Chapter 1 Basics of Processing

LPG TECHNOLOGY Chapter 2 Theoretical Principles of Fractionation
Chapter 2
Theoretical Principles
of Fractionation
ETS (Rev.1) Nov. 2006 Page 1 of 28

Chapter 2 Contents
2.1 INTRODUCTION
2.2 VAPOR PRESSURE
2.3 PARTIAL PRESSURE
2.4 FUNDAMENTALS
2.4.1 Laws governing the volatility characteristics of liquid
2.4.2 Basic Gas Laws
2.4.3 Volatility Effect on Tower Design
2.5 EQUILIBRIUM CONSTANT ("K" values)
2.6 BOILING POINT CALCULATION
2.7 DEW POINT CALCULATION
2.8 FLASH CALCULATION

Chapter 2
Theoretical Principles of Fractionation
2.1 INTRODUCTION
A detailed discussion of the entire theory of fractional distillation and all the
problems connected herewith is not possible within the scope of this Course
and has not been attempted. The most important features of this vast subject
have been dealt with and a number of references are given which should
enable the reader to tackle any specific problem requiring a deeper
knowledge of the various methods used in fractionation calculations. Since
the majority of the Group's technologists are engaged in other fields than
design work, complete discussion of tray-to-tray calculations has been
omitted. However, it is felt that the technologist should be familiar with simple
column evaluations, boiling point, dew point and flash calculations and be
able to interpret intelligently design work should the necessity arise.
2.2 VAPOR PRESSURE

A gas or vapor consists of molecules in random and chaotic motion. Millions
of small particles moving in all directions in the air in the room, they collide
with each other repeatedly.
There are many collisions between molecules in a gas. The molecules of a

vapor in a container repeatedly have collisions with the walls of the container.
When many gas molecules collide repeatedly with the walls of a container,
these collisions add up to a pressure exerted on the walls. If the temperature
of a gas is increased, the molecules in the gas move faster. As the
molecules move faster (at higher temperatures) and the collisions become
more violent, molecules in a closed container strike the walls with more force.
The pressure, therefore, increases.
The pressure of a gas in an open container cannot be increased, since some

of the gas would escape to equalize the pressure with the surroundings. The
pressure of a gas in an open container cannot be increased by increasing the
temperature.

Like the molecules of gases, the molecules of a liquid are constantly in

motion. Unlike the molecules of gases, the molecules of a liquid are held
close together by natural attraction between the molecules. In a liquid, the
attraction between molecules tends to keep each molecule confined to a
small space. Within this space a molecule is usually in violent motion. The
violent motion of the molecules at the surface of a liquid causes many of
these molecules to escape from the liquid. If the temperature of a liquid is
increased, the motion of the molecules becomes more violent.
If an empty container is partially filled with liquid, molecules escape from the
surface of the liquid, forming a vapor in the space above the surface. Gas
molecules which strike the surface of a liquid tend to stick to the liquid. Thus,
molecules may be escaping the liquid and returning to the liquid from the gas
at the same time. When a vessel contains both a liquid and a vapor,
molecules are continually going from the liquid to the vapor or gas and from
the vapor to the liquid. When the number of molecules leaving the liquid
equals the number entering the liquid, the gas and the liquid are said to be in
equilibrium with each other. So at equilibrium, equal numbers of molecules
pass between the liquid and the vapor, or gas.
When more molecules are escaping the liquid than returning, the liquid is
said to be evaporating. The process in which a greater number of molecules
leave the liquid than enters it is called evaporation. When more molecules
are entering the liquid from the vapor than are escaping the liquid, the vapor
is condensing. The process in which a greater number of molecules enter
the liquid than leave it is called condensation.
When the temperature of a liquid is increased, the pressure of the vapor in

equilibrium with it increases and maintains equilibrium. When a liquid and a
vapor are at equilibrium, the pressure of the vapor is called the vapor
pressure of the liquid.
The pressure of a gas or vapor above the surface of a liquid in a closed

container is not necessarily the same as the vapor pressure of the liquid. In
order for the pressure of the gas to be equal to the vapor pressure of the
liquid, the gas and the liquid must be in equilibrium with each other.
When liquid in an open container is heated until the vapor pressure equals
the pressure of the atmosphere, evaporation becomes very rapid, and the
liquid boils.

If the pressure over a boiling liquid is increased, the boiling temperature is

increased and if the pressure over a boiling liquid is decreased, the boiling
temperature is decreased. Since the pressure of the atmosphere on the top
of a mountain is lower than at sea level, liquids boil at lower temperatures on
top of a mountain.
The vapor pressures for different liquids at the same temperature are not the
same.
2.3 PARTIAL PRESSURE

The pressure that a gas exerts on the walls of a container depends on the
number of collisions between the molecules and the container wall. If more
molecules are present, there are more collisions and a greater pressure. If
two containers of the same volume are filled with gas to the same pressure
and temperature, each contains the same number of gas molecules. For the
same volume and temperature, the greater the number of molecules in a gas,
the greater the pressure of the gas must be.
When two or more gases are mixed, each gas exerts a pressure on the walls
of the container. Although these separate pressures cannot be measured,
the total pressure can be measured. The total pressure of a gas mixture is
equal to the sum of the pressures of the different gases in the mixture; the
separate pressures of the gases are called partial pressures.
If a closed container is partially filled with a mixture of two liquids, molecules

of both liquids escape to the gas from the liquid and return to the liquid from
the gas. When the number of molecules escaping equals the number
returning- for both components, the gas and the liquid are said to be at
equilibrium with each other. At equilibrium, the number of molecules
escaping from the liquid is equal to the number returning to the liquid for each
component. The drawing shows a tank containing a mixture of two
components, one heavy and one light. An example of such a system would
be butane-hexane, where butane would be the light molecules and hexane
the heavy molecules.

At equilibrium the number of light molecules escaping from the liquid is equal
to the number returning to the liquid. Also, at equilibrium the number of
heavy molecules escaping from the liquid is equal to the number of heavy
molecules returning to the liquid. However, at equilibrium the number of light
molecules escaping and returning to the liquid is not equal to the number of
heavy molecules escaping and returning to the liquid. Light molecules are
able to escape the liquid more rapidly than the heavy ones. Therefore, at
equilibrium, there are more light molecules escaping and returning to the
liquid. Because the light molecules are able to escape the liquid faster than
the heavy ones, the light molecules tend to concentrate or to be enriched in
the vapor. For example, if the liquid contains half light and half heavy
molecules at equilibrium, the gas contains more light molecules than heavy
molecules.

2.4 FUNDAMENTALS
2.4.1 Laws Governing the Volatility Characteristics of Liquid
Fractional distillation is an operation which is based on the differences in
volatility or different escaping tendencies of the products which have to be
separated. It is obvious that for solving the numerous problems in technical
fractionation a thorough knowledge of the fundamental laws and rules
governing the volatility characteristics of systems consisting of two or more
components is a prerequisite.
Henry's Law
This law states that at a given temperature the partial vapour pressure of a
relatively volatile substance above its solution (in a relatively non-volatile
solvent) is proportional to its concentration in the solution.
This can be expressed by:
pi = Ci xi .. (1)
Where:
xi = mole fraction of a certain component in the liquid,

pi = partial vapour pressure of this component,
Ci = proportionality factor.
In general, this law holds only for low concentrations of component i. In

certain cases, however, it is applicable throughout the entire range of
concentrations. Such solutions are said to behave ideally and on
extrapolating Henry's law in such cases to the pure compound (i.e. increasing
the concentration of the dissolved substance) we see that, since when x i
becomes 1, Ci equals pi, this factor is then equal to the vapour pressure (P i)
of the pure substance and to the system pressure.
Thus the mathematical expression becomes:
pi = Pi xi .. (2)
In this form and restricted to ideal solutions Henry's law is known as Raoult's
law.

