Chapter III: Solid-Liquid Extraction

1–DEFINITIONS
Solid-liquid extraction is the fundamental operation aimed at,
immersion in a liquid and dissolution to extract one or more components
of a solid.
This is an operation of transfer or exchange of matter between a phase.
solid containing the material to be extracted and a liquid phase.
The scope of solid-liquid extraction is very broad, the large
number of terms used to define operations and circulating products
impose the definition of some commonly used terms.
The extraction liquid, called solvent, dissolves one (or more) constituent
solid or liquid, called solute(s) to give a solution or extract (solvent+
solvent(s)). The solid depleted in solvent(s) is called raffinate or residue; it is inert.
or insoluble. The names of surverseousousverses are used to designate the
outgoing phases of industrial equipment operating continuously. The solution
Extract solid inert from the upper part, the inert solid from the lower part.
One can note definitions of some solid-liquid extractions respecting a
specific operating procedure :
Leaching: it applies
essentially in hydrometallurgy or in the case of groundwater contamination
groundwater by landfill waste: the divided solid is brought into contact with a
liquid flowing hot or cold, which dissolves the solute.
Maceration is the more or less prolonged cold contact of a liquid.
and solid (plants) with a view to extracting the soluble parts. This operation is
frequently used for perfume extraction.
Percolation involves bringing a bed of particles into contact with a fluid.
generally warm flow, to continuously extract the solute. The preparation of
The café is part of this operation.
The decoction involves putting a solid divided into suspension in a
liquid boiling. This is the principle sometimes used for tea. When the fluid
flows over the solid at a slightly lower temperature than the temperature
boiling and then letting the mixture cool down, this is an infusion.
Elution consists of extracting the solute bound to the surface of a solid by the solvent. It is
the process implemented by chromatography.
 2- EXAMPLES OF SOLID-LIQUID EXTRACTION
The agri-food, pharmaceutical, and perfumery industries use
frequently this type of operation using a solvent: water, alcohol or solvents
chlorinated organics.
A few examples can be cited.
Caffeine is extracted with water from coffee and tea. Decaffeinated coffee is obtained by
its elimination of caffeine from the green bean or by means of chlorinated solvents.

Natural perfumes are extracted from plants (flowers, roots, stems) by the
alcohols or fats and produce tinctures, infusions or ointments.
Cooking oils (rapeseed, soybean, sunflower, peanut) are extracted from
oilseeds by pressing and then extraction with hexane.
Gold and silver are isolated from ores by dissolving in a solution of
potassium cyanide.
Copper is extracted from low-grade ores (< 1.5%) in the form of
sulfate by sulfuric acid or a solution of ferric sulfate.
3. EXTRACTION MECHANISM: STEPS OF THE TRANSFER OF
SUBJECT
3.1. Elementary Processes
Solid-liquid extraction is carried out by intimate contact of the solvent with the
solid and followed by decantation and filtration. It is defined as the result of
transfer of the solute present in the solid to the liquid. This transfer requires a certain
time and introduces the notion of extraction speed which is governed by three processes
elementary (figure 1).
1 - Passage of the solvent into the solid and dissolution of the solute within the particles of the
solid
2 - The diffusion of the solute from the center to the surface of the particle

3 - The diffusion of the solute from the surface of the particle to the core of the solvent
 Figure 1: Mechanism of solute transfer during solid-liquid extraction.
3.2. Parameters affecting the transfer of matter
The nature of the solvent: It must be selective, having a high capacity for
dissolution, a low boiling point, low viscosity and being so
possible non-toxic, non-flammable and non-explosive.
The temperature: An increase in temperature generally increases solubility.
of the solute in the solvent and the diffusion coefficient of the solute within the solvent.
A temperature that is too high may degrade thermosensitive molecules.
• Degree of agitation: keeps the solid in suspension, homogenizes the liquid and
favors the exchange of heat and matter at the surface of the solid.
Residual concentration of the solute: the extraction rate depends on the rate of
solvent saturation. In the case where the solute is a liquid in a porous solid, the
the proper dissolution of the liquid is quick and the transfer speed mainly depends on the
diffusion speed in the liquid film on the surface of the solid. Nevertheless, in the case
from plant cells, with very impermeable walls, it is internal diffusion (dialysis)
which is very slow and regulates the transfer speed because the dissolution rate of
solute in the solvent has only a negligible effect. This amounts to saying that agitation
the vigorous movement of particles in the solvent has little influence on a phenomenon of
dialysis.
Humidity: this factor is important in the case of hydrophobic solvents because the
Diffusivity is inversely proportional to the moisture content of the solid.
3.3. Concept of transfer stage: mixing tank - decanter
The entire process can be experimentally broken down by a container.
decanting mixer that ensures contact between the liquid solvent and the solid then the
mechanical separation of the two phases (figure 2).
 Figure 2: Blending decanter tank.
The design of the ideal stage is that of an extraction for which the solution,
separated from the solid (liquid extract) is in equilibrium with the solution that is located at
contact of solid (refined solid). This amounts to considering that these 2 liquids have a
same composition⇒ composition of the liquid solution (B + C) = composition of the
liquid solution (c C + c B).
This description of figure 2 represents what is done in a reactor
discontinu (extraction in a separating funnel in the laboratory). The whole
constitutes the unit floor symbolized by the following simplified diagram:

Figure 3: Representation of a theoretical or ideal floor.

In steady state, the balance on the solute can be written as:
Lixi+ SIyi = Loxo + Soyo
In the industry, extractions are often carried out through continuous operations.
due to the large tonnage of material to be processed and by counter-current methods.
They are characterized by an uninterrupted pathway of the solid and the solvent.
There are many types of devices that allow these operations: bed extractors
mobile or fixed and immersion extractors.
The diagram of the process is then represented by a series of trays (figure 4).
 Figure 4: Representation of a continuous liquid-solid extraction.
4. REPRESENTATION OF BALANCES IN SOLID EXTRACTION
LIQUID
4.1. The triangular diagram and the distribution diagram
From the conjugate lines of the ternary diagram on the curve
Binodal, it is possible to represent the distribution diagram y = f(x)
characterizing the phases at equilibrium (figure 5).
The A'P part of the binodal curve represents the solid phase (y), the C'P part
represents the liquid phase (x).
From a mixture M, two phases at equilibrium are obtained at equilibrium.

composition x = and y = respectively translating the mass fractions

B in the liquid and B in the solid.

Figure 5: Representation of equilibria: The conjugation line LS Corresponding

au point H. x, y : Fractions massiques du soluté des phases liquide et solide
4.2. Modified ternary diagram
The extraction mechanisms involve many elementary processes.
adsorption, absorption, diffusion, partial or total solubility ... To simplify
The study in the case of solid-liquid extraction allows us to make some assumptions.
simplifiers.
4.2.1. Simplifying hypotheses
The solute B to be extracted is soluble in any proportion in solvent C.
There is no selective adsorption of solution B + C on the inert solid A.
Contact time and agitation are important.
These assumptions reflect ideal situations for which the concentration
from the solution (B + C) to the heart and to the surface of the solid A and that of the liquid phase

(B + C) around the solids are identical: xi= y·

i

Under these conditions, the equilibrium curve y = f(x) coincides with the lerabisector
translated by vertical conjugation lines (SL). The representation on the
the curve y = f(x) then offers no interest.
If the solid Aestinsoluble is dissolved in solvent C, the liquid part of the curve C'P
from figure 5 is then conflated with side CB of the right triangle.
4.2.2. Representation of the balance curve of the compositions of the overflows and
subverses (figure 6)
When all the simplifying conditions are met, the diagram
ternary (A + B + C) is represented by carrying

z= based on X = and is with :

Mass of solid A Inert [kg] or [mole]
B: Mass of the liquid solute [kg] or [mole]
C: Mass of the liquid solvent [kg] or [mole]
Index S: Means that the constituent is on the surface or in the solid (subverse)
Index L: Means that the constituent is at the heart of the liquid phase (overflow) These
masses can be converted into flow rates in the case of continuous processes [kg/h]
you [mole/h]
x: Mass or molar ratio of solute BLand the liquid solution (solvent CL+
solution BLof the overflow with 0 < x < l
y: Mass or molar ratio of solute BS and the liquid solution (solvent CS+
solute BS) in the subverse with 0 < y < l
z: Mass or molar ratio of solid A and liquid solution (solvent C +
solute B) in the underflow or in the overflow with 0 < z <
Since in figure 6 the overflow curve is not horizontal, it means
that the solution (B + C) at the core of solid A is adherent to the surface and z varies with
the composition and of the liquid phase. When the mass of solution (Bs + Cs) retained
by the solid is independent of the composition, the curve of the compositions of
subverses is then a horizontal.
For the composition of the solution of a subverse Sndata, we find the value
of andSnon the x-axis. That of the overflow L is x LThe curve L'L (figure 6)
Indicate that the solid is soluble in solvent C so that z.L≠ 0.

Figure 6: Ternary diagram solid A - solvent - C solute - B with the lines of

vertical conjugations.
5. CASE OF CONTINUOUS SOLID-LIQUID EXTRACTION
5.1. Single-stage extraction
The analysis of the phase separation process in the mixing decanter tank
returns to consider in a general way that on a given plate a mixture of
mass flow rate M leads to two currents, the overflow L and the underflow S (fig. 7).
permanent regime the overall material balance is written as:

M=L+S (1)

Figure 7: Single-stage extraction.

Let the compositions defined previously in Figure 6 with:

xL= yS= etxM=

zL= zS= and zM=

Index L: the considered composition is that of the liquid phase in the overflow
Index S: the composition considered is that at the surface of the solid in the subverse.
Index M: the composition considered is that of the mixture
The material balance for the overflow:
[Link]= [Link]+ [Link](2)
The material balance for the underflow leads to:
[Link]= [Link]+ [Link](3)
Relations (1) and (2) lead to:

= (4)

The relations (1) and (3) lead to:

= 5

The equality of equations (4) and (5) means that the points M(xMandM), L(xL,yL) and
S(xS,yS) are aligned on figure 8

With: (6)

Figure 8: Representative points of currents S and L resulting from the mixture M.

Relations (4) and (5) can also be written as:

= et= (7)

This means that the position of point M between L and S is determined by the rule.
inverse segments and is accessible through the liquid phase flows of the
surverse L and the underverse S.
 5.2. Case of continuous liquid-solid counter-current extraction in stages
multiples
5.2.1. Introduction
We will analyze continuous counter-current extraction in multiple stages.
in which there is a mixture of solid and solvent, extraction and separation
mechanics of solids and solutions.
We will assume that we are in equilibrium conditions at
subverse variable. We have seen that in this case the subverse curve is not
linear and if we have xi= yiThe conjugate lines are vertical.
The overflow current L and the undercurrent S are indexed with that of the plateau
from which the phase originates.

We place ourselves in the situation of a permanent regime. For an extraction

solid-liquid in n stages we have the diagram of figure 9.
5.2.2. Relation between the phases in equilibrium
According to the diagram in Figure 9, the phases L and S of the same index leave the same
plateau; they are in equilibrium.

Figure 9: Solid-liquid extraction diagram.

The hypotheses retained for the notion of equilibrium amounts to saying that the liquid of
the subverse inside and on the surface of the solid Sihas the same composition as the
liquid Liof the overflow, either yi= xi, or the conjugate lines are
verticals.
5.2.3. Relation between the intersecting phases
With the help of Figure 9, we can perform the mass balances between plateau i.
any part of the column and one end of the column.
Overall assessment:

L1+ Si= Li+1 + S08

⇒ L1- S0 = Li+1 Si= P (9)
P represents the net mass flow rate at each point of the column.
Let it be:

x= y= etz =
 The mass balances on the fractions and z are carried out based on the data from
Figure 10 for which we have taken a general case since the
The curve of the surface is not confused with the x-axis.
The mass balance on the fraction x and y is written from (9):
Li+1xi+1 SIyi= Pxp= (Li+1 Si) xp10
[Link] the net flow of B in the column.
The mass balance on fraction A is written from (9):
Li+1zi+1 SizI= Pzp= (Li+1 Si) zp(11)
[Link] the net flow of A in the column.
The relations (10) and (11) lead to:

= = (12)

Relation (12) translates the alignment of points L.i+1 (xi+1, zi+1)i(yi, zi) and P(xp,zp)
(figure 10).
Point P has no physical significance on the diagram but constitutes a
construction hub. This relationship between the intersecting phases Li+1 and Siis in
particularly applicable to the 2 ends of the column.

Figure 10: Assessment of the overlapping phases Si; and Li+1.

The knowledge of the titles of these phases allows for the positioning of point P in
drawing the lines L1S0and L0Sn. Indeed, the L phases1and S0intersect at one end
and the L phases0and Snat the other end.
 5.2.4. Determination of the number of theoretical trays
Starting from point L1the phase balance L1and S1gives us point S1in
drawing the vertical in L1The overflow S1cross the under verse L1These two points are
aligned with P. The trace of S1P gives L2who is in equilibrium with S2We obtain S.2
drawing the vertical in L2………etc.
We count the number of conjugate lines (the vertical ones) that give the
equilibrium number, hence the number of plates. We obtain for our construction
(figure 10) 4 plateaus.
5.2.5. Relations to calculate the inflow and outflow rates
Let point Q (figure 11) be the intersection of segments S.0L0 and SnL1. The rule of
inverse segments allow us to write that the ratio of mass balances is
accessible with the ratio of the length of two segments, namely:

= and =
Thus, measuring the length of the segments allows access to the ratio of
incoming flows and then outgoing flows that must be equal in steady state. It
It is also possible to check if the flows of the overflow and the underflow are
constants throughout the column.

Figure 11: Calculation of flows L and S.

5.3. Effectiveness of the tiers