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CH3551 MASS TRANSFER-II 9. Distribution Coefficient: The distribution coefficient is characteristics of the solute and the solvent
UNIT III -LIQUID-LIQUID EXTRACTION pair. It determines the ratio of solute in the two solvents.
**************************************************** In dilute solutions at equilibrium, the ratio of the concentrations of the solute in the two phases is
Liquid - liquid extraction - solvent characteristics-equilibrium stage wise contact calculations for batch and called as the distribution coefficient or distribution constant K. Thus,
continuous extractors- differential contact equipment-spray, packed and mechanically agitated contactors and C
K E
their design calculations-packed bed extraction with reflux. Pulsed extractors, centrifugal extractors- CR
Supercritical extraction Where,
**************************************************** CE - Concentrations of the solute in the extract.
LIQUID-LIQUID EXTRACTION CR - Concentrations of the solute in the raffinate phases.
Liquid- liquid operation is also known as ―Solvent Extraction‖. Separation of one or more The distribution coefficient can also be given in terms of weight fraction of the solute in the two
component in a mixture by contacting with another phase which is liquid. phases in contact at equilibrium.
Extraction involves the separation of the constituents (solutes) of a liquid solution by contact
y*
with another insoluble liquid called as solvent. K' 
Solutes are separated based on their different solubilities in different liquids. Separation is achieved x
when the substances constituting the original solution is transferred from the original solution to the other Where,
liquid solution. y* - The weight fraction of the solute in the extract.
Example: Separation of certain components of petroleum base components of the oil by acetone is an x -The weight fraction of the solute in the raffinate.
example of extraction. APPLICATIONS
i. Separation of acetic acid from dilute solution with water is done mere economically by extraction
followed by distillation than distillation alone because of high latent heat of vaporisation of water.
ii. Long chain fatty acids can be removed from vegetable oils economically by extraction with liquid
propane than high vacuum distillation technique.
iii. Separation of petroleum products that have about the same boiling range. Separation of aromatics
from Tube oil fractions using furfural as a solvent.
iv. Recovery of penicillin from the fermentation broth using butyl acetate.
v. Metal separation such as Uranium – Vanadium, Tungsten – molybdenum and the fission products
The two liquids are insoluble on allowed to settle two layers are formed. The layers are formed from of atomic energy process are more economical by liquid extraction.
two liquids. Three stages are involved in the process. DIFFERENCE BETWEEN DISTILLATION AND EXTRACTION
i) Bringing the feed mixture and the solvent into intimate contact.
ii) Separation resulting two phases.
iii) Removal and recovery of the solvent from each phase.
TERMINOLOGIES
1. Immiscible: In capable of mixing (or) reaching homogeneity.
2. Feed: The feed is the stream of liquid containing the solute to be extracted as it enter; the column.
3. Solvent (B): Liquid extraction is the separation of the constituents of a liquid by contact with another
insoluble liquid called solvent. (or) The liquid added to bring about the extraction is known as the
solvent.
4. Extract (E): The extract is the exit stream containing the desired product. The layer which is rich in
solvent is known as ―Extract‖ (solvent-rich product)
5. Raffinate (R): The raffinate is the exit stream that has been depleted of the desired product. The
(Residual liquid from solute) other layer, composed of the remainder of the original solution plus
some of the solvent is known as Raffinate.
6. Separation: Separated on the basis of relative solubility. The distribution coefficient determines the
ratio of the concentration of the solute in each solvent.
7. Solute (C): The constituents distribute themselves differently between the two layers. The
constituent of the liquid solution which is extracted by the solvent is known as solute.
8. Liquid Equilibria: Extraction involves the use of systems composed of at least three substances and
although most part the insoluble phase is chemically very different, generally all three components
appear at least to some extent in both phases.
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NOTATION SCHEME FOR EXTRACTION (iv) The solvent may lead to the formation of two or three partially miscible liquids. A
i. A is the feed solvent, B is the extracting solvent (A and B are pure and substantially insoluble and C are completely soluble, while A and B, and B and C dissolve only to limited extent
liquids) and C is the solute that will distribute between two phases. in each other (two pairs partially miscible). It is observed occasionally and not desired.
ii. Feed solutions (F) to be separated by extraction are comprised of A and C. The most commonly encountered possibility (after addition of a solvent to a reed solution) is that
iii. The above mentioned letters will be used to indicate the quantities and the locations of mixtures given by type (ii). In liquid extraction, the equilibrium data (i.e., equilibrium compositions of the phases) can
on the phase diagrams to follow. be presented by using triangular coordinates (e.g., equilateral triangular coordinates) as well as by using
iv. For batch operations, quantities are measured in mass (or weight) and that for continuous rectangular coordinates.
operations in mass/time. Therefore, In case of type (i) possibility, rectangular coordinates are commonly used to show the equilibrium
E = mass or mass/time of solution E, i.e., an extract or extract phase, shown on a phase relationship between the phases wherein the composition of the solute in one phase is plotted against the
diagram by point E. composition of the solute in another phase in equilibrium with it.
R = mass or mass/time of solution R, i.e., a raffinate or raffinate phase shown on a phase The equilibrium data in case of type (iii) and type (iv) possibilities are often presented by using
diagram by point R. equilateral triangular coordinates.
B = mass or mass/time of solvent B. EQUILATERAL TRIANGULAR COORDINATES/EQUILATERAL TRIANGULAR DIAGRAM
x = weight fraction of C in the A-rich phase, i.e., in the raffinate phase. The equilateral, triangular diagrams are extensively used for graphical presentation of the
y = weight fraction of C in the B-rich phase, i.e., in the extract phase. compositions of ternary systems/mixture. In the case of an equilateral triangle, we know that the sum of the
In case of immiscible liquids/insoluble liquids: perpendicular distances from any point inside the triangle to its three sides is equal to the altitude of the
x Mass C Mass C triangle, so we can assume here that the altitude represents 100% composition and the perpendicular distances
X  
1  x  Mass non - C in the raffinate phase Mass A to the three sides represent the percentages or fractions of the three components.
y Mass C Mass C
Y  
1  y  Mass non - C in the extract phase Mass B
X=Weight fraction ‗C‘ in the raffinate liquid on a (B-Free) basis (Mass C /Mass A + Mass C)
Y = Weight fraction ‗C‘ in the Extract liquid on a (B- Free) basis (Mass C /Mass A + Mass C)
N = Weight fraction ‗B‘ on a (B- Free) basis (Mass B /Mass A + Mass C)
TERNARY SYSTEMS
In extraction operation generally ternary systems are involved. The solute distributes between solvent
rich phase called extract and solvent lean phase called raffinate.
The schematic following figure indicates the various streams involved in a typical liquid—liquid
extraction operation. The equilibrium concentration of such systems can be represented in a triangular
coordinate system.
Here we are considering a ternary system comprising of components A, C and B, so in above figure,
the apexes of the triangle are marked with.100 % A, 100 % C and 100 % B (each apex representing the pure
component).
Any point on a side of the triangle represents the locus of all possible mixtures of two out of any three
components, i.e., it represents a binary mixture and any point inside the triangle represents a mixture of all
three components.
Therefore, a side AC represents the locus of all possible mixtures of A and C only, i.e., it represents a
binary mixture of A and C. Similarly, a side AB represents a binary mixture of A and B, and a side BC, a
binary mixture of C and B. For example, point D marked on the side AB represents a binary mixture
containing 80 % A and 20 % B. In a Binary mixture containing 80% A and 20% B. Mixture containing same
ratio of A to B.
The addition of a new solvent to a binary liquid mixture of the solute in a solvent may result in the The corners of the triangle labelled A, B and C corresponds to the pure components A, B and C
formation of several types of mixture/may yield different types of mixture: respectively. The side of the triangle opposite to the corner labelled A implies the absence of A. Therefore, the
(i) The solvent may be completely immiscible with the feed solvent. This is the ideal case. horizontal lines across the triangle show increasing percentage of A from zero at the base to 100% at the apex.
(ii) The solvent may be partially miscible with the feed solvent, forming one pair of Any point within the triangle represents a mixture consisting of all three components. If the two
partially miscible liquid. If A is the feed solvent, C is the solute and B is the extracting components are marked with their compositions then the third one is fixed because of the property of a
solvent, then C dissolves in A and B completely while A and B dissolve only to a limited triangle.
extent in each other. This is the most common type. The property, of an equilateral triangle is that the sum of the three perpendicular distances from any
(iii) A homogeneous solution may be formed, and then the solvent selected is not suitable point within the triangle to the sides of the triangle is always equal to the height of the triangle or altitude of
and should be rejected. the triangle.
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The mixture indicated by any point P consists of the three components A, B and C in the ratio of the R ( xE  xM )
 ------------------- (4)
perpendiculars PN, PM, PQ. The perpendicular distance from point P to the base AB, PQ represents the E ( xM  xR )
composition of C in the mixture at P. Component balance from graph,
Similarly, the perpendicular distances PM (to the base AC) and PN (to the base BC) represent the R(line RL)  E(line ET)  M (line MO) ------------------- (5)
compositions of B and A in the mixture at P respectively. So xP = 0.40.
Sub M = (R + E) in equation (5),
If R kg of a mixture at point R is added to E kg of a mixture at point E (in following figure), then the
R(line RL)  E(line ET)  ( R  E)(line MO)
new mixture resulted (M kg) is shown on the straight line RE at point M, such that :
R(line RL)  E(line ET)  R(line MO)  E(line MO)
R Line ME X E  X M
  ------------------- (1) R(line RL)  R(line MO)  E(line MO)  E(line ET)
E Line RM X M  X R
R(line RL  line MO)  E(line MO  line ET)
Where,
R (line MO  line ET)
xR – The weight fraction of C in R (Raffinate) 
xE – The weight fraction of C in E (Extract) E (line RL  line MO)
xM - The weight fraction of C in M (Mixture) R (line ET  line MO)

