CHE-396 Senior Design Extraction

Liquid-Liquid Extraction

Senior Design CHE 396

Matrix Corporation
Zachary Fijal
Constantinos Loukeris
Zhaleh Naghibzadeh
John Walsdorf

Prof. Andreas Linninger

Akhil Jain

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CHE-396 Senior Design Extraction

Table of Content

Introduction ___________________________________________________________ 3
Flowsheet _____________________________________________________________ 3
Process Operation ______________________________________________________ 4
Limitations ____________________________________________________________ 5
Applicability ___________________________________________________________ 6
Theory________________________________________________________________ 7
Theory – Ternary Phase Diagram__________________________________________ 8
Theory - General Flow Sheet for Extractor Design ___________________________ 10
Properties ____________________________________________________________ 21
Costs ________________________________________________________________ 23
Case Study ___________________________________________________________ 25
Alternatives___________________________________________________________ 30
References ___________________________________________________________ 31

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CHE-396 Senior Design Extraction

Introduction
Extraction is a process that separates components based upon chemical
differences rather than differences in physical properties. The basic principle behind
extraction involves the contacting of a solution with another solvent that is immiscible
with the original. The solvent is also soluble with a specific solute contained in the
solution. Two phases are formed after the addition of the solvent, due to the differences
in densities. The solvent is chosen so that the solute in the solution has more affinity
toward the added solvent. Therefore mass transfer of the solute from the solution to the
solvent occurs. Further separation of the extracted solute and the solvent will be
necessary. However, these separation costs may be desirable in contrast to distillation
and other separation processes for situations where extraction is applicable.

Flowsheet

Figure 1. Extraction Flowsheet for an Extractor Column

A general extraction column has two input stream and two output streams. The
input streams consist of a solution feed at the top containing the solute to be extracted and
a solvent feed at the bottom which extracts the solute from the solution. The solvent
containing the extracted solute leaves the top of the column and is referred to as the
extract stream. The solution exits the bottom of the column containing only small

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CHE-396 Senior Design Extraction

amounts of solute and is known as the raffinate. Further separation of the output streams
may be required through other separation processes.

Process Operation
There are certain design variables that must be assigned in an extraction process.
Ø Operating Temperature
Ø Operating Pressure
Ø Feed Flow Rate
♦ Composition
♦ Temperature of entering stream
♦ Pressure of entering stream
As in many separation processes, the pressure and temperature conditions play a
large role in the effectiveness of the separation. In order for a good split of the feed the
pressure and temperature must be such so as to ensure that all components remain in the
liquid phase. The process will be adversely affected if one or more of the components are
allowed to become a vapor, or the extraction may not occur at all if a large enough
portion of a component is allowed to vaporize. In addition, the temperature should be
high enough that the components are all soluble with one another. If extremes in
temperature are present, finding a suitable solvent for extraction can be problematic.
This is however generally not the case since one of the biggest benefits in the extraction
process is that it can be done at ambient pressures and temperatures.
In many applications, a separation process is desired where an extreme
temperature will destroy the desired product such as the pharmaceutical industry. For
these applications, extraction is ideally suited, since the only temperature requirement is
that dictated by the solubility. At this point the biggest challenge would be finding a
suitable solvent for the extraction.
We can also use the pharmaceutical industry in another example for the benefits
of extraction and this has to do with the volumes involved for effective extraction. The
extraction process can become very expensive if the solvent needed to be used is costly
these expenses can be contained if a batch process is being used and this is often the case
in medicines. In a non-batch process the solvent would need to be constantly supplied

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CHE-396 Senior Design Extraction

and this would involve either a huge amount of solvent or another separation process in
order to recycle the solvent.

Limitations
We must consider the under what extremes extraction can be used as separation
process.
1. Suitable Solvent [1]
• Solvent partially soluble with the carrier.
• Feed components immiscible with the solvent.
• Solute is soluble in the carrier and at the same time completely or partially soluble
in the solvent.
• Different densities than the feed components for a phase separation to facilitate
and maintain the capacity of the extractor high.
• Extremely high selectivity for the solute for the solvent to dissolve the maximum
amount of solute and the minimum amount of the carrier.
• Large distribution coefficient to reduce the theoretical number of stages
contributing to a greater efficiency
• Low viscosity increases the capacity of the extraction column and does not allow
for the settling rate of dispersion to be slow.
• Chemically stable and inert toward other components of the system
• Low cost, nontoxic, and nonflammable
2. Equipment
• Interfacial tension and Viscosity
• High interfacial tension and viscosity leads to more power being supplied to
maintain rapid mass transfer throughout the extraction process.
• Low interfacial tension and viscosity leads to the formation of an emulsion.
3. Temperature preferred to be higher since solubility increases, but temperature not
higher than the critical solution temperature.
4. Pressure for condensed system must be maintained below the vapor pressure of the
solutions such that a vapor phase will not appear and interrupt liquid equilibrium.

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CHE-396 Senior Design Extraction

5. Separation may only occur for compositions in the region between the feed
composition and that apex of the carrier.

Applicability
With all the key components in the design of an extractor system to be discussed,
the equipment selection can be evaluated. We must determine which extractor would
apply for the situation at hand. The specifications for each of these different systems are
relatively the same. The following design constraints should be placed on each system in
order to optimize the individual process -- (1) maximize surface area of mass transfer,
and (2) adjust flow feeds for maximum solute recovery. [2]
In general, there are three main types of extractors to focus on:
• Mixer-settlers

Mixer-settlers are used when there will only be one equilibrium stage in the
process. For such a system, the two liquid phases are added and mixed. Due to
their density differences, one phase will settle out and the mixture will be
separated. The downfall to this type of extractor is that it requires a large-volume
vessel and a high liquid demand. [1]
• Contacting columns
Contacting columns are practical for most liquid-liquid extraction systems. The
packings, trays, or sprays increase the surface area in which the two liquid phases
can intermingle. This also allows for a longer flow path that the solution can
travel through. In the selection of a packing, it is necessary to select a material
that is wetted by the continuous phase. [1] Lastly, the flow in a column should
always be counter-current.
• Centrifugal contractors
Centrifugal contractors are ideal for systems in which the density difference is
less than 4%. In addition, this type of system should be utilized if process
requires many equilibrium stages. [2] In these systems, mechanical devices are
used to agitate the mixture to increase the interfacial area and decrease mass
transfer resistance. [1]

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CHE-396 Senior Design Extraction

Many different types of centrifugal contractors exist, and each has its own guidelines for
operation and selection. A more detailed view can be found in. [1]
Table 1. Advantages and disadvantages of the various liquid-liquid extractor types [1].

Unit of Operation Advantages Disadvantages

Mixer-Settler • Efficient • Large floor

• Low head room
• Induces good contacting
• Can handle any number
of stages
Columns • Small investment costs
(without agitation) • Low operating costs
Columns • Good dispersion
(with agitation) • Low investment costs
• Can handle any number
of stages
Centrifugal Extractors • Can separate small
density differences
• Short holding time
• Small liquid inventory
• High set-up costs
• High operation costs
• High head room
• Difficult to scale up
from lab
• Less efficient than
mixer-settler
• Difficult to separate
small density
differences
• Does not tolerate high
flow ratios
• High set-up cost
• High operating and
maintenance costs
• Cannot handle many
stages

Theory
When talking about liquid-liquid extraction, liquid-liquid equilibrium must be
considered. This is best represented by equating the chemical potential of both liquid
phases:
µi = µi
LI LII
(1)
This relationship reduces to an expression, which is dependent only on the liquid mole
fractions and activity coefficients:
γ =γ
LI LI LII LII
i xi i xi (2)
We can use activity coefficient models, such as UNIFAC (UNIquac Functional-group
Activity Coefficient), UNIQUAC (universal quasichemical), and NRTL (nonrandom

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CHE-396 Senior Design Extraction

two-liquid) to determine the mole fractions. All three models above apply for liquid-
liquid equilibrium, it rolls down to which is easier to use and what properties we have
available. For a multi-component system, the UNIQUAC equation for the liquid-phase
activity coefficient is represented as follows: [3]
ln γi = ln γi (combinator ial ) + ln γi (residual ) (3)
The combinatorial and residual activities are based on the statistical mechanical
theory and allowed the local compositions to result from the size and energy differences
between the molecules in the mixture. The relationships for these two activities are made
available to us through.

Theory – Ternary Phase Diagram

We then are able to relate this data from the activity into a ternary phase diagram.
Ternary phase diagrams are unique in that they show all three components of a reactor
system on one plot. There are general principles that govern ternary phase diagrams, and
those are the following:
• Sum of the perpendicular distances from any point within the triangle
to the three sides equals the altitude of the triangle.
• Each apex of the triangle represents one of the pure components.
• Any point of a side of the triangle represents a binary mixture.
• Lines may be drawn parallel to the sides of the equilateral triangle for
the plotting of the compositions.

Figure 2. Phase diagram for a three component system. [2]

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CHE-396 Senior Design Extraction

