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Another
product Another
phase poorer phase brought
in a solute in to contact
feed
Introduction: Separation
Process-3
After the contacting, the two phases may
now be separated
The choice of phase and conditions will
ensure that one of the phases in contact
will be depleted or enriched in one or
more components of the original mixture.
Solid-Liquid Liquid- Solid Solid to Liquid extracting copper from ores using
extraction H2SO4 sol
crystallization Liquid- Solid Liquid to Solid Sugar from conc. sugar solutions
Other separation
processes
Adsorption, Crystallization,
cyclonic separation
Centrifugation , Chromatography,
Distillation
reliability, simplicity, and low-capital
cost
But energy consuming
Absorption
Stripping
Humidification
dehumidification
Vapour-liquid Separation Process:
DISTILLATION
Process in which a liquid or vapour or a vapour -liquid
mixture of two or more substances is separated into its
component fractions of desired purity, on the basis of
difference in relative volatility(or boiling point),
by the application and removal of heat
relies on differences in the concentrations of components
in the liquid and vapour phases at equilibrium.
This is related to components differences in the
1. Volatilities 2. vapour pressures 3. boiling points
The components that make up the mixture
distribute themselves unequally in both the vapour and liquid
Applications of distillation
1. separate crude oil into fractions for specific uses
such as transport, power generation and heating.
2. Water is distilled to remove impurities-salt from
sea water.
3. Air is distilled to separate its components - notably
oxygen, nitrogen and argon- for industrial use.
4. Distillation of fermented solutions- used since
ancient times to produce distilled beverages with a
higher alcohol content-whiskey, gin etc
5. Small-scale Purification of liquid mixtures:
i. benzene-toluene; Acetic acid acetone
ii. methanol or ethanol from water
iii. production of deuterium(heavy water)
Equilibrium between phases.
At equilibrium the compositions,
temperature and pressure of the
contacting phases remain constant-
no change with time.
The relationship between the
compositions of a V and a L at
equilibrium at some constant
pressure/temperature is the vapour-
liquid equilibrium (VLE)data.
Data may tabulated or presented
Equilibrium between
phases1
When two phases(V-L) of different
compositions are brought into
contact there is transfer of solute or
redistribution of solutes between the
phases.
The composition of the phases as a
result changes with time until
equilibrium is attained.
The compositions of the phases at
equilibrium is a measure of the
Equilibrium between
phases 2
The important variables affecting the
compositions at equilibrium of a solute in
the contacting phases are:
Temperature of phase
pressure of phase
saturated vapour
subcoole saturated liquid
d liquid
Distribution of Components in the Phases
VS Temp. 3
0 Super heated
vapour
subcooled liquid
changes in distribution of components in
the phases with temperature. 3
(a): Liquid-phase; no vapour T = 86 oC Conc. of benzene Liquid: x = 0.40;
Vapour: y = 0.00
(b): Liquid-phase; first bubble of vapour produced. T = 95.2 oC (Bubble
Point - solution about to boil). Conc. of benzene Liquid: x = 0.40; Vapour:
y = 0.61
(c): Vapour-Liquid Mixture; continued vaporization of liquid as heat is
added T = 98.0 oC Conc. of benzene Liquid: x = 0.31; Vapour: y = 0.52
(d): Vapour-phase; last droplet of liquid remains T = 101.6 oC (dew point)
Conc. of benzene Liquid: x = 0.21; Vapour: y = 0.40
(e): Vapour-phase only, no liquid T = 108 oC .The process is unsteady-
state in nature.
NOTE: from the above Figure.
As heating continues, vaporization occurs over a range of boiling
points.
At any time when 2 phases - vapour and liquid - are present, the
conc. of benzene (more volatile component) in the vapour (y) is always
higher than that in the liquid (x). The reverse is true for toluene (less
volatile component).
2 types of phase diagrams:
Constant-pressure phase diagrams
called
T-x-y diagram
Isobaric phase diagram
boiling point diagram
boiling point-concentration diagram
commonly used for distillation
calculations
Constant-temperature- phase diagrams
P-x-y diagram
Isothermal phase diagram
Constant Pressure Phase
Diagram
PHASE DIAGRAMs 1:T-x-y (Constant
Pressure)
the distribution of components in the liquid and
vapour phases is a function of temperature
the bubble-point and the dew-point of a binary
mixture at constant pressure.
Liquids of different composition at the same
pressure will boil at different temperatures- bubble-
point curve
Vapours of different composition at the same
pressure will condense at different temperatures-
dew-point curve
boiling of a liquid mixture takes place over a range
of boiling points.
