Petroleum Refining

Engineering

Sequencing of Distillation Columns

See Process Design & Integration by Robin Smith
 Sequencing of Distillation Columns

Typical
NGL
Fractionator
Distillation
Train
 Sequencing of Distillation Columns

The direct and indirect sequences of simple distillation

columns for a three-product separation
 Sequencing of Distillation Columns

Alternative
sequences for
the separation
of a
four-product
mixture
Sequencing of Distillation Columns
Sequencing of Distillation Columns

Number of possible distillation sequences

using simple columns
 Sequencing of Distillation Columns

Choice of Sequence for Simple Nonintegrated Distillation Columns

 Heuristics (Rules of Thumb) have been proposed for the
selection of the sequence for simple nonintegrated
distillation columns
 These heuristics are based on observations made in
many problems and attempt to generalize the
observations.
 Although many heuristics have been proposed, they can
be summarized by the following four that are frequently
used.
 Sequencing of Distillation Columns

Heuristics
Heuristic 1.
Separations where the relative volatility of the key components
is close to unity or that exhibit azeotropic behaviour should be
performed in the absence of nonkey components. In other
words, do the most difficult separation last.
Heuristic 2.
Sequences that remove the lightest components alone one by
one in column overheads should be favoured. In other words,
favour the direct sequence.
 Sequencing of Distillation Columns

Heuristics (Continued)
Heuristic 3.
A component composing a large fraction of the feed should be
removed first.
Heuristic 4.
Favour splits in which the molar flow between top and bottom
products in individual columns is as near equal as possible.

Difficulties can arise when the heuristics

are in conflict with each other.
 Sequencing of Distillation Columns
An Example

Data for a mixture of alkanes to be separated by distillation

 Sequencing of Distillation Columns

Heuristic 1.
Do D/E split last since this separation has the smallest relative
volatility.
Heuristic 2.
Favour the direct sequence.
A / BCDE
Heuristic 3.
Remove the most plentiful component first.
ABCD / E
Heuristic 4.
Favour near-equimolar splits between top and bottom products.
ABC / DE 408.3 kmol/h & 498.9 kmol/h
 Sequencing of Distillation Columns

 All four heuristics are in conflict here. Heuristic 1 suggests

doing the D/E split last, whereas Heuristic 3 suggests it
should be done first. Heuristic 2 suggests the A/B split first
and Heuristic 4 the C/D split first.
Take one of the candidates and accept, say, the A/B split first
Repeat the Process
Heuristic 1. Do D/E split last
Heuristic 2. B / CDE
Heuristic 3. BCD / E
Heuristic 4. BC / DE 362.9 kmol/h & 498.9 kmol/h
 Sequencing of Distillation Columns

Again the heuristics are in conflict

Heuristic 1 again suggests doing the D/E split last, whereas again
Heuristic 3 suggests it should be done first. Heuristic 2 suggests
the B/C split first and Heuristic 4 the C/D split first. This process
could be continued and possible sequences identified for further
consideration. Some possible sequences would be eliminated,
narrowing the number down.
 The conflicts that have arisen in this problem have not been
helpful in identifying sequences that are candidates for further
evaluation.
 A little more intelligence could be used in the application of the
heuristics and they could be ranked in order of importance.
 Sequencing of Distillation Columns

Sequences Based on Quantitative Measures

 Rather than relying on heuristics that are qualitative, and can
be in conflict, a quantitative measure of the relative
performance of different sequences would be preferred.
 A physical measure that can be readily calculated is the
vapour flow up the columns.
 This provides an indication of both capital and operating
costs.
 There is clearly a relationship between the heat duty required
for the reboiler and condenser to run the distillation and the
vapour rate since the latent heat of vaporization relates these
parameters.
 Sequencing of Distillation Columns

Sequences Based on Quantitative Measures

 The heat duty in the reboiler relates directly to the cost of hot
utility for the distillation (e.g. cost of steam). The heat duty in
the condenser relates directly to the cost of cold utility for the
distillation (e.g. cost of cooling water or refrigeration).
 There is also a link between vapour rate and capital cost,
since a high vapour rate leads to a large diameter column.
High vapour rate also requires large reboilers and condensers.
Thus, vapour rate is a good indication of both capital and
operating costs for individual columns.
 Consequently, sequences with lower total vapour load would
be preferred to those with a high total vapour load.
 Sequencing of Distillation Columns

Underwood Equations for Minimum Reflux

The Underwood Equations can be used to predict the minimum
reflux for multicomponent distillation:
 The equations assume that the relative volatility and molar
overflow are constant between the zones of constant
composition.
 There are two equations. The first is given by:
 Sequencing of Distillation Columns

