GUIDED BY S.R.SHAH
Introduction
Liquid-liquid extraction (also known as solvent extraction) involves the separation
of the constituents (solutes) of a liquid solution by contact with another insoluble
liquid.
The solvent-rich product of the operation is called the extract, and the residual
liquid from which solutes has been removed is the raffinate
In some operations, the solutes are the desired product, hence the extract stream
is the desirable stream.
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The simplest liquid-liquid extraction involves only a ternary (i.e.3 components)
system.
The solution which is to be extracted is called the feed, and the liquid with which
the feed is contacted is the solvent.
The feed can be considered as comprising the solute A and the "carrier" liquid C.
Solvent S is a pure liquid.
During contact, mass transfer of A from the feed to the solvent S occurs, with little
transfer of C to S.
The solvent (with the solute) is then permitted to separate from the carrier liquid.
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Important Industrial Applications Of Liquid Liquid Extraction
Separation of 10% to 30% acetic acid in aqueous solution by using ethyl acetate or
ethyl ether as solvent.
Recovery of uranium from ore rich liquor. Solvent for this case is alkyl phosphate
in kerosene.
Separation of long chain fatty acids from vegetable oil by using propane as solvent.
Phosphoric acid and boric acid are finally purified by liquid-liquid extraction.
Liquid-liquid extraction is used for the separation of the mixture of aromatic and
paraffinic hydrocarbons of nearly the same molar mass and having close boiling
points (e.g., a mixture of benzene and haxane). For this case, solvents used are
liquid sulphur dioxide, diethylene glycol or sulpholane. Extractive distillation is
also used for the same application.
In the petroleum refinery the separation of pure benzene and toluene from
aromatic rich feed stock is carried out by extraction. In this case, sulpholane is
used as solvent.
For dearomatisation of raw hexane fraction (or for the production of food grade
hexane) using N-methyl pyrrolidone (NMP) as solvent.
For dearomatisation of the straight run kerosene fraction (or for the production
of superior kerosene) using sulpholane as solvent.
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In the manufacturing process of MTBE, methanol is separated from the rnixturt3
of methanol and C4 stream by using water as solvent.
For extraction of unsaturated fatty acids from a mixture of fatty acids Ming
fulphural as solvent.
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Desirable Solvent Properties
Selectivity
The relative separation or selectivity is defined as the ratio of ratios
of solute to nonsolute components in extract phase to the same in
raffinate phase at equilibrium. It is represented as (or ).
Distribution Coefficient
Distribution coefficient K or m is the ratio of mass fraction of solute
in extract phase to mass fraction of solute in raffinate phase at
equilibrium.
Recoverability
It is always necessary to recover the solvent from extract phase for
reuse. Hence, selected solvent must be easily recoverable from the
extract phase. In most of the cases, solvent is separated from extract
phase by distillation. If selected solvent is to be separated or
recovered by distillation than it should preferably not form an
azeotrope with the solute and also it should provide higher value of
relative volatility. Lesser value of latent heat of vaporization of
solvent is also desirable for low cost of recovery. Later is not an
attractive solvent for extraction as it forms azeotrope or non-ideal
solution with many organics and it has very high value of latent
heat of vaporization.
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Capacity
Capacity of a solvent to extract the solute is measured in terms of
maximum solubility of the solute in solvent or in terms of solubility
limit. Higher the solubility limit, lesser is the amount of solvent
required. Solute should be significantly soluble in the selected
solvent.
Density
Low solubility of solvent in the raffinate phase is desirable. Solvent
which is more insoluble is preferred. More insoluble solvent can
separate wide range of composition of the feed mixture. Also, it
gives less solvent loss and adds less impurity in the final raffinate.
Generally, a solvent which is more insoluble provides higher
selectivity.
Interfacial Tension
A high interfacial tension promotes rapid coalescence and generally
requires high mechanical energy for agitation to produce small
droplets. Conversely, low interfacial tension requires lesser
mechanical energy for agitation to produce small droplets but at
the same time it provides slow coalescence rates. Usually interfacial
tension decreases with increase in solute concentration and
increase in mutual solubility and falls to zero at plait point. Very
high and very low interfacial tension of selected solvent is not
desirable, otherwise higher collision rate is more important, hence
moderately high interfacial tension is preferred.
Chemical Reactivity
The solvent should be inert towards the other components of
extraction system and to the common materials of construction.
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Design Of Counter Current Multi-Stage Extractor
Process design of extractor can be divided in the following steps:
F + Sm =E1m +RNP
RNP Sm = F E1m = Rm
Rm is a difference point. It represents net low outward at the last stage NP and is
equal to net flow inward at first stage. On an equilateral triangular coordinates; when
operating line from AR matches with tie line, infinite number of stages are required for
the desired separation. To find Sm, extend the tie lines and allow them to intersect SRNP .
A line joining the equilibrium compositions of extract and raffinate phases is called a tie
line.
Among all such points, a point that is farthest from S, if all points are on the left-
hand side of S or a point which is nearest to S, if all points are on the right-hand side of S,
represents Rm, the difference point for minimum solvent.
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In most of the cases but not in all cases, tie line which is on extension passes through F
gives the location of RM. After finding the location of Rm, locate E1m. Draw the line
E1mRNP which intersects line FS at XMm.
F + Sm = Mm
By substituting the value of XMm from the graph, one can find Sm
Where
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