Engineering Encyclopedia: Distillation Process

Engineering Encyclopedia
Saudi Aramco DeskTop Standards
Distillation Process
Note: The source of the technical material in this volume is the Professional
Engineering Development Program (PEDP) of Engineering Services.
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Chapter : Process For additional information on this subject, contact

File Reference: CHE10401 R.A. Al-Husseini on 874-2792
Engineering Encyclopedia Process
CONTENTS PAGES
NOMENCLATURE................................................................................................. 1
Subscripts ..................................................................................................... 2
VAPOR-LIQUID EQUILIBRIUM (VLE) RELATIONSHIPS ............................... 3
Ideal and Nonideal Gases ............................................................................. 3

Vapor Pressure ............................................................................................. 4
Ideal Mixtures - Dalton's, Raoult's Laws...................................................... 4
Two-Component Example ................................................................ 5
Mixtures Approximated as Ideal....................................................... 6
Fugacity........................................................................................................ 7
Equilibrium K-Values................................................................................... 7
Relative Volatility....................................................................................... 10
Nonideal Liquids ........................................................................................ 10
Equations Of State...................................................................................... 11
EQUILIBRIUM SEPARATION CALCULATIONS............................................. 12
Equilibrium Diagram.................................................................................. 12
Vapor-Liquid Phase Diagrams ................................................................... 14
Bubble Point and Dew Point ...................................................................... 15
Equilibrium Flash Separation ..................................................................... 16
One-Stage Flash.............................................................................. 16
Representation of Petroleum with Pseudocomponents............................... 19
DISTILLATION PROCESS PARAMETERS 20
Conventional Distillation Column.............................................................. 20

Reflux ......................................................................................................... 21
Major Equipment........................................................................................ 22
McCabe-Thiele Diagram ............................................................................ 22

Effect of Reflux on Required Stages .......................................................... 24

Minimum Reflux ........................................................................................ 25
Total Reflux - Minimum Stages ................................................................. 26
Stages Versus Reflux.................................................................................. 27
Simulations with PROCESS/PRO II .......................................................... 27
Steps in Column Design ............................................................................. 28
Column Operating Pressure, Temperature ................................................. 30
Tray Efficiency........................................................................................... 31
SAUDI ARAMCO DISTILLATION PROCESSES .............................................. 33
Crude Stabilization and Sweetening........................................................... 33

Condensate Stripping ................................................................................. 35
Crude Distillation ....................................................................................... 36
Atmospheric Unit............................................................................ 38
Vacuum Unit................................................................................... 40
NGL Fractionation...................................................................................... 43
NGL Fractionators...................................................................................... 44
WORK AID 1: CALCULATE VLE PARAMETERS USING THE IDEAL

GAS LAW ................................................................................... 49
WORK AID 2: CALCULATE THE WATER VAPOR CONTENT OF

GASES IN EQUILIBRIUM WITH WATER .............................. 52
WORK AID 3: DETERMINE THE TOTAL PRESSURE OF AN IDEAL

GAS MIXTURE .......................................................................... 55
WORK AID 4: REDUCE THE H2S CONTENT OF CRUDE

STABILIZER BOTTOMS ........................................................... 56

NOMENCLATURE
a Relative volatility.
B Bottoms rate, mole/hr.
C1, C 2 Hydrocarbons with 1, 2 ... number of carbons.
D Distillate rate, mole/hr.
EO Overall column efficiency.
f Feed tray number.
f Fugacity.
F Feed rate, mole/hr.
F Fugacity factor.
H Enthalpy.
K Distribution coefficient (K = y/x), also called K factor or equilibrium K.
L Liquid rate, mole/hr.
MABP Mean average boiling point.
n Next to a hydrocarbon name, it indicates a normal (paraffin) isomer.
n Number of moles.
n Tray number.
N,N+1 N is the top stage in a column. N+1 is the condenser.
P Pressure, absolute.
PP Partial pressure.
PT Total pressure.
Q Heat Duty.
R Gas constant. For values, see Work Aid 1.
R Reflux rate, mole/hr.
Sp Gr Specific gravity.
T Temperature, absolute.
t Temperature.
TB Boiling point.
V Vapor rate, mole/hr.
V Volume.
VP Vapor pressure.
x Mole fraction in the liquid phase.
y Mole fraction in the vapor phase.
Saudi Aramco DeskTop Standards 1

Z Compressibility factor.
z Mole fraction in the feed.
Subscripts
1,2 Value refers to component 1,2, ... or measurement 1,2, ...

A,B, Value refers to component A, B, ...
B Value refers to bottoms.
C, c Value refers to condenser.
D Value refers to distillate.
eff Effective value.
f Value refers to feed tray.
HC Value refers to hydrocarbon.
HK Value refers to heavy key.
i Value refers to component i.
j Value refers to component j.
N Value refers to tray N.
n, n – 1,
n + 1, ... Value refers to tray n, n – 1, n + 1, ...
PT Value refers to total pressure.
R Value refers to reboiler.
V Value refers to vapor.
VP Value refers to vapor pressure.
w Value refers to water.

VAPOR-LIQUID EQUILIBRIUM (VLE) RELATIONSHIPS
A vapor-liquid system is considered to be in equilibrium when there are no longer any

detectable changes occurring in the system. Generally, a system is assumed to be in
equilibrium when the mass, energy, and composition of each phase remain constant with time.
An example of a system in equilibrium is a mixture of water and air in a closed vessel. After
some time, there will be no change in temperature, in the amount of water in the vapor phase,
or in the number of gas molecules dissolved in the water. The system is in equilibrium.
Equilibrium also applies to systems that are not static. We may have equilibrium in an
overhead condenser separator of a distillation column. The vapor and liquid leaving the
separator are in equilibrium, and their compositions can be described by relationships for
systems in equilibrium.
Ideal and Nonideal Gases
Ideal gases are those whose behavior can be described by the ideal gas law, which is stated
mathematically as:
PV = nRT or PV = 1.0
nRT
The ideal gas law indicates that the product of pressure, P, times volume, V, is proportional to
the number of molecules of the component times the absolute temperature, T. R is an ideal gas
proportionality constant.
Gases tend to behave as ideal gases at temperatures higher than their critical temperature and
pressures well below their critical pressure.

When the ideal gas law does not apply, the gases are called nonideal or real.
PV ≠ 1
nRT
The compressibility factor, Z, expresses the deviation from the ideal gas equation. It can be
used to predict real gas properties. The compressibility factor is the ratio of the real gas
volume to that of the ideal gas at the same temperature and pressure:
PV = ZnRT or PV = Z
nRT
For an ideal gas, the compressibility factor is 1.0. The compressibility factor, Z, can be
obtained from generalized graphs such as those in Maxwell, pages 148-153, or the GPSA
Engineering Data Book, Chapter 16.
Vapor Pressure
The vapor pressure of a pure component at a given temperature is the pressure that is exerted
by the component when it is in the liquid phase. Vapor pressure is a unique property, and it is
a direct function of temperature. A material having a higher vapor pressure at the same
temperature than another is said to be more volatile.
Vapor pressure and temperature are often related by means of the Antoine equation:
Log (VP) = A – B
T+C
where A, B, and C are constants for a particular compound over a relatively narrow
temperature range, usually not over 100°C. Values of these constants for various compounds
and the temperature ranges for which the constants apply appear in a number of references.
The Antoine equation is often plotted in charts with the horizontal axis in a reverse absolute
temperature scale and a vertical axis in a logarithmic scale.
Ideal Mixtures - Dalton's, Raoult's Laws
Ideal mixtures, gas or liquid, consist of components that do not interact with each other
chemically or physically. The concept of ideal mixtures has formed the basis for many
quantitative relationships describing equilibrium. Of particular interest are Dalton's law of
partial pressures and Raoult's law relating the pressure exerted by a component in the vapor
phase to its concentration in the liquid phase.

Dalton's law states that the total pressure of a mixture of gases is equal to the sum of the
partial pressures of the mixed gases. Thus,
∑PPi = PT = PP1 + PP2 + PP3 + ...
Dalton also postulated that the partial pressure of an ideal gas in a gas mixture is proportional
to its mole fraction, that is, the relative number of molecules of that gas in the mixture. Thus,
PPi = yi PT
Raoult's law, relating the partial pressure in the vapor phase to the liquid phase composition,
is expressed as:
PPi = xi VPi
Combining Dalton's and Raoult's laws results in an expression describing mixtures of ideal
vapors and liquids in equilibrium.
PT = ∑PPi = ∑yi PT = ∑xi VPi
and for component i,
yi = xi (VPi/PT)
Two-Component Example
Let's assume that we have an ideal mixture of propane and n-butane at 100°F. The vapor
pressures of the two components at 100°F are:
• Propane 13 atm = 191 psia (Component 1).
• n-Butane 3.5 atm = 52 psia (Component 2).
The total pressure, PT, of the mixture can be calculated from:
PT = PP1 + PP2 = x1VP1 + x2VP2
PT = 191x1 + 52(1-x1) = 52 + 139x1
This last equation indicates that the total pressure of an ideal binary mixture is a linear
function of the composition. This relationship is illustrated in Figure 1, which shows that the
total pressure is the sum of partial pressures and is a straight line between the vapor pressure
of n-butane (x1 = 0) and propane (x1 = 1.0).

