Chapter 9 Principles of Liquid-Liquid Extraction (LLE)

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 1930s when the first large-scale LLE process was in operation
2

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
3

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

On the contrary to the distillation, the LLE operation does not requires heat as a separating agent; the separating agent for the LLE operation is the second liquid phase

Accordingly, 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

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.g., benzene, 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, vitamin A, and vitamin E can be de-natured at moderate temperatures)
6

It is important to note that, in many applications, the downstream process that separates solvent from the solute(s) is more expensive than the extraction operation itself Hence, 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

Additionally, 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.e. green)

Note that, in the liquid-liquid extraction, 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

The ideal solution should also yield a high distribution ratio

A complete LLE process can be illustrated in Figure 9.1

Figure 9.1: A complete LLE process

(from Separation Process Engineering by Wankat, 2007)

The feed containing the first solvent and the solute is fed into the extraction unit (or the extractor)
9

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), which comprises the first solvent

and the solute; note that the raffinate phase is also called the carrier-rich product (the carrier is, in fact, the first solvent) The extract phase (or just the extract), which contains the second solvent and the extracted solute; in some textbooks/ references, the extract phase is also called the solvent-rich product
10

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, while the stream with lower density is fed bottom-up; 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 9.1) is then passed into the solvent recovery unit, in which the second solvent
is separated from the solute

11

An industrial example of the complete LLE process can be illustrated in Figure 9.2 The feed containing acetic acid and water is to be separated to yield glacial acetic acid (with the

concentration of acetic acid of, at least, 99.8 wt%)

by the LLE process Note that the normal boiling points of acetic acid and water are 118 and 100 oC, respectively Although the difference in boiling tempera-

tures of these two species is relatively large, it is

not practical and economical to separate this mixture by distillation

12

Figure 9.2: An illustration of a complete liquidliquid extraction process

(from Separation Process Principles by Seader and Henley, 2006)

13

This is due mainly to the fact that the heat

capacity (or the specific heat: cp ) of water is

relatively high; thus, it requires a considerable amount of heat or energy to vaporise water Additionally, since, by considering the normal boiling temperatures of the two species in the mixture, water is more volatile than acetic acid, at steady state, 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

Since the vapour phase contains a high amount of water, it requires a high amount of heat load (at the re-boiler) to vaporise the mixture containing a high amount of water

Accordingly, the cost of providing heat/energy for vaporising the mixture with a high amount of

water increases drastically, thus, rendering distillation uneconomical

Hence, an alternative separation technique must be considered, and it is found that, to sepa-

rate acetic acid from water, the LLE process

seems to be the promising choice

15

In Figure 9.2, 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, two separate phases are settled and can be divided into
16

 the extract phase, whose composition is as follows: o ethyl acetate o water o acetic acid (the solute) (note that this phase is rich in ethyl ace83.5% 8.3% 8.2%

tatethe second solvent or the solvent)

the raffinate phase, with the following composition: o ethyl acetate o water o acetic acid (the solute) (note that this phase is rich in waterthe first solvent or the carrier)
17

7.1% 92.8% 0.1%

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 9.2) for further separation

In this distillation column (the upper one in Figure 9.2), acetic acid is separated from ethyl

acetate and water

Since its boiling point is higher than those of

ethyl acetate (n.b.p. = 77 oC) and water, it

emerges from the distillation column as the bottom product
18

Ethyl acetate and water exit the column as the top product; 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, since the extract phase contains a low amount of water (but a high amount of ethyl acetate), the heating load, at the re-boiler, reduces dramatically (note that the

heat capacity of ethyl acetate is much lower than

that of water)

19

The bottom product of the liquid-liquid extractor, or the raffinate phase, is sent to another distillation column (the lower one in Figure 9.2)

In this distillation, 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, it is rather easy to separate it from the other two species by distillation; additionally, as a high puri-

ty of the bottom product, which contains mainly

water with only a very small amount of acetic acid, is not required, a high heating load at the

re-boiler is not necessary

20

From the example as illustrated in Figure 9.2, it is evident that the LLE process alone does not yield an ultimate separation; to obtain a highly

purified product, further separation process is

required However, the LLE process makes further separation much easier, cheaper, less energy-consum-

ing, and more efficient

Several types of liquid-liquid extraction equipment are employed in various industries, which can be divided into Mixer-Settler For this type of L-L extractor, two liquid phases are mixed in the first unit, called a mixer
21

The resulting mixture is then sent to the

subsequent unit, where the extract and the raffinate phases are allowed to be settled and separated into two distinguished phases

Figures 9.3 illustrates the mixer-settler unit

Figure 9.3: A mixer-settler

(from Separation Process Engineering by Wankat, 2007)

22

 Spray Column A spray column, as shown in Figure 9.4, is the simplest and oldest type of L-L extractor

Figure 9.4: A spray column

(from Separation Process Principles by Seader and Henley, 2006)

23

In this type of L-L extractor, either light or heavy phase/stream or both can be sprayed or dispersed into small droplets, using nozzles

Normally, there are no plates (stages) or packings in the column; thus, the throughputs are

large, meaning that the contact time between

two phases is relatively short

Accordingly, the extraction efficiency for this type of extractor is rather low

Hence, despite its low cost, the spray co-

lumn is rarely used for industrial applications

24

 Packed Column The configuration of the packed column is

similar to that of the spray column, except that,

for the packed column, packings are packed within the extractor column, as shown 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, respectively

Plate Column In the plate-column type L-L extractor, as depicted in Figure 9.6, sieve trays (or plates) are

added into the column

25

Figure 9.5: A packed-column type L-L extractor

(http://lewis.armscontrolwonk.com)

The plates enhances the contact between the light and the heavy phases, thus improving the extraction efficiency

26

Figure 9.6: A plate-column type L-L extractor

(http://www.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

 Columns with Mechanical Agitation To increase the contact and mass transfer

between the light and the heavy phases, a device

that enables mechanical agitation within the column of the L-L extractor is added to the system, as illustrated in Figure 9.7

Figure 9.7: A Rotating Disc Contactor (RDC)

(http://www.liquid-extraction.com)
28

The L-L extracting unit as depicted in Figure 9.7 is commonly called the rotating disc contactor

The discs or the rotors are generally ro-

tated radially, thus enhancing the mixing within

the stage (or between the two stators, as shown in Figure 9.7)

Normally, the discs and the stators have

holes, through which the light and the heavy

phases flows

For some instances, the discs may be agitated in the vertical direction
29

Note, 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 9.1: 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, as inter-stage pumping is required High investment cost Large space requirement

Table 9.1: Advantages and disadvantages of different liquid-liquid extraction equipment (cont.)
Type Continuous, counter-current flow contactors (with no mechanical agitation); e.g., spray, packed, and plate columns Continuous, counter-current flow contactors (with no mechanical agitation); e.g., 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

In addition to counter-current cascades or

counter-current extraction, 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, as illustrated in Figure 9.8

Figure 9.8: A cross-flow L-L extraction unit

(from Separation Process Engineering by Wankat, 2007)

Note that, in this type of extraction cascade, the fresh solvent is fed to each stage
32

In addition to liquid-liquid extraction (LLE) and solid-liquid extraction (SLE), when there are two solid species mixed together, and we want to

separate one solid species from another, a technique called a washing may be used

In the washing process, the soluble solid is extracted from the insoluble one using a solvent

For example, we can separate salt from a mix-

ture of sand and salt, 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

During the mixing, 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, in which the mixture is divided into 2 phases: the overflow phase, which is the solution of solvent and soluble solid (i.e. the salt (in water) solution for this Example) the underflow phase, which comprises

insoluble solid (i.e. sand) and the solution

of solvent and soluble solid (i.e. the salt solution)

34

The main purpose of this operation (i.e. the washing) is to have as pure insoluble solid as

possible

The washing process can be illustrated in Figure 9.9

Figure 9.9: The washing process

(from Separation Process Engineering by Wankat, 2007)

35

From Figure 9.9, O and U represents the flow rates of the

overflow and underflow phases, respectively

x j and y j are the concentrations of soluble solute (solid) in the underflow and over-

flow phases, respectively

Note that the washing can be categorised as the extraction, as the solute is extracted from the

carrier in the similar manner to that of the LLE

process, except that the solute and the carrier are solid A similar process to the washing, which still employs the principle of the LLE process, is the leaching
36

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 () using hot water as a solventin an espresso machine the leaching of liquid tea from tea leaves using hot water as a solvent

37

 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

Figure 9.10: A schematic diagram of washing

(from Separation Process Engineering by Wankat, 2007)

38

In Figure 9.10, 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, a number of research works reveal that, by replacing the liquid solvent with the super-critical fluid, the efficiencies of the ex-

traction (either liquid or solid), the washing, and

the leaching are enhanced substantially

39

The super-critical fluid is the fluid whose tem-

perature and pressure are higher than the critical point (Tc & Pc ) as shown in Figure 9.11

Figure 9.11: A phase (P-T) diagram that indicates the super-critical region
(from Separation Process Engineering by Wankat, 2007)

40

The critical temperatures (Tc ), pressures (Pc ) and densities (rc ) of selected pure substances are illustrated in Table 9.2:

Table 9.2: The critical temperatures, pressures, and densities of selected substances
Substance CO2 Propane (C3H8) Water
Tc

( C)
o

Pc

(atm) rc (g / mL)
72.8 41.9 0.47 0.22 0.32

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

This may be because of the following reasons:

The densities and the viscosities of SCFs

are lower than those of liquids, 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, which results

in high mass transfer rates

Note that, of many SCFs available, supercritical CO2 is found to be the most popular SCF;

this may be because super-critical CO2

42

 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 systems pressure, as shown in Figure 9.12

For example, for napthalene dissolved in super-critical CO2 (at a high pressure, e.g., 150 atm), when the systems pressure is dropped to ~50 atm, the solubility of napthalene in supercritical CO2 is reduced from ~10-110-2 to ~10-4 10-5 (or by ~1,000 folds)
43

Figure 9.12: 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, as it can easily be separated completely from the desired products (by lowering the systems pressure as described recently)

44