CHE449 - Merged
CHE449 - Merged
CHE449 - Merged
CHAPTER 1
FUNDAMENTALS Of MEMBRANE
SEPARATION PROCESSES
DIFFERENT TYPES OF MEMBRANES
DEFINITION of a MEMBRANE
Sterilization of pharmaceuticals
Purification of antibiotics
Recovery of vaccines and antibiotics
from fermentation broth
APPLICATION OF MEMBRANE
TECHNOLOGY IN PETROCHEMICAL
INDUSTRY
Artificial kidney/liver/pancreas
Separation of cells from tissue and/or cell
fractionation
Blood oxygenation with membranes
Controlled drug delivery
One Step Separation of Plasma from Whole
Blood Without Centrifugation (Diagnostic
applications).
For separation, we need difference in properties of
the components in the mixture
2260 kJ/kg
Feed: Water Basis: 1 kg Density : 1000 kg/3 Volume of feed: 10 -3 m3
Condenser and Reboiler Duties≈ 2260 kJ
Membrane Separation
Separation at ambient conditions: Generally no need for preheating
Concentration polarisation,
membrane fouling.
Low membrane life time.
Low selectivity or flux.
Up-scaling factor is more or less
linear.
Schematic Representation of a
Membrane Process
Single module: Smallest unit in which membrane area is packed.
Feed
Retentate
Membrane
Permeate
Retentate : The stream containing species which do not pass through the
membrane
Membrane configuration
Hollow fiber
Flat-sheet Spiral wound Tubular Capillary
DIFFERENT TYPES of MEMBRANES
Asymmetric membrane Dense membrane
Asymmetric membrane:
The structural and transport properties vary over the
cross-section.
Consists of skin layer (0.1 to 1 micron) and highly
porous layer (100-200 micron).
Skin represents actual selective barrier of the
membrane and its thickness controls the flux.
Porous sublayer serves only as a support and has little
effect on the separation characteristics.
Asymmetric membrane
Electron Microscope Pictures
Of Asymmetric Membranes
Symmetric membrane
Morphology Symmetric
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DRIVING FORCE: CONCENTRATION DIFFERENCE
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DIALYSIS
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DRIVING FORCE: TEMPERATURE DIFFERENCE
SPIRAL WOUND
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CHE 449
MEMBRANE PROCESSES and
SEPARATION of MIXTURES
CHAPTER 2
MICROFILTRATION
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• Membrane pore size < Solute size • Membrane pore size >Solute size
• Solute particles are physically
• Solute particles can pass through
blocked from passing into or
the membrane.
through the membrane.
• Solute particles adsorb on the pore
• This sieving mechanism is called
wall.
surface filtration.
TYPES OF MICROFILTRATION CONFIGURATION
Selection of a Membrane
HOW
Initially Later on
Homogeneous Solution Heterogeneous Solution
Single phase Two phases:
Transparent solution Phase 1: Polymer rich phase
Polymer is completely dissolved (Matrix)
Phase 2: Polymer lean phase
(Pores)
Turbid solution
Step 1: Polymer is dissolved in a solvent Step 2:Homogeneous solution is cast Step 3: Homogeneous solution
And homogeneous solution is formed. on a suitable support with a knife is transformed into a
heterogeneous solution
Polymer should be
immiscible
in the precipitation bath
Phase Inversion Time: Precipitation Time
Instantaneous Delayed
YES !
Critical Question
Casting solution :
Add additives into casting solution.
Change the temperature of the casting solution.
Change the solvent
Coagulation bath :
Add additives into coagulation bath.
Change the temperature of the coagulation bath.
Change the nonsolvent type
Objective: Manufacture MF Membrane with Wet Phase
Inversion Technique
Very very thin dense skin layer (Almost no skin layer is desired)
• First the larger pores will get emptied, as the pressure increases more
and more smaller pores are progressively emptied.
2
rp Cos
P
γ: Surface tension of the liquid.
rp: Radius of a capillary shaped pore.
θ: Contact angle between solid (membrane) and liquid (=0)
ΔP:Pressure difference applied through the membrane
Based on pore size /pore size distribution, you can
check if the membrane is suitable for your application
Suppose you have different membrane samples supplied by different
companies.
You want to select the one which has the least fouling tendency
Best membrane
which showed
the lowest flux
decline
Mode of Operation: Constant Flux
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FOULING DURING MICROFILTRATION
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Which factors control degree of fouling ?
