Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Evaporation
Single Effect, Multiple Effect
Distillation
Simple, Azeotropic, Extractive, Reactive
Difficulty
Extraction Of
Simple, Fractional, Reactive
Separation
Adsorption
Pressure Swing, Temperature Swing
Crystallization
Melt, Solvent
Membranes
MF, UF, NF, RO
Difficult
Typical Applications
Solvent (S)
Solute in Raffinate 0.2
Fraction Unextracted U 0.2
Solute in Feed 1.0
0.8
Conc.Solute in Extract 50 7.92
Distribution Coefficient M
Conc.Solute in Raffinate 0.2
99
Extraction Factor
E S M 50 7.92 4.0
F 99
Cross Flow Extraction
E1 E2 E3 E4
B+C B+C B+C B+C
A+B
R1 R2 R3 R4
F A
C C C C
F + S = M1 R1 + S = M 2 R2 + S = M 3 R3 + S = M 4
B
F
R1 M1 E1
R2 E2
M2 E3
R3 M3
R4 M4 E4
A C
Countercurrent Flow Extraction
E1
C
B+C B+C E3
A+B
R1 R2 R3 R4
F A
B+C B+C E4
E2
B
Equations
F+S=M
E1 + R 4 = M
F + S = E1 + R4 F
F E1 = R4 S = D
R1 E1
R2 M E2
R3 E3
R4 E4
D
A S C
Countercurrent Extraction
B+C Extract (E):
Solute Rich Stream
Continuous Phase
Dispersed Phase
C
Solvent (S)
Raffinate (R):
A Solute Lean Stream
Bench Scale Test Apparatus
Baffle
Thermometer
Tempered
Water Out
1 Liter Flask
Tempered
Water In
Drain
Simple Extraction
Process Solute Free Graphical
Scheme Basis Solution
E EI
F yAE FI
YBE
yBE YBE = yBE
xAS
xBF N yCE XBF = xBF
xAF
N yAR+ yCE
1.0
1.0
S SI Y
yAS YBS = yBF
YBS
yBS R yAS+ yCS RI
yCS xAR XBR = xBR
1.0 xBR xAR+ xCR XBR XBF
xCR
FI=F(xAR)
X
1.0
SI=S(yAS+yCS) m = YB* Distribution Coefficient
EI=E(yAE+yCE) on Solute Free Basis
XB*
RI=R(xAR+xCR)
Typical LLE Equilibrium Curve
Extract Composition (Wt Fract., Solute Free)
0.09
0.08
0.07
0.06
0.05
0.04
0.03
0.02
0.01
0.00
0.000 0.005 0.010 0.015 0.020
0.12
0.10
1
0.08
0.06
0.04
0.02
2
0.00
3
0.000 0.020 0.040 0.060 0.080 0.100 0.120
0.12
0.10
1
0.08
0.06
0.04
0.02 4
5 2
6
3
0.00
0.000 0.020 0.040 0.060 0.080 0.100 0.120
ys
x
LOG f m 1 1 1
ys E E
xn m
n
LOG E
F1 0.4
0.3
0.1
0.08
0.06
0.04
0.03
0.02
S1 0.01
0.008
YBS
0.006
0.004
R1 0.003
XB 0.002
R Factor
E = Extraction 0.001
0.0008
E = m (S1/F1) 0.0006
0.0005
1 2 3 4 5 6 7 8 10 15 20
Feed B+C+(A)
A+B
Extraction
Stripping
Raffinate
Recovery
Solvent
C C
Solvent (A) (A+B)
C
(A+B)
A+(B+C)
A (B+C) B (C)
Removal of Phenol from Wastewater
Extract
Wastewater Feed
0.1 8 % Phenol
Extraction
Stripping
Raffinate
Recovery
Solvent
Recycled
Solvent
Raffinate
< 1 ppm Phenol
Biological Treatment Phenol
Or
Carbon Adsorption
ppb Phenol
Recovery of Acetic Acid from Water
Using a Low Boiling Solvent
Extract
Aqueous Feed
20 - 40 %
Acetic Acid
Extraction
Stripping
Raffinate
Recovery
Solvent
Recycled
Solvent
Typical Solvents:
Ethyl Acetate Raffinate
Butyl Acetate
Water Feed
0.1 5 %
Mixed Acids
Dehydration
Extraction
Recovery
Recovery
Solvent
Acid
Raffinate
< 1,000 ppb
Mixed Acids
Organic
Water
Extraction
Caustic (Mild)**
contain caustic. Mid-
Feed would be mild acid.
Water + Salts
Series Extraction
Extract Solvent 1
Feed Solvent 2
B+C C
A+B D
Extractor #1
Extractor #2
Raffinate Product
A B+D
Re-Extraction
Feed From
Reaction
Section
Recycle Water
Scrub Extraction
Re-Extraction
Phosphate
Extraction
Feed
HCL Rock
Digester
Scrub Solv.
Solvent
Raffinate Phosphoric
to Disposal Acid to
Recovery
Organo-Metallic Catalyst Recovery
Organic
Cobalt
Catalyst
Preparation
Feed
Extraction Organo-Metallic
Catalyst
Reactor
Slipstream
Separator
Makeup
Water Effluent
Organic
(200 ppm Cobalt)
Product
Water Effluent
(1 ppm Cobalt)
Fractional Extraction
Process Scheme
EI
(A-Rich)
SI2 YAE,YBE
XAS2,XBS
2
NR
F1I
XAF,XBF
NS
S 1I
XAS1,XBS1
RI
(B-Rich)
XAR,XBR
Extraction of Flavors and Typical Products:
Orange Oil
Lemon Oil
Aromas Peppermint Oil
Cinnamon Oil
Aqueous Alcohol
Extraction
Distillation
Distillation
Essential Oil
Solvent 1
Solvent 2
Hydrocarbon
Aqueous
Recycle
Distillation
Distillation
Extraction
Extraction
Solvent 2
Solvent 1
Mixed
Isomer
Feed
Aqueous
Raffinate
Reflux
Isomer 1 Isomer 2
Major Types of Extraction Equipment
Mixer Column
Centrifugal
Settlers Contactors
Reciprocating
Rarely used Used in: Used in: Used in: Used in:
- Refining - Refining - Nuclear - Chemicals
- Petrochemicals - Petrochemicals - Inorganics - Petrochemicals
- Chemicals - Refining
- Pharmaceutical
Characteristics
Feed Inlet
Mix Settle Phase separate in a single
tank
Batch Processing only
Requires multiple solvent additions for
more than one stage (crossflow operation)
Typically used for small capacity
operations or intermittent processing
Sight Glass
Outlet
Mixer / Settlers
Characteristics
Handle very high flowrates
Good for processes with
Light Phase In
relatively slow reactions
(residence time required)
Provide intense mixing to
promote mass transfer
Require large amount of
floor space
Suitable when few theoretical
Heavy Phase Out stages required
Large solvent inventory (and
losses)
Centrifugal Extractor
Characteristics
Countercurrent flow via centrifugal
force
Low residence time ideally suited for
some pharmaceutical applications
Handles low density difference
between phases
Provide up to several theoretical
stages per unit
High speed device requires
maintenance
Susceptible to fouling and plugging
due to small clearances
Packed Column
Characteristics
Extract (E)
High capacity:
Feed (F)
20-30 M3/M2-hr (Random)
500-750 gal/ft2-hr (Random)
40-80 M3/M2-hr (Structured)
1,000-2,000 gal/ft2-hr (Structured)
Poor efficiency due to backmixing and
wetting
Limited turndown flexibility
Affected by changes in wetting
characteristics
Solvent (S) Limited as to which phase can be
dispersed
Raffinate (R)
Requires low interfacial tension for
economic usefulness
Not good for fouling service
Sieve Tray Column
Characteristics
Extract (E)
Feed (F)
High capacity: 30-50 M3/M2-hr
750-1,250 gal/ft2-hr
Primary
Interface Good efficiency due to minimum
backmixing
Multiple interfaces can be a problem
Limited turndown flexibility
Affected by changes in wetting
characteristics
Limited as to which phase can be
