Thermodynamic efficiency in distillation

Fundamentals

It is important to recognise that the key to improving the design and energy efficiency of
distillation systems is how their ‘efficiency’ is defined. If a column operates at a reflux ratio of 10%
above the minimum reflux ratio it is generally considered reasonably efficient because the reboiler
and condenser loads are close to the minimum for the particular separation. However, a much
better indication of efficiency is found from thermodynamic consideratiomP4 which take proper
account of the degradation of energy in a process. Energy degradation can be particularly
important in distillation processes. The amount of work or energy made available by a reversible
steady state flow process is given by

w= (H-HI)) - Ts(S-So) (1)

The work available, W, is termed ‘exergy’ and represents the amount of work or ‘available energy’
that can be obtained from an ideal reversible process or conversely the work needed to drive a
reversible process. Exergy therefore represents an ideal limiting value for a process - either the
maximum available work or the minimum required work. With real processes the driving forces for
heat and material transfer always result in irreversibility, energy degradation and net increase in
total entropy. Exergy is therefore ‘lost’ and the amount of work needed by the process increases
above the ideal mínimum.

Distillation systems achieve separation by the use and degradation of energy. Consider a column
that con- sumes a quantity of energy & at the reboiler and rejects a quantity of energy Qc at the
condenser. The work value of energy Qi at temperature Ti is:

and to achieve a given separation an amount of work or exergy is needed as given by

w,,, = WR - WC (4)

If the temperature differences between the heat source and the reboiler and between the
condenser and the heat sink are small then the work requirement is minimised. However, the
actual work requirement is much increased if these temperature differences are large.
Application and efficient design

In distillation the major sources of thermodynamic irreversibility are energy degradation from the
relatively high temperature of the reboiler, through the column, to the condenser temperature,
and the irreversible mixing of liquid and vapour phases which are not in equil- ibrium. Many
schemes which reduce distillation work consumption are based on reducing energy degradation by
reducing temperature differences. For multiple columns, energy integration between columns
reduces the overall work requirement because of the reduced temperature differences at
reboilers and condensers5-7. However it is not always pragmatic to energy-integrate columns with
other columns or other sections of the overall process. The thermodynamic efficiency of the
distillation columns themselves then becomes increas- ingly important if energy (and capital)
savings are to be realised, particularly for distillation columns which operate at temperatures
below ambient. Because of the high cost of energy at low tempera- tures, cryogenic gas processing
plants use many techniques to reduce energy degradation and mixing irreversibilities so as to
improve thermodynamic efficiency. Double effect distillation, where the heat rejected by a
condenser is used to reboil another column, is conventional. Column pressures can be optimised
to give small temperature differences in the condenser/ reboiler and high thermodynamic
efficiency. Heat pumping is conventional and again enables small temperature driving forces to be
used. Multiple columns for a single distillation duty are often used - the use of two or three energy
integrated columns for the denitro- genation of natural gas is not unusual and the use of side
condensers and reboilers is commonplace. All of these methods rely on reducing overall work
consumption by reducing energy degradation through the column system. This may or may not be
successfulin reducing capital cost. An alternative distillation method that reduces energy
consumption directly, and is worthy of further consideration, is thermal coupling.

Thermal coupling

Introduction

The energy consumption of distillation systems may be reduced by using ‘thermal coupling’ of
columns wherein the columns are linked directly by process streams. This technique has long been
practised in cryogenic pro- cessing where the incentive for reducing energy consumption is very
great. The conventional method of recovering argon from air relies on the use of thermal coupling.
A gaseous mixture of argon and oxygen is withdrawn from the upper column of a ‘classical’ double
column arrangement and is passed to a side rectifier ‘argon column’ as shown in Figure 1. Argon is
withdrawn from the top of this column and the argon- depleted oxygen liquid from the base is
returned to the upper column. The energy consumption is lower than if conventional distillation
columns were used and this reduces the process power consumption and capital cost.