Membrane properties
Feed conditions • Narrow pore size distribution
• Heat treatment • Use of hydrophilic polymers
• PH adjustment
• Addition of complexation agents,
• Chlorination
Module design
• Adsorption onto
activated carbon, • Use of various kinds of turbulence
chemical promoters may reduce fouling
clarification
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Critical Questions
Whole milk contains 2.6% (w/w) casein (on average), and the
separation of casein micelles from whey protein is important.
Concentrated casein can be used in the following applications:
• Mixed with cream for production of cheese
• Used for standardization of milk
• Used for production of dried native casein which is used
as food additive.
• Used for development of edible coatings and bio-active peptides.
4)Journal of Dairy Science Volume 92, Issue 11, November 2009, Pages 5357-
5362
Permeate ???
DIAFILTRATION
Continuous DF, as opposed to batch DF: The product (i.e., the final
retentate) is being continuously withdrawn from the system during the
entire course of filtration.
Suppose N:1 (Single stage )
q f qd q p qr q: Volumetric flowrates
Retentate
Feed Diluant Permeate
q f C f qd C d q p C p qr C r
Diluant is pure : No solute in it
Cp Cr 1
Rejection of solute : R R 1 Y
Cr C f qp
1 1 R
q f
N:1 (Single stage )
Cr 1
Y
C f qp
1 1 R
q f
For N stages
Cr 1
Y N Cf: Fresh feed
Cf q concentration
1 1 R
p
q f Cr:Retentate
concentration
at the end of Nth stage
Calculation of Required Membrane Area
Permeate ???
m3/s m3/m2.s
If we know amount permeated (qp ) and solution flux
through the membrane, we can calculate the area
qp P
J
Area Rm Rc
Rm: Mass transfer resistance of the membrane
Rc: Mass transfer resistance of the cake layer
ΔP: Transmembrane pressure difference through the membrane
Which factors determine the solution flux ?
• Pore size
• Porosity
• Pore connectivity
• Pore shape
How can we find the resistances (needed for flux calculation ) ?
Membrane Resistance
P
J pure water
Rm
Measure pure water flux through the membrane at the constant
ΔP
P
Rm
J pure water
Cake Layer Resistance
Measure solution flux (e.g. skim milk) through the membrane at the
constant ΔP
P
RTotal
J
Rc RTotal Rm
Cr
Y Design Criteria Depending on the product
Cf requirement, you can set
this value
Casein 96 97 98 100
ß-lactoglobulin 78 88 92 99
1200
Area (m2)
900
600
300
0
0 0.1 0.2 0.3 0.4 0.5 0.6
Lactoglobulin concentration in retentate/Feed
1400
1200
1000
Area (m2)
800
N=1
N=2
600
400
200
0
0 0.1 0.2 0.3 0.4 0.5 0.6
Lactoglobulin concentration in retentate/Feed
400
350
300
Area (m2)
250
N=2
200 N=5
150 N=10
100
50
0
0 0.1 0.2 0.3 0.4 0.5 0.6
Lactoglobulin concentration in retentate/Feed
Multistage Cocurrent Diafiltration Unit
1400.00
1200.00
1000.00
Area (m2)
800.00
N=1
N=2
600.00
400.00
200.00
0.00
0 0.1 0.2 0.3 0.4 0.5 0.6
Lactoglobulin Concentration in Retentate /Feed
Multistage Cocurrent Diafiltration Unit
300.00
250.00
Area (m2)
200.00
N=2
150.00 N=5
N=10
100.00
50.00
0.00
0 0.1 0.2 0.3 0.4 0.5 0.6
Lactoglobulin Concentration in Retentate /Feed
Multistage Cocurrent Diafiltration Unit
8.00
Diluant Requirement (m3/h)
7.00
6.00
5.00
N=2
4.00 N=5
N=10
3.00
2.00
1.00
0.00
0 0.1 0.2 0.3 0.4 0.5 0.6
Lactoglobulin Concentration in Retentate /Feed
Multistage Countercurrent Diafiltration Unit
10.00
Diluant Requirement (m3/h)
8.00
6.00 N=2
N=5
N=10
4.00
2.00
0.00
0 0.1 0.2 0.3 0.4 0.5 0.6
Lactoglobulin concentration in retentate/Feed
The Comparison of Area Requirement for Cocurrent and
Countercurrent
Flow Configurations
Cr
Y Design Criteria
Cf
The Comparison of Diluant Requirement for Cocurrent and
Countercurrent
Flow Configurations
Cr
Y Design Criteria
Cf
CASE STUDY 1
CHAPTER 3
ULTRAFILTRATION
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Some Applications of Ultrafiltration
Commonly Used Production Technique: Phase Inversion
Membrane Properties
Pe
J v P
l
J v P
Pe
l Osmotic pressure difference
Membrane
thickness Transmembrane
pressure
CONCENTRATION POLARIZATION
cio x
J v c i cip Di i
dc dci J
dx
Cib
v
ci cip Di
x 0
dx
k Di /
Mass transfer coefficient of the solute
J Total J solvent
Specification of Commercial Ultrafiltration Membranes
ΔP ΔP3
Amount of water ΔP2
permeated (L)
ΔP1
Slope1
Membrane
Time (h)
ΔP3 >ΔP2 > ΔP1
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q f q p qr
q f C f q p C p qr C r
Permeate
Cp Cp
Rejection of pectine : R R 1 Cr
Cr 1 R
Cp
Cf
q f 1 q p
1 R 1 R
1 R
qp
R
Suppose N: 2
C p1 C f N=2
qf qR1 Cp2 C f 2
C p 2 C p1
qp1 qR2
C pN qp2
Design objective: 0 .1 Number of stages?
Cf
C pN
C pN C f N
ln N ln N 9
C
f
Case 1: 0.76 For each stage !
TMP
T ( C) (Bar) A1(m2) A2(m2) A3(m2) A4(m2) A5(m2) A6(m2) A7(m2) A8(m2) A9(m2) Atotal(m2)
40 0.2 18.63 16.63 14.85 13.26 11.84 10.57 9.43 8.42 7.52 111.14
40 0.8 16.50 13.25 10.64 8.55 6.87 5.51 4.43 3.56 2.86 72.17
40 2 19.82 18.92 18.05 17.23 16.44 15.69 14.98 14.29 13.64 149.07
30 0.2 18.51 13.77 10.25 7.63 5.68 4.22 3.14 2.34 1.74 67.28
20 0.2 24.84 22.40 20.20 18.22 16.43 14.81 13.36 12.04 10.86 153.17
C pN
C pN C f N
ln N ln N 4
C
f
qf qR1 qR2
qp2 qR3
qp1
qp3
Permeate
Overall mass balance around the unit-1
q f qr 3 q p1 qr1 (1)
Solute balance around the unit-1
qr 1 q p 2 q r 2 (3)
Solute balance around the unit-1
q p 2 q p 3 qr 3 (5)
Solute balance around the unit-3
q p 2C p 2 q p 3C p 3 qr 3Cr 3 (6)
Degrees of Freedom (df) Analysis
Unknowns : qr1, qp1, Cp1, Cr1, qr2, qp2, Cp2, Cr2, qr3, qp3, Cp3, Cr3
Cp Cp
Rejection of pectine : R R 1 Cr
Cr 1 R
C p1 C p2 C p3
1 2 3
Cf C r1 C p2
• Don’t forget , design parameters (or decision variables) change
depending on the nature of the separation
Procedure:
Set Ɵ1 Ɵ2 Ɵ3 values
Cf: Known, find Cp1 and from rejection values, you can
calculate Cr1.
Using set values, you can calculate
Cp1, Cr1, Cp2, Cr2, Cp3, Cr3
q f qr 3 q p1 qr1 (1)
Solute balance around the unit-1
Ax=b
Overall mass balance around the unit-1
q p 2 q p 3 qr 3 (5)
Solute balance around the unit-3
q p 2C p 2 q p 3C p 3 qr 3Cr 3 (6)
qr1 qp1 qr2 qp2 qr3 qp3
1 1 0 0 -1 0
Cr1 Cp1 0 0 -Cr3 0
-1 0 1 1 0 0
A= -Cr1 0 Cr2 Cp2 0 0
0 0 0 -1 1 1
0 0 0 -Cp2 Cr3 Cp3
qf
qr1
qfCf
qp1 x=A-1b
b= 0 x= qr2
0
qp2 Inverse of the
0
qr3 matrix
0
qp3
Solving linear set of equations in Excel
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C p1 C p2 C p3
1 2 3 Cpfinal
Cf C r1 C p2 (g/L) %Reduction
C p1 C p2 C p3
1 2 3 Area1 Area2 Area3 Atotal
Cf C r1 C p2 (m2) (m2) (m2) (m2)
C pN
C pN C f N
ln N ln N 2
C
f
Design-1
qR1
qf=900 L/h
Cf=1310 g/L A1=13.8 m2
qp2=392.8 L/h
Cp2=327.5 g/L
Design-2
qR1 qR2
qf=900L/h A1=5.7 m2 A2=3.6 m2
Cf=1310g/L qR3
qp2 =153.1 L/h
Cp2=465.3 g/L A3=1.7 m2
qp1=244.2 L/h
Cp1=393 g/L qp3 =73.4 L/h
Cp3=183.6 g/L
Permeate
qp=317.6L/h
Cp=344.6 g/L
Design-1: Design -2
qp=317.6 L/h
qp=392.8 L/h
Cp=344.6 g/L
Cp=327.5 g/L
N=3
N=2
A1=5.7 m2
A1=13.8 m2
A2=3.6 m2
A2=9.1 m2
A3=1.7 m2
Atotal=22.9 m2
Atotal=10.9 m2
CHAPTER 4
NANOFILTRATION
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NANOFILTRATION
Developed after 1970’s. Why ?
