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Extraction is a process where one or more liquid solute(s) are removed from the liquidphase feed (called “the first liquid phase”) by another liquid phase (called “the second liquid phase” or the “solvent”); since all materials [i.e. the solute, the first liquid phase, and the second liquid phase (or the solvent)] in this operation are in liquid state, this operation is commonly called the “liquid-liquid extraction (LLE)”
In addition to liquid-liquid extraction (LLE), the liquid or solid solute(s) can be removed from the solid-liquid mixture (i.e. the feed) by another liquid (the solvent); such operation is called the “solid-liquid extraction (SLE)”
It is believed that the extraction has a long history, which can be dated back to the Roman time; at the time, the Romans separated gold and silver from molten copper using the molten lead as a solvent
However, it was not until the early 1930’s when the first large-scale LLE process was in operation
Lazar Edeleanu (a Romanian chemist: 18611941) removed aromatic and sulphur compounds from liquid kerosene by the LLE process using liquid sulphur dioxide at the temperature as low as 10-20 oF as a solvent; by removing such compounds from kerosene, it yields clean kerosene suitable to be used as a fuel for residential lighting The liquid-liquid extraction can be divided into 2 main cases: Case I: While the liquid solute(s) can be dissolved in both liquid phases (i.e. the first and the second liquid phases), the first and the second liquid phases are not dissolved in each other); this kind of LLE is called the immiscible liquidliquid extraction
Case II: In this case, the liquid solute(s) is (are) still dissolved in both liquid phases, and some amounts of the first liquid phase are dissolved in the second liquid phase or vice versa; this kind of LLE is called the miscible liquidliquid extraction
In reality, almost all liquid-liquid extraction operations are the miscible LLE; however, for simplification, especially in the introduction level, it is usually assumed that the immiscible LLE is valid
the LLE operation can separate two liquid phases from each other at low temperatures This makes the LLE operation suitable for separating materials that may decompose or de-nature at elevated temperatures or for separating materials whose boiling temperatures (or volatilities) are close to each other 5 . the separating agent for the LLE operation is the second liquid phase Accordingly.On the contrary to the distillation. the LLE operation does not requires heat as a separating agent.
vitamin A. benzene. and vitamin E can be de-natured at moderate temperatures) 6 . toluene) from paraffins using sulpholane as a solvent The extraction of vanilla from the oxidised liquors using toluene as a solvent The separation of vitamin A from fish-liver oil using propane as a solvent The extraction of vitamin E from vegetable oil using propane as a solvent (note that vanilla..g.Examples of the uses of extraction are The separation of penicillin from the broth (the liquid phase obtained from biological processes) using butyl acetate as a solvent The separation of aromatic-ring hydrocarbons (e.
in many applications. the downstream process that separates solvent from the solute(s) is more expensive than the extraction operation itself Hence.It is important to note that. the selection of the solvent is very critical for the extraction system The ideal solvent (or the second liquid phase) should be capable of extracting the solute(s) from the first liquid phase not be dissolved in the first liquid phase be easy to be separated from the solute(s) by a simple and inexpensive separating technique 7 .
“green”) Note that. the solvent should also be non-toxic non-reactive or chemically stable non-corrosive non-flammable or non-explosive readily available inexpensive environmentally friendly (i. the ratio of the concentration (normally presented in “mole fraction”) of the solute in the second liquid phase (yi ) to that in the first liquid phase (x i ) is called the “distribution ratio”: Kd = 8 yi xi .e. in the liquid-liquid extraction.Additionally.
The ideal solution should also yield a high distribution ratio A complete LLE process can be illustrated in Figure 9. 2007) The feed containing the first solvent and the solute is fed into the extraction unit (or the extractor) 9 .1: A complete LLE process (from “Separation Process Engineering” by Wankat.1 Figure 9.
in some textbooks/ references. in fact. which comprises the first solvent and the solute. the extract phase is also called the solvent-rich product 10 . which contains the second solvent and the extracted solute. the first solvent) The extract phase (or just the extract). note that the raffinate phase is also called the carrier-rich product (the carrier is.Another solvent (the second solvent) is also fed into the extractor counter-currently to the feed. to remove the solute from the first solvent After the system reaches the steady state. the mixture is separated into 2 distinguished phases: The raffinate phase (or just the raffi- nate).
while the stream with lower density is fed bottom-up. in which the second solvent is separated from the solute 11 .Note that the feeding point of the feed (the first solvent and the solute) and solvent depends on the density of each stream The stream with higher density or specific gravity (SG) is normally fed from the top of the extractor.1) is then passed into the solvent recovery unit. this flow scheme allows one stream to be in good contact with another stream. thus enhancing the separation efficiency The resulting extract phase (or the loaded sol- vent stream in Figure 9.
respectively Although the difference in boiling tempera- tures of these two species is relatively large.8 wt%) by the LLE process Note that the normal boiling points of acetic acid and water are 118 and 100 oC. 99. at least. it is not practical and economical to separate this mixture by distillation 12 .2 The feed containing acetic acid and water is to be separated to yield glacial acetic acid (with the concentration of acetic acid of.An industrial example of the complete LLE process can be illustrated in Figure 9.
2: An illustration of a complete liquidliquid extraction process (from “Separation Process Principles” by Seader and Henley.Figure 9. 2006) 13 .
since. it requires a considerable amount of heat or energy to vaporise water Additionally. thus. the vapour (or gas) phase contains a high amount of water the liquid phase contains a high amount of acetic acid To obtain the vapour phase. the liquid mixture has to be re-boiled at the re-boiler 14 . water is more volatile than acetic acid.This is due mainly to the fact that the heat capacity (or the specific heat: cp ) of water is relatively high. by considering the normal boiling temperatures of the two species in the mixture. at steady state.
an alternative separation technique must be considered. to sepa- rate acetic acid from water. rendering distillation uneconomical Hence. it requires a high amount of heat load (at the re-boiler) to vaporise the mixture containing a high amount of water Accordingly. the LLE process seems to be the promising choice 15 . the cost of providing heat/energy for vaporising the mixture with a high amount of water increases drastically.Since the vapour phase contains a high amount of water. and it is found that. thus.
In Figure 9.2. two separate phases are settled and can be divided into 16 . water in the feed is the first solvent (or the carrier) acetic acid in the feed is the solute Note that the feed is fed from the top of the L-L extraction unit The recycle solvent. which contains mainly ethyl acetate (~96%) is used as the second solvent The second solvent is fed from the bottom of the unit Eventually. after the LLE process is at steady state.
the extract phase.3% 8.2% tate—the second solvent or the solvent) the raffinate phase. whose composition is as follows: o ethyl acetate o water o acetic acid (the solute) (note that this phase is rich in ethyl ace83.1% 92.5% 8. with the following composition: o ethyl acetate o water o acetic acid (the solute) (note that this phase is rich in water—the first solvent or the carrier) 17 7.1% .8% 0.
it emerges from the distillation column as the bottom product 18 .Note that the concentration of acetic acid in the feed is ~22% The extract phase is then sent to the distillation column (the upper distillation column in Figure 9.b. = 77 oC) and water.p. acetic acid is separated from ethyl acetate and water Since its boiling point is higher than those of ethyl acetate (n.2).2) for further separation In this distillation column (the upper one in Figure 9.
reduces dramatically (note that the heat capacity of ethyl acetate is much lower than that of water) 19 . the heating load. at the re-boiler.Ethyl acetate and water exit the column as the top product. since the extract phase contains a low amount of water (but a high amount of ethyl acetate). after being condensed at the condenser ethyl acetate and water can be separated from each other using a two-phase decanter The recovered ethyl acetate can then be used as the recycle solvent for the LLE process It is noteworthy that.
it is rather easy to separate it from the other two species by distillation.2) In this distillation. is not required. water and acetic acid is separated from ethyl acetate Since the boiling temperature of ethyl acetate is much lower than those of water and acetic acid.The bottom product of the liquid-liquid extractor. a high heating load at the re-boiler is not necessary 20 . as a high puri- ty of the bottom product. additionally. is sent to another distillation column (the lower one in Figure 9. which contains mainly water with only a very small amount of acetic acid. or the raffinate phase.
which can be divided into Mixer-Settler For this type of L-L extractor. cheaper. called a mixer 21 . to obtain a highly purified product. it is evident that the LLE process alone does not yield an ultimate separation. two liquid phases are mixed in the first unit. and more efficient Several types of liquid-liquid extraction equipment are employed in various industries. further separation process is required However.From the example as illustrated in Figure 9. the LLE process makes further separation much easier.2. less energy-consum- ing.