IDEAL MIXTURES
PROPANE - n-BUTANE SYSTEM PRESSURE
FIGURE 1
Mixtures Approximated as Ideal
The mixtures that can be approximated as ideal must satisfy the following requirements:
• Total pressure of the system must be below 200 psia.
• The components must be chemically similar, for example, butane and pentane, both of
which are paraffins. A mixture of an aromatic component and a paraffin such as
benzene and hexane cannot be approximated as ideal.
• The components must be close boiling; that is, they must have similar boiling points.
• The system pressure and temperature must not be near the critical pressure and
temperature of the mixture.

Using ideal mixture correlations in calculations results in approximate compositions or

conditions (P, T). The error may be acceptable for a simple operation, such as a flash drum
separation. The same correlations used in a superfractionator, where tray-to-tray calculations
compound the error, may produce unacceptable results.
Fugacity
The vapor-liquid equilibrium of an ideal mixture can be described by:
PPi = yiPT = xi VPi
To improve the accuracy of prediction, we can replace the pressures by analogous fugacities:
fPPi = yifPT = xifVPi
where: fPPi = Fugacity of i in either phase of the system.

fPT = Fugacity of i as a pure saturated liquid (or vapor) at its vapor
pressure corresponding to the equilibrium temperature of the system.
fVPi = Fugacity of i as a pure vapor at the equilibrium temperature pressure of the
system.
Generalized correlations have been developed for the ratio of fugacity to pressure for pure
hydrocarbons as a function of reduced temperature and reduced pressure. A correlation of
this type was used in conjunction with the vapor pressure charts to develop the fugacity
function charts for individual hydrocarbons. The fugacity function given by these charts is
defined as:
Fi = fVPi PT / fPT = PT yi /xi
The fugacity function, Fi, may be considered a corrected vapor pressure and used in place of
vapor pressure in any equation pertaining to liquid-vapor equilibrium.
Values for fugacity functions can be obtained from sources such as Maxwell's Data Book on
Hydrocarbons. Fugacities for petroleum fractions can be obtained from a generalized graph
in Maxwell.

Equilibrium K-Values
The definition of equilibrium K-value, also called K-factor or distribution coefficient, of

component i in a mixture is given in the following equation:
y
Ki = xi
i
The K-value is simply the ratio of the vapor to the liquid mole fraction of i. This ratio has no
special thermodynamic significance, but has found extensive use in high-pressure VLE work.
For ideal systems where Raoult's law applies, it can be expressed as:
yi VPi
Ki =
xi = PT
It can also be expressed in terms of fugacities as:
yi fVPi
Ki =
xi = fP
T
Equilibrium K-values are useful in simple VLE hand calculations. K-values can be obtained
from graphs or nomographs like the De Priester nomograph, Figure 2. K-values are a
function of temperature and pressure. For nonideal mixtures, K-values are also a function of
composition.

DE PRIESTER NOMOGRAPH
Relative Volatility

Relative volatility is a relation widely used in distillation. It is defined by:
yi /xi Ki
α ij = =
yj /xj Kj
Relative volatility is a measure of separability. The larger the value of αij, the easier the
separation. For close boiling components, such as pentane and isopentane, the relative
volatility approaches 1.0.
Because the value of relative volatility is not as sensitive to temperature as other measures of
equilibrium, it is used in a number of shortcut distillation calculations. For ideal mixtures
(Raoult's law applies), the relative volatility of two components is equal to the ratio of their
vapor pressures.
VPi
α ij =
VPj
The small effect of temperature on relative volatility is the reason for using relative volatility
in shortcut distillation calculations. Relative volatility data for only two or three points in the
column provide results of acceptable accuracy.
Nonideal Liquids
In liquids and liquid mixtures, the distances between molecules are much smaller than in
gases, and the forces attracting molecules to each other are much greater. Nonideal behavior
of liquids is indicated by heat of mixing and nonadditivity of volumes when two liquids are
mixed. The deviation from ideality is greater for chemically dissimilar substances. The
activity coefficient, γ, measures the deviation from ideal liquid solution behavior. Using the
coefficient in Raoult's law results in:
yi PT = PPi = γixi VPi
Activity coefficients are used in a number of VLE methods such as the Chao-Seader and the
Grayson-Streed correlations. The Chao-Seader correlation requires relatively short
computing times. It was used extensively in the '60s and '70s when computing was costly.
Hydrocarbon VLE methods using activity coefficients have been replaced by the more
rigorous equations of state.

Equations Of State
Equations of state (EOS) predict the PVT behavior of gases and liquids. The simplest EOS is
the one for ideal gases. Per mole of gas:
P = RT/V
In general, real fluids deviate from ideal fluids in two ways: there are variations in the sizes
and shapes of the molecules, and specific interactions between molecules, such as polarity or
hydrogen bonding, must be considered. The large variations in size and shape of molecules
have a great effect on PVT behavior.
The Soave-Redlich-Kwong (SRK) and the Peng-Robinson (PR) equations of state are among
the best known.
SRK equation of state. The Soave-Redlich-Kwong EOS is a two-parameter equation of the

following form:
P = RT - a
V-b V(V+b)
a = • • (1 - cij) ( ai aj ) (xi xj)

where: i j
b = • xi bi
i
The parameters a and b must be specified for each component in a mixture and then combined
as a function of composition. The a parameter is temperature-dependent. In addition, a
binary interaction parameter, cij, is used to calculate the aij term for mixtures, to improve
vapor-liquid equilibrium calculations.
PR equation of state. The Peng-Robinson EOS is similar to the SRK equation of state,
except that it has an expanded volume term:
P = RT - a
V-b V(V+b) +b (V-b)
The a parameter varies with temperature. Both constants use the same mixing equations as
the SRK equation of state.

EQUILIBRIUM SEPARATION CALCULATIONS
Equilibrium Diagram
Figure 3 depicts a simple flash separation. The feed consists of two components: propane
and n-butane. The feed temperature and composition vary. Figure 3 lists vapor and liquid
concentrations of propane, and the distribution coefficients (K1 and K2) for propane and n-
butane for five temperatures. Pressure is fixed at 100 psia. The feed composition is not the
same for all temperatures.
At 70°F, the mole fraction of propane in the liquid phase is 0.746. Its mole fraction in the vapor
phase is higher, 0.907, since propane is the more volatile of the two components. The
distribution coefficient, K1, for propane is equal to the ratio y1/x1 = 0.907/0.746 = 1.22.
VAPOR-LIQUID EQUILIBRIUM
F V ,y 1
Comp 1 = C 3
100 psia
psiapsia psia ( P = 100 psia
psiapsia psia
)
Comp 2 = nC 4
= 100 psia L,x 1
psiapsia psia
y y
Temp, o F x1 y1 K1 = x1 K2 = x2
1 2
70 0.746 0.907 1.22 0.37
80 0.607 0.832 1.37 0.43
100 0.376 0.644 1.71 0.57
120 0.191 0.398 2.09 0.74
140 0.035 0.087 2.49 0.95
FIGURE 3
Figure 4 is an equilibrium diagram for the propane/n-butane system using the data from
Figure 3 at 100 psia. The horizontal axis indicates the mole fraction of the more volatile
component, propane, in the liquid phase. The vertical axis indicates its mole fraction in the
vapor phase. The equilibrium line connects all the (x1, y1) points. Given the mole fraction in
the liquid phase, you can use the equilibrium line to obtain the mole fraction in the vapor
phase. Given the mole fraction in the vapor phase, you can find the mole fraction in the
liquid phase.

EQUILIBRIUM DIAGRAM
FIGURE 4
Figure 4 contains a second line, the reference line. It is simply the diagonal of the diagram:
for all the points on the reference line, y = x. The reference line makes it easier to see the
differences between the vapor and the liquid phase compositions. Since by convention the
horizontal axis represents the composition of the more volatile component, y1 is larger than
x1. Therefore, the equilibrium line is above the reference line. Large differences in y1, x1
mole fractions indicate large differences in the volatility of the two components. Accord-
ingly, equilibrium lines bulging away from the reference line are indicative of mixtures that
are easy to separate by successive vaporization and condensation steps, that is, by multistage
distillation.
For some mixtures, there is a reversal in relative volatilities and the equilibrium line intersects
the y = x reference line. Because the vapor and liquid fractions at that point are equal, these
mixtures cannot be separated by distillation. Such mixtures are called azeotropes.

