CHE-396 Senior Design

Extraction
Liquid-Liquid Extraction
Senior Design CHE 396
Matrix Corporation Zachary Fijal Constantinos Loukeris Zhaleh Naghibzadeh John W
alsdorf
Prof. Andreas Linninger Akhil Jain
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CHE-396 Senior Design
Extraction
Table of Content
Introduction ___________________________________________________________ 3 Flows
heet _____________________________________________________________ 3 Process Ope
ration ______________________________________________________ 4 Limitations ____
________________________________________________________ 5 Applicability _______
____________________________________________________ 6 Theory___________________
_____________________________________________ 7 Theory – Ternary Phase Diagram____
______________________________________ 8 Theory - General Flow Sheet for Extract
or 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 difference
s rather than differences in physical properties. The basic principle behind ext
raction involves the contacting of a solution with another solvent that is immis
cible with the original. The solvent is also soluble with a specific solute cont
ained 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 transfe
r of the solute from the solution to the solvent occurs. Further separation of t
he extracted solute and the solvent will be necessary. However, these separation
costs may be desirable in contrast to distillation and other separation process
es 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 inp
ut streams consist of a solution feed at the top containing the solute to be ext
racted and a solvent feed at the bottom which extracts the solute from the solut
ion. The solvent containing the extracted solute leaves the top of the column an
d is referred to as the extract stream. The solution exits the bottom of the col
umn containing only small 3
CHE-396 Senior Design
Extraction
amounts of solute and is known as the raffinate. Further separation of the outpu
t streams may be required through other separation processes.
Process Operation
There are certain design variables that must be assigned in an extraction proces
s. Ø Operating Temperature Ø Operating Pressure Ø Feed Flow Rate Composition Temperatu
re of entering stream Pressure of entering stream As in many separation processe
s, the pressure and temperature conditions play a large role in the effectivenes
s of the separation. In order for a good split of the feed the pressure and temp
erature must be such so as to ensure that all components remain in the liquid ph
ase. 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 en
ough 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 c
an be problematic. This is however generally not the case since one of the bigge
st benefits in the extraction process is that it can be done at ambient pressure
s and temperatures. In many applications, a separation process is desired where
an extreme temperature will destroy the desired product such as the pharmaceutic
al industry. For these applications, extraction is ideally suited, since the onl
y 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 ext
raction and this has to do with the volumes involved for effective extraction. T
he 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 ne
ed 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 pro
cess in order to recycle the solvent.
Limitations
We must consider the under what extremes extraction can be used as separation pr
ocess. 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 densitie
s 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 t
he solvent to dissolve the maximum amount of solute and the minimum amount of th
e carrier. • Large distribution coefficient to reduce the theoretical number of st
ages contributing to a greater efficiency • Low viscosity increases the capacity o
f the extraction column and does not allow for the settling rate of dispersion t
o 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 ma
intain rapid mass transfer throughout the extraction process. • Low interfacial te
nsion and viscosity leads to the formation of an emulsion. 3. Temperature prefer
red to be higher since solubility increases, but temperature not higher than the
critical solution temperature. 4. Pressure for condensed system must be maintai
ned below the vapor pressure of the solutions such that a vapor phase will not a
ppear 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 com
position 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 wo
uld apply for the situation at hand. The specifications for each of these differ
ent systems are relatively the same. The following design constraints should be
placed on each system in order to optimize the individual process -- (1) maximiz
e surface area of mass transfer, and (2) adjust flow feeds for maximum solute re
covery. [2] In general, there are three main types of extractors to focus on: • Mi
xer-settlers Mixer-settlers are used when there will only be one equilibrium sta
ge 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 wil
l be separated. The downfall to this type of extractor is that it requires a lar
ge-volume vessel and a high liquid demand. [1] • Contacting columns Contacting col
umns are practical for most liquid-liquid extraction systems. The packings, tray
s, or sprays increase the surface area in which the two liquid phases can interm
ingle. This also allows for a longer flow path that the solution can travel thro
