Basics of Distillation

V. K. Kapoor

Dehradun

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 Distillation
• Distillation major refinery process for separating
constituents from liquid mixture by vaporization of
mixture to group of components

• Continued importance with modernization, new units

construction, revamps and capacity expansion

• Liquid mixture vaporized yielding vapor phase

containing mixture of controllable composition different
from original mixture

• Present global ADU and VDU capacity are ~86 and ~ 28

million bpcd
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• Current Indian Refining Capacity ~ 185
MMTPA

• Current Indian demand ~ 140 MMTPA

• Refining Capacity expecting high jump in

India
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 DISTILLATION HISTORY
 Use of distillation backs in history to about 50 B.C.

 Industrial exploitation of this separation process

started in 12th century to produce alcoholic
beverages

 By 16th century, distillation was being used in the

manufacture of vinegar, perfumes, oils and other
products.

 Early distillation was basically batch stills to

produce ethanol 4
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Crude Oil

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• Early small towers had one or two large bubble
caps per tray

• Liquid and vapor traveled through column and

mixed on outer ring of bubble cap

• Later tray efficiency became more important, flow

on tray began to be studied and several types of
trays and flow patterns developed.

• Tray columns appeared in 1820s along with feed

preheating and use of internal reflux
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• Distillation by application, removal of heat

• Component separation from mixture by

distillation depend on difference in boiling
points of components and relative volatility

• Distillation based on fact that vapor of boiling

mixture richer in components having lower
boiling points

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• Vapor cooled & condensed, condensate
contain more volatile components.
Original mixture contain more of less
volatile material

• Distillation consumes enormous energy,

in cooling & heating requirement
contributing more than 50% of plant
operating costs

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• Vapor pressure of liquid at particular
temperature is equilibrium pressure exerted
by molecules leaving and entering liquid
surface

• Energy input raise vapor pressure

• Vapor pressure related to boiling

• Liquid boil when its vapor pressure equal

surrounding pressure

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• Ease with which liquid boils depend on
volatility

• Liquid with high vapor pressures (volatile

liquids) boil at lower temperatures

• Vapor pressure and boiling point of liquid

mixture depend on relative amount of
component in mixture

• Distillation because of differences in

volatility of components in liquid mixture

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• Boiling point diagram show how equilibrium
compositions of components in liquid
mixture vary with temperature at fixed
pressure

• Consider example of liquid mixture

containing 2 components (A and B) - binary
mixture

• Boiling point of A at which mole fraction of A

is 1

• Boiling point of B at which mole fraction of A

is 0

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tB

tA

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• A more volatile component, has lower boiling
point than B

• Upper curve in diagram called dew-point curve

• Lower one called bubble-point curve

• Boiling diagrams vary with pressure

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 Effect of pressure

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Boiling Point Diagram for n-butane, n-heptane
• Dew-point temperature at which saturated
vapor start to condensing

• Bubble-point temperature at which liquid

start boiling

• Region above dew-point curve shows

equilibrium composition of superheated
vapor

• Region below bubble-point curve show

equilibrium composition of sub cooled liquid
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 Vapour Pressure and
Boiling
• Sub cooled liquid, mole fraction A=0.4
(point A) heated

• Concentration remains constant until

bubble-point (point B) reached when
boiling starts

• Vapor evolved in boiling has

equilibrium composition given C, ~0.8
mole fraction A richer than original
liquid

• Difference in liquid & vapor comp.

basis for distillation 19
 Raoults Law
• Boiling Point Diagram determined experimentally

• May be computed from pure component vapor

pressure data

• Calculation based on Raoult’s law

• At constant temperature, partial pressure of one

component of mixture is equal to mole fraction of
that component multiplied by it’s vapor pressure
in pure state at this temperature
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Boiling Point Diagram- Chloroform
Acetone

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Boiling Point Diagram Benzene-
Ethanol

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• A is more volatile than B

• From Raoults law,

pA= PA x ; pB = PB (1- x)

p A& pB - partial pressure over solution ;

PA & PB - vapor pressure of pure components A &
B at solution temperature respectively

P = (pA+ pB ) = PA x + PB (1- x)

From Dalton’s law, y mole fraction of A in vapor

y = pA / (pA+ pB ) = (PA x) / P
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= (PA x) / [PA x + PB (1- x)]
 Example- Benzene and
Toluene mixture, obey
Raoults Law .