Vapor-Liquid Phase Diagrams
Phase diagrams are used to describe two-phase systems by plotting two of the three
independent variables (composition, temperature, and pressure) at a constant value of the third
variable. Figure 5 is a phase diagram at constant pressure for the binary mixture of propane
and n-butane. The two lines indicate the temperatures at which a phase change takes place.
The temperatures and concentrations (at the diagram pressure) below the two
lines correspond to an all-liquid mixture. In the region between the two lines, the vapor and
liquid phases are present. Above the lines, there is only a vapor phase.
The phase lines in Figure 5 were drawn from data in Figure 3. For example, at 120°F, the
point on the liquid phase line corresponds to x1 = 0.191 and the point on the vapor line to y1
= 0.398 (see Figure 3, 120°F, x1, y1 data). The phase diagram can be used to determine the
compositions of the vapor and liquid phases from the pressure and temperature at equilibrium.
PHASE DIAGRAM
FIGURE 5

Bubble Point and Dew Point
The phase diagram can also be used to determine the phase transition points. Figure 6 is an
example for a mixture of 45% propane and 55% n-butane at 70°F. The phase diagram in
Figure 6 indicates that the mixture at 70°F is in the liquid phase. If the temperature is
increased at constant pressure, 100 psia, the mixture will be liquid up to 92°F, at which point
vaporization begins. This is the bubble point of the mixture, the temperature and pressure at
which a liquid is in equilibrium with an infinitesimal amount of vapor.
BUBBLE POINT AND DEW POINT
FIGURE 6
Between 92°F and 117°F, the mixture is in two phases, vapor and liquid. At 117°F, all of the
liquid is vaporized. This is the dew point, the temperature and pressure at which vapor is in
equilibrium with an infinitesimal amount of liquid. At temperatures above the dew point,
there is only a vapor phase. The liquid phase line is the bubble point curve; the vapor phase
line is the dew point curve.

Equilibrium Flash Separation
The equilibrium flash separator is the simplest equilibrium process for engineers to consider.
The process involves the separation of a two-phase feed into vapor and liquid in a vessel. The
feed is at a desired temperature and pressure, achieved by heating, cooling, pumping, or
letting down with a control valve.
Calculations of the compositions and the relative amounts of the liquid and vapor phases at
any given pressure and temperature involve a tedious trial-and-error solution. Since flash
calculations can be performed easily by computer, manual methods for multicomponent flash
calculations are not discussed here. Instead, phase and equilibrium diagrams will be used in a
binary system to demonstrate and reinforce the concept of equilibrium.
One-Stage Flash
Figure 7 shows an equilibrium separation. A propane and n-butane vapor mixture from a
distillation column is cooled to 120°F at 100 psia . The vapor and liquid are separated and the
vapor is condensed and collected in a second drum. Calculations are done to find the
composition of the liquid in the two drums and the minimum temperature required to
condense the vapor leaving the first drum. For simplicity, assume that the entire system is at
100 psia. The system is a one-stage flash. The second drum merely collects the condensed
liquid. It is not an equilibrium stage.
ONE-STAGE FLASH
FIGURE 7

The required compositions can be determined using a phase diagram for the propane/ n-
butane system at 100 psia. The liquid in the flash drum is represented by a point
(T, x1) = (120°F, 0.19) on the bubble point curve of the phase diagram at 120°F (Figure 8).
Similarly, the vapor is represented by a point on the dew point curve at 120°F (T, y1) =
(120°F, 0.4). Thus, the propane mole fractions in the liquid and vapor phases are 0.19 and
0.4, respectively.
The minimum cooling required to condense the vapor leaving the first drum corresponds to its
bubble point temperature. This is the maximum temperature at which all the vapor from the
first drum can be condensed. Since the vapor from the first drum and the liquid from the
second drum have the same composition, the bubble point can be located by drawing a
vertical line between the dew point and the bubble point curves. The temperature obtained,
96°F, is the minimum temperature required to condense the vapor from the first drum.
ONE-STAGE FLASH ON A PHASE DIAGRAM
FIGURE 8

The equilibrium in the flash drum is represented in the equilibrium diagram by a point, y1, x1
= 0.4, 0.19 (Figure 9). Condensation in the second drum is represented by a horizontal line
from y1, x1, to the reference line, y1, x'1, where x'1 is the mole fraction of the liquid of the
first drum, which is equal to y1. The equilibrium diagram does not provide temperature
information. Therefore, it cannot be used to determine the equilibrium concentrations or the
temperature of the second drum. However, if the composition of one phase is known, it can
be used to determine the composition of the other phase.
ONE-STAGE FLASH ON AN EQUILIBRIUM DIAGRAM
FIGURE 9

Representation of Petroleum with Pseudocomponents
Computer simulations of distillation columns break the hydrocarbon streams fractionated into
their constituents. Generally, hydrocarbons with five or six carbons are identified as
individual components. Hydrocarbons with more than five or six components are represented
by narrow fractions. The narrow fractions are defined by their volume average boiling point
(VABP) and their average gravity. In other words, components boiling within certain ranges
are represented in the simulation as one component. Such a component is called a
pseudocomponent.
Figure 10 illustrates the division of a wide petroleum fraction into 11 pseudocomponents.

The fraction can be divided into pseudocomponents of equal volume or equal boiling range.
Alternatively, there can be an increased number of components in the region where the
distillation column will split the products. In this case, the engineer has used few components
in the middle of the curve where the curve is flat. This provides an accurate description of the
material. However, if this material is to be divided into fractions, more components in the
region of the division should be included.
PROCESS/PRO II and HYSIM offer a variety of options for representing petroleum fractions
and determining their pseudocomponents.
PSEUDOCOMPONENT BREAKDOWN
FIGURE 10

DISTILLATION PROCESS PARAMETERS
Conventional Distillation Column
Distillation is the separation of the constituents of a liquid mixture by partial vaporization of

the mixture, followed by separate recovery of the vapor and liquid. The more volatile (light)
constituents of the mixture are obtained in increased concentration in the vapor, while the less
volatile (heavy) constituents are components concentrated in the liquid residue, also called the
bottoms. The vapor is most frequently condensed by cooling and is called the distillate or
overhead product. In most petroleum processing plants, the terms distillation and
fractionation are used interchangeably.
Figure 11 shows a conventional distillation column that has one feed stream and two product
streams. The section above the feed is the rectifying or enriching section. In the rectifying
section, the concentrations of the light components increase toward the top of the tower; that
is, the light product is enriched. The section of the column below the feed is the stripping
section. Here the light components are stripped out of the liquid as it descends the column.
In binary distillation, the feed contains only two components.
Frequently in multicomponent distillation, a light component that must be recovered in the

distillate is also present in the residue in important amounts, while components lighter than
this component are present only in small amounts. This component is called the light key. In
the case of a depropanizer, for example, the light key is the propane, with a concentration in
the residue of 0.7%.
Similarly, a heavy component present in the distillate in important amounts is called the heavy
key. If more than one of the heavy components is present in the distillate in important
amounts, then the more volatile component is the heavy key. In a depropanizer, where both
the isobutane and the n-butane are present in the distillate in important amounts, the heavy
key is the isobutane. Key components are used in shortcut distillation calculations and in
some tray and packing efficiency calculations. Frequently product specifications are based on
the concentration of key components, for example, 0.7% maximum propane in the
depropanizer bottoms.

CONVENTIONAL DISTILLATION COLUMN
FIGURE 11
Reflux
Part of the liquid condensed from the vapor leaving the column top is returned to the column
as reflux. The reflux provides the liquid for the contact with the vapor in the rectifying
section of the column. The important role of reflux in distillation will be discussed in later
sections.
The proper definition of reflux ratio is the mole ratio of reflux to total distillate, liquid plus
vapor. Often, the ratio of reflux to liquid distillate is also called reflux ratio. The mole ratio
of liquid to vapor between the column stages is called internal reflux ratio.