3 illustrates the mixer-settler unit Figure 9. 2007) 22 .3: A mixer-settler (from “Separation Process Engineering” by Wankat. where the extract and the raffinate phases are allowed to be settled and separated into two distinguished phases Figures 9.The resulting mixture is then sent to the subsequent unit.
as shown in Figure 9. Spray Column A spray column.4.4: A spray column (from “Separation Process Principles” by Seader and Henley. 2006) 23 . is the simplest and oldest type of L-L extractor Figure 9.
despite its low cost.In this type of L-L extractor. the throughputs are large. the spray co- lumn is rarely used for industrial applications 24 . there are no plates (stages) or packings in the column. meaning that the contact time between two phases is relatively short Accordingly. either light or heavy phase/stream or both can be sprayed or dispersed into small droplets. thus. the extraction efficiency for this type of extractor is rather low Hence. using nozzles Normally.
as depicted in Figure 9.5 Note that the spaces at the top and the bottom of the column are the settling zones for the light and the heavy phases.6. respectively Plate Column In the plate-column type L-L extractor. except that. Packed Column The configuration of the packed column is similar to that of the spray column. for the packed column. sieve trays (or plates) are added into the column 25 . as shown in Figure 9. packings are packed within the extractor column.
5: A packed-column type L-L extractor (http://lewis. thus improving the extraction efficiency 26 .armscontrolwonk.Figure 9.com) The plates enhances the contact between the light and the heavy phases.
6: A plate-column type L-L extractor (http://www.Figure 9.cheresources.com) The principal purpose of the addition of the trays or plates is the same as per the distil- lation column. in which the plates allows the contact between the down-coming liquid phase and the rising vapour phase 27 .
com) 28 . a device that enables mechanical agitation within the column of the L-L extractor is added to the system.liquid-extraction. as illustrated in Figure 9. Columns with Mechanical Agitation To increase the contact and mass transfer between the light and the heavy phases.7 Figure 9.7: A Rotating Disc Contactor (RDC) (http://www.
through which the light and the heavy phases flows For some instances.7) Normally. the discs may be agitated in the vertical direction 29 .The L-L extracting unit as depicted in Figure 9. thus enhancing the mixing within the stage (or between the two stators. the discs and the stators have holes. as shown in Figure 9.7 is commonly called the “rotating disc contactor” The discs or the rotors are generally ro- tated radially.
as inter-stage pumping is required High investment cost Large space requirement .Note.1: Advantages and disadvantages of different liquid-liquid extraction equipment Type Mixer-Settler Advantages Good contacting Can handle wide flow ratio between the feed and the solvent High efficiency Can be scaled up easily 30 Disadvantages Large hold-up time High power cost. once again. that the spaces at the top and the bottom of the column are the settling zones for the light and the heavy phases. respectively The advantages and disadvantages of various types of L-L extractors are summarised in Table 9.1 Table 9.
counter-current flow contactors (with no mechanical agitation).g.g. e..) Type Continuous. spray.Table 9.1: Advantages and disadvantages of different liquid-liquid extraction equipment (cont.. RDC Good dispersion and Moderate to large mixing High efficiency Reasonable cost easy throughput Cannot handle high flow ratio emulsifying systems Advantages Low operating cost Simple construction Disadvantages Cannot handle high flow ratio Scale-up is rather difficult Low investment cost Large throughput Scale-up is relatively Cannot handle 31 . counter-current flow contactors (with no mechanical agitation). packed. and plate columns Continuous. e.
In addition to counter-current cascades or counter-current extraction.8: A cross-flow L-L extraction unit (from “Separation Process Engineering” by Wankat. which is the most common extraction scheme. other configuration of the extraction cascades can also be employed One type of such other cascades is a crossflow cascade. 2007) Note that. in this type of extraction cascade. the fresh solvent is fed to each stage 32 .8 Figure 9. as illustrated in Figure 9.
we can separate salt from a mix- ture of sand and salt.In addition to liquid-liquid extraction (LLE) and solid-liquid extraction (SLE). a technique called a “washing” may be used In the washing process. and we want to separate one solid species from another. when there are two solid species mixed together. the soluble solid is extracted from the insoluble one using a solvent For example. using pure water as a solvent In the washing process. water and the mixture of sand and salt are mixed together in a mixer 33 .