Now we will establish equation (1), we get E (line MO  line RL)
The Mixture Rule, R line EP
  (ET  MO)  EP and (MO  RL)  PS
E line PS
R line ME

E line RM
R ( xE  xM )
 ------------------- (7)
E ( xM  xR )
SYSTEM ENCOUNTERED IN EXTRACTION
1. One Pair Partially soluble
2. Two Pair Partially soluble
3. Two partially soluble liquids and one solid
1. One Pair Partially soluble
The above figure shows that the addition of R kg of mixture at R to E kg of mixture at E results in the Example of Three liquid systems
formation of M kg of new mixture at M. Water (A) – Methyl isobutyl ketone (B) – Acetone (C)
Assumptions
Raffinate = R
Extract = E
Mixture = M
Mass fraction of solute in raffinate, Extract, Mixture = xR, xE , xM
Line RL represents the weight fraction of C in R = xR
Line MO represents the weight fraction of C in M = xM
Line ET represents the weight fraction of C in E = xE
Overall material balance,
R  E  M ------------------- (2)
Individual component balance,
RxR  ExE  MxM ------------------- (3) Consider a system C (acetone), A (water) and B (methyl isobutyl ketone, MIK) at 298K (25°C)
Sub M = (R + E) in equation (3), wherein acetone is the solute, water is the diluent (feed solvent) and methyl isobutyl ketone is the solvent used
RxR  ExE  MxM to extract acetone, i.e., extracting solvent.
RxR  ExE  ( R  E ) xM Acetone and water are completely miscible, and acetone and MIK are completely miscible while
water and MIK are partially miscible with each other.
RxR  ExE  RxM  ExM
Water (A) and MIK (B) dissolve to a limited extent in each other to give rise to the saturated liquid
RxR  RxM  ExM  ExE
solutions (A - rich) at D and co_ rich) at G. Apex C represents 100 % acetone, and apexes A and B represent
R( xR  xM )  E ( xM  xE ) 100 % water and 100 % MIK respectively.
R ( xM  xE ) Along a side AB the concentration of C is zero and same is true for A and B along BC and AC

E ( xR  xM ) respectively.
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Every mixture of MIK and water (binary mixture) of composition lying between points D and G say 3. Rectangular Coordinates
at H forms two liquid phases (layers) of compositions at D and G and the relative amounts of phases depend Data for ternary systems (three component systems) are frequently presented on equilateral triangular
upon the position of H according the mixture rule equation. diagrams.
R Line ME X E  X M However, for engineering calculations, a right-angled triangle/a right-angled triangular diagram is
 
E Line RM X M  X R more convenient for presenting the data since ordinary rectangular-coordinate graph paper may be used in
constructing the diagram.
From diagram
i. A & C – Completely soluble In case of equilateral triangles, the coordinate scales are always the same. In order to expend one
ii. A& B, B & C – Soluble only to limited extent concentration scale relative to the other, rectangular coordinates are used.
iii. (A – C) – Feed solvent The following figure shows the use of rectangular coordinates for presenting the equilibrium data
wherein concentrations of B are plotted as abscissas and concentrations of C as ordinates.
iv. Tie line parallel to Base line –Solutropic system
v. Liquid ‗C‘ dissolves completely in A and B and A and B dissolves only to a limited extent One can use unequal scale to expand the plot as desired. The following equation is applicable to all
in each other to give a saturated solution. mixtures on figures irrespective of any inequality of the scales.
D- Indicates saturated liquid ‗B‘ in ‗A‘ (A-Rich). R Line ME X E  X M
vi.  
vii. G- Indicates saturated liquid ‗A‘ in ‗B‘ (B-Rich). E Line RM X M  X R
viii. D- Binary mixture that separates in 2 soluble liquid phase like ‗D‘ in ‗G‘
ix. The curve DRPEG indicates the binodal curve.
x. Solubility line RE indicates the equilibrium composition – Tie line.
xi. P – Plait point.
xii. Usually the tie line are not parallel, changes their slope in one direction. In some system,
one of the tie line may be horizontal with base is known as Solutropic System.
2. Two Pair Partially soluble
Example of Three liquid systems
Chlorobenzene (A) - Methyl ethyl ketone (C) - water (B).

One of the important factors in selecting a solvent for extraction is the selectivity of the solvent and is
given by,
yE* . Weight fraction of A in R

xR . Weight fraction of A in E
The selectivity has the same significance in extraction as the relative volatility has in distillation. So it
is a measure of the separation by extraction.
When the selectivity is equal to one, separation by extraction is not possible. For all practical
operations, the selectivity should be greater than one.
Here A and C are completely miscible in one another, while the pairs A – B and B – C are partially The selectivity in extraction and the relative volatility in distillation are analogous. Poor selectivity
miscible in one other, i.e., they show only limited solubility. (near unity) means large solvent to feed ratios and so a large number of extraction stages will be required for a
The equilibrium-relationship in such a case is as shown in above figure; points D and G represent the specified separation.
mutual solubilities of A and B and points I and H represent the mutual solubilities of B and C. CHOICE OF SOLVENT FOR EXTRACTION
The second figure shows the corresponding distribution curve. Any mixture outside ate band between Any Particular liquid to be used as a solvent for extraction will not possess all the properties
these solubility curves forms a homogeneous single phase solution. considered desirable for extraction and hence, some compromise is usually necessary in selecting the best
From diagram solvent out of various possible liquid solvents available.
i. A & C – Completely soluble While selecting a solvent for extraction, the qualities such as selectivity, recoverability, distribution
ii. A& B, B & C – Partially soluble with one another coefficient, density, etc. should be given consideration.
iii. D & G – Mutual solubilities i. Selectivity
iv. A & B, I & H represent the mutual solubilities of B & C The ratio of concentration ratio of solute to the feed solvent in extract phase to that in the
v. Curved lines DRI (A - rich / raffinate) and GEH (B - rich) are the ternary solubility curves. raffinate phase is called as selectivity or separation factor.
vi. The mixture such as M within these curves forms two liquid phases in equilibrium  Weight fraction of C 
represented by points R and E.  Weight fraction of A 
vii. RE – Tie line.  E
 Weight fraction of C 
 Weight fraction of A 
 R
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If selectivity, 1. STAGE WISE EQUIPMENT

β >1 Means higher selectivity, less solvent requirements & good separation is occur. In stage wise contact, it is presumed that each stage has facilities
β = 1 Means no separation occur. (i) Contacting the feed solution and the extracting solvent (insoluble liquids).
ii. Recoverability (ii) Separating the product streams.
As solvent should be recovered for reuse usually by distillation, it should not form an Each stage involved in the extraction operation represents a theoretical or equilibrium stage so that
azeotrope with extracted solute. For low cost recovery, the relative volatility should be high. The the product streams, i.e., the extract and raffinate leave the stage in or equilibrium with each other.
latent heat of vaporisation of the solvent should be small whenever the solvent is to be volatilised Therefore a combination of a mixer and settler forms a stage (represents a stage). In multistate
(vaporised). operations, mixers and settlers may be arranged in cascades as needed.
iii. Distribution coefficient: i. SINGLE STAGE CONTACT EXTRACTION
Higher values (>1) of the distribution coefficient are generally desirable as then less A single stage extraction operation may be performed in a batch wise or continuous manner.
amount of solvent and less number of extraction stages are required for a given extraction duty. a. Tertiary system – One pair partially miscible
 y*  Let F be the mass of feed solution (for batch) or mass per unit time of feed solution (for continuous)
K    > 1
'
containing solute C and feed solvent A with xF mass/weight fraction of C is fed to a final stage.
 x
The feed solution is contacted with mass S1 (or mass per unit time) of a solvent containing principally
iv. Capacity:
B with yS weight fraction of C.
It is the ability of the solvent to dissolve the extracted solute. In ternary systems with one
If the solvent is pure B, yS = 0 and S1 = B. After contacting and phase separation, we get the
pair partially miscible, solvent can dissolve an infinite amount of solute and this result in generally
equilibrium raffinate R1 and extract E1 each one is measured in mass or mass per unit time.
lower solvent requirements than for ternary systems with two pairs partially miscible.
v. Density:
The difference in density of saturated liquid phases should be larger for physical
separation of phases.
vi. Insolubility of solvent
The solvent insoluble in original (feed) liquid solvent should be preferred and it should
have high solubility for solute to be extracted, as then small amount of solvent are required.
vii. Interfacial tension:
The interfacial tension should be high for the coalescence of emulsions to occur more Assumptions:
readily, as the same is of greater importance than the dispersion. 1. Let F be the mass of feed solution (in kg) containing solute C and feed solvent A with x f
vii. Others: mole fraction of C is feed to single stage
The solvent should be 2. The feed solution is contacted with mass S , of a solvent containing principally B with ys
a. Stable at chemically. weight fraction of C
b. Chemically inert towards the other components. 3. If the solvent is pure B, ys = 0 and S1 = B
c. Non-corrosive towards the common materials of construction. 4. After contacting and phase separation we get equilibrium Raffinate R1 and Extract E1
d. Non-toxic. 5. Let x1 be the weight fraction of C in Raffinate
e. Non-flammable. 6. Let y1 be the weight fraction of C in Extract
f. Cheap (available at low cost). 7. Let xf - Mass fraction of C in Feed
g. Low viscosity (desired for better mass transfer rates and settling of dispersions). 8. Let Ys –mass fraction of C in solvent
h. Low freezing point. 9. If the solvent is pure (B) ,Ys =0 the S1 = B
i. Low vapour pressure for ease in handling and storage. Overall material balance,
METHODS OF EXTRACTION F  S1  M1  E1  R1 ------------------ (1)
Liquid-liquid extraction operations may be carried out by using: The point M1 can be located on the line FS1 by mixture rule, equation (1) becomes,
(1) Stage wise equipment F Line length M1S1
 ------------------ (2)
i. Single stage contact extraction S1F Line length FM1
a. Co-Current ( ) Let, xM1 is the weight fraction of C in mixture M1
b. Counter –Current ( ) Individual material balance,
c. Cross – current ( ) ( ) FxF  S1 yS  M1 xM 1  E1 y1  R1 x1 ------------------ (3)
ii. Multi –stage Extraction
Sub [(F + S1) = M1] in equation (3),
(2) Differential contact/continuous contact equipment
FxF  S1 yS  ( F  S1 ) xM 1  E1 y1  R1 x1
FxF  S1 yS  FxM 1  S1 xM 1 ------------------ (4)
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FxF  FxM  S1 xM  S1 yS Total material balance: (Solvent free basis)

F ( xF  xM 1 )  S1 ( xM 1  yS ) F   S   M1  E1  R1 ------------------ (7)
Component balance (C),
S1 ( xF  x M 1)
 ------------------ (5) F xF  S yS  M1xM  E1 y1  R1x1 ------------------ (8)
F ( xM 1  y S )
Component balance (B),
Consider the equation,
F N F  S N S  M 1N1  E1N E  R1N R ------------------ (9)
E1 y1  R1 x1  M1 xM 1
Sub [(M1 - E1) = R1] in equation (3), Let, [(M'1 - E'1) = R'1] we get,
E1 y1  (M1  E1 ) x1  M1xM 1 M1xM  E1y1  R1x1

E1 y1  M1 x1  E1 x1  M1 xM 1 M1xM  E1 y1  (M1  E1) x1

E1 y1  E1x1  M1xM 1  M1x1 M1xM  E1y1  M1x1  E1x1

E1 ( y1  x1 )  M1 ( xM 1  x1 ) M1xM  M1x1  E1 y1  E1x1

E1 ( xM 1  x1) M1( xM  x1 )  E1( y1  x1 )

 ------------------ (6)
M 1 ( y1  x1 ) ( xM  x1 ) E1
 ------------------ (10)
Note: ( y1  x1 ) M 1
Expression can be used to find out the amount of solvent required for the particular separation.
Quantity of Extract can be obtained from equation (6).

c. Single stage operation – Immiscible solvents

When the extraction solvent and feed solvent are insoluble (immiscible) and remain so over a
concentration range of the solute involved then all A fed with the feed solution will remain in the raffinate
b. Single stage extraction solvent free co-ordinates (raffinate will contain only A and C) and all B in the solvent fed will remain in the extract (extract will
contain only C and B).
In such cases, there is no need to use a triangular graph or rectangular graph described earlier. In this
case, the solute concentrations are expressed on a C-free basis and the equilibrium solute concentrations are
Solvent Free Basis plotted as shown in following figure.
E  E
F  F
S  S
R  R
y1  y1

Suppose that F mass or mass/time of feed solution containing A kg of A and C kg of C is contacted

Assumptions: with a solvent containing B kg of B and after providing a sufficient contact time and applying settling, the
1. Where E' indicates mass of the extract in solvent free basis phases are removed in equilibrium with each other.
2. F',S',R' indicates mass of feed , solvent ,and raffinate in solvent free basis Let,
3. xF, yS', y1',x1 - weight fraction of C in feed ,solvent , extract and raffinate in solvent free basis Mass C kg C
XF   in the Feed
4. N- Weight of solvent in solvent free basis Mass A kg A
5. NF ,NS, NE',NR – Weight of solvent in feed ,solvent , extract and raffinate in solvent free basis Mass C kg C
X1   in the Raffinate
Mass A kg A
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Mass C kg C From this type of arrangement, we get a single final raffinate whereas we get a separate extract from
Y1   in the Extract
Mass B kg B each stage and the extracts from all the stages can be combined to get the composited extract (E).
Mass C kg C The figure indicates that different amounts of solvent of the same solute composition are used.
YS   in the Extraction Solvent For Stage-1
Mass B kg B
Overall material balance,
For an equilibrium stage/theoretical stage, the effluent streams leave the stage in equilibrium, so X 1
and Y1 (mass ratios of C in the raffinate and extract respectively) are in equilibrium with each other. M1  F  S1
Material balance of solute C gives F  S1  M1  E1  R1 ------------------ (1)
X F A  BYS  X 1 A  Y1B Material balance of solute ‘C’,
X F A  X 1 A  Y1B  BYS FxF  S1 yS  M1 xM 1  E1 y1  R1 x1 ------------------ (2)
 A( X 1  X F )  B(Y1  YS ) FxF  S1 yS  M1 xM 1 ------------------ (3)

(Y1  YS ) A FxF  S1 yS  ( F  S1 ) xM 1
 ------------------ (1)
( X1  X F ) B FxF  S1 yS  FxM 1  S1 xM 1
Equation (1) is the equation of the operating line for a single stage operation. The operating line FxF  FxM 1  S1 xM 1  S1 yS
 A F ( xF  xM 1 )  S1 ( xM 1  yS )
passes through points (XF, YS) and (X1, Y1) and has a slope of    .
 B S1 ( xF  xM 1 )
If the extraction solvent is pure (contains no solute) then YS = 0 and so, Equation (1) reduces to  ------------------ (4)
F ( xM 1  y S )
(Y1  0) Y1 A
  ------------------ (2) From equation (3) becomes,
( X1  X F ) ( X1  X F ) B
FxF  S1 yS  M1 xM 1
Equation (2) is the equation of the operating line for a single stage extraction when the solvent is pure
FxF  S1 yS
B. xM 1  ------------------ (5)
M1
It is a straight line that passes through points (XF, 0) and (X1, Y1) and has a slope of (-A/B). The
operating line given by Equation (2) is plotted in below figure. From equation (2) becomes,
M1xM 1  E1 y1  R1x1
M1xM 1  E1 y1  (M1  E1 ) x1
M1xM 1  E1 y1  M1x1  E1x1
M1xM 1  M1x1  E1 y1  E1x1
M1 ( xM 1  x1 )  E1 ( y1  x1 )
E1 ( xM 1  x1 )
 ------------------ (6)
M 1 ( y1  x1 )
M 1 ( xM 1  x1 )
E1  ------------------ (7)
( y1  x1 )
For Stage-2
d. Multi Stage Cross Current Extraction – Partially miscible solvent Overall material balance,
M 2  R1  S2
R1  S2  M 2  E2  R2 ------------------ (8)
Material balance of individual at solute ‘C’,
R1 x1  S2 yS  M 2 xM 2  E2 y2  R2 x2 ------------------ (9)
R1 x1  S2 yS  M 2 xM 2 ------------------ (10)
R1 x1  S2 yS  ( R1  S2 ) xM 2
R1 x1  S2 yS  R1 xM 2  S2 xM 2
It is simply an extension of single stage extraction. This can be performed in a batch or continuous R1 x1  R1 xM 2  S2 xM 2  S2 yS
manner. Figure shows a three-stage cross-current extraction operation. R1 ( x1  xM 2 )  S2 ( xM 2  yS )
Here the raffinate from any stage acts- as the feed for the next stage and as the raffinate moves from
stage to stage it is contacted with a fresh solvent each time.
 P a g e | 15 P a g e | 16

