BASIC OPERATIONS

Distillation & Filtration

Dr. George Georgiadis PhD

Introductions
 Dr. George Georgiadis

 Born 1957 – Married Christina (We have 3 children).

 Brunel University PhD Graduate 1988
 Lived and worked in UK 1969 – 1992
 Imperial College-Scientist/Junior Lecturer 1988-1992
 Cyprus Petroleum Refining Technologist 1992 - 2000
 Hijet International – Technical Manager – Houston
 Glomacs/ Petroknowledge – Senior Consultant
 Chartered Member of RSC and AIChE
 Approved Safety Inspector
 Lecturer – European University – Nicosia Cyprus
 Associate Professor – Huddersfield University - UK
 Course Instructor
Dr. George Georgiadis
George is a Senior Consultant with AZTECH specializing in Oil
and Gas; Process Technology, Safety and the Environment.
He has graduated from Brunel University in West London
(Uxbridge) and holds a B.Sc. Degree in Industrial Chemistry an
M.Phil. in Catalysis and a Ph.D. degree in Surface Science.
He is a Chartered Member of the Royal Society of Chemistry
(UK) and a Member of the American Institute of Chemical
Engineers (USA).
George is an Approved Safety Inspector (ASI) – Cyprus
Petroleum Refinery Ltd.
 George’s field of expertise includes:
Industrial Chemistry –
British Technology Group (UK),
Imperial College of Science and Technology London UK and
HIJET, Inc. Houston USA and Cyprus
Process Technologist – Cyprus Petroleum Refinery Ltd. Cyprus
Environmental Scientist – Municipality of Larnaca Cyprus
He has acted as a consultant to a number of industries in
Cyprus and the Kingdom of Saudi Arabia and delivers regular
training seminars in the Middle East, Gulf States namely UAE
Oman and KSA.
His career is long and varied in the sectors of Science,
Technology and Consultancy Services.
He has held appointments as Technical Director, Board
Member, Project Manager and Senior Management.
Day 1 INTRODUCTION TO DISTILLATION

Introduction to distillation

The concept of Unit Operations

Vapor-liquid equilibria

Distillation operating variables

Design, Operation, Control

Column and tray design and efficiency

• The most fundamental energy
flow for living creatures is
sunlight,.
• Before oil was discovered 200
years ago, the only source of
energy came from the sun and a
solar collector!
• In simple terms a solar collector
is a piece of land with trees
vegetables and some animals.
• People worked on the land and
could feed their families.
 Origin of Petroleum
• 3000 BC: Fertile Crescent & Baku Seeps
• Oil seeps noted along banks of Euphrates
• Azerbaijan – Persia’s land of fire
• Ancient Persians and Sumatrans also
believed petroleum had medicinal value.
• Boats along the Euphrates were constructed
with woven reeds and sealed with pitch.
 Origin of Distillation

1000 A.D. scientists discovered distillation and produced kerosene.

Distillation by retort using the alembic.

 Origin of Distillation
 This was lost after the 12th
century!
 “Rediscovered” by a
Canadian geologist called
Abraham Gesner in 1852
 With the emergence of chemical engineering as a
discipline at the end of the 19th century, scientific rather
than empirical methods could be applied.
 The developing petroleum industry in the early 20th
century provided the impetus for the development of
accurate design methods such as the McCabe-Thiele
method and the Fenske equation.
 The availability of powerful computers has also allowed
direct computer simulation of distillation columns.
 Distillation
• Distillation is a method of separating mixtures based on differences
in their volatilities in a boiling liquid mixture. Distillation is a physical
separation process, and not a chemical reaction.
• Uses:-
1. Crude oil
2. Water is distilled to remove impurities
3. Air is distilled to separate its components
4. Distillation of fermented solutions to produce distilled beverages
with a higher alcohol content.

