Distillation Sequencing

Consider now the particular case in which a homogeneous multicomponent fluid

mixture needs to be separated into a number of products, rather than just two
products. As noted previously, distillation is the most common method of separating
homogeneous fluid mixtures and in this chapter, the choice of separation will be
restricted such that all separations are carried out using distillation only. If this is the
case, generally there is a choice of order in which the products are separated that
is, the choice of distillation sequence.
11.1 DISTILLATION SEQUENCING USING SIMPLE COLUMNS Consider first the design
of distillation systems comprising only simple columns. These simple columns
employ:
one feed split into two products;
key components adjacent in volatility, or any components that exist in small
quantities between the keys will become impurities in the products;
a reboiler and a condenser.
If there is a three-component mixture to be separated into three relatively pure
products and simple columns are employed, then the decision is between two
sequences, as illustrated in Figure 11.1. The sequence shown in Figure 11.1a is
known as the direct sequence in which the lightest component is taken overhead in
each column. The indirect sequence, as shown in Figure 11.1b, takes the heaviest
component as bottom product in each column.
If the distillation columns have both reboiling and condensation supplied by utilities,
then the direct sequence in Figure 11.1a often requires less energy than the indirect
sequence in Figure 11.1b. This is because the light material (Component A) is only
vaporized once in the direct sequence. However, the indirect sequence can be more
energy-efficient if the feed to the sequence has a low flowrate of the light material
(Component A) and a high flowrate of heavy material (Component C). In this case,
vaporizing the light material twice in the indirect sequence is less important than
feeding a high flowrate of heavy material to both of the columns in the direct
sequence.
For a three-component mixture to be split into three relatively pure products, there
are only two alternative Chemical Process Design and Integration R. Smith 2005
John Wiley & Sons, Ltd ISBNs: 0-471-48680-9 (HB); 0-471-48681-7 (PB) sequences.
The complexity increases significantly as the number of products increases. Figure
11.2 shows the alternative sequences for a four-product mixture. Table 11.1 shows
the relationship between the number of products and the number of possible
sequences for simple columns1.
Thus, there may be many ways in which the separation can be carried out to
produce the same products. The problem is that there may be significant

differences in the capital and operating costs between different distillation

sequences that can produce the same products.

11.2 PRACTICAL CONSTRAINTS RESTRICTING OPTIONS Process constraints often

reduce the number of options that can be considered. Examples of constraints of
this type are:
1. Safety considerations might dictate that a particularly hazardous component be
removed from the sequence as early as possible to minimize the inventory of that
material.
2. Reactive and heat-sensitive components must be removed early to avoid
problems of product degradation.
3. Corrosion problems often dictate that a particularly corrosive component be
removed early to minimize the use of expensive materials of construction.
4. If thermal decomposition in the reboilers contaminates the product, then this
dictates that finished products cannot be taken from the bottoms of columns.
5. Some compounds tend to polymerize when distilled unless chemicals are added
to inhibit polymerization.
6. There might be components in the feed to a distillation sequence that are difficult
to condense.
11.3 CHOICE OF SEQUENCE FOR SIMPLE NONINTEGRATED DISTILLATION COLUMNS
Heuristics have been proposed for the selection of the sequence for simple
nonintegrated distillation columns1.
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 four2:
Heuristic 1. Separations where the relative volatility of the key components is close
to unity or that exhibit azeotropic behavior 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 favored. In other words, favor the direct sequence.
Heuristic 3. A component composing a large fraction of the feed should be removed
first.
Heuristic 4. Favor splits in which the molar flow between top and bottom products in
individual columns is as near equal as possible.
In addition to being restricted to simple columns, the observations are based on no
heat integration (i.e. all reboilers and condensers are serviced by utilities).

Difficulties can arise when the heuristics are in conflict with each other, as the
following example illustrates.

