Ghulam Murtaza, Junaid Jamil , Usama Iqbal, Hafiz

Zia, Muhammad Umair

Term Report
Distillation is a process of separating the component substances from a liquid mixture by
selective evaporation and condensation. Distillation may result in essentially complete separation
(nearly pure components), or it may be a partial separation that increases the concentration of
selected components of the mixture. In either case the process exploits differences in the volatility of
mixture's components. In industrial chemistry, distillation is a unit operation of practically universal
importance, but it is a physical separation process and not a chemical reaction.

Commercially, distillation has many applications. For example:

 In the fossil fuel industry distillation is a major class of operation in obtaining materials
from crude oil for fuels and for chemical feed stocks.
 Distillation permits separation of air into its components — notably oxygen, nitrogen,
and argon — for industrial use.
 In the field of industrial chemistry, large ranges of crude liquid products of chemical
synthesis are distilled to separate them, either from other products, or from impurities, or from un
reacted starting materials.
 Distillation of fermented products produces distilled beverages with a high alcohol content, or
separates out other fermentation products of commercial value.

An installation for distillation, especially of alcohol, is a distillery. The distillation equipment is a still.

Types of Distillation:

Batch distillation:
Heating an ideal mixture of two volatile substances A and B (with A having the higher volatility, or
lower boiling point) in a batch distillation setup (such as in an apparatus depicted in the opening
figure) until the mixture is boiling results in a vapor above the liquid which contains a mixture of A
and B. The ratio between A and B in the vapor will be different from the ratio in the liquid: the ratio in
the liquid will be determined by how the original mixture was prepared, while the ratio in the vapor
will be enriched in the more volatile compound, A (due to Raoult's Law, see above). The vapor goes
through the condenser and is removed from the system. This in turn means that the ratio of
compounds in the remaining liquid is now different from the initial ratio (i.e., more enriched in B than
the starting liquid).

The result is that the ratio in the liquid mixture is changing, becoming richer in component B. This
causes the boiling point of the mixture to rise, which in turn results in a rise in the temperature in the
vapor, which results in a changing ratio of A : B in the gas phase (as distillation continues, there is
an increasing proportion of B in the gas phase). This results in a slowly changing ratio A : B in the
distillate.

If the difference in vapor pressure between the two components A and B is large (generally
expressed as the difference in boiling points), the mixture in the beginning of the distillation is highly
enriched in component A, and when component A has distilled off, the boiling liquid is enriched in
component B.

Continuous distillation:
Continuous distillation is an ongoing distillation in which a liquid mixture is continuously (without
interruption) fed into the process and separated fractions are removed continuously as output
streams occur over time during the operation. Continuous distillation produces a minimum of two
output fractions, including at least one volatile distillate fraction, which has boiled and been
separately captured as a vapor, and then condensed to a liquid. There is always a bottoms (or
residue) fraction, which is the least volatile residue that has not been separately captured as a
condensed vapor.

Continuous distillation differs from batch distillation in the respect that concentrations should not
change over time. Continuous distillation can be run at a steady state for an arbitrary amount of time.
For any source material of specific composition, the main variables that affect the purity of products
in continuous distillation are the reflux ratio and the number of theoretical equilibrium stages, in
practice determined by the number of trays or the height of packing. Reflux is a flow from the
condenser back to the column, which generates a recycle that allows a better separation with a
given number of trays. Equilibrium stages are ideal steps where compositions achieve vapor–liquid
equilibrium, repeating the separation process and allowing better separation given a reflux ratio. A
column with a high reflux ratio may have fewer stages, but it refluxes a large amount of liquid, giving
a wide column with a large holdup. Conversely, a column with a low reflux ratio must have a large
number of stages, thus requiring a taller column.

Main Components of Distillation Columns

Distillation columns are made up of several components, each of which is used either to
transfer heat energy or enhance material transfer. A typical distillation contains several
major components:
 a vertical shell where the separation of liquid components is carried out
 column internals such as trays/plates and/or packings which are used to
enhance component separations
 a reboiler to provide the necessary vaporisation for the distillation process
 a condenser to cool and condense the vapour leaving the top of the column
 a reflux drum to hold the condensed vapour from the top of the column so
that liquid (reflux) can be recycled back to the column
The vertical shell houses the column internals and together with the condenser and re
boiler, constitute a distillation column. A schematic of a typical distillation unit with a
single feed and two product streams is shown below:
Basic Operation and Terminology
The liquid mixture that is to be processed is known as the feed and this is introduced
usually somewhere near the middle of the column to a tray known as the feed tray. The
feed tray divides the column into a top (enriching or rectification) section and a bottom
(stripping) section. The feed flows down the column where it is collected at the bottom in
the reboiler.