Solvent (S)
dispersed
Raffinate (R)
RDC Extractor
Reasonable capacity:
20-30 M3/M2-hr Light
Phase Out
Limited efficiency due to Heavy
axial backmixing Phase In
Stators Rotors
Light
Phase In
Interface Interface
Control
Heavy
Phase Out
Scheibel Column
Characteristics Gearbox Variable Speed
Drive
Reasonable
capacity:
Light
15-25 M3/M2-hr Phase Out
Heavy
350-600 gal/ft2-hr Phase In
Rotating
High efficiency due Shaft
to internal baffling Horizontal Vessel
Outer Baffle Walls
Good turndown
capability (4:1) and
high flexibility
Best suited when
many stages are
required Turbine Horizontal
Light
Impeller Inner Baffle
Not recommended Phase In
Sparger
Good turndown capability (4:1) Center Shaft
& Spacers
Uniform shear mixing Metal Baffle
Plate Tie Rods
Best suited for systems that Perforated & Spacers
emulsify Plate
Teflon
Light
Baffle Plate
Phase Inlet
Sparger
Interface Interface
Control
Heavy
Phase Out
Karr Column Plate Stack Assembly
Pulsed Extractor
Characteristics
Compressed
Light
Reasonable capacity: Air
Phase Out
Heavy
20-30 M3/M2-hr Phase In
Best suited for nuclear Timer
applications due to lack of seal
Solenoid
Also suited for corrosive Valves
applications since can be
Air
constructed out or non-metals
Limited stages due to
Exhaust
backmixing Liquid
Light
Limited diameter/height due Phase In
Pulse
Leg
to pulse energy required
Interface Interface
Control
Heavy
Phase Out
Comparison Plot of Various
Commercial Extractors
20
Scheibel
Efficiency / Stages per Meter
10 RZE
Kuhni Key
6
Graesser Karr Graesser = Raining Bucket
4 PFK MS = Mixer Settler
RDC PSE SE = Sieve Plate
FK = Random Packed
2 FK PFK = Pulsed Packed
MS PSE = Pulsed Sieve Plate
SE
1 RDC = Rotating Disc Contactor
RZE = Agitated Cell
.06 Karr = Karr Recipr. Plate
0.4 Kuhni = Kuhni Column
Scheibel = Scheibel Column
0.2
1 2 4 6 10 20 40 60 100
Capacity M3/(M2 HR)
Column Selection Criteria
Static Column
A static column design may be appropriate when:
Interfacial tension is low to medium: up to 10-15
dynes/cm
Only a few theoretical stages are required, and
reduction in S/F is not an economic benefit
No operational flexibility required
There is a large difference in solvent to feed
rates
Column Selection Criteria
Agitated Column
Agitated columns are generally more economical when:
More than 2-3 theoretical stages are required
Interfacial tension is moderate to high, although
low interfacial tensions may also be economical
A reduction in solvent usage is beneficial to the
process economics
The process requires a wide turndown as well as
the ability to handle a range of S/F ratios
Column Selection Criteria
Rotating Disc Contactor (RDC)
Systems with moderate to high viscosity, i.e. >
100 cps
Systems that are residence time controlled, for
example, slow mass transfer rate with few
theoretical stages required
Systems with a high tendency towards fouling
Column Selection Criteria
Scheibel Column
Systems that require a large number of stages
due to either theoretical stage requirements or
low mass transfer rates