S2 ( x1  xM 2 ) M n xMn  M n xn  En yn  En xn
 ------------------ (11)
R1 ( xM 2  yS ) M n ( xMn  xn )  En ( yn  xn )
From equation (10) becomes, En ( xMn  xn )
R1 x1  S2 yS  M 2 xM 2
 ------------------ (19)
M n ( y n  xn )
R1 x1  S 2 yS M n ( xMn  xn )
xM 2  En  ------------------ (20)
M2 ( yn  xn )
R1 x1  S2 yS We can use equal amount of solvent for each time. The amount of solute extracted, i.e., amount of
xM 2  ------------------ (12)
R1  S 2 solute in the composited extract is
From equation (9) becomes, Solute in the composited extract = E1y1 + E2y2 +……+ Enyn
M 2 xM 2  E2 y2  R2 x2 Composited extract = E1 + E2+ .......+ En
Here one can also make use of rectangular coordinates. Graphically represent of multistage cross
M 2 xM 2  E2 y2  (M 2  E2 ) x2
current extraction on triangular co-ordinates shown in fig. The solvent amount used for extraction S1, S2, and
M 2 xM 2  E2 y2  M 2 x2  E2 x2
S3 as are have same composition they are represented by point S.
M 2 xM 2  M 2 x2  E2 y2  E2 x2
M 2 ( xM 2  x2 )  E2 ( y2  x2 )
E2 ( xM 2  x2 )

M2 ( y2  x2 )
M 2 ( xM 2  x2 )
E2  ------------------ (13)
( y2  x2 )
For nth Stage
Overall material balance,
M n  Rn 1  Sn
e. Multi-Stage Cross Current Extraction- Immiscible solvents
Rn1  S n  M n  En  Rn ------------------ (14)
Here we are considering a case where the feed solvent and extraction solvent are completely
Material balance of individual at solute ‘C’, immiscible. In such cases, the raffinate from all stages will contain only A and C and the extract from
Rn1 xn1  S n yS  M n xMn  En yn  Rn xn ------------------ (15) each stage contain only B and C.
Rn1 xn1  S n yS  M n xMn ------------------ (16) Further, all A in the feed solution will be there in all raffinates and the extract from each stage
Rn1 xn 1  S n yS  ( Rn1  S n ) xMn contain all the solvent B fed to that stage.
In such a case, we will express the concentration of C in all the streams in terms of a mass ratio (i.e.,
Rn 1 xn 1  S n yS  Rn 1 xMn  S n xMn
mass of C/mass of A or B) of solute C.
Rn 1 xn 1  Rn 1 xMn  S n xMn  S n yS
Rn1 ( xn1  xMn )  S n ( xMn  yS )
Sn (x  x )
 n 1 Mn ------------------ (17)
Rn 1 ( xMn  yS )
From equation (16) becomes,
Rn1 xn1  S n yS  M n xMn
Rn1 xn1  S n yS
xMn 
Mn Case (i)
Consider the equal amount of solvent is used in each stage and the solvent is pure B (YS =0).
Rn1 xn 1  S n yS
xMn  ------------------ (18) Mass C kg C
Rn1  S n XF   in the Feed
Mass A kg A
From equation (15) becomes,
Mass C kg C
M n xMn  En yn  Rn xn X1, X 2 , X 3   in the Raffinate from stage 1,2,3,....
Mass A kg A
M n xMn  En yn  ( M n  En ) xn
Mass C kg C
Y1 , Y2 , Y3   in the Extract from stage 1,2,3,....
M n xMn  En yn  M n xn  En xn Mass B kg A
B = Amount of pure solvent (B) added in each stage
 P a g e | 17 P a g e | 18

For Stage-1 (iv) So draw a line through X1 on the x-axis of slope (-A/B) to cut the equilibrium curve at E 2.
Material balance for solute ‘C’, Point E2 gives the compositions X2 and Y2 of the raffinate and the extract leaving the stage
AX F  AX1  BY1 ------------------ (1) -2.
 BY1  AX1  AX F (v) Adopt the above mentioned procedure to get the compositions X3 and Y3 of the final
raffinate and extract leaving the stage-3.
 BY1  A( X1  X F )
When the equilibrium relationship is given by Y = mX
Y1 A
  ------------------ (2) Then the equilibrium curve is represented by a straight line of slope m.
( X1  X F ) B In such cases, for equal amounts of solvent pure B used for each stage in a multistage extraction, we
Equation (2) is the operating line equation for stage-1 of slope (-A/B) and passing through points can derive the equations for obtaining the composition of the final raffinate and the number of stages required.
(XF, 0) and (X1,Y1). Derivation for obtaining the composition of the final raffinate and the number of stages required
For Stage-2 Material balance of solute over stage-1,
Material balance for solute ‘C’, AX F  AX1  BY1 ------------------ (1)
AX1  AX 2  BY2 ------------------ (3) Let, Y  mX
 BY2  AX 2  AX1 So, Y1  mX 1 ------------------ (2)
 BY2  A( X 2  X1 ) Sub equation (2) in equation (1), we get
Y2 A AX F  AX1  BmX1
  ------------------ (4)
( X 2  X1 ) B AX F  ( A  Bm) X1
Equation (4) is the operating line equation for stage-2 of slope (-A/B) and passing through points A
X1  X F ------------------ (3)
(X1, 0) and (X2, Y2). ( A  Bm)
For Stage-3 Material balance of solute over stage-2,
Similarly, for the stage-3 we can write, AX1  AX 2  BY2 ------------------ (4)
Y3 A Y  mX
  ------------------ (5) Let,
(X3  X2) B So, Y2  mX 2 ------------------ (5)
For stage-n Sub equation (5) in equation (4), we get
Similarly, for the stage-n we can write, AX1  AX 2  BmX 2
Yn A
  ------------------ (6) AX1  ( A  Bm) X 2
( X n  X n 1 ) B
A
As the equal amount of solvent are used for each stage , the slope of operating line equation for all X2  X 1 ------------------ (6)
( A  Bm)
stage is same (-A/B) so the operating line in this case are the parallel to each other on Y vs X plot.
Sub equation (3) in equation (6), we get
Now, we will do the graphical construction for a three-stage extraction.
A
(i) Plot Y v/s X. X2  X1
(ii) The operating line for stage-1 passes through F (XF, 0) and E1 (X1, Y1) on the equilibrium ( A  Bm)
curve and has a slope of (-A/B). A  A 
X2   X F 
( A  Bm)  ( A  Bm) 
2
 A 
X 2    X F ------------------ (7)
 ( A  Bm) 
So equation (7) for n-stages becomes,
n
 A 
X n    X F ------------------ (8)
 ( A  Bm) 
n
Xn  A 
   ------------------ (9)
X F  ( A  Bm) 
Taking ln on above equation we get,
n
(iii) Drop a vertical through E1 to cut the x-axis at R1(X1). The operating line for stage-2 passes X   A 
ln  n   ln  
through points (X1, 0) and (X2, Y2) and has a slope of (-A/B).  XF   ( A  Bm) 
 P a g e | 19 P a g e | 20

