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Chapter 14.

Washing, Leaching, and Supercritical Extraction

A number of other separation processes can be analyzed, at least under limiting conditions, using
McCabe-Thiele diagrams or the Kremser equation with an approach very similar to that used for
absorption and stripping. These processes all require addition of a mass-separating agent. If flows are not
constant, the trianglar diagram method developed for extraction can often be extended to these
separations. This method is developed for leaching (or solid-liquid extraction) in Section 14.4.
14.1 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, and if there were
several solutes we assumed that they were independent. 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.
Of course, the assumptions required to use a McCabe-Thiele analysis or the Kremser equation may not be
valid for a given separation. 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.
In the remainder of this chapter these principles will be applied to generalize the McCabe-Thiele
approach and the Kremser equation for a variety of unit operations. A listing of various applications is
given in Table 14-1.
Table 14-1. Applications of McCabe-Thiele and Kremser procedures

14.2 Washing
When solid particles are being processed in liquid slurries, the solids entrain liquid with them. The
removal of any solute contained in this entrained liquid is called washing. To be specific, consider an
operation that mines sand from the ocean. The wet sand contains salt, and this salt can be removed by
washing with pure water. The entrained liquid is called underflow liquid, because the solids are normally
removed from the bottom of a settler as shown in Figure 14-1A. 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 (Perry and
Green, 1997, p. 18-64). The solids and entrained underflow liquid exit from the bottom of the settler, and
clear overflow liquid without solids is removed from the top. In washing, the solute (salt) is not held up
or attached to the inert solid (sand). 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. The
separation can be done in single-stage, cross-flow, and countercurrent cascades. A variety of different
equipment have been developed for washing and leaching, which use essentially the same equipment
(Coulson et al., 1978).
Figure 14-1. Countercurrent washing; (A) two-stage mixer-settler system, (B) general system

The equilibrium condition for a washer is that solute concentration is the same in both the underflow and
overflow liquid streams. This statement does not say anything about the solid, which changes the relative
underflow and overflow flow rates but does not affect concentrations. Thus, the equilibrium equation is

where y = mass fraction solute in the overflow liquid and x = mass fraction solute in the underflow liquid.
For the mass balance envelope on the countercurrent cascade shown in Figure 14-1B, it is easy to write a
steady-state mass balance.

where Oj and Uj are the total overflow and underflow liquid flow rates in kg/h leaving stage j. The units
for Eq. (13-30) are kg solute/h. To develop the operating equation, we solve Eq. (14-2) for yj+1:
In order for this to plot as a straight line, the underflow liquid and overflow liquid flow rates must be
Often the specifications will give the flow rate of dry solids or the flow rate of wet solids. The underflow
liquid flow rate can be calculated from the volume of liquid entrained with the solids. Let ε be the
porosity (void fraction) of the solids in the underflow. That is,

and then

We can now calculate the underflow liquid flow rate, Uj. Suppose we are given the flow rate of dry
solids. Then the volume of solids per hour is

and the total volume of underflow is

Then the volume of underflow liquid in m3 liquid per hour is

and finally the kg/h of underflow liquid

In these equations ρf is the fluid density in kg/m3 and ρs is the density of dry solids in kg/m3.
If the solids rate, ε, ρf, and ρs are all constant, then from Eq. (14-5d) Uj = U = constant. If U is constant,
then an overall mass balance shows that the overflow rate, Oj, must also be constant. Thus, to have
constant flow rates we assume:
1. No solids in the overflow and solids do not dissolve. This ensures that the solids flow rate will be
2. ρf and ρs are constant. Constant ρf implies that the solute has little effect on fluid density or that the
solution is dilute.
3. Porosity ε is constant. Thus, the volume of liquid entrained from stage to stage is constant.
When these assumptions are valid, O and U are constant, and the operating equation simplifies to

which obviously represents a straight line on a McCabe-Thiele plot. Note that this equation is similar to
all the other McCabe-Thiele operating equations we have developed. Only the nomenclature has changed.
An alternative way of stating the problem would be to specify the volume of wet solids processed per
hour. Then the underflow volume is


If densities and ε are constant, volumetric flow rates are constant, and the washing problem can be solved
using volumetric flow rates and concentrations in kg solute/m3.
Note that we could have just assumed that overflow and underflow rates are constant and derived Eq.
(14-6). However, it is much more informative to show the three assumptions required to make overflow
and underflow rates constant. These assumptions show that this analysis for washing is likely to be
invalid if the settlers are not removing all the solid, if for some reason the amount of liquid entrained
changes, or if the fluid density changes markedly. The first two problems will not occur in well-designed
systems. The third is easy to check with density data.
The McCabe-Thiele diagram can now be plotted as shown in Figure 14-2. This McCabe-Thiele diagram
is unique, since temperature and pressure do not affect the equilibrium; however, temperature will affect
the rate of attaining equilibrium and hence the efficiency, because at low temperatures more viscous
solutions will be difficult to wash off the solid.
Figure 14-2. McCabe-Thiele diagram for washing
The analysis for washing can be extended to a variety of modifications. These include simulation
problems, use of efficiencies, calculation of maximum U/O ratios, and calculations for cross-flow
systems. The Kremser equation can also be applied to countercurrent washing with no additional
assumptions. This adaptation is a straightforward translation of nomenclature and is illustrated in
Example 14-1. Brian (1972) discusses application of the Kremser equation to washing in considerable
Washing is also commonly done by collecting the solids on a filter and then washing the filter cake. This
approach, which is often used for crystals and precipitates that may be too small to settle quickly and is
often a batch operation, is discussed by Mullin (2001) and Harrison et al. (2003).

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 four-stage countercurrent washing system is
used. The underflow entrains approximately 3 kg liquid/kg dry calcium carbonate solids. 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.
A. Define. Recovery is defined as 1 – xout/xin. Thus, recovery can be determined even though xin is
B and C. Explore and plan. If we pick a basis of 1 kg dry calcium carbonate/h, then O = 8 kg wash
water/h and U = 3 kg/h. This problem can be solved with the Kremser equation if we translate
variables. To translate: Since y = overflow liquid weight fraction, we set O = V. Then U = L. this
translation keeps y = mx as the equilibrium expression. It is convenient to use the Kremser equation
in terms of x. For instance, Eq. (12-31) becomes

D. Do it. Equilibrium is y = x; thus, m = 1. Since inlet wash water is pure, yN+1 = 0. Then
, m O/U = (1)(8)/3, and N = 4. Then Eq. (14-8) is
Recovery = 1 — xN/x0 = 0.98755
E. Check. This solution can be checked with a McCabe-Thiele diagram. Since the xN value desired is
known, the check can be done without trial and error.
F. Generalize. Recoveries for linear equilibrium can be determined without knowing the inlet
concentrations. This can be useful for the leaching of natural products because the inlet
concentration fluctuates. The translation of variables shown here can be applied to other forms of
the Kremser equation.

The washing analysis presented here is for a steady state, completely mixed system where the wash water
and the water entrained by the solid matrix are in equilibrium. When filter cakes are washed, the
operation is batch, the system is not well mixed because flow is close to plug flow, and the operation is
not at equilibrium since the entrained fluid has to diffuse into the wash liquid. This case is analyzed by
Harrison et al. (2003).
14.3 Leaching with Constant Flow Rates
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. 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. An espresso machine just does the
leaching faster into a smaller volume of water. Instant coffee and tea can be made by leaching ground
coffee beans or tea leaves with hot water and then drying the liquid to produce a solid. There are many
other commercial applications of leaching such as leaching soybeans to recover soybean oil (a source of
biodiesel), leaching ores to recover a variety of minerals, and leaching plant leaves to extract a variety of
pharmaceuticals (Rickles, 1965; Schwartzberg, 1980, 1987).
The equipment and operation of washing and leaching systems are often very similar. In both cases a solid
and a liquid must be contacted, allowed to equilibrate, and then separated from each other. Thus, the
mixer-settler type of equipment shown in Figure 14-1 is also commonly used for leaching easy-to-handle
solids. A variety of other specialized equipment has been developed to move the solid and liquid
countercurrently during leaching. Coulson et al. (1978), Lydersen (1983), McNulty (2008), Miller (1997),
Prabhudesai (1997), and Schwartzberg (1980, 1987) present good introductions to this leaching
In leaching, the solute is initially part of the solid and dissolves into the liquid. In washing, which can be
considered as a special case of leaching, the solute is initially retained in the pores of the solid and the
solid itself does not dissolve. In leaching, the equilibrium equation is usually not y = x, and the total
solids flow rate is usually not constant. Since diffusion rates in a solid are low, mass transfer rates are
low. Thus, equilibrium may take days for large pieces such as pickles, where it is desirable to leach out
excess salt, or even years for in-situ leaching of copper ores (Lydersen, 1983). A rigorous analysis of
leaching requires that the changing solid and liquid flow rates be included. This situation is very similar
to partially miscible extraction and is included in Section 14.4. In this section we will look at simple
cases where a modified McCabe-Thiele or Kremser equation can be used.
A countercurrent cascade for leaching is shown in Figure 14-3A. We will consider the (idealized) case
where entrainment of liquid with the solid underflow can be ignored. The assumptions are: