used due to they high accuracy.
In Table 5.B below an overview is given of the most common used references on with the
density tables are based for Liquefied gases such as Ethylene, Propylene, Butadiene, Vinyl
Chloride Monomer, etc..
Page No. 9
TABLE 5.B.
References for Density Tables of Liquefied Gases
Density
Vapour
Density
Saturated
Critical Value
Liquid
Saturated
Vapour
Pressure
(1)
(1)
(2)
(9)
Ethylene
(3)
(3)
(3)
(3)
Propylene
(4)
(4)
(4)
(4)
1,3-Butadiene
(1)
(1)
(2)
(9)
Ammonia
(5)
(5)
(5)
(5)
VCM
(7)
(8)
(6)
(7)
LPG
(1)
(C4 mix)
& MM
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
Page No. 10
TANK INVENTORY
From the tank measurements the steps in the determination of the tank inventory are as
follows:
a)
b)
c)
Page No. 11
d)
Make the following corrections - from the cargo tank calibration tables - which are
necessary:
d 1.
Trim correction
The liquid level on the level gauge a cargo tank depends on the trim of the
vessel. Depending on the location of the level gauge on the cargo tank,
depending on the liquid level and depending on the draft of the vessel, a
positive or a negative correction must be applied.
List correction
For a similar reason as for the trim correction, a correction for the list of the
vessel should be applied
Page No. 12
d 3.
Float correction
The float is of the level gauge is lowered to the liquid surface. A buoyancy
correction for the float, depending on the density of the liquid must be applied.
d 4.
Tape correction
This temperature correction must compensate for the change in the vertical
position of the gauge relative to the tank floor, due to thermal effects on the tank
wall and also for the contraction in the gauge wire. The correction due to the
temperature is made against the certified standard gauge temperature. This
correction is function of the liquid level in fact to the length of the tape exposed to
the vapour phase) and the temperature of the vapour phase.
e)
From the corrected liquid level calculate liquid volume using the cargo tank
calibration tables;
f)
Calculate the vapour volume as the total tank volume minus the liquid volume,
again with due allowance for temperature;
The cargo tanks of a gastanker as well as the cargo measurement equipment is
calibrated at ambient conditions. Due to thermal effects on the cargo tank steel
during loading operations, the used material will be subject to a shrinkage. A
shrinkage correction for both, liquid and vapour volume should be applied.
g)
Calculate the liquid mass as the product of liquid volume and liquid density.
(see section 6.3 here below)
h)
Calculate the vapour density (see section 4) from the average vapour temperature
and pressure;.
Page No. 13
i)
Calculate vapour mass as the product of vapour volume and vapour density
The vapour phase density is based upon the ideal gas laws and is calculated at tank
pressure and at average vapour temperature. The vapour mass is based upon the
product of a volume and a density, both evaluated at the average temperature of
the vapour phase.
j)
Calculate total mass as the liquid mass plus the vapour mass.
(see section 6.2 and 6.3 here below)
Appendix 3 shows a sheet which can used for the calculation routine. Obviously, the NGC
templates, containing the same information are to be used on board of our fleet.
special application; and D-Tables, Generalised lubricating oils. For low density products
and products at low temperature, the old edition - 1952 of Tables 53 and Table 54 should
continue to be used. Obviously this practice will give results which are less accurate
compared to those resulting from the second option.
Appendix 4 shows numerical calculations for an LPG mixture using different calculation
methods resulting in different liquid quantities.
6.3. SUMMARY
The different options to calculate both, the quantity of Liquid as well the quantity vapour
phase in a tank are summarised here below:
6.3.1. From Liquid density at observed temperature
Liquid
Density at
Actual
Temperature
Liquid
Volume at
actual
Temperature
Vapour Density
at Actual
Temperature
How?
How?
Costald
Francis
Formula
Density Tables
(pure
compounds)
Molecular Weight
Formula
Page No. 15
Vapour
volume at
Actual
Temperature
Liquid Density
at Reference
Temperature
(15 C)
Liquid Volume
at Reference
Temperature
(15 C)
How?
Vapour Density
at Actual
Temperature
How?
Pressure
Hydrometer
Molecular Weight
Formula
Calculated from
Composition
ASTM D 2598
Costald
Francis
Formula
Density Tables
(pure
Compounds )
Page No. 16
Vapour
volume at
Actual
Temperature
loading
recirculation
warm vapour
Plant production
FIGURE 7.1 . LOADING TERMINAL GENERAL ARRANGEMENT
Page No. 17
Figure 7.1 shows an arrangement of a terminal in which two tanks are used for the storage of
refrigerated product. One tanks may be used to service the ship loading, whilst the other
receives the material from the production plant. The loading line to the ship is usually cooled
down before loading operations by the provision of a circulation line back to the tanks.