X   A  f. Continuous Multistage Counter current Extraction-System of three liquids-one pair partially miscible
ln  n   n. ln   The following figure is a schematic diagram of a typical continuous multistage counter current
 XF   ( A  Bm) 
extraction operation. Here raffinate and extract streams flow from stage to stage in a counter current fashion.
X 
ln  n 
n  XF  ------------------ (10)
 A 
ln  
 ( A  Bm ) 
If A, B, XF and n are known, and then calculate the composition of the final Raffinate Xn leaving
stage n by using equation (9).
If A, B, XF and Xn are known, and then calculate the number of stage by using equation (10).
Case (ii) Above figure shows a typical continuous multistage countercurrent extraction operation when,
Insoluble liquid –Unequal amounts of solvent, solvent contains some amount of solute. each circle represents an extraction arrangement involving a mixer and a separator.
(i.e., B ≠ constant throughout and YS ≠ 0). Here, raffinate and extract streams flow from stage to stage in a counter current fashion. In this
Material balance of solute over stage-n, type of arrangement, the feed solution (F) is fed to the first stage which leaves it as raffinate (R1) which
AX n 1  BnYS  AX n  BnYn ------------------ (11) then passes through further stages and leaves from the nth stage as final raffinate Rn.
AX n 1  AX n  BnYn  BnYS The fresh solvent enters the nth stage and passes through the stages in the opposite direction and
finally leaves the first stage as final extract E1.
A( X n 1  X n )  Bn (Yn  YS )
So with this type of unit, we obtain two final products - (i) Raffinate Rn. and (ii) Extract E1.
A (Yn  YS )
 Material balance over stage-1,
Bn ( X n 1  X n ) F  E2  E1  R1 ------------------ (1)
A (Yn  YS ) F  E1  R1  E2   R ------------------ (2)
  ------------------ (12)
Bn ( X n  X n 1 ) Where,
This is the equation of the operating line for stage-n. It is a straight line on X-y coordinates of slope (- ∆R - Difference point, the represent the net flow outward at the stage-1.
A/Bn) and passes through points (Xn-1, YS) and (Xn, Yn). Overall material balance (entire unit-stages 1 to n),
The graphical construction for a three-stage extraction is shown in below figure where each operating F  En 1  M  E1  Rn ------------------ (3)
line is drawn with a slope appropriate to that stage. Each of the operating lines drawn meets the equilibrium Let En+1 = S,
curve at a point whose coordinates is the equilibrium compositions of raffinate and extract from that stage.
F  S  M  E1  Rn ------------------ (4)
In this case, it is not possible to obtain the raffinate of concentration smaller than that in equilibrium
Material balance for solute ‘C’ over entire unit,
with the entering solvent.
Equations (11) and (12) are also used with the concentrations of solute expressed as mass/volume, in FxF  SyS  MxM  E1 y1  Rn xn ------------------ (5)
which case X and Y are expressed in terms of mass solute/volume, and A and B are expressed in terms of FxF  SyS  MxM
volume (for batch) or volume per unit time (for continuous operations). FxF  SyS
xM  ------------------ (6)
M
Let M = F+S,
FxF  SyS
xM  ------------------ (7)
FS
Rearranging the equation (4) we get,
F  E1  Rn  S   R
Where,
∆R - Difference point, the represent the net flow outward at the stage-n.
Material balance over stage-n,
Rn 1  S  En  Rn
Rn 1  En  Rn  S   R ------------------ (8)
The graphical procedure for determining the number of stages required to pass from an initial
In this case, if YS = 0 then point F (XF, 0) is on the x-axis. For unequal amounts of solvent, the concentration of feed solution F to a final raffinate concentration Rn is shown in following figure using
operating lines are not parallel but for equal amounts, the operating lines are parallel to each other. rectangular coordinates. The construction procedure for obtaining the number of stages on the equilateral
triangle is identical with this.
 P a g e | 21 P a g e | 22

Where the triangles representing stages are constructed between the equilibrium curve and the
operating line starting from (XF, Y1) and covering (Xn, Yn+1).

g. Multistage Counter current Extraction-Immiscible solvents

Consider that A and B are completely immiscible so that the solvent content of all extracts and the A
content of all raffinates are constant (i.e., A kg of A in the feed solution will be there in the raffinate leaving PROBLEMS
each stage of the cascade and the same is true for B kg of B in the extract). 1. A solution containing 5% acetaldehyde and 95% toluene is to extracted with water in 5 stages cross
current extraction unit to extract acetaldehyde. Toluene and water are essentially insoluble. If 25 Kg of
water each time are used per 100kg of feed, calculate the amount of acetaldehyde extracted and final
concentration of exit solution.
The equilibrium relationship is given as
y = 2.2 x
Where, y = kg of acetaldehyde/kg H2O
x = kg of acetaldehyde/kg Toluene
The concentration of solute C is expressed in terms of mass ratio as: Data Given:
X = (mass C/mass A) in the raffinate phase (raffinate streams) Feed, F = 100kg
Y = (mass C/mass B) in the extract phase Acetaldehyde present in feed, C = 5% = 5kg
YS = (mass C/mass B) in the solvent used Toluene present in feed, A = 95% = 95 kg
Material balance of the solute ‘C’ over stage-1, Solvent (Water), B = 25kg
AX F  BY2  AX1  BY1 ------------------ (1) Number of stages = 5
Material balance of the solute ‘C’ over entire unit, Cross current extraction
AX F  BYn 1  AX n  BY1 ------------------ (2) Equilibrium relationship, y = 2.2x
Amount of acetaldehyde extracted =?
AX F  AX n  BY1  BYn 1
Final concentration =?
A( X F  X n )  B(Y1  Yn 1 ) Solution:
A (Y1  Yn 1 ) Multi stage cross current extraction,
 ------------------ (3) Mass C
B (XF  Xn) XF 
Mass A
A
( X F  X n )  (Y1  Yn 1 ) 5
B XF   0.0526
95
A
( X F  X n )  Y1  Yn 1 Number of cross current stage, n = 5
B
Equilibrium Relation,
A
Yn 1  ( X n  X F )  Y1 ------------------ (4) y = 2.2 x
B
Where, m = 2.2
Note, Multistage cross –current extraction: Immiscible solvent,
Yn+1, = Ys = mass ratio of solute in solvent used. n
 A 
Equation (3) is the equation of a straight line of slope A/B on X - Y coordinates. This is the operating Xn   .X F
line which passes through the points (XF, Y1) and [Xn,Yn+1 (= Ys)].  A  Bm 
5
In equation (3), X. and Y can also be expressed as mass/volume in which case A and B are expressed  95 
Xn     0.05263
as volume/time.  (95  25  2.2) 
The graphical construction of the number of stages required to pass from X F to Xn is shown in
following figure. X n  0.0054
 P a g e | 23 P a g e | 24

Final raffinate solution contain 0.0054 kg of Acetaldehyde per 1 kg of toluene y1 A


Final raffinate solution = 1+ 0.0054 = 1.0054 kg (x1 - x F ) B
0.0526
Wt % of Acetaldehyde in raffinate solution =  100 y1

99
1.0054 (x1 - x F ) 150
= 5.23% by wt.
y1
0.0054 Slope    0.66
Amount of Acetaldehyde in final exit solution =  95 (x1 - xF )
1
= 0.5130 kg Plot a graph between X and Y,
Amount of Acetaldehyde removed from feed solution = (5.23 – 0.5130) fix the slope at -0.66
= 4.717 kg From graph,
2. Nicotine in water solution containing 1% nicotine is to be extracted with kerosene at 20°C. (293K) x1 = 0.0042 kg C /kg A
Water and kerosene are essentially immiscible. The equilibrium data are as y1 = 0.0038 kg C /kg B
X= Kg nicotine/ kg water 0 0.001 0.0024 0.0050 0.0075 0.0099 0.204 Nicotine removed from water = A (xF -x1)
Y = kg nicotine/kg Kerosene 0 0.0008 0.0019 0.0045 0.0068 0.0091 0.0187 = 99 (0.0101 – 0.0042)
Where X = kg Nicotine / kg water, Y = kg Nicotine / kg kerosene.
= 0.5841 Kg
i. Determine the percentage extraction of nicotine if 100 kg of feed solution is extracted
once with 150 kg of solvent. 0.5841
ii. What is the percentage extraction of 3 cross current stages if 50 kg of solvent is used every Percentage extraction of nicotine =  100
1
time? = 58.41%
Data Given: Case (ii) - Three cross current stages if 50 kg of solvent is used every time
Feed, F = 100 kg A
Solvent, B = 150kg Slope  
B
Amount of nicotine in feed = 1%
99
Weight fraction of nicotine = (1/100) = 0.01 Slope  
50
Weight fraction of water in feed = (1 - 0.01) = 0.99
Slope   1.98
Three cross current stages = 50 kg of solvent/stage
Percentage extraction of nicotine in one stage = ? Plot a graph between X and Y, fix the slope at -1.98
Percentage extraction of nicotine in three stage = ? From graph,
Solution: x3 = 0.0034 kg C /kg A
Case (i) - 100 kg of feed solution is extracted once with 150 kg of solvent Nicotine removed from water = A (xF –x3)
Amount of nicotine in feed solution, C = 1kg = 99 (0.0101 – 0.0034)
Amount of water in feed solution, A = 99kg = 0.6633 Kg
0.6633
XF 
Mass C Percentage extraction of nicotine   100  66.33 %
Mass A 1
Kg of C 3. Water—dioxane solution is to be separated by extraction process using benzene as solvent. At 25°C the
XF  equilibrium distribution of dioxane between water and benzene is as follows:
Kg of A
1
XF   0.0101
99
Mass Balance At these concentrations water and benzene are substantially insoluble. 1000 kg of a 25% dioxane water
Nicotine in feed + Nicotine in solvent = Nicotine in Extract + Nicotine in Raffinate solution is to be extracted to remove 95% of dioxane. The benzene is dioxane free.
Ax F + By S = Ax 1 + By 1 (i) Calculate the benzene requirement for a single batch operation.
Ax F + 0 = Ax 1 + By 1 i.e., ys = 0 (pure solvent)  (ii) Calculate the benzene requirement for a five-stage cross-current operation with 600 kg of
Ax F = Ax 1 + By 1 solvent used in each stage.
Ax F - Ax 1  By 1
Data Given:
A(x F - x1 )  By 1 Feed, F = 1000 kg
y1 A Amount of dioxane in feed = 25%