Condensation of a vapour mixture takes place over
a range of condensation points
VLE for Benzene toluene at 1 atm
Acetone water system
P=101.3k P=344.7 P=344.7
Pa 3 3
T [K] x1 y1 T [K] x1 y1 T [K] x1 y1
[mol/mo [mol/mo [mol/mo [mol/mo [mol/mo [mol/mo
l] l] l] l] l] l]
368.25 0.008 0.138 395.65 0.017 0.349 423.85 0.014 0.249
363.25 0.016 0.277 393.15 0.024 0.398 415.45 0.036 0.395
355.25 0.033 0.479 385.15 0.055 0.518 409.55 0.078 0.507
349.35 0.052 0.604 379.15 0.107 0.608 404.25 0.144 0.582
345.35 0.072 0.675 375.95 0.194 0.67 402.75 0.229 0.618
342.65 0.094 0.719 374.45 0.273 0.695 402.15 0.341 0.65
340.75 0.117 0.738 373.05 0.388 0.718 401.45 0.444 0.665
338.15 0.171 0.776 372.15 0.545 0.747 399.75 0.559 0.7
336.45 0.237 0.8 371.95 0.633 0.768 398.85 0.754 0.781
335.15 0.318 0.822 371.75 0.778 0.83 398.55 0.842 0.845
334.15 0.42 0.839 371.55 0.89 0.903 399.15 0.925 0.912
333.05 0.554 0.863 371.35 0.95 0.951
331.35 0.736 0.909
PHASE DIAGRAM: features
bubble-point curve or saturated liquid line.
vapour-liquid region
Since xB = 1 xA PA / x A PA (1 x A )
AB
PB /(1 x A ) PB x A
Daltons Law
PA = y A P T ; P B = ( 1 - y A ) P T y A (1 x A )
AB
x A (1 y A )
y (1 x )
x (1 y )
With the understanding that concentrations are in terms of the MVC and
simplifying,
x
y
1 ( 1) x
Effect of non-constant relative volatilities
on predicted VLE data
benzene-toluene (ideal solution) ethanol-water (non-ideal solution
Effect of Non-constant Relative Volatilities on
Predicted Equilibrium Curve Data
benzene-toluene (ideal solution) ethanol-water (non-ideal solution
xA=1-xB
Since:
T1
T2
T3
Note that from Raoults law:
The partial pressure PA varies linearly with xA.
the partial pressure PB varies linearly with xA.
total pressure PT varies linearly with xA.
shown as PT vs. x; PA vs. x and PB vs. x
respectively in the Figure.
Temperatures should be between the boiling
points of the pure components
Constant-temperature(P-x-y) phase diagram
for an ideal solution
From Raoults law the partial pressures PA and PB vary
linearly with xA as shown
The total pressure varies linearly with xA . This is shown
as PT vs. x in the Figure
Substituting for XA from
Pi0 in kPa, T in K )
Antoines Log(10) Pi0 =A- [B/(T+C)]
equation is
Antoine constants A, B and C for some typical liquids are provided in the Table
VLE Data(P-x-y) from vapour
pressure data
Ideal
behavio
ur
Ideal Solution & Raoult's Law
Ideal Solution: obeys Raoult's Law:
Raoult's Law:PA =PA0 XA
Where
PA =equilibrium partial pressure of a component A,
at a fixed temperature T
PA0 =vapour pressure of pure liquid A at temperature
T
xA = mole fraction of A in the liquid
Note1: The vapour pressure is constant at constant
temperature.
Note2: PA0 =f(T)
Characteristics of Ideal Solutions
The average intermolecular forces of attraction and
repulsion in the solution are unchanged on mixing the
pure liquids
The vol. of the solution varies linearly with composition
There is neither absorption nor evolution of heat in
mixing the liquids
The total vapour pressure of the solution varies linearly
with composition (in mole fraction)
Ideality requires that molecules be similar in size,
structure, and chemical nature:
the nearest approach is the optical isomers. In practice,
many solutions or organic compounds in a homologous
series are considered approximately ideal.
VLE Data : Non-Ideal Solutions
do not obey Raoult's Law
Most solutions show, at least to some
extent, non-ideal behaviour-show
deviations from ideal
equation for describing non-ideal
solutions: Henry's Law: PA=HxA
H=Henrys constant
mole fraction of A in liquid
Henry's Law also used to determine
solubility of gases in liquids
Deviation from Raoult's Law:
activity coefficients
Deviation from Raoult's Law can be
accounted for by the use of activity
coefficients
most of the non-ideal behaviour is caused
by liquid-phase effects.
In the liquid-phase, the molecules are
much more closely spaced together
than in the vapour space
attractive and repulsive forces among the
molecules have larger effects than
vapour-phase
Deviation from Raoult's Law:
activity coefficients
When chemically dissimilar components are mixed
together, there can be repulsion or attraction between
dissimilar molecules.
If the molecules repel each other, they exert a higher
partial pressure than if they were ideal.
In this case the activity coefficients are greater than unity
(called a positive deviation from Raoults law).