ugh. 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 fo
r systems in which the density difference is less than 4%. In addition, this typ
e 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 guid
elines for operation and selection. A more detailed view can be found in. [1]
Table 1. Advantages and disadvantages of the various liquid-liquid extractor typ
es [1].
Unit of Operation Mixer-Settler • • • •
Advantages Efficient Low head room Induces good contacting Can handle any number
of stages • Small investment costs • Low operating costs
Disadvantages • Large floor • High set-up costs • High operation costs • High head room •
Difficult to scale up from lab • Less efficient than mixer-settler • Difficult to se
parate small density differences • Does not tolerate high flow ratios • High set-up
cost • High operating and maintenance costs • Cannot handle many stages
Columns (without agitation)
Columns (with agitation)
• Good dispersion • Low investment costs • Can handle any number of stages • Can separat
e small density differences • Short holding time • Small liquid inventory
Centrifugal Extractors
Theory
When talking about liquid-liquid extraction, liquid-liquid equilibrium must be c
onsidered. This is best represented by equating the chemical potential of both l
iquid phases:
µi
LI
= µi
LII
(1)
This relationship reduces to an expression, which is dependent only on the liqui
d mole fractions and activity coefficients:
γ xi i
LI LI
= γ xi i
LII
LII
(2)
We can use activity coefficient models, such as UNIFAC (UNIquac Functional- roup
Activity Coefficient), UNIQUAC (universal quasichemical), and NRTL (nonrandom
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CHE-396 Senior Desi n
Extraction
two-liquid) to determine the mole fractions. All three models above apply for li
quidliquid equilibrium, it rolls down to which is easier to use and what propert
ies we have available. For a multi-component system, the UNIQUAC equation for th
e liquid-phase activity coefficient is represented as follows: [3]
ln γ= ln γ(combinator ial ) + ln γ(residual ) i i i
(3)
The combinatorial and residual activities are based on the statistical mechanica
l theory and allowed the local compositions to result from the size and ener y d
ifferences between the molecules in the mixture. The relationships for these two
activities are made available to us throu h.
Theory – Ternary Phase Dia ram
We then are able to relate this data from the activity into a ternary phase dia
ram. Ternary phase dia rams are unique in that they show all three components of
a reactor system on one plot. There are eneral principles that overn ternary
phase dia rams, and those are the followin : • Sum of the perpendicular distances
from any point within the trian le to the three sides equals the altitude of the
trian le. • Each apex of the trian le represents one of the pure components. • Any
point of a side of the trian le represents a binary mixture. • Lines may be drawn
parallel to the sides of the equilateral trian le for the plottin of the compos
itions.
Fi ure 2. Phase dia ram for a three component system. [2]
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CHE-396 Senior Desi n
Extraction
The ternary phase dia ram may be constructed directly from experimental data. Th
e saturation curve (miscibility boundary), represented by JDPEK in Fi ure 2, can
be obtained experimentally by a cloud point titration. For example, a solution
containin 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 oc
curs. Then the composition is know for the mixture of the three components and c
an plotted onto the ternary phase dia ram. [1] Tie lines are lines that connect
points on the miscibility boundary. The tie lines may also be presented onto the
ternary phase dia ram from an experiment. A mixture may be prepared with compos
ition that of point H (40% A, 40% C, 20% B) from Fi ure 2. If we allow it to equ
ilibrate, then we can chemically analyze the final extract (E) phase and the raf
finate (R) phase. [1] Point F is a feed composition into the extractor while poi
nt S is the solvent feed to the extractor. Point H represents the composition of
the two feeds at equilibrium. This point is determined by summin the feed (F)
and solvent (S) compositions for each component. Points R and E are the composit
ions of the raffinate and extract from the unit, respectively, and the line betw
een 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 th
e 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 equilibri
um between all three components. The area under the curve is the re ion where tw
o 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 operati
n line. Althou h this dia ram is not the basic theory behind liquid-liquid extr
action, it is helpful to review this procedure before continuin with an in-dept
h discussion. In addition to the above-mentioned considerations, equilibrium con
straints must be satisfied. This implies that γ =γ AE AR (4)
where γ is the activity coefficient for the solute A in the extract and γ is the act
ivity AE AR coefficient of A in the raffinate. This condition is one of the most
important aspects of
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CHE-396 Senior Desi n
Extraction
liquid-liquid extraction since it allows for calculations and assumptions that b
ased on equilibrium systems (e. . the ternary phase dia ram). 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 xR
*
(5)


