PHYSICAL PROPERTIES Page 1 of 12

PHYSICAL PROPERTIES

1.General:

Many physical properties of pure hydrocarbons can be correlated with specific gravity and normal boiling point as independent variables. However, for use
in the petroleum industry, these correlations must also be applicable to petroleum fractions which are mixtures of a large number of components, usually
having a wide variation in boiling points.

While the average specific gravity is a property of the petroleum fraction which can be measured directly, just as in the case of pure compounds, there is
not an analogous average normal boiling point for a mixture. By integrating or averaging its distillation curve (temperature vs. Liquid volume percent
distilled), a volume average boiling point can be determined for the mixture. However, as Watson and Nelson and Smith and Watson have pointed out, this
has no special significance as a true average boiling point and many physical properties can be better correlated by the use of some other average boiling
point, i.e., weight average, molal average, etc. Consequently, in all correlations involving boiling points of petroleum fractions, the proper average should
be used.

2.Average Boiling point of petroleum fractions

Since a distillation curve is usually available and a volume average boiling point is readily obtained therefrom, the other average boiling points are given as
a function of these data. Some charts are based on an assay (TBP) distillation of the whole crude, while the other chart refers to the 10% (or ASTM)
distillation of the fraction itself.

Blue book chart 2-10 was derived empirically from crude assay fractions of a number of crudes. For narrow boiling fractions, all of the average boiling
points approach each other and the volume average boiling point may be used for any of the others. Then, by appropriately combining the volume average
boiling points of the narrow cuts, the various average boiling points of wider cuts were determined. The weight and molal average boiling points of the
wider cuts were calculated directly by combining the narrow cuts on the basis of their weight and mole fractions, respectively. The manner since it is not a
direct average or integral of its fractional parts. As used here in, mean average boiling point is defined as the boiling point which best correlates the
molecular weight of petroleum fractions. Consequently, the mean average boiling point for wider cuts was determined indirectly from the generalised
molecular weight chart.

Although Smith and Watson proposed a cubic average boiling point for the correlation of characterisation factor, specific gravity-boiling point relations for
the different crudes indicate that the present mean average boiling point can be used for correlating viscosity, but the present data indicate that the volume
average is the proper boiling point.

Since these boiling point correlations were developed directly from crude assay distillations, Blue Book Chart 2-20 should always be used if an assay is
available. Otherwise, the 10%(or ASTM) distillation of the fraction may be used in conjunction with Blue Book Chart 2-11. The latter was derived from the
crude assay chart and an empirical correlation between the two types of distillation curves. The difference between the two types of curves at zero slope
represents the thermometer stem corrections for the 10% distillations.

The volume average boiling point, tv, is readily obtained from a distillation curve which is in the form of volume % distilled versus temperature. The
computation under various conditions is as follows:

Distillation curve True-boiling Point ASTM

For whole crudes

For crude fractions

The other average boiling points are correlated to volume average boiling point on the basis of the slope of the distillation curve.

In the case of light hydrocarbon mixtures, where the analysis is know, the volume weight, and molal average boiling points can be calculated directly from
the boiling points of the components and their volume, weight, and mole fractions, respectively. On the other hand, the mean average boiling point must be
determined indirectly from the average molecular weight of the mixture. Up to an average molecular weight of 80, the molecular weight-boiling point
relation for normal paraffins may be used for this purpose, but for higher molecular weights the generalised charts should be employed. See Blue book
charts 2-13 and 2-14.

3. Characterisation Factor

Watson and Nelson introduced characterisation factor as an index of the chemical character of pure hydrocarbons and petroleum fractions. The
characterisation factor of a hydrocarbon is defined as the cube root of its molal average boiling point in Deg R (TB) divided by its specific gravity (s) (60
F/60 F), or

Characterisation factor is given as a function of gravity in Deg. API and boiling point in Deg F for hydrocarbons and petroleum fractions. See Blue Book
Chart 2-20.

That characterisation factor is only an approximate index of the chemical nature of hydrocarbons is indicated by its variation with boiling point both for
members of a homologous series and for fractions from the same crude. However, it has considerable value in that it can be applied to the entire boiling
range of a crude and it has been generally accepted by the petroleum industry.

The use of characterisation factor is illustrated in Blue book chart 2-20.

Characterisation factor is used to calculate specific gravity of petroleum fractions and specific heat of petroleum fractions vapours. See Blue book charts 8-
31/8-32/8-33 and 7-32/7-33

Characterisation factor is one of a number of indexes to the chemical nature of pure hydrocarbons and petroleum factions. It is, perhaps, the most useful
index because it can be related to many physical properties and is a guide to the paraffinicity of a fraction.

Typical factors for various stocks are:

Paraffin hydrocarbons 12.6 - 13.2

Olefin hydrocarbons 12.3 - 12.8

Diolefin hydrocarbons 11.6 - 12.1

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Naphthenic hydrocarbons 11.0 - 11.7

Aromatic hydrocarbons 9.8 - 10.6

Pennsylvania crudes 12.2 - 12.5

Mid-continent crudes 11.8 - 12.0

Gulf coast crudes 11.0 -11.5

Cracked gasolines 11.5 - 11.8

Cracking plant feeds 10.5 - 11.5

Recycle stocks 10.0 - 11.0

Cracked residuum 9.8 - 11.0

3.1 Pseudo-components Breakdown

In some cases it is necessary to break down a petroleum fraction into a series of hypothetical components and estimate for each of these components the
fugacity equilibrium constants so that vaporisation-condensation calculations may be made by the component method. This is particularly important where
the system involved contains light hydrocarbons as well as the petroleum fraction, and it is not practical to apply an empirical calculation method to the
estimation of the phase equilibrium conditions.

The number of components into which the fraction must be broken is dependent upon the type of computation to be made and the accuracy desired. For
example, in calculating the dew points, the higher boiling portion of the fraction is the most important, whereas in calculating bubble points, the lower
boiling portion is the most important. In any event, such a hypothetical component breakdown will result in groups of actual components lumped together
and identified as a single hypothetical components. For each of these hypothetical components, it is necessary to estimate or assign properties in order to
permit computing the fugacities. The properties required are the density, the molecular weight, and the critical conditions. From these properties, plus the
boiling points and the percentages of each, it is possible to compute the mols of each component and to estimate the phase equilibrium distribution
constants.

To obtain the pseudo components, the true boiling point distillation curve of the petroleum fraction is divided into hypothetical components by means of the
chord area method. This involves drawing plateaus in such a way that the shaded areas above and below the curve balance. Each of these components is
identified by its average boiling point on this TBP curve. The volume percents of the components are then read from the lower scale.