Vapor pressure of pure

Components at different
• temp and 760 mm Hg are
given

Boiling point diagram to be

plotted calculating x and y
compositions

Given: One set of value

stated below:

Vapor pressure for benzene

and toluene in mm Hg at 82
degree C - 811 and 314
respectively
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• PA =811 PB = 314

811x + 314(1- x) =760

Hence x= 0.897

y = (811) ( 0.897) / 760 = 0.958

Similar calculations can be made at

interval of about 5 to 10 degrees
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 Relative Volatility
• A binary system of A (MVC) and B, vapor phase in
equilibrium with liquid phase

• Relative volatility of A with respect to B defined by eqn:

AB= (yA/ xA)  ( yB / xB ) = (yA/ yB) (xB / xA)

= (y / 1-y)  (1-x / x)

y = (PA x) / P ; 1- y = PB (1- x) / P

 = PA  PB

y & x : components mole fraction in vapor and liquid phases

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• For vapor liquid separation operations,
an index of relative ease of separation for
two chemical species i and j given by
relative volatility alpha defined as ratio of
their K values

• αij = Ki / Kj = Pi / Pj

• Pi and Pj vapor pressures of components

i and j at given temperature.
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 Distillation
• Distillation favored over other separation
techniques such as crystallization when;

– Relative volatility greater that 1.2

– Products thermally stable

– Large rates desired

– No corrosion, precipitation or explosion issues

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• Distillation - technique to separate components
according to their relative volatility

• Relative volatility measures ease of separation

• For high relative volatility, component having

greater tendency to vaporize and easier to
separate from other by distillation

• When component have similar tendency to

vaporize, relative volatility approaches unity
and can not be separated by distillation
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• Number of theoretical stages to separate
two species to desired degree strongly
dependent on value of index.

• Greater departure of relative volatility

from value of one fewer equilibrium
stages required for desired degree of
separation

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• When relative volatility low, less than 1.05,
separation become difficult because large number
of stages required

• Higher relative volatility, more separable are two

components; this connotes fewer stages in
distillation column to effect same separation
between overhead and bottoms products

• Lower pressures increase relative volatilities in most

systems
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Realtive Volatility and Concn
of MVC in Vapor Phase
•

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Source H. Kister ,
 Effect of Pressure on
Relative Volatility
•

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Source C. S. Robinson et a, Elements of Fractional Distillation
FRACTIONAL DISTILLATION
• Mixture of liquids of different boiling points
heated

• Vapor contain a higher mole fraction of

liquid with lower boiling point than original
liquid; i.e. vapor enriched in more volatile
component

• This vapor condensed, resultant liquid has

been enriched in more volatile component
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• 1:1 molar mixture of benzene (b.p. 80.1C) and
toluene (b.p. 110.6 C) heated

• It boils at 92.2C, composition of vapor ( hence its

condensate) is 71.3 : 28.7 benzene : toluene

• If vapor condensed and brought to boiling point its

vapor has mole ration of 86.4 : 13.6

• Third cycle produce condensate of 94.4 : 5.6

benzene:toluene
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• In distillation column many such cycles
performed continuously, allowing almost
complete separation of liquid components

• More volatile components drawn from top of

column and least volatile concentrate in lower
part

• In practice, distillation carried out

continuously
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Rectifying Column

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 Reflux Ratio
• Ratio L / D termed as external reflux ratio

• Heat requirement for separation with given feed

and reflux temperatures determined by reflux ratio
used

• As ratio increased, condenser duty increase,

separation per plate increases

• At total reflux minimum number of theoretical

plates required for given separation
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• In distilling petroleum not just 2
components, but many components

• Same principles apply, by feeding heated

oil to fractional distillation column,
withdrawing liquid from various trays,
separate oil into varying fractions

• Withdrawing liquid from intermediate

trays, some light product bubbling
through liquid on each tray present 39
• Can be removed by passing steam
through withdrawn fraction in stripper

• Mixture of steam and light material

obtained as top product from stripper
returned to main distillation column.

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 Distillation
• Rectification / stripping

• Flash Distillation

• Differential Distillation

• Steam Distillation

• Vacuum Distillation (VDU)

• Azeotropic distillation 41
• Stripping remove light material from heavy product.

• Rectification remove heavy material from a light

product.

• Fractionation remove light material from heavy product

and heavy material from light product same time.

• Complex fractionation multiple products from single /

complex towers with recycle streams. Example of
multiple product tower refinery crude distillation tower
making cuts of naphtha (gasoline), kerosene (jet fuel),
and diesel from same tower.
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• Fractionation refers to units that have both
reboiler and condenser. Facilities attached to
bottom of tower to put heat in tower and to top of
tower to take heat out of tower.This normally
called distillation

• Stripping unit has no method at bottom of the

tower to put heat in. External stream supplied
from outside to strip material from liquid

• Distillation equipment - two major categories,

trays and packing
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Source The Distillation Group Inc
• Azeotropic & extractive distillation - addition of
mass separating agent (MSA) modify thermodynamic
behavior Many azeotropic and extractive distillation
configurations in use

• Azeotropic distillation - MSA forms minimum boiling

azeotrope with some feed component. Azeotrope taken
overhead MSA rich phase decanted and returned to
column as reflux.

• Extractive distillation uses MSA that increases

volatility difference between compounds to be separated.
Example - sulfolane to increase relative volatility
difference between similar molecular weight aromatic
and paraffinic hydrocarbons. Sulfolane unit combines
liquid-liquid extraction, extractive distillation and
solvent stripping in one process.
Source The Distillation Group Inc
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 Flash Distillation
• A definite amount of liquid is vaporised in still

• Vapor and residual liquid held in close intimate

contact, at end of operation vapor in equilibrium
with residual liquid

• Vapor separated and condensed

• Continuous process

• No rectification in flash distillation

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 Differential Distillation

• In differential distillation vapor generated by

boiling liquid is withdrawn as soon as it is
formed and condensed

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 Steam / Vacuum Distillation
• Problems appear in distillation of reduced crude, lubes,
glycerine, fatty acids, aniline, turpentine oil etc:

• B.P. of material high,decomposes thermally before reaching

b.p.at atmospheric pressure

• Vaporization temperature difficult to reach and direct fire

dangerous or detrimental to quality

• Solution to lower distillation temp. to vaporize liquid without

degradation by operating in vacuum. Steam distillation an
older method. Liquid vaporized in stream of inert carrier
vapor whose liquid phase immiscible with material
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 Product Separation
• Crude contain innumerable components falling in small
close boiling cuts.

• Individual separation not possible.

• Design based on TBP/EFV/ASTM data

• Increasing closeness of boiling points of two successive

cuts, separation difficult task

• Expressed as difference between ASTM 50% boiling

points of two successive cuts Larger difference renders
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separation better
 ASTM Gap
Defined as difference between 5% boiling point
of heavy fraction and 95% boiling point of
preceding lighter cut.

Ta = 5% BOILING POINT OF HF
Ta
Tb = 95% BOILING POINT OF LF
Tb ASTM GAP = Ta - Tb

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•
 TBP OVERLAP

• If ASTM gap not available TBP overlap taken

into account.
TBP overlap difference between FBP and IBP
of successive fractions

LF
TBP OVERLAP

HF

Volume % distilled 51
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 PRE-FLASH DRUM

TO STABILISER

PREHEATED CRUDE

CRUDE COLUMN

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 PRE-FLASH DRUM

• Higher crude preheat temperature

• Used if high light ends. Temperature ~ 1800c

• 5% to 6% vaporisation

• Used in revamps for capacity enhancements

• Reboiler/steam stripped

• costlier than single column

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•

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 t-130 C
p-40psig

•
t-118C,
70psig,

260 C, 45psig

170 psig 379 C

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•
 TRAY EFFICIENCY
• Compare vapor temperature leaving tray and liquid
temperature leaving tray Efficiency 100 % if both
same

• If there are 10 trays where vapor temp exiting top

tray and liquid temp draining from bottom tray are
equal, then 10 trays are behaving as single perfect
tray, but each tray has 10 % efficiency

• Poor tray efficiency is caused by two factors:

– Flooding

– Dumping
 Flooding
• When flooding starts on tray , all trays above that point
will also flood, but trays below will go dry

• An early indication of flooding in distillation column is

loss of liquid level in bottom of column

• If downcomer clearance is too great, downcomer

becomes unsealed Vapor flows up downcomer and trays
above flood

• If under downcomer clearance too small, then liquid

backs up in downcomer and trays above flood
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•In addition to downcomers and tray decks JET FLOOD
containing froth and foam, there is a
quantity of spray , or entrained liquid ,
lifted above froth level on tray deck

•Force that generates this entrainment is

flow of vapor through tower Spray height Spra
of this entrained liquid is function of two y
factors
–Foam height of tray
–Vapour velocity through tray

•High vapour velocities combined with high

% heavy key components in overhead
foam levels will cause spray to hit
underside of tray above

•This causes mixing of liquid from lower Incipient flood

tray with liquid on upper tray This
backmixing reduce tray efficiency Reflux
• When vapor velocity increases, foam height increase
until downcomer filled with foam

• Further increase in vapor flow cause noticeable

increase in foam height of tray deck , which then
increases spray height

•When spray height from tray below hits tray above,

this is called incipient flood point, or initiation of jet
flooding

•Incipient flood point called best efficiency point in

distillation trays, where most efficient operation takes
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place
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