One of the last essential points to the theory ehind liquid-liquid extraction i
s mass transfer. The driving force for this mass transfer arises from the concen
tration difference of the solute in
each of the solvents. In general, it is assu
med that the system is at an equili rium state
when mass transfer is occurring.
Solute fluxes in the raffinate and extract can e expressed as N = KE⋅ (xEi - xE)
A⋅ N = KR⋅ (xRi - xR) A⋅
(6)
(7)
where KE and KR are the overall mass transfer coefficients, A is the cross-secti
onal area, xE and xR are the concentrations of solute in the extract and raffina
te 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 gen
eral flowchart can e utilized for almost any process. Figure 3 (a) illustrates
a general ternary diagram for a desired solute (C), an extracting
solvent (B) an
d a carrier solvent (A). In this process, depicted in Figure 3 ( ), we will assu
me 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. Ta le 2 summarize

s the components, flows, and unknowns of such a system. The
following steps can
e utilized to determine the extract composition

and the num er of stages needed
for most liquid-liquid extraction pro lems.
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CHE-396 Senior Design
Extraction
(a)


( )
Figure

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



Ta le 2. Ta le summarizing the general extraction phase diagram and process diag
ram in Figure 3.
Stream F S
Components A and C B
E R
A with large C concentration B with small C concentration
Is the composition given? Yes Yes, usually pure or relatively pure component B N
o, determined from calculation Yes, recovery amount needed of solute C from desi
gn specifications


Is the flow rate

given? Yes No, determined y calculation

No, determined from co
mponent mass alance No, determined from component mass alance
where: is the carrier solvent A is

the solvent used to extract a certain B compo
nent is the component that is to e extracted from C A
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CHE-396 Senior Design
Extraction
Step 1:
Determine the
minimum solvent-to-feed ratio (S/F)min. This
calculation n
eeds to e completed


ecause E1, the extract composition, needs to e found.
Thi
s procedure

egins y drawing an operating line from S to R that extends

eyond
the oundaries of the diagram. Next, each tie line is considered to e a pinch p
oint, 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 een est
a lished, a line is drawn
from Pmin, through F (the feed composition), and to th
e other side of the equili rium curve.
Figure 4. Sample Ternary Diagram used to calculate Pmin for Step 1 of the genera
l 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 alance around the system can e
u
tilized to determine the mixing point (point M in Figure 5). This is completed
y saying that:
F + Smin = R + E1 = M
(8)