Low volume applications in which a relatively
small column is required
Systems that process relatively easily, without a
tendency to emulsify and/or flood
Column Selection Criteria
Karr Reciprocation Plate Column
Difficult systems that tend to emulsify and/or
flood easily
Systems in which the hydraulic behavior varies
significantly through length of the column
Sometimes requiring non-metallic internals, such
as Teflon due to wetting characteristics or
corrosive materials
Fouling applications that may have tars
formations and/or solids precipitation
The Three Cornerstones of Successful
Extraction Applications
Successful
Application
Sound environmental
principles
Toxicity
Safety
Organic Group Interactions
Solvent Class
Solute Class 1 2 3 4 5 6 7 8 9 10 11 12
1 Phenol 0 0 - 0 - - - - - - + +
2 Acid, thiol 0 0 - 0 - - 0 0 0 0 + +
3 Alcohol, water - - 0 + + 0 - - + + + +
4 Active H on multihalogen 0 0 + 0 - - - - - - 0 +
5 Ketone, amide with no H on N,
- - + - 0 + + + + + + +
sulfone, phosphine oxide
6 Tertiary amine - - 0 - + 0 + + 0 + 0 0
7 Secondary amine - 0 - - - + + 0 0 0 0 +
8 Primary amine, ammonia, amide,
- 0 - - + + 0 0 + + + +
with 2H on N
9 Ether, oxide, sulfoxide - 0 + - + 0 0 + 0 + 0 +
10 Ester, aldehyde, carbonate,
- 0 + - + + 0 + + 0 + +
phosphate, nitrate, nitrite, nitrile
11 Aromatic, olefin, halogen, aromatic
multihalogen, paraffin without + + + 0 + 0 0 + 0 + 0 0
active H, manahalogen paraffin
12 Paraffin, carbon disulfide + + + + + 0 + + + + 0 0
1 - 4 = H donor groups
5 12 = H acceptor groups
12 = Non-H bonding groups
Liquid-Liquid Extraction Scale-Up
Hot Oil
Raffinate
Feed Solvent
KMPS Pilot Plant Services Group
S S
C C
R R
A A
Solvent is Heavy Phase A A
R R
S S
C C
Primary
Solvent Solvent Interface
Dispersed Primary Continuous
Interface
F F
A+B E A+B E
B+C B+C
Factors Effecting which Phase is
Dispersed
Flow Rate
For Sieve Tray and Packed Columns disperse the higher flowing phase
For all other columns disperse lower flowing phase
Viscosity
For efficiency disperse less viscous phase
Viscous drop
C C Continuous Dispersed
(c d)
A+B
Droplets tend to repel each other
C+B C+B
Less energy required to maintain dispersion
Interface Behavior
Actions to control unstable interface Light Phase Heavy Phase
Dispersed Dispersed
As extraction proceeds, interface normally
grows in thickness and forms a rag layer
that stabilizes at some thickness
Rag
If rag layer continues to grow, some action Layer
must be taken
1. Rag Draw
Continuously withdraw a portion of the Growing
interface and pass through a filter to Uncontrolled
remove interfacial contamination Interface
2. Reverse Phases Filter
Often a stable interface can be controlled
by reversing which phase is dispersed
1 2
Entrainment
Entrainment involves carrying over a small portion of one phase out the wrong end
of the column.
F F F F
1 OR 2 OR 3
S S S S
R
R
R R
Flooding
Flooding the point where the upward or downward flow of the dispersed phase
ceases and a second interface is formed in the column.
