Unit Operation

ECH3117

LIQUID LIQUID EXTRACTIONS

 LEARNING OUTCOMES

• To describe principles of extraction process

• Use equilibrium and operating line data to
calculate stages
• Describe and classify extraction equipment
• Describe and explain multi stage extraction
process
• To describe continuous and batch systems
 SCOPE OF EXTRACTION

Liquid – Liquid Solid – Liquid Supercritical fluid

(leaching)
Single stage Single stage Properties

Multistage Multistage Process Concept

Countercurrent Countercurrent
Equipment Equipment After process
LIQUID LIQUID
EXTRACTION
Extraction is Used in a Wide Variety of Industries

Chemical •Washing of acids/bases, polar compounds from organics

• Recovery of active materials from fermentation broths

Pharmaceuticals • Purification of vitamin products
• Recovery of phenol, DMF, DMAC
Effluent Treatment • Recovery of acetic acid from dilute solutions
• Recovery of caprolactam for nylon manufacture
Polymer Processing • Separation of catalyst from reaction products
• Lube oil quality improvement
Petroleum • Separation of aromatics/aliphatics (BTX)
• Separation of olefins/parafins
Petrochemicals • Separation of structural isomers
• Decaffeination of coffee and tea
Food Industry • Separation of essential oils (flavors and fragrances)
• Copper production
Metals Industry • Recovery of rare earth elements

Inorganic Chemicals • Purification of phosphoric acid

Nuclear Industry • Purification of uranium

 Introduction
 In order to separate one or more of the
components in a mixture, the mixture is
brought into contact with another phase
 The two phase pair can be gas-liq,
vapour-liquid, liquid-liquid, fluid-solid
 Here, we consider Liquid-Liquid
extraction or solvent extraction
 LL Extraction is a process where one or
more solute (s) are removed from one
liquid phase by transferring those solute
to another liquid phase (solvent)
 Liquid-Liquid Extraction
Definition
- Separation of one or more component in a mixture by contacting with
another phase which is liquid

- Such a process is also referred to as liquid extraction or solvent

extraction

- 3 stages are involved in the process i.e.:

– i) bringing the feed mixture and the solvent into intimate contact
– ii) separation of the resulting two phases, and
– iii) removal and recovery of the solvent from each phase
 Introduction

 In LLE, no vaporization is needed, thus

extraction can be performed at low
temperature
 The two LL phases are chemically quite
different which leads to a separation of
the components according to physical
and chemical properties
 Alternative to evaporation and distillation

Paul Ashall 2007

 Liquid-liquid extraction principles

 Feed phase contains a component, i (solute) which is to

be removed.
 Addition of a second phase (solvent phase) which is
immiscible with feed phase but component i is soluble in
both phases.
 Some of component i (solute) is transferred from the feed
phase to the solvent phase.
 After extraction the feed and solvent phases are called
the raffinate (R) and extract (E) phases respectively.

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 Liquid-Liquid Extraction
Basic Concept
1. Before C
(solvent)
A+ B

(mix)

2. After (result)

C
C+A (solvent)

A+ B C+B
(mix)
 LL Extraction - principles

 Normally one phase is an organic phase while the other is an

aqueous phase.
 Under equilibrium, the distribution of solute i over the two
phases is determined by the distribution law.
 After the extraction, the two phases can be separated because
of their immiscibility.
 Component i is then separated from the extract phase by a
technique such as distillation and the solvent is regenerated.
 Further extractions may be carried out to remove more solute.
 Liquid liquid extraction can also be used to remove a
component from an organic phase by adding an aqueous
phase.

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 Extraction: Sequence of events

• Mixing or contacting

• Phase separation

• Collection of separate phases

 Extraction

Separating funnel. The ether layer with a dissolved yellow

compound is on top and an aqueous layer is at the bottom

An organic MTBE solution is extracted with aqueous sodium

bicarbonate solution. This base removes benzoic acid as benzoate but
leaves non-acidic benzil (yellow) behind in the upper organic phase.
 Example - Penicillin G

 6-aminopenicillanic acid (6-APA) is

manufactured by GSK in Irvine. It is used to
manufacture amoxicillin and ‘Augmentin’.

 Fermentation products (penicillin G broth) are

filtered (microfiltration) and extracted at low pH
with amyl acetate or methyl isobutyl ketone. The
penicillin G is then extracted further at a higher
pH into an aqueous phosphate buffer.

Paul Ashall 2007

 Choice of solvent
Factors to be considered:
 Selectivity
 Distribution coefficient
 Insolubility of solvent
 Recoverability of solute from solvent
 Density difference between liquid phases
 Interfacial tension
 Chemical reactivity
 Cost
 Viscosity, vapour pressure
 Flammability, toxicity

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 Selectivity

β = (mass fraction B in E)/(mass fraction A in E)

(mass fraction B in R)/(mass fraction A in R)

β>1

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 Insolubility of solvent

Preferred solvent – A and S have limited solubility

B

A S
B
S very soluble in A and A very soluble in S

A S
RECOVERABILITY OF SOLVENT AND
SOLUTE
 No azeotrope formed between solvent and solute
 Mixtures should have a high relative volatility
 Solvent should have a small latent heat of vapourisation

DENSITY
A density difference is required between the two phases.

INTERFACIAL TENSION
The larger the interfacial tension between the two phases the more readily
coalescence of emulsions will occur to give two distinct liquid phases but the more
difficult will be the dispersion of one liquid in the other to give efficient solute
extraction.

CHEMICAL REACTIVITY
Solvent should be stable and inert.
 Physical properties

For material handling:

1. Low viscosity
2. Low vapour pressure
3. Non-flammable (high flash point)
4. Non-toxic
 Distribution coefficient, K

•  

Large values are desirable since less solvent is required for

a given degree of extraction
 Immiscible liquids

•  

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 Partially miscible liquids
B
 Example water – MIBK
 Consider a solute acetone.
 Need to use a triangular phase %S %
diagram to show equilibrium P
compositions of MIBK-acetone-
A A
water mixtures. %B
A S
 Characteristics are single Each apex of triangle represents 100%
phase and two phase regions, pure component
tie lines connecting equilibrium B
phase compositions in two
phase region.
 More details later
E
M
R
S
A mixture of overall composition M will split into two
phases – E & R. R phase is in equilibrium with E phase
R/E = line ME/line MR
 Extraction Mode
• To achieve desired efficiency, do multi stages efficiency

Single stage
Batch
(common)
Multi stage
Extraction
Mode
Co-current
Continuous
Counter
current
(common)
 Extraction Mode
feed
Single raffinate
solvent Stage
extract

Batch Single stage

solvent solvent solvent

feed raff raff Final raff

Stage 1 Stage 2 Stage 3

extract extract extract

Composited extract

Batch Multi Stage – cross current

 Extraction

feed raff raff

Stage Stage Stage Final raffinate
solvent 1 extr 2 extr 3 Final extract

Continuous – co current

feed raff raff

Stage Stage Stage Final raffinate
Final extract 1 2 3 Solvent
extr extr
Continuous – counter current
 Equilibrium Relations in Liquid-Liquid
Extraction
1. Phase Rule
• 3 components
• 2 phases in equilibrium
• No of degree of freedom = 3
 Equilibrium Relation in Extraction
2. Triangular phase diagram and Equilibrium
data
• Triangular coordinates are use to
represent the equilibrium data of 3
component system
• Each corner represents a pure
component A,B,C
• M – mixture of A,B,C
• The perpendicular distance from pt M to
base AB represents mass fraction xc of C in
mixture M
• The perpendicular distance from pt M to
base CB represents mass fraction xA of A in
mixture M
• distance from pt M to base AC represents
mass fraction xb of B in mixture M
• xA + xB + xC =0.4+0.2+0.4 =1
 Triangular phase diagram-partially
miscible components
Example – isobutyl ketone (A)-
water (B) – acetone (C)
Liq C dissolves completely in A
or B
Liq A is partially soluble in B
Two phase region is included
inside below the curved
envelope
An original mixture of
composition M will separate into
two phases a and b which are in
equm tie line thru point M
The two phases are identical at
point P, the plait point
 Equilibrium Relations in LL Extraction
• Acetone (solute) dissolve completely in CE (solvent) or Water
(carrier)
• TCE is slightly soluble in water and water is slightly soluble in
TCE
• Original composition M (mixing point) will separate into 2 phase
Raffinate and Extract
• The 2 phases are identically at point P, the plait point
Solute
Acetone