In order to maintain the pressure in each tank within close limits, a reliquefaction system is
provided which is used to prevent higher pressures being reached. To prevent the possibility
of a vacuum in the shore a warm vapour input is supplied to each tank to allow rapid
generation of vapour and a rapid increase in pressure.
When a ship is being loaded a vapour return may be connected to allow vapour to flow from
the ship back to the shore. This vapour return may be directed to the shore tank being
discharged, although provision is also made to flare this vapour, should it be of unacceptable
quality. Therefore in many cases the manifold valve on the vapour return line is kept closed
and should be considered only as being a safety measurement in case of an emergency.
The figure shows that the reliquefaction system is a common system between tanks and
vapour may, therefore, be interchanged between the tanks. When the product is being run
from the production facility to one of the tanks the rise in liquid level will force out vapour into
the reliquefaction common-header. A falling liquid level in the shore tank being discharged will
need to be replaced by vapour from one or more of the various sources. Similar vapour
movements are also possible during the discharge process.
Above illustrate that the vapour and liquid movements ashore or between shore and ship
during the loading of a gastanker are quite complex and these depend very much upon the
rate, the temperature and the nature of the product which is transferred. Provided the loading
rate is such that the ship reliquefaction plant can cope with any vapour generated by pumping
power and other heat input to the flowing liquid, it is possible to load without the need for a
vapour return. Under these conditions of a relatively low loading rate the vapour movements
around the system are minimised. In such a circumstances, comparison between ship and
terminal figures may be more relevant.
In order to overcome some problems the use of an accurate flow metering system is the only
possible solution. This requires the metering of the liquid to the ship and the metering of the
vapour return in case this is used. .
The question of flowmeter types is discussed in section 7.2, but although metering is not
available on many terminals it will overcome both the problems associated with ship vapour
returns.
Ship / shore quantity comparison is relevant provided that :
Proper calibration of both ships and shore tanks are available;
The shore tank(s) is (are) separated from other means, such as shore flare, production
units, truck- or railcar loading,
The liquid line system from the shore tank to the ships manifold is full before and after
loading;
The temperature of the product (i.e. density) in the shore line should be the same as in the
shore tank, both before and after loading;
No vapours to be released from the ships cargo tanks to the shore flare, except when an
accurate flow meter is available.
Page No. 18
7.2. FLOWMETERING
The use of flowmetering at terminals has the advantage of giving a measurement uncertainty
which is independent of the total quantity of cargo transfer. This is unlike the situation with
static measurement where the uncertainty with large cargoes is much less, in percentage
terms than with small cargoes. The uncertainty of flowmetering is about the same as that of
static measurement for large loads, with the no vapour return qualification.
The minimum requirement for flowmetering is the measurement of liquid to the ship, when no
vapour return is used, or the metering of both liquid and vapour return quantities.
The most widely used liquid flowmeter for LPG cargo measurement is the turbine meter,
which may be used for both refrigerated and ambient temperature product. This meter,
because it contains rotating parts, shows small random variations in calibration and,
therefore, must be installed with the provision for proving. For ambient temperature products
this prover may be of the loop type in which an inflated sphere is moved between mechanical
detectors. This type of prover cannot be used under refrigerated conditions because the
sphere becomes inelastic at low temperatures. For refrigerated products a piston prover must
be used, with a metal piston with low temperature seal materials replacing the sphere.
In order to correctly use the flowmeter the relationship between the K factor, defined as
number of pulses per unit volume, and flow rate should be programmed into the flow
computer servicing the meter. This calibration is continuously applied to the meter during
cargo loading.
The vortex meter is starting to be used for some liquid loading lines. This meter may be
thought of as an obstruction within the pipe which causes vortices to be generated on each
side of the obstruction. The principle is exactly that which causes a flag to flap on a flag pole
as it moves from side to side with the wind generated vortices.
By counting the vortices the fluid flow rate may be determined quite accurately. The meter
has two advantages over the turbine meter. Firstly, it contains no moving parts and therefore
needs no prover; secondly, it is significantly cheaper. Although the use of this meter is still in
its infancy it promises to be of great value in LPG service. Evidence exists that uncertainties
as low as those of turbine meters on LPG can be achieved with vortex meters, that is of the
order of 0.3% on volume.
