Operações Unitárias III

Outubro
2019
Extração Líquido-Líquido

Prof. Dr. A. A. Chivanga Barros

 HIERARQUIAS DAS TECNOLOGIAS DE
SEPARAÇÃO

OKAY Physical Separations

Decantation, Coalescing, Filtration, Demisting
Easy

OKAY Evaporation
Single Effect, Multiple Effect

OKAY Distillation
Simple, Azeotropic, Extractive, Reactive

Difficulty
Extraction
OKAY Simple, Fractional, Reactive
Of
Separation

OKAY Adsorption
Pressure Swing, Temperature Swing

Crystallization
Melt, Solvent

Membranes
OKAY MF, UF, NF, RO
Difficult
 EQUILÍBRIO ENTRE FASES CONDENSADAS

Diagrama de Fases de 3 Componentes

F=C–P+2
F=5–P
Se P=1, F = 4, F’ = 3
P, T constantes
Triângulo de Gibbs
 Aplicações Típicas

• Remove products and pollutants from dilute aqueous streams

• Wash polar compounds or acids/bases from organic streams
• Heat sensitive products
• Non-volatile materials
• Azeotropic and close boiling mixtures
• Alternative to high cost distillations
 Uso da extração LL na indústria
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

 Water Azeotrope Azeotrope Typical Reduction
Organic Compound BP [°C]
Solu. [%] B.P. [°C] Water [%] Level
Remoção de organicos da água

Methylene Chloride 40 2.0 38.1 1.5 < 50 ppb

Distillation
Acetone 56.2 Infinite Non Azeotropic < 50 ppb

Methanol 64.5 Infinite Non Azeotropic < 50 ppb

Benzene 80.1 0.18 69.4 8.9 < 50 ppb

Distilação vs. ELL

Toluene 110.8 0.05 85.0 20.2 < 50 ppb

Formaldehyde -21 Infinite Non Azeotropic < 1,000 ppm

Formic Acid 100.8 Infinite 107.1 22.5 < 500 ppm

Acetic Acid 118.0 Infinite Non Azeotropic < 500 ppm

Pyridine 115.5 57 92.6 43 < 10 ppm

Extraction

Aniline 181.4 3.60 99.0 80.8 < 10 ppm

Phenol 181.4 8.20 99.5 90.8 < 10 ppm

Nitrobenzene 210.9 0.04 98.6 88.0 < 10 ppm

Dinitrotoluene (2,4) 300.0 0.03 99 – 100 > 90 < 10 ppm

Dimethyl Formamide 153.0 Infinite Non Azeotropic < 10 ppm

Dimethyl Acetamide 166.1 Infinite Non Azeotropic < 10 ppm

n-Methylpyrrolidone 202.0 Infinite Non Azeotropic < 10 ppm

 Extract (E)

A–0
B – 50
C – 0.8
Feed (F)
50.8
Extração simples em um único

A – 99
B–0
C–1
100
A–0 A – 99.0
B – 50
Raffinate (R) B–0
C–0 C – 0.2
50 99.2

Solvent (S)

Solute in Raffinate 0.2

Fraction Unextracted U   0.2
Solute in Feed 1.0
0.8
estágio

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
 Extração em fluxo cruzado
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 = M2 R2 + S = M3 R3 + S = M4
B

F
R1 M1 E1
R2 E2
M2 E3
R3 M3
R4 M4 E4
A C
 Extração em contracorrente
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 + R4 = M
F + S = E 1 + R4 F
F – E 1 = R4 – S = D
R1 E1

R2 M E2
R3 E3
R4 E4 D
A S C
 Extração em contracorrente
B+C Extract (E):
Solute Rich Stream

A+B Primary Interface

Feed (F)

Continuous Phase

Dispersed Phase

C
Solvent (S)

Raffinate (R):
A Solute Lean Stream
 Equipamento de extração em
batelada
Variable Speed Drive