The ternary phase diagram may be constructed directly from experimental data.
The saturation curve (miscibility boundary), represented by JDPEK in Figure 2, can be
obtained experimentally by a cloud point titration. For example, a solution containing
components A & C with some composition is made, and then component B is added until
the onset of cloudiness due to the formation of a second phase occurs. Then the
composition is know for the mixture of the three components and can plotted onto the
ternary phase diagram. [1]
Tie lines are lines that connect points on the miscibility boundary. The tie lines
may also be presented onto the ternary phase diagram from an experiment. A mixture
may be prepared with composition that of point H (40% A, 40% C, 20% B) from Figure
2. If we allow it to equilibrate, then we can chemically analyze the final extract (E) phase
and the raffinate (R) phase. [1]
Point F is a feed composition into the extractor while point S is the solvent feed to
the extractor. Point H represents the composition of the two feeds at equilibrium. This
point is determined by summing the feed (F) and solvent (S) compositions for each
component. Points R and E are the compositions of the raffinate and extract from the
unit, respectively, and the line between them forms the tie line. The tie lines move above
and below this line based on the relationship between the raffinate and the extract. Point
P represents the plait point. At this point, only one liquid phase exists and the
compositions of the two effluents are equal. The curve represented by JRDPEK is the
equilibrium between all three components. The area under the curve is the region where
two liquid phases will exist. Above the curve, there will only be one liquid phase. If a
line is drawn from F to E or from S to R, this will represent the operating line. Although
this diagram is not the basic theory behind liquid-liquid extraction, it is helpful to review
this procedure before continuing with an in-depth discussion.
In addition to the above-mentioned considerations, equilibrium constraints must
be satisfied. This implies that
γ
AE = γ
AR (4)

where γ
AE is the activity coefficient for the solute A in the extract and γ
AR is the activity

coefficient of A in the raffinate. This condition is one of the most important aspects of

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CHE-396 Senior Design Extraction

liquid-liquid extraction since it allows for calculations and assumptions that based on
equilibrium systems (e.g. the ternary phase diagram).
One consideration to be made is for the separation factor. We want this factor to
as far away from unity as possible. This leads to a better separation in the extraction
process. The separation factor is represented as follows: [4]
*
y
β= E (5)
xR

One of the last essential points to the theory behind liquid-liquid extraction is
mass transfer. The driving force for this mass transfer arises from the concentration
difference of the solute in each of the solvents. In general, it is assumed that the system
is at an equilibrium state when mass transfer is occurring. Solute fluxes in the raffinate
and extract can be expressed as

N = KE⋅A⋅(xEi - xE) (6)

N = KR⋅A⋅(xRi - xR) (7)

where KE and KR are the overall mass transfer coefficients, A is the cross-sectional area,
xE and xR are the concentrations of solute in the extract and raffinate respectively, and xEi
and xRi are the concentrations of solute in each phase at the liquid-liquid interface.

Theory - General Flow Sheet for Extractor Design

With the key components of liquid-liquid extraction discussed, the following
general flowchart can be utilized for almost any process. Figure 3 (a) illustrates a general
ternary diagram for a desired solute (C), an extracting solvent (B) and a carrier solvent
(A). In this process, depicted in Figure 3 (b), we will assume that the feed (F) contains
components A and C. A solvent (S) is introduced in such a way that it will extract C
from the feed. The raffinate composition (R) is specified with respect to the recovery of
C that is needed. Table 2 summarizes the components, flows, and unknowns of such a
system. The following steps can be utilized to determine the extract composition and the
number of stages needed for most liquid-liquid extraction problems.

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CHE-396 Senior Design Extraction

(a) (b)
Figure 3. (a) A general ternary phase diagram using for designing an extractor, and (b) a general
process diagram relating the ternary phase diagram to physical meaning.

Table 2. Table summarizing the general extraction phase diagram and process diagram in
Figure 3.

Stream Components Is the composition given? Is the flow rate given?

F A and C Yes Yes
S B Yes, usually pure or No, determined by
relatively pure component calculation
B
E A with large C No, determined from No, determined from
concentration calculation component mass balance
R B with small C Yes, recovery amount No, determined from
concentration needed of solute C from component mass balance
design specifications
where:
A is the carrier solvent
B is the solvent used to extract a certain
component
C is the component that is to be extracted from
A

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CHE-396 Senior Design Extraction

Step 1: Determine the minimum solvent-to-feed ratio (S/F)min. This calculation needs to
be completed because E1, the extract composition, needs to be found. This
procedure begins by drawing an operating line from S to R that extends beyond
the boundaries of the diagram. Next, each tie line is considered to be a pinch
point, and a line drawn from each tie line to the operating line is designated a P1,
P2, … ,Pn. The Pi farthest away from R is called Pmin. After Pmin has been
established, a line is drawn from Pmin, through F (the feed composition), and to
the other side of the equilibrium curve.

Figure 4. Sample Ternary Diagram used to calculate Pmin for Step 1 of the general procedure for
designing an extractor.

This point will represent E1. Figure 4 represents a general ternary diagram for a
Pmin calculation. After E1 is known, a mass balance around the system can be
utilized to determine the mixing point (point M in Figure 5). This is completed by
saying that:

F + Smin = R + E1 = M (8)

Solving for Smin/F, we will obtain the minimum solvent-to-feed ratio as

S min ( x A )F − ( x A )M
= (9)
F ( x A )M − ( x A ) S

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CHE-396 Senior Design Extraction

where (xA)i ’s are the fractions of A (the solute) in the feed (F), the solvent (S), and
at the mixing point (M). Generally, a solvent-to-feed ratio for an extraction system
is 1.5 times Smin/F:

(S/F)actual = 1.5(S/F)min (10)

This point can be found on the diagram by saying that (S/F) = FM / MS , and the
new mixing point (M’) can be determined by moving along the FS line until the
new ratio point is reached.