In addition to the boiling points for each component, as obtained from the TBP distillation curve, the densities must be obtained. This may be done directly
if the density vs volume percent distilled curve is also available. Such a curve may be available at the same time the TBP distillation is obtained. If such a
density of gravity curve is not available, then the gravities must be estimated. This may be done based on the characterisation factor of the whole fraction,
which is assumed constant within the boiling range of the fractions by changing the boiling point; and back calculating through the constant
characterisation factor it is possible to obtain the corresponding specific value for any boiling point.

Having the boiling points and densities of each hypothetical component, the next step is to estimate from correlations the critical temperatures and
pressures and the molecular weights of each hypothetical component. With these, the calculations of the fugacities and equilibrium constant proceed in
straightforward manner, using available correlations in the Exxon Blue Book or similar.

4. Density

Specific gravity and API (American Petroleum Institute) gravity are expressions of the density or weight of a unit volume of material. The specific gravity is
the ratio of the weight of a unit volume of oil to the weight of the same volume of water at a standard temperature. Unless otherwise stated, both specific
gravity and API gravity refer to these constants at 60 F. An exception is the use of 77 F (25 C) in connection with asphalts and road oils.

Corresponding values of API gravity ( 0 to 100), specific gravity, and pounds per gallon are given in Blue book charts 8.11 through 8.17 as well as pounds
per barrel, barrels or cubic meters per long ton, etc.

The Baume scale of gravity for liquids lighter than water, used previously by the industry, differs slightly from API gravity by the use of constants of 140 and
130 rather than 141.5 and 131.5.

Specific gravity or API gravity are measured by means of hydrometers (D287), pycnometers (D941 and D1217), or the chainomatic specific gravity balance
if very many small samples (15cc) must be tested. For viscous oils or semisolid bitumens a pycnometer (D70) or weighing bottle may be used, for solids an
analytical balance (D71) equipped with a pan straddle.

Most products are sold on a basis of volume delivered and corrected to 60 F by means of standard tables of volume corrections. Weight is important in
determining freight rates, tanker cargoes, and the power required in pumping. Gravity or weight determines whether a product will sink or float in water or
will separate from water. In other respects gravity is not of much direct significance, but the test is so simple and so widely used that it assumes importance
as a means of judging many other properties and in controlling plant operations.

4.1 Density of Gaseous Hydrocarbons

There are no charts for density of gases; it is calculated based on:

T - Temperature Deg R

P - Pressure PsiA

A. Molecular Weight lb/mol

u - Compressibility factor

V - Volume Cuft

R - Gas constant = 10.72 Cuft/Lbmol

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p - Density of gas = Lb/Cuft

u is obtained from Blue Book Charts 8-41 through 8-45

4.2 Density of Liquid Hydrocarbons

Temperature changes cause variations in the volume of liquid hydrocarbons; these variations are expressed in the form of an expansion factor. As in the
cases of many physical properties of petroleum fractions, thermal expansion is more sensitive to average boiling point than it is to gravity, although both
independent variables are necessary to correlate the data properly. Up to 1.25 multiples of the volume at 60 F and 1 atm, it was found that gravity could be
neglected and that the thermal expansion could be represented by the molal average boiling point alone. Above this expansion of 1.25 volumes, gravity is
introduced into the correlation in the form of characterisation factor of 12.0 and the other 11.0. Interpolation and extrapolation may be made on the basis of
characterisation factor or, if preferred, gravity, which is also given for each curve.

The relationship between temperature MOL average boiling point and thermal expansion off hydrocarbon liquids is illustrated in Blue Book charts 8-31
through 8-35. (Maxwell P143).

5. Viscosity

The viscosity of an oil is a measure of its resistance to internal flow and is an indication of its oilyness in the lubrication of surfaces. In the centimeter-gram-
second system the unit of viscosity is the poise or centipoise. Viscosity may be defined as the force in dynes required to move a plane of 1 sq.cm area, at a
distance of 1 cm from another plane of 1 sq cm area, through a distance of 1 cm in 1 sec.

The relative viscosity is the ratio of the viscosity of the liquid to that of water 68 Deg F. The viscosity of water at 68 F is 1.022 centipoises, and hence the
relative viscosity and the viscosity in centipoises are numerically equal. Two other common terms are kinematic viscosity, which is the viscosity in
centipoises divided by the specific gravity at the same temperature, and fluidity, which is the reciprocal of viscosity. The units of kinematic viscosity are
stokes and centistokes. The English unit "reyn" (1 lb-sec per sq in) is equal to 69 x 10^ 5 centipoises.

The common viscosimeters do not read directly in centipoises. All employ arbitrary scales of viscosity. The Saybolt Universal Viscosity (D88) is the time,
measured in seconds, required for the efflux of 60 cc of oil from a container tube at a constant temperature through a calibrated orifice in the bottom of the
tube. The procedure involves straining the oil to remove particles that might lodge in the orifice, bringing the oil to a constant temperature by means of a
constant-temperature bath, and accurately measuring the time for efflux. The Saybolt Furol Viscosity (D88) is determined exactly as is the Universal
viscosity except that a larger orifice is used. The viscosity of lubricants is usually reported as Saybolt Universal seconds at 100,130, or 210 F and of fuel oil
as Saybolt Furol seconds at 122 or 210 F. See section 9 of EBB.(Maxwell P162).

6. Molecular Weight

The laboratory determination of the molecular weight of crude oil and its fractions is done through a complex and time consuming procedure. Fortunately it
was found that it correlates very well with other properties which are easier to determine in the laboratory correlations for molecular weight using single or
multiparameter graphs are found in several of the data sources listed before.

7. Applications to Mixtures

7.1. Boiling Points

Molal Average Boiling Point (MOL ABP)

Weight Average Boiling Point (WABP)

Volume Average Boiling Point (VABP)

These three can be calculated by linear blending of the corresponding boiling point of fractions with the amount (mol wt. Or vol) of each fraction.

The mean average boiling point (MABP) correlates with molecular weight so it can be calculated from it after the mol wt of the mixture has been
determined by linear blending.

7.2 Viscosity of Gas mixtures

Given the viscosity of the individual components of a gas mixture, the final viscosity of the blend can be obtained as follows

Correct for pressure. See EBB chart 9-87.

7.3 Viscosity of liquid mixtures

Viscosity of liquid mixtures is calculated based on the viscosity blending index (VBI) and the volume fraction of the components, as shown in the following
example:

Viscosity of Liquid Mixtures

Component Volume fraction Visc. @ 50 F, Cs VBI

A 0.5 15.0 36.4

B 0.3 31.5 31.8

C 0.2 131.0 24.7

___ ____

1.0 32.73

Viscosity for 32.73 VBI = 26.7 Cs

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VBI Charts. See EBB 9-61 (Maxwell P173)

7.4 Density of Liquid mixtures

The density of liquid hydrocarbon mixtures is calculated by direct linear blending of the densities of the components and their corresponding volume
fractions do not blend Deg API; blend:

Specific gravity or lb/gal

lb/cu ft

all expressed at the same temperature.