Heat is supplied to the reboiler to generate vapour. The

source of heat input can be any suitable fluid, although in
most chemical plants this is normally steam. In refineries,
the heating source may be the output streams of other
columns.  The vapour raised in the reboiler is re-introduced
into the unit at the bottom of the column. The liquid
removed from the reboiler is known as the bottoms
product or simply, bottoms.

The vapour
moves up the column, and as it exits the top
of the unit, it is cooled by a condenser. The
condensed liquid is stored in a holding vessel
known as thereflux drum. Some of this liquid
is recycled back to the top of the column and
this is called the reflux. The condensed liquid
that is removed from the system is known as
the distillate ortop product.

Thus, there are internal flows of vapour and liquid within the column as well as external
flows of feeds and product streams, into and out of the column.
 COLUMN INTERNALS
Trays and Plates
The terms "trays" and "plates" are used interchangeably. There are many types of tray
designs, but the most common ones are :
Bubble cap trays
A bubble cap tray has riser or chimney fitted over each hole, and a
cap that covers the riser. The cap is mounted so that there is a
space between riser and cap to allow the passage of vapour. Vapour
rises through the chimney and is directed downward by the cap,
finally discharging through slots in the cap, and finally bubbling
through the liquid on the tray.

Valve trays
In valve trays, perforations are covered by liftable caps. Vapour flows lifts the caps,
thus self creating a flow area for the passage of vapour. The lifting cap directs the
vapour to flow horizontally into the liquid, thus providing better mixing than is
possible in sieve trays.
 
Sieve trays
Sieve trays are simply metal plates with holes in
them. Vapour passes straight upward through the
liquid on the plate. The arrangement, number and
size of the holes are design parameters.

Because of their efficiency, wide operating range, ease of maintenance and cost factors,
sieve and valve trays have replaced the once highly thought of bubble cap trays in many
applications.

Liquid and Vapour Flows in a Tray Column

The next few figures show the direction of vapour and liquid flow across a tray, and across
a column.
Each tray has 2 conduits, one on each side, called ‘downcomers’. Liquid falls through the
downcomers by gravity from one tray to the one below it.The flow
across each plate is shown in the above diagram on the right.

A weir on the tray ensures that there is always some liquid (holdup)
on the tray and is designed such that the the holdup is at a suitable
height, e.g. such that the bubble caps are covered by liquid.

Being lighter, vapour flows up the column and is forced to pass

through the liquid, via the openings on each tray. The area allowed
for the passage of vapour on each tray is called theactive tray area.

The picture  on the left is a

photograph of a section of a pilot
scale column equiped with bubble
capped trays. The tops of the 4
bubble caps on the tray can just be
seen. The down- comer in this case is
a pipe, and is shown on the right. The frothing of the liquid
on the active tray area is due to both passage of vapour
from the tray below as well as boiling.

As the hotter vapour passes through the liquid on the tray

above, it transfers heat to the liquid. In doing so, some of
the vapour condenses adding to the liquid on the tray. The
condensate, however, is richer in the less volatile
components than is in the vapour. Additionally, because of
the heat input from the vapour, the liquid on the tray boils,
generating more vapour. This vapour, which moves up to
the next tray in the column, is richer in the more volatile components. This continuous
contacting between vapour and liquid occurs on each tray in the column and brings about
the separation between low boiling point components and those with higher boiling points.

Tray Designs
A tray essentially acts as a mini-column, each accomplishing a fraction of the separation
task. From this we can deduce that the more trays there are, the better the degree of
separation and that overall separation efficiency will depend significantly on the design of
the tray. Trays are designed to maximise vapour-liquid contact by considering the
 liquid distribution and
 vapour distribution
on the tray. This is because better vapour-liquid contact means better separation at each
tray, translating to better column performance. Less trays will be required to achieve the
same degree of separation. Attendant benefits include less energy usage and lower
construction costs.
 Liquid distributors - Gravity (left), Spray (right)

Packings
There is a clear trend to improve separations by supplementing the use of trays by
additions of packings. Packings are passive devices that are designed to increase the
interfacial area for vapour-liquid contact. The following pictures show 3 different types of
packings.