Figure 5. A general ternary phase diagram showing the mixing point based on the (S/F)min (M)
and the actual mixing point (M’).

Step 2: Determine the extract (E) composition. This calculation is done very easily after
the first step. A line should be drawn from the raffinate composition, through
the new mixing point (M’) and to the other side of the equilibrium line. This
will be the extract composition of solute-rich solvent.

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CHE-396 Senior Design Extraction

Step 3: Find operating point. The operating point is a graphical point that represents the
difference in the overall flow; in addition, it is merely a point for which
calculations are computed around on a graph. Draw a line connecting the solvent
(S) and raffinate (R) points on the diagram. Follow this line beyond the diagram
to the left and right – this is the operating line. Draw a line connecting the extract
(E) and the feed (F). The point at which these two lines intersect (P) is the
operating point. Figure 6 depicts such a diagram for this calculation.

Figure 6. A ternary phase diagram depicting the procedure for determining the operating point
(P) and number of stages for an extraction column.

Step 4: Calculate the number of stages. Following the tie line from point E to the other
side of the equilibrium curve will give the composition of an intermediate
raffinate stage. Another operating line is drawn from the operating point, through
this intermediate point, and ends at point E’. This is a stage of the system. This
procedure should be repeated until stages have been constructed to R, the raffinate
composition. Figure 6 shows this procedure for a general case.

Step 5: Calculate unknown flowrates. Since the extract and raffinate flows have not been
specified up to this point, this would be an appropriate level at which to be this.
This involves an overall mass balance on individual components. For the sake of
generality, choose A and B. It follows that

xAF(F) +xAS(S) = xAR(R) + xAE(E) (11)

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CHE-396 Senior Design Extraction

xBF(F) +xBS(S) = xBR(R) + xBE(E) (12)

where the xA’s and xB’s are the fractions of A and B for the specified streams,
and F, S, R, and E are the flow rates of the feed, solvent, raffinate, and extract. R
and E are the only unknowns, and they can be solved for by a simple system of
equations.
Step 6. Determination of Extraction Column Diameter [1]
• The diameter of the column must be large enough to permit two phases to flow
counter-currently through the column without flooding.

• Estimation of column diameter for liquid –liquid contacting devices is far more
complex and uncertain than liquid-vapor contactors due the larger number of
important variables.

• Variables necessary for calculating extractor column diameter include:

• Individual phase flow rates
• Density differences between the two phases
• Interfacial tension
• Direction of mass transfer
• Viscosity and density of continuos phase
• Geometry of internals

• Column diameter may be best determined through scale-up of laboratory test runs.
The necessary experimental data are obtained by:
• Use laboratory or pilot plant test unit with system components of interest.
• Use laboratory or pilot plant test unit with a diameter of one inch or more.
• Measurements of superficial velocities in each phase are made.
• The sum of these velocities may be assumed to hold constant for larger
scaled-up commercial units.
• The superficial velocity data will be used to calculate the column diameter
through the following correlation derivation.

• The following notation is utilized in the correlation derivation:

• uD = Actual average velocity of the dispersed (droplet) liquid phase
• uC = Actual average velocity of the continuous liquid phase
• UD = Superficial velocity of the dispersed liquid phase
• UC = Superficial velocity of the continuous liquid phase
• φD = Volume fraction of dispersed liquid phase in column
• ur = Average droplet rise velocity relative to the continuous phase
• C = Capacity Parameter

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CHE-396 Senior Design Extraction

• CD = Drag Coefficient
• ρM = Density (volumetric mean)
• ρD = Density of dispersed phase
• ρC = Density of continuous phase
• f{1-φD} = Factor which accounts for hindered rising effect of other
droplets
• u0 = Characteristic rise velocity for a single droplet
• µ = Viscosity (subscript will determine component)
• σ = Interfacial tension (subscript will determine component)
• AC = Column cross sectional area
• DT = Column diameter
• g = Acceleration due to gravity
• MD = Mass flowrate of the dispersed phase
• MC = Mass flowrate of the continuous phase

Figure 7. Counter-current flows of dispersed and continuous liquid phase in a column.

