CHAPTER IX

Washing, Leaching
 Generalized McCabe-Thiele and Kremser
Procedures
• The McCabe-Thiele procedure has been applied to flash distillation,
continuous countercurrent distillation, batch distillation, absorption,
stripping, and extraction.
• What are the common factors for the McCabe-Thiele analysis in all these
cases?
• All the McCabe-Thiele graphs are plots of concentration in one phase vs.
concentration in the other phase.
• In all cases there is a single equilibrium curve, and there is one operating
line for each column section.
• It is desirable for this operating line to be straight. In addition, although it
isn’t evident on the graph, we want to satisfy the energy balance and mass
balances for all other species.
• In order to obtain a single equilibrium curve, we have to specify
enough variables that only one degree of freedom remains.
• For binary distillation this can be done by specifying constant
pressure.
• For absorption, stripping, and extraction we specified that pressure
and temperature were constant.
• In general, we will specify that pressure and/or temperature are
constant, and for multisolute systems we will assume that the solutes
are independent.
• To have a straight operating line for the more volatile component in distillation we assumed that
constant molal overflow (CMO) was valid, which meant that in each section total flows were
constant.

• For absorption, stripping, and extraction we could make the assumption that total flows were
constant if the systems were very dilute.

• For more concentrated systems we assumed that there was one chemical species in each phase
that did not transfer into the other phase; then the flow of this species (carrier gas, solvent, or
diluent) was constant.

• In general, we have to assume either that total flows are constant or that flows of nontransferred
species are constant.

• These assumptions control the concentration units used to plot the McCabe-Thiele diagram.
• If total flows are constant, the solute mass balance is written in terms of fractions, and fractions are plotted
on the McCabe-Thiele diagram.

• If flows of nontransferred species are constant, ratio units must be used, and ratios are plotted on the
McCabe-Thiele diagram.

• The McCabe-Thiele operating line satisfies the mass balance for only the more volatile component or the
solute.

• In binary distillation the CMO assumption forces total vapor and liquid flow rates to be constant and
therefore the overall mass balance will be satisfied.

• In absorption, when constant carrier and solvent flows are assumed, the mass balances for these two
chemicals are automatically satisfied.

• In general, if overall flow rates are assumed constant, we are satisfying the overall mass balance.

• If the flow rates of nontransferred species are constant, we are satisfying the balances for these species.
• The energy balance is automatically satisfied in distillation when the CMO assumption is valid.

• In absorption, stripping, and extraction the energy balances were satisfied by assuming constant
temperature and a negligible heat of absorption, stripping or mixing.

• In general, we will assume constant temperature and a negligible heat involved in contacting the
two phases.

• The Kremser equation was used for absorption, stripping, and extraction. When total flows,
pressure, and temperature are constant and the heat of contacting the phases is negligible, we
can use the Kremser equation if the equilibrium expression is linear.

• When these assumptions are valid, the Kremser equation can be used for other separations.
• If the assumptions are not valid, the results of the analysis could be
garbage.
• To determine the validity of the assumptions, the engineer has to
examine each specific case in detail.
• The more dilute the solute, the more likely it is that the assumptions
will be valid.
Washing
Ø In industry, sometimes solute in the liquid slurries (Slurry: Solid mixed with liquid) should be removed
Ø Examples: Butter, casein and cheese washing in the dairy industry . Casein is washed with water to reduce its lactose
content

Ø Consider sand mined from ocean. The wet sand contains salt, and this salt can be removed by
washing with pure water.

Ø Washing is done by mixing solid (sand) and wash liquor (water) together in a mixer and
sending the mixture to a settler or a thickener.

Ø Two streams are obtained from the settler: a) Underflow liquid: Exit from the bottom of the settler
b) Overflow liquid: Does not contain any solid, clear liquid removed from the top of the settler.

Ø In washing, the solute (salt) is not held up or attached to the inert solid (sand).

Ø The salt is assumed to be at the same concentration in the underflow liquid as it is in the overflow
liquid. Thus, it can be removed by displacing it with clear water.

Ø The separation can be done in single-stage, cross-flow, and countercurrent cascades.

Countercurrent Washing

Notation:

U: Underflow liquid flowrate x: Mass fraction solute in the underflow liquid

O: Overflow liquid flowrate y:Mass fraction solute in the overflow liquid

Equilibrium Relationship:

Solute concentration in the underflow = Solute concentration in the overflow

x= y
Component Mass Balance Around the Envelope for the Solute:

Slope becomes constant if the undeflow ( U) and overflow (O) liquid flowrates are constant.
Ø Most of the time dry solid flowrate , UDs, kg solid/h) will be known. Then , how can we calculate the underflow
liquid flowrate , U , (kg fluid /h)

Ø Underflow liquid: Solid + Liquid

Ø ε : Volume fraction of liquid in underflow liquid : Volume of liquid / Total volume

Ø 1-ε: Volume fraction of solid in underflow liquid: Volume of solid /Total volume

U = (U Ds )
(e) rf
1- e rs
kg underflow = kg fluid

kg underflow kg solid m 3 liquid m 3 total kg fluid m 3 solid

= 3 3 3
hr hr m total m solid m liquid kg solid

If the solids rate, ε, ρf, and ρs are all constant, U and O will be constant
When do we achieve constant U and O values ?

Ø No solids in the overflow and solids do not dissolve. Solid flowrate remains constant

Ø Solution is dilute then ρf and ρs are constant.

Ø Porosity ε is constant. Thus, the volume of liquid entrained from stage to stage is constant.

Operating Line

Straight line , can be solved with two data points

 0.7

0.6
Equilibrium line

0.5

Mass frac solute in the overflow liquid

0.4

0.3

0.2

Operating line
0.1

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Mass fracsolute in the underflow liquid

y=x Equilibrium
y=x Line
Example 14 – 1. Washing

In the production of sodium hydroxide by the lime soda process, a slurry of calcium
carbonate particles in a dilute sodium hydroxide solution results. A three – stage
countercurrent washing system is used. The underflow entrains approximately 3 kg
liquid/kg dry calcium carbonate solids and inlet composition of NaOH is. 5 wt. %.
The inlet water is pure water. If 8 kg wash water/kg dry calcium carbonate solids is
used, predict the recovery of NaOH in the wash liquor.
 Ø We can assume slurry is dilute, therefore, U and O can be assumed constant.

0 (kg/h)
ySN=1
Entering pure 0, y1=?
Stage N=3 Stage N-1 Stage 1
Exiting underflow F=U (kg/h)
(Raffinate) xA0=0.055
U
xAN=?
A: Solute washed by water
D: Calcium carbonate particles
S: Solvent: Water

Operating Line for the Washing Unit

𝑈 𝑈
𝑦!"# = 𝑥! + 𝑦$"# − 𝑥$ Ø We don’t need individual U and O values ,instead we need to know U/O
𝑂 𝑂
 𝑮𝒊𝒗𝒆𝒏: 𝑦$"# = 0 ; 𝑥% = 0.05
𝑈 𝑈
𝑦!"# = 𝑥! + 𝑦$"# − 𝑥$
𝑂 𝑂

Given: 3 kg liquid/kg dry calcium carbonate solids (T1) and 8 kg wash water/kg dry calcium carbonate solids (T2)

𝑈 𝑘𝑔 𝑙𝑖𝑞𝑢𝑖𝑑 𝑘𝑔 𝑑𝑟𝑦 𝑠𝑜𝑙𝑖𝑑

= 𝑥 = 0.375
𝑂 𝑘𝑔 𝑑𝑟𝑦 𝑠𝑜𝑙𝑖𝑑 𝑘𝑔 𝑤𝑎𝑠ℎ 𝑤𝑎𝑡𝑒𝑟

𝑈 3
= = 0.375
𝑂 8

𝑦!"# = 0.375𝑥! + 𝑦$"# − 0.375𝑥$

𝑦!"# = 0.375𝑥! − 0.375𝑥$

𝐴𝑠𝑠𝑢𝑚𝑒 𝑥$ = 0.0025

𝑥% = 0.05 → 𝐹𝑟𝑜𝑚 𝑜𝑝𝑒𝑟𝑎𝑡𝑖𝑛𝑔 𝑙𝑖𝑛𝑒 𝑗 = 0 𝑦# = 0.375 0.05 + 0 − 0.375 ∗ 0.0025 = 0.0178

 0.06

After drawing 3 stages, we read xN value as 0.0025.

0.05
This value is the same as what we assumed at the
Equilibrium line beginning.
Mass frac solute in the overflow liquid

0.04

So , our assumed xN value is correct.

0.03

0.02 1 𝑥$
x0, y1 𝑅 =1−
𝑥%

0.01 Operating line 0.0025

2 𝑅 =1−
0.05
3
𝑅 = 0.95x100
0
0 0.01 0.02 0.03 0.04 0.05 0.06
xN, yN+1
Mass fracsolute in the underflow liquid % Recovery of NaOH from the slurry is 95 %
y=x Equilibrium Line
 Leaching with Constant Flow Rates

Ø Leaching, or solid-liquid extraction, is a process in which a soluble solute is removed from a solid
matrix using a solvent to dissolve the solute.

Ø The most familiar examples are making coffee from ground coffee beans and tea from tea leaves.
The complex mixture of chemicals that give coffee and tea their odor, taste, and physiological
effects are leached from the solids by the hot water.

Ø Other leaching examples: leaching ores to recover a variety of minerals, and leaching plant leaves
to extract a variety of pharmaceuticals.

Ø Washing and leaching are similar separation processes. In both cases solute in a solid is extracted.
In leaching, solvent is used for extraction, while, in washing, water is the solvent.

Ø Commonly used leaching systems: Mixer Settler Type and Countercurrent Units
Tea Bag: Solid Matrix (Diluent )
Green Tea Leaf: (Solute which will be extracted)

Hot water (Solvent used to extract green tea)

 Countercurrent leaching with constant flowrates
Assumptions
1. The system is isothermal.
2. The system is isobaric.
3. No solvent dissolves into solid.
4. No solvent entrained with the solid.
5. There is an insoluble solid backbone or matrix.
6. The heat of mixing of solute in solvent is negligible.
7. The stages are equilibrium stages.
8. No solid is carried with the overflow liquid.

Underflow (Raffinate) Solvent Phase (Extract)

Solid x
x Solvent A: Solute extracted
D: Diluent (Solid)
S: Solvent
Solute

Mass transfer between solid and liquid phase

Underflow (Raffinate phase)
 Equilibrium Curve

Operating Line
 Leaching with Variable Flow Rates

xA,N+1
xD,N+1
Solid Feed

The calculation procedure for countercurrent leaching operations is exactly the same as for LLE:
1. Plot the equilibrium data.
2. Plot the locations of known points.
3. Find mixing point M.
4. Locate EN.
5. Find the Δ point.
6. Step off stages.
Feed: 1000 kg /h meal Solvent Phase: 662 kg/h

xA=0.2 (Oil:Solute to be extracted) yA=0

xD:0.8 (Solid ) yS=1 (Pure solvent )
Eo=662 kg/h
yS0=1
Entering solvent yA,N+1
Stage 1 Stage 2 Stage N
Exiting underflow F=RN+1=1000 kg/h
(Raffinate) xA,N+1=0.2
R1
xA1=0.04
 yD=0 No meal (solid) is extracted
yS=1-yA
Ø Relates the distribution of mass fraction of each component between solid (undeflow or raffinate ) phase and
extract phase
Ø Solve the problem like an extraction problem.

Procedure:
• Plot equilibrium data
• Plot locations of streams E0=S, RN+1=F, and R1.
• Use the lever-arm rule to find mixing point, M. Point M was found along the line E0RN+1 from equation given
below;
0 +(1000)(0.2)
xA,M = =0.120
662+1000

• Then points EN and Δ were found.

• Step off the stages in exactly the same way as for a triangular diagram for extraction.
 0.5
Conjugate
Line

0.4
EN
3
Saturated Raffinate
E2
0.3

yA or xA 2
F=RN+1
0.2 R3

Saturated Extract
M
E1
R2 Δ
0.1
1
R1
0 E =S
0
0 0.2 0.4 0.6 0.8 1
yD or xD