These strangely shaped pieces are supposed to impart good vapour-liquid contact when a
particular type is placed together in numbers, without causing excessive pressure-drop
across a packed section. This is important because a high pressure drop would mean that
more energy is required to drive the vapour up the distillation column.

 
Structured packing
 Packings versus Trays
A tray column that is facing throughput problems may be de-bottlenecked by replacing a
section of trays with packings. This is because:
 packings provide extra inter-facial area for liquid-vapour contact
 efficiency of separation is increased for the same column height
 packed columns are shorter than trayed columns
Packed columns are called continuous-contact columns while trayed columns are
called staged-contact columns because of the manner in which vapour and liquid are
contacted.

Tray Efficiency:

In the previous analysis, we have assumed that the vapor leaving each tray was
in equilibrium with the liquid leaving the same tray. This analysis assumed that the trays are
operating at 100% efficiency. However, in actual practice, the trays are not perfect, i.e. there
are deviations from ideal conditions.

Except when temperature changes significantly (for example, in presence of exothermic

chemical reaction) from tray to tray, the assumption that vapour and liquid leaving the trays are
at the same temperature is often reasonable. The equilibrium with respect to mass transfer,
however, is not often valid. This can be due to:

(1) Insufficient time of contact

(2) Insufficient degree of mixing
Recall: When we used the McCabe-Thiele Method for continuous distillation operation, we already noted that not all
triangles are of the same size.

Therefore in actual operation the vapor and liquid streams leaving a tray are not in equilibrium.
To achieve the same degree of separation desired, more trays will have to be added to
compensate for the lack of perfect separability. The actual number of trays required can
be adjusted using the tray efficiency.

We will look at 2 types of tray efficiency: Overall Efficiency and Murphree Efficiency.

Overall Efficiency

We define the overall tray efficiency EO as:

EO is applied throughout the whole column, i.e. every tray is assumed to have the same
efficiency. The advantage is that it is simple to use, but it must be bear in mind that in actual
practice, not all the trays have the same efficiency.

The advantage is that it is simple to use, but it must be bear in mind that in actual practice, not
all the trays have the same efficiency.

The overall efficiency has been found to be a complex function of the following:

Geometry and design of the contacting trays

Flow rates and flow paths of vapour and liquid streams

Compositions and properties of vapour and liquid streams

Values of EO can be predicted by any of the following 4 methods:

Comparison with performance data from industrial columns for the same or similar systems

Scale-up of data obtained with laboratory or pilot plant columns

Use of empirical efficiency models derived from data on industrial columns

Use of semi-theoretical models based on mass and heat transfer rates

The Drickamer-Bradford empirical correlation is given as:

The use of the equation is restricted to the range of data below, and is intended mainly for
hydrocarbon mixtures.

Average temperature 157 - 420 oF

Pressure 14.7 - 366 psia
Liquid viscosity 0.066 - 0.355 cP
Overall Efficiency 41 - 88 %

The O'Connell correlation is given as:

( Viscosity measured in centiPoise )

The relative volatility is determined for the 2 key components at average column conditions.

Murphree Efficiency

The Murphree Tray Efficiency EM , is based on a semi-theoretical models that assumes that the
vapour between trays is well-mixed (uniform composition), that the liquid in the downcomers is
well-mixed (uniform composition), and that the liquid on the tray is well mixed and is of the
same composition as the liquid in the downcomer leaving the tray.

It is defined for each tray according to the separation achieved on each tray. This can be based
on either the liquid phase or the vapor phase. For a given component, it is equal to the change
in actual concentration in the phase, divided by the change predicted by equilibrium condition.
Referring to the Figure below, we have:
 

Vapor phase: 

Liquid phase: 

[ Back on Top ]

The Figure below showed that the vapour phase efficiency is the fraction of the vertical height (change in
vapour phase mole fraction) between the operating line and the equilibrium curve.

Once the Murphree Efficiency is known, it can be easily be used on the McCabe-Thiele design,
in the form of a "pseudo" equilibrium line. This is shown in the Figure below.
 FACTORS AFFECTING DISTILLATION COLUMN OPERATION
The performance of a distillation column is determined by many factors, for example:
feed conditions

 state of feed
 composition of feed
 trace elements that can severely affect the VLE of liquid mixtures

internal liquid and fluid flow conditions

state of trays (packings)

weather conditions

Some of these will be discussed below to give an idea of the complexity of the distillation
process.

  Feed Conditions
  The state of the feed mixture and feed composition affects the operating lines and
hence the number of stages required for separation. It also affects the location of
feed tray. During operation, if the deviations from design specifications are
excessive, then the column may no longer be able handle the separation task. To
overcome the problems associated with the feed, some column are designed to have
multiple feed points when the feed is expected to containing varying amounts of
components.
  Reflux Conditions
  As the reflux ratio is increased, the
gradient of operating line for the
rectification section moves towards a
maximum value of 1. Physically, what
this means is that more and more liquid
that is rich in the more volatile
components are being recycled back
into the column. Separation then
becomes better and thus less trays are
needed to achieve the same degree of
separation. Minimum trays are required
under total refluxconditions, i.e. there is
no withdrawal of distillate.

On the other hand, as reflux is

decreased, the operating line for the
rectification section moves towards the
equilibrium line. The ‘pinch’ between
operating and equilibrium lines becomes
more pronounced and more and more
trays are required.This is easy to verify using the McCabe-Thiele method.

The limiting condition occurs at minimum reflux ration, when an infinite number of
trays will be required to effect separation. Most columns are designed to operate
between 1.2 to 1.5 times the minimum reflux ratio because this is approximately the
region of minimum operating costs (more reflux means higher reboiler duty).
  Vapour Flow Conditions
  Adverse vapour flow conditions can cause

 foaming
 entrainment
 weeping/dumping
 flooding

Foaming
Foaming refers to the expansion of liquid due to passage of vapour or gas.
Although it provides high interfacial liquid-vapour contact, excessive foaming
often leads to liquid buildup on trays. In some cases, foaming may be so bad
that the foam mixes with liquid on the tray above. Whether foaming will occur
depends primarily on physical properties of the liquid mixtures, but is
sometimes due to tray designs and condition. Whatever the cause, separation
efficiency is always reduced.
Entrainment
Entrainment refers to the liquid carried by vapour up to the tray above and is
again caused by high vapour flow rates. It is detrimental because tray
efficiency is reduced: lower volatile material is carried to a plate holding liquid
of higher volatility. It could also contaminate high purity distillate. Excessive
entrainment can lead to flooding.
Weeping/Dumping
This phenomenon is caused by low vapour flow. The pressure exerted by the
 vapour is insufficient to hold up the liquid on the tray. Therefore, liquid starts
to leak through perforations. Excessive weeping will lead to dumping. That is
the liquid on all trays will crash (dump) through to the base of the column
(via a domino effect) and the column will have to be re-started. Weeping is
indicated by a sharp pressure drop in the column and reduced separation
efficiency.
Flooding
Flooding is brought about by excessive vapour flow, causing liquid to be
entrained in the vapour up the column. The increased pressure from
excessive vapour also backs up the liquid in the downcomer, causing an
increase in liquid holdup on the plate above.  Depending on the degree of
flooding, the maximum capacity of the column may be severely reduced.
Flooding is detected by sharp increases in column differential pressure and
significant decrease in separation efficiency.
  Column Diameter
  Most of the above factors that affect column operation is due to vapour flow
conditions: either excessive or too low. Vapour flow velocity is dependent on column
diameter. Weeping determines the minimum vapour flow required while flooding
determines the maximum vapour flow allowed, hence column capacity. Thus, if the
column diameter is not sized properly, the column will not perform well. Not only will
operational problems occur, the desired separation duties may not be achieved.
  State of Trays and Packings
  Remember that the actual number of trays required for a particular separation duty
is determined by the efficiency of the plate, and the packings if packings are used.
Thus, any factors that cause a decrease in tray efficiency will also change the
performance of the column. Tray efficiencies are affected by fouling, wear and tear
and corrosion, and the rates at which these occur depends on the properties of the
liquids being processed. Thus appropriate materials should be specified for tray
construction.
  Weather Conditions
  Most distillation columns are open to the atmosphere. Although many of the columns
are insulated, changing weather conditions can still affect column operation. Thus the
reboiler must be appropriately sized to ensure that enough vapour can be generated
during cold and windy spells and that it can be turned down sufficiently during hot
seasons. The same applies to condensors.
These are some of the more important factors that can cause poor distillation column
performance. Other factors include changing operating conditions and throughputs,
brought about by changes in upstream conditions and changes in the demand for the
products. All these factors, including the associated control system, should be considered
at the design stages because once a column is built and installed, nothing much can be
done to rectify the situation without incurring significant costs. The control of distillation
columns is a field in its own right, but that's another story

References:
Chemical Engineering by Coulson and Richardson Volume 6
University of Michigan Online Enyclopedia