Baffle
Thermometer

Tempered
Water Out

1 – Liter Flask

Tempered
Water In
Drain
 Process Scheme Solute Free Basis Graphical Solution

E EI
F yAE FI
YBE
yBE YBE = yBE
xAS
Extração Simples

N yCE XBF = xBF N yAR+ yCE

xBF 1.0 xAF
1.0

m
Y

=
e
S SI

op
Sl
I

->
I S

ve
/
F

ur
=

C
e

m
yAS Sl
op

riu
YBS = yBF

lib
YBS ->

ui
e
yBS R R I Lin

Eq
yAS+ yCS
ing
at
yCS xAR Op
e r
XBR = xBR
1.0 xBR XBR XBF
xAR+ xCR
xCR X
1.0 FI=F(xAR)
SI=S(yAS+yCS) m = YB* Distribution Coefficient on
EI=E(yAE+yCE) Solute Free Basis
XB*
RI=R(xAR+xCR)
Curva de Equlíbrio da Extração LL
0.09

0.08

0.07
Extract Composition (Wt Fract., Solute Free)
0.06

0.05

0.04

0.03

0.02

0.01
LLE

0.00
0.000 0.005 0.010 0.015 0.020

Raffinate Composition (Wt Fract., Solute Free)

 Gráfico utilizado para a determinação do NPT
95% Soluto de extração, S/F = 1.0 Base mássica

Extract Composition (Wt Fract., Solute Free)

0.00
0.02
0.04
0.06
0.08
0.10
0.12

0.000
3
2

0.020
1

0.040
0.060

Raffinate Composition (Wt Fract., Solute Free)

0.080
0.100
(0.136, 0.114)

0.120
Gráfico utilizado para a determinação do NPT
98% Soluto de extração Extraction, S/F = 1.0 Base mássica
(0.136, 0.118)
0.12

Extract Composition (Wt Fract., Solute Free)

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

Raffinate Composition (Wt Fract., Solute Free)

Equação de Kremser

 ys  
  x  
LOG f m 1 1   1 
ys   E  E 
 xn  m  
n LOG E

Where: n = Number of theoretical stages required

xf = Conc. of solute in feed on solute free basis
xn = Conc. of solute in raffinate on solute free basis
ys = Conc. of solute in solvent on solute free basis
m = Distribution coefficient
E = Extraction factor = (m)(S/F)
 YBE 1.0
0.8 E = 0.3
E1 0.6

0.4

F1 0.3
Cáclculos de Engenharia

0.2

XBF 0.1
Kremser Type Plot

0.08
0.06

0.04
0.03

E
0.02

=
1. 3
XBR/XBF = Fração não extraida
0.01

S1
0.008
0.006

0.004

E=2
YBS 0.003

0
0.002

R1
XBR 0.001
0.0008
0.0006
0.0005
E = Factor de Extração 1 2 3 4 5 6 7 8 10 15 20
E = m (S1/F1)
NPT
 AA+AE
AE
Feed B+C+(A)
Sistema típico de Extração

A+B
AA+Agua

Stripping
Raffinate

Recovery
Solvent
Extraction
AE

C C
Solvent (A) (A+B)
C
(A+B)
AE
ÁGUA+AE

A+(B+C)

A (B+C) ÁGUA AA B (C)

Remoção do fenol da água residual

Extract

Wastewater Feed
0.1 – 8 % Phenol

Stripping
Raffinate

Recovery
Solvent
Extraction
Recycled
Solvent

Raffinate
< 1 ppm Phenol
Biological Treatment Phenol
Or
Carbon Adsorption

ppb Phenol
Recuperação do ácido acétido da água, usando
solvente com baixo ponto de ebulição

Extract

Aqueous Feed
20 - 40 %
Acetic Acid

Stripping
Raffinate

Recovery
Solvent
Extraction
Recycled
Solvent

Typical Solvents:
Ethyl Acetate Raffinate
Butyl Acetate

Aqueous Raffinate Acetic Acid

Recuperação do ácido carboxilico de águas residuais
usando solvent com baixa temperature de ebulição
Formic Acid
Water 99%+ Purity