See EBB Section 8

8. Prediction of Equilibrium Flash Vaporisation

When a liquid mixture is heated without allowing the vapor to separate from the unvaporized liquid ( so that vapor and liquid are in equilibrium ) until the
desired final temperature is reached, the vaporisation occurs as an equilibrium flash. For a given temperature, an equilibrium flash will vaporise a greater
percentage of the initial liquid than will the described TBP and ASTM distillation methods. The difference occurs because the lighter fractions of the vapor
tend to act as an inert and have the effect of reducing the total pressure on the system, thus permitting additional liquid vaporisation.

Since modern distillation units use the continuous equilibrium flash process, equilibrium flash vaporisation data is essential for design work. The TBP
apparatus can be operated under equilibrium conditions but the distillation is lengthy and expensive. As the design engineer needs equilibrium data for
various fractions as well as the whole crude, an empirical correlation has been developed for predicting the equilibrium flash vaporisation curve (FVC) from
either the TBP or ASTM distillation curve. The prediction from TBP data is preferred because of the inaccuracies in the ASTM distillation method.

The method for predicting the atmospheric flash curve for a whole crude (or any crude fraction) is as follows: See EBB 13-20 and 13-21.(Maxwell P228)

l Draw a straight line, called the distillation reference line (DRL), through the 10% and 70% points of the distillation curve. Determine the slope and
record the 50% point of the DRL.
l Using the uppermost graph, determine the slope of the flash reference line (FRL). Using the centre graph, determine the 50% point of the FRL.
Draw the FRL as a straight line having the determined 50% point and 10%-70% slope.
l Record the temperature difference between the distillation curve and the DRL at 10% intervals. Multiply each difference by the corresponding factor
given on the upper chart. Add the resulting temperature difference to the FRL and draw the atmospheric flash curve through the resulting points.

THERMAL PROPERTIES

1. Specific Heat

The specific heat of a material is defined as the quantity of heat required to raise the temperature of a unit weight of material through a temperature
difference of one degree. Universally the oil industry uses the English system in which the specific heat is defined as the number of British Thermal Units
(Btu) required to raise the temperature of 1 lb of oil 1 Deg F and is expressed as Btu per degree Fahrenheit.

The specific heat of petroleum fractions is a nearly linear function of temperature. It is also dependent on the specific gravity.

Since hydrocarbon vapours deviate considerably from a perfect gas, except at low pressures, their specific heats are a function of pressure as well as
temperature. However, vapor specific heats at high pressures have limited application as enthalpy correlations may be more readily used for thermal
calculations. For this reason, the specific heat charts for gases and vapours (EBB charts 7-23, 7-26, 7-32, 7-33) are given only for low pressures (0 - 1
atm)where deviations from a perfect gas are so small that specific heat may be considered to be a function of temperature alone. The specific heat of a
mixture of two or more gases at low pressures may be calculated from either their weight fractions multiplied by their specific heats or their mole fractions
by their molal heat capacities (MCp)

The charts for the specific heat of hydrocarbon liquids were developed directly from liquid specific heat data on pure hydrocarbons and petroleum fractions.

For the sake of consistency, the enthalpy charts are used in preference to specific heat chart but, at the same time, it is desirable to include an
independent correlation of such a fundamental thermal property.

The specific heat of liquid mixture is a linear blend of specific heat of the components and the weight fraction of each in the mixture.

2. Latent Heat

The latent heat of vaporisation of any compound is the difference in enthalpy between its saturated vapor and its saturated liquid at constant temperature
and may be expressed either as a function of temperature or as a function of vapor pressure. The latent heats of low boiling hydrocarbons and, also,
higher-boiling normal paraffins of even boiling point are plotted against vapor pressure.

While the use of temperature instead of vapor pressure as he correlating variable would have advantages, it would also result in the curves crossing each
other, thus making the plots difficult to read.

The latent heat charts were derived by using a direct proportionality between the molal heats of vaporisation of any two hydrocarbons at the same reduced
pressures. For the lower boiling hydrocarbons, the latent heat data were smoothed out and extrapolated by the use of a reference compound (ethane,
butane or hexane).

The latent heat of vaporisation of other hydrocarbons may be calculated from the normal paraffin curves by the use of this same relation. That is, the
unknown compound will have the same molal heat of vaporisation as a paraffin of the same normal boiling point at the same reduced pressure. In the case
of petroleum fractions, the mean average boiling point is used for the normal boiling point and the reduced pressure is computed from the pseudo-critical
pressure of the mixture.

Since the difference in enthalpy between the liquid and the saturated vapor of a petroleum fraction always involves change of enthalpy of the vapor at
constant temperature in addition to latent heat, except at low pressures, the enthalpy correlations are much more convenient to use than these individual
thermal properties. See EBB charts 7-36 through 7-39.(Maxwell P94-97)

3. Enthalpy

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The enthalpy or heat content of low-boiling paraffins, olefins and aromatics is given by the EBB charts 7-42 through 7-59. These charts can be applied to
mixtures of light hydrocarbons on the basis of the following assumptions:

1. The enthalpies of individual components of a mixture are additive in the liquid phases, that is, the molal heat content of the mixture equals the sum
of the products of the molal heat contents of the components by their mole fractions.
2. The enthalpies of individual components are additive in the vapour phase at low pressures (0-1 atm)
3. The change in enthalpy of the vapour with pressure at constant temperature is the same for a mixture as for a single compound having the same
molecular weight as the mixture.

Above the critical temperature a dashed line is shown for the heat content of the gas in solution. This line was based on the assumption that the gas in
solution at any temperature would have the same partial density and enthalpy as the pure compound at a pressure corresponding to an extrapolation of its
vapour pressure curve above the critical point. Obviously, this is only a rough approximation since both a vapour pressure curve and an ideal liquid
solution are meaningless in this region.

3.1 Enthalpy of Petroleum fractions

The enthalpy of petroleum fractions is given by EBB charts 7-62 through 7-75 for both paraffinic stocks, having a characterisation factor of 12.0, and non-
paraffinic stocks, having a characterisation factor of 11.0 over a mean average boiling point range from 200 Deg F to 800 Deg F. Theoretically, these
charts represent pure hydrocarbons of the designated characterisation factor and boiling point, they may be applied to petroleum fractions if the following
assumption is made in addition to the three previous ones pertaining to light hydrocarbon mixtures:

The average difference between the enthalpy of the vapour at low pressures (0-1 atm) and the enthalpy of the liquid, at constant temperature, is the same
for a mixture of chemically similar hydrocarbon as for a single compound of the same molecular weight (or mean average boiling point).