Solving for Smin/F, we will o tain the minimum solvent-to-feed ratio as
S min ( x A )F − ( x A )M = F ( x A )M − ( x A ) S
(9)
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CHE 396 Senior Design
Extraction
where (xA)i ’ are the fractions of A (the solute) in the feed (F), the solvent (S)
, and s at the mixing point (M). Generally, a solvent to feed ratio for an extra
ction 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 eas
ily 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. T
his ) 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 repr
esents 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 s
olvent (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 op
erating 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 t
he other side of the equilibrium curve will give the composition of an intermedi
ate raffinate stage. Another operating line is drawn from the operating point, t
hrough 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, t
he 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’ and xB’ are the fractions of A and B for the specified streams, s s an
d 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 o
f equations. Step 6. Determination of Extraction Column Diameter [1] • The diamete
r of the column must be large enough to permit two phases to flow counter curren
tly through the column without flooding. • Estimation of column diameter for liqui
d –liquid contacting devices is far more complex and uncertain than liquid vapor c
ontactors due the larger number of important variables. • Variables necessary for
calculating extractor column diameter include: • Individual phase flow rates • Densi
ty differences between the two phases • Interfacial tension • Direction of mass tran
sfer • Viscosity and density of continuos phase • Geometry of internals • Column diame
ter may be best determined through scale up of laboratory test runs. The necessa
ry experimental data are obtained by: • Use laboratory or pilot plant test unit wi
th 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 ph
ase are made. • The sum of these velocities may be assumed to hold constant for la
rger scaled up commercial units. • The superficial velocity data will be used to c
alculate the column diameter through the following correlation derivation. • The f
ollowing notation is utilized in the correlation derivation: • uD = Actual average
velocity of the dispersed (droplet) liquid phase • uC = Actual average velocity o
f the continuous liquid phase • UD = Superficial velocity of the dispersed liquid
phase • UC = Superficial velocity of the continuous liquid phase • φ = Volume raction
o  dispersed liquid phase in column D • ur = Average droplet rise velocity relati
ve to the continuous phase • C = Capacity Parameter
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CHE-396 Senior Design
• • • • • • • • • • • • •
Extraction
CD = Drag Coe icient ρM = Density (volumet ic mean) ρD = Density of dispe sed phase
ρC = Density of continuous phase f{1-φ } = Factor which accounts or hindered risin
g e ect o  other D droplets u0 = Characteristic rise velocity or a single drop
let µ = Viscosity (subscript will determine component) σ = Interfacial ten ion ( ub 
cript will determine component) AC = Column cro  ectional area DT = Column dia
meter g = Acceleration due to gravity MD = Ma  flowrate of the di per ed pha e
MC = Ma  flowrate of the continuou  pha e
Figure 7. Counter-current flow  of di per ed and continuou  liquid pha e in a co
lumn.
• Diameter Calculation Procedure Step A – Determination of Column Total Capacity Fig
ure 7 illu trate  lower den ity liquid droplet  ri ing through the den er downwa
rd flowing continuou  liquid pha e. The actual average velocitie  of each compon
ent relative to the column wall are:
uD =
UD φ D
(13)
uC =
UC 1− φ D
(14)
The average droplet rise velocity relative to the continuous phase is the sum o 
these equations:
ur =
UD Uc + φ 1− φ D D
(15)
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CHE-396 Senior Design
Extraction
This relative velocity may also be expressed in terms o  the orces acting upon
the droplet including drag orces, gravitational orces, and buoyancy orces. Th
ese variables are combined into one parameter called C:
4d p g (16) C= 3C D I  the droplet diameter dp is not known C may be obtained
ugh a correlation provided in Seader [1] equation (6-42), which was developed th
rough experimental data rom operating equipment. Taking into account density an
d rising e ects o  other components the relative velocity may be expressed as:
1 ρ − ρD 2 (1 − φ )2  {1 − φ } u r = C C (17) D D ρ C F om expe imental data,
hat the ight-hand of the equation may be exp essed as: 1
u  = u 0 (1 − φD )
(18)
Eliminating the relative velocity by combining equation (17) and (18) gives:
UD UC + = u 0 (1 − φ ) D 1− φ φ D D
(19)
This equation is a cubic in φ . A graph o  UD/u0 vs. φ may be generated at some D D
value o  UC/uo. This graph represents the holdup curve or the liquid-liquid ext
raction column. A typical value o  UC/uo may be assumed 0.1.
Figure 8. Typical holdup curve or liquid-liquid extraction
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CHE-396 Senior Design
Extraction
At ixed UC, an increase in UD results in a increased value o  holdup φ until the
