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MEMBRANE SEPARATIONS

The most rapidly advances area of filtration technology.


There are three major types of membrane-based filtration
techniques:
(1) microfiltration,
(2) ultrafiltration, and
(3) reverse osmosis
They are classed according to the particle size they
commonly remove from solutions.

Types of membrane filtration

There are three major types of membrane-based filtration techniques:


microfiltration, ultrafiltration, and reverse osmosis.

Types of membrane filtration

Microfiltration
Retain particles as small as 0.1 m.
- They retain even the smallest bacteria.
- They will not retain dissolved proteins.
Used extensively in bioprocesses as sterile filter for both
liquid and gas streams.
They are used to filter-sterilize heat-sensitive media.

Types of membrane filtration

Ultrafiltration
Being able to retain dissolved proteins with molecular
weights as low as a few thousand.
Rated in terms of their molecular-weight cutoff.
Widely used in the separation of biological products.

Types of membrane filtration

Reverse Osmosis
Retain not only proteins but also dissolved ionic salts and
small organic molecules with MW in the hundreds.
Used most extensively in the purification of water and the
concentration of biological and food processing streams.

Types of membrane filtration

Diafiltration

An alternative method of operating an ultrafilter.


Repeated or continuous addition of fresh solvent
(usually water) in an ultrafiltration system.
To wash out any contaminants not retained by
the
membrane.

Types of membrane filtration: diafiltration (2/2)

A continuous countercurrent diafiltration


system:

A+B
B

A
water

Electrodialysis
Employ semi-permeable ion-exchange membranes that
are impervious to water.
The separation is electrically driven instead of pressuredriven.

Cross-Flow Filtration
Most of the pressure drop in conventional filtration
comes from the cake.
* Concentration
polarization:
accumulation of
solute near the
membrane surface

Cross-Flow Filtration

* We may wish that we could filter without a filter cake.


Use filtration where cross flow is dominant.

ULTRAFILTRATION
Ultrafiltration is a membrane process; it involves solvent
transport under pressure.

ULTRAFILTRATION (2/6)

Because of the range of pore sizes in an ultrafiltration


membrane, there is no absolute cutoff point.

_____________

ULTRAFILTRATION (3/6)

Ultrafiltration processes have three distinctive


characteristics:
(1)

Use of high cross flow


Reduce cake formation or concentration
polarization.

(2)

Dominated by the membrane

In conventional filtration, the choice of


filter medium usually has little effect on flow
through the cake.

(3)

Filtration performance depends on the


membrane
geometry in actual equipment.

ULTRAFILTRATION (4/6)

ULTRAFILTRATION (5/6)

______________________________________________________

For hollow fiber, feed streams generally need to be


prefiltered.

ULTRAFILTRATION (6/6)

Operation of a batch ultrafiltration:

* Ultrafiltration slows down as the solute concentration


increases.
Re-dilution once or twice may be useful before
finally collecting the retentate.

ANALYSIS OF ULTRAFILTRATION

In ultrafiltration, the species transported is the solvent and


the chief force is the transmembrane pressure (P).
Solvent velocity force on solvent
Darcy's
law:

k
P
v

ANALYSIS OF ULTRAFILTRATION (2/4)

Darcy's
law:
where

k
P
v

jv

P
L p P
( Rm R p )

= thickness the membrane


= viscosity of the permeate
jv = the volume of solvent per area per time (or
the solvent velocity)
Rm = membrane resistance
Rp = resistance of the polarized boundary layer
Lp = the permeability

ANALYSIS OF ULTRAFILTRATION (3/4)

Taking the osmotic pressure into consideration,

jv L p P

jv LP ( P )

ANALYSIS OF ULTRAFILTRATION (4/4)

jv LP ( P )
where = the osmotic pressure

= a reflection coefficient
*=1
The membrane rejects all solutes.
*=0

The membrane freely passes both solvent


and solute.

Estimation of Osmotic Pressurethe vant Hoff


equation (1885)
= c1RT
where c1 = molar concentration of solute (mol/L)
R = gas law constant (0.082 L atm mol1 K1)
T = absolute temperature
The vant Hoff equation should only be used at low
molar concentrations.
At higher concentrations, the vant Hoff equation
significantly underpredicts the osmotic pressure.

The vant Hoff equation (2/4)

* Osmotic pressure of aqueous sucrose solutions at 30C:

__________
____________

The vant Hoff equation (3/4)

The vant Hoff equation can be readily used for many


types of biotechnology products, particularly
macromolecules.
Their maximum concentrations are often much less
than 1 molar.