Water Feed

0.1 – 5 %
Mixed Acids

Dehydration

Recovery
Solvent

Recovery
Acid
Extraction

Raffinate
< 1,000 ppb
Mixed Acids

Recovered Solvent Acetic Acid

99%+ Purity
Clean Up
 Neutralização/lavagem de ácidos ou bases ou
componentes polares com substâncias organicas

Organic
Water

** Organic Feed could

Extraction
Caustic (Mild)**
contain caustic. Mid-
Feed would be mild acid.

Feed (Organic + Acid) **

Water + Salts
 Extração em série

Extract Solvent 1
Feed Solvent 2
B+C C

A+B D

Extractor #1

Extractor #2
Raffinate Product
A B+D

Extractor 1 & 2 May Differ By:

- Temperature
- pH
- Solvent
 Recuperação de Caprolactama
Extract

Lactam Oil Phase

65 – 70% Caprolactam Water

Am. Sulphate Ext.

Lactam Oil Ext.

Re-Extraction
Feed From

Reaction
Section

Ammonium Sulphate Phase

Solvent
2 – 3% Caprolactam Raffinate

AQ Waste to Am. Sulph. Lactam Oil to

Discharge Waste to Recovery
Discharge
Purificação do ácido fosfórico via extração ll

Recycle Water

Scrub Extraction

Re-Extraction
Phosphate

Extraction
Feed
HCL Rock Digester

Scrub Solv.
Solvent
Raffinate to Phosphoric
Disposal Acid to
Recovery
Recuperação catalitico de Organo-Metalicos
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)
Extração fracionada
Esquema do processo

EI
(A-Rich)

SI2 YAE,YBE

XAS2,XBS2
NR
F1I
XAF,XBF
NS
S1I
XAS1,XBS1

RI
(B-Rich)
XAR,XBR
 Typical Products:
Extração de essencia de flores e aromas Orange Oil
Lemon Oil
Peppermint Oil
Cinnamon Oil

Aqueous Alcohol

Distillation
Solvent 1

Distillation
Solvent 2
Extraction
Essential Oil

Hydrocarbon

Oil Essential Extract

Separation of Structural Typical Applications:
m. p. - Cresol
Isomers Xylenols
2 , 6 - Lutidine
3 , 4 - Picoline
pH Adjust Solvent 1 Recycle Solvent 2 Recycle
(Optional)
pH Adjust
(Optional)

Aqueous
Recycle

Distillation
Solvent 2
Distillation
Solvent 1
Extraction

Extraction
Mixed

Isomer
Feed

Aqueous
Raffinate

Reflux

Isomer 1 Isomer 2
 Tipos de equipamentos de extração

Mixer Settlers Column

Contactors Centrifugal

Used primarily in the metals Used primarily in the

industry due to: pharmaceutical industry due to:
- Large flows Static Agitated - Large flows
- Intense mixing - Intense mixing
- Long Residence time - Long Residence time
- Corrosive fluids - Corrosive fluids
- History - History

Spray Packed Tray Pulsed Rotary

Reciprocating

Rarely used Used in: Used in: Used in: Used in:
- Refining - Refining - Nuclear - Chemicals
- Petrochemicals - Petrochemicals - Inorganics - Petrochemicals
- Chemicals - Refining
- Pharmaceutical

Example: Example: Example: Example: Example:

- Random - Sieve - Packed - RDC - Karr
- Structured - Tray - Scheibel
- SMVPTM - Disc & Donut
 Tanque de mistura/decantação

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
Misturadores / Settlers

Characteristics
• Handle (lidar) very high
flowrates
Light Phase In • Good for processes with
relatively slow reactions
(residence time required)
• Provide intense mixing to
promote mass transfer
• Require large amount of floor
space
• Suitable (adequada) when few
Heavy Phase Out
theoretical stages required
• Large solvent inventory (and
losses)
Centrifugal Extractor