Fully thermally coupled distillation

In the distillation of multi-component mixtures a more reversible separation can be achieved when
each section of a column removes only one component from the product stream of that section 7-
10. This is the basis of the fully thermally coupled arrangement advocated by Petlyuk et al.’ for
ternary mixtures and shown in Figure 2. In the upstream ‘prefractionator’ a crude separation is
performed so that component B is split between the top and bottom of the column. The upper
section of the prefractionator separates components AB from C whilst the lower section separates
BC from A. Thus, both column sections remove only one component from the product stream of
the section. This is also the case for all four sections of the downstream main column. In this
column configuration irreversible mixing and heat transfer are minimised and this makes the
‘Petlyuk arrangement’ a more energy efficient method for separating ternary mixtures than the
conventional distillation schemes - the ‘direct’ sequence and ‘indirect’ sequence shown in Figures
3 and 4. The term ‘direct’ refers to the fact that the lightest component is with- drawn from the
top of each successive column whereas the term ‘indirect’ applies when the heaviest com- ponent
is withdrawn from the base of each successive column.
Side columns

The benefit of withdrawing only one

component from each section of a
column is also demonstrated by
thermally coupled side columns as
shown in Figures 5 and 6. These
arrangements require less energy
than conventional distillation
because they do not suffer from the
mixing irreversibilities that are
inherent in conven- tional distillation
of multi-component mixtures.

In the direct and indirect sequences

of Figures 3 and 4 the flow of the
middle component B is highly
significant. In the first column of the
direct sequence (Figure 3) the upper
part of the column separates A from
B whilst the extreme lower part of
the column separates B and C. The
concentration of component B is
therefore at a maximum at some
point below the feed as shown in
Figure 7. By the analogous argument,
in the indirect sequence (Figure 4)
the concentration of component B is
at a maximum at some point above
the feed. By withdrawing a side
stream from the point at which the
concentration of component B is
maximised, the distillation of B from either C (direct sequence) or A (indirect sequence) is made
much easier. Component B can be isolated with reduced energy consumption if a side column is
used to distil the sidedraw and isolate B as a product. Because less energy is consumed in isolating
B, total column vapour rates are reduced and capital savings are made. The Petlyuk system
ensures all components are always moving in the correct direction for separation so irreversibility
is minimised. The side column arrangements are different in that they only prevent the flow of the
intermediate component from going in the wrong direction but this can result in large energy
savings compared with conventional schemes. The Petlyuk system and similar column
arrangements have received limited attention until recently”. There is evidence that they are
advantageous for close-boiling distillation*~12 but uncertainty in the design of such systems and
perceived inflexibility to changes in feed conditions have led to very little industrial use. In
contrast, the side rectifier and side stripper shown in Figures 5 and 6 are well proven industrially
and for many separations they can save almost as much energy as the Petlyuk scheme. They can
also be designed using proprietary process simulation packages which is not the case with fully
thermally coupled systems. Tedder and Rudd13 showed that side rectifiers and side strippers can
be cost-effective for any ternary separation where less than half the feed leaves in the middle
product or where low purity of the middle product is acceptable. Glinos and Malone14J5 showed
that the reduction in vapour rate by use of a side stripper or side rectifier can be up to 50%
compared with conventional column arrangements. Such a reduction would clearly lead to savings
in energy and capital cost compared with non thermally coupled columns. To better understand
the value of thermally coupled side columns a comparison of the minimum work consumption of
both thermally coupled and conven- tional columns was carried out16. This found that the
minimum work required by thermally coupled systems is the same as a conventional two column
arrangement because the reduced energy load achieved with thermally coupled systems is
counteracted by their greater energy degradation (the temperature span from reboiler to
condenser is greater) (see Equations (3a), (3b) and (4)). Therefore, considered in isolation,
thermally coupled columns do not give an improvement in thermodynamic efficiency because they
do not reduce work consumption. However, they do require lower energy loads and thus,
depending on heat source and sink temperatures, they can be very attractive. Linnhoff et aL5 also
concluded that the attraction of side columns depends on how they can be energy integrated into
a process. This is also why thermal coupling may be preferred, as discussed by Tedder and Rudd13,
where the energy load for the separation of the middle component is small and/or where
optimisation of the feed state to the primary column is possible. Maybe of the greatest
significance is the fact that because energy flows are lower with thermally coupled side columns
than with conventional columns, equip- ment sizes and therefore capital costs are reduced. It can
be said that distillation schemes that exhibit similar thermodynamic efficiency do not necessarily
exhibit similar costs. It is also clear that there is a real incentive for better understanding of side
column distillation.