The premises where distillation is carried out, especially

distillation of alcohol, are known as a distillery.
The application of distillation can roughly be
divided into:
a) Batch distillation,
b) Continuous distillation,
 The main difference between batch distillation
and continuous distillation is that the former is
performed batch-wise, whereas Continuous
distillation often occurs continuously.
 Batch Distillation process
 As the name suggests it is carried out in batches
 It is useful for low capacity and high purity
chemicals
 Based upon the difference in the volatility of the
component present in the sample mixture
 It hold some advantageous feature over the
normal distillation process such as flexible
process, separates several component in one go
using one column, economical process,
 In batch distillation, the composition of the source
material, the vapors of the distilling compounds
and the distillate change during the distillation.
 In batch distillation, a still is charged (supplied)
with a batch of feed mixture, which is then
separated into its component fractions which are
collected sequentially from most volatile to less
volatile, with the bottoms (remaining least or non-
volatile fraction) removed at the end.
 The still can then be recharged and the process
repeated.
 Design of conventional Batch
Distillation Column
 The pot is filled with liquid mixture
and heated.
 Vapor flows upwards though the
column and condenses at the top.
 Part of the liquid is returned to the
column as reflux, and the
remainder withdrawn as distillate.
 Nothing is added or withdrawn
from the still until the run is
completed.
 Continuous Distillation
 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.
 Given a feed of a specified composition, the main
variables that affect the purity of products in continuous
distillation are the
 reflux ratio
 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.
 and the number of theoretical equilibrium stages (practically, the
number of trays or the height of packing).
 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 as time passes during
the operation.
 Continuous distillation produces at least two output
fractions, including at least one volatile distillate fraction,
which has boiled and been separately captured as a
vapor 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
 In continuous distillation,
the source materials,
vapors, and distillate are
kept at a constant
composition by carefully
replenishing the source
material and removing
fractions from both vapor
and liquid in the system.
 This results in a better
control of the separation
process.
 Distillation is an equilibrium stage operation.
 In each stage, a vapor phase is contacted with a
liquid phase and mass is from vapor to liquid
and from liquid to vapor.
 The less volatile, "heavy" or "high boiling",
components concentrate in the liquid phase; the
more volatile, "light", components concentrate in
the vapor.
 By using multiple stages in series with recycle,
separation can be accomplished.
 Fractional Distillation
 Accomplishes the same thing as Multiple Simple Sequential
Vaporization / Condensation Cycles.
 A Fractionating Column, of which there are many types
containing a variety of packing materials, subjects the mixture to
many Vaporization/Condensation Cycles as the material moves
up the column toward the Distillation Head, which is attached to
the Condenser.
 With each cycle within the column, the composition of the vapor
is progressively enriched in the lower boiling liquid.
 This process continues until most of the lower boiling
compound is removed from the original mixture and condensed
in the receiving flask
Schematic of Distillation
 Fractional Distillation (Cont.)

 When the lower boiling liquid is effectively removed from the

original mixture, the temperature rises and a second fraction
containing some of both compounds is produced.
 As the temperature approaches the boiling point of the higher
boiling point compound, the distillate condensing into the third
receiving flask is increasingly pure in the higher boiling point
compound.
 Column Efficiency:
 A common measure of the efficiency of a Fractionation
Column is given by its number of Theoretical Plates
 One Theoretical Plate is equivalent to a Simple Distillation,
i.e., one Vaporization / Condensation Cycle.
 The smaller the boiling point difference, the greater the number
of theoretical plates a fractionating column must have to
achieve separation of mixtures
 Volume Increments