Characteristics
• Countercurrent flow via centrifugal
force
• Low residence time ideally suited
(adequada) for some pharmaceutical
applications
• Handles (lidar) low density difference
between phases
• Provide up to several theoretical stages
per unit
• High speed device requires
maintenance
• Susceptible to fouling (incrustração)
and plugging (obstrução) due to small
clearances (folgas)
 Colunas de recheios

Extract (E)
Characteristics
Feed (F)
• High capacity:
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
(Má eficiência devido a mistura posterior e
umedecimento)
• Limited turndown (reduzir) flexibility
• Affected by changes in wetting characteristics
• Limited as to which phase can be dispersed
Solvent (S)
• Requires low interfacial tension for economic
usefulness (utilidades)
Raffinate (R)
• Not good for fouling (incrustação) service
 Colunas com pratos

Extract (E)
Feed (F)
Characteristics
Primary
Interface • High capacity: 30-50 M3/M2-hr
750-1,250 gal/ft2-hr
• Good efficiency due to minimum
backmixing
• Multiple interfaces can be a problem
• Limited turndown flexibility
• Affected by changes in wetting
characteristics
Solvent (S)
• Limited as to which phase can be dispersed

Raffinate (R)
 RDC Extractor

Characteristics Drive Motor Gearbox

• Reasonable capacity:
20-30 M3/M2-hr Light
• Limited efficiency due to axial Phase Out
Heavy
backmixing Phase In

• Suitable for viscous materials

Vessel Shaft
• Suitable for fouling materials Walls

• Sensitive to emulsions due to

high shear mixing
• Reasonable turndown (40%)

Stators Rotors
Light
Phase In

Interface Interface
Control

Heavy
Phase Out
 Scheibel Column

Characteristics Gearbox Variable Speed

Drive
• Reasonable capacity:
15-25 M3/M2-hr
Light
350-600 gal/ft2-hr Heavy Phase Out
• High efficiency due Phase In

to internal baffling Rotating

Shaft
• Good turndown Horizontal Vessel
Outer Baffle Walls
capability (4:1) and
high flexibility
• Best suited when
many stages are
required
• Not recommended for Turbine Horizontal
Light
highly fouling Impeller Inner Baffle
Phase In
systems or systems
Interface
that tend to emulsify Interface
Control

Heavy
Phase Out
Scheibel Column Internal Assembly
 Karr Reciprocating Column
Drive
Characteristics Assembly
Seal Light
• Highest capacity: Phase Out
30-60 M3/M2-hr
750-1,500 gal/ft2-hr
Heavy
• Good efficiency Phase Inlet Spider Plate

• Good turndown capability (4:1) Sparger

Center Shaft
• Uniform shear mixing & Spacers
Metal Baffle
Plate
• Best suited for systems that emulsify Tie Rods
Perforated & Spacers
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: Phase Out Air
20-30 M3/M2-hr Heavy
Phase In
• Best suited for nuclear
Timer
applications due to lack of seal
Solenoid
• Also suited for corrosive Valves
applications since can be
constructed out or non-metals Air

• Limited stages due to backmixing

• Limited diameter/height due Liquid Exhaust

to pulse energy required Light

Pulse
Phase In
Leg
Interface Interface
Control

Heavy
Phase Out
 Comparison Plot of Various
Commercial Extractors
20
Scheibel
10
RZE
Kuhni Key
6
Graesser Karr Graesser = Raining Bucket
4 PFK MS = Mixer Settler
Efficiency / Stages per Meter

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

Proper Solvent Meaningful Pilot Accurate Scale-

Selection Tests Up
Selection Based on: Testing Based on: Scale-Up Based on:

• Sound thermodynamic • Actual feed stocks • Proven techniques

principles
• Full process including solvent • Proper safety factors
• Sound economic principles recovery
• Availability
• Recoverability • Wide range of operating
conditions
• 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,
phosphate, nitrate, nitrite, nitrile - 0 + - + + 0 + + 0 + +

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

• Theoretical scale-up is difficult

• Complexity of processes taking place within an extractor
 Droplet Breakup
 Coalescence
 Mass Transfer
 Axial and radial mixing
 Effects of impurities
• Best method of design:
Pilot testing followed by empirical scale-up
Pilot Plant Configuration
• Determine type of column to be used based on process considerations

• Use the same kind of equipment for the production unit

• Determine diameter and height of pilot column based on experience

Type of Column Diameter Height

Packed 3” to 4” 3’ to 6’ per Theoretical Stage (TS)

Tray 4” to 6” 4’ to 5’ Trays per TS
Karr 1” 1’ to 3’ per TS
Scheibel 3” 3 to 6 Actual Stages per TS (Approx. 3” to 6”)
Continuous Extraction Pilot Plant
Arrangement
Variable Speed Drive
Extract

Hot Oil

Raffinate

Feed Solvent
KMPS Pilot Plant Services Group

KMPS maintains a pilot plant dedicated to

extraction R & D and applications testing
Possible Extraction Column
Configurations
Solvent is Light Phase
B+C E B+C E
F F
A+B Primary A+B
Interface
Solvent Solvent
Primary
Dispersed Continuous Interface

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

Diffusion rate inside the drop is

inhibited by viscosity
• For capacity – disperse more viscous phase

Viscous continuous phase

Drop rise or fall will

be inhibited
Factors Effecting which Phase is
Dispersed
Surface Wetting
• Want the continuous phase to preferentially set the internals – this
minimizes coalescence and therefore maximizes interfacial area.
Droplets coalesce. Droplets retain shape.
Interfacial area lost. Maximizes interfacial area.

Importance of maintaining droplets

Assume – 30% holdup of dispersed phase in 1 M3 of solution

Droplet Droplet Number Droplet Interfacial

Diameter Volume Droplets SA [M2] Area
[m] [M3] [M2/M3]
100 0.3 7.16x1010 1.26x10-7 9022
300 0.3 2.65x109 1.13x10-6 2995
500 0.3 5.73x108 3.14x10-6 1796
Factors Effecting which Phase is
Dispersed
Marangoni Effect
• Coalescence is enhanced by mass transfer from
droplets continuous phase

C Mass Transfer Direction

A+B A+B
Dispersed Continuous
(d c)
• Droplets tend to coalesce
A • Must be counteracted by additional energy

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.

Entrainment is controlled by:

1.) Increased settling time inside the column
2.) Coalescer inside the column
3.) Coalescer external to the column
E
E E
E

F F F F

OR OR
1 2 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.

Flooding can be caused by:

• Increased continuous phase flow rate which increases drag on droplets
F2 > F1
f f
Primary Interface Primary Interface

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 f2
Primary Interface Primary Interface

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
Ideal Plug Flow Actual Flow

Y Y

X X

This “axial” or “back” mixing causes concentration

gradients that decrease driving force and therefore
increase HETS
Generalized Scale-up Procedure
Pilot Scale Commercial Scale
f1 f2

Q1
Q2
Feed Rate
Feed Rate
H1

H2

D1

Basic Scale-up Relationships:

D2/D1 = K1(Q2/Q1 )^M1
D2
H2/H1 = K2(D2/D1 )^M2
f2/f1 = K3(D2/D1)^M3 Where:
K1, M1 = Capacity Scale-up Factors
K2, M2 = Efficiency Scale-up Factors
K3, M3 = Power Scale-up Factors
Application – Scheibel Column