Many hydrocarbon systems closely approach the hypothetical ideal solution

and Raoult's law can therefore be applied in these cases without introducing
too serious an error. Mixtures of paraffins and Naphthenes are, in general,
very nearly ideal, while mixtures of aromatics with Naphthenes or paraffins
are further away from ideal solutions.
It must be realized, however, that ideal behaviour only occurs with

substances as closely related as hydrocarbons, and is most uncommon for
other instances.
A particularly simple case where Raoult's law is not valid is the case of two or
more components completely immiscible in the liquid phase. In this case the
total pressure is independent of the relative amounts in which these
components are present and is simply equal to the sum P = P i of the vapour
pressures of the pure components at the given temperature. The total
pressure is therefore higher than the vapour pressure of any component.
Such a system is called a pseudo-azeotrope.
Dalton's Law
The second important law underlying the theory of fractional distillation is

Dalton's law regarding partial pressures and their additively. Mathematically,
Dalton's law is expressed as follows:
pi = P yi and pi = P . (3)
Where:
pi = partial pressure of component i,
P = total pressure of system,
yi = mole fraction of component i in the vapour phase.
It follows from (2) and (3) that
Pi xi = P yi (4)
yi Pi

xi P
yi = xi Pi / P. (5)

From equation (4) (known as Raoult-Dalton's law) it follows that the

concentration of any component in a vapour which is in equilibrium with a
liquid mixture can be calculated by multiplying the concentration of that
component in the liquid phase by the ratio of the vapour pressure of the pure
component to the total pressure of the system. All concentrations are to be
expressed as mole fractions.
2.4.2 Basic Gas Laws

The particular relationships between gas temperature, pressure, and volume
have been formulated into three laws;
Boyle's Law,
Charles' Law, and
General Gas Law.
These laws describe how temperature, pressure, and volume of a gas are
related to each other. If a change occurs in one of these properties, the
change will affect one or both of the other two.
Boyle's Law
Boyle's Law deals with the relationship of pressure to a volume of gas. The
illustration in Figure 2.2 shows a piston in a cylinder filled with gas. The
pressure in the cylinder is related to the number of collisions between the
molecules of the gas and the molecules of the cylinder walls. As the
molecules collide, a force is applied over the area of the wall. When the
piston is moves into the cylinder the volume of the cylinder decreases. With
less volume, the space between the molecules is reduced, resulting in more
collisions between the gas molecules, as well as more collisions between the
gas molecules and the container walls. One other effect should also be
noted. With a decreased volume, the inner surface area of the container is
smaller. The overall result of increased collisions and reduced area is an
increase in pressure. If the piston is retracted, the volume of the cylinder
increases the number of collisions decreases, and pressure decreases.

Figure 2.2 Boyle's Law Example
Boyle's Law states that at a given temperature, the pressure of a gas varies
inversely with its volume. This means that if volume increases, pressure
decreases, and if volume decreases, pressure increases. Boyle's Law can be
represented mathematically, as follows:
P1 V1 = P2 V2 (Temperature constant) (6)
One example of where the principle of Boyle's Law applies is in the operation
of a gas or air compressors.
Charles' Law
Charles' Law deals with the relationship between temperature and volume.
Charles' Law states that at a given pressure, the temperature of a gas varies
directly with its volume. This means that if temperature increases, volume
increases, and if temperature decreases, volume decreases. Charles' Law
can be represented mathematically, as follows:
V1 / T1 = V2 / T2 (Pressure constant) (7)
Figure 2.3 illustrates what happens if a balloon is heated. The heat increases
the temperature of the gas molecules in the balloon, which, in turn, increases
the motion of the molecules. The increased motion causes the molecules to
try to move apart. The molecules push on the walls of the balloon, causing
the balloon to expand, and thus increasing the volume of the gas.

Figure 2.3 Charles' Law Example
The General Gas Law

The General Gas Law expresses the interrelationship between temperature,
pressure, and volume. This law can be stated as follows: pressure times
volume, divided by temperature is constant (PV/T = Constant) for a certain
amount of gas. It should be noted that the General Gas Law only applies
when temperatures and pressures are expressed in absolute units.
According to the General Gas Law, if a certain amount of gas is confined in a

given volume, and the volume is decreased, both pressure and temperature
will increase. This is a result of an increase in the molecular activity of the
gas. This is the principle that is at work in an air compressor: as the volume
of air is decreased, the pressure and temperature increase.
The temperatures of compressed air can become high enough to cause

operating problems such as the breakdown of lubricating oil's ability to
lubricate. As noted earlier, high temperatures reduce oil's viscosity. In
extreme cases, the temperatures can be high enough to cause combustion of
the oil.
The General Gas Law is sometimes referred to as the "ideal" gas law,
because it is a highly theoretical concept. However, the concept is extremely
useful in analyzing real gases, because real gases react in much the same
way as ideal gases.
The General Gas Law relates the properties of temperature, pressure, and
volume of a gas. It can be stated in terms of the following formula:
PV/T = Constant (8)

This formula is often represented in the following way:
P1V1/T1=P2V2/T2. (9)
With this formula, changes in a set of conditions from one state (1) to another
(2) can be related mathematically.
The perfect gas law is written for a single set of conditions as
P x V = n x R x T........................ (10)
Where:
P = Absolute pressure (psia)
V = Volume (cubic feet)
T = Absolute temperature (R)
n = Number of molecules
R = Gas constant (10.72 for units shown)
1 = Condition 1
2 = Condition 2
Actual gas mixtures vary in performance from the relationships defined by the
perfect gas law due to the molecular interaction of different molecules. This
deviation is called the compressibility factor and is a number that expresses
the deviation of a particular gas mixture from the relationships expressed by
the perfect gas laws. The symbol for the compressibility factor is z (can be
calculated from Appendix 10). Using this factor, the real gas law becomes.
P x V = z x n x R x T(11)
2.4.3 Volatility Effect on Tower Design
Briefly, here are some of the factors that dictate the design of a column.
As you might guess, two important factors are

1. The throughput, or flow rate of material, and

2. The ease of separation.
One way to quantify the relative ease of separation is to compare the
volatilities of the components to be separated.
Because the boiling points change with pressure, it is more convenient to
look at curves as shown in Figure 2.4 from these curves we can find the
boiling point of a compound at any pressure, or conversely, the vapor
pressure of a compound at any pressure.
Figure 2.4 Vapor Pressure Light Hydrocarbons
For example, we see the vapor pressure of propane at 100F is 190 psia; and
the vapor pressure of propylene is 226 psia at 100F. The ratio of these two
vapor pressures is an expression of their relative volatilities. 226/190 = 1.2.
This ratio is defined as (alpha). The nearer alpha is to 1, the greater the
difficulty of separation. The more difficult separations require more trays in a

column and more reflux. All this requires more energy. The separation of
normal butane and i.pentane is much easier. Alpha at 100F equals 52/20 or
2.6. This separation would require fewer trays and less energy.
Alpha is somewhat higher at lower temperatures. Therefore, other things

being equal, it is desirable to operate at lower temperatures and, thereby,
lower pressures. However, "other things are not equal" and there is a limit as
to how low a pressure we can operate. That limit is usually the temperature of
the cooling water for the overhead condenser. Because we must condense
the overhead product, we must have a coolant whose temperature is below
the boiling range of the overhead. Usually it is not economically practical to
refrigerate the coolant, so water or air is normally used. The available coolant
temperature is usually the factor that establishes the tower design pressure.
To see how alpha affects tower design, let's look at two separations. First, a
depropanizer - a distillation column designed to separate propane from
i.butane and heavier components. Alpha is 190/72 or 2.6. Although there are
heavier components in the bottom and lighter components in the overhead,
we need only consider what we call the key components, namely the
heaviest major component in the overhead and lightest major component in
the bottoms. For this separation, propane from butane, the tower typically
requires 30 trays, 5 to one reflux, and is about 50 ft. in height. The diameter
is largely dependent on the throughput.
In contrast, let's look at a tower to separate ethyl benzene and xylene. Alpha
is approximately 1.08. A tower for this separation has about 350 trays and
uses 100 to 1 reflux. A large depropanizer tower might cost about $500,000,
while an ethyl benzene-xylene tower might cost about $5 million. Of course,
there is a considerable difference in the cost of utilities to operate these two
columns.
An additional factor that determines tower size is purity of product. As we say

earlier, each equilibrium stage has less of the impurity than the adjacent
stage. It follows then that we must specify the desired purity. That is, the mole
fraction of an impurity that we will accept in the product. For our depropanizer
we might accept, say, 1 to 2 % butane in the overhead propane product and
we much tolerate a loss of 2 % propane in the bottoms.

Obviously, to achieve a lower concentration of butane in the overhead, and

still maintain the low loss of propane in the bottom, would require more trays,
more reflux, and consequently, a taller and larger diameter tower with its
attendant increase in investment and utility costs. To summarize, the height
of a tower and number of trays is largely dependent on the relative volatility of
the key components and the permissible mole fraction of these key
components in the products.
2.5 EQUILIBRIUM CONSTANT ("K" Values)

The fact that components in a non-ideal mixture do influence the volatility of
the other components results in deviations from Raoult Daltons law which
are of the same order of magnitude as the ones which can be corrected for
by the introduction of fugacities. As the theoretical treatment of this subject is
very complicated, a solution of the problem is found by introducing the
concept of k values.
yi
For a number of pure hydrocarbons and a few other compounds the x
i
ratios for mixtures have been determined experimentally over a wide range of
temperatures and pressures, and the values thus obtained, the so-called k
values, have been plotted versus P and T in "k value charts" (see Appendix
9).
It should be mentioned that some of the k charts are based on experimental

data and some of the graphs are calculated from fugacities.
Using k values, equation (4) becomes:
yi
xi
= ki or yi = ki xi .. (12)
Applications
It is possible to calculate boiling points, dew points, vapour pressures and

dew pressures of mixtures.

2.6 BOILING POINT CALCULATION

The boiling point of a mixture (at a given pressure) is defined as the
temperature at which, when the temperature of the liquid mixture is raised,
the first infinitesimal amount of vapour escapes as a bubble. This
temperature is also known as the "bubble point". The vapour will contain a
certain amount of each component, depending on the volatility of that
component, and it is clear that if the concentration in the vapour phase (y i) is
expressed in mole fraction, yi must equal 1.
Starting with a liquid of known composition the problem has to be solved by

trial and error, since at a given pressure the temperature has to be found, at
which the corresponding ki values, when multiplied by xi, result in yi values
adding up to 1.
The following example illustrates the procedure:
System pressure: 150 psia
By graphical interpolation we find a boiling point of 169F under 150 psia.

With this temperature a check calculation should be made and, if necessary,
the procedure should be repeated within narrower limits until the correct
value is found. In those cases, where no k values of the components are
available, the vapour pressure will have to be used.
Vapour pressures should not, however, be used in combination with k

values.

Example: Determine the bubblepoint of the mixture shown at 4.0 580 psia
assuming that the C7+ fraction has the properties of C8. This is
a trial-and-error solution. One must guess a temperature, find
Ki and calculate Ki xi. The right temperature has been
assumed when Ki xi = 1.0 (or 100).
This solution is the final try at T = -14C (7F). Since percentages rather than
mol fractions are used, the right-hand column should sum to 100.
Vapour Pressure Calculation for Hydrocarbon Mixtures
The calculation of the vapour pressure of mixtures at a given temperature is

very simply made if Raoult-Dalton's law is valid. The mole fraction of each
component is multiplied by the vapour pressure of the component at
the desired temperature and the values obtained are added together.
The sum represents the vapour pressure of the mixture.
A more exact method would be to use k values and to determine the boiling
pressure for the given temperature in essentially the same fashion as has
been shown in the preceding section for the determination of the bubble point
at a given pressure.