D looding point is reached at the maximum o  Figure 8:
∂ D U ∂ D φ
=0 UC
(20)
On the other hand, with UD ixed, UC may be increased until the looding point i
s achieved at:
U ∂ C ∂ D φ
=0 UD
(21)
Inserting these derivatives into equation (19) results in the ollowing expressi
on or φ at looding conditions. The subscript  denotes looding: D
U 1 C + 8 − 3 U (φ)  = D U 4 C − 1 U D
.5
(22)
Apply derivatives of Equation (19) into Equation (22), the expression solved sim
ultaneously resulting in Figure 9 for the variation of total capacity as a funct
ion 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 r
atio and will be essential for calculating the column diameter. The phase flow r
atio is found by:
U C MD ρC = UD M C ρD
(23)
Step B – Dete mination of Cha acte istic Rise Velocity The dimensionless quantity
[(u0µCρC)/(σ∆ρ)] may be assumed to be app oximately 0.01, as found by (Olney). The efo e t
he cha acte istic ise velocity fo  a single d oplet may be exp essed as:
uo =
.01 ⋅σ ⋅(∆ρ) µ C ⋅ρC
(24)
Step C – Dete mination of the supe ficial velocities at 50% of flooding value
The column ext acto  should be ope ated at 50% of the flooding velocity fo  best
pe fo mance. The sum of the supe ficial velocities is found by eading the tota
l capacity f om figu e 9 and multiplying by the cha acte istic ise velocity the
n divide the quantity by two:
(UC +
UD )50%Flooding
(UD + U c )f u0 = 2
(u 0 )
(25)
Step D – Dete mination of the Total Volumet ic Flow ate The total volumet ic flow
ate is a function of the mass flow ates:
U U Q total = D + C ρ D ρC
(26)
Step E – Dete mination of Column C oss-Sectional A ea The c oss-sectional a ea is
the total mass flow ate divided by the sum of the supe ficial velocities at 50%
of flooding: AC = Q Total (Uc + Ud )50%Flood (27)
Step F – Dete mination of Column Diamete  The column diamete  may be found f om th
e c oss-sectional a ea:
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CHE-396 Senio  Design
4 A 2 DT = c π
1
Extraction
(28)
Ste 7. Determining the Height of the Column [1] • HETS (Height Equivalent to a Th
eoretical Stage) will be considered since it can be alied directly to determin
e column height from the number of equilibrium stages. • For a well designed and e
fficiently oerated column, exerimental data suggest the dominant hysical ro
erties influencing HETS are: • Interfacial tension • Phase viscosities • Density diffe
rence between hases • HETS is best estimated by conducting small-scale laboratory
exeriments with the systems of interest to determine the diameter of the colum
n as discussed in ste 6. • These values are scaled to commercial-size column by a
ssuming that the HETS varies with the column diameter raised to an exonent, whi
ch may vary from .2 to .4 deending on the tye of system. For the general aro
ximation in ste A, the exonent is arbitrarily set at 1/3. Figure 10 lots HETS
for columns and rotary contactor
Figure 10. HETS as a function of diameter vs. interfacial tension • Height Calcula
tion Procedure Ste 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 secified interfac
ial tension for the comonent system. Ste B - Solve for HETS The value of (x) i
s known from above as well as the column diameter:
HETS = (x )⋅D T
1/ 3
(29) Ste C - Determine the Height of the Column The total height of the column
is derived from the number of equilibrium stages derived in Ste 4 multilied by
the HETS: Total Height = (HETS)(Number of Equilibrium Stages) (30)
To comare calculated results to the erformance of several tyes of extractor c
olumn (Seader) has rovided average values of HETS and the sum of suerficial ve
locities (see Table 3). Table 3. Performance of Several Tyes of Column Extracto
rs Extractor Tye Packed Column Sieve-Plate Column Rotating Disk Contactor Karr
Column 1/HETS, (m-1) 1.5 – 2.5 .8 – 1.2 2.5 – 3.5 3.5 – 7.0 UD+Uc, (m/hr) 12 – 30 27 – 60 1
– 30 30 – 40
Proerties
The following are a artial list of the needed hysical roerties in liquid-liq
uid extraction searations. It is by no means comlete, other roerties will be
needed for some of the calculations, and esecially those needed to size the di
ameter of the column. It is however comlete as it relates to the described theo
ry. • Temerature lays a smaller role in extraction than in other searation roc
esses. It is only deendent uon the temeratures of the streams fed into the co
lumn. There is not a heating requirement for the rocess and ∆H of mixing i  gener
ally in ignificant. For the e rea on , extraction can be regarded a  an i otherm
al proce .
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CHE-396 Senior De ign
Extraction
• Pre ure al o play  only a mall role in extraction. When combined with the temp
erature con ideration  it i  only nece ary that the mixture remain in the twoph
a e liquid region. The fact that extraction proce e  can be run at i othermal a
nd i obaric condition  i  quite beneficial to the pha e tability of the y tem.
Pha e tability from a thermodynamic tandpoint i  temperature and pre ure dep
endent and ince the e are not changing the tability of the pha e  will not cha
nge. • Activity coefficient  are the mo t important phy ical property in the extra
ction proce . The rea on for thi  i  that the e are u ed to determine the mi ci