Plait Point
Extract P
F Fe
E ed
Mixing point
R Raffinate
Tie-lines
S
TCE Water

Solvent C Carrier
 Equilibrium data on rectangular coordinates
Triangular diagrams have some Two phase region inside
disadvantages due to special envelope, one phase region
coordinates outside
Hence rectangular coordinates is Water rich layer – raffinate, i
used- fig 12.5.3 (A-acetic acid, B- Solvent rich layer – extract, g
water, C-isopropyl ether solvent)
Tie line - gi connects raffinate to
Solvent B and C are partially miscible
extract
Concen of C is plotted on vertical Raffinate composition – x
axis, and A on x axis
Extract composition - y
Conc of B is obtained from
difference,
• Mass fraction C is designated
xB = 1.0 – xA - xC
by yc in extract layer and xc in
yB = 1.0 – yA - C raffinate layer
• To construct tie line gi using
equilibrium yA – xA plot below
the phase diagram, vertical line
to gi is drawn
Equilibrium Relations in Liquid-Liquid Extraction

•Eqm data on a rectangular

coordinates
•Read composition of A and
C from curve, Calculate B by
deducting 1)
•x – composition of solute in
raffinate
•y composition of solute in
extract
 Triangular phase diagram

• Another common type of

phase diagram is shown as in
Figure 12.5.4
• Solvent pairs B/C and A/C are
partially miscible
• Example styrene (A)-
ethylbenzene (B)-diethylene
glycol (C)
• Chlorobenzene (A)- methyl
ethyl ketone (B) –water (C)

Paul Ashall 2007

 example

• Am original mixture weighing 100 kg and

containing 30 kg isopropyl ether C, 10 kg
acetic acid (A) and 60 kg water (B) is
equilibrated and the equilibrium phases
separated. What are the composition of
the two equilibrium phases?

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 Single Stage Extraction
L
• Single stage
V

V + L = M ( Overall balance total mass kg)

Lo + V = L1 + V = M (general)
2 1

For component A
Lox + V y = L x + V y = Mx
AO 2 A2 1 A1 1 A1 AM

For component C
Lox + V y = L x + V y = Mx
cO 2 C2 1 C1 1 C1 CM
 SINGLE STAGE EXTRACTIONS –
lever arm rule

• Lever-arm rule for graphical addition

L y A  x AM L yC  xCM
 
M x AM  x A M xCM  xC

• Rearranging L(kg ) VM

M (kg ) LM

• Kg L/ kg V is equal to length line VM/length line LM

 example

• The composition of the two equilibrium

layers as in Figure 12.5.1are for the
extract layer (V), yA=0.4, yB=0.02 and
yc=0.94. Raffinate layer (L); xA=0.12,
xB=0.86, xC=0.02. The original mixture
contained 100 kg dan xAM=0.10.
Determine the V and L.

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 Single Stage Equilibrium Extraction –
single stage equilibrium

2. Consider separation of A from a mixture of A and B by

solvent C in a single equilibrium stage
 stream enter , Lo, V2 in equilibrium with stream Leave V1,
L1
Lo + V2 = L1 + V1 = M
Lo xAo + V2 yA2 = L1 xA1 + V1 yA1 = M xAM
Lo xCo + V2 yC2 = L1 xC1 + V1 yC1 = M xCM
xA + xB + xC =1
To solve the three equations, use fig 12.5.6 b
Lo, V2 known, can calculate M, xAM , xCM from above equations
Plot Lo, V2, M in 12.5.6.
Use trial and error, tie line is drawn thru point M which locates
the composition of Li and V1
Find V1 and L1 from above equations
Multistage Countercurrent Extractions