(x F - x1 ) B Amount of dioxane in feed, C = 250kg
 P a g e | 25 P a g e | 26

Amount of water in feed, A = 750kg 750

Slope  
Amount of solvent used in each stage, B = 600kg 600
Weight fraction of dioxane, xF = (25/100) = 0.25 Slope   1.25
Weight fraction of water in feed = (1 - 0.25) = 0.75 Plot a graph between X and Y, fix the slope at -1.25
Five cross current stages = 600 kg of solvent/stage From graph,
Pure solvent, YS = 0 X5 = 0.0175
Dioxane in extract = 95% = 0.95 (X  X5)
Dioxane in raffinate = 5% = 0.05 Percentage Recovery  F  100
XF
Benzene requirement for single stage =?
(0.333  0.0175)
Benzene requirement for five stage =? Percentage Recovery   100
Solution: 0.333
Solvent = Amount of Feed (or) Raffinate in each stage Percentage Recovery  94.74%
B = F (or) R
EXTRACTION EQUIPMENTS
x 0.051 0.189 0.252
In liquid-liquid extraction operation, two phases must be brought into an intimate contact for mass
y 0.052 0.225 0.32
transfer to occur and then the phases are separated. This operation may be carried out batch wise or
x
X 0.054 0.233 0.337 continuously.
(1  x) Whenever we are dealing with simple systems and quantities to be handled are small, batch wise
y procedure is adopted and when large quantities are to be handled and several contacts are required,
Y 0.0548 0.29 0.471
(1  y ) continuous operation becomes economical.
Case (i): Benzene requirement for a single batch operation Types of Extraction Equipment
F = 1000 kg Most of the extraction equipments are operated continuously with either successive stage contacts or
A = 750kg differential contacts. Industrial extraction equipments are classified as:
C = 250kg 1. Stage-type extractors
YS = 0 2. Differential (continuous contact) extractors.
xF = 0.25 1. Stage-type extractors
0.25 In stage-type extractors, the two phases are allowed to mix together so as to reach equilibrium and
XF   0.333
0.75 then are separated before being passed counter current to each other. Advantages of stage-type contactors
X R  0.05  0.333  0.0167 include simplicity of design, no axial mixing, and high stage efficiency. These units are large and bulky
owing to the requirement of a separator for the phase separation after each stage.
Plot a graph between X and Y and Locate XR, Find corresponding Y1
Mixer-settler (single and multistage), plate column, pulsed sieve plate column, etc. are examples
From graph,
of stage-type equipment/extractor.
Y1 = 0.0175
2. Differential extractors
A Y Y
 1 S In differential extractors, the two phases are always in continuous contact. These are compact for a
B XF  XR
given throughput and require small floor space.
750 0.0175  0 In case of plate column, packed column, spray column used for extraction operation, the phase inter-

B 0.333  0.0167 dispersion and counter current flow are produced by the force of gravity acting on the density difference
B  13555.71 kg between phases.
Case (ii): Benzene requirement for a five-stage cross-current operation with 600 kg of solvent In case of mixer settlers, rotating disc contactors, the phase inter-dispersion is produced by
used in each stage. mechanical agitation and counter-current flow is still produced by gravity.
Packed column, spray column, pulsed packed column, rotating disc contactors, etc. are
examples of differential extractors.
i. Mixer-Settlers
A mixer-settler is a single-stage extraction device which comprises of a mixer for contacting the two
liquid phases to effect mass transfer and a settler for mechanical separation of the phases. It is the simplest
time of extractor and has many variations.
In case of extraction operations carried out a batch wise manner/fashion, the mixer told settler may be
A the same unit (i.e., mixing and settling is carried out in the same piece or equipment/in the same equipment)
Slope  
B in following figure.
 P a g e | 27 P a g e | 28

ii. Perforated plate/Sieve Tray Tower/Column

These are multistage, counter current contactors wherein the axial mixing of the continuous phase is
confined to the region between trays, and re-dispersion occurs at each tray resulting into effective mass
transfer.
These are very effective, especially for systems of low interfacial tension both with respect to the
liquid handling capacity and extraction efficiency.
The perforations in the plates are about 1.5 to 4.5 mm in diameter and the plate/tray spacings are
usually 150 to 600 mm.
The following figure shows a perforated plate tower wherein the light liquid is dispersed. General
arrangement of the plates and down corners is the same as that used for gas-liquid contact except that no
weir is needed.
Light liquid (dispersed phase) is introduced at the bottom, passes through the perforations in the plate
in the form of fine droplets, which rise through the heavy continuous phase, coalesce into a layer beneath the
plate, and again re-disperses through the plate above.
Heavy continuous phase liquid is introduced at the top, passes across each plate and flows downward
from a plate above to the plate below via down corner.
It consists of a vertical tank/vessel incorporating a turbine or propeller agitator. It is provided with The principal interface is maintained at the top, light liquid is removed from the top and heavy liquid
charging nozzles at the top and a discharge connection provided with a sight glass at the bottom. The feed from the bottom. The heavy liquid can be dispersed in which case, the tower is turned so that the down
solution to be extracted is taken into the agitated vessel, required amount of the solvent is added, and the corner of each plate becomes the up comer.
whole mass is agitated for a predetermined time.
At the end of mixing cycle, agitation is stopped and settling is applied for the phase separation.
Afterwards, the raffinate and extract phases are withdrawn from the bottom discharge connection into
separate receivers.

iii. Spray Tower/Column

For continuous extraction operation, the mixer and settler are separate units shown in above figure.
Spray towers are the simplest of differential contactors. In its simplest form, it consists or on empty
The mixer is a small baffled-agitated tank provided with inlet-outlet connections and the settler is frequently
tower provided with inlet and outlet connections at the top and bottom, for introducing and removing the
a continuous gravity decanter (simple settler with a coalescer for emulsifying liquids).
heavy and light liquid phases.
In this extractor, the two phases are in continuous contact with each other in the mixer under
Due to maximum freedom for a liquid movement, as the shell is empty, there will be severe axial
thorough agitation before flowing to the settler for the phase separation.
mixing in these extractors and hence it is practically very difficult to obtain the equivalent of more than one
One phase is usually dispersed into the other in the form of small droplets so as to produce large
or two theoretical stages even with tall towers.
interfacial areas resulting in a faster extraction.
In these towers, mixing and settling proceeds simultaneously and there is a continuous transfer of
These units are employed in industries such as petrochemical, fertilizer; metallurgical, etc.
material between phases, and the composition of each phase changes as it flows through the tower.
Advantages of mixer-settlers
Either light or heavy phase may be dispersed (i.e., introduced in the tower in the form of fine drops),
(i) High stage efficiency
but generally the phase with high flow rate and the phase of which the viscosity is high should be dispersed.
(ii) Good flexibility
Spray towers are operated into two distinct ways
(iii) Capacity to handle liquids of high viscosity
a. Either light phase dispersed.
(iv) High capacity.
b. Heavy phase may be dispersed.
 P a g e | 29 P a g e | 30

When light phase is to be dispersed, it is introduced through a nozzle from the bottom, droplets rise downward and remainder of the void space is filled with drops of light liquid which rise through the
through the heavy phase and finally coalesce to form a liquid-liquid interface at the top. continuous phase and finally coalesce to form a liquid-liquid interface at top.
In operation, where the heavy phase is dispersed, it enters the tower from the top, droplets fall The light liquid leaves the tower from the top and heavy liquid leaves from the bottom. There is a
through the light-phase and finally coalesces to form a liquid-liquid interface at the bottom of the tower and continuous transfer to material between phases, and the composition of each phase changes as it flows
then leaves the tower in the form of stream through the bottom outlet. through the tower/column. Usually the packing material should be such that it should preferentially get
In this case, the light phase is introduced at the bottom, flows as a continuous phase and ultimately wetted by the continuous phase.
leaves the tower from the top. The following figure shows both methods of operating spray towers.
Though the spray tower is simple to construct, its performance is poor because of considerable
recirculation of the continuous phase (axial mixing) and little turbulence in it.
In spray towers, the droplets of dispersed phase rise or fall through the continuous phase under the
influence of gravity, thus there is a limit for the amount of dispersed phase that can pass through the tower
for any given flow rate of the continuous phase.