The measurement of gas vapour should not be ignored. If the liquid is metered during ship
loading, the vapour return if used- must also be metered. Ultrasonic meters offer the best
possibility here mainly because they can scope with the wide range of flow rates typically
found in vapour return lines. The ultrasonic meter measures the time of flight of a sound
signal passing diagonally across the pipe. The times both in the direction of and against the
fluid flow are required in order to determine flow rate. This meter also requires no prover and
gives no obstruction to the flow. These meters are often not calibrated since their
performance can be determined from their installation admittedly with a worse uncertainly
than could be expected with liquid metering. However this does not have a major effect on
the overall measurement uncertainty since the liquid mass is always much greater than the
vapour mass.
Page No. 19
The Coriolis mass flow has the advantages of a high accuracy. The measurement principle is
based on the controlled generation of Coriolis forces. These forces are always present in
systems when both transitional (straight line) and rotational (revolving) movements occur
simultaneously. This principle has been adapted so an oscillation replaces the rotational
movements. Two parallel measuring pipes with fluid flowing through them, are made to
oscillate in antiphase so they act like a tuning fork. When mass is flowing through, there is a
phase shift between the inlet and the outlet. As the mass flow increases, the phase difference
also increases. This phase shift is determined using electro-dynamic sensors at the inlet and
outlet. The measurement principle operates independently of temperature, pressure viscosity,
conductivity or flow profile.
8. FUTURE DEVELOPMENTS
Today manufacturers of flow meters are promoting the use of Coriolis (mass) meters for LPG or
Chemical gases, either refrigerated or pressurised. These meters are particularly usefull where
products are traded on a mass basis since a single measurement of mass should have a better
uncertainty than the combination of volume and density. They also have the theoretical advantage
that they can be calibrated on -say- water and used for any other product. Corriolis meters have a
very stable long term performance which means that they can be calibrated on water in a flow
laboratory and on site using a mobile prover. Subsequently they can be recalibrated on water to
confirm that no unacceptable shift has taken place.
Most static measurement is carried out with float gauges. Uncertainties are dependent on application
and on calibration of the level gauge itself and on the volume calibration of the tank. For larger
parcels, i.e. ships loading, static measurement can match metering systems and have the advantage
of simplicity.
It is very difficult to specify measurement uncertainties in a standard since they will very dependent
on installation, calibration, operating procedures etc
Accuracy of static measurement is dependent on the accuracy of the calibration of the volume of the
cargo tank and on the accuracy of the calibration of the instrumentation (levels, temperature and
pressure). Volume calibration of a cargo tank is performed upon new building of the vessel or after
some structural cargo tank modifications. Besides some custom requirements for the verification and
certification of the accuracy of the instrumentation of a gastanker, no international standard exist until
today in this respect. Measurement uncertainties are found at every stage of product movements and
it is a necessity to implement regular and rigorous procedures to reduce this uncertainty to a
minimum. Obviously, the implementation of quality standards such as ISO, ISM, require well
maintained and well calibrated equipment
Page No. 20
9. CONCLUSIONS
The quantity calculation of liquefied gases differs from those of other products due to the nature of
the product. A reasonable amount of product exist as vapour. The only proper way to calculated
the vapour quantity is by using the molecular weight formula. The molecular weight formula reflect
the condition (temperature and pressure) as well as the nature (molecular mass) of the vapour.
Liquefied gases are handled in closed spaces from which air is totally excluded. The use of a
density in air is irrelevant and should be considered as a theoretical approach. Therefore cargo
quantities should be expressed as a mass (vacuo), rather than in weight (air).
The latest editions of the ASTM Table 53B and Table 54B are not applicable for gas calculations.
When using ASTM tables, reference should be made to the old ASTM Table 53 and 54 which are
obviously less accurate.
The Costald method provides in a density calculation method for LPGs and mixture of chemical
gases at their actual liquid temperature. Volume corrections to a standard temperature of 15 C
are not necessary.
Empirical formulas are available for the density calculation of many pure chemical gases such as
Ethylene, Propylene, Ammonia Anhydrous, They provide in a good correlation between the
liquid temperature and the liquid density for particular products.
The layout of many of the terminals for loading liquefied gases make that ships quantity figures
are the most reliable. A proper calibration of ships cargo tanks as well as their measurement
systems (level, temperature and pressure) is necessary. They implementation of international
calibration standards in this context is desirable.
Page No. 21