bility of the olute in both of the olvent  involved. While there are many diff
erent equation  available to determine a particular activity ome are better tha
n other  for our purpo e . When working with liquid-liquid y tem  the NRTL and
the UNIFAC model  are the mo t accurate in predicting the activitie  of the liqu
id  involved. Although better than uch predictive model  uch a  Van Laar or Ma
rgule  they till fall hort of perfection. Once a predictive model ha  been plo
tted on a diagram it will mo t likely be nece ary to fix the exact equilibrium
line experimentally for the mo t accurate data. The activity coefficient  al o d
etermine the partition factor which will determine whether or not a good eparat
ion i  po ible. • Vi co ity i  a property that cannot be overlooked, it  pre ence
appear  in two different area , flooding and choice of equipment. Flooding i  a
phenomenon that can occur in extraction ju t a  it can for other unit operation
 we will encounter. Vi co ity i  al o valuable in the determination of what typ
e of y tem to u e for extraction. Component  having a high vi co ity cannot be
u ed in pray or packed column .
22
CHE-396 Senior De ign
Extraction
Co t 
Several economic trade-off exi t for the de ign of an extraction proce . The to
tal co t of the proce  will be directly related to the key extraction de ign va
riable  and type of extraction equipment utilized. The following i  a brief anal
y i  of everal de ign variable  that effect the economic balance: Ø At a fixed o
lvent feed ratio, the amount of olvent extracted increa e  with increa ed numbe
r of tray . Thu , the value of the unextracted olute may be balanced again t th
e co t of the extraction equipment required to recover it. Ø For a fixed extent of
reaction, the number of tage  required decrea e  a  the olvent rate or reflux
ratio increa e . The capacity of the equipment nece ary for handling the large
r liquid flow mu t increa e with the larger reflux rate. Thu , the co t of the e
quipment pa e  through a minimum when the minimum number of tage  are utilized
. Ø A  reflux ratio and olvent rate  are increa ed the extract olution  become m
ore dilute. Therefore, the co t of olvent removal i  increa ed a  well a  the o
perating co t for increa ed utilitie .
A  a re ult of the e economic balance  the total annualized co t (inve tment & o
perating co t ) mu t pa  through a minimum at the optimum olvent reflux rate.
Further co t mu t be con idered for the recovery of the aturated raffinate prod
uct a  well a  the extract. Co t model  have been developed for the variou  type
 of extractor de ign. The following are model  for a column type extractor, mix
er- ettler, and continuou  centrifugal extractor. Ø Column Type Extractor Dougla 
document  co t correlation  for column in general. [5] The capital co t refer  t
o the purcha e co t plu  the in tallation co t of the column:
M & S 1.066 .802 Capital Co t of Column $ = H (2.18 + Fc ) 101.9D 280
(
)
23
CHE-396 Senior De ign
Extraction
(31)
Where D = diameter (ft), H = height (ft) Fc = co t factor = Fp (pre ure co t ef
fect ) + Fm (material co t effect ) (The e value  may be found in Dougla )
Depending on the column extractor type, tray  or packing internal  may be u ed.
Dougla  ha  upplied a co t model for the purcha e and in tallation of the e mat
erial  ba ed upon correction factor  to the following model:
M & S 1.55 Capital Co t of Internal  $ = 4.7D H ⋅Fc 280
(32) The correction factor i  the um of the correction factor  for the pacing,
internal type, and internal material. [5] The total capital co t i  the capital
co t of the column plu  the capital co t of the internal . To annualize thi  in
ve tment, pecify a payback period n, and divide the total capital co t over thi
 time period:
Capital Co t of Column + Capital Co t of Internal  Total Annualized Capital Co t
= n
(33) Operating co t  add to the at Total Annualized Co t (TAC). The operating co
t :
.04$ M & S Electicity = kWhr 600 20000$ M & S Labor = Wor
intenance = Yr
(34,35,36) including the utilitie , labor, and maintenance co t . Pratt ha  e ti
mated the e co t a  of 1977. Inflation of the e value  may be accounted for u in
g the M&S index: Therefore the Total Annualized Co t for a column type extractor
i : Total Annualized Co t (TAC) = Total Annualized Capital Co t + Operating Co 
t (37)
24
CHE-396 Senior De ign
Ø Mixer-Settler Type Extractor
Extraction
Wood  e tabli he  a co t model for mixer- ettler extractor which include : carbo
n teel mixer- ettler, labor and maintenance, explo ion-proof motor, drive, pipin
g, concrete, teel, in trument , electrical, in ulation, and paint:
De ired Capacity M & S Capital Co t = Reference Co t Reference Capacity 600
apacity M & S Capital Co t = 14.8 103 10 103 600
.70 n
(38,39) The de ired capacity mu t be pecified in term  of Mgal/yr. The e capita
l co t mu t be added to the operating co t a  de cribed in the column extractor
ection. Ø Continuou  Centrifugal Extractor Wood  e tabli he  a co t model for con
tinuou  centrifugal extractor  ba ed upon a centrifugal extractor made of 316 t
ainle  teel including flexible connector , explo ion-proof motor, variable pe
ed driver, in trumentation, pump , labor, and maintenance:
Capital Co t =
.58 3 De ired Capacity M & S 51 10 3 600