e.During the mixing. sand) and the solution of solvent and soluble solid (i. the salt (in water) solution for this Example) the underflow phase. which is the solution of solvent and soluble solid (i. in which the mixture is divided into 2 phases: the overflow phase. the salt solution) 34 . salt is extracted from the sand + salt mixture by the fact that only salt can be dissolved in water The resulting mixture is then allowed to be settled in a settler (a settling tank) or a thickener. which comprises insoluble solid (i.e.e.
the washing) is to have as pure insoluble solid as possible The washing process can be illustrated in Figure 9.9: The washing process (from “Separation Process Engineering” by Wankat.e. 2007) 35 .The main purpose of this operation (i.9 Figure 9.
From Figure 9. O and U represents the flow rates of the overflow and underflow phases.9. except that the solute and the carrier are solid A similar process to the washing. respectively x j and y j are the concentrations of soluble solute (solid) in the underflow and over- flow phases. is the “leaching” 36 . which still employs the principle of the LLE process. as the solute is extracted from the carrier in the similar manner to that of the LLE process. respectively Note that the washing can be categorised as the extraction.
On the contrary to the washing. in which the main goal is to obtain the insoluble solid with a high purity. the main purpose of the leaching is to obtain as many soluble solid (solute) in the solvent as possible Examples of the leaching include: the making of liquid coffee from coffee beans (เมล็ดกาแฟ) using hot water as a solvent—in an espresso machine the leaching of liquid tea from tea leaves using hot water as a solvent 37 .
10 Figure 9. the recovery of soybean oil (a source of bio-diesel) from soybean seeds using an organic compound (normally hexane) as a solvent The general configuration for the leaching is as depicted in Figure 9.10: A schematic diagram of washing (from “Separation Process Engineering” by Wankat. 2007) 38 .
10. a number of research works reveal that.In Figure 9. the efficiencies of the ex- traction (either liquid or solid). the washing. by replacing the liquid solvent with the super-critical fluid. and the leaching are enhanced substantially 39 . Fsolid Fsolv Yj Xj = the flow rate of insoluble solid = the flow rate of solvent = the concentration of the soluble solid in the solvent = the concentration of the soluble solid in the insoluble solid Recently.
11: A phase (P-T) diagram that indicates the super-critical region (from “Separation Process Engineering” by Wankat.11 Figure 9. 2007) 40 .The super-critical fluid is the fluid whose tem- perature and pressure are higher than the critical point (Tc & Pc ) as shown in Figure 9.
The critical temperatures (Tc ).47 0. and densities of selected substances Substance CO2 Propane (C3H8) Water Tc ( C) o Pc (atm) rc (g / mL) 72.22 0.2: Table 9.9 0. pressures (Pc ) and densities (rc ) of selected pure substances are illustrated in Table 9.8 41. pressures.32 31 97 374 217.7 An interest of using super-critical fluid (SCF) as a solvent for extracting compounds from either solid (in the SLE process) or liquid (in the LLE process) is increasing the past two decades 41 .2: The critical temperatures.
supercritical CO2 is found to be the most popular SCF. of many SCFs available. which results in high mass transfer rates Note that. this may be because super-critical CO2 42 . thus resulting in low pressure drops during the extraction process The diffusivities (especially in solids) of SCFs are much higher than those of liquids (~10 folds) There is no phase boundary.This may be because of the following reasons: The densities and the viscosities of SCFs are lower than those of liquids.
for napthalene dissolved in super-critical CO2 (at a high pressure.12 For example. 150 atm). as shown in Figure 9. when the system’s pressure is dropped to ~50 atm. e.g. the solubility of napthalene in supercritical CO2 is reduced from ~10-1–10-2 to ~10-4– 10-5 (or by ~1. is readily available is inexpensive is non-toxic can be used at low temperatures To separate the extracted solute from the mixture of SCF + solute.. it can be done easily by lowering the system’s pressure.000 folds) 43 .
12: A regeneration of super-critical fluid (SCF) by a pressure-swing system (from “Separation Process Engineering” by Wankat. 2007) Note also that super-critical CO2 is commonly used in food and pharmaceutical industries.Figure 9. as it can easily be separated completely from the desired products (by lowering the system’s pressure as described recently) 44 .
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