• Diameter Calculation Procedure

Step A – Determination of Column Total Capacity
Figure 7 illustrates lower density liquid droplets rising through the denser downward
flowing continuous liquid phase. The actual average velocities of each component
relative to the column wall are:

UD
uD = (13)
φD

UC
uC = (14)
1 − φD

The average droplet rise velocity relative to the continuous phase is the sum of these
equations:
UD Uc
ur = + (15)
φD 1 − φD

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CHE-396 Senior Design Extraction

This relative velocity may also be expressed in terms of the forces acting upon the
droplet including drag forces, gravitational forces, and buoyancy forces. These
variables are combined into one parameter called C:

 4d p g 
C= 3C 
 (16)
 D 
If the droplet diameter dp is not known C may be obtained through a correlation
provided in Seader [1] equation (6-42), which was developed through experimental
data from operating equipment. Taking into account density and rising effects of
other components the relative velocity may be expressed as:
1
ρC − ρD 2
( )
1
u r = C
 ρ 
 1 − φD
2 f {1 − φ }
D (17)
 C 
From experimental data, Gayler et al. found that the right-hand of the equation may
be expressed as:

u r = u 0 (1 − φD ) (18)
Eliminating the relative velocity by combining equation (17) and (18) gives:

UD UC
+ = u 0 (1 − φD ) (19)
φD 1 − φD

This equation is a cubic in φD. A graph of UD/u0 vs. φD may be generated at some
value of UC/uo. This graph represents the holdup curve for the liquid-liquid extraction
column. A typical value of UC/uo may be assumed 0.1.

Figure 8. Typical holdup curve for liquid-liquid extraction

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CHE-396 Senior Design Extraction

At fixed UC, an increase in UD results in a increased value of holdup φD until the

flooding point is reached at the maximum of Figure 8:

∂UD 

 ∂φ 
 =0 (20)
 D UC

On the other hand, with UD fixed, UC may be increased until the flooding point is
achieved at:

∂U C 

 ∂φ 
 =0 (21)
 D UD

Inserting these derivatives into equation (19) results in the following expression for
φD at flooding conditions. The subscript f denotes flooding:

.5
 U C 
1 + 8
U   − 3
  D 
(φ)f = (22)
U C  
4
U   − 1
 D  

Apply derivatives of Equation (19) into Equation (22), the expression solved
simultaneously resulting in Figure 9 for the variation of total capacity as a function of
phase flow ratio:

Figure9. Total Capacity vs. Phase flow ratio

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CHE-396 Senior Design Extraction

The total capacity may be read directly from the figure for a given phase flow ratio
and will be essential for calculating the column diameter. The phase flow ratio is
found by:

U C MD ρC
= (23)
UD M C ρD

Step B – Determination of Characteristic Rise Velocity

The dimensionless quantity [(u0µCρC)/(σ∆ρ)] may be assumed to be approximately
0.01, as found by (Olney). Therefore the characteristic rise velocity for a single
droplet may be expressed as:

.01 ⋅σ ⋅(∆ρ)
uo = (24)
µ C ⋅ρC

Step C – Determination of the superficial velocities at 50% of flooding value

The column extractor should be operated at 50% of the flooding velocity for best
performance. The sum of the superficial velocities is found by reading the total
capacity from figure 9 and multiplying by the characteristic rise velocity then divide
the quantity by two:

(UD + U c )f 
 (u 0 )
 u0 
(UC + UD )50%Flooding = (25)
2

Step D – Determination of the Total Volumetric Flowrate

The total volumetric flow rate is a function of the mass flow rates:

UD U C 
Q total = 
ρ + ρ  (26)
 D C 

Step E – Determination of Column Cross-Sectional Area

The cross-sectional area is the total mass flowrate divided by the sum of the
superficial velocities at 50% of flooding:

Q Total
AC = (27)
(Uc + Ud )50%Flood
Step F – Determination of Column Diameter
The column diameter may be found from the cross-sectional area:

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CHE-396 Senior Design Extraction

1
 4 A c 2
DT = 
 
 (28)
 π 

Step 7. Determining the Height of the Column [1]

• HETS (Height Equivalent to a Theoretical Stage) will be considered since it can be

applied directly to determine column height from the number of equilibrium stages.

• For a well designed and efficiently operated column, experimental data suggest the
dominant physical properties influencing HETS are:
• Interfacial tension
• Phase viscosities
• Density difference between phases

• HETS is best estimated by conducting small-scale laboratory experiments with the

systems of interest to determine the diameter of the column as discussed in step 6.

• These values are scaled to commercial-size column by assuming that the HETS varies
with the column diameter raised to an exponent, which may vary from .2 to .4
depending on the type of system. For the general approximation in step A, the
exponent is arbitrarily set at 1/3. Figure 10 plots HETS for columns and rotary
contactor

Figure 10. HETS as a function of diameter vs. interfacial tension

• Height Calculation Procedure

Step A - Find Value of HETS/DT1/3

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CHE-396 Senior Design Extraction

Using Figure 10 to determine the value (x) of HETS/DT1/3 at a specified interfacial

tension for the component system.

Step B - Solve for HETS

The value of (x) is known from above as well as the column diameter:

HETS = (x )⋅D T
1/ 3

(29)
Step C - Determine the Height of the Column
The total height of the column is derived from the number of equilibrium stages
derived in Step 4 multiplied by the HETS:

Total Height = (HETS)(Number of Equilibrium Stages) (30)

To compare calculated results to the performance of several types of extractor column

(Seader) has provided average values of HETS and the sum of superficial velocities
(see Table 3).

