Distillation Calculation

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Chapter : Process For additional information on this subject, contact
File Reference: CHE20502 R.A. Al-Husseini on 874-2792
Engineering Encyclopedia
Saudi Aramco DeskTop Standards
Distillation Calculations
Engineering Encyclopedia Process
CONTENTS PAGES
BINARY DISTILLATION..................................................................................... 1
Conventional Distillation Column............................................................... 1
Material Balance Equations......................................................................... 2
Equilibrium Stages ...................................................................................... 7
Total Condenser .......................................................................................... 8
Partial Condenser ...................................................................................... 10
Bottom Section of the Tower..................................................................... 11
Feed........................................................................................................... 13
McCabe-Thiele Diagram........................................................................... 15
Effect of Reflux on Required Stages ......................................................... 16
Minimum Reflux ....................................................................................... 17
Total Reflux - Minimum Stages ................................................................ 18
Stages vs. Reflux ....................................................................................... 19
Multicomponent Distillation...................................................................... 20
COLUMN DESIGN.............................................................................................. 21
Steps in Column Design ............................................................................ 21
Basis .......................................................................................................... 21
Tower Operating Pressure, Temperature................................................... 25
Stages vs. Reflux ....................................................................................... 28
Tray Efficiency.......................................................................................... 29
SIMULATION FUNDAMENTALS..................................................................... 33
Capabilities................................................................................................ 34
Input Data Requirements........................................................................... 34
Characterization of Petroleum Fractions ................................................... 35
Petroleum Fraction Distillations ................................................................ 36
Crude Assays............................................................................................. 41
Component Selection ................................................................................ 43
Thermodynamic Systems In PRO/II
TM
.................................................... 46
Rigorous Distillation.................................................................................. 47
Simulations with PRO/II
TM
...................................................................... 47
Ras Tanura Plant 10 Depropanizer............................................................ 48
Rigorous Simulation with PRO/II
TM
........................................................ 50
Shortcut Distillation Simulations with PRO/II
TM
.................................... 56
Specifications and Control Variables ........................................................ 57
Feed Location............................................................................................ 58
Sidestream Location .................................................................................. 58
Compare Results to Plant Operation.......................................................... 59
Uses of Simulations................................................................................... 59
SIMPLIFIED DISTILLATION CALCULATIONS ............................................. 61
Distillate and Bottoms Compositions ........................................................ 61
Distillate Drum Conditions........................................................................ 63
Temperature and Pressure of Tower Top and Bottom............................... 63
Tower Pressure and Temperature Changes ............................................... 64
Enthalpy Balances ..................................................................................... 66
Other Shortcut Calculations....................................................................... 68
NOMENCLATURE.............................................................................................. 69
Subscripts .................................................................................................. 70
GLOSSARY ......................................................................................................... 71
Saudi Aramco DeskTop Standards 1
BINARY DISTILLATION
Conventional Distillation Column
A conventional distillation column has one feed stream and two product streams (Figure 1).
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.
a
Condenser Q
C
Vapor Distillate
Condenser
Separator
Overhead Liquid Product
D
X
H
D
D
Enriching
or Rectifying
Section
High Boiling Components
From Vapor to Liquid
Low Boiling Components
From Liquid To Vapor
Feed
Stripping
Section
F
X
H
F
F
Reboiler
Q
R
Bottoms Product
B
X
H
B
B
R
Conventional Distillation Column
Figure 1
Material Balance Equations
The algebraic equations obtained by making component balances around two envelopes in the
top section of the column are shown in Figure 2.
Envelope 1:
V
n
y
n
= L
n+1
x
n+1
+ Dx
D
Dividing by V
n
we obtain:
y
n
=
L
n+1
V
n
x
n+1
+
D
V
n
x
D
Envelope 2:
a
c
y
c
Q
x
c
L
c
L
N+1
N
N1
n+1
n
n1
n2
V
n
V
n2
L
n1
L
n+1
(1)
(2)
V
N
Two Material Balance Envelopes
For The Top Section Of A Distillation Column
Figure 2
where:
x,y = Concentrations in the liquid and vapor phase
V = Vapor mole rate
L = Liquid mole rate
D = Distillate mole rate
n,n+1, ... Subscripts indicating tray number
If we assume constant molar overflow:
L = L
n+1
= L
n
= L
n-1

V = V
n+1
= V
n
= V
n-1

The assumption of constant molar overflow depends upon two prior assumptions.
The two components must be assumed to have identical molar heats of vaporization.
All heat effects (heats of solution and heat leak to or from the column) must be assumed
to be zero.
It follows from these two assumptions that a mole of vapor must be formed for each mole of
vapor that condenses within a stage. Therefore, within any section of the column where no
material or energy is added or withdrawn, both the moles of liquid overflow from stage to
stage and the moles of vapor ascending the column must be constant. The material balance
around the two envelopes can then be expressed by the generalized form of the equations:
y
n
=
L
V
x
n+1
+
Dx
D
V
A similar equation can be derived for the bottom section of the tower:
y
n
=
L
V
x
n+1
-
Bx
B
V
where B = Bottoms mole rate.
Since L, F, D, B, x
D
, and x
B
are constant, equations (1) and (2) are linear, of the form:
y = ax - b
and can be represented by a straight line with a slope a = L/V. Such a line, when plotted in an
x-y diagram, is called the operating line.
Each point on an operating line represents the vapor-liquid concentrations of two internal
streams (vapor to a tray, liquid from a tray) that have been cut by the material balance
envelope (Figure 3).
aa
Binary Distillation Operating Line
Figure 3
For a given concentration, xn, of the light component in the liquid leaving tray n, the
operating line can be used to find yn-1, the concentration of the light component in the vapor
entering the tray from below. In conventional distillation
y
n
-1 > x
n
that is, the vapor entering a stage from below is richer in light components than the liquid
leaving the stage. As a result, in conventional distillation the operating line is above the y = x
line.
Equilibrium Stages
The vapor and liquid leaving a stage are in equilibrium. The relationship between the
concentration of their compositions is represented by the equilibrium line (Figure 4). The
point (y
n
,x
n
) on the equilibrium line, for example, represents the concentration of the light
component in the vapor (y
n
) and the liquid (x
n
) leaving the tray.
a
1.0
0 0.25 0.5 0.75 1.0
Equilibrium
Line
Operating
Line
(y , x )
n+1 n+1
(y , x )
n-1 n-1
(y , x )
n n
y
n+1
n+1
n
n1
y
n
x
n+1
y
n1
x
n
x
n-1
(y ,x )
n n+1
x
0.75
0.5
0.25
0
y
(y ,x )
n n-1
Binary Distillation Equilibrium Stages
Figure 4
For a given concentration x
n
of the light component in the liquid, the concentration in the
vapor entering the tray is y
n-1
(from the operating line) and the concentration in the vapor
leaving the tray is y
n
(from the equilibrium line). Given the concentration of the light
component in the vapor or liquid of a stage, Figure 4 can be used to obtain the concentrations
in the liquid and vapor of adjacent stages. For example, a horizontal line at yn must pass
through the point (yn,x
n+1
) on the operating line, since yn and x
n+1
represent passing streams.
Likewise, a vertical line (dotted) at x
n
must intersect the operating line at point (y
n-1
,x
n
). The
equilibrium stages above and below stage n can be located by a vertical line through (yn,x
n+1
)
to find (y
n+1
,x
n+1
) and a horizontal line through (y
n-1
,x
n
) to find (y
n-1
,x
n-1
). You can work
up or down the column through alternating use of the equilibrium and operating lines.
Total CondenserError! Bookmark not defined.
Equation 1 represented the operating line for the top section of the column as:
y
n
=
L
V
x
n+1
+
D
x
D
V
The operating line can be constructed if two points are known or if one point and the slope are
known. Usually, the known point is the intersection of the operating line with the 45
diagonal (y = x). The slope is L/V.
The top equilibrium stage in a column is the condenser/overhead drum (N+1). If the
condenser is a total condenser, then the concentration of components in the column overhead,
y
N
, and the liquid distillate, x
N+1
or x
D
, are the same:
y
N
= x
D
This signifies that the (y
N
,x
D
) point of the operating line lies on the diagonal y = x line
(Figure 5).
a
1.0
0 1.0
Equilibrium
Line
x
D
0
y
x
D
=x
c
=y
N
x
N
x
N-1
y
c
y
N
y
N-1
Dx
D
V
x
Binary Distillation Total Condenser
Figure 5
For a total condenser with no subcooling, the slope of the operating line is:
L
V
=
L
N+1
V
N
=
RD
1+R D
=
R
1+R
where R is the external reflux ratio
R = L
N+1
/D
If the reflux is subcooled, the additional liquid condensed on the top tray has to be taken into
account in order to calculate the internal reflux ratio L/V.
