02638762/97/$10.00+0.

00
q Institution of Chemical Engineers

NON-EQUILIBRIUM MODELLING OF DISTILLATION

J. A. WESSELINGH
Department of Chemical Engineering, University of Groningen, Groningen, The Netherlands

here are nasty conceptual problems in the classical way of describing distillation
columns via equilibrium stages, and ef ciencies or HETPs. We can nowadays avoid
these problems by simulating the behaviour of a complete column in one go using a
non-equilibrium model. Such a model has phase equilibria, multi-component mass transfer,
heat transfer, and ow models built in.
Keywords: distillation; design; operation; non-equilibrium; multi-component

INTRODUCTION

EFFICIENCY AND HETP

This is a lecture on the way that we engineers model

distillation. How we have done such modelling, how we
would like to do it, and how far we have come at this
moment. The ideas that I will be bringing forward are not
my own. I owe them mostly to R. Krishna, R. Taylor, H.
Kooijman and A. Gorak. These are people who have spent a
fair bit of their lives developing modern multicomponent
simulation methods of distillation. I am just using their
results.

Of course, we engineers have found ways of coupling our

theoretical models to practical equipment. The two concepts
mostly used for this purpose are (Figure 3):

the (Murphree vapour) `ef ciency of a tray or plate and

the `height equivalent to a theoretical plate (HETP) for
packings.

When using a Murphree ef ciency, we assume that the

change in vapour composition on a real tray is a certain
fraction of that obtained in an equilibrium stage. This allows
us to approximate the behaviour of real trays. The concept
works quite well for binary separations; the two components
there have equal ef ciencies. Also the ef ciencies are often
fairly constant along a column, and therefore an ef ciency is
a useful way of summarizing practical experience. It often
has a value of about 0.7.
For packings, we look at the composition of the liquid at a
certain height. We then assume that further up in the
column, we will be able to nd vapour with a composition
that is in equilibrium with the liquid considered. The
difference in height between these two points is the HETP.
Also here, this works fairly well for binary mixtures. The
HETPs are the same for the two components and they are
often fairly constant along a column. Experience shows that
the value of the HETP is usually a few tenths of a metre.
Although the ef ciency and the HETP have been useful
for summarizing experience on trays and packings, these
concepts have two serious de ciencies:

EQUILIBRIUM STAGE
Chemical plants consist of separate pieces of equipment
(Figure 1). Some of these will probably be distillation
columns. Any description of distillation begins with the
concept of `stages : fairly large parts of the column that
have well de ned boundaries. For a tray column, we can
regard a single tray as a stage. There is no natural boundary
to the stages in packed columns (unless we consider packed
sections as stages). Even so, we engineers try also to
subdivide packed columns into stages, sometimes with
ludicrous results.
There are well de ned ows entering and leaving any
stage. These can be the main vapour and liquid ows
through the column, or feed or drawoff ows. They may
consist of mass or heat. Conceptually, the simplest kind of
stage is the `equilibrium stage or `theoretical plate . For
such a stage (which does not exist in reality), the (vapour
and liquid) streams leaving the stage are assumed to be in
equilibrium (Figure 2). This implies that the chemical
potential of any component has the same value in vapour
and liquid, and also that vapour and liquid have the same
temperature.
With the equilibrium stage model we can simulate many
of the properties of real systems. To describe an equilibrium
stage, we `only need phase equilibrium data (thermodynamics) and mass and energy balances. The model is
beautifully consistent, and has attracted the attention of
generations of engineers and thermodynamicists. However,
it has one great weakness: it has no direct connection to real
equipment.

they are not easily related to the construction and

behaviour of equipment, and

in multicomponent mixtures, their behaviour is extremely
confusing.
I even think that these two concepts may be retarding the
development of distillation, and will argue that there are
good reasons to give them a less prominent position than
they have today.
`EXACT MODELS
If we do not wish to use ef ciencies or HETPs, what
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WESSELINGH

Figure 3. Tray ef ciency and `Height Equivalent to a Theoretical Plate

(HETP) lead to real equipment.