0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
0-65 oC 9.0
65-70 oC

70-75 oC

75-80 oC

80-85 oC

85-90 oC

90-95 oC

95-100 oC

100-105 oC

o
105-110 oC

Temperature Increments ( C)
110-115 oC
Simple & Fractional Distillation

115-120 oC

120-125 oC

125-130 oC
Simple
Fractional
Simple & Fractional Distillation
 Azeotropic Distillation
 An azeotrope is a mixture of two or more liquids (chemicals) in
such a ratio that its composition cannot be changed by simple
distillation.
 This occurs because, when an azeotrope is boiled, the resulting
vapor has the same ratio of constituents as the original mixture.
 Because their composition is unchanged by distillation,
azeotropes are also called constant boiling mixtures.
 positive azeotrope is 95.63% ethanol and 4.37% water (by weight).
Ethanol boils at 78.4°C, water boils at 100°C, but the azeotrope boils
at 78.2°C.
 negative azeotrope is hydrochloric acid at a concentration of 20.2%
and 79.8% water (by weight). Hydrogen chloride boils at −84°C and
water at 100°C, but the azeotrope boils at 110°C.
 Azeotropic distillation
 Azeotropic distillation usually refers to the specific
technique of adding another component to generate a
new, lower-boiling azeotrope that is heterogeneous
(e.g. producing two, immiscible liquid phases), such
as the example below with the addition of benzene to
water and ethanol.
 In actual fact, this practice of adding an entrainer
which forms a separate phase is a specific sub-set of
(industrial) azeotropic distillation methods, or
combination thereof.
 In some senses, adding an entrainer is similar to
extractive distillation.
 Example
• Distillation of ethanol/water, using normal distillation
techniques, ethanol can only be purified to approximately
96% .
• Some uses require a higher percentage of alcohol, eg.
when used as a gasoline additive.
• Material separation agent
• The addition of a Material Separation Agent, e.g. benzene.
• Molecular sieves
• For the distillation of ethanol for gasoline addition, the
most common means of breaking the azeotrope is the use
of molecular sieves.
 Vacuum Distillation
 Vacuum distillation is a method of
distillation whereby the pressure above the
liquid mixture to be distilled is reduced to
less than its vapor pressure causing
evaporation of the most volatile liquid(s).
 This distillation method works on the
principle that boiling occurs when the vapor
pressure of a liquid exceeds the ambient
pressure.
 Temperature sensitive materials require
vacuum distillation to remove solvents from
the mixture without damaging the product.
 This technique is also very useful for compounds
which boil beyond their decomposition
temperature at atmospheric pressure and which
would therefore be decomposed by any attempt
to boil them under atmospheric pressure.
 Dimethyl sulfoxide usually boils at 189 °C.
 Under a vacuum, it distills at only 70 °C.
Advantages of Vacuum Distillation
 Industrial-scale vacuum distillation has several advantages.
 Vacuum distillation columns typically used in oil refineries
have diameters ranging up to about 14 meters (46 feet), heights
ranging up to about 50 meters (164 feet), and feed rates
ranging up to about 25,400 cubic meters per day (160,000
barrels per day).
 Vacuum distillation increases the relative volatility of the key
components in many applications
 Vacuum distillation can improve a separation by:
 Prevention of product degradation or polymer formation
because of reduced pressure leading to lower tower bottoms
temperatures.
 Increasing capacity, yield, and purity.
 Molecular Distillation
 A special application of the simple distillation is molecular distillation,
known also as evaporative distillation or short path distillation.
 Theory of molecular distillation:-
The mean free path of a molecule is defined as the average distance
through which a molecule can move without coming into collision with
another. For material that are regarded as non volatile under ordinary
conditions of temperature and pressure are generally removed by this by
increasing the mean free path.
 Characteristics of the molecular distillation process:-
 Very high vacuum
 Evaporating surface must be close to the condensing surface
 The liquid area is large to avoid boiling and evolution of the vapors is from
surface only.
 Application of molecular distillation:-
 Purification of oils
 Separating of vitamins
 Flash Distillation/ Equilibrium Distillation
 Flash Distillation is a single stage separation technique
 Flash evaporation is the partial vaporization that occurs when a saturated liquid
stream undergoes a reduction in pressure by passing through a valve or other
device.
 If the valve or device is located at the entry into a pressure vessel so that the flash
evaporation occurs within the vessel, then the vessel is often referred to as a flash
drum.
 If the saturated liquid is a single-component liquid (for example, liquid propane or
liquid ammonia), a part of the liquid immediately "flashes" into vapor.
 Both the vapor and the residual liquid are cooled to the saturation temperature of
the liquid at the reduced pressure.
 This is often referred to as "auto-refrigeration" and is the basis of most
conventional vapor compression refrigeration systems.
 If the saturated liquid is a multi-component liquid (for example, a mixture of
propane, isobutane and normal butane), the flashed vapor is richer in the more