Reverse osmosis (RO) membranes: Have
low flux at relatively low pressures,
resulted in a considerable energy cost
The quality of the obtained permeate with
RO is often too
good.
Thus, membranes with lower rejections of
dissolved components, but with a higher
water permeability were desired .
Such low-pressure RO membranes became
known as nanofiltration membranes.
Some Applications for NF systems are:
•Water softening
Membrane deterioration
Catalyst recycle
Performance of NF Membranes
• Rejection of solutes
• Recovery
Solvent Flux
J v L p P
Solute Flux
J s C 1 J v C
Lp: Hydraulic permeability of solvent
C f Cp
C
Cf
ln
Cp
For pure water
J v L p P J s C 1 J v C
Js C
1 J v
Jv
Slope=Lp
C C
ΔP
Js
C
Slope= 1
C
Jv
C
Rejection mechanisms in NF
400.00
For partially rejected
Js 300.00
1 solutes
C 200.00
Cp
C C f C p R 1 C RC f
Cf
Membrane : NF-200
Procedure:
• Assume Cp value
• Calculate osmotic pressure difference
C f Cr
Feed iC f RT Cf
2 Feed Permeate
Permeate iC p RT
We should check the assumed Cp values for each salt
Js J s C
J s J wC p Cp
Jw J v L p P
• If CpAssumed –Cpcalculated > Tolerance , iteration should be
continued with new Cp values!
• Once iteration is calculated, then we can apply total and
component mass balances
q f q p qr q f C f q p C p qr C r
C f Cr qp
qp q f Area
C C Jw
p r
CHE 449
MEMBRANE PROCESSES and
SEPARATION of MIXTURES
CHAPTER 5
REVERSE OSMOSIS
Applications of RO Process
.
When does rising
stop?
Feed: I w:Water
Membrane
Salt +H2O Pure Water: II S: Salt
w I − w II = w (P I − P II ) − w ( I − II )
This is OSMOSIS
Diffusion of water from pure water side (II) to salt solution side (I)
Case 2: (P I
−P II
) = ( I
− II
) wI = wII
Case 3:
(P I
−P II
) ( I
− II
) wI wII
• The concentrate of a stage is used as feed stream for the next stage.
• Permeate of one pass serves as the feed for the next pass in a two-
pass RO system.
4 different companies provided following the technical data sheet for the
membrane modules. Which one do you suggest the farmer buy ?
COST ????
Larger the area of the module, the higher the cost. Thus, we should
calculate the area of each module to meet the requirements!
Single-Pass System
Given Data:
Capacity:qf: 10 m3/hour. Recovery:qp/qf:0.75
Cf: Salt concentration in brackish water: 3000 ppm
Cp: Desired salt concentration in treated water (permeate): 200 ppm
J w = Pew (P − )
Pew: Permeability constant of water
ΔP: Pressure difference applied through the membrane
Δπ:Osmotic pressure difference applied through the membrane
= iCRT
Cs: Solute (NaCl) concentration (mole/L)
R: Gas constant (0.08314 L.Bar/mole. K
T: Temperature (K)
+ −
i: Number of ions dissociated in water. NaCl → Na + Cl
For NaCl i:2
Rate of permeation (L/h) =Flux x Area
J w = Pew (P − )
To calculate flux under desired operating conditions, we
Should know Pew.