Figure 1. Plant, separation equipment and stages.

should we do? The dream of the modern engineer is to

subdivide each piece of equipment into zillions of little
elements dx dy dz, each of which will contain part of one
of the phases in the equipment (Figure 4). We should then
set up difference forms of the Navier-Stokes equations to
de ne the hydraulic ows, the Fick or Maxwell-Stefan
equations to calculate diffusion ow, Fourier equations for
energy transfer and all required balances and boundary
conditions. These myriads of equations are then to be solved
by our brilliant parallel supercomputer algorithms, and they
will tell us everything we wish to know. Such a model can
be used for trays, for packings or for any piece of
equipment. It will deliver beautiful and impressive multidimensional colour plots. It will describe unsteady,
turbulent, chaotic two phase ow, the breaking up and
coalescence of drops, their moving and deforming boundaries, interfacial motion and mass transfer, incomplete and
irregular wetting of packings, gas and liquid entrainment...
Unfortunately, there are still a few problems. For a
realistic simulation of the important phenomena in a
column, my guess is that we would need elements with
dimensions of about one micrometer. That is one million
elements per metre, or 101 8 elements per m3 of column. This
number is almost 109 times the number of bytes on the two
Gigabyte hard disk of the multimedia computer that you are
thinking of buying for educating the kids (and for using
yourself in the evening to hone your communication skills).
So it looks as if we still have a long way to go before we can

Figure 2. The equilibrium stage.

simulate the details of multiphase ow. Of course this also

means that the subject is a challenging one, and possibly a
good topic to let our students and young engineers sharpen
their teeth. However, with this approach, we should not
expect complete solutions to practical problems in the short
term.
NON-EQUILIBRIUM MODEL
Current non-equilibrium models are less ambitious. They
contain a smaller number of elements per m3 than the
`exact models above. Say, ve, instead of the 101 8 that we
were considering. We choose these elements such that they
allow a simple simulation of what we think are the
important characteristics of our mass transfer equipment:

the equilibrium distribution of all components between

the two phases (thermodynamics),
the effects of large scale ow and mixing patterns and
the effects of diffusional heat and mass transfer resistance
near phase interfaces.
How few elements we choose, is a balancing act. With too
few elements our model will not be realistic, with many
elements it will be impossible to obtain the model
parameters (although..., with 101 8 elements, you do not
need any model parameters).
EQUILIBRIUM DISTRIBUTION
At the interface between the two phases, we assume (also
in the non-equilibrium model) that equilibrium exists. (In
absorption with a chemical reaction, this may not be true,
but we do not consider that here). To describe the
equilibrium, we need a thermodynamic model of the

Figure 4. Exact models: the dream of the modern engineer.

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Figure 5. Even in a structured packing, ow is not ideal.

Figure 7. More realistic ow models.

mixtures considered. In multicomponent distillation and

absorption two kinds of models are in common use:

especially near walls and due to the contacting planes

between packing elements.
On trays, the vapour is often assumed to pass upwards in
plug ow. (I do not know whether anybody has ever been
able to check how well or how poorly this holds.) The liquid
has a cross ow pattern; at the sides of columns there can
more or less stagnant zones. On short tray passes the overall
effect is often similar to that of complete mixing of the
liquid. If we have a spray of drops on the tray, there will be a
range of drop sizes and the behaviour of small and large
drops may differ considerably. We may expect small drops
to attain equilibrium more rapidly than large drops.
Something similar applies to bubbles of different sizes in
a froth.
The simplest ow model is that where both phases are
assumed to be ideally mixed (Figure 6). This model only
contains two bulk phases with convective ows in and out.
In addition it contains three other elements: the phase
interface and two mass transfer resistances on either side of
the interface. We discuss these elements in the next section.
In the examples that we discuss further on, we will also be
using ow models which are a bit more realistic (Figure 7):

multicomponent equations of state such as the SoaveRedlich-Kwong and Peng-Robinson equations and
Gibbs excess energy models, such as the Wilson, NRTL
and UNIQUAC / UNIFAC models.