Carbon and plastic packings get preferentially wetted by organic liquids and ceramic by aqueous
solutions. The packing size should not be greater than one-eighth the tower diameter.
The dispersed phase distributor is always embedded in the packing whenever the dispersed phase
droplets do not wet the material of a packing support to avoid premature flooding (drops will have difficulty
in entering the column).
Packed columns are easy to construct. They can be made to handle corrosive liquids at a reasonable
Additional light phase fed to the bottom of the tower (wherein the light liquid is dispersed) in excess
cost. Their performance is better than spray column.
of that flows upwards under the influence of gravity will be rejected through the bottom of the tower and the The chief disadvantage of packed column is that the solids tend to collect in the packing and cause
tower is then said to be flooded. channelling.
Advantages: v. Rotating Disk Contactor (R.D.C)
a. It is simple in construction. For systems of high interfacial tension, good dispersion is achieved by mechanical agitation of the
b. Does not contain any internal structures like plate packings. liquids which in turn results in good mass transfer rates.
c. Gives high throughputs per unit cross-sectional area. Rotating disk contactor is a mechanically agitated counter current extractor wherein agitation is
Disadvantages: brought with the help of rotating disks which usually runs at much higher speed than turbine type impellers.
a. Low efficiency due to axial mixing in the continuous phase. It consists of a cylindrical column that is divided into a number of compartments formed by a series
b. Necessity for a tall tower to affect a given degree of separation. of stator rings. Each compartment contains a centrally located horizontal rotor disk that creates a high degree
iv. Packed tower/Column of turbulence inside the column.
Randomly packed towers used for gas-liquid contact are also adopted for liquid-liquid extraction. As The diameter of the rotor disk is less than the opening in the stationary stator rings; usually the disk
packing provides large interfacial area for the phase contacting and causes the drop to coalesce and reform, diameter is 33 to 66 % of the column diameter. Recommended compartment height for a column of diameter
the mass transfer rates in packed towers are very high than those obtained with spray towers as packings cut of 2 m is 200 to 300 mm.
down the recirculation of the continuous phase. The tower is provided with inlet and outlet connections at the top and bottom for light and heavy
Packed towers are used in the petroleum industry. Packed towers are unsuitable to handle dirty phases. The following figure represents rotating disk contactor for light phase dispersed.
liquids, suspensions or high viscosity liquids. Packed tower shown in following figure is arranged for the In these units, disk disperses the liquids and impels them outward towards tower wall, where the
light phase dispersed. stator rings create quiet zones wherein the two phases can separate.
It consists of a cylindrical shell filled with packings, packings rest on a support plate and the shell is It has reasonable capacity, low operating cost and high efficiency. With corrosive liquids, it is very
provided with inlet-outlet connections at the top and the bottom for introduction and withdrawal of liquid difficult to maintain the internal moving parts (maintenance problem a major disadvantage).
phases. It is commonly used in the petroleum industry particularly for furfural extraction, separation of
The heavy liquid phase is fed from the top and the light liquid (dispersed through a distributor) is fed aromatics from aliphatics, etc. and pharmaceutical industries.
from the bottom. A large portion of the void space in packings is filled by the continuous phase which flows
 P a g e | 31 P a g e | 32

Pulsing amplitude of 5 to 25 mm are generally recommended with frequencies of 100 to 260

cycles/minute.

Advantages:
1. Limited efficiency due to axial back mixing.
2. Suitable for viscous materials.
The pulsation causes the light liquid to be dispersed into the heavy phase on the upward stroke and
3. Suitable for fouling materials.
4. Sensitive to emulsions due to high shear mixing. heavy liquid phase to jet into the light phase on the downward stroke. The column has no moving parts, low
vi. York-Scheibel Column axial mixing and high extraction efficiency.
This column is provided with mixing and horizontal packed compartments arranged alternately as In the pulse columns (either sieve plate or packed) the height required for a given number of
shown in following figure. theoretical contacts is often less than one-third that needed in the non-pulsing column.
Mixing is done by a turbine impeller which is attached to a mechanically driven central shaft. The Pulse columns are extensively used for processing radioactive solutions in atonic-energy work.
packed compartments are provided with wire mesh to reduce axial mixing. viii. Centrifugal Extractor
A centrifugal extractor also known as a centrifugal contactor or annular centrifugal contactor uses the
rotation of the rotor inside a centrifuge to mix two immiscible liquids outside the rotor and to separate the
liquids in the field of gravity inside the rotor.
This way, a centrifugal extractor generates a continuous extraction from one liquid phase
(fermentation broth) into another liquid phase (organic solvent).
Working:
Two immiscible liquids of different densities are fed to the separate inlets and are rapidly mixed in
the annular space between the spinning rotor and stationary housing. The mixed phases are directed toward
the centre of the rotor by radial vanes in the housing base.
As the liquids enter the central opening of the rotor, they are accelerated toward the wall. The mixed
phases are rapidly accelerated to rotor speed and separation begins as the liquids are displaced upward.
A system of weirs at the top of the rotor allows each phase to exit the rotor where it lands in a
collector ring and exits the stage. Flow from between stages is by gravity with no need for inter-stage
pumps. The centrifugal contactors thus act as a mixer, centrifuge and pump.
vii. Pulse Column
A pulse column may contain ordinary packings or sieve plates without down comers. Applications of
oscillating pulse to the content of such columns increase the efficiency because the pulse increases both
turbulence and interfacial areas.
Reciprocating pump is a common mechanical pulsing device which pulses the entire contents of the
column at a frequent interval, so that a rapid reciprocating motion of relatively small amplitude is
superimposed on usual flow of the liquid phases. Bellow or diaphragms made of steel teflon, etc. are also
used as pulsing device.
A pulsed sieve plate column is a vertical column with a large number of sieve plates without down
corners. The perforations in the plates of such column are smaller than non-pulsing column (1.5 to 3 mm
diameter).
 P a g e | 33 P a g e | 34

Configuration of Centrifuge
i. Mix and separation.
ii. Separation by direct feed.
iii. Multi-stage processing.
i. Mix and separation
The mix & separation configuration is the standard operation for centrifugal contactors used
for liquid-liquid extraction processes. The two liquids (typically an aqueous phase (heavy) and an organic
phase (light)) enter the annular mixing zone where liquid-liquid dispersion is formed and extraction occurs
as solutes (e.g. dissolved metal ions) are transferred from one phase into the other.
Inside the rotor, the liquids will be separated into a heavy (blue) and a light (yellow) phase by their
respective densities. This proportion of each phase (phase ratio), total flow rate, rotor speed, and weir sizes
are varied to optimize separation efficiency. The separated liquids are discharged without pressure and flow
by gravity to exit the stage. Description
ii. Separation by direct feed The system must contain a pump for the CO2, a pressure cell to contain the sample, a means of
For applications requiring only separation of a pre-mixed dispersion (e.g. oil/water separation in maintaining pressure in the system and a collecting vessel.
environmental clean-up), the direct feed offers the option to feed the mixed liquid stream at a low sheer force The liquid is pumped to a heating zone, where it is heated to supercritical conditions. It then passes
directly into the rotor. Inside the rotor, the liquids will be separated into a heavy (blue) and a light (yellow) into the extraction vessel, where it rapidly diffuses into the solid matrix and dissolves the material to be
phase. This principle is used to optimize the separation efficiency. The separated liquids will be discharged extracted.
without pressure. The dissolved material is swept from the extraction cell into a separator at lower pressure, and the
iii. Multi-stage processing extracted material settles out. The CO2 can then be cooled, re-compressed and recycled, or discharged to
Typically for solvent extraction processes in stage-wise equipment such as the centrifugal contactor, atmosphere. The following processes are explained the supercritical fluid extraction in detail.
we would have multiple contactors in series for extraction, scrubbing, and stripping (and perhaps others). i. Pumps
The number of stages needed in each section of the process would depend on process design requirements  Carbon dioxide (CO2) is usually pumped as a liquid, usually below 5°C and a pressure of about
50bar.
(necessary extraction factor).
 The solvent is pumped as a liquid as it is then almost incompressible; if it was pumped as a
In this case, four interconnected stages provide a continuous process in which the first stage is a
supercritical fluid, much of the pump stroke would be "used up" in compressing the fluid, rather than
decanting stage. The next two stages show a counter current extraction. The last stage is neutralization as a
pumping it.
cross stream interconnection. Neutralization as a cross stream inter-connection.
 For small scale extractions (up to a few grams / minute), reciprocating CO2 pumps or syringe
ix. Supercritical fluid extraction
pumps are often used. For larger scale extractions, diaphragm pumps are most common.
A supercritical fluid (SCF) is any substance at a temperature and pressure above its critical point,
 The pump heads will usually require cooling, and the CO 2 will also be cooled before entering the
where distinct liquid and gas phases do not exist. It can effuse through solids like a gas,
pump.
and dissolve materials like a liquid.
ii. Pressure vessels
In addition, close to the critical point, small changes in pressure or temperature result in large
 Pressure vessels can range from simple tubing to more sophisticated purpose built vessels with quick
changes in density.
release fittings.
Supercritical fluids are suitable as a substitute for organic solvents in a range of industrial and
 The pressure requirement is at least 74bar, and most extractions are conducted at less than 350 bar.
laboratory processes.
 However, sometimes higher pressures will be needed, such as extraction of vegetable oils, where
Carbon dioxide (CO2) and water are the most commonly used supercritical fluids, being used
pressures of 800bar are sometimes required for complete miscibility of the two phases.
for decaffeination and power generation, respectively.
 The vessel must be equipped with a means of heating.
Supercritical fluid extraction (SFE) is the process of separating one component (the extractant) from
 It can be placed inside an oven for small vessels, or an oil or electrically heated jacket for larger
another (the matrix) using supercritical fluids as the extracting solvent.
vessels.
Extraction is usually from a solid matrix, but can also be from liquids. SFE can be used as a sample
 Care must be taken if rubber seals are used on the vessel, as the Supercritical carbon dioxide may
preparation step for analytical purposes, or on a larger scale to either strip unwanted material from a product
dissolve in the rubber, causing swelling, and the rubber will rupture on depressurization.
(e.g. decaffeination) or collect a desired product (e.g. essential oils).
iii. Pressure maintenance
Carbon dioxide (CO2) is the most used supercritical fluid, sometimes modified by co-solvents such
 The pressure in the system must be maintained from the pump right through the pressure vessel. In
as ethanol or methanol.
smaller systems (up to about 10 mL/min) a simple restrictor can be used.
Extraction conditions for supercritical carbon dioxide are above the critical temperature of 31°C
 This can be either a capillary tube cut to length, or a needle valve which can be adjusted to maintain
and critical pressure of 74bar.
pressure at different flow rates.
Addition of modifiers may slightly alter this. The discussion below will mainly refer to extraction
 In larger systems a back pressure regulator will be used, which maintains pressure upstream of the
with CO2, except where specified.
regulator by means of a spring, compressed air, or electronically driven valve.
 P a g e | 35 P a g e | 36