These charts may be interpolated and extrapolated linearly with both characterisation factor and mean average boiling point. Occasionally, in interpolating
between two adjacent boiling point charts the pressure and temperature of the vapour will be such that they fall inside of the "dome" of the higher boiling
point chart. Since it is impossible to use the charts in this region, it is recommended that the two adjacent lower boiling point charts be extrapolated
upward.

4. Gas Compression

Gases are heated by compression unless the heat of compression is removed. In actual practice a portion, but not all, of this heat is removed. The
calculation of the theoretical power is customarily based on either of two extreme assumptions: either that all of the heat is removed continuously during
compression (isothermal), or that none at all is lost (adiabatic).

The second assumption of no heat loss, i.e., of adiabatic compression, is much more universally used because the results are much closer to actual
performance and also because the adiabatic efficiency afforded by a compressor is nearly independent of the properties of the gas being compressed. An
additional assumption is also made in this case of perfect gases, namely that the specific heat is constant. Under these circumstances the adiabatic
equation of state of a perfect gas becomes

Actual gases do not fulfil either of the assumptions used in deriving the adiabatic power equation; the perfect gas law is not obeyed exactly, and specific
heats are not constant but increase with both temperature and pressure. (Specific heats of monatomic gases at low pressure are independent of
temperature). Nevertheless the equation does, by good fortune, give reasonably accurate results for actual gases unless the gas-law deviation is very
large.

When imperfect gases are compressed, the use of thermodynamic charts such as Mollier diagrams is recommended. The steps involved in the use of
these charts are outlined below.

1. Locate the point corresponding to inlet pressure and temperature - record enthalpy H1.
2. Follow the line of constant entropy to outlet pressure, record enthalpy H2 and temperature t2 (discharge temperature for ideal compression).
3. Work of compression = H2 - H1, or
4. Repeat for each stage.
1. Divide by efficiency to secure brake horsepower.

Discharge temperature of compressed gasses - for many purposes it is customary to take the ideal adiabatic temperature as close enough. This may be
computed by the equation,

However, it is equally easy to obtain a better value by a heat balance as follows:

While, strictly speaking, these equations apply only to ideal gases, they may be used with very little error for light hydrocarbons and mixtures of light
hydrocarbons and inert gases under the following conditions:

l When inert gases (non-hydrocarbon) are present, the above limitations are calculated ass follows:

Molecular weight - Calculated for the hydrocarbon portion only.

U - Calculated for the hydrocarbon portion, using an "effective" hydrocarbon pressure

Outlet pressure - based on final "effective" hydrocarbon pressure

Although u for hydrocarbon portion alone is used to determine whether the simplified equations are applicable, the value of u used in the horsepower
equation of EBB chart 7-80 is the average u for the whole mixture. Thus, when inert gases are present:

The values of u for inert gases can usually be assumed as 1.00, but if u is calculated it should be determined for each gas at its effective pressure

The average value of "a" to be used in the equations is determined by first finding values of "a" at the average compression temperature for the paraffin
portion, the olefin portion, and the individual inert gases, using chart. The individual values of "a" are then averaged as follows:

The term SCF in the horsepower equation refers to gas at 60 Deg F and 1 atm. Where 1 lb. Mole is equal to 380 SCF.

As a time-saver in calculating horsepower, EBB chart 7-83 gives the theoretical horsepower required to compress a million CF per day of gas at 100 Deg F
as a function of "a" and the compression ratio. It should be emphasised that the curves apply directly only for u initial=1.00 and for an initial temperature of
100 Deg F. For any other conditions, the value from the curve must be multiplied by the actual u initial and by

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EBB chart 7-83 also gives a curve of compression efficiency Vs. Compression ratio for single stage reciprocating compressors which also applies to two-
stage units without intercooling. Dividing the theoretical horsepower by this efficiency factor gives the brake horse power required. There is no simple
correlation of this nature available for the efficiency of centrifugal compressors, however. Also there is no simple correlation available relating the actual
final temperature to the theoretical final temperature calculated. In general, the final temperature will be close to the theoretical for reciprocating
compressors. For centrifugal compressors, it will be higher than theoretical by an amount roughly corresponding to the additional enthalpy of compression
required compared to theoretical.

4.1 Use of Mollier Diagrams

Enthalpy change ( or horsepower requirement ) and final temperature for adiabatic compression may also be calculated form the Mollier diagrams, and
when the simplified adiabatic compression charts are not applicable, the Mollier diagrams must be used. Charts are included for methane, ethane,
propane , butane, ethylene, and propylene. These charts can be interpolated and extrapolated to cover light hydrocarbon mixtures.

The Mollier diagrams may also be used for mixtures of light hydrocarbons and inert gases (non-hydrocarbons) by considering the latter to be paraffins with
fictitious molecular weights as follows:

Diatomic gases (such as CO, H2, N2 ) : 10

Triatomic gases (such as CO2, H2S,SO2) : 16

This method is reliable under the following conditions:

Mol% Olefins in Hydrocarbon portion Mol% inert gases

0 Up to 40

50 Up to 25

100 Up to 10

P-V-T RELATIONSHIPS OF HYDROCARBONS

1. General

The behaviour of fluids with change in pressure, volume or temperature comprises basic information for design and operation in petroleum refining. A
knowledge of inter-relationships of these factors for hydrocarbons and their mixtures is essential to the solution of frequent practical engineering problems
involving flow of fluids, diffusional processes, and capacity considerations, and is required in the evaluation of thermodynamic properties of fluids.

The use of PVT data is involved much more frequently and is of considerably greater importance in the consideration of gases than it is in the case of
liquids, consequently, the major part of this review is devoted to behaviour of gases.

Much of the PVT data in the literature are presented in the form of graphs. These graphs nearly always assume a rather characteristic form, and
consideration of such a graph will be helpful in visualising the general relationships involved.

2. Thermal expansion of liquids

The expansion of petroleum fractions with temperature is a function of the specific gravity, the pressure, and the viscosity of the liquid. The expansion may
also be correlated with the specific gravity, the pressure, and the molal average boiling point. Correlation curves are presented on the latter basis in the
EBB, Section 8, and on both basis in the Kellogg Data Book.(Maxwell P143).

3. Ideal Gas Relationships

Boyle’s and Charles’ laws

The ideal gas equation represents the limit approached by actual gases, and can only be used as an approximation for real gases or vapours. At low
pressures and at high temperatures, in certain pressure ranges, the behaviour of actual gases approach the conditions expressed by the ideal gas law,
and the equation can be used satisfactorily for many engineering calculations. Care must be exercised in utilising the ideal gas law with pressures much
above one atmosphere, particularly with the heavier vapours. For example, ideal gas law calculations for gas oil vapours may be in error by 5% and more
at a pressure of only one atmosphere, while 50 psig the error for gasoline vapours may be 15% or higher.