If the molecules attract each other, they exert a lower
partial pressure than if they were ideal.
Activity coefficients are less than unity (negative
deviations).
Activity coefficients are usually calculated from
experimental data
general guidelines for vapourliquid mixtures in
terms of their nonideality
a. Mixtures of isomers usually form ideal solutions.
b. Mixtures of close-boiling aliphatic hydrocarbons
are
nearly ideal below 10 bar.
c. Mixtures of compounds close in molar mass and
structure:
frequently do not deviate greatly from ideality
(e.g. ring compounds, unsaturated compounds,
naphthenes etc.).
d. Mixtures of simple aliphatics with aromatic
compounds:
deviate modestly from ideality
Deviation from Raoult's Law:
activity coefficients
PA= PA0 xA A
PB=PB= PB0 xB B
where
A is the (liquid-phase) activity coefficient of
component, A
B is the (liquid-phase) activity coefficient of
component, B
Activity coefficient=f(T & composition)
1. determined experimentally
2. predicted using various equations
PT=PA+PB= PA0 xA A +PB0 xB B
Deviation from Raoult's Law: activity coefficients
For ideal solutions: A= B =1
simple distillation
After time (t + dt) , vapour dL is produced,
composition of A in the vapour is y
The vapour is assumed to be in equilibrium
with the residue liquid.
The liquid in the still is thus reduced from L to
(L - dL), liquid composition changed from x to (x
- dx).
Rayleigh Equation: material
balance on A
Initial moles in still(at t) = moles left in
still(at t+dt) + moles vaporized(within dt)
i.e. amt. in still at t=amt. in still at t+dt +
amt. vapourised within dt
Moles of A=total moles x mole fraction of A
Since
xL = (x - dx) (L - dL) + y dL
xL = xL - x dL - L dx + dx dL + y dL
Neglecting the term dx dL(product of 2
small quantities), the equation reduces to:
Rayleigh Equation: material
balance on A
Simplifying
yA
Separat
or
heater
xA
Equilibrium or Flush Distillation
where
F, V and L are flow rate of feed, vapor and liquid phases.
xA
xF, yA and xA are mole fraction of component A in feed,
vapor and liquid.
( f 1) xF
yA xA
f f
Where
f = V/F = molal fraction of the feed that is vaporized and withdrawn
continuously as vapor.
1-f = molal fraction of the feed that remains as liquid 106
FLASH (EQUILIBRIUM) DISTILLATION:
mixture of A (MVC) and B (LVC)
The feed is preheated before entering the separator
As such, part of the feed may be vaporized.
The heated mixture then flows through a pressure-
reducing valve to the separator.
In the separator, separation between the vapour and
liquid takes place.
A produced in the vapour depends on the condition
of the feed
i.e. how much of the feed is entering as vapour state,
which in turn is controlled by the amount of heating.
In other words, the degree of vapourization of the
feed affects the concentration (distribution) of A in
vapour phase and liquid phase.
Separation in Flash Distillation1
If no vapourization takes place, then the liquid
leaving the separator will have the same
composition as the feed.
If total vapourization occurs, the vapour will also
have the same composition as the feed.
Clearly, for effective separation, there must be some
vapour-liquid mixture present.
This means that there exists a certain relationship
between the extent of heating, and the concentration
in the vapour and liquid streams.
f =molal fraction of the feed that is vaporized
and withdrawn continuously as vapour
Therefore, for 1 mole of binary feed mixture, (1- f) is
the molal fraction of the feed that leaves continuously
as liquid
Separation In Flash Distillation2
yD = mole fraction of A in vapour leaving
xB = mole fraction of A in liquid leaving
xF = mole fraction of A in feed entering
the greater the heating, the larger the
value of f.
If the feed is completely vapourised, then
f = 1.0
Thus, the value of f can vary from
0 (no vapourization) to
1 (total vapourization).
Flash Distillation: material
balance for the MVC (A)[1mole of
feed]
1. x = f y + (1 - f) x
F D B
f yD = xF - (1 - f) xB
Re-arrange to yield:
Feed:F
Bottoms:B
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The McCabe-Thiele
Method
uses the equilibrium curve diagram to
determine the number of theoretical
stages (trays) required to achieve a
desired degree of separation.
It is a simplified method of analysis making
use of several assumptions,
very useful tool for the understanding of
distillation operation.
The VLE data must be available at the
operating pressure of the column.
The McCabe-Thiele Method.2
Information required :
feed condition (temperature, composition)
distillate compositions
bottom compositions
the reflux ratio - the ratio of reflux liquid over the
distillate product.
to determine number of theoretical stages required
for a given separation
Main assumption
1) Equimolar overflow through the tower between the
feed inlet and the top tray and the feed inlet and bottom
tray.