2.2 10

(40) The de ired capacity i  in unit  of Mgal/yr. A  above, the capital co t mu 

t be added to the operating co t a  defined in the column extractor ection.
Ca e Study
Que tion for Liquid-Liquid Extraction An extractor i  to be de igned uch that a
cetone will be extracted from a feed mixture of 30% acetone and 70% ethyl acetat
e. Water will be u ed to extract the acetone, and the water i  a umed to be pur
e. The raffinate will have a compo ition of 7% acetone and 93% ethyl acetate (po
int B), while the extract will have a compo ition of 12% acetone, 8% ethyl aceta
te, and 80% water (point D). A ternary pha e diagram i  given for thi 
25
CHE-396 Senior De ign
Extraction
y tem, along with corre ponding tie line . The feed to the column ha  a flowrat
e of 20,000 kg/hr and the olvent-to-feed ratio i  a umed to be 1.75. Determine
: • The number of tage  needed for thi  problem… • The olvent, extract and raffinate
flowrate … • The height and diameter of the column… • The co t of thi  trayed column…
D
S
Solution to Liquid-Liquid Extraction Ca e Study • The number of tage  needed for
thi  problem… The number of tage  can be tepped-off in a fa hion analogou  to th
at pre ented in the Theory Section of thi  paper. the operating line i  drawn fr
om S to B and i  extended to the left of the diagram. Another line i  drawn from
F to D and inter ect  the operating line from S to B – thi  i  the operating poin
t. The tie line from point D i  followed to the other ide of the equilibrium cu
rve. From thi  point, another operating line i  drawn back to the operating poin
t. The point at which i  line inter ected the extract ide of the equilibrium cu
rve i  located, and the tie line i  drawn back to the other ide of the curve to
obtain another point from which to draw another operating line. The total numbe
r of tage  i  four once all the equilibrium line  have been drawn.
26
CHE-396 Senior De ign
• The olvent, extract and raffinate flowrate …
Extraction
Since the ba i  behind extraction proce e  i  ma  con ervation -- a  it i  wit
h any proce  – a material balance i  done around the proce . Thi  i  analogou  t
o the ma  balance  done in the Theory Section (Feed + Solvent = Extract + Raffi
nate). In addition, we recall that S/F = 1.75. From the de ign pecification , i
t follow  that
S = 1.75 F
S = 1.75 ⋅F = 1.75(20,000 kg/hr) = 35,000 kg/hr
After determining S (the olvent feed rate), we can complete the nece ary mater
ial balance  to olve 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) Thi  yield : E = 43,750 kg/hr R
= 10,714 kg/hr It i  een that thi  method doe  not give a 100% ma  balance. T
hi  i  accounted for by a uming that the graphical method i  not a  accurate a 
one would like, but it practical for our de ign purpo e . • The height and diamet
er of the column… The fir t tep i  to e tabli h all nece ary phy ical propertie 
. Much of thi  information i  available in Lange’ Handbook of Chemi try. Sub cript
D i  the  di per ed liquid pha e (organic) and ub cript C i  the continuou  l
iquid pha e (inorganic). ρAcetone = 791 kg/m3 ρEthyl Acetate = 789 kg/m3
Use the o ganic phase composition data f om above to find density of the o ganic
phase:
27
CHE-396 Senio  Design
ρO ganic = (.3)(791) + (.7)(789) = 789.6 kg/m3 ρIno ganic = 1000 kg/m3 σ = .001955 lbf
/ft µ C = .000021 lbf 
Extraction
Calculate the pha e flow ratio from the ma  flow rate  and den itie 
kg kg 20000 1000 3 UD MD ρC h m = = kg kg UC M C ρD 35000 789.6 3 h
Using Figu e 9 and the phase flow atio find the total column capacity
(UC +
UD )f
u0
= .34 (D-less)
Dete mine the cha acte istic ise velocity
lbf g . ⋅ 2104 . .01⋅ 001995 .01⋅σ⋅(∆ρ) ft cm 3 uo = = lbf ⋅s g µ C ⋅ρC 1 .000021
ft s
Calculate supe ficial flooding velocity (UD + UC)f = (.34)(.19988 ft/s) = .06795
9 ft/s Calculate supe ficial velocity at 50% of flooding velocity (UD + UC)50% F