The former are primarily used for high pressure equilibria of

simple mixtures, such as those which dominate the oil
industry. The latter are useful for strongly non-ideal
mixtures at not-too-high pressures, such as are often found
in the chemical industry.
These are the same equations that we use in equilibrium
stage calculations. They yield both the distribution coef cients of all components and their enthalpies. In nonequilibrium calculations we use the same equations to
obtain the driving forces for mass transfer (which are the
chemical potential gradients, as we shall see a little further
on).
LARGE SCALE MOTIONS
Motions of gas and liquid on the scale of a tray or
packing, have a large effect on equipment performance. The
ideal ow pattern in separation equipment is usually
countercurrent plug ow. Modern structured packings give
patterns that are fairly close to this ideal. However, even
here, things like turbulence, differences between the
channels, and maldistribution of liquid or vapour at feed
points do cause deviations from ideality (Figure 5).
Entrainment of liquid by the vapour, and of vapour by the
liquid, causes backmixing. In large, long column sections,
irregularities of the ow have been found to develop,

on a tray: liquid mixed, vapour mixed or in plug ow, and

Figure 6. The simplest non-equilibrium model.

Figure 8. Complicated ow patterns using simple elements.

Trans IChemE, Vol 75, Part A, September 1997

no entrainment or backmixing,
in a packing: both phases in plug ow, no maldistribution.
Even these models are not always adequate.
There are many different ways to describe more
complicated ow patterns (Figure 8). We can approximate
plug ow by stacking a number of mixed elements. When a
phase consists of coarse and ne parts (such as large and

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WESSELINGH

small drops), we may split it in two pseudo phases. We may

expect a convective exchange between these pseudo phases.
Entrainment and backmixing can be simulated by allowing
extra ows going in and out of each phase. Finally,
maldistribution can be simulated using parallel stages with
different ow ratios. As already mentioned, the problem
with these more complicated models is that we do not know
their parameters well enough.
MASS TRANSFER
The second important mechanism in our models is the
description of mass and heat transfer between the phases (and
pseudo phases). In most equipment, ow of both phases is
highly turbulent. (This applies both to the continuous and the
dispersed phase.) Turbulence provides a rapid levelling of
concentration and temperature differences. So on not-toolarge scales (say up to ten centimetres), the concentrations
and temperatures in the bulk of uids can be taken as
homogeneous. However, near phase interfaces, turbulence
dies out (Figure 9). Eddies do not pass across interfaces. Near
these interfaces, only three transport mechanisms remain, all
of which are much slower than turbulence:

`drift : convective transport of both heat and matter due to

an overall displacement of matter across an interface,

diffusion: the transport of matter due to composition
gradients and molecular motion within the uid and
conduction: the transport of energy by a temperature
gradient and molecular motion.
The layers (or ` lms ) where turbulence does not dominate
transport, are very thin: roughly one tenth of a millimetre in
gases and ten micrometres in liquids.
The traditional description of mass transfer begins with
Fick s law. This states that ux of a component (in a binary
mixture) is proportional to the concentration gradient of that
component and a diffusivity. In addition, the component
may also be carried along by drift:
dx
Ni = - ctotal Di i + Ntotal xi
(1)
dz , ) ) & ( ) ) *
, )))))))& ( )))))))*
diffusion

drift

For most engineering applications, a difference approximation of this equation suf ces:
D
Ni = - kibinary ctotal D xi + Ntotal xi kibinary = i
(2)
d

The parameter kibinary is a binary ` lm theory mass transfer

coef cient. We could also have used a more realistic
`surface renewal theory to obtain it.
Unfortunately, the description above does not transfer
well to mixtures with more than two components. (And
most mixtures do contain more than two components!) This
is for two reasons:

it does not take the interactions between the different

components into account and
it does not allow for the fact that the driving force for
mass transfer is not the concentration gradient, but the
gradient of the chemical potential.

The rst effect is often important, especially for the

behaviour of trace components. The second effect can be
important is systems where liquid resistance dominates.
If we do take all the trouble to make a non-equilibrium
model of a column, we can best use a fundamental
multicomponent model of mass transfer through the interface. A good choice are the Maxwell-Stefan equations.
These equations consider each component i in turn. The
driving force on i will cause it to move with respect to
the mixture. This motion is counteracted by friction with the
other species j.
The driving force is the chemical potential gradient:
dl i
(driving force on i) = (3)
dz
This is a real driving force, with units of Newton per mole. If
we have equilibrium, we have no gradients, no driving
forces and no motion. The chemical potential contains
contributions due to mole the fraction and the activity
coef cient of i:
l i = RT ln(c i xi ) + const
(4)
The contribution of the mole fraction gradient is similar to
that of the concentration in the Fick equation. However, that
equation does not consider the effect of non-ideality via the
activity coef cient.
The friction force between i and j (per mole of i) is
proportional to the local mole fraction of j, a friction
coef cient f i ,j and the difference in drift velocities between
the two components:

=xf

(friction)i,j

j i, j

(ui

- uj )

(5)

When we equate the driving force with the sum of all

friction forces on i, we obtain the Maxwell-Stefan
equations:
dl i
- dz

=S

n
j =1

xj f

i,j

(ui - uj )

(6)

These equations allow a consistent description of diffusion

in mixtures with any number of components.
We are usually not interested in species velocities through
the interface, but in their uxes:
Ni

=cu

i i

(7)

Also, we will also normally use multicomponent diffusion

coef cients instead of friction coef cients:
RT
ij =
(8)

Figure 9. Mass transfer resistances: the ` lm near interfaces.

ij

Finally, we will use a difference form of the resulting

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Figure 10. The NE-model contains a `drawing of the column.

equations, which contain the multicomponent mass transfer

coef cients:
kij

i, j

(9)

We will not write out these equations; they are not

enlightening. The important thing to understand, is that the
multicomponent diffusivities and mass transfer coef cients
can be estimated fairly well from binary data.
In the actual numerical calculations it is handier to use the
inverse of our equations. We can write these in a form which
reminds us of the Fick equations. In this formulation, the
mass transfer coef cients have been corrected for the effects
of thermodynamic non-ideality:
(N) = - ctotal [k ](D x) + (x)Ntotal

(10)

You should not be misled by the simple form of these

equations. Especially the matrix of mass transfer coef cients is a very complicated (and incomprehensible)
function.
In addition to the mass transfer equations, we need heat
transfer equations. These require estimates of the heat
transfer coef cients in both phases, and they must
incorporate heat transport through the interface due to drift.
I have restricted myself to a brief (and incomplete)
summary of what is required for the description of heat and
mass transfer. If you really want to understand the subject,
the best reference is the book by Taylor and Krishna1 . You
must reckon on spending quite some time however;
multicomponent mass transfer is not a simple subject.
However, using the results of others is not at all that
dif cult. A simpler introduction is given in Wesselingh and
Krishna2 .
MODEL REQUIREMENTS
For the equilibrium stage model, we only need two kinds
of physical properties:

vapour / liquid equilibria and

enthalpies.
The non-equilibrium model gives a much more complete
description of the equipment. However, it does require
much more data. Here we need, in addition to the two sets
above, all properties that are required to describe the ow,
Trans IChemE, Vol 75, Part A, September 1997

heat transfer and mass transfer in the equipment, such as:

densities
viscosities,
friction coef cients,
surface tension,
interfacial area,
diffusivities,
thermal conductivity,
heat and mass transfer coef cients,

and so on. We need these for the different mixtures in every

element of the equipment, not only for the separate
components. This means that we need a substantial
database.
The second point in which equilibrium and nonequilibrium models differ greatly is in how detailed the
equipment must be described. In the equilibrium model, we
only need to give the number of stages and the location of
the different feed and withdrawal points. The nonequilibrium model, in contrast, needs to contain a complete
`drawing of the column (Figure 10):

the number of trays in the different sections,

the diameters of the sections,
the tray heights,
the downcomer con gurations,
the hole diameters,
the free areas,
the weir heights,
and so on and so on...
When we are designing a column, we can leave it to the
program to determine all these parameters. However, when
we are simulating an existing column, we must provide all
these data. This input can be quite a burden.
All examples have been worked out using ChemSep
version 3.03. This is a non-equilibrium modelling program
written by Ross Taylor and Harry Kooijman3 . (It also contains
ash and equilibrium models). ChemSep is available for
educational institutions for a small fee and it runs on IBMtype personal computers. (ChemSep requires a 386 or better,
and 4 Mbytes of memory. It is a DOS program, but it also
runs under Windows 3.1 and Windows 95). ChemSep has a
friendly menu based input, and extensive graphic and tabular
output options.
A program that is similar, and available commercially, is
RATEFRAC from Aspen Technologies. RATEFRAC can