Partial Condenser
A partial condenser condenses only part of the overhead vapor. The vapor and liquid
produced are in equilibrium; therefore, the point (y
c
,x
c
) is on the equilibrium curve. If all the
condensed liquid is returned to the column while all the vapor is withdrawn for overhead
product (Figure 6a), then D
v
= D and y
c
= x
D
, where D and x
D
refer to the total overhead
product.
a
N
N-1
N-2
(a)
D = D
V
N
Q
C
y
C
x
C
L
N + 1
V
N
N-1
N-2
(b)
D
V
N
Q
C
y
C
x
C
L
N + 1
V
x
C
x
D
D
D
L
y = x
C D X =
D
D y + D x
v L c
D + D
v L
Vapor Product Vapor and Liquid Product
c
Partial Condenser
Figure 6
If both vapor and liquid are withdrawn as product (Figure 6b), then D = D
v
+ D
L
and
x
D
=
D
V
y
c
+ D
L
x
c
D
V
+ D
L
Just as with a total condenser, the top operating line must always intersect the y = x diagonal
at x
D
regardless of the way the product is withdrawn (Figure 7).
a
x
D
x
c
x
N
y
N
y
N-1
y
c
y
x
x
D
x
c
x
N
y
N
y
N-1
y
c
y
x
(a)
(b)
Partial Condenser
Figure 7
Bottom Section of the Tower
A similar approach can be used to derive similar equations and graphical representations for
the bottom of the column. Figures 8 and 9 illustrate the differences between two types of
bottoms drawoffs.
In Figure 8 the bottoms product is withdrawn from the tower, and it has the composition
of the liquid leaving Tray 1. The reboiler vaporizes all liquid.
In Figure 9 the bottoms product is withdrawn from a kettle type reboiler. In this case x
B
is in equilibrium with y
R
and x
B
< x1.
The figures show that the kettle reboiler provides an additional stage. The more common
recirculating reboilers withdraw material from the bottoms product line, similar to Figure 8.
However, they vaporize only part of the liquid. These reboilers provide less than one
theoretical stage, the exact number depending on the fraction vaporized and on the tower
bottom internals. In some arrangements, the bottom product and the reboiler feed are drawn
from the tower bottoms by separate nozzles. Baffles direct the recirculated reboiler liquid to
the product drawoff nozzle providing nearly one theoretical stage. (See ChE 205.05,
Drawoffs).
a
y
x
x
I
= x
B
3
2
1
x
2
y
1
y
2
x
1
R
y
y
1
Q
R
y
R
B
x =x
1
x
2
B
B, x
Bottoms Product from Tower - Recirculating Reboiler
Figure 8
a
Q
R
y
R
3
2
1
x
2
y
1
y
2
x
1
D, x
D
0
B
x
1
x
2
x
y
x
R
y
y
1
Bottoms Product from Reboiler - Kettle Reboiler
Figure 9
Feed
The effect of a feed on the internal phase rates in the column depends on the thermal
condition of the material introduced. The feed may be anything from a subcooled liquid to a
superheated vapor. The thermal condition of the feed stream is represented by q, defined by:
q =
heat to convert 1 mole of feed to a saturated vapor
molar heat of vaporization
For a partially flashed feed at the feed-stage conditions, q is simply the fraction of the feed
that is liquid. The following values of q result from these definitions.
Subcooled liquid feed : q > 1.0
Feed at bubble point : q = 1.0 Vertical
Partially flashed feed : 1.0 > q > 0
Vapor feed at dew point : q = 0 Horizontal
Superheated vapor feed : q < 0
In an x-y diagram, the thermal condition of the feed is represented by the q line. The q line
starts from the diagonal x = y line, at x = x
F
. The slope of the q line is equal to q/(q-1). The
two operating lines (above and below the feed) intersect each other on the q line, at some
point between the equilibrium curve and the x = y diagonal. Figures 10a and 10b illustrate
the q line and its possible positions.
a
1.0
0 1.0
q Line
x
0
y
x
F
q Li ne
(a)
1.0
0 1.0
q > 1
x
0
y
q = 1
q = 0
q < 0
1.0 > q > 0.0
x
F
q-Line Position
(b)
FIGURE 10
McCabe-Thiele Diagram
The graphical representation of a distillation column in x,y axes through its operating and
equilibrium lines is called a McCabe-Thiele diagram. Figure 11 is a McCabe-Thiele diagram
for an eight-stage distillation column with a total condenser and a kettle type reboiler.
a
1.0
0 1.0
x
F
x (Liquid Mole Fraction)
Q
C
D
V
8
V
1
L =B
1
L
2
Q
R
F
8
7
5
4
3
2
Reboiler i s Tray 1
q Line
8
7
5
6
4
2
3
1
x
D
0
x
B
6
Binary Distillation: McCabe-Thiele Diagram
Figure 11
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.
Effect of Reflux on Required Stages
Figure 12 illustrates the effect of reflux on the required stages to achieve a specified
separation (x
B
,x
D
). We observe that the required stages increase as the reflux is decreased
and the operating line slope reduced. When reflux is reduced, the number of required stages
is increased.
a
1.0
0 1.0
x
B
Q
C
D
V
13
V
1
L =B
1
L
2
Q
R
F
Reboi ler is Tray 1
q Line
5
4
2
3
1
x
D
13
12
11
9
8
7
6
5
4
3
2
10
Higher
Reflux
Reduced Reflux
Lower Slope
More Stages
6
x
F
x
Effect of Reflux on Required Stages
Figure 12
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 13). 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 x minimum reflux.
a
V
1
L =B
1
L
2
8
7
5
4
3
2
9
10
6
Infinite
Stages
Min. Reflux
L/V
X
D
q Line
X X X 1.0
1.0
y
0
F B
X
1
Minimum Reflux
Figure 13
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 14). A material
balance around either end of the column and cutting between any two stages will show that
for any stage n,
L
n+1
= V
n
, L/V = 1.0, x
n+1
= y
n
a
4
1.0
0 1.0
Q
C
D = 0
V
8
V
1
L = B = 0
1
L
2
Q
R
6
5
4
3
2
Equilibrium
Line
x
D
Operating
Line
Slope = 1.0
y
6
5
1
3
2
x
x
B
Total Reflux - Minimum Stages
Figure 14
There is one operating line for the entire column passing through x
B
and x
D
, 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 vs. 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 15.
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 only by a
very large reflux increase.
a
Minimum Number Of Stages
Refl ux
Stages vs. Reflux
Figure 15
Multicomponent Distillation
The operation of a multicomponent distillation column with c components (i = 1, 2,...c) and N
stages (n = 1, 2,...N) can be described by three sets of equations: equilibrium, material
balance, and enthalpy balance. These equations are solved numerically by computers. (F =
feed rate, f = feed stage)
y
ni
= K
ni
x
ni
n = 1, 2, ..., N
Equilibrium
relationships
y
ni
i=1
c
= 1
n = 1, 2, ..., N
x
ni
i=1
c
= 1
n = 1, 2, ..., N
V
n+1
y
n+1,i
= L
n
x
ni
+ DX
Di (n = 1, 2, ..., f-2)
Material
Balances
V
f
y
fi
+ V
F
y
Fi
= L
f-1
x
f-1,i
+ DX
Di
V
n+1
y
n+1,i =
L
n
x
ni
Bx
Bi (n = f, f+1, ..., N-1)
FX
i
= DX
Di
+ Bx
Bi
V
n+1
H
n+1
= L
n
h
n
+ DH
D
+ Q
c (n = 1, 2, ..., f-2)
Enthalpy
Balances V
f
H
f
+ V
F
H
F
= L
f-1
h
f-1
+ DH
D
+ Q
c
V
n+1
H
n+1
= L
n
h
n
- Bh
B
+ Q
R
(n = f, f+1, ..., N-1)
FH = Bh
B
+ DH
D
+ Q
c
- Q
R
COLUMN DESIGN
Steps in Column Design
Below is a list of steps typically followed in designing a distillation column. The following
sections focus on some of the key steps.
Define basis.
Determine operating conditions: pressure, temperature.
Perform distillation simulations.