2.7 DEW POINT CALCULATION

The dew point of a mixture is the temperature at which, when the
temperature of the vapour is lowered, the first infinitesimal droplet of
condensate is formed. This temperature is of practical importance for
establishing the top temperature of a fractionating column. In the case of a
dew point calculation the vapour composition is known and by dividing the Y i
values by the corresponding ki values one arrives at x i values which should
add up to 1. At trial and error calculation similar to that carried out for the
bubble point leads to the dew point. The same remarks regarding the use of
k values and vapour pressures as made under "Boiling Point Calculation"
also apply to the dew point calculation.
Calculation of Dew Pressure
The dew pressure at a given temperature is the pressure at which

condensation starts to take place and is, therefore, an important value in
connection with partial condensation for making reflux. According to
Raoult-Dalton's law:
yiP
xi = Pi
yi
and since xi = P P = 1
i
1
P = yi
Pi
For the calculation of P (the dew pressure) the molal concentration of each
component is divided by its vapour pressure and the values obtained are
added together. The reciprocal of the sum is the dew pressure.
Also in this case a more exact solution can be obtained by using k values and
determining dew pressures at the given temperature by trial and error.

Example: Determine the dewpoint of the mixture shown at 4.0 580 psia,
assuming the C7+ fraction has the properties of C8.
These results are for an assumed temperature of 153C. It is obtained after a

series of trials.
2.8 FLASH CALCULATION

So far we have only considered vaporization and condensation of
infinitesimal amounts of material at the boiling and dew points. In many
cases it is desired to know the amount and composition of the vapour in
equilibrium with liquid at temperature and pressure conditions in between the
bubble point and the dew point. For instance, the degree of vaporization of a
crude oil or some other feedstock after leaving the furnace is an important
item in design calculations. Often it is desired to know the amount vaporized
at a series of temperatures and pressures for a given material. When such a
series of values is plotted against temperature with pressure as a parameter,
the resulting graph is called a "flash curve". A flash calculation is based on a
combination of a material balance and vapour liquid equilibrium relations.

Assume a feed of 'n' components and take F moles of total feed as a basis.
Let V = total moles of feed-vapour
L = total moles of feed-liquid
So V + L = F
xi = mole fraction of component i in the liquid phase
Yi = mole fraction of component i in the vapour phase
Zi = mole fraction of component i in the total feed
ki = k value for component i at flash conditions.
The following material balance for a component holds true:
Lxi + VYi = Fzi

Or Lxi + Vki xi = Fzi
Vk i x i
Lxi (1 + Lx i
) = Fzi
Fz i
Hence Lxi = 1 k V
i
L
This is the most convenient form of the so-called flash equation. When
V
temperature and pressure are set, a value of L
is assumed and Lxi for all
components is calculated.
V
Now as L xi = L xi = L, and as V = F L, the assumed value of L
can be
checked against the calculated one. The flash calculation has to be repeated
V
until the calculated L
value is equal (within the limits of k value accuracy) to
V
the assumed value of L
When the above-mentioned procedure has been finished the vapour-liquid
composition of the feed at the given temperature and pressure can be
Lx i Lx i
calculated from: xi = = Lx
L i
Fz i Lx i
and y i = k i xi or yi =
V
By keeping the pressure constant and changing the temperature, a series of

values of V (all in mole fractions) at different temperatures can be obtained
and a flash curve for the pressure under consideration can be plotted.

