L/O/G/O

單元操作(三)
Chapter 23
Leaching and Extraction

化學工程學系 李玉郎
 Leaching
Solid extraction , dissolve soluble matter from its mixture with an
insoluble solid

solid (solute A+ inert B)

concentrated solution (A+C)
overflow phase (liquid)
solvent (C)

extracted solid (A+B+C)

underflow phase (slurry)
Liquid extraction
Separate two miscible liquids by use of a solvent
2
 Leaching

 Percolation of solvent through stationary solid beds

done in a tank with a perforated false bottom
extraction battery  a serious of such tank
Shank’s process  extraction battery in countercurrent
operation
diffusion battery  a series of pressure tank operated with
countercurrent solvent flow.
( solvent is volatile , force–pressure is required )

3
 Moving-bed leaching
(a) Bollman extractor

4
(b) Rotocel extractor  countercurrent extraction
fresh solvent feed ,
last compartment
before the discharge
point

5
 Dispersed – solid leaching
Solid is dispersed in the solvent by mechanical agitation in a tank
or flow mixer. The leached residue is then separated by settling or
filtration.

Principles of Continuous Countercurrent Leaching

Ideal stages in countercurrent leaching
assumption : solute–free solid is insoluble in the solvent, solid flow rate is
constant

solvent
solid
( solute,
L : flow rate of retained liquid on the solid contaminated solvent )
V : flow rate of overflow solution FIGURE 23.2
6 .
Countercurrent leaching cascade
 Solution retained by entering solid: xa
Solution retained by leaving solid: xb
Fresh solvent entering the system: yb
Concentrated solution leaving the system: ya

Assumption : concentration of liquid retained by the solid leaving

any stage ( xn ) = ( yn ) the liquid over flow from the
stage. ( xe = ye )
 attained simply or with difficulty depending on the structure of
the solid.

7
 Operation Line
material balance to the control surface shown upward

Total solution : Vn+1 + La = Va + Ln --- (23.1)

Solute : Vn+1 yn+1 + La xa = Ln xn + Va ya --- (23.2)

Solving for yn+1 gives to operating–line equation, which is the same as

that derived earlier for the general case of an equilibrium–stage cascade
[Eq. (20.7)] :
 Ln  Va ya  La xa

yn 1   
 xn  --- (23.3)
 Vn 1  Vn 1

OP line : passes through ( xa , ya ) and ( xb , yb )

slope  LV ( if flow rate constant )

8
Variable underflow : if the density and viscosity of solution change with
x , solid from lower number of stage retain more liquid

( L1 > L2 > … ; Ln–1 > Ln > Ln+1 )

slope of OP line varies from unit to unit

 Number of ideal stages for constant underflow

(1) in leaching , xe = ye , EQ line is straight ( y = mx , m = 1 )
(2) constant underflow , OP line is straight
Eq (20.24) can be used

n[( yb  yb* ) /( ya  ya* )]

N --- (20.24)
n[( yb  ya ) /( yb*  ya* )]

9
 EQ : y = x
ya* = xa , yb* = xb = ( yN )
Eq (20.24) can not be used if La ≠ L ( solution in feed differs from solution
in underflow ). In such case , the performance of 1st stage is calculated by
material balance, ad then apply Eq (20.24) to the remaining stages.

 Number of ideal stages for variable underflow

1. determine terminal points by material balance. ( xa , ya ) ; ( xb , yb )
2. find intermediate point
L is function of x Overall mass balance mass balance to solute
choose xn  Ln  Vn+1  yn+1
Eq (23.1) Eq (23.2)
3. plot the OP curve : ( xa , ya ) , ( xn , yn+1 )1 , ( xn , yn+1 )2 , ( xb , yb )
( only one intermediate point is enough usually to plot OP curve, unless change of L and
V are large or two curves are very close )
10
 ya
xb
Lb Va

11
 oil benzene
Vb = 10 + 655 Va
yb = (0.015) ya
N 1 solid : 1000 kg
La oil : 400 kg
oil 60 kg xa (425)
ben. : 25 kg
Lb = ? xb = ? (0.941)

12
Solution :
x , y : mass fraction of oil , solvent : Benzene
Vb = 10 + 655 = 655 kg yb = 10 ⁄ 655 = 0.015

determine xb by trial Lb × xb = 60
kg
if xb = 0.1 , solution retained is 0.505 kg  solid
60
then Lb = 1000 × 0.505 = 505 , and xb = = 0.119 ( ≠ 0.1 try value )
505
assume xb = 0.119 ,  solution retained is 0.507
60
Lb = 0.507 × 1000 = 507 , xb = = 0.118 ( close enough )
507
Benzene at Lb = 507 – 60 = 447 , Lb = 507

13
 oil : 10
Ben : 655
b a
Vb oil :
Ben :
N 1
Lb
oil : 60 oil : 400
La
Ben : 447 Ben : 25
At solid inlet
La = 400 + 25 = 425
xa = 400 ⁄ 425 = 0.941
Overall balance to get Va , ya
oil in extract 400 + 10 – 60 = 350 Va = 350 + 233 = 583
benzene in extract 655 + 25 – 447 = 233 ya = 350 ⁄ 583 = 0.60

Ans : (a) ya = 0.6 , (b) xb = 0.118

(c) Lb = 507 kg / h , (d) Va = 583 kg / h
14
 y2 (0.408)
Vb = 665 V2
yn+1 = ? Va = 583
yb = 0.015
ya = 0.6
n 1
La = 425
Lb = 507 xn = 0.3 xa = 0.941
xb = 0.118 (Ln = 530) x1 = 0.6
(e) L1 = 595
determine the inlet and exit concentrations for the first stage :
x1 = ya = 0.6
kg
solution retained : 0.595 kg  solid
L1 = 0.595 × 1000 = 595 kg
kg
V2 = L1 + Va – La = 595 + 583 – 425 = 753 h
oil balance V2 y2 + La xa = Va ya + L1 x1
753 y2 + 425 × 0.941 = 583 × 0.6 + 595 × 0.6  y2 = 0.408
15
terminal point ( x1 , y2 ) = ( 0.6 , 0.408 )
( xb , yb ) = ( 0.118 , 0.015 )

determine an intermediate point , choose xn = 0.3

kg
solution retained : 0.53 , Ln = 0.53 × 1000 = 530 h
kg
Vn+1 = Va + Ln – La = 583 + 530 –425 = 688 h

Vn+1 yn+1 = Va ya + Ln xn – La xa ,  yn+1 = 0.158

intermediate point ( 0.3 , 0.158 )

16
 ( xa , ya ) = ( 0.941 , 0.6 )
( x1 , y2 ) = ( 0.6 , 0.408 )
( xb , yb ) = ( 0.118 , 0.015 )
( xn , yn+1 ) = ( 0.3 , 0.158 )
y

 4 ideal stages are required

FIGURE 23.3
McCabe–Thiele diagram for leaching (Example 23.1). 17
 concentrated solution
If solute is of limited solubility and the concentrated solution reaches
saturation  solvent input to stage N should be large enough that all
liquid, except that adhering to the underflow from stage 1 should be
unsaturated. V y (saturate)
N 2 1
x
Stage efficiency

Solid of permeable  rate of leaching is largely governed by the rate

of diffusion through the solid.
Solid of impermeable  a strong solution is confined on the solid
surface , the approach to equilibrium is rapid.
η1
18
 Liquid Extraction

 Applied when distillation is ineffective  close – boiling mixtures ,

substances that cannot withstand the temperature of distillation.
 utilizes chemical differences
 Example : separate petroleum products that have different chemical
structures but about the same boiling range.
 When either distillation or extraction may be used, the choice is usually
distillation.
 extraction offer greater flexibility in choice of operation conditions
( choice of solvent and temperature)

19
 Extraction Equipment

 two phases must be brought into good contact.

 because two liquid phases have comparable densities, energy for mixing
and separation is usually small. That is,
hard to mix and harder to separate (energy is supplied )

 can be operated batchwise or continuously ( if gravity flow

is used)

solvent
extract ( solvent plus
extracted solute )
feed
raffinate
mix and settle
20
 Mixer – settlers
Batchwise  may be the same unit
Continuous process

typical :
mixing  5 min
settling  10 min

screen or pad of glass

fiber  promote the
coalescence of droplets

21
Spray and packed extraction tower

 differential contacts, mixing and settling proceed

simultaneously and continuously.
phases : continuous, dispersed phases ,
extracted phases , raffinate phases

 choice of dispersed phase :

1) phase with higher flow rate may be dispersed to
give a higher interfacial area.
2) phase with more viscosity give higher settling
velocity
Wettability  continuous phase wet
packing FIGURE 23.5
Spray tower; A, nozzle to
distribute light liquid.
22
 Rate of mass transfer is relatively low compared to distillation or
absorption.
 contact is more effective in the region where the drop are formed
( due to higher mass transfer rate in newly formed drops, or back
mixing of the continuous phase )
So , effective method to increase the mass transfer stages :
1. redisperse the drops at frequent intervals throughout the tower.
2. fill the tower with packing: ring, saddles , … , the packing causes the drops
to coalescence and reform, thus , increase the number of stages.

Flooding velocity in packed towers

 flow rate of one phase is held constant, and that of the other increases
gradually. A point is reached where dispersed phase coalesces , both phases
leave : together through the continuous phase outlet .
 The larger the flow rate of one phase at flooding , the smaller is that of
the other.
23
 Flooding velocities in packed columns can be estimated from the
empirical equation9 1/ 3 0.3
  0.15
1.54  0.41 1   g   c 
2
0.5 2 av 0.5
V s ,c (1  R ) ( )  C1 ( )   2      0.5  (23.4)
g d  av  c    ( av ) 
where R  V s , d V s ,c
V s ,c ,V s ,d = superficial velocities of continuous and dispersed phases at
flooding, respectively, m/s
c = viscosity of continuous phase, Pa · s
σ = interfacial tension between phases, N/m
ρd = density of dispersed phase, kg/m3
Δρ = density difference between phases, kg/m3
av = specific surface area of packing, m2/m3
ε = fraction voids or porosity of packed section
α = 1.0 for continuous-phase wetting, 1.2 for dispersed-phase wetting
C1 = function of packing type
The function C1 is 0.28 for Raschig rings of Intalox saddles. Values for other
packings range9 from 0.204 to 0.42. For a given system the term V s ,c (1  R 0.5 ) 2 is
const. 24
 Baffle towers (檔板塔)

Disc–and doughnut Side–to–side

( with or without scraper )

 can handle dirty solutions containing suspended solids.

 flow liquid is smooth , it is valuable for liquids that emulsify easily.
 not effective mixers , each baffle equivalent to only 0.05–0.1 ideal
stage.

25
 Perforated – plate towers (多孔塔板)

Figure 23.6
(a) perforations in horizontal plates. (b) cascade weir tray with mixing
and settling zones.

dispersed phase  light liquid , rising through perforated plate

continuous phase  heavy liquid , flow down the plate through downcomers.
 cascade weir tray  reduces the quantity of oil carried downward by the solvent
and increases the effectiveness of the extractor.
Perforations : 1½ – 4½ mm , plate spacing : 150 – 600 mm.

26
 Pulse columns (脈衝塔)

 Agitation is provided by external means  reciprocating pump:

pulses the entire contents of the column at frequent intervals.
 Tower may contain ordinary packing  pulsation disperses the
liquids and eliminates channeling.
Special sieve–plates may also be used : holes are smaller , 1.5~3 mm
diameter.
 used almost for processing highly corrosive radioactive liquids.
No down comers are used.
 HETP  1/3 of unpulse column.

27
Agitated tower extractors

28
 Agitated tower extractors

 Mechanical energy is provided by internal turbines or other agitators,

mounted on a central rotating shaft.
a) flat disks disperse the liquids and impel them outward toward the tower
wall, stator tings create quiet zones in which the two phase can separate.
b) the regions surrounding the agitators are packed with wire mesh to
encourage coalescence and separation. Each mixer–settler is 300–600
mm high. ( η > 100% sometimes )
 The problem of maintaining the internal
moving parts may be a serious
disadvantage, particularly where the
liquids are corrosive.

29
Principles of extraction
Questions about ideal stages , stage efficiency , minimum ratio between
the two streams , … same important as in distillation.
Extraction
phase,
 Extraction of dilute solutions y

change in flow rate can be neglected , Solvent (s)

 yi 
KD    is constant  distribution coefficient.
 xi 
Diluent (b)
E : extraction factor (equivalent to stripping factor ) + solute (a)
x
K DV Raffinate
E phase
L

30
 V yo = 0
 If (1) one single stage , (2) pure solvent
L
 x 1

 fraction of solute remaining     x x0
 x0  1  E y
 x E
 fraction of recovery 1   
 x  1 E V y = L ( x0 – x )
 0 
V y x0
 1 E 1 
x0
Cascade  V y V
 KD  E Lx x x
Lx L
Kremser equation [ Eqs. (20.24) , (20.25) , (20.26) , (20.28) ] can be used.

V L

31
(a) y = 0 , V L= 0.06 , KD = 80 V
y=0
K DV x 1
E  80  0.06  4.8   0.172 L
x0 1  E
L
E x x0
fraction of recovery  0.828
1 E
 x1  y
1  
 x0 

material balance V ( y1 – y0 ) = L ( x0 – x1 )
0
V y1 = L ( x0 – x1 ) , y1 = KD x1
 VK   VK D 
 x1  D  1  x0   E 
 L   L 
x1 1
  0.172
x0 1  E 32
(b) two stages extraction , ( same value of E )
x1 1 x2 1 V V
 , 
x0 1  E x1 1  E y=0 y=0
x2 1
   0.0297 L x0 x1 x2
x0 1  E 2

recovery : 1  x2  0.9703 or 97%

x 0

(c) using Eq (20.28) the same recovery as (b)

n[( xa  xa* ) /( xb  xb* )]

N
n E

33
 n[( xa  xa* ) /( xb  xb* )]
N
n E
xb
 0.03 , let xa = 100 , xb = 3 xa ya
xa
100
V ( ya – 0 ) = L ( 100 – 3 )
L 100  97
ya  (97)   1617
V 6
ya 1617 L = 100 V=6
xa 
*
  20.2
KD 80
xb* = 0 n[(100  20.2) /(3  0)]
N  2.09
n 4.8
3 xb y = 0
Compare : based on 100 volume aqueous b
(b) (c)
2 stage 2.09 …countercurrent flow
V : 62 V : 6 1
concentration
lower higher
of extract 34
Extraction of concentrated solutions ; phase equilibria
phase diagram :
Type I  partial miscibility of solvent (s) and diluent (b) ,
complete miscibility of solvent and the component to be
extracted (a).

Solvent (s)

Diluent (b)
+ solute (a)

35
 Extraction of concentrated solutions ; phase equilibria

Extracted
solute
curve ACE : extract layer (MIK)
curve BDE : raffinate layer (water)

E : plait point ( the composition of

two phases approach each other )

tie lines : slope up to left

 extract phase is richer
in acetone.

a = 0.232
s = 0.725
b = 0.043

solvent
diluent
36
in Extract :
H2O < 2%, (for Csolute = 0)
 as acetone concentration
increases, water content also
increases.
as shown 
yA
maximum at yA = 0.27
yH 2O

37
Type II  The solvent ( aniline ) is only
partially miscible with both
The other components.

FIGURE 23.9
System aniline-n-heptane-
MCH at 25oC: a, solute,
MCH: b, diluent, n-heptane;
s, solvent, aniline. (After
Varteressian and Fenske.16) methyl
cyclo
hexane

38
 Use of McCabe – Thiele method

yA : mass fraction of solute in extract phase , V

xA : mass fraction of solute in raffinate phase , L

equilibrium data : yA , xA values at two ends of tie lines.

OP line : Eq (23.3)
 L  V y  La xa
yn 1   n  xn  a a
 Vn 1  Vn 1
 two terminal points ( xa , ya ) , ( xb , yb )
one ( or more ) intermediate points.

39
 La = 100 Va = ?
Solution : xA = 0.4 A = 39.6
EQ curve : from Fig 23.8 A = 40
H2O : n
MIK : 100 – m
determine terminal point H2O = 60

Base : feed 100 mass per hour , La = 100 , xa = 0.4

acetone : A = 40 ; H2O = 60
A in extract ( 99% recovery ) : 40  0.99 = 39.6
A in raffinate (99% recovery) : 40  0.01 = 0.4
Lb= ?
let n : mass of H2O in extract A = 0.4
H2O : 60 – n Vb = 100 (MIK)
m : mass of MIK in raffinate MIK : m yb = 0
Va = 39.6 + n + ( 100 – m ) = 139.6 + n – m ... (1) 40
 At the bottom Vb = 100 Va = 39.6 + n + ( 100 – m ) = 139.6 + n – m
Lb = 0.4 + ( 60 – n ) + m = 60.4 + m – n ... (2)
assume : n , m are small and tend to cancel
Va  140 , Lb  60  ( will be adjusted after calculating n , m )
39.6 n: H2O
(extracted)  yAa   0.283  yH2O = 0.049 ... ( n ) m: MIK
140
0.4  0 Fig 23.8
(raffinate)  xAb   0.0067  xMIK = 0.02 ... ( m )
60
 139.6  m 
from (1)  n     0.049 ... (3)
 1  0.049  V
a
n
if m is small , n ≒ 7.2  0.049
139.6  n  m m = 1.09
 60.4  n  m n = 7.14
(2)  m     0.02 ( n = 7.2 )
60.4  m  n
 0.02
 0.98 
Lb
 m ≒ 1.1 used to revise n by Eq (3)  n 41
= 7.1
n: H2O
m: MIK
 calculate Va = 139.6 + n – m (1)  ya
Lb = 60.4 + m – n ... (2)  xb

39.6
Va = 139.6 + 7.1 – 1.1 = 145.6 ; ya   0.272 ( 1st : 0.283 )
145.6
0.4
Lb = 60.4 + 1.1 – 7.1 = 54.4 ; xb   0.0074 ( 1st : 0.0067 )
54.4
terminal points : ( 0.4 , 0.272 ) ; ( 0.0074 , 0 )

Find an intermediate point on the operation line

y = 0.03
pick yA = 0.12  yH2O = 0.85  used to revise V  L  xA
Fig 23.8 MIK

assume amount of MIK in VMIK  100 ( MIK in raffinate is small , (1.1) )

100
V yMIK  100 V  117.6
0.85 43
 100
V yMIK  100, V   117.6
0.85 xA = 0.4 ya = 0.272
overall balance :
L  V + Lb – Vb
 117.6 + 54.4 – 100 = 72.0 L V
balance to A : xA = ? yMIK = 0.85
L xA  V yA + Lb xb – Vb yb yA = 0.12

= 117.6  0.12 + 54.4  0.0074 – 0

= 14.5 0.4
14.5
xA   0.201  rough value
72 A = 0.4
MIK = 1.1 MIK
Lb = 54.4 Vb = 100
xb = 0.0074 yb = 0

44
 xA = 0.4 ya = 0.272
Calculate corrected values of V , L , xA
xA = 0.201  xMIK  0.03 L V
Fig 23.8 xMIK yMIK =
= 0.03 0.85
balance to MIK : yA =
0.12
L xMIK + Vb = Lb xb,MIK + V yMIK
A = 0.4
MIK = 1.1 MIK
72  0.03 + 100 = 1.1 + V (0.85) Lb = 54.4
Vb = 100
xb = 0.0074 yb = 0

V = 101.1/0.85 = 118.9 ( revised )

1st assume : 100 mole MIK (V=117.6)
revised L = 118.9 + 54.4 – 100 = 73.3 ( overall balance )
VyA  0.4  0 118.9  0.12  0.4
revised xA    0.2
73.3 73.3
intermediate point ( 0.2 , 0.12 )
From Fig 23.11 , N = 3.4 stage
45
46
Countercurrent extraction of
type II systems using reflux

Solvent plays the same part in

extraction that heat does in distillation
47
Limiting reflux ratios RD

 L L
   
 D  min D
RD → ∞ (total reflux) , min. No. of plates

 
RD = L D , No. of plate is ∞
min

Practical examples of extraction with reflux

aniline – heptane – methylcyclohexane ( MCH ) system ( Fig23.9 )

  MCH  in extract only modestly greater than that in raffinate

 heptane
 great many stage is needed.
 Low solubility of MCH and Heptane in aniline ( solvent )
 large flow of solvent. 48
Sulfolane process
Enrichment of the extract by countercurrent washing with another
liquid ( dissolve in the extract , can be easily removed )  extraction
of aromatics compounds.

(五環硫氧烷)

Extract :
nearly all aromatic and few %
distillation : ( azetropic distillation )
paraffine and nophthenes
(suefolane and hydrocarbons form light hydrocarbon + water 
type I system with plait point) azetropic ( low boiling Temp. ).
boiling points overlap
Backwash :
low boiling hydrocarbons ( countersolvent or reflux )
49
50
 Special Extraction Techniques

(1) recovery of sensitive biological products  using only aqueous

phases.

Example : separation of proteins

two aqueous phase : (a) polyethylene glycol

( 80 ~ 90% water ) (b) dextran (葡萄聚醣) or phosphate salts

partition coefficient : 0.01 ~ 100 ( dependent on pH )

51
(2) Supercritical Fluid Extraction

Extraction with a solvent held at pressure and temperature above the

critical point of the solvent.
Advantage : 1. selective dissolving power
2. low viscosity, low density, high diffusivity ( 100 times of
ordinary liq. )  easily penetrates porous or fibrous
solids.
3. solute can be recovered by changing T and P.
4. does not affect the characteristic flavor and aroma of
extracted materials

Disadvantage : high pressure.

52
Phase equilibria 
Tc = 31.06oC
useful solvent for supercritical extraction : CO2
Pc = 73.8 bar
In supercritical region :
no distinction between liquid and gas , no phase transition , the
supercritical fluid acts like a very dense gas or light mobile liquid.

Solubility and selectivity : strong function of T and P.

 total extraction of solutes  pressure is highest.
 selective removal of odor – producing volatile compnents 
close to critical point (solubilities are smaller, but selectivity for the most
volatile component is much higher )

Commercial process : Decaffeination of coffee

Caffeine  ( 0.7 to 3% )  0.02%
53
54
Vb , yb Vn+1 , yn+1 yn , Vn Va , ya

N n 1 La
xn
Lb , xb L1 xa
Ln
x1