• Need to recover more solute, repeat single

stage process to increase % removal
• If use co current or cross current,
– waste of fresh solvents
– Obtain a dilute solute product in outlet extract stream
• Use counter current. Best method
– Use less solvent
– Obtain more concentrated exit extract stream
 Multistage Counter Current
Extractions
solvent
extract
V2 V3 Vn Vn+1 VN VN+1
V1

1 2 n N

Lo, L1 L2 Ln-1 Ln LN-1 LN

feed
(contains solute A) raffinate
• Feed stream contain A to be extracted enters one end of
process
• Solvent stream enters at other end
• Extract and raffinate flow countercurrently from stage to
stage
 MultiStage Calculation
Overall material balance for component C: Equation 12.7.3

Lo xCO  V N 1 yCN 1 LN xCN  V1 yC1

xCM  
Lo  V N 1 LN  V1
Overall material balance for component A: Equation 12.7.4

Lo x AO  V N 1 y AN 1 LN x AN  V1 y A1
x AM  
Lo  VN 1 LN  V1
 Continuous multistage countercurrent
extraction
 Use equation 12.7.3 and 12.7.4 to calculate coordinates
of pt M on phase diagram which ties together the two
entering streams Lo and VN+1 and two exit streams V1 and
LN
 Usually Lo and VN+1 are known, desired exit composition
xAN is set.
 If we plot Lo,VN+1 and M on Fig 12.7.2, a straight line must
connect these three points
 Then V1 , LN and M must lie on one line. V1 and LN must
also lie on phase envelope.
 Examples

• Pure solvent isopropyl ether at the rate of VN+1 = 600 kg/h

is being used to extract an aqueous solution of Lo = 200
kg/h containing 30 wt% acetic acid (A) by countercurrent
multistage extraction. The desired exit acetic acid
concentration in the aqueous is 4%. Calculate the
compositions and the amounts of the ether extract V1 and
the aqueous raffinate LN . Use eqm data from appendix
A3.

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Paul Ashall 2007
Minimum solvent rate

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 Theoretical Stages
Determination of the number of theoretical stages required for
countercurrent extraction
• The operating point, , is determined from the intersection of lines LoV1
and LN VN+1 or from the following equation:
Lo xo  V1 y1 Ln xn  Vn 1 y n 1 LN x N  VN 1 y N 1
x   
Lo  V1 Ln  Vn 1 LN  VN 1
• To construct the tie line, use the
equilibrium data, plotted below
the phase diagram
 Liquid-Liquid Extraction

Example 1: Number of stages in countercurrent extraction

Pure isopropyl ether of 450 kg/h is being used to extract an aqueous solution
of 150 kg/ h with 30 wt% acetic acid (A) by countercurrent multistage
extraction. The exit acid concentration in the aqueous phase is 10 wt%.
Calculate the number of stages required.
Solution
The known values are :
VN+1 = 450 y AN+1 = 0 y CN+1 = 1.0 LO =150
xA0 = 0.30 xB0 = 0.70 xC0 = 0 xAN = 0.10

Figure 12.7-5 pg 721 (Geankoplis)

 Liquid-Liquid Extraction
Solution
• For the mixture point M, xCM=0.75 and xAM=0.075 (solved from equation):
• The point M is plotted and V1 is located at the intersection of line LNM with
the phase boundary to give yA1=0.072 and yC1 = 0.895.
• The lines LoV1 and LNVN+1 are drawn and the intersection is the operating
point, . (Alternatively, the operating point can be calculated from the
previously given equation)
• Starting at Lo, draw the line Lo , which locates V1, .
• Then a tie line through V1 locates L1 in equilibrium with [Link] tie line data
are obtained from a plot of the equilibrium data)
• Next, line L1  is drawn to locate V2. A tie line through V2 gives L2
• A final tie line gives L3, which has gone beyond the desired LN
• Hence, about 2.5 theoretical stages are needed
 Countercurrent stage extraction with
immiscible liquids
•  
 continued

A graphical procedure may be used to analyse these

systems. The number of theoretical stages (n) required to
pass from xF to xn is found by drawing in ‘steps’ between
the operating line and the equilibrium curve (yn, xn).
In practice equilibrium conditions may not be attained and
extraction efficiency will be less than 100% thus requiring
more stages in practice than the above analysis would
suggest.
Also partial miscibility of the solvents has to be considered in
the separation process.