Underwood Equations for Minimum Reflux

Above equation can be written for all NC components of the feed and
solved for the necessary values of θ. There are (NC − 1) real positive values
of θ that satisfy this equation, and each lies between the α’s of the
components.
 Sequencing of Distillation Columns

Underwood Equations for Minimum Reflux

The second equation is then written for each value of θ obtained
to determine the minimum reflux ratio, Rmin:

To solve this equation, it is necessary to know the values of not

only αi,j and θ but also xi,D. The values of xi,D for each
component in the distillate in above equation are the values at
the minimum reflux and are unknown. Rigorous solution of the
Underwood equations, without assumptions of component
distribution, thus requires the first equation to be solved for (NC
− 1) values of θ lying between the values of αi,j of the different
components.
 Sequencing of Distillation Columns
Underwood Equations for Minimum Reflux
A Simplification
 The calculation of Rmin can be simplified significantly by
making some reasonable assumptions regarding the component
distributions to approximate xi,D.
 It is often a good approximation to assume that all of the
lighter than light key components go to the overheads and all
of the heavier than heavy key components go to the column
bottoms. Also, if the light and heavy key components are
adjacent in volatility, there are no components between the
keys, and all xi,D are known, as the key component split is
specified by definition. The first equation can then be solved
by trial and error for the single value of θ required that lies
between the relative volatilities of the key components.
 This value of θ can then be substituted in second equation to
solve for Rmin directly, as all xi,D are known.
 Sequencing of Distillation Columns

Actual Vapor Flow Calculation

A simple mass balance around the top of the column for
constant molar overflow, at minimum reflux gives:
Vmin = D (1 + Rmin)
where Vmin = minimum vapour load (kmol/s)
Rmin = minimum reflux ratio
D = distillate flowrate (kmol/s)

The above equation can also be written at finite reflux.

Defining RF to be the ratio R/Rmin (typically R/Rmin = 1.25):
V = D (1 + RF.Rmin)
 Sequencing of Distillation Columns

Effect of Feed Condition

 If the feed is partially vaporized, the vapour flow below the
feed will be lower than the top of the column.
 For above ambient temperature separations, the cost of
operating the distillation will be dominated by the heat load
in the reboiler and the vapour flow in the bottom of the
column.
 For below ambient temperature separations, the cost of
operating the column will be dominated by the cost of
operating the refrigerated condenser and hence the vapour
flow in the top of the column.
 Sequencing of Distillation Columns

Effect of Feed Condition

If constant molar overflow is assumed, the vapour flow in the
bottom of the column V is related to the vapour flow in the top
of the column by
V’ = V – F(1 − q)
where V’ = vapour flow below the feed (kmol/s)
V = vapour flow above the feed (kmol/s)
F = feed flowrate (kmol/s)
q = thermal condition of the feed
= heat required to vaporize one mole of feed/molar
latent heat of vaporization of feed
(= 0 for saturated vapour feed, or 1 for saturated liquid).
 Sequencing of Distillation Columns

Effect of Feed Condition

 In most cases, a saturated liquid feed is normally
preferred.
 The calculation is repeated for all the columns in the
sequence and the vapour loads summed to obtain the
overall vapour load for the sequence.
 Different sequences can then be compared on the
basis of total vapour load.
 Sequencing of Distillation Columns

Separation of Aromatics – An Example

The mixture of aromatics, as given in the table on next slide, is to be
separated into five products. The xylenes are to be taken as a mixed
xylenes product. The C9’s in the table are to be characterized as C9H12
(1-methylethylbenzene). The recoveries are to be assumed to be 100%.
Relative volatilities are to be calculated from the Peng–Robinson EoS,
assuming that all interaction parameters are zero. Pressures of each
column are to be minimized such that either the bubble point of the
overhead product is 10◦C above the cooling water return temperature
of 35◦C (i.e. 45◦ C) or a minimum of atmospheric pressure. Assume
the ratio of actual to minimum reflux to be 1.1 and that all columns are
fed with a saturated liquid. Neglect pressure drop across each column.
Determine the rank order of the distillation sequences on the basis of
total vapour load calculated from the Underwood Equations.
Sequencing of Distillation Columns

Separation of Aromatics – An Example

Data for five-product mixture of
aromatics to be separated by distillation
 Sequencing of Distillation Columns

Separation of Aromatics – An Example

Relative volatilities
of the feed to the
sequence at 1 atm.
 Sequencing of Distillation Columns

Separation of Aromatics – An Example

Sequences for
the separation of
the mixture of
Aromatics.
 Sequencing of Distillation Columns

Separation of Aromatics – An Example

The best
sequences
in terms of
vapour load
for the
separation
of the
mixture of
aromatics
 Sequencing of Distillation Columns