• Extraction of nitrated organics from spent acid stream

using an organic solvent
• Reduce nitrated organic compounds from 3.9% to less
than 50 ppm
• S/F ratio fixed by process at 3.9
• Equilibrium data indicated that 4.5 theoretical stages
required
• Commercial design: 3,900 lb/hr (270 GPH) spent acid
feed
Scheibel Column Pilot Plant Setup
Nitrated Organics Extraction
Variable Speed
Drive
Interface

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

600 14” Dia. = 430 GPH/FT2

Rate in Commercial Column 530

Column Capacity
For Dia. < 18”
[GPH/FT2]

[GPH/FT2]
300
For Dia. ≥ 18”

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” (D )
1

• Expanded Head Diameter = 20” (D )

2
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 Feed Acrylate Feed (H2O + Alcohol)
(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

• Select optimal run from test results

* Run 8:
Feed Rate = 150 cc/min
Solvent Rate = 45 cc/min
Specific Throughput (Q) = 560 GPH/FT2
• Production column design
* Diameter – direct scale-up based on specific throughput
* Height – HCOMM = ƒ (H)PILOT
* Agitation Speed – SPMCOMM = ƒ (SPM)PILOT
Karr Column Pilot Plant Scale-up Procedure
Methanol Extraction from Acrylate

• H = (D / D ) x H
COMM COMM PILOT
0.38
PILOT

• H = (45/1) x (6 feet) = 26 feet

COMM
0.38

• SPM = (D / D ) x SPM
COMM PILOT COMM
0.14
PILOT

• SPM = (1/45) x (200 SPM) = 117 SPM

COMM
0.14

• Where:
* HCOMM = Height Commercial Column
* HPILOT = Height Pilot Column
* DCOMM = Diameter Commercial Column
* DPILOT = Diameter Pilot Column
* SPMCOMM = Commercial Strokes Per Minute
* SPMPILOT = Pilot Strokes Per Minute
Karr Column Pilot Plant Scale-up
Methanol Extraction from Acrylate

• Diameter = 45” (D )
1

• Expanded Head Diameter = 68” (D )

2

• Plate Stack = 26’-0” (A)

• Overall Height = 36’-8” (B)

A D1 B

D2
Extraction Experience

KMPS has supplied over 300

extraction columns.
Questions?
Calcular a quantidade de solvente requerido para reduzir a concentração do pesticida-A  ys  
de 10% para 1% em 10000kg/h de um fluxo aquoso usando dicloro-etileno como
  x  
LOG f m 1 1   1 
ys   E  E 
solvente.

 xn  m  
O coeficiente de partição para o sistema é 1.
n LOG E
Concentração da alimentação (base livre de soluto):
Xf = 0.1/(1-0.1) = 0.111
1.0
0.8 E = 0.3
Especificação do rafinado: 0.6

Xr = 0.01/(1-0.01) 0.4

Xf/Xr = 11 0.3
0.2

Requerimento de DCE
0.1
1 estágio: S = 10*1000/1 = 10000 kg/h 0.08
0.06
para operação em corrente-cruzada:
0.04
2 estágios: S = 2*1000/1 [(11)1/2 1 ] = 4632 kg/h 0.03

XBR/XBF = Fração não extraida

4 estágios: S = 4*1000/1 [(11)1/4 1 ] = 3284 kg/h

E
=
0.02

1. 3
para operação em contra-corrente:
2 estágios: 2701 kg/h 0.01
0.008
0.006
4 estágios: 1402 kg/h
0.004

E=2
0.003

0.002

0
Where: n = Number of theoretical stages required
xf = Conc. of solute in feed on solute free basis 0.001
xn = Conc. of solute in raffinate on solute free basis 0.0008
0.0006
ys = Conc. of solute in solvent on solute free basis 0.0005

m = Distribution coefficient 1 2 3 4 5 6 7 8 10 15 20
E = Extraction factor = (m)(S/F)
E = Factor de Extração
E = m (S /F )
1 1 NPT
 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 
0.2
Conc.Solute in Raffinate
99
Extraction Factor    
E  S M   50 7.92  4.0
F 99