= Feed − Permeate
Feed = iC f RT
= Feed − Permeate
Permeate = iC p RT
J w = Pew (P − )
P = 28 bar = 6.1 − 0.17 = 5.93 bar Pew = ?
Cp
R = 1− C p = (1 − R )C f
Cf
For module A
Jw
Pew = Pew =
480
= 21.7 L / m 2 h.bar
(P − )
Case 1:
➢ Recovery: 75 %
➢ Desired salt concentration in the permeate will be
100 ppm, 200 ppm and 500 ppm
Case 2:
➢ Desired salt concentration in the permeate: 200 ppm
➢ Recovery of water will be 50 %, 75 % and 90 %
All other design conditions will the same as reported in the problem.
We should apply component (for salt) mass balance around the unit
qp
q f C f = qr C r + q p C p We know the recovery S = Re cov ery =
qf
C f − SC p Cr = 11400 ppm
Cr =
1− S
Cr = C f − C p C f − SC p
Cr =
1− S
Correct result
Cr = 2800 ppm Cr = 11400 ppm
qp
A=
Pew (P − )
C f + Cr
Feed = iC f RT Cf =
2
C f + Cr
Feed = iC f RT Cf =
2
Cr = C f − C p Cr = 2800 ppm Feed = 2.46 bar
The error in area calculation becomes larger as the salt rejection increases
ENERGY CONSUMPTION IN RO PROCESSES
Se =
(q P )/
f f p − T qr Pr
Pf, Pr:Feed and retentate pressures
qp
Schematics of a reverse osmosis system (desalination) using a
pressure exchanger.
1:Sea water inflow
2: Fresh water flow (40%)
3:Concentrate Flow (60%)
4:Sea water flow (60%)
5: Concentrate (drain)
A: High pressure pump flow (40%), B: Circulation pump,
C:Osmosis unit with membrane, D: Pressure exchanger
Case Study- In recent years your company has been experiencing water
shortage problem. Therefore, they would like to install a desalination
plant to process sea water. The salt content of sea water was measured
as 35000 ppm. The desalination unit will have a capacity of 20000 m3/day and
recovery rate of water will be 50 %. The plant will be operated 7884 h/year.
You have been asked to evaluate three possible designs.
1) Membrane module integrated with a turbine for energy recovery
2) Membrane module integrated with a pressure exchange unit for energy
recovery
3) Standalone system (No energy recovery unit).
The design should allow maximum 1 bar pressure drop through the
membrane module.
Prepare a feasibility report on your choice. In your report you should compare
these three alternatives and explain the reasons for your choice. To convince
your boss, you should compare the feasibility of your design with others
available in the literature.
Additional Data Supplied :
Efficiency of high pressure pump: 84 %; Cost of pump: 25000 $
Efficiency of turbine: 80 % ; Cost of turbine: 3000 $/kW
Efficiency of pressure exchange device : 98 % ; Cost of pressure
exchanger: 300000 $
Power Cost: 0.06 $/kWh
Labor Cost: 0.01 $/m3; Maintenance Cost: 0.01 $/m3; 0.01 $/m3;
Chemical Cost: 0.01 $/m3
Critical Step: Choosing a suitable membrane
Performance Criteria for RO Membrane Selection
Selectivity= A / B
fcp: Describes the effect of concentration polarization
Water flux
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q f = qr + q p q f C f = qr C r + q p C p
J salt = J TotalC p
kg salt/L
kg salt/m2.h L/m2.h
qp
Design Criteria: Set the recovery of water : S S=
qf
J salt = J W aterC p = B(C f − C p )
If we rearrange this equation, it becomes
BC f
Cp =
JW ater + B
q p = Sq f qr = q f − q p
q f C f − q pC p
Cr =
qr
Calculation Procedure
• Assume Cp value
• Calculate Cr value.
C f + Cr Permeate = iC p RT
Feed = iC f RT Cf =
2
• You can do this iteration very easily in Excel using Solver/Goal Seek
Recovery: 50 %
As the recovery of water increases, the total cost and specific energy
consumption increases significantly too !
RO MEMBRANES
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From single stage to two-stage RO
To minimize specific energy consumption
Permeate pass to achieve
higher permeate
quality
Seawater RO: The average water permeate flux : 12-17 L/m2.h (LMH)
Feed pump pressure: 55-80 bar,
The recovery ratio: 35-50%
Salt rejection : 99.4-99.7%.
• Higher-permeability membranes
• Installation of energy recovery devices
• Use of more efficient pumps
Minimum energy:
Thermodynamic limit