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 continued

y
y1,xF

yn+1,xn
x

Paul Ashall 2007

 Countercurrent stage extraction with
immiscible liquids

• Extraction of nicotine with immiscible liquids

• An inlet water solution of 100 kg/h containing 0.010 wt fraction nicotine (A)
in water is stripped with a kerosene stream of 200 kg/h containing 0.0005
wt fraction nicotine in a countercurrent stage tower. The water and
kerosene are essentially immiscible in each other. It is desired to reduce
the concentration of the exit water to 0.0010 wt fraction nicotine. Determine
the theoretical number of stages needed. The equilibrium data are as
follows in C5, with x the wt fraction of nicotine in water and y in kerosene

x y x y
0.00101 0.00080 0.00746 0.00682
0 6
0.00246 0.00195 0.00988 0.00904
9
0.00500 0.00454 0.0202 0.01885
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Paul Ashall 2007
 Equipment
A) Mixer settlers for extraction
• Mechanical mixer is often used to provide efficient mass transfer between
two liquid phases
• One phase is usually dispersed into the other in the form of small droplets
• Small droplets provide large interfacial areas and faster extraction
• The droplets must not be too small as larger settling time will be required
• Efficiency 75-100%
• Example
 Equipment
B) Spray columns
• Either the light or the heavy phase may be dispersed
• In (a), the light phase enters from a distributor at the bottom of the column, rises
through a heavier phase and finally coalesces to form liquid interface at the top
of column
• In (a) heavy phase enter at top, fill tower as continuous phase and flows out
• In (b) the heavier phase is dispersed, where the interface is held at the bottom
of the tower’
• Has large back mixing in continuous phase
• Rarely used
 Equipment
C) Perforated plate/ sieve tray extraction tower
• Similar to sieve tray in distillation
• The rising droplets of the light solvent liquid are dispersed
• The dispersed droplets coalesce below each tray and are then returned on each tray
by passing through the perforations
• Heavy aqueous liquid flows across each plate, where it is contacted by the rising
droplets and then passes through the downcomer to the plate below
• Holes = 0.32 – 0.64 cm diameter
• % open tray area = 15-25% of column crosssectional area
 Equipment
D) Packed column
• Packing such as Raschig rings or Berl saddles cause droplets to coalesce
and redisperse at frequent intervals throughout tower
• Packing increases the interfacial area and considerably increases mass
transfer rates compared to spray columns
• Unsuitable for use with suspensions or high viscosity liquids
Equipment – Packed Extraction Tower
• More efficient than spray tower
• Still have back mixing
• Used only when only a few stages are needed
• Flooding occurs when increasing the dispersed or
continuous flow rates causes both phases to leave at the
outlet of continuous phase
• Flooding can be found using flooding correlation by
Crawford and Wilke

• Figure 12.6.3
 Equipment : Mechanically Agitated
Extraction Towers

• Many types. 2 Important Towers are

– Scheibel
– Karr
 Mechanically Agitated Extraction Towers

Scheibel
• a series of rotating turbine agitators form
dispersion which coalesce on passing
through the knitted mesh
• Mixture then pass through outer settling
zone
• Tower operates as a series of mixer-
settler extraction units
• Operates at high efficiency
 Mechanically Agitated Extraction Towers

• Scale up from total combined flowrate

0.4
D2  Q2 
  
D1  Q1 

• Scale up from diameter D1 to D2, HETS

varies 0.5
 HETS2   D2 
    
 HETS1   D1 
 Mechanically Agitated Extraction Towers

• Karr reciprocating plate tower

– Perforated trays moved up and down to
increase agitation and to pulse liquid
– This results in uniformDdrop-size distributions
2
D1

(uniform shear force through tower

crosssection)
– Amplitude of plate movement = 100-150
strokes/min
– Plate spacing = 5-15 cm
 Mechanically Agitated Extraction Towers

• In scaling up a small tower with diameter D1 to D2,

throughput per unit area (Vc +VD), plate; constant plate
spacing and amplitude.
0.14
 SPM 2   D1   HETS2   D2 
0.38
         
 SPM 1   D2   HETS1   D1 
EXTRACTIONS

DESIGN
 Design Towers for Extraction
1. Operating line equation for relatively immiscible liquids
– L (feed liq) and V ( solvent stream) are immiscible
– Solute A relatively dilute in L and V
– Raffinate – outlet feed stream
– Extract – outlet solvent stream
– Overall material balance around dashed box (Figure 12.7.7)

 x   y1   x1   y 
L'    V '    L'    V '  
1 x   1  y1   1  x1  1 y 

– L’ = kg feed B/h; V’ = kg solvent/h,

– y =mass fraction A in solvent stream V; x = mass fraction A in feed L
stream
– Op line equation will be slightly curved when plotted on x-y diagram
(Figure 12.7.7.b)
– Can used mole fraction and molar flow rates
 Design Towers for Extraction
2. Limiting solvent flows and optimum L’ /V’
– Usually L2 and x2 are set.
– x1 – set by us
– y1 – fixed by process requirement
– When op line has max slope and touch eqm line at point P,
solvent flow is at min value V’min.
– y is max = y2
– Optimum flowrate is taken as 1.2-1.5 x V’min (often 1.5)
– if eqm line curve and concave upward,
• V’min – when op line is tangent to the eqm line (not
intersecting)
 Design Towers for Extraction
3. Analytical equations for no of trays
– Same as stripping in gas-liq separations
x  y /m 
ln  2 1 (1  A)  A A  L / mV
 x1  y1 / m 
N
ln(1 / A)

– A may vary in tower if eqm and op line are curvy

– At concentrated top of tower, slope m2 or tangent at point y2 on
eqm line is used
A AA
– At bottom or dilute end, slope m1 at point 1x12 on eqm line is used
– A1 =L1/m1V1 and A2 =L2/m2V2 and (use dilute m1)
– To calculate efficiency


x2  x1 if N(1is/ A
known
) N 1  (1 / A) 
x2  y1 / m (1 / A) N 1  1
 Design Packed Tower for Extraction using Mass
Transfer Coefficients
• Similar to stripping in absorption
• Eqtns for dilute solution and immiscible solvents are
identical to stripping
x1
dx L
z  H OL N OL  H OL  1 H OL  '
x * x K x aS
x2

• If op and Eqm lines are straighta and dilute, eqtn 1 can be

integrated to give

x1  x2
N OL 
( x *  x) M
( x1*  x1 )  ( x2*  x2 )
where ( x *  x) M 
ln[( x1*  x1 ) /( x2*  x2 )]
 Design of Packed Tower for Extraction by Mass
Transfer Coeffcient

y1  y2
N OL 
( y  y*) M
( y1  y1* )  ( y2  y2* )
where ( y  y*) M 
ln[( y1  y1* ) /( y2  y2* )]

• NOL can also be determined by

1   x2  y1 / m 
N OL  ln (1  A)   A
(1  A)   x1  y1 / m 
Example 12.7.4

DESIGN
SUPERCRITICAL FLUID EXTRACTION
 Introduction SFE

• Supercritical Fluid Extraction (SFE) is the process of

separating one component (the extractant) from another (the
matrix) using supercritical fluids as the extracting solvent.
Extraction is usually from a solid matrix, but can also be from
liquids.
• Eg
– decaffeination = removing caffeine from coffee beans
– Collection of essential oils
• Common SFE fluid is CO2, sometimes modified by co-solvents
such as ethanol or methanol.
• Extraction conditions for supercritical CO2 are above the critical
temperature of 31°C and critical pressure of 74 bar
 Supercritical Fluid Extraction
• Supercritical fluid (SF) has
both gas and liq properties
above its critical Tc and Pc
• Lower viscosity than liquid
– (able to dissolve materials)
• Gas like permeation of solid
structures
– (able to penetrate substances
easily)
• Higher density than gas
• Higher solubility than gas