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WESSELINGH

be incorporated in the ow schemes of complete processes;

the current version of ChemSep only allows this to a limited
extent. However, RATEFRAC does take more time to learn,
and it is a little more expensive.
EXAMPLES
To give you an idea of how non-equilibrium modelling
works in practice, I will discuss three examples:
1. a depropanizer: a high pressure column from an oil
re nery with four components, equipped with sieve trays,
2. the non-isothermal absorption of acetone from a nitrogen/
acetone mixture into water in a conventional packed column
and
3. the extractive distillation of methyl cyclohexane using
phenol as a solvent in an old column with bubble cap trays.
In the rst example, we have relatively ideal solutions and
small heat effects. In the second example, heat effects are
important. The last example considers a strongly non-ideal
mixture with varying ows. These are examples from a
course that myself, A. Gorak, H. Kooijman and T. Reith
regularly give to graduate students in chemical engineering.
All examples can be done by our students within an hour
(experienced engineers only need a fraction of these times).
A DEPROPANIZER
Our rst example is a column from an oil re nery
(Figure 11). The feed contains four components. In order of
volatility: pentane, butane, propane and ethane. (In a real
column there would be more, but this is enough to show
most of the behaviour of the column). The column is to split
the feed between butane and propane.
We will use the Peng Robinson equation of state to
describe the phase equilibria and enthalpies. We choose the
top temperature at 408 C (to allow cooling with ambient air).
With the `Flash unit of ChemSep, we nd that we need a
pressure of 22 bar. With a total condenser, 28 sieve trays, a
partial reboiler and a boiling point feed on stage 16,
combined with a re ux ratio of 2, we obtain the desired
separation. (This is not necessarily an optimal design, but
we may change it later.) It takes me about two minutes to get

Figure 11. A depropanizer.

Figure 12. Flow rates in the depropanizer.

the required data into the program. I use `design mode , so

that the program sizes the column for me, and I do not need
to provide any other data than the type of internal used
(sieve trays). The run converges without dif culty on my
486 DX 66 MHz machine in 21 seconds. Output graphs
show ow rates (Figure 12) which are almost constant in the
two sections, except for a sharp increase of the liquid ow at
the feed tray.
The ows of the components vary strongly along the
column (Figure 13), with ethane and propane being
concentrated in the top and the other components in the
bottom. The two minor components (ethane and pentane)
have constant ow rates in the greater part of the two
sections, the rates only changing rapidly at the ends of the
column. The propane ow generally decreases as we
pass down the column, while butane increases. There are
however several irregularities. These are mainly because
propane is displaced by the minor components in certain
parts of the column. Similar remarks can be made on
butane. We see that the trays above the feed stage do not
provide much separation between butane and propane;
this is an indication that we should put the feed on a higher
tray.
The transfer rates of the components on the different trays
differ wildly (Figure 14), showing how complicated such a
system is. In the greater part of the column the transfer rates
of ethane and propane are negative, which means that they

Figure 13. Component ow rates in the depropanizer.

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NON-EQUILIBRIUM MODELLING OF DISTILLATION

Figure 14. The mass transfer rates on each stage of the components in the
depropanizer.

are moving into the vapour. The opposite holds for butane
and pentane.
We can get out any amount of detailed information on the
column. I restrict myself to the preliminary tray layout
provided (as geometrical parameters) by the program
(Figure 15). You can immediately nd out what the effects
are of modifying the design (for example the tray height, or
the free areas) by running the program again. Or you can
check whether all trays are operating within their hydraulic
limits, and how this changes if you modify the design. This
is one of the beautiful things of non-equilibrium models.
The non-equilibrium model does not use ef ciencies.
However, from its results, it can calculate the ef ciencies of
each component on each tray. These are shown in Figure 16
and I advise you to look at these carefully. The rst thing to
be noted is that all four ef ciencies are different. The second
is, that they vary wildly along the column. The two minor
components have extreme values of - 200% (yes, negative!)
and + 200% (far larger than the 100% maximum expected
for a tray with a mixed liquid). Even the ef ciency of butane
varies between 70% and 110%. Remember that these are
results for a simple, almost ideal mixture; they are typical of
any multicomponent separation.
My experience is, that many engineers have dif culty in

Figure 15. The tray layout of our depropanizer.