3.1 Real gas relationships - Pure gases

3.2 Equations of State

3.3 Compressibility Factors

Some interesting generalities may be observed from the compressibility factor curves (commonly called u charts)

1. The maximum deviation for the curves shown is at the critical point
2. Below the isotherm, Tr = 1.0, the lines end at the reduced pressure corresponding to the vapour pressure beyond which the gas can no longer exist
as a stable state.
3. At pressures below Pr = 2, gases at temperatures 2.5 times the critical value behave almost as ideal gases.
4. When Tr is greater than 2.5, the deviations for all pressures are towards volumes greater than the ideal.
5. At Pr = 10, all gases deviate approximately the same amount regardless of temperature.

There is evidence of some change in compressibility factor with increasing molecular weight for low molecular weight hydrocarbons when the temperature
is above the critical, and to provide for this effect the EBB presents three charts covering molecular weight ranges of less than 20, 20 to 40, and greater
than 40 (EBB charts 8-41 through 8-45).

4. Behaviour of Gaseous Mixtures

In refinery operations it is usually necessary to deal with the mixtures of gases rather than a single pure gas and consequently relationships expressing the
behaviour of mixtures are of great importance. For mixtures of ideal gases, each individual gas acts as if it alone were in the system.

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Refer Dalton’s and Amagat’s laws.

5. Average Boiling Points

Since the critical properties and pseudo-critical properties of petroleum fractions are correlated with various types of average boiling points, it is advisable
to discuss these average boiling points before taking up the determination of critical properties.

Four types of average boiling points find use in the correlation of critical properties of petroleum fractions, 1. The volumetric average, 2. The weight
average, 3. The molal average, 4. The mean average. For mixtures of known composition, these various boiling points may be readily derived from the
concentrations, molecular weights, densities, and boiling points of the individual components, but for a petroleum fraction of unknown composition the
boiling points are derived from either a Crude Assay Distillation or a 10% (ASTM) Distillation of the fraction with corrections obtained from the correlation
charts presented in the EBB charts 2-10 and 2-11. The corrections are based on the slope of the distillation curve, the gravity of the fraction, and the
volumetric average boiling point. The volumetric average boiling point, as determined from the 10%(ASTM) Distillation is defined as

With the slope and volume average boiling point calculated from the distillation curves, the EBB charts 2-10 and 2-11 should be consulted for
corresponding values of weight average, molal average, and mean average boiling points.

6. Critical Properties

A knowledge of the true critical properties of a mixture is of importance in determining the limits of temperature and pressure at which a mixture can be
separated into its components by fractional distillation. The critical temperature of a mixture always lies between the extremes for the individual
components and may be estimated for a mixture of light hydrocarbons by adding the critical temperatures of the individual components on a weight fraction
basis. Using this procedure, the critical temperature will usually be within 25 Deg F of the correct temperature. The true critical pressure, however,
frequently exceeds that of any of the components and estimation of the value is less simple. An equation which gives quite satisfactory results is the
equation of Benedict.

In which Yn is the mol fraction of the nth component whose critical pressure is Pcn, and whose normal atmospheric boiling point is Tn Deg R.

7. Pseudo-critical Properties

The computation of vapour densities in the temperature and pressure ranges encountered in most hydrocarbon processes necessitates recognising
deviations from the ideal gas law. This may be done by the compressibility factor, the volume residual, or by an analytical equation of state, employing
generalised methods with reduced pressure and temperature parameters. Thermodynamic equations may use the same generalised methods.

For pure components, the reduced conditions are calculated from the critical point and the resulting generalised correlations and derivations are of
sufficient accuracy for practically all process engineering calculations. Thermodynamic properties of mixtures may be computed from the properties of the
individual components by combining the partial quantities for the components in the proper fashion. Another method is to use an equation of state with
constants from combining component constants. Both of these methods are lengthy for multi component hydrocarbon systems so it is desirable to use
generalised methods where possible. In applying generalised methods to mixtures, average critical conditions instead of true critical conditions must be
used in computing the reduced temperatures and pressures for the system. Such an average critical temperature and pressure was proposed in 1936 by
Kay and is known as the pseudo-critical point. By using reduced conditions computed from pseudo-critical as the dependent variables, the PVT data fit the
same generalised correlations that had been previously developed from the PVT data of pure component. This is a very useful and important concept in
the applications of thermodynamics to hydrocarbons. The pseudo critical is ordinarily used with graphical correlations such as compressibility factor or the
volume residual. It may also be used with analytical equations of state thus applying equations of state developed for pure components to mixtures by
means of reduced conditions calculated from the pseudo-critical temperature and pressure for the entire mixture.

It has already been mentioned that in order to obtain agreement between the correlations of the compressibility factor, u, for mixtures and pure gases,
resort must be made to the use of "pseudo" critical properties in the case of mixtures. For all except mixtures of compounds having very similar properties,
these pseudo-critical properties are determined, they may be employed in exactly the same manner as are critical properties for a pure substance in
obtaining the u factor describing deviation of the behaviour of a mixture from the ideal gas law.

For a mixture of known composition, the pseudo-critical properties of the mixture may be calculated from the true critical properties of the individual
components by merely weighing on a molal basis.

8 Comparison of Ideal and Empirical solutions

It has been stated above that values obtained using the empirical methods involving pseudo-critical constants and compressibility factors are much more
accurate than ideal solutions obtained from Dalton’s or Amagat’s Law.

EQUILIBRIUM SEPARATION

1. Vapour Pressure

Vapour pressure is an indication of the pressure that a material will develop within a closed container and is particularly significant for materials whose
boiling points are so low that they cannot be distilled at atmospheric pressure without serious loss. The test is important with respect to safety in transport,
vapour lock in gasoline feed systems, types of storage tanks employed and the starting characteristics of motor fuels.

Vapour pressure is one of the most fundamental and useful properties of a hydrocarbon. The relationships that exist between the vapour pressure and the
PVT data and the latent heat of vaporisation constitute an interesting subject for thermodynamic study. Vapour pressure data and correlations are reported
in the technical literature, some in connection with PVT data, some in connection with latent heats of vaporisation, while others are vapour pressure data
only.

When vapour pressures of pure hydrocarbons are plotted on rectangular co-ordinates, a parabolic shaped curve results. This curve is not convenient for
plotting and smoothing experimental data or for interpolating and extrapolating vapour pressures. Accordingly, considerable attention has been devoted to
the development of graphical and analytical methods of correlating vapour pressures. Two graphical methods of particular interest are those of Cox and
Coates-Brown.