looding Velocity = (.067959 / 2)ft/s (3600 s/min) = 122.327 ft/h  Dete mine the
total volumet ic flow ate:
kg kg UD UC 20000 h  35000 h  35.3146ft 3 = = + + ρ m3 D ρC 78
30.5 h 
Q total
Dete mine c oss-sectional a ea:
ft 3 2130.5 h  = ft 122.327 h  = 17.4165ft 2
AC =
Q Total (Uc + U d )50%Flood
Calculate the diamete  of the column:
28
CHE-396 Senio  Design
17 4A 2 4 ⋅ .4165 2 DT = c = = 4.70ft π π
1 1
Extraction
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 Sol
ve for HETS using the determined column diameter
HETS = 6.4 ⋅D T
1/ 3
= 6.4 ⋅4.71/ 3 = 10.728ft
Thus, the column height is: Total Height =(HETS)(Number of Equilibrium Stages) =
(10.728)(4) = 42.9ft
Extraction Column Dimensions
Diameter, ft Height, ft • The cost of this trayed column… Using Douglas [5] correlat
ion for caital costs:
1061 1.066 42.9.802 = $40,965.50 101.9 ⋅4.7 280 1061 1.55 Tray Cost $ = 4.7 ⋅4
8411.32 280
4.70 42.9
Column Cost $ =
(
)
(
)
Assuming a ayback eriod of six years, n = 6 Total Annualized Caital Cost = ($
40,965 + $8411) / 6 years = $8229.33 / yr. The oerating cost of electricity, la
bor, and maintenance are negligible in contrast to the oerating cost associated
with solvent recovery through further searations. Further, introducing a new m
aterial into the rocess to extract a solute result in new material cost and is
a function of solvent recovery. Total Annual Cost = $8229 + oerating costs + so
lvent & roduct recovery cost
29
CHE-396 Senior Design
Extraction
Alternatives
In the case where extraction does not aly for a certain feed, we must consider
our other otions. Alternatives to extraction include the following: 1. Distill
ation
• • •
Extractive Azeotroic Reactive
2. 3.
Crystallization Adsortion
In discussing distillation, we must evaluate under what conditions extraction wo
uld be valid over distillation. Extraction is referred to distillation for the
following reasons: [1] • Case of dissolved or comlexed inorganic substance in org
anic or aqueous solutions • Removal of a comonent resent in small concentrations
• A high-boiling comonent is resent in relatively small quantities in a waste s
tream • Recovery of heat-sensitive materials, where extraction may be less exensi
ve than vacuum distillation • Case of searation of a mixture according to chemica
l tye rather than relative volatility • Case of the searation of close-melting o
r close-boiling liquids, where the difference in solubilities can be exloited • C
ase of mixtures that form azeotroes If the situation does not meet any of the a
bove reasons, then distillation can be considered. For examle, if the boiling 
oints of two comonents where not close, then distillation would be referred ov
er extraction. Using crystallization over extraction, one would have to consider
the difference in the freezing oints of the comonents and also have informati
on for a solid-liquid hase diagram. This diagram is necessary to determine the
eutectic oint, which is the oint where one comonent becomes fused into the ot
her.
30
CHE-396 Senior Design
Extraction
Liquid adsortion could be used for certain comonents by contacting a liquid mi
xture with a orous solid. The solid acts as the adsorbent and must be insoluble
in the liquid mixture. There is no available theory regarding adsortion equili
brium curves; however, exerimental data at a fixed temerature is used for lot
ting curves
References
1. Seader, J.D. and Henley, E.J. Searation Process Princiles. John Wiley and S
ons. New York, 1999. 2. Strigle, R.F. Packed Tower Design and Alications. Gulf
Publishing Comany. Houston, 1994. 3. Sandler, S.I. Chemical and Engineering Th
ermodynamics. John Wiley and Sons. New York, 1998. 4. Treybal, R.E. Mass Transfe
r Oerations. McGraw-Hill. New York, 1980. 5. Douglas, J.M. Concetual 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 Proerties of Gases and Liquids. 4th
Ed. McGraw-Hill. New York, 1987.
31