Estimate tray efficiencies.
Design hardware.
This section covers the basis, operating conditions, and tray efficiencies. The following
section covers simulation fundamentals. Hardware design is covered in Module 5.
BasisError! Bookmark not defined.
Feed Rate and Composition
Feed rate and composition are normally determined by upstream processing. However, the
following points should be considered: Has the feed basis been sufficiently defined? If the
feed rate and/or composition will be affected by expected changes in upstream processing,
has the limiting case been selected? Will it be necessary to study other cases? If more than
one feed is involved, are the feeds sufficiently different to consider feeding to different trays?
Product Recovery and Purity
Product specifications, which are often based on the requirements of downstream processing,
are usually expressed as concentrations of specific components. Sometimes, however,
product specifications are defined in terms of such qualities as vapor pressure, flash point, and
viscosity. For some specifications, stage-to-stage iterative calculations cannot be converged
directly. In these cases it becomes necessary to relate the product-stream quality specification
to the concentration of a specific component or group of components in the product, so that
the design alternatives can be evaluated. This is why key components should always be
selected. Their separation serves as an effective measure for adjusting a design to meet the
required specifications.
A product often has multiple specifications on component concentrations. When possible
changes in operating conditions or multiple product specifications exist, the engineer must
select the limiting design basis for the process calculation and equipment sizing. For most
operation alternatives, the limiting design will be obvious by inspection. Others may require
a short-cut evaluation to select the limiting case of key component split and/or feed
concentration and rate.
Once the product specifications are established, recovery objectives may be similarly set or
may be a legitimate subject for economic study. For an economic study, the relative recovery
and total composition of the product streams can be varied over a limited range within the
specifications by adjusting such variables as reflux and number of stages until the economics
of the design are optimized. Another product recovery consideration is whether the product
stream should be a vapor or a liquid. The choice between vapor or liquid product is usually
established by operations in the downstream unit. However, it can also be influenced by such
items as control scheme, energy conservation, and intermediate storage capabilities.
Feed Condition
It is often desirable to change the thermal condition of the feed. The thermal condition of the
feed, also called the feed quality or vaporization, influences the reflux ratio and reboiler duty
required for a given separation. The following factors should be considered in choosing the
feed condition (Figure 16).
a
Feed Preheat
Figure 16
If cooling or heating is particularly expensive in a given situation, the optimum will shift
towards a lower consumption of the more expensive utility. For example, if the column
reflux is expensive (e.g., obtained by refrigeration), reflux requirements can be
minimized by cooling the feed. Conversely, if reboiling is expensive, this requirement
can be reduced by increasing the degree of feed vaporization.
The feed condition also affects the internal tower loadings, the vapor and liquid rates.
Vaporized feeds, for example, increase the vapor and liquid loadings above the feed,
requiring a larger tower diameter and investment. In existing units, the hydraulic
capacity of the tower and the condenser and reboiler capacities may limit the feasible
feed temperature range. A good starting point for column calculations is to preheat the
feed to its bubble point.
Occasionally, heat economy will provide an incentive to increase feed preheat to the
extent that it can be obtained by heat exchange with the bottoms; energy will be
conserved that otherwise would have been wasted.
In a sequence of towers, the feed to a downstream tower is usually produced directly off
the distillate drum or the bottoms of the previous tower. The condition of this feed can
be adjusted to give the lowest overall total cost in terms of utility costs and investments
for the towers. Alternatives for towers in sequence can lead to very complex
optimization problems. Such evaluations are usually not made unless the utility costs
are high.
Variability of Conditions
Distillation calculations are based on steady-state operation. It is also assumed that the feed
composition, feed and product rates, and product specifications are all well defined.
However, this is seldom the case in actual operation. Small fluctuations in operating
conditions will occur; they can be handled by an effective control system provided they occur
over a range reasonably close to the design basis. In addition to the small fluctuations that
can be controlled, large fluctuations that require major changes in tower operation can be
caused by:
Changes in feed composition resulting from projected changes in raw materials (crude
oil, or feedstocks) to be processed.
Changes in the operation of upstream units when different grades of products are made
or when different raw materials are processed.
Changes in throughput due to low initial demand or seasonal fluctuations.
Changes in product purity due to seasonal variations or different grades of product.
Tower Operating Pressure, Temperature
Tower 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. In many cases, the
refrigeration temperature levels are established by considering the requirements for a
number of steps in the process: they will not necessarily be optimum for a given step.
Factors such as the availability of refrigerant fluids, type of compressor, and the number
of compressor stages are also important in such an analysis.
Lower pressure increases the relative volatility and improves the ease of separation.
Therefore, the total stages and/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.
The reboiler must operate below the critical conditions of the bottoms stream. Usually,
the design is limited to an approach of about 50F to the critical temperature. This can
sometimes limit the maximum pressure in a column, particularly in light hydrocarbon
towers.
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. Fouling can be caused by the polymerization of materials such as
diolefins. Lower reboiler temperatures also minimize degradation of gas treating amines
such as DGA.
Subcooling external reflux will increase the internal reflux. Therefore, subcooled reflux
will reduce the overhead vapor rate and the external reflux rate required for a given
separation, but the required internal reflux will remain the same.
The overall design approach usually resulting from considering these factors is to select the
lowest design pressure in accordance with the allowable approach to the cooling medium
temperature. If the resulting reboiler temperature, at the design condenser pressure plus the
estimated pressure drop through the tower, is too high, then the tower overhead must be
refrigerated. In this case, the required reboiler maximum temperature is set first. Then the
reboiler pressure is determined. Finally, the condenser temperature and pressure are
established. When excessive fouling conditions are encountered, a quick economic
evaluation may be required to establish whether refrigeration or a spare reboiler should be
used.
Although the tower operating pressure is normally established as a design constraint,
occasionally it can be considered a design parameter. For example, in a high-pressure
superfractionator with large reflux requirements, such as a propylene-propane splitter, a
possible design alternative to reducing reflux or stage requirements is a lower pressure
operation with a refrigerated tower overhead. This is described graphically in the McCabe-
Thiele Diagram for a binary mixture in Figure 17.
a
1.0
x (Liquid Mole Fraction)
1
2
2
3
4
5
3
6
7
8
4
9
5
10
6
11
7
x
D
Slope = R/(R + D)
Upper
Operating Line
x
q Line
F
Lower
Operating Line
Equilibrium Line @ P
1
Equilibrium Line @ P
2
Dx
x
B
0.8
0.6
0.4
0.2
0
0 0.2 0.4 0.6 0.8 1.0
P < P
2 1
1
D
R + D
Effect of Column Pressure on Distillation:
McCabe-Thiele Diagram
Figure 17
Figure 17 shows that if the same degree of fractionation is to be maintained, the points x
B
and
x
D
must remain fixed. Decreasing the pressure from P
1
to P
2
raises the equilibrium curve.
Therefore, for the same reflux ratio (same operating line slopes) fewer stages (7 compared to
12) are required to effect the same separation. Conversely, for the same number of stages, the
operating line slopes must change. This translates to lower reflux requirements.
Stages vs. Reflux
In many tower systems, the economics are sensitive to the number of stages and the
corresponding reflux. In complex or expensive tower systems it may be desirable to study
this relationship. Occasionally, there is an economic incentive in terms of energy costs to
reduce reflux requirements as far as practical. This limit is usually set by the accuracy of
estimates for vapor-liquid equilibrium ratios. For such cases, it is necessary to establish
minimum reflux requirements.
Minimum reflux is the lowest reflux that can be used to obtain the desired separation in a
hypothetical tower having an infinite number of stages. The binary McCabe-Thiele diagram
in Figure 12 showed that as the reflux ratio is reduced, the slope of the enriching section
operating line decreases until one of the operating lines first intersects the equilibrium curve
(Figure 13). At this point, called pinch, an infinite number of stages is required for a given
separation. In a multicomponent system, one way of getting a good estimate of the minimum
reflux is by stage-to-stage techniques. This is done by running a series of cases with
increasing stages and the desired specifications. As shown in Figure 15, the cases are plotted
as reflux versus stages and extrapolated to find the minimum reflux. This can be expensive in
terms of computer time. Alternatively, the PRO/II
TM
distillation shortcut option provides
approximate minimum reflux, total reflux, and intermediate points.
The best reflux is the one that provides the best economics in terms of total cost. The total
cost must take into account investment for the tower, reboiler, and condenser and the
operating costs, mainly reboiler heat. Figure 18 represents typical cost curves. The most
economical reflux often ranges between 1.1 and 1.5 times the minimum reflux ratio, with
superfractionators closer to 1.1 and columns providing rough separation closer to 1.5.
a
Total Cost
Operating
Cost
Investment
Cost
1.5 1.0
R/D/(R/D) min.
Cost
Economic Balance Between Plates and Reflux
Economic Balance Between Stages And Reflux
Figure 18
Tray Efficiency
Definitions
Point Efficiency, E
OG
. The point efficiency E
OG
is a measure of the effectiveness of vapor-
liquid contacting at a given point on a tray. It expresses the actual separation in a differential
volume element of tray liquid (point), compared to the theoretically obtainable separation at
equilibrium:
E
OG
=
y
p,n
- y
p,n-1
y
*
p,n
- y
p,n-1
where:
EOG = Point efficiency, dimensionless.
y
p,n
= Mole fraction of a component in the vapor leaving a given point on tray n.
y
p,n-1
= Mole fraction of a component in the vapor entering a given point on tray n
(coming from tray n-1).
y*
p,n
= Mole fraction of a component in the vapor which would be in equilibrium
with the liquid at a given point on tray n.
Point efficiency is a function of the mass transfer properties of the system and the quality of
contact between vapor and liquid (clear liquid height, froth height, froth density).
Tray Efficiency, EMV. The tray efficiency EMV is a measure of the contacting effectiveness of
an entire tray. It is defined in terms of average compositions from the whole tray:
E
MV
=
y
n
- y
n-1
y
*
n
- y
n-1
where:
EMV = Tray (Murphree, vapor) efficiency, dimensionless.
y
n
= Average mole fraction of a component in the total vapor leaving tray n.
y
n-1
= Average mole fraction of a component in the vapor entering tray n (coming
from tray n-1).
y*
n
= Mole fraction of a component in the vapor which would be in equilibrium
with the liquid leaving tray n.
Tray efficiency is a function of the point efficiency and the quality of mixing on the tray.
Overall Efficiency, EO. 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. EO is related to EMV and the relative slope of the equilibrium and operating
curves.
Additional information on tray efficiencies can be found in the following distillation books:
H. Z. Kister, DistillationDesign; M. J. Lockett, Distillation Fundamentals; B. D. Smith,
Design of Equilibrium Stage Processes; or Perry's Chemical Engineer's Handbook.
Approximate Tray Efficiencies
Approximate tray efficiencies for hydrocarbon mixtures can be predicted using the fluidity
method, Figure 19.
Reprinted from J. B. Maxwell, Data Book on Hydrocarbons, P. Van Nostrand Co., Inc., pg
245.
a
120
110
100
90
80
70
60
50
40
30
20
10
120
110
100
90
80
70
60
50
40
30
20
10
1 2 3 4 5 6 7 8 9 10 11 12 13 14
Average Fluidity of Liquid on Plates, (Centipoises)
-1
Onl y Data on Hydrocarbon Mixtures Were
Used in This Correlation, and There Were
Insufficient Data on Other Types to Justi fy
a More General Use. However, There
Was Some Evidence that the Curve Is a
Littl e Conservative for Alcohol-Water
Mi xtures.
Approximate Tray Efficiencies - Fluidity Method
Figure 19
Approximate tray efficiencies for a wider variety of separation systems can be predicted using
the viscosity-volatility method in Figure 20 developed by F. J. Lockhart and C. W. Leggett.
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. Efficiencies from plant data (next section) are
more reliable, especially when there are data from several units.
Source: Equilibrium-Stage Separation Operations in Chemical Engineering by E. J. Henley and J. D. Seader,
Copyright , 1958. Reprinted by permission of John Wiley and Sons Inc.
Approximate Overall Tray Efficiencies
Viscosity-Volatility Method
Volatility
Fractionators: Relative volatility of key components.
Hydrocarbon Absorbers: 10 times the K value of the key component.
Adapted from E. J. Henley, J. D. Seader, Equilibrium-Stage Separation Operations in
Chemical Engineering.
Figure 20
Efficiencies from Plant Data
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 21.
Above Feed Below Feed
Crude Stabilizer 25
Atmospheric Crude Unit
Top 70-80
Bottom (above Flash Zone) 50-60
NGL Fractionation 90 65-85
(DeC
3
..DeC
5
) (Low-end if
very heavy
components
are present)
Reformer Feed Stripper 85 75
Kero/Diesel Hydrotreater
Stripper 80-90 30-35
H
2
S/Amine Absorber 10-25
Typical Overall Efficiencies, %
Figure 21
SIMULATION FUNDAMENTALS
Flowsheet Simulations are steady-state models of one or more process unit operations. The
most common unit operations used in simulations of distillation operations are the distillation
towers themselves, sidestrippers, flashes, and compressors. Other unit operations often found
in
simulations include reactors, and heat exchangers.
Figure 22 is a diagram of a depropanizer. It is a typical distillation tower with associated pre-
heat exchanger, condenser, distillate drum, and reboiler. For any number of reasons, as
discussed later, a simulation of the unit may be required. Information needed for the
simulation includes feed composition, temperature, and pressure, pre-heater duty and/or outlet
temperature, tower parameters such as the number of trays and pressures, condenser type and
duty, reflux rate, and , reboiler type and duty. With this information, a simulation could be
constructed to answer many questions about the process. Some of these answers could be
obtained from plant tests. However, plant tests are costly and cannot be used to evaluate
potential major process revamps.
a
120 F
C
C
i-C
n-C
i-C
n-C
C
C
2
3
4
5
6
4
7
5
+
0.2%
44.7%
6.7%
21.5%
6.7%
9.7%
6.2%
4.3%
Feed
Q = 23.3
MM Btu/hr
P = 267 psig
Data From Dwg NA-637118
Sh 1 of 8, Rev. 1
Summer Conditions
276 F
P = 272 psig
0
1
29
30
43
Reflux
10 - C.1
Depropanizer
130 F
0
262 psig
Disti llate
Sour Propane
to ADIP
Treaters
150 psig Steam
Condensate
Bottoms To
Debutanizer
Ras Tanura Plant 10 Depropanizer
Figure 22
Capabilities
Commercial simulation programs such as PRO/Il
TM
and HYSIM
TM
allow the use of large
numbers of components, including molecular components and petroleum fraction
pseudocomponents. These programs have pre-defined unit operation modules for each of the
processes listed above. The user defines an array of parameters for each of the unit operation
modules and defines the sequence of streams linking the modules in the flowsheet. Parameters
defined by the user include feed stream composition, temperature, enthalpy, the unit
conditions, and product specifications.
Additional features of the programs include tower hardware (tray and packing) rating and
design correlations, stream calculator and report writer, single and multi-variable controller
for optimization, and facilities for adding user-written subroutines.
The wide array of capabilities offered by commercial simulation programs make steadystate
flowsheet modeling a powerful tool for design, process improvement, troubleshooting,
debottlenecking, and many other uses.
Input Data Requirements
Several types of data are required for flowsheet simulation. Rates, temperatures, pressures,
and compositions must be specified for all feed streams. Compositions can be defined by
slates of one or more pure components (i.e. butane) or by slates of petroleum fraction
pseudocomponents. As discussed later, the breakdown, or division, of the fraction must be
specified.
Thermodynamic methods are defined, either for the entire flowsheet or for individual unit
operations. Examples include various equation-of-state models and liquid phase activity
coefficient models. The choice of the thermodynamic method is important since different
models can yield very different vapor-liquid equilibrium behavior.
Also needed are parameters describing the unit operation models, such as the distillation
tower itself and associated sidestrippers. Examples include: tower top and bottom pressures,
type of condenser (e.g. partial or total), number of theoretical stages, position of sidestream
draws, and feed location.
Each simulation program solves the mass and energy balance equations to give the unique
solution to the process problem. However, each program allows different solution techniques.
The solution techniques are called convergence algorithms. Although the programs each have
a default method, the user can choose from a number of different methods if the solution is
problematic. For example, the PRO/II
TM
Rigorous Distillation Module offers the IO (Inside-
Out; default), the SURE, and the CHEMDIST convergence algorithms. All methods result in
the same answer to a problem.
The specifications and control variables are probably the most crucial and most often
overlooked input data items in a simulation. Specification variables are defined by the user.
Examples are product rates and qualities that must be achieved by the process simulation.
They are fixed by the user in the simulation at defined values. On the other hand, control
variables are varied to meet the values defined for the specifications. The simulation program
adjusts the control variables until the values of the specifications are attained. More
information regarding specifications and control variables is provided in a later section.
Except in rare circumstances, distillation simulation programs such as PRO/II
TM
do not require
the user to provide initial solution estimates. However, PRO/II
TM
does require the user to
choose a initial estimate generation method. Methods include those for conventional and
refining applications. In some cases, an initial solution estimate (e.g. vapor and liquid loading
profiles) may be necessary for solution convergence.
Characterization of Petroleum Fractions
To understand how to simulate unit operations that process crude petroleum or petroleum
fractions, it is necessary to review information about their nature, analysis, and representation
as narrow fractions or pseudocomponents.
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 1000F. Because of the large number of components involved, a
complete component-by-component analysis of a crude oil sample is not practical. For this
reason, the composition of any given oil is approximated by a true boiling-point distillation,
commonly called TBP or 15/5 distillation. This method is a batch distillation using a large
number of stages (15) and a high reflux-to-distillate ratio (5:1) so that the temperature at any
point on the temperature-volumetric yield curve represents the actual (true) boiling point of
the hydrocarbon material present at that volume percentage point.
TBP distillations are time consuming and are normally run only on crude oils and not on
petroleum fractions. Instead, a faster distillation procedure is used to analyze petroleum
products and intermediate fractions. These procedures were developed by the American
Society for Testing Materials and are called ASTM distillations. These methods are rapid
batch distillations employing no trays or reflux between the stillpot and the condenser. The
only reflux available is that generated by heat losses from the apparatus. These test methods
are used in control laboratories throughout the world and products are generally transferred
with ASTM specifications. In recent years, refineries started employing gas chromatography
distillation (GCD) analyses for products. GCD produces results equivalent to TBP
distillation.
Petroleum Fraction Distillations
A complete component-by-component analysis of crude oil or its fractions is not practical
because of the large number of components. For this reason, the composition and the
vaporization characteristics of petroleum fractions are represented by various distillation
methods. Of these, the ASTM and 15/5 or TBP (true boiling point) are the most widely
accepted and best standardized. The simple, inexpensive ASTM distillation is universally
preferred for routine product testing and refinery operation control. Although seldom
available, data on a 15/5 basis are required for refinery planning, engineering, designing
fractionator towers, and evaluating major refining processes.
15/5 Distillation
15/5 is a standardized, accurate laboratory batch distillation that is used for crude assays and
feed or product separations. The fractionator has 15 theoretical plates, calibrated under total
reflux conditions, and is operated adiabatically with automated reflux of total condensate.
The reflux ratio employed is 5:1 at atmospheric pressure and 2:1 at low pressures (2-10 mm
Hg absolute). A maximum vapor temperature of 430
F is normal for atmospheric operations,

while 700
F is the maximum atmospheric equivalent vapor temperature (
F AET) for
operations at 10 mm pressure. The usual practical limit at 2 mm Hg absolute is 800
F AET.
Generally, 15/5 vapor temperatures are approximations of true boiling points; they are not
necessarily equivalent to those from an efficient analytical distillation such as GCD.
The term true boiling point (TBP) is ambiguous. Theoretically, a TBP distillation utilizes a
distillation system that is able to make very close separations; each compound present in the
mixture will thus be separated at its own boiling point and in the quantity present in the
original mixture. The concept is illustrated in Figure 23 for two components A and B boiling
at T
A
and T
B
at the total pressure of the distillation. The stepwise plot (solid lines) represents
an ideal TBP distillation. Component A, boiling at a lower temperature, is recovered first.
Recovery of Component B starts after all of Component A is recovered. The distillation
temperature then increases to T
B
.
a
T
T
B
TA
0 100
Percent Distilled
Stepwise Plot of an Ideal TBP Distillation
Figure 23
The smooth curve in Figure 23 (broken line), represents an actual curve with imperfect
fractionation, such as results from a 15/5 distillation. Recovery of Component B starts before
the recovery of A is complete. As a result, the temperature of the distillation increases
gradually, reflecting the increasing concentration of B in the distillate.
Figure 24 shows similar curves for a mixture with seven components. If the mixture, like
most petroleum fractions, contains many components, the TBP or 15/5 fractionation will
produce a smooth curve (Figure 25).
a
T
0 100
Percent Distilled

a
0 100
Percent Distilled
T
TBP Curve for Seven Components TBP Curve of a Complex Mixture
Figure 24 Figure 25
ASTM Distillations
ASTM distillation procedures were developed by the American Society for Testing Materials.
These methods are rapid batch distillations that employ no trays or reflux between the stillpot
and the condenser. The only reflux is that generated by heat losses from the apparatus.
ASTM test methods are used in control laboratories throughout the world.
ASTM distillation data are considered to be roughly equivalent to those from a one-plate
batch distillation. Figure 26 lists common ASTM distillations for petroleum products.
ASTM Range Pressure
Maximum Vapor
Temp.,
F
Reproducibility
,
F
D-86 Naphtha and Atm 480 5 - 10
Group 1&2 Kerosene
D-86 Middle Atm 760 5 - 10
Group 3&4 Distillates
D-158 Distillates Atm 760 Not Defined
and Gas Oil
D-1160 Heavy Atm 620 15 - 20
Distillates &
Residua
under vacuum
D-216 Natural Atm
Gasoline
ASTM Distillation Procedures
Figure 26
In ASTM distillation, the thermometer reading when the first drop is recovered is the initial
boiling point (IBP).
The amount of distillate collected in the graduate may be recorded at specified temperature
intervals, or the temperature may be recorded when the amount of distillate reaches specified
levels. The maximum temperature, when the last vapor comes off, is recorded as the end
point or final boiling point (FBP).
The total amount of distillate collected is recorded as the recovery, and the volume of material
(if any) remaining in the flask is recorded as the residue. The difference between the volume
of the initial sample and the sum of the recovery and residue, is the distillation loss.
Gas Chromatographic Distillation (GCD)
Gas chromatographic analytical techniques are used to obtain a breakdown of components in
petroleum fractions. The results are automatically converted by a computer associated with
the instrument into distillations that approximate 15/5 results.
Equilibrium Flash Vaporization (EFV)
A flash curve indicates the relative amounts of feed vaporized as a function of the flash
temperature (Figure 27). Pressure is constant. The amount vaporized is usually expressed as
a fraction or percentage of the feed on a mole, weight, or volume basis.
a
F, z
1
V, y
1
L, x
1
T, P
0.0 1.0 V
o
Constant Pressure
Equilibrium Flash Curve
Equilibrium Flash Vaporization
Figure 27
The separation between light and heavy components in a flash separation is relatively poor,
because there is only one equilibrium stage. The vapor product is in equilibrium with the
liquid product, and the flash curve is relatively flat when compared to the curves from
multistage distillation processes.
EFV curves are seldom run because of the time and expense involved. They are almost
always limited to crude oil or to reduced crude samples (atmospheric tower bottoms liquid)
that are being evaluated as vacuum tower charge stocks. The EFV initial boiling point is the
bubble point of the fraction under study, and the EFV final boiling point is its dew point.
Distillation Curve Relationships
Figure 28 illustrates the difference in the shapes of 15/5, ASTM, and EFV curves. The
steepest curve is the 15/5 because it provides the best separation between the components.
EFV is relatively flat, reflecting the poor separation obtained from one-stage flash.
Techniques for converting the results of one method to another will not be covered here.
Conversion techniques can be found in the API Technical Data Book.
a
0 10 20 30 40 50 60 70 80 90 100
LV % Di stilled
Constant Pressure
Distillation Curves
Figure 28
Crude Assays
The complete and definitive analysis of a crude oil, usually called a crude assay, is
considerably more detailed than a TBP curve and a whole crude API gravity. A complete
crude assay will contain some or all of the following:
Properties such as whole crude gravity, viscosity, sulfur content, and pour point.
Plots of properties such as TBP curve, mid-volume plot of gravity, viscosity, sulfur.
Light-ends analysis through C
8
and C
9
.
Properties of fractions (naphthas, middle distillates, gas oils, and residua) -- yield as
volume percent, gravity, sulfur, viscosity, octane number, diesel index, flash and fire
point, freeze point, smoke point, pour point, vapor pressure, etc.
Properties of lube distillates, if the crude is suitable for the manufacture of lube
basestocks.
Properties of asphalts, if the residua have suitable characteristics for preparation of
asphalts.
Detailed studies of fractions for various properties, such as octane number versus yield
for naphthas or viscosity versus yield for lubestocks.
EFV curve run at atmospheric pressure and/or phase diagram, although this is rarely
done.
Curves from the Saudi Aramco assay of Abqaiq GOSP 283 are shown in Figure 29. The
curves provide TBP, gravity, and sulfur content data.
Crude Assay Curves
Figure 29
Component Selection
Heavy Hydrocarbons Applications
For heavy hydrocarbon distillation the feed or feeds can be broken into a number of
pseudocomponents, or narrow boiling fractions. The optimal number and spacing of these
pseudocomponents depend on the application. Typically, 50 or more pseudocomponents are
used to describe a single crude oil. The results are more accurate when a large number of
components is used. However, the number of components representing a system in computer
simulations of distillation columns affects execution time for the program and the amount of
printout that the engineer receives and analyzes. Also, some simulation programs limit the
number of components they can accept. In selecting the components, the engineer may
consider the following:
It is not desirable to represent wide boiling ranges or very large quantities by single
components.
A better definition of the system (more components) is needed:
- At the point where the split is made.
- Around product quality specifications (e.g., 95% ASTM).
Distillation columns with multiple products, for example, atmospheric crude units need
more components than two-product columns. Breakdown of crude to 50 - 100
components for the simulation of an atmospheric crude unit is common.
When product specifications are used as simulation specifications (e.g., 95% ASTM),
too few components may result in discontinuities in properties, convergence difficulties,
and erratic results.
Very few components are needed to represent heavy petroleum fractions that remain in
the liquid phase.
As a general rule, no single pseudocomponent should be defined to cover a wide boiling
range. An exception is permitted for vacuum resid or similar material where assay data is
undefined, quality specifications may not be stringent, and the material has a single
disposition (e.g. asphalt).
Computer simulation programs such as PRO/Il
TM
can be used to break heavy hydrocarbon
streams into pseudocomponents. Generally, hydrocarbons with more than five or six carbon
atoms are represented by pseudocomponents. These narrow fractions are defined by their
volume average boiling points and average gravities. In other words, molecules boiling within
a certain range are represented in the simulation as one component.
Figure 30 illustrates the division of a petroleum fraction into 11 pseudocomponents. The
fraction shown in the figure is divided into pseudocomponents of regularly spaced volume
percent off (5, 10, 20, 30, 45,..., LV% off). The fraction could have been divided into
pseudocomponents by regular boiling temperature ranges.
aa
TBP
1 2 3 4 5 6 7 8 9
11
10
0 5 10 20 30 60 70 80 90 40 50 95 98 100
Vol. %
Divide TBP Curve Into
Pseudocomponents
Pseudocomponent Breakdown
Figure 30
A larger number of pseudocomponents should be defined over the boiling range including a
nominal cut point or a product quality specification. A larger number of pseudocomponents
allows better characterization of fractionation and hence, better characterization of stream
properties dependent on the characterization of fractionation.
Property Correlation Discontinuities
It is important to note that some physical property correlations have numerical discontinuities.
For example, a correlation for a property may be linear over a range of low temperature, while
over a higher range of temperatures the correlation may be quadratic. At the temperature
where the two correlations intersect, the predicted property may be ill-defined or
discontinuous. If values of the property are specified in the simulation, more
pseudocomponents should be defined over the boiling range or the simulation may not
converge.
Key Components and Light Ends Applications
For simulation of a conventional distillation column with specific components (e.g., propane
and butane), it is convenient to define key components for a separation. These keys are
usually defined as light and heavy. The light key is the lightest component expected to exist in
significant quantity in the bottoms product. Similarly, the heavy key is the heaviest
component expected to exist in quantity in the overhead distillate. The intermediate
components are then called intermediate or distributed keys.
When key components are defined, it is much easier to specify and identify the degree of
separation achieved in the simulation. For example, it may be desired to fractionate a mixture
of components into an overhead with no more than 0.5 wt.% of the light key in the bottoms
product and no more than 0.5 wt.% of the heavy key in the overhead distillate. These
concentrations can be specified in the input data and recorded in the output data with
reference to the key component names. Key components are defined to make separation
easier to define and analyze.
Thermodynamic Systems In PRO/II
TM
PRO/II
TM
offers a large selection of thermodynamic methods. Selecting the right method for
the system simulated is important in order to obtain the correct results. Figure 31 lists the
main Saudi Aramco distillation practices and the recommended thermodynamic methods.
Optional acceptable methods are in parenthesis.
Distillation Process Approx. Pressure,
psia
Method
Crude Stabilization 30 BK10
Condensate Stripping 250-470 SRK (PR)
Crude Fractionation Vacuum - 50 BK10
NGL Fractionation
Demethanizer 160 (No Condenser) SRK (PR)
Deethanizer 430 (50-210
F) SRK (PR)
Depropanizer 330 SRK (PR)
Debutanizer 140 SRK (PR)
Saudi Aramco Distillation Processes
Suggested Thermodynamic Methods
Figure 31
Rigorous Distillation
The rigorous simulation is the most complete description of the distillation operation. Stage-
to-stage calculations are made and all mass and energy transfers are accounted for. The
rigorous simulation can handle many different distillation applications. These include crude
fractionation units, catalytic and steam cracker fractionation units, strippers, absorbers, NGL
fractionators, and the more complex conventional applications: azeotropic and extractive
distillation.
The PRO/II
TM
rigorous distillation module offers a wide variety of features such as multiple
feeds, products, recycles, heaters, coolers, pumparounds, bypasses, and pumpbacks. Also
featured are user-defined stream property calculation, multiple case study management, and
stream report writing capabilities. In addition, PRO/II
TM
offers single and multi-variable
control for unit and flowsheet optimization. Although the optimization capability is limited, it
can be used, for example, to select the best location for a tower feed subject to defined
process constraints.
Simulations with PRO/II
TM
PRO/II
TM
is a flowsheet simulator. The main unit operations that will be 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 PRO/II
TM
can be used to
accomplish complex objectives. The PRO/II
TM
input manual provides further information on
simulations.
Ras Tanura Plant 10 Depropanizer
Figure 22, in the beginning of the Simulation Fundamentals section, is a process flow diagram
of the Ras Tanura Plant 10 Depropanizer. The main features of the depropanizer are:
43 actual trays.
Total condenser.
Kettle reboiler.
Feed on Tray 2.
NGL feed at 120F preheated with 23.3 MMBtu/hr steam.
Tower pressures.
- Bottom 272 psig
- Top 267 psig
- Separator 262 psig
Figure 32 is the simulations setup. The objective of the simulation is to determine the
depropanizer product yields and operating conditions that meet product specifications.
Provided are:
Feed quality and rate.
Feed preheat duty.
Column pressure and pressure drop.
Top and bottoms product specifications.
In the following section, the depropanizer is simulated first with PRO/II
TM
Rigorous
Distillation.
a
Vapor
Product
T1
277 psia
T2
T15
T14
DC3
T34
T35
Distillate (DIST)
Spec iC + nC = 2.4 mole%
4 4
Column Overhead
(OVHD)
PRHT
120 F
0
(FEED)
Q = 23.3MM
Reflux
(RFL)
Reboiler Vapor
(RBV)
Tower Bottoms
to Reboiler
(RBL)
Bottoms Product (BTM)
SPEC C = 0.7 Mole%
3
Q
Reb
(NGL)
C2
C3
iC4
nC4
iC5
nC5
nC6
nC7
nC8
46
9107
1362
4381
1362
1983
1273
582
296
0.2
44.7
6.7
21.5
6.7
9.7
6.2
2.9
1.4
COMP. LB MOLE/H MOLE%
NGL
TOTAL
TEMP, F
PRESS., psia
20392.0
120.0
350.0
100.0
Cond.
Q
O
Ras Tanura Plant 10
Depropanizer Simulation Setup
Figure 32
Rigorous Simulation with PRO/II
TMError! Bookmark not defined.
The depropanizer was simulated with a total of 35 trays. They were calculated as follows:
Actual trays above feed : 14
Efficiency (see section on efficiency) : 0.8
Theoretical trays 14 x 0.8 : 11.2
Condenser : 1.0
Total theoretical trays above feed : 12.2, call it 12
Actual trays below feed : 29
Efficiency multiplier : 0.75
Theoretical trays 29 x 0.75 : 21.8
Kettle reboiler : 1.0
Total theoretical trays below the feed : 22.8, call it 23
Total column theoretical trays : 35
Please note that in PRO/II
TM
Tray Number 1 is the condenser or the top tray.
Figure 33 is a printout of the simulation input. It was generated with the previous version of
the program. The syntax may be different; however, the content is the same. We observe that
the feed preheat exchanger was simulated with a FLASH unit operation. The DUTY=23.3
was specified in the ADIABATIC specification line. In the column unit operation we observe
the following:
Trays 35, IO convergence algorithm.
Feed FEED on Tray 14.
Stream printout requested with TFLOW.
Total condenser (TYPE=3).
Estimated condenser and reboiler duties.
Column pressure and pressure drop.
Distillate product specification: 2.4 mole% iC4+nC4.
Distillate product specification: 0.7 mole% C3.
Variables corresponding to the specifications are the condenser and reboiler duties.
Figures 34 to 37 are the printouts of the input and the results. The input file is typical in that
the data is grouped in blocks. Component, Thermodynamic, Stream, and Unit Operations
blocks are shown in this example. The output data gives the solution tower stage
temperatures, pressures, net liquid and vapor flow rates, feed and product rates, and duties in
vertical columns. Also given are stream total and component flow rates, temperatures,
pressures, enthalpies, and other physical property data.
Rigorous Simulation Input
Figure 33
Output: Column Profile Printout
Figure 34
Output: Stream Conditions and Composition
Figure 35
Figure 36
Figure 37
Shortcut Distillation Simulations with PRO/II
TM
The Shortcut Distillation unit operation of PRO/II
TM
is a useful tool for obtaining approximate
tray and heat and material balance information. It can be used for screening alternatives or
preparing input for the more complex rigorous simulations. Because it uses correlations
rather than tray-to-tray calculations, it does not have the potential convergence difficulties of
the rigorous simulations.
The shortcut specifications are very similar to the rigorous ones. In short, very little
additional time is required to prepare the input. The shortcut distillation has two model
options. The first is used for conventional columns such as the NGL fractionators. The
second should be used for complex, multiproduct columns where the reflux from section to
section is minimal, such as crude distillation units.
The output provides information on:
Product rates and compositions.
Temperatures, reboiler and condenser duties.
Required trays at five reflux ratios.
Minimum reflux.
Minimum number of trays.
Specifications and Control Variables
Specifications and control variables are most likely the most important items in a simulation.
As previously defined, the specifications are specified by the user. Typical examples include
the following:
product rate, yield, quality, and temperature
stage temperature, net liquid and vapor rates
phase split and component concentrations
reflux rate or reflux ratio
Depending on the application, many other variables can be chosen as specified. The
specifications are defined in the simulation input data set.
Control variables are variables that are adjusted by the simulation program to achieve the
values defined for the specifications. Typical examples include the following:
product rate
heater and cooler duty
recycle rate
reflux rate or reflux ratio
Many other variables can be chosen to be controlled. As with the choice of specifications, the
choice of control variables depends on the application.
It is useful to think of the specifications and control variables in terms of pairs. The solution
to the mass and energy balance equation set for the simulation is uniquely defined as long as
an equal number of specification and control variables are used. For example if a particular
variable is specified (specification), then a corresponding variable must be controlled
(control). Furthermore, if either a single control variable is identified and no corresponding
specification is identified, no unique solution to the simulation problem can exist.
Consequently, the numbers of specifications and control variables must be equal.
The program solution algorithm attempts to adjust the control variables so as to match the
desired specification values. If no solution is reached, the simulation has failed to converge,
and the user is informed of this fact. Usually, the user has made one of two errors. One
common mistake is that of specifying an infeasible separation. Given the feed condition and
unit operation definition, the required separation is simply not possible. In this case, the
degree of separation should be relaxed and the simulation attempted again.
Another common mistake is that of defining specifications and control variables that are not
physically related. If the value of the specification is not affected significantly by changes in
the control variable, then it is possible that no value of the control variable will suffice to meet
the required value of the specification value. In this case the control variable should be
changed and the simulation attempted again.
Feed Location
Feed location is more important than is often realized. A misplaced feed point can require
excessive reflux for a given number of stages and vice versa. By definition, the optimum feed
stage location is that point in the column where the desired specifications can be achieved
with the minimum number of stages at a given reflux rate. Alternatively, it is that point in the
column where the desired specifications can be achieved at the lowest reflux rate for a given
number of stages.
A rule of thumb for determining whether the feed stage has been properly located is to check
whether the ratio of the light key to the heavy key in the feed liquid, or vapor, is
approximately the same as in the liquid (or vapor) from the feed stage. This is an accurate
method for a binary system. For a multicomponent system, the best feed stage would be
somewhat higher in the column if the amount of components in the feed that are lighter than
the light key is significantly greater than the amount of components that are heavier than the
heavy key.
PRO/II
TM
can determine the best feed tray location through the flowsheet optimizer. For more
information, refer to Section 133.2 of the PRO/II
TM
manual.
Sidestream Location
Occasionally, a second tower can be eliminated by a properly located sidestream. Techniques
similar to those mentioned in the discussion of feed location can also be used here.
Sidestreams requiring good back-end fractionation are taken from the tower rectifying section
as liquid. The goal of good back-end fractionation is to minimize the presence of the high-
boiling or heavy components. Sidestreams may be stripped in a sidestream stripper to remove
light components (see Module 205.04, Crude Distillation).
Sidestreams requiring good front-end fractionation are normally taken from the stripping
section. Such a stream will have a significant back-end tail, because it has been in contact
with heavy components in the column.
Compare Results to Plant Operation
When the user has obtained a converged simulation of an existing unit, an evaluation of the
simulation is necessary. The simulation results must be compared to existing unit operation.
For all distillation towers, stage and product temperatures, product rates and qualities, and
condenser and reboiler duties should be checked. Simulation values for all of these variables
should be reasonably close to measured values. Appropriate explanations must be developed
if the simulated values are not close to the measured values. The measured data could be in
error, the simulated feed composition could be different from the actual, or the tower internals
could be damaged. Any number of reasons could help to explain why simulated results differ
from measured results.
The task becomes more complex for heavy hydrocarbon fractionation applications. Due to
the large number of sidestream draws and pumparounds in these cases, many more data items
must be compared. The most important items to be compared are: net liquid rates, total draw
stage net liquid rates (should be close to zero), pumparound rates and return temperatures,
flash zone temperature, and overflash rate.
Uses of Simulations
Simulations can be used for many purposes. These include:
unit design
product quality and yield improvement
energy minimization
parametric studies for "What if?." analysis
troubleshooting
revamps
debottlenecking
optimization
planning studies
resource management
Parametric studies can often be made only with a simulation. A simulation could be used to
determine the required reboiler duty for a better separation with an existing tower. The effect
of changes in feed composition and temperature on product composition at fixed rates could
be estimated. The effect of reduced tower pressure on reboiler duty at fixed key component
concentrations could be determined.
In conclusion, many questions cannot be answered directly, if at all, using only plant tests.
With a properly specified and controlled simulation, many process improvement and design
concepts can be evaluated quickly and at minimal cost.
SIMPLIFIED DISTILLATION CALCULATIONS
The use of computers has greatly simplified distillation column calculations. Still, there are a
number of computations, mainly simple heat and material balances, that are done faster with
hand calculators. Such calculations are useful in setting up rigorous simulations, quick
screening of alternatives, checking plant data measurements, and obtaining information on
process flows that are not measured directly.
Distillate and Bottoms Compositions
An estimate of the product compositions is often necessary to initiate rigorous simulations.
As mentioned earlier, the components in the primary separation are called the key
components. Before any calculations are begun, the number of components should be
minimized. Trace noncritical components should be dropped, and non-key components
should be grouped.
The simplest method for estimating product rates is to assume a perfect split of the key
components. A perfect split assumes that the light key and lighter components go overhead
while the heavier key and heavier components go out in the bottoms. A better estimate is
based on the specific requirements for key-component compositions in the products. For
instance, the required specification might be a maximum of 3% light key in the bottoms and a
maximum of 1% heavy key in the distillate, in which case the compositions are estimated
accordingly. In separations where many components are distributed, or many components are
involved in the specifications, it is better to assume a perfect split or just make a rough guess
as to the terminal product compositions. Figure 38 is an example.
Feed Rate : 100 moles/hr
Feed Components : 25 moles/hr Propane
: 25 moles/hr Butane
: 25 moles/hr Pentane
: 25 moles/hr Hexane
Desired Separation : Debutanizer feed stream to achieve 92% recovery of butane in
overhead product with less than 5% C5+ in overhead product.
Expected Products:
Component Distillate, mole/hr Bottoms, mole/hr
Propane 25 0
Butane 23 2
Pentane 2.5 22.5
Hexane 0 25
50.5 49.5
Determine Distillate And Bottoms Compositions
Figure 38
Distillate Drum Conditions
The distillate drum conditions are often set by the temperature of the cooling medium. Once
an acceptable temperature is established, the drum conditions are determined through bubble
point or dew point calculations, depending on whether the overhead product is liquid or
vapor. To simplify calculations, several components can be grouped together. Sufficiently
accurate results can be obtained by omitting small amounts of components heavier than the
main components (e.g., 2% C
4
+ in the depropanizer overhead) or by averaging boiling points.
Light components can have a big effect on the required bubble point pressure (e.g., ethane in
the depropanizer overhead).
If the overhead product is all liquid, the overhead temperature is simply the dew point
temperature for the overhead product. If the overhead product is all vapor, the temperature
calculation is more complicated. The composition for the dew point calculation is then based
on the combined distillate vapor product plus reflux. The reflux composition is the dew point
composition of the overhead product at the distillate drum conditions. The reflux rate must be
guessed.
Temperature and Pressure of Tower Top and Bottom
Once the distillate drum pressure has been established, the pressures at the top and bottom of
the tower are fixed within narrow limits and the top and bottom temperatures can be
determined. Because of the condenser pressure drop, the tower top pressure is 2-5 psi higher
than the distillate drum pressure. The pressure at the bottom of the tower will typically be
another 5 to 10 psi higher than that at the top of the tower due to tower pressure drop
corresponding to about 0.2 psi per tray. The bottoms temperature can be calculated from the
pressure and estimated composition through bubble point calculations. Again, for
approximate results, components can be grouped together.
Tower Pressure and Temperature Changes
Often distillation towers are operated at fixed pressures. There are advantages, however, in
operating a tower at the lowest feasible pressure. At lower pressures, the relative volatility of
components is greater, and as a result, separation is easier. This effect of lower pressure can
be used to increase the purity of the products or to operate the tower with reduced reflux and
lower utilities consumption.
For towers with total condensers, the minimum operable pressure at the condenser drum
(reflux drum) is the vapor pressure of the distillate at the drum temperature. A quick way to
estimate the effect of pressure change on the distillate drum temperature and vice versa, is to
use a Temperature - Vapor Pressure graph. For towers with distillate that is a petroleum
fraction, such as a naphtha splitter, Figure 39 can be used. For example:
The design distillate drum pressure of a tower is 2 atm and its temperature (bubble point
design) is 200F. We want to estimate how much we can lower the tower pressure if we
improve the condenser capacity and lower the temperature to 150F.
The 2 atm and 200F temperature coordinates in Figure 39 intercept at a point that
determines the normal boiling point of the drum liquid, about 242F. We move from this
point parallel to the adjacent constant Normal Boiling Point lines (we maintain constant
distillate drum quality) and stop at the new temperature, 150F. The pressure that
corresponds to 150F is 0.8 atm.
Figure 39 can also be used to determine the effect of temperature or pressure changes at the
tower bottom or at any intermediate points. For example, by following the procedure in the
example above we can find that a pressure reduction in a crude unit tower top (not distillate
drum) from 3 atm to 2.6 atm (6 psi reduction), will reduce the tower top pressure from 300F
to 280F.
Pressure-Temperature Relationships
Figure 39
Enthalpy Balances
There are two methods of conducting heat balances. The first method equates the process
heat required to the process heat removed.
Heat Required = Sum (Products x Enthalpy Change) + Reboiler Duty
Heat Removed = Condenser Duty + Other Cooler Duties
Heat Required = Heat Removed
An overhead condenser enthalpy balance example with this method is illustrated in Figures 40
and 41. The method in Figure 41 equates the heat entering the system to the heat leaving.
Heat In = Sum (Feeds x Enthalpy) + Reboiler Duty
Heat Out = Sum (Products x Enthalpy) + Condenser Duty + Other Cooler Duties
Heat In = Heat Out
a
Ovhd
Cond.
Reflux
Q
c
T
c
T
o
D
L
D
v
H O
2
Overhead Condenser Enthalpy Balance
Figure 40
a
Reflux
Cool + Condense
Calculation Model
Vapor Dist.
Cool Only
Liquid Dist.
Cool + Condense
H O
Cool +
Condense
2
T
o
H
o
H
o
H
o
Q
c
t
c
h
c
h
c
h
c
Overhead Condenser Enthalpy Balance Model
Figure 41
Both methods produce the same results when used with accurate data. However, the first
method is more suitable for hand calculations. Because it deals with smaller numbers
(enthalpy changes rather than enthalpies) it is less prone to errors, especially when reading
enthalpies from not-so-exact graphs. Computer simulation programs use the second method.
Useful sources of data are the specific heat and enthalpy charts of Maxwell's Data Book on
Hydrocarbons. Figure 42 is an example of a heat balance envelope for the calculation of the
overhead condenser duty (reboiler duty calculated from the steam consumption).
aa
Q
c
Q
Reb
Q
F
Q
B
Q
D
Enthalpy Balance For Condenser Duty
Figure 42
Other Shortcut Calculations
Most distillation books and Perry's Chemical Engineer's Handbook (6th Edition, pages 13-
37) cover a number of shortcut procedures for estimating minimum reflux, number of column
trays, distribution of non-key components. Because of their complexity and the availability of
computer-based alternatives, they will not be covered here.
NOMENCLATURE
Relative volatility.
B Bottoms rate, mole/hr.
C
1
, C
2
... Hydrocarbons with 1, 2 ...carbons.
D Distillate rate, mole/hr.
E
MV
Tray (Murphree vapor) efficiency.
E
O
Overall column efficiency.
E
OG
Point efficiency on a tray.
F Feed rate, mole/hr.
f Feed tray number.
H Enthalpy.
K Distribution coefficient (K = y/x) also called K factor or equilibrium
K.
L Liquid rate, mole/hr.
n Next to a hydrocarbon name it indicates a normal (paraffin) isomer.
n Tray number.
N,N+1 N is the top stage in a column. N+1 is the condenser.
P Pressure, absolute.
Q Heat duty.
q q-line slope. See text.
R Reflux rate, mole/hr.
T Temperature, absolute.
V Vapor rate, mole/hr.
x Mole fraction in the liquid phase.
y Mole fraction in the vapor phase.
z Mole fraction in the feed.
Subscripts
1,2, Value refers to component 1, 2, ... or measurement 1, 2.
B Value refers to bottoms.
C, c Value refers to condenser.
D Value refers to distillate.
f Value refers to feed tray.
HK Value refers to heavy key.
i Value refers to component i.
j Value refers to component j.
LK Value refers to light key.
N Value refers to tray N.
n, n-1,
n+1, Value refers to tray n, n-1, n+1, ...
R Value refers to reboiler.
r Value refers to rectifying section.
s Value refers to stripping section.
V Value refers to vapor.
GLOSSARY
binary distillation Distillation of a mixture containing two components.
bottoms The bottom (heavy) product of a distillation column. A
synonymous term is residue.
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.
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.
DGA Diglycolamine, an amine used in gas treating.
distillate The overhead (light) product of a distillation column. It may
be vapor, liquid, or both.
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.
enriching section The section of the distillation column above the feed.
fractionation Distillation in which the vapor is contacted continuously and
countercurrently with a condensed portion of the vapors.
heavy key A heavy component that must be recovered with the residue
and is present in the distillate in important amounts.
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.
light key A light component that must be recovered with the distillate
and is present in the residue in important amounts.
multicomponent
distillation
Distillation of a mixture containing more than two components.
operating line A line in the McCabe-Thiele diagram that corresponds to the
compositions of vapor and liquid between stages.
overhead The vapor leaving the top of the column.
packing Devices providing countercurrent vapor-liquid contact in
distillation columns.
partial condenser A condenser that condenses part of the vapor.
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.
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. Recirculating reboilers operate either
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.
residue The bottom (heavy) product of a distillation column. A
synonymous term is bottoms.
sidestream A tower product stream removed from a tray other than the top
or bottom.
stages Contact points of the vapor and liquid in a column, such as that
which occurs on column trays. The term theoretical stages is
used to indicate that equilibrium is reached at the contact point
between 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.
total condenser A condenser that condenses all of the vapor.
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.

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