11.4 DISTILLATION SEQUENCING USING COLUMNS WITH MORE THAN TWO

PRODUCTS
When separating a three-product mixture using simple columns, there are only two
possible sequences, Figure 11.1. Consider the first characteristic of simple columns.
A single feed is split into two products. As a first alternative to two simple columns,
the possibilities shown in Figure 11.6 can be considered. Here three products are
taken from one column. The designs are in fact both feasible and cost-effective
when compared to simple arrangements on a stand-alone basis (i.e. reboilers and
condensers operating on utilities) for certain ranges of conditions. If the feed is
dominated by the middle product (typically more than 50% of the feed) and the
heaviest product is present in small quantities (typically less than 5%), then the
arrangements shown in Figure 11.6a can be an attractive option3. The heavy
product must find its way down the column past the sidestream. Unless the heavy
product has a small flow and the middle product a high flow, a reasonably pure
middle product cannot be achieved. In these circumstances, the sidestream is
usually taken as a vapor product to obtain a reasonably pure sidestream. A large
relative volatility between the sidestream Product B and the bottom Product C is
also necessary to obtain a high purity sidestream. A practical difficulty with this
arrangement should, however, be noted. Whilst it is straightforward to split a liquid
flow in a column, it is far less straightforward to split a vapor flow as shown. The
flow of vapor up the column must somehow be restricted to allow a split to be made
between the vapor that must continue up the column and the vapor sidestream.
This can be achieved by the use of a baffle across the column diameter, or vapor
tunnels in the tray downcomers. However, taking a vapor sidestream is more
problematic than taking a liquid sidestream.

In summary, single-column sidestream arrangements can be attractive when the

middle product is in excess and one of the other components is present in only
minor quantities. Thus, the sidestream column only applies to special circumstances
for the feed composition. More generally applicable arrangements are possible by
relaxing the restriction that separations must be between adjacent key components.
Consider a three-product separation as in Figure 11.7a in which the lightest and
heaviest components are chosen to be the key separation in the first column. Two

further columns are required to produce pure products, Figure 11.7a. This
arrangement is known as distributed distillation or sloppy distillation. The distillation
sequence provides parallel flow paths for the separation of a product. At first sight,
the arrangement in Figure 11.7a seems to be inefficient in the use of equipment in
that it requires three columns instead of two, with the bottoms and overheads of the
second and third columns both producing pure B. However, it can be a useful
arrangement in some circumstances. In new design, the three columns can, in
principle, all be operated at different pressures. Also, the distribution of the middle
Product B between the second and third columns is an additional degree of freedom
in the design. The additional freedom to vary the pressures and the distribution of
the middle product gives significant extra freedom to vary the loads and levels at
which the heat is added to or rejected from the distillation. This might mean that
the reboilers and condensers can be matched more cost-effectively against utilities,
or heat integrated more effectively.
If the second and third columns in Figure 11.7a are operated at the same pressure,
then the second and third columns could simply be connected and the middle
product taken as a sidestream as shown in Figure 11.7b. The arrangement in Figure
11.7b is known as a prefractionator arrangement. Note that the first column in
Figure 11.7b, the prefractionator, has a partial condenser to reduce the overall
energy consumption.
Comparing the distributed (sloppy) distillation in Figure 11.7a and the
prefractionator arrangement in Figure 11.7b with the conventional arrangements in
Figure 11.1, the distributed and prefractionator arrangements typically require 20 to
30% less energy than conventional arrangements for the same separation duty. The
reason for this difference is rooted in the fact that the distributed distillation and
prefractionator arrangements are fundamentally thermodynamically more efficient
than a simple arrangement. Consider why this is the case.
Consider the sequence of simple columns shown in Figure 11.8. In the direct
sequence shown in Figure 11.8, the composition of Component B in the first column
increases below the feed as the more volatile Component A decreases. However,
moving further down the column, the composition of Component B decreases again
as the composition of the less-volatile Component C increases.