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535

Figure 16. Murphree vapour ef ciencies of the components in the

depropanizer.

believing these results. They know from experience that

binary ef ciencies are fairly constant and well behaved. So I
have added one calculation for a similar column, but now
with a binary feed of only propane and butane (Figure 17).
Here, indeed, we see that the ef ciencies of the two
components are equal, and that they have a more or less
constant value of about 85%.
From this example we see that experience with binary
mixtures does not translate to multicomponent mixtures in a
straightforward manner. For a binary, an ef ciency may be a
useful way of summarizing experience. However in multicomponent mixtures, ef ciencies are hardly predictable.
They are different for all components and may vary from
minus in nity, through zero, up to plus in nity. In my
experience, ef ciencies in multicomponent separations are
thoroughly confusing. Chemical engineers should abandon
the use of ef ciencies. Non-equilibrium models have made
them irrelevant.
There are many other aspects of binary distillation, that
do not translate well into multicomponentmixtures. Figure 18
shows the McCabe-Thiele diagram of the two key components (also provided by ChemSep). In the rst instance it
looks much like that of a binary mixture. A closer inspection
shows that the operating lines are strongly curved. In this
example they even run through a small loop near the feed
stage. There are other differences between this example and a
proper binary. Here, although the feed is at its boiling point,

Figure 17. With a binary mixture, ef ciencies are equal and well behaved.

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WESSELINGH

Figure 18. The pseudo-binary McCabe-Thiele diagram of the depropanizer.

the feed line is not vertical. A close look at the diagram shows
that the `stairs do not extend up to the equilibrium line. This
is understandable; we are dealing with a non-equilibrium
model. However, we have seen that the ef ciencies of the
propane and butane are not equal, so the height of each step
cannot be a direct measure of the vapour ef ciency as it is in a
binary mixture.
A PACKED ABSORBER
Our next example (Figure 19) seems to be a simple
problem, suitable for an introductory lecture in separation
processes. We are to absorb a small amount of acetone from
a large stream of nitrogen. The solvent is water, and the
column is lled with Raschig rings (as it should be in any
good, old fashioned exercise). You might think this problem
could be adequately described using the Kremser equation
and theoretical plates with a constant height (HETP). Let us
have a look, again using ChemSep.
I did this exercise using the NRTL equations for the phase
equilibria of the ternary mixture acetonenitrogenwater,
and the Onda equations for mass transfer in the packing.
Both phases were taken to be in plug ow and the column
consisted of 30 elements of one third of a metre each. The
solvent ow is close to the minimum value and under these
conditions ChemSep will not converge in one go. I had to
begin with a large solvent ow. Then I used the results as
starting values for a new run. In eight runs, I brought the
solvent ow back from 2000 to 500 mol s- 1 . This may sound
a lot of work, but each run only took about ten seconds.

Figure 19. The acetone absorber.

Figure 20. Mass transfer rates of the components in the absorber.

Figure 20 shows the mass transfer rates in the different

sections. We see that acetone absorbs throughout the
column, but in an irregular manner. Nitrogen (which is
hardly soluble in water) absorbs so little that this is not
visible in the plot. The most spectacular component is
water. Water condenses at about the same rate as acetone in
the upper part of the column, but evaporates with high rates
in the bottom sections. This means that there is a large
internal water recycle in the column, which carries a
substantial amount of heat. All this shows up in the
temperature pro le (Figure 21). We see notable differences
in temperature between gas and liquid. (We have also
plotted the interface temperature; this shows that the greater
part of the temperature difference is in the gas phase). If you
have a good look, you will see that the interface temperature
is higher than the bulk liquid temperature in the top of the
column, but lower in the bottom. This means that the
direction of heat transfer changes (at just about the position
of the temperature bulge). The situation is obviously far
more complicated than the simple textbook problem that we
had in mind!
The non-equilibrium model does not use HETPs.
However, from its results, it can calculate the HETPs of
each component in each element. These are shown in Figure
22 and I advise you to look at these carefully. The rst thing
to be noted is that all three HETPs are different. The second
is that they vary wildly along the column. Nitrogen has an

Figure 21. Temperature pro les in the absorber.

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Figure 22. HETPs of the components in the absorber.