 Whichever is used, heating must be supplied, as the adiabatic expansion of the CO2 results in 9. What is plait point?
significant cooling. 10. Mention the applications of liquid -liquid extraction.
 This is problematic if water or other extracted material is present in the sample, as this may freeze in 11. What is stage efficiency?
the restrictor or valve and cause blockages. 12. Define selectivity?
iv. Collection 13. Explain how the interfacial tension will affect the extraction process.
 The supercritical solvent is passed into a vessel at lower pressure than the extraction vessel. 14. Define Extract.
 The density, and hence dissolving power, of supercritical fluids varies sharply with pressure, and 15. What is Lixiviation?
hence the solubility in the lower density CO2 is much lower, and the material precipitates for 16. Define Raffinate.
collection. 17. What is LLE?
 It is possible to fractionate the dissolved material using a series of vessels at reducing pressure. 18. What is partitioning?
 The CO2 can be recycled or depressurized to atmospheric pressure and vented. 19. What is solvent extraction?
V. Heating and cooling 20. Differentiate between raffinate and extract in extraction process.
 This is an important aspect. The fluid is cooled before pumping to maintain liquid conditions and 21. Define separation factor.
then heated after pressurization. 22. Name any four parameters to be considered in selection of solvent for extraction process.
 As the fluid is expanded into the separator, heat must be provided to prevent excessive cooling. 23. Mention the equipment used in single stage and multi stage extraction.
 For small scale extractions, such as for analytical purposes, it is usually sufficient to pre-heat the 24. Define critical solution temperature.
fluid in a length of tubing inside the oven containing the extraction cell.
 The restrictor can be electrically heated, or even heated with a hairdryer. Big Questions
 For larger systems, the energy required during each stage of the process can be calculated using 1. Solvent requirement for a single batch operation and for a five. Cross current stage with
the thermodynamic properties of the supercritical fluid. equal amount solvent in each stage.
Advantages 2. Explain the working principle and operation of anyone differential contact extraction
1. The properties of a supercritical fluid can be altered by varying the pressure and temperature, equipment with a diagram.
allowing selective extraction. 3. Draw the neat stretch and explain the working of centrifugal extractors.
2. Diffusivities are much faster in supercritical fluids than in liquids, and therefore extraction can occur 4. With neat sketches, explain the working principle of Rotating disk contactor and Schebile
faster. type extractor.
3. An extraction using an organic liquid may take several hours, whereas supercritical fluid extraction 5. Describe the principle and constructional features of various extraction equipments with neat
can be completed in 10 to 60 minutes. sketches.
Applications 6. Explain with schematic diagram Multistage Cross-current Extraction
1. Supercritical fluid chromatography is now often used as an analytical tool. 7. Explain the factors to be considered in the choice of solvent for extraction.
2. This analytical technique has been successfully used to separate oligomers and high molecular weight 8. Explain briefly:
polymers. (l) LLE (or) Explain the effect of temperature on LLE.
3. Supercritical fluids are used as the extracting solvents for the removal of poly-aromatic hydrocarbons (2) Selectivity
from soil.
(3) Distribution coefficient
4. SFE applications in the food, pharmaceutical, and fine chemical industries.
5. Decaffeinating of coffee and tea extraction of vegetable and fish oils. (4) Solutropic system.
6. Extraction of flavors from natural resources. 9. Describe the design methodology to evaluate the number of theoretical stages in a multi
7. Extraction of ingredients from spices and red peppers. stage counter-current extractor for extracting partial miscible systems. State the importance
8. Extraction of fat from food products. of design parameters.
9. Extraction from natural products Photo–resist cleaning Precision part cleaning. 10. Explain with a neat sketch the working of a mechanically agitated contactor for Extraction
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UNIVERSITY IMPORTANT QUESTIONS 11. Nicotine in water solution containing 1% nicotine is to be extracted with kerosene at 20°C.
Two Marks Water and kerosene are essentially immiscible. The equilibrium data are as follows:
1. What is the range of selectivity of the solvent? X 0 0.001011 0.00246 0.00502 0.00998
2. What is the use of Bolman extractor? Y 0 0.000807 0.001961 0.00456 0.00913
3. What are the salient features of pulse extraction column? Where X = kg Nicotine I kg water, Y = kg Nicotine /kg kerosene.
4. What is the condition of selectivity in liquid liquid extraction? (a)Determine the percentage extraction of nicotine if 100 kg of feed solution is
5. Define distribution coefficient and state its importance. extracted once with 150 kg of solvent.
6. What is the slope of operating line? (b)What is the percentage extraction of 3 cross current stages if 50 kg of
7. What is the relation between extraction and solubility? solvent is used every time?
8. Write the properties of a good solvent for extraction.
 P a g e | 37

12. A solution of nicotine in water containing 1 % nicotine is to be extracted with kerosene at

293 K. Water and kerosene is essentially insoluble.' Assume the equilibrium relationship to
be: Y= 0.9X
Where, Y = Kg nicotine/Kg kerosene
X = Kg nicotine/kg water
(1) Determine the percentage extraction of nicotine if 100 Kg of feed solution
is extracted with 150 Kg of solvent.
(ii) Repeat for 3 theoretical extractions using 50 Kg solvent each time.
13. A solution of 5% acetaldehyde (A) and 95% toluene is to be extracted with water in a five-stage
cross current extraction to extract acetaldehyde. Toluene and water arte essentially insoluble. If 25 kg
of water l00 kg feed is used, find the amount of acetaldehyde extracted and the final concentration.
The equilibrium relation is given by: Y=2.20X; Y=(kg acetaldehyde /kg water); X=(kg
acetaldehyde/kg toluene) (Both by theoretical arid graphical method)
14. How many kg of minimum solvent required for 1000 kg per hour of dioxane water solution
extracted continuously in counter current fashion and how many theoretical stages required if
900' kg per hour of solvent is required. The equilibrium data.
Weight % dioxane in water: 5.1 18.9 25.2
Weight % dioxane in water: 5.2 22.5 32
15. Water-dioxane solution forming an azeotrope, hence it is treated with benzene. Equilibrium
distribution of dioxane between water and benzene at 25°C· is given be1ow:
Wt% dioxane in water: 5.1 18.9 25.2
Wt% dioxane in benzene: 5.2 22.5 32
16. A solution containing 18% (by weight) acetone in water is to be extracted with pure Mono-
chlorobenzene by countercurrent extraction process. Mono-chlorobenzene and water are immiscible
in the operating condition.
x' kg acetone/
0.025 0.0738 0.1609 0.2675
kg water
y' kg acetone/
0.0288 0.0704 0.1566 0.2370
kg mono-chlorobenzene
In order to obtain a raffinate with 1% acetone concentration estimates the following.
(1) Minimum amount solvent needed per kg of feed and
(2) The theoretical number stages needed if the solvent used is 1.2 times the
minimum.
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