Major Equipment
The column or tower is the main piece of equipment in a distillation unit. It contains vapor-
liquid contacting devices, trays in most cases, packing less frequently. Typical major
auxiliary equipment of a column includes the condenser, the condenser separator, and the
reboiler. The condenser condenses the reflux and the part of the distillate that is removed as
liquid. When all the overhead vapor from the column is condensed, it is called total
condenser. The condenser separator separates any vapor distillate from the liquid and
provides surge capacity for the reflux and the distillate.
The reboiler vaporizes part of the liquid leaving the bottom tray of the column. This vapor,
playing a role similar to that of the reflux, contacts the descending liquid and strips the lighter
components. The heat source of the reboiler may be steam, or a process fluid; the reboiler
may also be a gas- or fuel-fired furnace.
McCabe-Thiele Diagram
The graphical representation of a binary system (two components) distillation column in x,y
mole fraction axes through its operating and equilibrium lines is called a McCabe-Thiele
diagram. Figure 12 is a McCabe-Thiele diagram for an eight-stage distillation column with
one feed, a total condenser, and a kettle type reboiler.
The slopes of the rectifying (top) and stripping section operating lines are equal to the internal
reflux ratios, L/V and L'/V', in these sections. The intersections of the operating lines with the
x = y line indicate the distillate and bottoms compositions. The column theoretical stages are
indicated by steps between the equilibrium and operating lines. The points of the steps that
are on the equilibrium line indicate the vapor, y, and liquid, x, compositions that are at
equilibrium on each column stage. The points that are on the operating lines indicate the
vapor and liquid compositions between stages.
The McCabe-Thiele technique can be used to determine the required stages for a given
separation or the expected product qualities for a given column. Compared to available
numerical techniques, it is too slow and not sufficiently accurate. However, it is an excellent
tool for demonstrating some of the principles of distillation. One of the simplifying
assumptions, for example, is that the vapor and liquid molar rates, V, L, in each section of the
column are constant. Additional information on the McCabe-Thiele diagram can be found in
ChE 205.03 and distillation textbooks.

McCABE-THIELE DIAGRAM
FIGURE 12

Effect of Reflux on Required Stages
Figure 13 illustrates the effect of reflux on the required stages to achieve a specified
separation (xB,xD). We observe that as the operating line slope is reduced (reflux decreased),
the change in composition from stage to stage is reduced and the required stages increase.
EFFECT OF REFLUX ON REQUIRED STAGES
FIGURE 13

Minimum Reflux
If the reflux is reduced to the point that the operating lines intersect each other at the
equilibrium line, the required number of stages becomes infinite (Figure 14). This reflux is
called the minimum reflux.
The minimum reflux does not represent a practical operation. However, it can be used to
compare the difficulty of separation for various product specifications. Also, the actual reflux
is often expressed in terms of minimum reflux; for example, a tower may normally operate at
1.1 × minimum reflux.
MINIMUM REFLUX
FIGURE 14

Total Reflux - Minimum Stages
Total reflux represents an operation where the feed and product streams of a column operating
at steady state are simultaneously blocked. The reflux is adjusted to maintain the level in the
accumulator, and the reboiler and condenser loads are adjusted to maintain the enthalpy
balance. When the column regains the steady state, it is operating at total reflux. All the
vapor entering the condenser is condensed and returned to the column as reflux, and all the
liquid entering the reboiler is vaporized and returned to the column (Figure 15).
TOTAL REFLUX - MINIMUM STAGES
FIGURE 15
There is one operating line for the entire column passing through xB and xD, and coinciding
with the y = x diagonal. The operating line has the maximum slope possible, and the
corresponding stages are the minimum number of stages that can provide the required
separation. A column with the minimum number of stages, similar to a column with
minimum reflux, does not represent a practical operation. However, it represents the
difficulty of separation, and it is used in shortcut calculations.
The concept of total reflux can also be applied to a steady-state operation with a feed and a
bottoms product. In this case, the bottoms composition is the feed composition.

Stages Versus Reflux
We have seen in the previous pages that there is a relationship between reflux and the
required number of stages in a column. This relationship is illustrated in Figure 16.
Operation of a distillation column near the minimum reflux or minimum number of stages is
not stable or economical. When a column operates, for example, near the minimum number
of stages, a reduction in tray efficiency, due to tray damage, can be compensated for only by a
very large reflux increase.
STAGES VERSUS REFLUX
FIGURE 16
Simulations with PROCESS/PRO II
PROCESS/PRO II is a flowsheet simulator. The main unit operations used for the simulation
of distillation columns are:
• Shortcut distillation.
• Rigorous distillation.
• Flash.
• Mixer/splitter.
• Exchanger.
The Multi-variable Controller and Flowsheet Optimizer options of PROCESS/PRO II can be

used to accomplish complex objectives. The PROCESS/PRO II input manual provides
further information on simulations.

Figure 17 is a printout of a column profile from a PROCESS simulation of a depropanizer.

We observe the following:
• The tray temperature is lowest at the tower top and highest at the bottom of the tower.
The gradual temperature change reflects the change in tray composition and, to a lesser
extent, the change in pressure. The top tray represents the condenser.
• The pressure changes very little from tray to tray. There is a 5 psi drop between the top
tray and the condenser.
• The liquid loadings increase sharply below the feed. The feed is 100% liquid as
indicated by capital L to the right of the feed rate.
• The vapor profile changes gradually as the composition and thermal condition changes.
There is a drop near the feed indicating subcooled feed.
Steps in Column Design
Below is a list of steps typically followed in designing a distillation column.
• Define basis.
• Determine tower operating conditions.
- Pressure, temperature.
• Define simulation components.
• Perform distillation calculations.
• Estimate tray efficiencies.
• Design hardware.
The following section focuses on two important operating conditions of a column: pressure
and temperature. A section on tray efficiencies follows. Hardware design is discussed in ChE
104.02.

SIMULATION TOWER PROFILE
THIS IS A PRINTOUT (SEE VG)
FIGURE 17

Column Operating Pressure, Temperature
Column pressure is normally selected so that the reflux and distillate can be condensed by the
available coolant. Allowances must be made for the condenser approach temperature,
fluctuations in product rate and composition, and the need for subcooling of reflux or liquid
distillate. Further considerations are:
• Use of a partial or a total overhead condenser.
• The limiting design pressure should correspond to the highest design temperature level
of the coolant, such as summer conditions for ambient air. Below is a list of typical
approach temperatures of the cooling medium and the heat-source for different reboiler
and condenser services:
Temperature approach to the cooling medium, °F:
Refrigeration 5 - 20
Sea water 10 - 25
Air 15 - 30
Temperature approach to the heat source, °F:
Process fluid 15 - 35
Steam 15 -100
Hot oil 35 -100
• Refrigeration of the overhead should be avoided if possible. When refrigeration cannot

be avoided, economics will normally dictate that the refrigerant temperature be as high
as possible in order to minimize refrigerant compression costs.
• Lower pressure increases the relative volatility and improves the ease of separation.
Therefore, the total stages or reflux ratio can be reduced while still meeting a given
design specification.
• Lower pressures will give a somewhat larger diameter tower (lower vapor density,
higher actual volume) and possibly a thinner tower shell. The exception may be towers
fractionating close-boiling components, where the improvement in relative volatility and
reduced reflux requirements more than compensate for the reduced density.

• With some heat-sensitive systems, severe fouling conditions in the reboiler and lower
tower stages can be avoided by reducing the tower pressure to reduce bulk liquid
temperatures. Lower reboiler temperatures minimize degradation of gas treating amines
such as DGA.
Tray Efficiency
The overall efficiency, EO, is a measure of the effectiveness of an entire column or section of
a column. This efficiency is the one most often used by designers in determining the number
of actual trays to provide. EO is simply the total number of calculated theoretical trays
required, divided by the total number of actual trays required for the separation.
Approximate tray efficiencies can be predicted using the fluidity method in Maxwell's Data
Book on Hydrocarbons or the viscosity-volatility method developed by F. J. Lockhart and
C. W. Leggett (E. J. Henley, J. D. Seader, Equilibrium-Stage Separation Operations in
Chemical Engineering, 1958, John Wiley and Sons, Inc.). Efficiencies from these two
sources do not take into account the tray geometry and the effects of fouling. As a result, the
approximate efficiencies may deviate considerably from the actual efficiencies and should not
be used for design.
More accurate tray efficiencies can be obtained using unit operating data. The unit can be
simulated and the simulation-actual heat and material balance and product quality matched
using the number of theoretical trays as a variable. Overall efficiency is the ratio of
theoretical to actual trays.
Vendors also use their own data and predictive methods to estimate tray efficiencies. Typical
tray efficiencies for some of the Saudi Aramco units are listed in Figure 18.