In the Cox type vapour pressure chart, log p is plotted against the reciprocal of the absolute temperature plus a numerical constant. This gives straight
lines for hydrocarbons with the lines for each series (i.e., paraffin, olefins, etc.) tending to intersect at a common focal point, thus forming a family of curves.
See EBB chart 4-50(Maxwell P42)

The vapour pressure charts need little explanation. The pure compound curves are rarely used, except when dealing with a single hydrocarbon, which may
happen in ethane or propane refrigeration or petrochemical manufacture. But in everyday refinery calculations, we are usually concerned with hydrocarbon
mixtures and any vapour pressure calculations in the light ends range should be done with the aid of the fugacity charts.

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Therefore, the fugacity charts can be used to determine the vapour pressure of hydrocarbon mixtures, and also, the loss of light hydrocarbons from
incompletely stripped lean oils in the dry gas of an absorber. Incidentally, this fact is frequently forgotten, and may result in the loss of valuable constituents
to fuel gas.

2. Fugacity

Fugacity functions are used extensively in all phases of light ends design work. Dew and bubble point calculations are carried out to determine tower
operating temperatures and pressures; relative volatilities set the plate requirements and minimum reflux ratios of distillation towers; flash calculations are
required at many points in a light ends plant calculation; the vapour pressure of hydrocarbon mixtures can be predicted by means of fugacities; absorber
towers are designed using fugacity functions and so on. A proper understanding of the meaning and the use of fugacities is therefore imperative when
embarking on a light ends design project.

The fugacity function of a given component will vary with the temperature and pressure of the system. These variations have been incorporated into the
EBB charts. However, fugacity is also affected by the compositions of both the liquid and vapour phases.

Blue Book charts do not hold over the whole temperature and pressure ranges encountered in refinery design. More accurate charts covering essentially
all conditions have been published by the M.W. Kellogg company. These charts are similar to the EBB charts, but average boiling points of the liquid and
vapour phases are introduced as additional parameters.

Blue book will give perfectly satisfactory answers when used within its limitations, the Kellogg data are only recommended when operating outside these
limitations.

Listed below are the recommended EBB limitations(Maxwell P49-67). When designing beyond these conditions, the Kellogg charts have to be used, since
serious underdesign may result otherwise.

2.1 Limitations of EBB fugacity charts

End use Limitation

Bubble point For rough calculation, EBB can be used all the way.

Dew point However, if in the least critical, the EBB answer should

Flash calculation be checked by Kellogg charts if pressure above 300

Vapour pressure psig.

Absorber Design Use EBB charts with appropriate characterisation factor

correction (chart 5-61) (Maxwell P67) up to 200 psig.

Above this pressure, use Kellogg charts, at least for

critical component.

Relative volatility EBB can be used up to 200 psig, Kellogg charts above

this pressure. When operating near 200 psig, the

relative volatility of the light key should be checked with

Kellogg fugacities.

2.2. How to find Fugacities

The fugacity functions of the light hydrocarbons are given in EBB charts nos. 5-11 to 5-31. However, in the course of light ends calculations, quite a
number of other components are encountered, and proper fugacities have to be used for these constituents. For ready reference, these components have
been listed below, together with some pointers for special cases.

Component

Light Hydrocarbons EBB charts 5-11 to 5-31 (Maxwell P49), also Relative Volatility charts 5-50 and 5-51.(Maxwell P64). If the liquid C1 through C8 is
highly aromatic or an absorber oil, use Activity coefficient correction chart No. 5-61 for C1 as given, (Maxwell P67) and the other line for C2 to C5 inclusive.
No correction for C6+

C9 and C10 The fugacity of these components can be roughly prorated from the fugacities of C6, C7 and C8, by noting that the relative volatility between
adjacent components in this range does not vary appreciably.

Heavy Hydrocarbons Use the "Petroleum Refiner Charts" Vol 28, No.7 P101- 112, July 1949.

H2S Fugacity chart for H2S has to be used.

Aromatics and other Hydrocarbons not Use generalised charts 5-40 and 5-41 (Maxwell P62-3) listed together with vapour pressure and critical properties

Concerning the use of Generalised Fugacity Charts Nos. 5-40 and 5-41, it is recommended that the method of calculation be checked with the aid of a
known component, such as propane or butane. This will avoid errors in the procedure which are only too easy to creep in unnoticed.

3. Bubble point

Bubble points are generally used to set the pressure of distillation towers, to determine the vapour pressure of a given mixture, and in plate-to-plate
calculations if they should be necessary.

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4. Dew Point

Dew point calculations are employed in setting tower pressures when the overhead product is a gas; they are used to determine the temperature of the top
plate in a light ends column. In general, they find application whenever it is desired to find out at what temperature or pressure condition a vapour starts
condensing.

If water is present, check whether or not it will condense before the hydrocarbon:

l If it does condense out first, then the dew point is obviously the point at which the water begins to drop out, i.e., where partial press water = vapour
pressure water. The hydrocarbon will only start condensing out at some later point after sufficient water has condensed out.
l If water will not condense out first, treat it as an inert component with infinite fugacity.

5. Flash calculations

The flash calculation is a method of predicting how a given hydrocarbon mixture will split into liquid and vapour at a certain temperature and pressure.
Besides composition, which is usually known, there are three primary variables.

1. Temperature, t
2. Pressure, p
3. Final liquid-vapour ratio, N=L/V

Given any two of these variables, the third can be determined by trial and error, and the distribution of each component between the liquid and vapour
phases can be predicted.

The flash calculation is used so extensively in light ends design work that special computers have been constructed to handle this problem. Especially
when the number or components involved is large, the trial and error becomes very tedious, and it is hoped that eventually a large proportion of these
calculations will be handled on the computer.

The flash calculation is carried out by a method very similar to that employed in the bubble and dew point calculations. First, a value is assumed for the
variable which is to be determined. Next, a particular flash equation is solved on the basis that the assumed value is the correct one. Finally, this procedure
is repeated, if the assumed value did not satisfy the flash equation. Depending on which variable is to be determined, a certain from of the flash equation
has been found to be most advantageous for trial and error.

Following are the derivations of these flash equations with an outline of the method to be employed in their application to actual problems. In all cases, it is
assumed that the composition of the feed, i.e., the zi’s are given.

5.1.Flash Case I Temperature given

Pressure given

Liquid - vapour ratio to be determined

Starting with the material balance for each component

We obtain,

from which it follows that

Therefore, the expression for the total final equilibrium vapour is given by

The calculation, therefore, is carried out as follows:

1. Assume a value of N
2. Substitute this value into the above equations to determine V
3. Calculate L by difference (L = Z-V) and N(=L/V)
4. Repeat this procedure until the value of N assumed in 1. Checks the calculated N obtained in step 3.

Since the p Ki- values are fixed in this problem (temperature and pressure are given), the numerator of the eqn, (8-7) does not vary from trial to trial. For
this reason, form (8-7) of the flash equation is particularly applicable for this case, as illustrated in the example below.

If inerts are present in the feed, the effective pressure of the hydrocarbons must be estimated by guessing a liquid vapour split and including all the inerts
in the vapour. While this effective pressure is used in looking up the proper p Ki- values, the total pressure is used in the flash calculation(i.e. when
substituting pN).

The presence of water introduces a complication which is as follows:

1. Calculate Vhc and Lhc as if no water were present

2. From the vapour pressure of water, determine the amount of water vaporised. If we call Vw the amount of water in the vapour phase, then

unless, of course, this value turns out to bee larger than the amount of water in the feed, Zw. In that case Vw is simply equal to Zw.

3. The final liquid-vapour ratio is then given by

This is the value of N which has to be compared with the assumed N to check the validity of the original assumption.

5.2 Flash case II Temperature given, Liquid-vapour ratio given, Pressure to be determined.

This type of problem crops up when it is desired that the operating pressure be found in a light ends tower, which is to make a specified amount of liquid
overhead product, the remainder of the overhead leaving the gas.

Start with material balance equation

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In this case, divide by xiL (i.e., li) and by a very similar series of operations as before we arrive at the expression for the total equilibrium liquid.

Equation (8-13) is very suitable for this case, since the numerators of the terms in the summation do not change from one trial to the next. The procedure is
as follows:

1. Assume a pressure, p, and look up pKi-values.

2. Substitute into equation 8-13 and solve for L*. * If the feed does not contain any water, step 3 can be eliminated since the given L can be compared
with the calculated value.
3. Calculate V by difference and determine Ncalc.
4. Repeat this procedure with different assumed pressures until the calculated N agrees with the given value.

Inerts and water are handled by procedures very similar to the ones described before.

5.3 Flash Case III Pressure given, Liquid-vapour ratio given, temperature to be determined.

Flash calculations of this kind occur predominantly in the determination of the preheat requirements for feeds to light ends towers. Both the liquid-vapour
split and the pressure are set by tower operating conditions, so that the temperature to which the feed has to be heated must be determined. The
procedure is to use eqn. (8-12) and to vary the assumed temperature until the calculated L agrees with the given value.

For convenience and ready reference, the various flash equations and procedures have been summarised in the following table:

Summary of Flash Calculations

Case Given Find Trials Eqn. To be used Final Balance

A special case of flash calculations should be pointed out here. Certain close cur mixtures have dew and bubble points which are not too far apart, such as
propane-propylene mixtures, or a blend of the various C4 - hydrocarbons. In such cases, it is futile to attempt flash calculations of the type discussed
above. The simplest method of handling these problems is by linear interpolation of the moles of vapour between the flash conditions, and the dew and
bubble points.

5.4 Relative Volatilities

For ideal mixtures, the relative volatility is defined as the ratio of the vapour pressure of the two components in question. By analogy, for non ideal
hydrocarbon mixtures, the relative volatility is given by the ratio of the fugacities. Thus, the relative volatility , , between components 1 and 2 in a
hydrocarbon system is given by

The relative volatility is an important variable in light ends fractionator design. Fugacity charts should be used up to 200 psig only. The relative volatility
curves in the EBB fugacity section have a somewhat wider range than the fugacity charts. However, they are essentially restricted to the systems in which
the binary involved are the keys.

6. Fractionation

The expression "fractionation" was originally meant to describe the process of separating two or more volatile substances into components of varying
boiling range, by heating and partially vaporising the original mixture and condensing the vapours to yield a condensate of lower boiling temperature than
the original liquid and a residual liquid of higher boiling temperature; these two fractions can then each be partially vaporised and the vapours condensed
to provide further separations, and by combining fractions of similar boiling points and repeating the process almost any desired degree of separation may
be obtained.

A modern plate distillation column accomplishes the same functions with a minimum of energy or fuel by utilising the heat content of vapours from one
plate to vaporise partially the liquid from another, and by utilising gravity to transfer less volatile fractions downward and more volatile fractions upward in
the column. Further heat economy is accomplished by heat exchange between distillate or bottoms and feed streams.

Important factors to be considered in the design of distillation equipment are the following:1.the boiling range of the stock; 2. The stability of the stock with
respect to heat; 3. The specifications of the products to be produced. The first two factors determine the temperature and pressure levels at which the
distillation equipment will be operated. Crude oil and refinery products are made up of hydrocarbons varying in boiling range from methane to asphalt. The
materials referred to as "light ends" (methane through C4’s or C5’s) are so low boiling that there is little likelihood of thermal decomposition under boiling
conditions. In these instances, it is generally necessary to operate the distillation equipment under pressure so that the distillate may be condensed with
available cooling water or a minimum degree of refrigeration.

At the high end of the boiling range scale, there are fractions desired as distillate products which have atmospheric boiling points above the temperature at
which cracking starts (about 700 Deg F for ordinary paraffin hydrocarbons). Therefore, to distill these materials, the system must be operated below
atmospheric pressure. This is done either by inducing a vacuum on the system or by reducing vapour pressure through the use of an inert gas such as
steam.

With respect to the third factor, the ultimate goal of any process design is a unit which will produce fractions which can be marketed directly, or with a
minimum of further processing.

6.1 Multicomponent distillation

The stepwise method for predicting the number of theoretical steps is slow and tedious for multicomponent systems, a number of approximate methods
have been developed. The best of these appears to be the one presented by Gilliland. Gilliland’s correlation is reproduced in chart 14-20 of the EBB.
(Maxwell P244).

6.2 Minimum trays

6.3 Minimum Reflux ratio

6.4 Tray efficiency EBB 12-41

6.5 Determination of required plates EBB chart 14-20.

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6.6 Location of Feed tray EBB 14-07

7. Crude Distillation

The design of a pipe still and the process analysis of pipe still operation are made to a large extent by the application of empirical data. A rigorous
theoretical treatment would make engineering calculations extremely tedious without significantly improving their accuracy. This is due to the extremely
large number of individual hydrocarbons which make up a single pipe still product.

The determination of the efficiency of fractionation in a pipe still is not measured by the degree of separation between two individual hydrocarbons in the
light and heavy products, but by the degree of separation of the distillation curves of contiguous products. This degree of separation is expressed as the
temperature difference between 95 percent point on the ASTM distillation of the light product and the 5 percent point of the heavy product. When the 5%
point occurs at a higher temperature than the 95% point, this difference is referred to as "gap" and when lower as an "overlap"

A high gap indicates good separation and, conversely, a high overlap shows that the separation is poor.