Table 3. Performance of Several Types of Column Extractors

Extractor Type 1/HETS, (m-1) UD+Uc, (m/hr)

Packed Column 1.5 – 2.5 12 – 30
Sieve-Plate Column .8 – 1.2 27 – 60
Rotating Disk Contactor 2.5 – 3.5 15 – 30
Karr Column 3.5 – 7.0 30 – 40

Properties
The following are a partial list of the needed physical properties in liquid-liquid
extraction separations. It is by no means complete, other properties will be needed for
some of the calculations, and especially those needed to size the diameter of the column.
It is however complete as it relates to the described theory.

• Temperature plays a smaller role in extraction than in other separation processes. It

is only dependent upon the temperatures of the streams fed into the column. There is
not a heating requirement for the process and ∆H of mixing is generally insignificant.
For these reasons, extraction can be regarded as an isothermal process.

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CHE-396 Senior Design Extraction

• Pressure also plays only a small role in extraction. When combined with the
temperature considerations it is only necessary that the mixture remain in the two-
phase liquid region. The fact that extraction processes can be run at isothermal and
isobaric conditions is quite beneficial to the phase stability of the system. Phase
stability from a thermodynamic standpoint is temperature and pressure dependent and
since these are not changing the stability of the phases will not change.

• Activity coefficients are the most important physical property in the extraction
process. The reason for this is that these are used to determine the miscibility of the
solute in both of the solvents involved. While there are many different equations
available to determine a particular activity some are better than others for our
purposes. When working with liquid-liquid systems the NRTL and the UNIFAC
models are the most accurate in predicting the activities of the liquids involved.
Although better than such predictive models such as Van Laar or Margules they still
fall short of perfection. Once a predictive model has been plotted on a diagram it will
most likely be necessary to fix the exact equilibrium line experimentally for the most
accurate data. The activity coefficients also determine the partition factor which will
determine whether or not a good separation is possible.

• Viscosity is a property that cannot be overlooked, its presence appears in two

different areas, flooding and choice of equipment. Flooding is a phenomenon that can
occur in extraction just as it can for other unit operations we will encounter. Viscosity
is also valuable in the determination of what type of system to use for extraction.
Components having a high viscosity cannot be used in spray or packed columns.

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CHE-396 Senior Design Extraction

Costs
Several economic trade-off exist for the design of an extraction process. The total
cost of the process will be directly related to the key extraction design variables and type
of extraction equipment utilized. The following is a brief analysis of several design
variables that effect the economic balance:

Ø At a fixed solvent feed ratio, the amount of solvent extracted increases with increased
number of trays. Thus, the value of the unextracted solute may be balanced against
the cost of the extraction equipment required to recover it.
Ø For a fixed extent of reaction, the number of stages required decreases as the solvent
rate or reflux ratio increases. The capacity of the equipment necessary for handling
the larger liquid flow must increase with the larger reflux rate. Thus, the cost of the
equipment passes through a minimum when the minimum number of stages are
utilized.
Ø As reflux ratio and solvent rates are increased the extract solutions become more
dilute. Therefore, the cost of solvent removal is increased as well as the operating
cost for increased utilities.

As a result of these economic balances the total annualized cost (investment &
operating costs) must pass through a minimum at the optimum solvent reflux rate.
Further cost must be considered for the recovery of the saturated raffinate product as well
as the extract.
Cost models have been developed for the various types of extractor design. The
following are models for a column type extractor, mixer-settler, and continuous
centrifugal extractor.

Ø Column Type Extractor

Douglas documents cost correlations for column in general. [5] The capital cost refers
to the purchase cost plus the installation cost of the column:

M & S 
Capital Cost of Column $ =  (
101.9D
1.066 .802
H )
(2.18 + Fc )
 280 

23
CHE-396 Senior Design Extraction

(31)
Where D = diameter (ft), H = height (ft)
Fc = cost factor = Fp (pressure cost effects) + Fm (material cost effects)
(These values may be found in Douglas)

Depending on the column extractor type, trays or packing internals may be used.
Douglas has supplied a cost model for the purchase and installation of these materials
based upon correction factors to the following model:

M & S 
Capital Cost of Internals $ =  4.7D H ⋅Fc
1.55
 280 
(32)
The correction factor is the sum of the correction factors for the spacing, internal
type, and internal material. [5]
The total capital cost is the capital cost of the column plus the capital cost of the
internals. To annualize this investment, specify a payback period n, and divide the
total capital cost over this time period:

Capital Cost of Column + Capital Cost of Internals 

Total Annualized Capital Cost =  
 n 
(33)
Operating costs add to the at Total Annualized Cost (TAC). The operating costs:

 .04$ M & S 

Electicity =   
kWhr  600 
 20000$ M & S 
Labor =   
 Worker ⋅Yr  600 
3%Total Capital Cost 
Maintenance =  
 Yr 
(34,35,36)
including the utilities, labor, and maintenance costs. Pratt has estimated these cost as
of 1977. Inflation of these values may be accounted for using the M&S index:
Therefore the Total Annualized Cost for a column type extractor is:
Total Annualized Cost (TAC) = Total Annualized Capital Cost + Operating Cost
(37)