volatile components than is the remaining liquid.
 Extractive Distillation
 Extractive distillation is defined as distillation in the presence of a
miscible, high boiling, relatively non-volatile component, the solvent, that
forms no azeotrope with the other components in the mixture.
 The method of extractive distillation uses a separation solvent, which is
generally nonvolatile, has a high boiling point and is miscible with the
mixture, but doesn't form an azeotropic mixture. The solvent interacts
differently with the components of the mixture thereby causing their
relative volatilities to change.
 The solvent must alter the relative volatility by a wide enough margin for a
successful result. The quantity, cost and availability of the solvent should
be considered. The solvent should be easily separable from the bottom
product, and should not react chemically with the components or the
mixture, or cause corrosion in the equipment. A classic example is of
aniline as suitable solvent.
 Vapor-Liquid-Equilibrium (VLE) Curves
 Constant pressure VLE data are obtained from
boiling point diagrams.
 VLE data of binary mixtures is often presented
as a plot, as shown in the figure on the right.
 The VLE plot expresses the bubble-point and
the dew-point of a binary mixture at constant
pressure.
 The curved line is called the equilibrium line and
describes the compositions of the liquid and
vapor in equilibrium at some fixed pressure.
 (VLE) Curves
 This particular
VLE plot shows a
binary mixture
that has a uniform
vapor-liquid
equilibrium that is
relatively easy to
separate.
 The next two VLE plots below on the other hand, show non-
ideal systems which will present more difficult separations.
 We can tell from the shapes of the curves and this will be
explained further later on.
 VLE curves are generated by
azeotropic systems
 An azeotrope is a liquid mixture which when
vaporized, produces the same composition as the
liquid.
 The two VLE plots below, show two different
azeotropic systems, one with a minimum boiling
point and one with a maximum boiling point.
 In both plots, the equilibrium curves cross the
diagonal lines, and this are azeotropic points where
the azeotropes occur.
 In other words azeotropic systems give rise to VLE
plots where the equilibrium curves crosses the
diagonals.
 Note the shapes of the respective equilibrium lines in
relation to the diagonal lines that bisect the VLE plots.
 Both plots are however, obtained from
homogenous azeotropic systems.
 An azeotrope that contains one liquid phase in
contact with vapor is called a homogenous
azeotrope.
 A homogenous azeotrope cannot be separated by
conventional distillation.
 However, vacuum distillation may be used as the
lower pressures can shift the azeotropic point.
 Vapor-liquid equilibria
 Distillation is an equilibrium stage operation. In
each stage, a vapor phase is contacted with a
liquid phase and mass is from vapor to liquid
and from liquid to vapor.
 The less volatile, "heavy" or "high boiling",
components concentrate in the liquid phase; the
more volatile, "light", components concentrate in
the vapor.
 By using multiple stages in series with recycle,
separation can be accomplished.
 Operating Principles:
 The feed to a distillation column may be liquid,
vapor, or mixture.
 It may enter at any point in the column, although
the optimal feed tray location should be
determined and used.
 More than one stream may be fed to the system,
and more than one product may be drawn.
 A column is divided into a series of stages.
 These correspond to a cascade of equilibrium
stages.
 Liquid flows down the column from stage to
stage and is contacted by vapor flowing upward.
Diagram of a typical industrial
distillation tower
 Distillation columns are built with a set of distinct
"trays" or "plates",
 These are also known as "stages".
 Each tray in a distillation column is designed to
promote contact between the vapor and liquid
on the stage.
 Distillation can be conducted in a packed
column or in a trayed column.
 Stages may be numbered from top down or
bottom up.
 When analyzing a stage, flows and compositions
take the number of the stage they leave.
 Generally "Tray 1" is the bottom tray of the
column, the reboiler "Tray 0" and number
upward
 this way of numbering simplifies computer based
calculations.
 The product leaving the top of the column is
called the overhead product, the "overhead", the
"top product", the distillate, or "distillate product".
 Distillate product may be liquid or vapor (or
occasionally both) depending on the type of
condenser used.
 Most of the time the distillate flow rate is
assigned the symbol D, and the composition xD
or yD.
 The product leaving the bottom of the column is
called the bottom product or "bottoms", and
given the symbol B, with composition xB.
 In some situations, notably petroleum refining,
one or more intermediate or "side-draw"
products may be removed from the column.
 Vapor leaving the top of the column passes
through a heat exchanger, the condenser, where
it is partially or totally condensed.
 The liquid which results is temporarily held in the
"accumulator" or reflux drum.
 A liquid stream is withdrawn from the drum and
returned to the top tray of the column as reflux
(R or L) to promote separation.
 The portion of the column above
the feed tray is called the
rectification section. In this
section, the vapor is enriched by
contact with the reflux.
 The portion of the column
below the feed tray is called the
stripping section.
 The liquid portion of the feed
serves as the reflux for this
section.
 The operating pressure of the column is typically
controlled by adjusting heat removal in the
condenser.
 The base of the column is typically used as a
reservoir to hold liquid leaving the bottom tray.
 A heat exchanger, the reboiler, is used to boil
this liquid.
 The vapor which results, the "boilup" (V) is
returned to the column on one of the bottom
three or four trays.
 In normal operation, there are five "handles" that
can be adjusted to manipulate the behavior of a
distillation column –
1. the feed flow,
2. two product flows,
3. the reflux flow,
4. and the boilup flow (or reboiler heat input).
 A normal column has a temperature gradient
and a pressure gradient from bottom to top.
 Large-scale industrial towers use reflux to
achieve a more complete separation of
products.
 Reflux refers to the portion of the condensed
overhead liquid product from a distillation or
fractionation tower that is returned to the upper
part of the tower as shown in the schematic
diagram of a typical, large-scale industrial
distillation tower.
 Inside the tower, the downflowing reflux liquid
provides cooling and condensation of the
upflowing vapors thereby increasing the efficacy of
the distillation tower.
 The more reflux the better the separation of lower
boiling materials from higher boiling materials.
 Alternatively, the more reflux is provided for a
given desired separation, the fewer theoretical
plates are required.
 Design and operation of a distillation tower
depends on
 the feed and products.
 Given a simple, binary component feed,
analytical methods such as the McCabe-Thiele
method or the Fenske equation can be used.
 The efficiencies of the vapor-liquid contact
devices (referred to as "plates" or "trays") used
in distillation towers are typically lower than that
of a theoretical 100% efficient equilibrium stage.
 Hence, a distillation tower needs more trays than
the number of theoretical vapor-liquid
equilibrium stages.
 Ideal Stages
 Stages maximize contact between the vapor and
the liquid.
 Some of the light component is vaporized and
leaves with the vapor;
 Some of the heavy component condenses and
leaves with the liquid.
 By definition, an ideal stage is one where the
vapor and liquid leave the stage in equilibrium.
 Consequently, the vapor composition
functionally depends on the liquid composition.
 Ideality is an approximation, but stage
efficiencies can be used to account for real
cases.
 A key result of the ideal stage assumption is that
liquid streams leaving an ideal stage are
assumed to be at their bubble point.
 Vapor streams leave at their dew point.
 When no azeotropes are present, both top and
bottom products may be obtained in any desired
purity
 if enough stages are provided and enough reflux is
available.
 In practice, there are limits to the number of
stages and to the amount of reflux, so not every
separation can be accomplished.
 Theoretical limits on performance are imposed
 by total reflux (minimum stages) and
 minimum reflux (infinite number of ideal stages).
 In industrial uses, sometimes a packing material
is used in the column instead of trays, especially
when low pressure drops across the column are
required, as when operating under vacuum.
 This packing material can either be random
dumped packing (1-3" wide) such as Raschig
rings or structured sheet metal.
 Liquids tend to wet the surface of the packing
and the vapors pass across this wetted surface,
where mass transfer takes place.
 Unlike conventional tray distillation in which
every tray represents a separate point of vapor-
liquid equilibrium, the vapor-liquid equilibrium
curve in a packed column is continuous.
 However, when modeling packed columns, it is
useful to compute a number of "theoretical
stages" to denote the separation efficiency of the
packed column with respect to more traditional
trays.
 Differently shaped packings have different
surface areas and void space between
packings.
 Both of these factors affect packing
performance.
 Another factor in addition to the packing shape and
surface area that affects the performance of
random or structured packing is the liquid and
vapor distribution entering the packed bed.
 The number of theoretical stages required to make
a given separation is calculated using a specific
vapor to liquid ratio.
 If the liquid and vapor are not evenly distributed
across the superficial tower area as it enters the
packed bed, the liquid to vapor ratio will not be
correct in the packed bed and the required
separation will not be achieved.
 The packing will appear to not be working properly.
 Height Equivalent of a Theoretical Plate
(HETP)
 The height equivalent of a theoretical plate (HETP) will be
greater than expected.
 The problem is not the packing itself but the mal-
distribution of the fluids entering the packed bed.
 Liquid mal-distribution is more frequently the problem than
vapor.
 The design of the liquid distributors used to introduce the
feed and reflux to a packed bed is critical to making the
packing perform to it maximum efficiency.
 Methods of evaluating the effectiveness of a liquid
distributor to evenly distribute the liquid entering a packed
bed has been done by Fractionation Research, Inc. (FRI).