Design of thermally coupled side columns

Lack of simple and reliable design methods is probably the major reason why thermal coupling has
not been widely applied outside of low temperature processing. However, a simple design method
is available15*‘6. In fact the familiar Fenske-Underwood-Gilliland method is as valid for thermally
coupled columns as it is for conventional distillation and can be used to generate ‘short cut’
designs for thermally coupled columns. These designs can provide sufficient information to assess
the value of thermal coupling for a given separation and provide initial estimates for a rigorous
process simula- tor. Results from rigorous simulation then enable assessment of whether the
energy and cost savings from using thermal coupling are significant enough to utilise the
technology rather than conventional distillation. The method presented is applicable to ternary
systems but any multi-component mixture requiring separation into three products can be
considered a pseudo- ternary”. The method is therefore appropriate to the separation of any
mixture of more than two components. A convenient basis for assessing distillation systems is by
comparing overall vapour rate. The lower the vapour rate the smaller the column diameter, the
smaller the reboiler, and the lower the energy consumption. Thus, the lower the vapour rate the
lower the capital and operating costs. Vapour rate is therefore a very good parameter for
evaluating distillation systems and can usually be determined quite easily. As the objective during
conceptual design is to be able to rapidly assess whether thermally coupled columns will provide
signifi- cant savings over conventional columns, detailed calcu- lation and costing is not justified.
Rigorous simulation is ultimately needed in any case to formally assess the best column
arrangements. The ‘classical’ heuristics used in the screening of conventional distillation column
sequences7 aim to reduce column vapour rates and can often be used to select between column
arrangements without any calcu- lations being necessary. However, they do not apply to thermally
coupled columns. To assess these columns, vapour rates must be calculated to compare overall
energy consumption against conventional column arrangements. Consider a situation where the
heuristics are used for selection between column arrangements but they give conflicting results
and it is not clear whether the direct or indirect sequence (Figures 3 and 4) is the better. To assist
the evaluation, column internal vapour rates are calcu- lated to provide a comparison between the
two systems. From knowledge of the feed condition and composition a material balance may be
defined by specifying desired recoveries of the
key components in the products and assuming
constant molal overflow. King’ details how the
split of non-key components can be
conveniently found from the Fenske equation.
The minimum vapour rates may be found from
the Underwood procedure by following a
standard textbook7,‘s or by a simple computer
program which should be readily available to
most designers. Identification of minimum
vapour rates is therefore relatively simple and is
conventional design practice. Often the
calculation of total vapour rate in this way is
sufficient to show which of the two sequences
will be cheaper. By applying the Fenske-
Underwood- Gilliland method the number of
column trays and total energy requirements can
be found. The application of the Fenske-
Underwood-Gilliland technique is normally
sufficient to now identify the better sequence,
but if necessary the results can be used as a
starting point for rigorous simulation and capital
cost estimation. The Underwood procedure
cannot be used to evaluate the side column
systems of Figures 5 and 6 as with conventional
columns because it is only applicable to single
feed columns consisting of two sections (one
above and one below the feed) with two
products. The state of the single feed must also
be known. However, by considering the function of the different column sections in terms of the
key components that they separate, the thermally coupled columns can be ‘transformed’16 into
two columns of two sections as shown in Figures 8 and 9.

The numbering system used in Figures 8 and 9 for the different column sections is exactly as for
Figures 5 and 6 to highlight what has been done. In terms of their performance and energy
requirements the ‘transformed columns are identical to the original thermally coupled columns.
The conventional Underwood method is now applicable because the condition of the ‘net feed’ to
a column can be used directly in the relevant equations153i6. For instance, in Figure 8, the ‘net
feed’ to the down- stream column is (Lsmin - T/smin) and the liquid fraction of the feed is given by:

The flowrate and composition of the ‘net feed’

is obtained from material balance around the
upstream column in the same way as for a
conventional column. From the feed condition, found by use of Equation (S), the minimum internal
flows in the downstream column can be found. By then modifying the sequence of Figure 8 back
to the actual arrangement of Figure 5, a feasible material and energy balance around the actual
columns can be fully defined. A similar treatment applies for Figure 6. The procedure employs the
standard Underwood method to handle subcooled and superheated feeds, i.e. the value of q can
range from large negative to large positive. By further use of the standard Fenske-Underwood-
Gilliland method the number of trays and overall energy requirements are found and as with the
conventional columns the better sequence of the two can then be determined.