As the boiling point of the products considered increases, even the distillation curve is discarded as a measure of successful pipe still operation. The
heavier materials must usually meet specifications other than distillation range. For example, lube distillates are produced to meet a certain viscosity
requirement, the only specification related to volatility being the flash point. As another example, the factors determining efficiency when considering heavy
stocks to be used for cracking are carbon and ash contents.

In a single flash type atmospheric crude pipe still, the feed is heated to a temperature which, at the operating pressure of the tower, will result in feed
vaporisation approximately equal to the total volume of distillates. It so happens that, in a large number of units, the temperature may actually limit the
volume of distillates to the maximum obtainable without encountering thermal degradation.

Reboiler type units, commonly employed in light ends fractionation, are able to improve separation by reboiling the bottoms, so that the reboiler vapours
can strip light material from the liquid descending from the feed plate. Bottoms reboiling is seldom practicable in a pipe still because the accompanying rise
in temperature would almost invariably exceed the maximum allowable temperature on the system. However, steam stripping is used to remove light
materials in the liquid phase from the feed section or flash zone. The benefits obtainable from steam stripping are less than from reboiling, but fortunately,
extremely good separation between bottoms and the next lighter product, while desirable, is not absolutely necessary.

Steam stripping is also used to remove light materials from side streams. These temperatures are sufficiently low that a reboiler could be used for this
purpose, and some companies do use reboilers on side streams. However, this company has found that side stream reboiling is practical only under
special circumstances.

Pipe stills usually are provided with more numerous side streams than is common for most other distillation equipment, and this complicates their design. It
will be apparent that reflux, operating lines, etc., if used, would vary for any section between side streams. Each section of the tower, between side
streams, is handled separately in the design. It is also more common with pipe stills than with other distillation equipment to provide separate controlled
reflux for particular sections of the tower by removing heat from that section. This is frequently accomplished by "pump-around" reflux, where liquid is
removed subcooled, and returned to the tower, rather than by removing vapour from the tower, condensing it and returning as a liquid as is most common
in other types of distillation equipment.

7.1 Calculation Methods

Whereas an exact analysis of the feed and products is required for a light ends tower calculation, a crude assay supplies the information needed for a pipe
still design. The crude assay will include a true boiling point curve (TBPC) of the crude, a plot of API gravities of various crude cuts versus the mid-boiling
points of the cuts, and will, in addition, supply other necessary information such as viscosities, pour points, etc. to enable the designer to determine the
various cut points for the products on the TBPC. The specifications to be met by each of the products, and thus the yield of each product, is normally a
problem of refinery balance.

8. Absorber and Stripper

The recovery of valuable hydrocarbons from multi component gaseous mixtures by absorption in a bubble plate column with a lean solvent oil followed by
steam stripping of the enriched solvent is an important operation in the natural gasoline and petroleum refining industries. The process design of the
equipment for carrying out these operations has received inadequate attention during the 17 years since Kremser’s paper on this subject first appeared. In
general, the methods offered have been either precise or convenient but not usually both. An accurate yet rapid method is required, particularly in view of
the fact that all hydrocarbon calculations involve multi components. In some cases it is possible to make such simplifying assumptions as constant
temperature, and constant oil and gas rates, and use average temperatures and rates in calculations. In most cases, however, variations in temperature
and rates must be allowed for in the design procedure.

Various types of solvent oils have been used in absorption. A light oil has the advantage of low molecular weight, which makes more moles per gallon and
therefore more absorbing capacity per gallon. With a light oil, however, there is always more loss of the solvent in the lean gas. Accordingly, a design
method must permit making calculations to determine the lean oil loss and also correct the recovery for the presence in the lean oil of some of the same
components being recovered from the wet gas. In other words, the absorption design method should be versatile enough to calculate performance when
the lean oil is light and not denuded and the temperature and rates vary.

Because of the nature of the absorption operation, i.e., absorption according to volatility and oil-gas quantities with no selection, it is necessary to take
along with the desired components some components that are not desired. For example, the recovery of butanes is accompanied by a recovery of lower
percentage of propane and ethane. These more volatile light components serve to load up the remaining recovery facilities and also increase the operating
pressures required.

These two features of the absorption process; namely, the loss of lean oil and the absorption of the unwanted lighter components, are sometimes reduced
by adding sponge oil and reboiling sections to the basic absorber. These additions make the process calculations more complicated and also increase the
cost of the apparatus but they make definite contributions to the performance. The use of sponge oil permits using a low molecular weight solvent.
Reboiling the bottom of an absorber deetthanizes the rich oil, making it possible to operate the stripper at a lower pressure and condense the recovered
components.

Under some conditions, a high pressure reabsorber is used on the off gas from a main low pressure absorber, thus segregating to a certain degree the
recovered light hydrocarbons through separate stripping of the rich oils. Sometimes two stripping stills, one at a high and one at a low pressure, are used
with a single rich oil. In this way more favourable operating conditions can be obtained.

There are several analytical and graphical methods for absorption and stripping calculations. The application of these methods to binary systems is simple
and straight forward; the application to multicomponent systems is somewhat more complicated and require the use of assumptions. The best known
procedures for absorption-stripping calculations are:

1. Kremser-Brown approximation: is based on the use of average values for absorption or stripping factors.

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2. Horton-Franklin Method: is based on the use of effective absorption or stripping factors for each component in the mixture, each effective factor
being evaluated at different plates in the towers.
3. Sherwood Graphical Method: is based on the theoretical plate concept and involves the graphical solution for the selected "key" component, the key
component being defined as that whose absorption or stripping factor is closest to unity. For condensable absorption recovery from wet gases,
butane is usually the key component. In stripping the key component may be pentane or even heavier.

This procedure includes algebraic or analytical solutions for all the components and provides a very clear graphical illustration of the diffusional driving
forces.

4. Edmister Effective Factor method: is based on the use of average effective absorption or stripping factors formulated as functions of the terminal
(top and bottom) conditions independent of the number of plates.

8.1 References

Edmister, W.C. Designer for Hydrocarbon Absorption and Stripping, Ind. Engg. Chem -35- 887 - (1943)

Hydrocarbon Absorption and Fractionation process design methods - Petroleum Refiner, May (1947) - March (1949)

Horton, G., and Franklin, W.B. Calculation of Absorber Performance and design: Ind. Engg. Chem 32-1384 - (1940)

Kremser A. Theoretical analysis of Absorption Process - National Petroleum News Vol.23 - no.21, p.48 (may 21, 1930)

Sherwood T.K. Absorption and Extraction - McGraw Hill, New York

Souders, Mott, Jr. And Brown G.G. Fundamental Design of Absorbing and stripping columns for complex vapours - Ind. Engg. Chem - 24- S19 (1932).

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