TYPICAL OVERALL EFFICIENCIES, %
Above Feed Below Feed
Crude Stabilizer 25
Atmospheric Crude Unit
Top 70-80
Bottom (above Flash Zone) 50-60
NGL Fractionation 90 65-85

(DeC3...DeC5) (Low-end if
very heavy
components
are present)
Reformer Feed Stripper 85 75
Kero/Diesel Hydrotreater
Stripper 80-90 30-35
H2S/Amine Absorber 10-25
FIGURE 18

SAUDI ARAMCO DISTILLATION PROCESSES
Crude Stabilization and Sweetening
Fluids flowing from oil and gas wells generally include a gas phase and a liquid phase in
equilibrium. The liquid phase consists primarily of crude oil, water, and dissolved salts.
Water and salts are removed in desalters. The crude oil is sent to stabilization plants. The
objective of crude stabilization is to remove light hydrocarbons and hydrogen sulfide (H2S)
from the crude in order to achieve an acceptable level of volatility for storage and trans-
portation and an acceptable concentration of H2S. Generally, it is not desirable to remove
from the crude any hydrocarbons beyond the required minimum.
There are two obvious advantages to retaining the lighter hydrocarbons in the stabilized
crude. First, liquids can be stored and transported to the user more economically than gas.
Second, retention of the lighter hydrocarbons in the liquid phase is especially important when
the separated gas has no market value and is being flared or compressed and re-injected.
Conversely, retention of too many light ends can cause problems. The quantity of light ends
that must be removed from the crude oil is controlled by the composition of the oil, the
ambient air temperature, the method of transportation, and economic considerations.
Refineries and tankers require crude oil to meet maximum vapor pressure specifications.
If the crude contains H2S, the H2S concentration must be lowered to reduce toxicity and
corrosion and to meet sales specifications.
For Saudi Aramco units, the H2S content is generally the controlling specification. The H2S
content specification in the stabilized crude leaving the units generally varies between 1 and
60 parts per million (ppm), and it is typically 10 ppm. At such low H2S contents, volatility
specifications, for example, 13 psia Reid vapor pressure (RVP), are normally met. The
maximum allowable H2S content in the stabilized crude is 70 ppm, however, the Ras Tanura
refinery requires a lower H2S content when maximizing NGL.
Figure 19 illustrates a typical stabilization unit, the Abqaiq Crude Stabilizer No. 17. Desalted
crude at ambient temperature is fed to the top tray. A set of reboilers provides the driving
force for stripping light material and H2S. Live steam is also injected in the reboiler return
line. The bottoms temperature is a function of the quality of stripping and is a good indication
of the H2S content in the bottoms.
The gas from the column overhead is sent to compression and recovery of light hydrocarbons.
The bottoms, the stabilized crude, is cooled and stored or shipped.

ABQAIQ CRUDE STABILIZER NO. 17
FIGURE 19

Condensate Stripping
The objective of condensate stripping is to remove ethane from condensed stabilizer overhead
vapor. Condensate stripping is a relatively simple fractionation process (Figure 20). The
feed, which is stabilizer gas that has been compressed and condensed, is sent to the top tray of
the tower. The tower is reboiled; however, there is no overhead condensing system or
external reflux. The feed condenses, providing the internal reflux required for fractionation.
The key product specification is the bottoms C2 content, which is controlled by the reboiler
duty. Due to the lack of overhead condenser and external reflux, there is no control on the
content of C3+ material in the tower overhead product. The tower pressure is typically
determined by downstream transportation and processing requirements for the overhead gas.
The overhead product is sent to gas plants for treating and separation of the light
hydrocarbons. The bottoms product is sent to NGL recovery units.
ABQAIQ CONDENSATE STRIPPER
FIGURE 20

Crude Distillation
Crude petroleum (oil) is a complex mixture of an extremely large number of hydrocarbons,
from gases like methane and ethane, to molecules having more than 70 carbon atoms and
boiling points above 1000°F. Because of this wide range of components, it is rarely used
directly as it is produced from the field. However, it can be refined and further processed into
any number of products according to boiling range. The objective of crude distillation is to
separate the crude into fractions according to boiling range. These fractions may be products
for sale or may be feedstocks for other refining or processing units.
In most refineries, the distillation of crude is carried out in two stages (Figure 21). The crude
oil is first heated and then fed to a fractionating tower that operates at a pressure slightly
above atmospheric pressure. This tower is usually called the atmospheric tower or column. It
yields several distillate products and a bottoms product, which is the residual liquid material
that could not be vaporized under the conditions of temperature and pressure existing in the
atmospheric tower. This bottoms liquid is then reheated to the maximum allowable
temperature, usually higher than the maximum temperature allowed for the feed to the
atmospheric tower, and fed to a fractionating tower operating at subatmospheric pressure.
This tower is usually called the vacuum tower or vacuum column.

PLANT 15 CRUDE UNIT - RAS TANURA REFINERY
FIGURE 21

Atmospheric Unit
Figure 22 is a simplified process flow diagram of the Ras Tanura Plant 15 Crude Unit. Crude
from storage is mixed with water for desalting and heated in a series of exchangers. The
exchangers typically utilize heat available in the crude unit. After the crude reaches about
250-290°F, it enters the desalter. Downstream of the desalter, the crude is flashed and the
vapors fed to the flash zone of the atmospheric unit. The purpose of the flash drum is to
remove light components that may vaporize upstream of the furnace and cause high pressure
drop and maldistribution between the furnace passes. The liquid from the flash drum is
pumped through a series of exchangers and fed to the furnace.
Following is a discussion of the main features of an atmospheric crude unit. Figure 23 shows
the Ras Tanura Unit 15 in greater detail.
Furnace
Generally, the furnace heats the crude to the highest temperature allowable for the crude
being processed. The furnace transfer temperature, also known as the coil outlet temperature
(COT), is the most significant parameter for achieving the desired total yield of distillates.
The COT is limited by the effect of temperature on cracking and the effects of the cracked
products on product quality. Other limitations on COT are coking of the furnace tubes or
tower internals and the maximum permissible furnace tube metal temperature (TMT).
The crude leaves the furnace partially vaporized and enters the atmospheric column at the
flash zone.
Bottoms and Sidestream Stripping

Liquid from the flashed feed plus the overflash enters the section of the column below the
flash zone, the stripping section. Superheated steam injected below the bottom tray removes
light components from the bottoms (vacuum unit feed). Excessive amounts of light
components in the feed to the vacuum unit increase the furnace duty and pressure drop and
increase the difficulty of maintaining vacuum.
Crude unit sidestream stripper towers are used primarily to achieve certain product
specification targets such as flash point and front-end distillation requirements. These
specifications are achieved through a combination of stripping steam and the number of
theoretical stages present in the stripper.

PLANT 15 ATMOSPHERIC CRUDE UNIT - RAS TANURA REFINERY
FIGURE 22

Pumparounds
Liquid from fractionator trays is pumped through exchangers and returned to a higher tray.
The cold liquid contacts and condenses the rising vapor. The purpose of the pumparounds
(PA) is to:
• Reduce the rate of vapor rising up the tower and thus reduce the required tower
diameter.
• Recover heat at higher temperature levels relative to the overhead condenser.
The trays between the pumparound draw and return are heat transfer trays, and their
contribution to the separation of components is minimal due to the backmixing of liquid.
Vacuum Unit
Reduced crude from the atmospheric unit bottom is fed to the vacuum unit , operated under
vacuum in order to recover additional distillate liquids (Figure 23). The reduced crude is
heated in the vacuum furnace, which provides the heat required to partially vaporize the feed.
Steam is added in the furnace to limit process stream temperatures and to reduce the
residence time, thereby minimizing coking and cracking. Typically two sidestream products
are taken: light (LVGO) and heavy (HVGO) vacuum gas oils (in addition to a small overhead
distillate or slop stream). The sidestreams are used for fuel oil or as cracker feed and are
condensed via pumparounds, which recover heat for reuse either for feed to cat crackers or
other conversion units. Ras Tanura Vacuum Unit 15 has three sidestreams. The top (S/C 6) is
a diesel blending component (recovery of light components, such as diesel, in the vacuum
units is not typical), while the heavier sidestreams and bottoms go to fuel oil. The LVGO
(S/C 7) and HVGO (S/C 8) are typically blended with vacuum resid to produce a variety of
fuel oil grades. In many refineries, the LVGO and HVGO are fed to fluid catalytic cracking
units and converted to lighter products.
Because fractionation between the sidestreams is usually not critical, fractionation sections are
not usually provided; only the amount of trays or packing required for heat transfer is
provided in the pumparounds. Packing is often used instead of trays to minimize the tower
pressure drop and maximize the sidestream or gas oil recovery. In the Ras Tanura Vacuum
Unit 15, there are four trays between the top (S/C 6) and the second (S/C 7) sidestreams to
provide the fractionation needed for the diesel oil (S/C 6) blending component. A wash
section, consisting of a Glitsch grid or a similar structured packing, is located above the flash
zone to reduce resid entrainment from the flash zone. A bottom steam stripping section
recovers distillate product from the feed flash liquid and the wash section liquid or overflash.
The tower vacuum is maintained by steam jet ejectors either alone or in combination with
mechanical vacuum pumps.

PLANT 15 VACUUM CRUDE UNIT - RAS TANURA REFINERY
FIGURE 23
Following are highlights of features particular to vacuum units.
Furnace Coil Outlet Temperature (COT) and Coil Steam

The coil outlet temperature is the most significant parameter for achieving the desired vacuum
pipestill cutpoint. A COT as high as 780°F has been achieved in practice, but 740 to 750°F is
more the norm in actual operations. The maximum permissible COT is limited by three
factors:
• Cracking, which yields noncondensible gases that potentially could overload the
overhead vacuum system.
• Coking of the furnace tubes or the tower internals, which limits the run length.
• Maximum permissible tube metal temperature.
Steam is added to the furnace radiant coil to suppress coking.

Bottoms Quenching
The bottoms is quenched to reduce the noncondensible gas produced through cracking, as
well as to reduce coking of the resid. If not quenched, the bottoms would produce
considerably more gas due to its high temperature and long residence time.
Wash Zone
The primary purpose of the fresh wash and overflash is to wash out the entrained pitch that is
removed from the feed flash vapor in the wash section. Fractionation requirements in the
wash section are minimal. Thus, the minimum fresh wash and overflash rates are set by the
minimum liquid rate required to wet the wash zone internals.
Steam Jet Ejectors

Due to their principle of operation, steam jet ejectors are virtually intolerant of increases in
vapor load and decreases in motive steam pressure and rate compared to their design values.
Common causes of difficulties in obtaining the desired vacuum are associated with:
• Insufficient heat removal in the condensers.
• Low motive steam pressure or rate.
• Excessive steam or air leakage into the system.
• Ejector cycling occurring when the vapor load to the ejector is reduced significantly
below design.

NGL Fractionation
Gas plants such as Uthmaniyah and Shedgum receive GOSP gas (for example, Uthmaniyah
GOSP), offgas from crude stabilization units (for example, Abqaiq), and nonassociated gas
KHUFF. The objective of NGL fractionation is to separate the raw hydrocarbon mixture into
individual products suitable for sale, injection into crude, or downstream processing.
Refineries such as Ras Tanura also produce gas and light hydrocarbons, often referred to as
light-ends, by removing the light fractions of the crude or by conversion (chemical reaction)
in units such as reformers and fluid catalytic crackers. NGL fractionation separates these
light-ends components.
The raw stream to be fractionated normally contains the hydrocarbon components shown
below in order of decreasing volatility (ease of vaporization) as denoted by increased boiling
points:
Atmospheric Pressure Vapor Pressure at

Light Hydrocarbon Boiling Point, °F 120°F, psia
Methane - 259 Critical temp. 116°F

Ethane - 127 Critical temp. 98°F
Propane - 44 225
iso-Butane 11 96
n-Butane 31 70
iso-Pentane 82 29
n-Pentane 97 22
Hexanes and Heavier 122-250 < 15
If fractionation is to be feasible, the top product and bottom product from a fractionator must
have different boiling points. The difference in boiling points between the top and bottom
products indicates the degree of difficulty in separating these products in a single fractionator.
The smaller the boiling point difference, the more difficult the separation; that is, the
separation will require more trays (tower size), more reflux (pump size, tower size), and
additional reboiler heat (reboiler size) to perform the job. This means that higher investment
will be required and greater operating costs will be incurred to distill the products.

The column pressures are generally set such that the condensing temperature of the overhead
products are the same. This permits the use of a single cooled utility system. This does not
apply to demethanizers and deethanizers, which normally require refrigeration. The last
column of the table on the previous page lists the vapor pressures of light hydrocarbons at
120°F. These are the pressures required to condense the hydrocarbons in a tower overhead
condenser and separator if we are to use a cooling medium, such as air in air fin coolers, that
can cool to 120°F. For instance, propane product separation may require a 225-psia operating
pressure using air coolers, while isobutane product separation may need only a 100-psia
pressure. The actual pressure of the tower may be somewhat different since the overhead
product is not pure. It generally contains small amounts of lighter and heavier components
that result in a different vapor pressure.
A single fractionator tower generally removes only one single finished product stream from
the raw feed mixture. A common order of fractionation in gas plants is to remove the ethane,
the propane, the butanes as a mix, and then the pentanes. Separation of the butane mix into
finished normal and isobutane products is then done last in another tower, the deisobutanizer.
Pentanes may be separated similarly. Other schemes remove more components in one tower
(for example, propane/butanes) and fractionate them in a separate tower (for example, a
C3/C4 splitter).
NGL Fractionators
The degree of fractionation required and the number of products vary from plant to plant and
are determined by factors such as product outlets, customer needs, and plant location. As a
result, there are several types of NGL fractionation towers, and many fractionation sequences
are found in refineries and gas plants. Figure 24 summarizes the main types of NGL
fractionators.

NGL (LIGHT-ENDS) FRACTIONATORS
Fractionator Products
Type of Fractionator Feed Stream Overhead Bottom Product

Product
Demethanizer (DeC1) GOSP, Methane C2+

Condensed Stripout
Deethanizer (DeC2) DeC1 Bottoms, Ethane, C2- C3+

Condensed Stripout
Depropanizer (DeC3) DeC2 Bottoms, Propane C4+

Condensed Stripper
Bottoms
Debutanizer (DeC4) DeC3 Bottoms Butane C5+
Debutanizer (DeC4) DeC2 Bottoms Propane + C5+

Butane
C3/C4 Splitter DeC4 Overhead Propane Butane
Deisobutanizer (DeiC4) DeC4 Overhead Iso-Butane n-Butane
Depentanizer (DeC5) DeC4 Bottoms Pentane C6+
Depentanizer (DeC5) DeC3 Bottoms Pentane + Butane C6+
C4/C5 Splitter DeC5 Overhead Butane Pentane
FIGURE 24
Figure 25 is a simplified process flow diagram of Yanbu deethanizer gas plant. Figures 26
and 27 are simplified process flow diagrams for the depropanizer, debutanizer, rerun, and
butane/pentane splitter of the Ras Tanura Plant 10 NGL fractionation. The figures illustrate
the flow sequence, operating conditions, and key product qualities.

YANBU FRACTIONATION AND TREATING: DEETHANIZER
FIGURE 25

RAS TANURA NGL FRACTIONATION PLANT 10

SIMPLIFIED PROCESS FLOW DIAGRAM
FIGURE 26

RAS TANURA PLANT 10 - NGL FRACTIONATION
FIGURE 27

WORK AID 1: CALCULATE VLE PARAMETERS USING THE IDEAL GAS LAW
a. Feed Rate.
Use the ideal gas law relationship.
PV = nRT
To calculate the number of moles (n) in the feed.
n = PV
RT
P, V, T for the feed are provided. Need to convert the pressure, P, from psia to psig.
R = 10.732 (psia-ft3)/(lb-mole °R) obtained from the attached table of fundamental

constants.
b. Drum Pressure.
Find the partial pressure of each component using Raoult's law.
PPi = xi VPi
Mole fractions of components in the drum liquid, xi, and vapor pressures, VPi, are
provided.
Add partial pressures to obtain the total pressure.
c. Vapor Composition.
Calculate the mole fraction of each component in the vapor phase using
yi = xi (VPi/PT)

Work Aid 1: Fundamental Constants (P. 2 of 3)
Name Symbol Value Units
Basic Constants
Velocity of light (vacuum) c 2.997925 × 108 m/s

Avogadro constant NA 6.02214 × 1023 molecules per g-mole
Planck constant h 6.6261 × 10-27 (ergs) (sec) per molecule
Faraday constant F 96,485.3 coulombs per g-mole
Absolute temperature of the
"ice" point:
0°C TOC 273.15 K
32°F T32F 491.67 °R
Pressure-volume product
for 1 g-mole of a gas at p=0 2,271.11 joules per g-mole
pV
0°C (32°F) and zero TOC 22.4141 (liters) (atm) per g-mole
pressure (ideal gas)
2.27111 × 106 (m3) (Pa) per kg-mole
359.039 (ft3) (atm) per lb-mole
5,276.42 (ft3) (psia) per lb-mole
Derived Constants
Elementary charge e= F 1.60218 × 10-19 coulombs

NA
p=0
pV
Gas constant TOC 8.3145 joules per (g-mole) (K)
R=
TOC
1.9872 cal per (g-mole) (K)
1.9859 Btu per (lb-mole) (°R)
82.058 (cm3) (atm) per (g-mole) (K)
1,545.4 ft-lb [force] per (lb-mole) °R
10.732 (psia) (ft3) per (lb-mole) (°R)
62.364 (mm Hg) (liter) per (g-mole) (K)
0.084784 (kg per cm2) (liter) per (g-mole) (K)
0.73024 (atm) (ft3) per (lb-mole) (°R)
554.99 (mm Hg) (ft3) per (lb-mole) (°R)
8,314.5 (Pa) (m3) per (kg-mole) (K)
Boltzmann constant k= R 1.38066 × 10-16 ergs per (molecule) (K)
NA

Work Aid 1: Fundamental Constants (Cont'd) (P. 3 of 3)
Name Symbol Value Units
Defined Constants
Standard gravity go 980.665 cm per sec per sec

32.174 ft per sec per sec
Standard atmosphere atm 1,013,250 dynes per cm2

14.696 psia
101,325 pascals
Standard millimeter of mm Hg 1 atm

mercury pressure 760
Calorie (thermochemical) cal 4.184 joules

4.184 × 107 ergs
Liter L 1,000 cm3
Mathematical Constants
π = 3.14159
e (base of natural logarithms) = 2.71828
loge10 = ln 10 = 2.30259
Temperature Conversions
C = (F – 32) / 1.8
F = 1.8 C + 32
K = C + 273.15
R = F + 459.67
R = 1.8 K
where:
C = degrees Celsius
F = degrees Fahrenheit
K = kelvins
R = degrees Rankine

WORK AID 2: CALCULATE THE WATER VAPOR CONTENT OF GASES IN

EQUILIBRIUM WITH WATER
a. Assuming that the partial pressure of water in the vapor phase is vapor pressure,
calculate the mole fraction of water in the vapor, yw, using:
yw = PPw
PT
Find the vapor pressure of water at 120°F from the attached steam tables.
Calculate the molar rate of dry gas. The standard volume of gas is 380 SCF/lb-mole.
From the molar rate of dry gas and the mole fraction of water in the vapor, calculate the
mole water rate in the gas.
Calculate the weight water rate in the gas.
(water MW = 18)
b. Dew Point.
Find pressure from PPW = ywPT. Use the attached steam tables to find corresponding
temperature.

PASTE-UP

PASTE-UP

WORK AID 3: DETERMINE THE TOTAL PRESSURE OF AN IDEAL GAS

MIXTURE
Determine the pressure of the mixture in the overhead condenser separator using the ideal gas
law:
PT = Σ PPi = Σ(xi VPi)
Add the condenser pressure drop to obtain the tower top pressure.

WORK AID 4: REDUCE THE H2S CONTENT OF CRUDE STABILIZER

BOTTOMS
Consider the effect of composition on equilibrium temperature.

GLOSSARY
absolute pressure Pressure measured with respect to zero pressure, as distinct

from pressure measured with respect to some standard
pressure.
API gravity An arbitrary scale expressing the gravity or density of liquid

petroleum products. The measuring scale is calibrated in
degrees API. It is calculated by the following formula:
°API = 141.5 – 131.5

Sp Gr 60°F/60°F
aromatics Unsaturated hydrocarbons identified by one or more benzene

rings or by chemical behavior similar to benzene. Aromatics
are usually more reactive and have higher solvency than
paraffins and naphthenes.
barrel Standard unit of measurement in the petroleum industry,

equivalent to 42 standard U.S. gallons.
binary distillation Distillation of a mixture containing two components.
boiling range The range of temperature, usually determined at atmospheric

pressure in standard laboratory apparatus, over which the
boiling or distillation of an oil begins, proceeds, and finishes.
bottoms The bottom (heavy) product of a distillation column. A

synonymous term is residue.
Btu British thermal unit. The quantity of heat required to raise the
temperature of one pound of water 1 degree Fahrenheit, at
60°F and at a pressure of 1 atmosphere.
bubble point The temperature and pressure at which a liquid is in

equilibrium with an infinitesimal amount of vapor.
bubble-point curve The temperature and pressure conditions at which an

infinitesimal amount of vapor (first bubble of vapor) is in
equilibrium with vapor. For a pure component, this curve is
the same as the vapor pressure curve.

butane Gaseous paraffinic hydrocarbon (C4H10), usually a mixture of

iso- and normal butane. Also called, along with propane,
liquefied petroleum gas (LPG).
C1, C2, C3, ... Hydrocarbons with 1, 2, 3, ..., of carbons.
carryover Entrainment in the overhead of a tower or drum.
characterization factor Factor that expresses variations in physical properties with

change in character of the stock. The ratio of the cube root of
the molar average boiling point, TB, in degrees Rankine
(°R = °F + 460), to the specific gravity at 60°F/60°F:
Kw = 3 TB / Sp Gr
It ranges from 12.5 for paraffinic stocks to 10.0 for aromatic

stocks. Also called Watson factor or Watson K or UOP K.
chromatography (gas) A method of separation based on selective adsorption capable

of identifying individual compounds. An analytical technique
for separating mixtures of volatile substances. The mixture is
inserted into the chromatographic column and washed down
with an inert gas. The column is packed with absorbent
materials that selectively retard the components of the sample.
CIT Coil inlet temperature, the temperature of a fluid entering a

furnace.
coking Formation of solid, carbon-rich material from hydrocarbons

heated at high temperatures.
column A vertical vessel containing contacting devices such as

trays or packing, used to perform separations such as
distillation or extraction. A synonymous term is tower.
compressibility factor The ratio of the actual volume occupied by a vapor to the
theoretical volume occupied by the same quantity of vapor
under identical conditions of temperature and pressure.
condenser A cooler condensing all (total condenser) or part (partial

condenser) of the overhead vapor of a column.

constant molar overflow Constant vapor and liquid rates in a section of a column.
See the assumptions and basis described in the text.
COT Coil outlet temperature, the temperature of a fluid leaving a

furnace.
countercurrent flow A system in which one fluid flows in one direction and
another fluid flows in the opposite direction.
critical point See critical state.
critical pressure The pressure necessary to condense a gas at the critical

temperature. Above the critical temperature, the gas cannot
be liquefied, no matter what pressure is applied.
critical state The pressure and temperature at which liquid or gaseous

phases reverse at the slightest change in conditions.
critical temperature The maximum temperature at which a gas can be liquefied by

pressure (critical pressure); above this temperature, the gas
cannot be liquefied, no matter what pressure is applied.
cut A fraction obtained by a separation process. (See also

fractional distillation.)
dew point The temperature and pressure at which a vapor is in

equilibrium with an infinitesimal amount of liquid.
dew-point curve The temperature and pressure conditions at which an

infinitesimal amount of liquid (first drop of liquid) is in
equilibrium with vapor. For a pure component, this curve is
the same as the vapor pressure curve.
distillate The overhead (light) product of a distillation column. It may

be vapor, liquid, or both.
distillates Products in the mid-boiling range, including kerosene,

turbo fuel, and heating oil. Also called middle distillates
and distillate fuels.
distillation The separation of the constituents of a liquid mixture by

partial vaporization of the mixture followed by separate
recovery of the vapor and liquid residue.

distillation curve Curve plotting the percentage of petroleum products distilled

versus the temperature.
distillation test Methods for determining the volatility characteristics of a

hydrocarbon liquid by progressively boiling off a sample
under controlled heating. If the boiling range is small, the
fluid is narrow cut, that is, having components with similar
volatilities. If the boiling range is wide, the fluid is wide cut.
end point (EP) In the distillation of liquids, the maximum temperature that
occurs during the test. Also called final boiling point (FBP).
enriching section The section of the distillation column above the feed.
equation of state Predicts the PVT behavior of gases and liquids.
equilibrium The state of a system under a constant environment when the

intensive properties remain unchanged with time. Net fluxes
of mass, energy, and chemical reactions in the system are
zero.
equilibrium flash separator Involves the separation of a two-phase bed into vapor and
liquid in a vessel.
equilibrium line Curve showing the relationship between the concentration of a

component in the liquid phase and its concentration in the
equilibrium vapor phase.
flash zone The intertray space where the crude fractionator feed is
introduced.
fractionation Distillation in which the vapor is contacted continuously

and countercurrently with a condensed portion of the
vapors.
fugacity The tendency of a substance to escape or disappear from the

phase in which it is present.
gauge pressure The pressure as shown by a pressure-registering instrument

(gauge). The gauge pressure, in pounds per square inch, is
approximately equal to the absolute pressure minus 14.7.

GCD Gas Chromatography Distillation. A chromatographic

technique that produces results approximating 15/5
distillations.

heavy key A heavy component that must be recovered with the

residue and is present in the distillate in important amounts.
Henry's law constant (H) Constant relating the equilibrium concentration of a gas
physically dissolved in a liquid to the gas partial pressure
above that liquid. Stated another way, Px = H[x] where Px is
partial pressure of component x in gas and [x] is the
concentration of x in liquid.
heterogeneous system One in which intensive properties are uniform from point to
point and thereby constitute a single phase.
HVGO Heavy VGO.
hydraulic limitation Maximum vapor or liquid rates above which a tower cannot
operate.
ideal gas Gases whose behavior can be described by the ideal gas law.
initial boiling point (IBP) In a distillation test, the fluid temperature at which the first
drop falls into a graduated cylinder.
internal reflux The liquid rate in a tower. Internal reflux may change due to
condensation by pumparounds, withdrawal of sidestreams,
introduction of feeds, and differences in condensation and
vaporization rates due to composition changes.
internal reflux ratio The liquid to vapor ratio, L/V, in a tower, where L is the
liquid from the tray and V is the liquid to the tray. It is
typically expressed on a mole/mole basis.
jet ejectors Steam-powered devices for generating vacuum.
jet flooding Overloading of the tray interspace with liquid, caused by

excessive entrainment.
kettle reboiler A type of reboiler acting as a vaporizer and a separator.

The kettle reboiler produces a vapor stream that is sent to
the tower and a liquid stream that is in equilibrium with the
vapor. The liquid is the tower bottom product.
K-factor Another term for equilibrium K-value.

knockout drum Drum for disengaging entrained liquid droplets from a stream
of a different phase, usually a gas stream.
K-value Ratio of the vapor to the liquid mole fraction of i.
letdown valve Valve in the line between higher pressure equipment and
lower pressure equipment. Examples are the valve between
the absorber bottom and hydrocarbon flash/skimming drum
and the valve between the rich/lean exchanger and
regenerator rich-solution inlet.
light ends Low-boiling-point hydrocarbons having up to five carbon

atoms, including butanes, butenes, pentanes, pentenes. Also,
any extraneous low-boiling fraction in a refinery process
stream.
light key A light component that must be recovered with the

distillate and is present in the residue in important amounts.
liquid-phase controlled Mass transfer rate limited mostly by liquid film resistance.
mass transfer
LNG Liquefied natural gas.
LPG Liquefied petroleum gas, mostly propane and butane.
LVGO Light VGO.
mid-boiling point (MBP) In a distillation test, the temperature at which 50% of the fluid
has collected in the cylinder.
multicomponent Distillation of a mixture containing more than two

distillation components.
Murphree tray or plate % approach to equilibrium between vapor and liquid streams
efficiency leaving a tower tray.
NGL Natural gas liquids.
noncondensibles Gases that cannot be condensed without refrigeration in the

pressure range of refinery units. The hydrocarbons usually
included are methane and ethane.

nonideal gas When the ideal gas law does not apply, the gases are called
nonideal or real.
normal boiling point The boiling point of a substance is the temperature at which it
boils. It varies with pressure. The normal boiling point is the
boiling point at atmospheric pressure.
operating line A line in the McCabe-Thiele diagram that corresponds to

the compositions of vapor and liquid between stages.
overflash The liquid leaving the wash section of a crude column to enter
the flash zone.
overhead The vapor leaving the top of the column.
PA Pumparound.
packing Devices providing countercurrent vapor-liquid contact in

distillation columns.
partial condenser A condenser that condenses part of the vapor.
phase A homogeneous portion of a system. A gas or a mixture of

gases, a liquid or a liquid solution, and a solid are examples
of phases.
plates Contact points of all the vapor and liquid in a column, such
as that which occurs on column trays. The term theoretical
plates is used to indicate that equilibrium is reached at the
contact point between all the vapor and all the liquid. The
actual plates reflect the obtained tray efficiency. A
synonymous term is stages.
pseudocomponent Components boiling within certain ranges are represented in

the simulation as one component, called a pseudocomponent.
pumparound Arrangement that removes heat from a stream pumped from a

tray to a higher tray.
quenching Rapid cooling, usually by mixing with a cold liquid.

reboiler A heater vaporizing part of the liquid leaving the bottom of

the distillation column. The vapor returned to the column
provides the stripping action in the bottom section.
recirculating reboiler A type of reboiler that sends both the vapor and liquid phases
to the distillation tower. It operates by natural circulation
(thermosyphon) or forced circulation.
rectifying section The section of the distillation column above the feed.
reflux Condensed overhead vapor that is returned to the top tray

of the distillation column.
reflux ratio Molar ratio of condensed water vapors to acid gas vapors
leaving the regenerator overhead condenser.
relative volatility A measure of separability.
residue The bottom (heavy) product of a distillation column. A

synonymous term is bottoms.
RVP Reid vapor pressure. A measure of volatility for hydrocarbon

mixtures.
S/C Sidecut. A distillation tower sidestream.
sidestream A tower product stream removed from a tray other than the
top or bottom tray.
slipstream A small stream of solution drawn off from a larger solution

stream.
sour water stripper Tower for desorbing H2S from sour water by stripping.
spec(s) Short for specifications(s).
stages Contact points of all the vapor and liquid in a column, such as
occurs on column trays. The term theoretical stages is used to
indicate that equilibrium is reached at the contact point
between all the vapor and the liquid. The actual stages reflect
the obtained tray efficiency. A synonymous term is plates.
stripping section The section of the distillation column below the feed.

stripping steam Steam introduced to the bottom of a tower for removing light
components from the descending liquid.
surge/storage drum or tank Vessel that provides liquid holdup capacity.
TBP True boiling point (temperature) of a component.
thermosyphon reboiler A type of reboiler that depends on natural circulation.
TMT Furnace tube metal temperature.
total condenser A condenser that condenses all the overhead vapor of a

column.
tower A vertical vessel containing devices such as trays or

packing, used to perform separations such as distillation or
extraction. A synonymous term is column.
tray efficiency See Murphree tray efficiency.
trays Horizontal devices providing cross-flow vapor-liquid contact

in distillation columns.
vacuum system The system in the overhead of a vacuum crude unit that
generates the subatmospheric pressures in the tower. It may
use steam ejectors, or a combination of vacuum pumps and
steam ejectors.
VGO Vacuum gas oil, a vacuum crude unit sidestream product.
VLE Vapor-liquid equilibrium.
wash zone The section of a crude fractionator between the flash zone and
the first sidestream.


Engineering Encyclopedia: Distillation Process

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Saudi Aramco DeskTop Standards

Chapter : Process For additional information on this subject, contact

VAPOR-LIQUID EQUILIBRIUM (VLE) RELATIONSHIPS ............................... 3

Ideal and Nonideal Gases ............................................................................. 3

EQUILIBRIUM SEPARATION CALCULATIONS............................................. 12

DISTILLATION PROCESS PARAMETERS 20

Conventional Distillation Column.............................................................. 20

Saudi Aramco DeskTop Standards

Effect of Reflux on Required Stages .......................................................... 24

SAUDI ARAMCO DISTILLATION PROCESSES .............................................. 33

Crude Stabilization and Sweetening........................................................... 33

WORK AID 1: CALCULATE VLE PARAMETERS USING THE IDEAL

WORK AID 2: CALCULATE THE WATER VAPOR CONTENT OF

WORK AID 3: DETERMINE THE TOTAL PRESSURE OF AN IDEAL

WORK AID 4: REDUCE THE H2S CONTENT OF CRUDE

Saudi Aramco DeskTop Standards

Saudi Aramco DeskTop Standards 1

1,2 Value refers to component 1,2, ... or measurement 1,2, ...

Saudi Aramco DeskTop Standards 2

VAPOR-LIQUID EQUILIBRIUM (VLE) RELATIONSHIPS

A vapor-liquid system is considered to be in equilibrium when there are no longer any

Ideal and Nonideal Gases

Saudi Aramco DeskTop Standards 3

Ideal Mixtures - Dalton's, Raoult's Laws

Saudi Aramco DeskTop Standards 4

∑PPi = PT = PP1 + PP2 + PP3 + ...

PT = ∑PPi = ∑yi PT = ∑xi VPi

and for component i,

• Propane 13 atm = 191 psia (Component 1).

• n-Butane 3.5 atm = 52 psia (Component 2).

The total pressure, PT, of the mixture can be calculated from:

PT = PP1 + PP2 = x1VP1 + x2VP2

PT = 191x1 + 52(1-x1) = 52 + 139x1

Saudi Aramco DeskTop Standards 5

PROPANE - n-BUTANE SYSTEM PRESSURE

Mixtures Approximated as Ideal

• Total pressure of the system must be below 200 psia.

Saudi Aramco DeskTop Standards 6

Using ideal mixture correlations in calculations results in approximate compositions or

The vapor-liquid equilibrium of an ideal mixture can be described by:

PPi = yiPT = xi VPi

fPPi = yifPT = xifVPi

where: fPPi = Fugacity of i in either phase of the system.

Fi = fVPi PT / fPT = PT yi /xi

Saudi Aramco DeskTop Standards 7

The definition of equilibrium K-value, also called K-factor or distribution coefficient, of

It can also be expressed in terms of fugacities as:

Saudi Aramco DeskTop Standards 8

Saudi Aramco DeskTop Standards 9

Relative volatility is a relation widely used in distillation. It is defined by:

yi PT = PPi = γixi VPi

Saudi Aramco DeskTop Standards 10

SRK equation of state. The Soave-Redlich-Kwong EOS is a two-parameter equation of the

a = • • (1 - cij) ( ai aj ) (xi xj)

Saudi Aramco DeskTop Standards 11

EQUILIBRIUM SEPARATION CALCULATIONS

Saudi Aramco DeskTop Standards 12

Saudi Aramco DeskTop Standards 13

Vapor-Liquid Phase Diagrams

Saudi Aramco DeskTop Standards 14

Bubble Point and Dew Point