Table 2-1
Sample Flash Calculation at 400F and 50 psia (Kuwait Crude)
Lower than 75 slightly

higher
than 70
Graphical, interpolation gives:
V = 29.2 mole %
L = 70.8 mole %
(1) Determined experimentally.
(2) From Shell Data Char.
(3) Graphical interpolation is only permitted if a well-defined point of intersection is
obtained. Extrapolation is never permitted. Figures thus obtained must be
verified by a subsequent check calculation.

Worksheet 2-1 Bubble Point Calculation

Equipment Number:
Bubble Point Conditions: Pressure ________________________ Pisa;
Convergence Pressure ____________________
Psia
Liquid
Trial Temperatures Final Temp
Mol. T= F T= F T= F T= F
Comp MW
Frac. Yi Yi
Ki Ki Yi Ki Yi Ki
Xi =ki xi =ki xi
C1 16 0. 0. 0. 0. 0.
C2 20 0. 0. 0. 0. 0.
C2 44 0. 0. 0. 0. 0.
iC4 58 0. 0. 0. 0. 0.
nC4 58 0. 0. 0. 0. 0.
iC5 72 0. 0. 0. 0. 0.
nC5 72 0. 0. 0. 0. 0.
nC6 86 0. 0. 0. 0. 0.
nC7 100 0. 0. 0. 0. 0.
nC8 114 0. 0. 0. 0. 0.
H2 2 0. 0. 0. 0. 0.
N2 28 0. 0. 0. 0. 0.
CO 28 0. 0. 0. 0. 0.
CO2 44 0. 0. 0. 0. 0.
H2S 24 0. 0. 0. 0. 0.
Total 1.0000 1.0000

Worksheet 2-2 Dew Point Calculation
Equipment Number:
Dew Point Conditions: Pressure ________________________ Pisa;
Convergence Pressure ____________________
Psia
Vapor
Trial Temperatures Final Temp
Mol. T= F T= F T= F T= F
Comp MW
Frac. x x
k K x K x K
y =y/k =y/k
C1 16 0. 0. 0. 0. 0.
C2 20 0. 0. 0. 0. 0.
C2 44 0. 0. 0. 0. 0.
iC4 58 0. 0. 0. 0. 0.
nC4 58 0. 0. 0. 0. 0.
iC5 72 0. 0. 0. 0. 0.
nC5 72 0. 0. 0. 0. 0.
nC6 86 0. 0. 0. 0. 0.
nC7 100 0. 0. 0. 0. 0.
nC8 114 0. 0. 0. 0. 0.
H2 2 0. 0. 0. 0. 0.
N2 28 0. 0. 0. 0. 0.
CO 28 0. 0. 0. 0. 0.
CO2 44 0. 0. 0. 0. 0.
H2S 24 0. 0. 0. 0. 0.
Total 1.0000 1.0000


Worksheet 2-2 Flash Calculation
Flash Vessel Number:
Flash Condition: Temperature __________________________ F
Pressure ______________________________ psia
Convergence Pressure ___________________ psia
Liquid
Trial Values of L Final L
Feed L= L= L= L= V=
Mol. x
Comp MW K x
y
Frac. x x =N/(L
= kx
+ VK)
N =N/(L +VK)
C1 16 0. 0. 0. 0. 0. 0.
C2 20 0. 0. 0. 0. 0. 0.
C2 44 0. 0. 0. 0. 0. 0.
iC4 58 0. 0. 0. 0. 0. 0.
nC4 58 0. 0. 0. 0. 0. 0.
iC5 72 0. 0. 0. 0. 0. 0.
nC5 72 0. 0. 0. 0. 0. 0.
nC6 86 0. 0. 0. 0. 0. 0.
nC7 100 0. 0. 0. 0. 0. 0.
nC8 114 0. 0. 0. 0. 0. 0.
H2 2 0. 0. 0. 0. 0. 0.
N2 28 0. 0. 0. 0. 0. 0.
CO 28 0. 0. 0. 0. 0. 0.
CO2 44 0. 0. 0. 0. 0. 0.
H2S 24 0. 0. 0. 0. 0. 0.
Total 1.0000 1.0000 1.0000
Worksheet 2-4 Flash Material Balance
Flash Vessel Number:

Lb Mols/Hr Lbs/Hr
Comp MW
Feed Liquid Vapor Feed Liquid Vapor
C1 16
C2 20
C2 44
iC4 58
nC4 58
iC5 72
nC5 72
nC6 86
nC7 100
nC8 114
H2 2
N2 28
CO 28
CO2 44
H2S 24

Total

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Chapter 1 Basics of Processing

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LPG TECHNOLOGY Chapter 2 Theoretical Principles of Fractionation

ETS (Rev.1) Nov. 2006 Page 1 of 28

2.2 VAPOR PRESSURE

2.3 PARTIAL PRESSURE

2.5 EQUILIBRIUM CONSTANT ("K" values)

2.6 BOILING POINT CALCULATION

2.7 DEW POINT CALCULATION

2.8 FLASH CALCULATION

ETS (Rev.1) Nov. 2006 Page 2 of 28

2.2 VAPOR PRESSURE

There are many collisions between molecules in a gas. The molecules of a

The pressure of a gas in an open container cannot be increased, since some

ETS (Rev.1) Nov. 2006 Page 3 of 28

Like the molecules of gases, the molecules of a liquid are constantly in

When the temperature of a liquid is increased, the pressure of the vapor in

The pressure of a gas or vapor above the surface of a liquid in a closed

ETS (Rev.1) Nov. 2006 Page 4 of 28

If the pressure over a boiling liquid is increased, the boiling temperature is

2.3 PARTIAL PRESSURE

If a closed container is partially filled with a mixture of two liquids, molecules

ETS (Rev.1) Nov. 2006 Page 5 of 28

ETS (Rev.1) Nov. 2006 Page 6 of 28

This can be expressed by:

xi = mole fraction of a certain component in the liquid,

In general, this law holds only for low concentrations of component i. In

Thus the mathematical expression becomes:

ETS (Rev.1) Nov. 2006 Page 7 of 28

Many hydrocarbon systems closely approach the hypothetical ideal solution

It must be realized, however, that ideal behaviour only occurs with

The second important law underlying the theory of fractional distillation is

It follows from (2) and (3) that

ETS (Rev.1) Nov. 2006 Page 8 of 28

From equation (4) (known as Raoult-Dalton's law) it follows that the

2.4.2 Basic Gas Laws

ETS (Rev.1) Nov. 2006 Page 9 of 28

Figure 2.2 Boyle's Law Example

P1 V1 = P2 V2 (Temperature constant) (6)

V1 / T1 = V2 / T2 (Pressure constant) (7)

ETS (Rev.1) Nov. 2006 Page 10 of 28

Figure 2.3 Charles' Law Example

The General Gas Law

According to the General Gas Law, if a certain amount of gas is confined in a

The temperatures of compressed air can become high enough to cause

PV/T = Constant (8)

This formula is often represented in the following way:

The perfect gas law is written for a single set of conditions as

2.4.3 Volatility Effect on Tower Design

As you might guess, two important factors are

ETS (Rev.1) Nov. 2006 Page 12 of 28

1. The throughput, or flow rate of material, and

Figure 2.4 Vapor Pressure Light Hydrocarbons

ETS (Rev.1) Nov. 2006 Page 13 of 28

Alpha is somewhat higher at lower temperatures. Therefore, other things

An additional factor that determines tower size is purity of product. As we say

ETS (Rev.1) Nov. 2006 Page 14 of 28

Obviously, to achieve a lower concentration of butane in the overhead, and

2.5 EQUILIBRIUM CONSTANT ("K" Values)

It should be mentioned that some of the k charts are based on experimental

Using k values, equation (4) becomes: