Solid-Liquid Extraction Notes
Solid-Liquid Extraction Notes
Solid-Liquid Extraction Notes
By
OJIJO, N. K. O
Department of Food Science & Technology
JKUAT
Introduction
Solid biological materials contain mixtures of components that can be classified as:
• Undesirable – these may be toxic principles that needs to be removed from the material e.g. removal
of gossypol from cotton seed cake. Gossypol has toxic effects on e.g. poultry when the seed cake
is used as feed.
• Desirable – these are components that find use as ingredients in food, nutraceutical, and
pharmaceutical applications. Example: oil extraction from vegetable seeds.
In order to separate the desired solute constituent or remove an undesirable solute component from the solid
material, the solid is contacted with a liquid phase. The two phases are brought into intimate contact and
the solute or solutes can diffuse from the solid to the liquid phase, which causes a separation of the
components originally in the solid. This process is called liquid-solid leaching (extraction) or simply
leaching (extraction). When an undesirable component is removed extraneously from a solid material with
water, the process is called washing. For example, washing of soil debris from potato tubers before peeling
to make French fries.
In the biological and food processing industries, many products are separated from their original natural
structure by liquid-solid extraction. Examples include:
• Extraction of sugar from sugar beet and sugarcane (e.g. cane and bagasse diffuser systems) with
water;
• Solvent extraction of vegetable oils from groundnuts, soybeans, flax seeds, castor beans, sunflower
seeds, or cotton seeds, using organic solvents such as hexane, acetone, and petroleum ether;
• Extraction of phytochemicals of pharmaceutical value from plant roots, leaves, and stems e.g.
extraction of artemisinin from Artemisia annua L. leaves; and
• Extraction of solubles from ground roasted coffee and tea leaves to make "'instant" coffee and
soluble tea, or indeed the extraction of caffeine from coffee beans and tea leaves to make
decaffeinated coffee and tea, respectively.
• Supercritical carbon dioxide (e.g. CO2 at temperatures beyond 31C and pressure beyond 74 bar;
note that atmospheric pressure is approximately 1 bar) can be used for the extraction of caffeine
from coffee and tea or extraction of hops for beer making. Other solvents for extracting food
constituents are given in the table below.
Hop plant, either of two species of the genus Humulus, nonwoody annual or perennial vines in the hemp
family (Cannabinaceae) native to temperate North America, Eurasia, and South America. The hops used in
the brewing industry are the dried female flower clusters (cones) of the common hop (H. lupulus) (see
below). Hops have been used almost exclusively for brewing purposes for 1,200 years or more. The brewing
value of the cones is based on their content of bitter (soft) resins, essential oils, and perhaps tannins. These
constituents, which are extracted from hops by boiling in wort (an aqueous infusion of malt), impart the
desired mellow bitterness and delicate hop aroma to brewed beverages and aid in their preservation.
The soluble constituents reside within the cellular matrix of biological materials. The rate of extraction may
be comparatively slow because the cell walls provide resistance to diffusion. Size reduction is often
necessary to facilitate solvent diffusion into the individual cells; but this should not be too destructive lest
all other undesirable cell components be expressed out with the desirable ones. For example, in sugar
extraction from sugar beet, the cells of the sugar beet are kept essentially intact so that sugar will diffuse
through the semipermeable cell walls, while the undesirable albuminous and colloidal components cannot
pass through the walls. On the other hand, the cell walls of soybeans and many vegetable seeds are largely
ruptured when the original materials are reduced in size to about 0.1 mm to 0.5 mm by rolling or flaking
and vegetable oil is then easily accessible to the solvent.
The process of leaching of solubles from solid matrices can be summarized as follows:
1. Mass transfer of solvent from the bulk solvent solution to the surface of the solid particle
2. Solvent penetration or diffusion into the solid.
3. Dissolution of solubles or solutes into the solvent.
4. Diffusion of the solute through the solid solvent mixture to the surface of the particle.
5. Transfer of solute to the bulk solution.
Steps 1 and 2 are generally quite rapid and are thus not rate-limiting. Usually the solvent is chosen to have
reasonable affinity for the desirable solute and so Step 3 may also not be rate-limiting. The 4th step is often
the one controlling resistance in the overall leaching process and can depend on a number of different
factors. In biological or natural substances, this resistance is constituted mainly by the cellular matrix. If
the cellular integrity is disrupted by the size reduction process, the leaching of the desirable solute is a
simple washing process. If the cells are left intact, the solute must diffuse out through the cell walls. These
two processes (washing and diffusion) often occur simultaneously and to varying degrees depending on the
extent of cell damage during size reduction, and their combined effect does not follow the simple diffusion
law with a constant effective diffusivity. As in the case of oil extraction from soybeans, cell rupture by
rolling and flaking enables penetration of the solvent into the solid matrix by capillary action. However, the
rate of diffusion of soybean oil from the soybean flakes into the solvent is not amenable to simple
interpretation.
Step 5 is often not rate limiting, as the resistance to mass transfer of the solute from the solid surface to the
bulk solvent is in general quite small compared to the resistance to diffusion within the solid itself.
𝜕𝐶𝐴
is the distance of diffusion (m). The term 𝜕𝑥
means the partial of 𝐶𝐴 with respect to 𝑥 or the rate of change
of 𝐶𝐴 with 𝑥 when the other variable time 𝑡 is kept constant.
For unsteady state diffusion, the mass balance for component A across the cube is given by:
Rate of input of A at 𝑥 is given by the molar flux times the cross sectional area, thus:
𝜕𝐶𝐴
𝑁𝐴𝑥 | = −𝐷𝐴𝐵 | (∆𝑦∆𝑧)
𝑥 𝜕𝑥 𝑥
Remember that the units of concentration 𝐶𝐴 is in kg mol m-3. Therefore, the mass balance of solute
across the cube can be constructed as follows:
𝜕𝐶𝐴 𝜕𝐶𝐴 𝜕𝐶𝐴
−𝐷𝐴𝐵 | (∆𝑦∆𝑧) = −𝐷𝐴𝐵 | (∆𝑦∆𝑧) + (∆𝑥∆𝑦∆𝑧)
𝜕𝑥 𝑥 𝜕𝑥 𝑥+∆𝑥 𝜕𝑡
Rearranging:
𝜕𝐶𝐴 𝜕𝐶𝐴 𝜕𝐶𝐴
−𝐷𝐴𝐵 | (∆𝑦∆𝑧) + 𝐷𝐴𝐵 | (∆𝑦∆𝑧) = (∆𝑥∆𝑦∆𝑧)
𝜕𝑥 𝑥 𝜕𝑥 𝑥+∆𝑥 𝜕𝑡
𝜕𝐶𝐴 𝜕 2 𝐶𝐴
= 𝐷𝐴𝐵
𝜕𝑡 𝜕𝑥 2
Which is known as Fick’s 2nd law for one dimensional diffusion. The law predicts how diffusion causes the
concentration to change with respect to time (i.e. relates the concentration CA with position x and time t)
and assumes a constant value of 𝐷𝐴𝐵 (which, however, may not always hold). For three dimensional
rectangular coordinates, the above equation becomes:
𝜕𝐶𝐴 𝜕 2 𝐶𝐴 𝜕 2 𝐶𝐴 𝜕 2 𝐶𝐴
= 𝐷𝐴𝐵 [ 2 + + ]
𝜕𝑡 𝜕𝑥 𝜕𝑦 2 𝜕𝑧 2
Analytical solutions to these partial differential equations are available for a variety of boundary conditions.
𝑑𝑚𝐴
= 𝑁𝐴 = 𝑘𝐿 𝐴(𝐶𝐴𝑆 − 𝐶𝐴 )
𝑑𝑡
𝑑𝑚𝐴
Where, – rate of mass transfer of solute (𝑁𝐴 ) in kg mol of 𝐴 dissolving per second, 𝐴 – surface area of
𝑑𝑡
particles (m ), 𝑘𝐿 – mass transfer coefficient (m s-1), 𝐶𝐴𝑆 – saturation solubility of the solid solute A (kg
2
mol m-3), and 𝐶𝐴 – concentration of 𝐴 in the solution at time 𝑡 (s) in kg mol m-3.
In a single stage extraction unit where V is the total volume of the solution and is constant:
𝑑𝑚𝐴 = 𝑉𝑑𝐶𝐴
That is, the change in mass of solute A in the bulk solution equals the product of the volume and change in
concentration. Therefore, substituting for 𝑑𝑚𝐴 , we have:
𝑑𝐶𝐴
𝑉 = −𝐴𝑘𝐿 (𝐶𝐴𝑆 − 𝐶𝐴 )
𝑑𝑡
Since,
𝐶𝐴𝑆 − 𝐶𝐴
ln(𝐶𝐴𝑠 − 𝐶𝐴 ) − ln(𝐶𝐴𝑆 − 𝐶𝐴𝑂 ) = 𝑙𝑛 ( )
𝐶𝐴𝑆 − 𝐶𝐴𝑂
Therefore, the solution approaches a saturated condition exponentially as shown in the curve below:
The solvent is brought into contact with the solid, solid and solvent are held in contact for the required time,
then the mixture is separated into two streams: a clear liquid stream or overflow (consisting of solution of
solvent and desired solute) and a residue stream or underflow (consisting of insoluble solid with some
adhering solution). Leaching can be batch, semi-batch, or continuous. It usually operates at an elevated
temperature to increase the solubility of the solute in the solvent. An equilibrium stage is reached when the
solution adhering to the solid in the underflow stream has the same composition as the clear liquid
constituting the overflow stream. The attainment of equilibrium takes time and depends on the driving force
(i.e. the extent of departure from equilibrium) and is generally measured by concentration differences.
Allowances can be made for non-attainment of equilibrium by assuming an efficiency for each stage.
𝑀𝑎𝑠𝑠 𝑜𝑓 𝐵 (𝑘𝑔)
𝑁=
𝑀𝑎𝑠𝑠 𝑜𝑓 𝐴 (𝑘𝑔) + 𝑀𝑎𝑠𝑠 𝑜𝑓 𝐶(𝑘𝑔)
On the other hand, the solute concentration is expressed as weight fractions with respect to the overflow
and the underflow streams, viz.:
𝐴 (𝑘𝑔) 𝐴 (𝑘𝑔)
Overflow: 𝑥𝐴 = 𝐴 (𝑘𝑔)+𝐶 (𝑘𝑔); Underflow: 𝑦𝐴 = 𝐴 (𝑘𝑔)+𝐶 (𝑘𝑔)
where 𝑥𝐴 is the weight fraction of solute A in the overflow liquid and 𝑦𝐴 is the weight fraction of A on a
solid B free basis in the liquid associated with the slurry or underflow. For the entering solid feed to be
leached, N is kg inert solid/kg solute A and 𝑦𝐴 = 1.0. For pure entering solvent N = 0 and 𝑥𝐴 = 0. For a given
system, it is often convenient to plot corresponding values of 𝑥𝐴 and 𝑦𝐴 .
For multi-stage vegetable oil extraction with a solvent in which the equilibrium is attained in each stage
(e.g. extraction of soybean oil using hexane), the concentration of the oil is the same in the overflow as it
is in the underflow. In this case, 𝑥𝐴 = 𝑦𝐴 and the equilibrium concentration diagram (plot of 𝑥𝐴 against 𝑦𝐴 )
is a straight line.
Leaching Calculations
Consider a generalized multi-stage contact equilibrium extraction process shown in the figure below.
There is a stage contact process operating with a number of stages and two contacting streams, the overflow
or light stream denoted by 𝑉 and the underflow or heavy stream denoted by 𝐿. An overall mass for the total
flow over the first 𝑛 stages would be given as mass entering = mass leaving the system, thus:
𝑉𝑛+1 + 𝐿𝑎 = 𝑉𝑎 + 𝐿𝑛
Where, V is the mass flow rate of the overflow stream, L is the mass flow rate of the underflow stream, 𝑥
is the concentration of the component being exchanged in the overflow and 𝑦 is the concentration of the
component being extracted in the underflow. The subscripts n denotes conditions at equilibrium in the nth
stage, n+1 denotes conditions at equilibrium in the (n+1)th stage and a denotes the conditions of the streams
entering and leaving stage 1, one being raw material and the other the product.
Whereupon, we have:
𝐿𝑛 𝑉𝑎 𝑥𝑎 − 𝐿𝑎 𝑦𝑎
𝑥(𝑛+1) = 𝑦𝑛 [ ]+[ ]
𝑉𝑎 + 𝐿𝑛 − 𝐿𝑎 𝑉𝑎 + 𝐿𝑛 − 𝐿𝑎
The above equation expresses the concentration in one stream in the (n+1)th stage in terms of the
concentration of the other streams in the nth stage. Thus, we have established a connection between flow
rates and composition of the contacting streams. The plot of 𝑥(𝑛+1) versus 𝑦𝑛 is called the operating line.
If the flow rates are the same in all the contact stages, then for the overflow:
𝑉𝑛+1 = 𝑉𝑛 … = 𝑉𝑎 = 𝑉
𝐿
Based on this simplified equation, the plot of of 𝑥(𝑛+1) versus 𝑦𝑛 will give a straight line whose slope is [𝑉]
𝐿𝑦𝑎
and intercept is 𝑥𝑎 − 𝑉
. The extractions to be effected in a given series of contact stages can be calculated
by combining the equilibrium and operating characteristics. Usually the equilibrium concentration curve
and the operating line are plotted together on one graph called the McCabe-Thiele plot. For example,
knowing the 𝑥 value in the 1st stage, 𝑥1 , the equilibrium condition gives the corresponding value of 𝑦 in
this stage, 𝑦1 . The above equations can be used to obtain 𝑦2 , then the equilibrium conditions will allow
prediction of 𝑥2 , and so on. This is illustrated in the following plot:
1.0
Equilibrium line
0.8 𝑦=𝑥
M
0.6
𝑥
Operating line
0.4 2
M
0.2 4
3
Starting with the entry conditions to stage 2 (Point M) on the operating line, we have the value of 𝑥 from
given or overall conditions. We proceed at constant 𝑥 to the equilibrium line and then read off the value of
𝑦 (i.e. 𝑦1 ). From 𝑦1 , we proceed vertically to the operating line at which the intercept gives the value of 𝑥2 .
Then we proceed horizontally to the equilibrium line and obtain the value of 𝑦2 . Then proceed vertically to
the operating line where the intercept gives the value of 𝑥3 and so on. A step pattern is traced out on the
plot whereby each step represents a stage in the process at which contact is provided between the streams
and equilibrium is attained. By such stepwise progression, it is possible to determine the number of stages
necessary to achieve the required separation.
The plots usually assume 100% efficiency, which is the ideal situation. In practice, the efficiency is much
lower than this. If the stepwise progression on the plots reveal that 2 stages would be sufficient to
accomplish a desired degree of separation, with a stage efficiency of 70%, the number of stages becomes:
2(100/70) 3.