Separation of Aromatics – An Example

The best
sequences
in terms of
vapour load
for the
separation
of the
mixture of
aromatics
 Sequencing of Distillation Columns

Separation of Aromatics – An Example

The best
sequences
in terms of
vapour load
for the
separation
of the
mixture of
aromatics
 Sequencing of Distillation Columns

Certain Points of Caution

 There are approximations associated with the Underwood Equations
due to which these tend to under predict the minimum reflux ratio.
This introduces uncertainty in the way that the calculations were
carried out.
 The differences in the total vapour load between different sequences
are small and these differences can be smaller than the errors
associated with the prediction of minimum reflux ratio and minimum
vapour load using the Underwood Equations. As long as the errors
are consistently low for all of the distillation calculations, the vapour
load from the Underwood Equations can still be used to screen
between options.
The results should be used with caution and options not ruled out
because of some small difference in the total vapour load.
 Sequencing of Distillation Columns

Distillation Sequencing using Columns with more than Two Products

 Sequencing of Distillation Columns

Distillation Sequencing using Columns with more than Two Products

Choosing
nonadjacent
keys leads to
the
prefractionator
arrangement
 Sequencing of Distillation Columns

Composition profiles for the middle product in the columns of

the direct sequence show remixing effects
 Sequencing of Distillation Columns

Composition profiles for the middle product in the prefractionator

arrangement show that there are no remixing effects
 Sequencing of Distillation Columns

Distillation Sequencing using Thermal Coupling

What is Thermal Coupling?

 A restriction of simple columns, used in earlier sequences, is
that they should have a reboiler and a condenser.
 It is possible to use material flows to provide some of the
necessary heat transfer by direct contact.
 This transfer of heat via direct contact is known as thermal
coupling.
 Sequencing of Distillation Columns

Distillation Sequencing using Thermal Coupling

(Thermal coupling of the direct sequence)
Sequencing of Distillation Columns

Thermal coupling of the direct sequence

(Alternate arrangement)
 Sequencing of Distillation Columns

Distillation Sequencing using Thermal Coupling

(Thermal coupling of the indirect sequence)
Sequencing of Distillation Columns

Thermal coupling of the indirect sequence

(Alternate arrangement)
 Sequencing of Distillation Columns

Thermal coupling of the prefractionator arrangement

Sequencing of Distillation Columns

Dividing-wall Column or Partitioned Column

 Sequencing of Distillation Columns

Advantages of Partition Columns over Conventional Arrangements

 The prefractionator arrangement requires typically 20 to 30%
less energy than the best conventional arrangement using simple
columns.
 The prefractionator column also requires less energy than the
side-rectifier and side-stripper arrangements, for the same
separation.
 The partition column requires typically 20 to 30% less capital
cost than a two-column arrangement of simple columns.
 In partitioned columns, the material is only reboiled once and
its residence time in the high-temperature zones is minimized.
This can be important if distilling heat sensitive materials.
 Sequencing of Distillation Columns

Disadvantages of Partition Columns

over Conventional Arrangements
 All of the heat must be supplied at the highest temperature and all
of the heat rejected at the lowest temperature of the separation.
 In general, partition columns are not suited to replace sequences of
two simple columns that operate at very different pressures.
 Another disadvantage of partitioned columns might arise from
materials of construction, if the two columns of a conventional
arrangement require two different materials of construction with
different costs.
 The hydraulic design of the partitioned column is needed such that
the pressure must be balanced on either side of the partition.
 Sequencing of Distillation Columns
Crude Oil Distillation

The thermally
coupled indirect
sequence for
crude oil
distillation
 Sequencing of Distillation Columns
Crude Oil Distillation

The thermally coupled indirect sequence with side stripper

arrangement
 Sequencing of Distillation Columns
Crude Oil Distillation

Substitute some (or all) of

the reboiling with direct
steam injection and
introduce intermediate
condensation
 Sequencing of Distillation Columns
Crude Oil Distillation

Reference: An Evaluation of a Progressive Crude Oil Distillation Scheme

by Steven Brunetti, Brian Howard, and Miguel Bagajewicz
 Sequencing of Distillation Columns
Crude Oil Distillation

Results of the study: An Evaluation of a Progressive Crude Oil

Distillation Scheme
 The results for a progressive scheme were mixed when
compared to conventional distillation.
 For lighter crudes, it was discovered that progressive
distillation provided no energetic benefit, and in fact
increased demand on both the hot and cold utilities.
 For a heavy crude, progressive distillation revealed a
significant reduction in the hot utility compared to
conventional distillation.

Reading Assignment: Study the paper (pdf available on Moodle)