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CHE-396 Senior Design Extraction

Ø Mixer-Settler Type Extractor

Woods establishes a cost model for mixer-settler extractor which includes: carbon-
steel mixer-settler, labor and maintenance, explosion-proof motor, drive, piping,
concrete, steel, instruments, electrical, insulation, and paint:
n
 Desired Capacity  M & S 
Capital Cost = Reference Cost
Reference Capacity 
  600 
  
.70
Desired Capacity  M & S 
Capital Cost = 14.8 ×103    
 10 ×103   600 
(38,39)
The desired capacity must be specified in terms of Mgal/yr. These capital cost must
be added to the operating cost as described in the column extractor section.

Ø Continuous Centrifugal Extractor

Woods establishes a cost model for continuous centrifugal extractors based upon a
centrifugal extractor made of 316 stainless steel including flexible connectors,
explosion-proof motor, variable speed driver, instrumentation, pumps, labor, and
maintenance:

.58
3 Desired Capacity  M & S 
Capital Cost = 51×10    
 2.2 ×103
 600 
(40)
The desired capacity is in units of Mgal/yr. As above, the capital cost must be added
to the operating cost as defined in the column extractor section.

Case Study
Question for Liquid-Liquid Extraction
An extractor is to be designed such that acetone will be extracted from a feed mixture of
30% acetone and 70% ethyl acetate. Water will be used to extract the acetone, and the
water is assumed to be pure. The raffinate will have a composition of 7% acetone and
93% ethyl acetate (point B), while the extract will have a composition of 12% acetone,
8% ethyl acetate, and 80% water (point D). A ternary phase diagram is given for this

25
CHE-396 Senior Design Extraction

system, along with corresponding tie lines. The feed to the column has a flowrate of
20,000 kg/hr and the solvent-to-feed ratio is assumed to be 1.75.

Determine:
• The number of stages needed for this problem…
• The solvent, extract and raffinate flowrates…
• The height and diameter of the column…
• The cost of this trayed column…

Solution to Liquid-Liquid Extraction Case Study

• The number of stages needed for this problem…

The number of stages can be stepped-off in a fashion analogous to that presented

in the Theory Section of this paper. the operating line is drawn from S to B and is
extended to the left of the diagram. Another line is drawn from F to D and intersects the
operating line from S to B – this is the operating point. The tie line from point D is
followed to the other side of the equilibrium curve. From this point, another operating
line is drawn back to the operating point. The point at which is line intersected the
extract side of the equilibrium curve is located, and the tie line is drawn back to the other
side of the curve to obtain another point from which to draw another operating line. The
total number of stages is four once all the equilibrium lines have been drawn.

26
CHE-396 Senior Design Extraction

• The solvent, extract and raffinate flowrates…

Since the basis behind extraction processes is mass conservation -- as it is with

any process – a material balance is done around the process. This is analogous to
the mass balances done in the Theory Section (Feed + Solvent = Extract +
Raffinate). In addition, we recall that S/F = 1.75. From the design specifications,
it follows that

S
= 1.75 S = 1.75 ⋅F = 1.75(20,000 kg/hr) = 35,000 kg/hr
F

After determining S (the solvent feed rate), we can complete the necessary
material balances to solve for R (the raffinate rate) and E (the extract rate):

F+S=E+R

Balance on acetone:

0(S) + (0.30)(20,000) = (0.07)(R) + (0.12)(E)

Balance on water:

0(F) + (1.0)(35,000) = (0)(R) + (0.80)(E)

This yields:

E = 43,750 kg/hr
R = 10,714 kg/hr

It is seen that this method does not give a 100% mass balance. This is accounted
for by assuming that the graphical method is not as accurate as one would like,
but it practical for our design purposes.

• The height and diameter of the column…

The first step is to establish all necessary physical properties. Much of this
information is available in Lange’s Handbook of Chemistry. Subscript D is the
dispersed liquid phase (organic) and subscript C is the continuous liquid phase
(inorganic).

ρAcetone = 791 kg/m3 ρEthyl Acetate = 789 kg/m3

Use the organic phase composition data from above to find density of the organic
phase:

27
CHE-396 Senior Design Extraction

ρOrganic = (.3)(791) + (.7)(789) = 789.6 kg/m3 σ = .001955 lbf/ft

µ
ρInorganic = 1000 kg/m3 C = .000021 lbf s

Calculate the phase flow ratio from the mass flow rates and densities

 kg  kg 
 20000  1000 3 
UD MD ρC  hr  m  = .72369
= =
UC M C ρD  kg  kg 
35000 789.6 3 
 hr  m 

Using Figure 9 and the phase flow ratio find the total column capacity

(UC + UD )f
= .34 (D-less)
u0

Determine the characteristic rise velocity

 lbf g 
.01⋅.001995 ⋅.2104 
.01⋅σ⋅(∆ρ)  ft cm 3  = .19988 ft
uo = =
µ C ⋅ρC  lbf ⋅s g  s
 .000021 2 ⋅1.0 
 ft cm 3 
Calculate superficial flooding velocity

(UD + UC)f = (.34)(.19988 ft/s) = .067959 ft/s

Calculate superficial velocity at 50% of flooding velocity

(UD + UC)50% Flooding Velocity = (.067959 / 2)ft/s (3600 s/min) = 122.327 ft/hr

Determine the total volumetric flowrate:

 kg kg 
 
UD UC   20000 hr 35000 hr 35.3146ft 3  ft 3
Q total = + = +   = 2130.5
ρ  kg  
 D ρC   kg
789.6 3 1000 3 
m3  hr
 m m 

Determine cross-sectional area:

 ft 3 
 2130.5 
Q Total
AC = = hr  = 17.4165ft 2
(Uc + U d )50%Flood  ft 
122.327 
 hr 
Calculate the diameter of the column:

28
CHE-396 Senior Design Extraction

1 1
 4A 2  4 ⋅17.4165 2
DT =  c  =   = 4.70ft
 π   π 

To find the height of the column use figure 10 with an interfacial tension of 29.15
dyne/cm. This results in a value of 6.4 for the y-axis.

HETS/DT1/3 = 6.4

Solve for HETS using the determined column diameter

HETS = 6.4 ⋅D T = 6.4 ⋅4.71/ 3 = 10.728ft

1/ 3

Thus, the column height is:

Total Height =(HETS)(Number of Equilibrium Stages) = (10.728)(4) = 42.9ft

Extraction Column Dimensions

Diameter, ft 4.70
Height, ft 42.9

• The cost of this trayed column…

Using Douglas [5] correlation for capital costs:

Column Cost $ = 
1061
(
101.9 ⋅4.7
1.066
)
42.9.802 = $40,965.50
 280 
1061
Tray Cost $ =  (
 4.7 ⋅4.7 42.9 = $8411.32
1.55
)
 280 
Assuming a payback period of six years, n = 6

Total Annualized Capital Cost = ($40,965 + $8411) / 6 years = $8229.33 / yr.

The operating cost of electricity, labor, and maintenance are negligible in contrast
to the operating cost associated with solvent recovery through further separations.
Further, introducing a new material into the process to extract a solute result in
new material cost and is a function of solvent recovery.

Total Annual Cost = $8229 + operating costs + solvent & product recovery cost

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CHE-396 Senior Design Extraction

Alternatives
In the case where extraction does not apply for a certain feed, we must consider
our other options. Alternatives to extraction include the following:
1. Distillation
• Extractive
• Azeotropic
• Reactive
2. Crystallization
3. Adsorption
In discussing distillation, we must evaluate under what conditions extraction
would be valid over distillation. Extraction is preferred to distillation for the following
reasons: [1]
• Case of dissolved or complexed inorganic substance in organic or
aqueous solutions
• Removal of a component present in small concentrations
• A high-boiling component is present in relatively small quantities in a waste stream
• Recovery of heat-sensitive materials, where extraction may be less expensive than
vacuum distillation
• Case of separation of a mixture according to chemical type rather than relative
volatility
• Case of the separation of close-melting or close-boiling liquids, where the difference
in solubilities can be exploited
• Case of mixtures that form azeotropes
If the situation does not meet any of the above reasons, then distillation can be
considered. For example, if the boiling points of two components where not close, then
distillation would be preferred over extraction.
Using crystallization over extraction, one would have to consider the difference in
the freezing points of the components and also have information for a solid-liquid phase
diagram. This diagram is necessary to determine the eutectic point, which is the point
where one component becomes fused into the other.

30
CHE-396 Senior Design Extraction

Liquid adsorption could be used for certain components by contacting a liquid

mixture with a porous solid. The solid acts as the adsorbent and must be insoluble in the
liquid mixture. There is no available theory regarding adsorption equilibrium curves;
however, experimental data at a fixed temperature is used for plotting curves

References
1. Seader, J.D. and Henley, E.J. Separation Process Principles. John Wiley and Sons.
New York, 1999.

2. Strigle, R.F. Packed Tower Design and Applications. Gulf Publishing Company.
Houston, 1994.

3. Sandler, S.I. Chemical and Engineering Thermodynamics. John Wiley and Sons.
New York, 1998.

4. Treybal, R.E. Mass Transfer Operations. McGraw-Hill. New York, 1980.

5. Douglas, J.M. Conceptual Design of Chemical Processes. McGraw-Hill. New York,

1988.

6. Hanson, C., Baird, M.H.I., Lo, T.C. Handbook of Solvent Extraction. John Wiley
and Sons. New York, 1983.

7. Reid, R.C., Prausnitz, J., Poling, B. The Properties of Gases and Liquids. 4th Ed.
McGraw-Hill. New York, 1987.

31