2) Liquid and vapor streams enter a tray, are
equilibrated, and leave.
McCabe-Thiele Method:
assumptions of the method
a. Constant Molal Overflow. The molar flow rates of
the vapor and liquid are nearly constant in each
section of the column. This also ensures the operating
lines are straight lines.
Reflux Ratio R = L /
D
ROL Characteristics:
i. Straight Line Equation
ii. Slope= R/(R+1),
Intercept =(xD /R+1),
iii. In addition, if xn = xD, then yn+1 = xD .
iv. Thus, the operating line passes through the
point (xD , xD) on the 45o diagonal line.
R changes, the slope and intercept
of the ROL
Rectifying Section: ROL
Introduction of Feed : the q-line
Consider the tray where the feed is introduced
(known as the feed tray location), say tray f :
1>q>0 0>q
Relating q with L and L; Vand
V
In addition, because the feed is cold, it will
also condense some of the rising vapour.
As a result, the amount of liquid flow in the
stripping section L' is much larger than the
liquid flow in the rectifying section L.
The vapour flow in the rectifying section V,
is lower than the vapour flow in the
stripping section V' because of the
condensation into the liquid.
Hence for case (a), we have L' > L and V' >
V.
Feed Section Operating Line (q-line)
Slope = R/(R+1)
Slope = q/(1-q)
Slope = L/
V
Ex 4.7 A continuous fractioning column is to be designed to
separate 30,000 kg/h of a mixture of 40 percent benzene and
60 percent toluene into an overhead product containing 97
percent benzene and a bottom product containing 98 percent
toluene. These percentages are by weight. A reflux ratio of 3.5
mol to 1 mol of product is to be used. The molal latent heats of
benzene and toluene are 7,360 and 7,960 cal/g mol,
respectively. Benzene and toluene from a nearly ideal system
with a relative volatility of about 2.5. The feed has a boiling
point of 95C at a pressure of 1 atm.
a) Calculate the moles of overhead product and bottom product
per hour.
b) Determine the number of ideal plates and the position of the
feed plate (i) if the feed is liquid and at its boiling point; (ii) if
the feed is liquid and at 20C (specific heat 0.44 cal/g.C); (iii) if
the feed is a mixture of two-thirds vapor and one-third liquid.
Example of use of McCabe Thiele
Method
Problem: Continuous distillation of Benzene
and Toluene. Feed is at 30,000 kg/h and 40
wt.% Benzene
Overhead product = 97 wt.% Benzene.
Bottom product = 98 wt.% Toluene
Reflux mole ratio = 3.5, Ideal System, alpha,
a = 2.5
Slope=Rm/(Rm+1)
XD/(Rm+1)
total reflux and minimum reflux ratio
The minimum reflux ratio and the
infinite reflux ratio place a constraints
on the range of separation operation.
Any reflux ratio between Rmin and Total
R will produce the desired separation,
with the corresponding number of
theoretical stages varying from infinity
at Rmin to the minimum number (Nmin at
Total R).
The choice of reflux ratio to use is
governed by cost considerations
Number theoretical Stages (N)
Vs. Reflux Ratio(R)
Costs versus Reflux Ratio
Steps/Procedure:
1. If the external reflux, Lo, is at its bubble point:
2. LR = Lo = (R) D
3. VR = LR + D
4. vs = VR - (1 - q ) F
5. Ls = LR + qF
. 7. Calculate slope of rectifying operating line:=[ R/(R+1)
. 8. Draw rectifying operating line from (xD , xD ) with slope= =[ R/(R+1) -
. 9. Draw stripping operating line from (xB , xB ) to the intersection
. of the q line with the rectifying operating line.
. 10. Check your calculations by seeing whether the slope of stripping
operating
. line is Ls/Vs.
. 11. Start from the xB point on the 45 line and step up from the stripping
operating line to the VLE curve.
. The first step corresponds to the partial reboiler. The next step is tray above, the next
is tray 2, and so on.
. 12. When this stepping procedure crosses the intersection of operating lines,
this is the optimum feed tray (i.e.? any other feed tray would require a
greater total number of trays). Thus the feed tray NF has been determined.
Steps/Procedure:
13. Switch to the rectifying operating line and
continue stepping.
14. When the xD point is crossed, this is the total
number of trays NT.
This last step may not go through the xD point exactly,
implying a noninteger
number of trays.
Dont let this worry you. In this procedure we have
assumed perfect or
theoretical or 100 percent efficient trays;
that is, trays on which the vapour and liquid streams
leaving the trays are in perfect phase equilibrium.
Actual industrial columns seldom achieve this ideal
situation, so an efficiency factor must be used to
determine the number of actual trays installed in the
column
Efficiencies
Overall efficiency for a column
Eo = N of Equil stages/N of Actual
Stages
In petroleum industry Eo = 0.6, is
used