Figure 1. Carbon dioxide pressure-temperature phase diagram

 Supercritical Extraction
• Density can be changed in continuous manner by
changing P
• Offers alternative to organic solvents (less env friendly)
• Applications
– Pharmaceutical and food processing (eg decaf coffee, alcohol free
beer)
– Extraction of spirits, medicinal components, essential oil, flavors
– Rapid removal of fouling components (eg oil, grease)

Normal Liq Supercritical Gas

fluid
Diffusivity (m2/s) 10-10 10-8-10-7 10-5
Density (kg/m3) 1000 200-700 1
Viscosity (cP) 0.5-1.0 0.05-0.10 0.10
 Supercritical Extraction
Table 1. Critical properties of various solvents (Reid et al, 1987)
Molecular Critical Critical
Critical density
Solvent weight temperature pressure
g/mol K MPa (atm) g/cm3
Carbon
dioxide (CO2) 44.01 304.1 7.38 (72.8) 0.469

Water (H2O) 18.02 647.3 22.12 (218.3) 0.348

Methane
(CH4) 16.04 190.4 4.60 (45.4) 0.162

Ethane (C2H6) 30.07 305.3 4.87 (48.1) 0.203

Propane
(C3H8) 44.09 369.8 4.25 (41.9) 0.217

Ethylene
(C2H4) 28.05 282.4 5.04 (49.7) 0.215

Propylene
(C3H6) 42.08 364.9 4.60 (45.4) 0.232

Methanol
(CH3OH) 32.04 512.6 8.09 (79.8) 0.272

Ethanol
(C2H5OH) 46.07 513.9 6.14 (60.6) 0.276

Acetone
(C3H6O) 58.08 508.1 4.70 (46.4) 0.278
 Supercritical Fluid Extraction
with CO2

• Replace Organic Solvents with CO2

• Substances easily degraded by heat can
be extracted
• Non-toxic for use in food products Non-
reactive and Non-flammable Easy
processing
• Environmentally safe
 SFE system
• The system must contain
– Compressor or pump for CO2:
• Carbon dioxide liquid is pumped to a heating zone, where it is heated to
supercritical conditions (usually below 5°C and a pressure of about 50 bar .)
– a pressure cell
• to contain the sample
• to maintaining pressure in the system
• as a collecting vessel.
– the extraction vessel
• rapidly sample diffuses into the solid matrix and dissolves the material to be
extracted.
– Separator
• dissolved material is swept from the extraction cell into a separator at lower
pressure
• the extracted material settles out.
– Cooler : The CO2 can then be cooled, re-compressed and recycled, or
discharged to atmosphere.
Supercritical Extraction
Supercritical Extraction
 After Extraction Process

• Change Conditions to alter Phase

Behavior
• Reduce Solubility by lowering the
pressure
• Equilibrium Phase comes out of solution
• Another example of this is crystallization
 Liquid Supercritical

• Solute of interest and initial solvent are

likely to be soluble
• Use tenary phase diagram
 Solid Supercritical
• Suitable for leaching process
• with conventional, solid need to be pulverized for
satisfactory solute recovery by extraction
• Particle size reduction less important in SF
• Eg: Extraction of caffeine from coffee beans
 Supercritical Extraction

Advantages Disadvantages
High mass transfer rates High pressure operations
High diffusion coefficients High plant capital cost
Wide range of feasible separations High maintenance cost
Easy solvent and product recovery
Non-toxic solvent
Favourable energy utilization
Physiologically harmless
Operation at ambient temperature
 Summary

• Eqm relation in liquid-liquid extraction

• Use Equilibrium and operating line
• Calculation of stages
• Single stage and multi stage system
• Liquid-liquid extraction equipment
• Design of extraction unit