Figure 24. Flows of the components in the extractive distillation.

extreme value of - 2.6 m (yes, negative!) and water of

+ 67 m. (You may argue that you are not interested in the
HETP of nitrogen, but the point is that an HETP can be
negative). Even the HETP of acetone varies from 0.4 to 1 m.
Remember that these are results for what you thought was a
simple introductory example.
From this example we see that experience with binary
mixtures does not translate to multicomponent mixtures in a
straightforward manner. For a binary, an HETP may be a
useful way of summarizing experience. However in multicomponent mixtures, HETPs are hardly predictable. They
are different for all components and may vary from minus
in nity, through zero, up to plus in nity. In my experience,
HETPs in multicomponent separations are thoroughly
confusing. Chemical engineers should abandon the use of
HETPs. Non-equilibrium models have made them irrelevant.

two components have close boiling points; they cannot be

separated by conventional distillation. However, they do
differ in polarity, MCH being the least polar of the two. We
separate them by adding a large excess of a polar, nonvolatile solvent (here phenol) to the liquid. This happens a
few trays below the top of the column. The activity of MCH
in phenol is larger than that of toluene, so it becomes the
most volatile and ends up in the top of the column.
I did this run using the UNIFAC model to describe the
(strongly non-ideal) vapour liquid equilibria. I used bubble
cap columns and the AIChE design method for bubble cap
trays. This to honour my predecessors of forty years back.
Also here, I needed to start with an excess of solvent to get
ChemSep to converge. Then I reduced the amount of solvent
until I got the ow pro les shown in Figure 24. This is not
an optimal design, but it can easily be improved. I had it
within half an hour. Large non-idealities do not pose any
exceptional problems to the non-equilibrium model.
You might ask how the tray ef ciencies behave. Well,
even worse than those of the depropanizer. They run all over
the place. However, that should be nothing new to you, so I
have not even plotted them.

EXTRACTIV E DISTILLATION
We will not spend much time on our last example. It is
only there to show that the non-equilibrium model is also
applicable to (what you think are) complicated non-ideal
mixtures. Here we consider the extractive distillation of
methyl-cyclohexane (MCH) and toluene (Figure 23). These

FINAL REMARKS
In this lecture, we have had a look at the background of
non-equilibrium modelling. We have seen that it can give us
quite a detailed understanding of what is going on in a
distillation column. It also allows us to see the effects of
changing any design parameter, including the effects of
equipment geometry. This is an important extension of
the classical analysis using equilibrium stages. The nonequilibrium models are also applicable to multicomponent
separations; they do not need ef ciencies or HETPs which
are not predictable in multicomponent mixtures. Finally,
modern non-equilibrium computer models of distillation
columns are quite easy to use. So I hope to have convinced
you that there is every reason to start using them.
Does this mean that there are no problems left to be
solved in distillation? Fortunately, not! Some of the many
kinds of problems we still have to live with are:

Figure 23. Extractive distillation of MCH/toluene using phenol as solvent.

Trans IChemE, Vol 75, Part A, September 1997

1. Big numerical models do not solve problems; they only

improve upon your solution. So you must have an idea of
what you are doing, so as to provide starting values.
Otherwise convergence is not assured.

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WESSELINGH

2. The results are only as good as the important parts of the

model are. During development of the non-equilibrium
model it has become clear that our knowledge of the details
of what happens inside a column is still very incomplete.
3. Even carefully written programs contain bugs.
There are several areas where we have found that current
models and correlations (at least those in open literature) are
inadequate:

correlations for interfacial areas

correlations for gas phase transfer coef cients
minimum load correlations and
descriptions of maldistribution in packed columns.

2. Wesselingh, J. A. and Krishna, R., 1990, Mass Transfer, (Ellis

Horwood, Chichester).
3. Taylor, Ross and Kooijman, Harry, ChemSep, (a program available for
educational institutes for a small fee from CACHE Corporation, P.O.
Box 7939, Austin, TX 78713-7939, USA.) You will need version 3.0 or
higher. (The program is continually being revised.) More information is
can be found on the WWW page of Taylor and Kooijman at http://
www.clarkson.edu/, chengweb/faculty/taylor/chemsep/chemsep.html.
You can also try http://www.che.utexas.edu:80/cache/

ADDRESS
Correspondence concerning this paper should be addressed to Professor
J. A. Wesselingh, Department of Chemical Engineering, University of
Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands.

It is time that we engineers try to get these data in order.

REFERENCES
1. Taylor, Ross, and Krishna, R., 1993, Multicomponent Mass Transfer,
(John Wiley & Sons, New York).

This paper is a plenary presentation from the Distillation and Absorption

1997 conference, Maastricht, The Netherlands, 8 10 September 1997. The
papers from the conference are to be published in the IChemE Symposium
Series, No 142.

Trans IChemE, Vol 75, Part A, September 1997