E E
F1 F2
Second
Interface
S S
R R
Flooding
Flooding can be caused by:
Increased agitation speed which forms smaller droplets which cannot
overcome flow of the continuous phase
Decreased interfacial tension forms smaller drops same effect as
increased agitation
f2 > f 1
f1 f
Primary Interface Primary Interface 2
E E
F1 F2
Second
Interface
S S
R R
Pilot Tests
Static Columns Agitated Columns
(Packed, Tray) (Scheibel, Karr)
N, S/F Process Factors N, S/F
D, H Column Variable D, H
(F+S) Variable (F+S),f
f
F
F
H
S D H
Flood S D
HETS
F+S
F+S
HETS MIN
HETS
f F+S
Extractor Flow Patterns
Y Y
X X
Q1
Q2
Feed Rate
Feed Rate
H1
H2
D1
Hot Oil
Organic
Extract
Aqueous
Spent Acid MCB Raffinate
Feed Solvent
Scheibel Column Pilot Plant Test Results
Nitrated Organics Extraction
Run # of Acid Feed MCB Feed Column Agitation Raffinate - Nit.
Stages [cc/min] [cc/min] Temp [C] Speed Org. Conc.
[RPM] [PPM]
1 18 300 185 82 400 856
2 18 300 185 80 500 776
3 18 300 185 84 600 328
4 18 380 235 43 500 963
5 18 380 235 91 600 159
6 18 380 235 73 500 563
7 18 380 235 74 700 148
8 36 380 235 78 500 16
9 36 380 235 78 600 11
10 36 300 185 70 600 15
11 36 300 185 83 650 13
12 36 240 150 54 600 47
Scheibel Column Scale-up Procedure
Nitrated Organics Extraction
530
Column Capacity
For Dia. < 18
For Dia. 18
[GPH/FT2]
[GPH/FT2]
300
100
157
5 10 15 20
[GPH/FT2] [IN]
Rate in 3 Dia. Pilot Scheibel Scheibel Column
Column Diameter
Scheibel Column Pilot Plant Scale-up
Nitrated Organics Extraction
Diameter = 14 (D1)
Expanded Head Diameter = 20 (D2)
D1
Bed Height = 9-6 (A)
Overall Height = 16-4 (B)
A B
D2
Application Karr Column
Alcohol Extraction from Acrylates
Extraction of methanol from an acrylate stream using
water as the solvent
Reduce methanol from 2.5% to less than 0.1%
S/F ratio specified by client as 0.32 wt. basis
Equilibrium data: distribution coefficient generated by
KMPS, with average value of 5.3
Commercial design: 36,900 lb/hr (4,660 GPH) acrylate
feed
Karr Column Pilot Plant Setup
Alcohol Extraction from Acrylates
Karr Column Variable
Speed Drive
1 Dia. x 8 Plate Stack
Plate Spacing from Top:
6 of 2
1 of 4
1 of 6
316SS Shaft, Plates
& Spacers
Hot Oil
Raffinate
(Acrylate Phase)
Extract
Water Acrylate Feed (H2O + Alcohol)
Feed (methyl or ethyl)
Interface
Karr Column Pilot Plant Test Results
Methanol Extraction from Acrylate
Run Plate Feed Rate Water Feed Agitator Interface Raffinate Raffinate
Stack [cc/min] Rate Speed Conc. Conc.
[cc/min] [SPM] Alcohol Water
1 1 150 45 100 Bottom 0.124 2.55
2 1 150 45 75 Bottom 0.165 2.83
3 2 150 45 110 Bottom 0.169 2.78
4 2 150 45 140 Bottom 0.112 2.72
5 2 180 54 100 Bottom 0.203 2.90
6 2 180 54 125 Bottom 0.146 3.08
7 2 180 54 150 Bottom 0.118 2.66
8 2 180 54 200 Bottom 0.078 2.73
9 2 210 63 175 Bottom 0.084 2.65
Notes:
Karr column with 1 dia. X 6 plate stack height.
Plate stack #1 is constant 2 plate spacing.
Plate stack #2 has variable spacing, from top: 4 of 2, 1 of 4, 1 of 6 spacing.
Feed is acrylate with approximately 2.5% methanol
Karr Column Pilot Plant Scale-up Procedure
Methanol Extraction from Acrylate
A D1 B
D2
Extraction Experience