The vant Hoff equation (4/4)

The vant Hoff equation is a special case of the Gibbs


equation for a binary system consisting of water and a
solute.
RT
Gibbs equation :
ln x 2
V2
where V2 is the molar volume of water, and x2 is the mole
fraction of water.
When x2 >> x1
n1
n1

ln x 2 ln(1 x1 ) x1
n1 n 2
n2

RT

V2

n1
c1 RT
n2

(Note: n2 V2 = total volume of water)

[Example] Ultrafiltration of a well-stirred suspension


containing 0.1 vol% yeast suspension gives a flux of 36
gal/ft2-day under a pressure difference of 130 psi. (a) What
is the value of Lp? (b) What is the water velocity through the
membrane?
Solution:
(a) The yeast cells have a very high molecular weight, so
that their molar concentration and the resulting osmotic
pressure will be small.
jv LP ( P ) L p P
gal
36 2
L p (130 psi) Lp = 0.28 gal/ft2-day-psi
ft - day
(To be continued)

[Example] Ultrafiltration of a well-stirred suspension containing 0.1 vol


% yeast suspension gives a flux of 36 gal/ft2-day under a pressure
difference of 130 psi. (a) What is the value of Lp? (b) What is the water
velocity through the membrane?

Solution (contd):
(b) The water velocity through the membrane = jv

gal 3785 cm 3
ft 2
day

36 2
ft - day
gal (30.48 cm) 2 24 3600 s

= 0.0017 cm/s
#

* Molecular Weight of Yeast Cell


d = 8 m

= 1.05 g/cm3
d 3
V
= 2.7 1010 cm3
6
MW = (6.02 1023)(2.7 1010)(1.05)
= 1.7 1014

Estimation of Surface Concentration


Material balance:
Rate of solute accumulation
= (rate of solute flow in)
(rate of solute diffuse out)

dc
0 cj v D
dx

B.C. 1: x = 0, c = c10
B.C. 2: x = , c = c1
D c10
j v ln c
1

[Example] We are carrying out the ultrafiltration of


chymotrypsin in a spiral wound module at a rate of 1.3 105
cm/s. The solution concentration is 0.44 wt%, the proteins
diffusion coefficient is 9.5 107 cm2/s, and the boundary
layer is about 0.018 cm thick. How high is the surface
concentration?
Solution:
D c10
j v ln

c1

1.3 10

9.5 10 7 c10

ln
0.018
c1

c10
1. 3
c1
#

A Simplified Case of Batch Concentration


Assumptions:
(1) There is little concentration polarization. c10 = c1

When (c10 c1)/c1 < 0.1, the effect of


concentration polarization can be neglected.
(2) The membrane rejects all the solute. = 1
c1 RT
dV

Ajv AL p ( P ) AL p P 1

dt
P

(V = liquid volume in the system)

n1 RT / P
dV

AL p P 1

dt
V

A Simplified Case of Batch Concentration (2/2)

n1 RT / P
dV

AL p P 1

dt
V

I. C.: t = 0, V = V0

1
n1 RT V0 n1 RT / P

t
ln
(V0 V )
AL p P
P V n1 RT / P

[Example] We want to ultrafilter 840 L of a solution


containing 0.061 wt% of a protein used as a vaccine for
herpes. This protein has a diffusion coefficient of 1.1 106
cm2/s and a molecular weight of 16,900. We would like to
get the concentration up to about 2% by weight. The
ultrafilter, which we hope to use, has eight hollow fiber
cartridges, each of which has a surface area of 1.20 m2. It
is cooled to 4C during the operation. The membrane in
these cartridges gives an initial flux of 5.7 105 cm/s
under a pressure drop of 31 atm. Assuming negligible
concentration polarization, estimate the time to complete
this filtration.
Solution:
1
n1 RT V0 n1 RT / P

t
ln
(V0 V )
AL p P
P V n1 RT / P
(To be continued)

[Example] We want to ultrafilter 840 L of a solution containing 0.061 wt% of a


protein used as a vaccine for herpes. This protein has a diffusion coefficient of 1.1
10-6 cm2/s and a molecular weight of 16,900. We would like to get the
concentration up to about 2% by weight. The ultrafilter, which we hope to use,
has eight hollow fiber cartridges, each of which has a surface area of 1.20 m2. It is
cooled to 4C during the operation. The membrane in these cartridges gives an
initial flux of 5.7 10-5 cm/s under a pressure drop of 31 atm. Assuming negligible
concentration polarization, estimate the time to complete this filtration.

Solution (contd):

1
n1 RT V0 n1 RT / P

t
ln
(V0 V )
AL p P
P V n1 RT / P

V0 = 840 L ;

0.061 %
V 840 L
25.62 L
2%

0.061% (840 10 3 ) g
n1
0.03 mol
16900 g/mol

n1 RT (0.03 mol)(0.082 L - atm/mol- K)(277 K)

0.02 L
P
31 atm

(To be continued)

[Example] We want to ultrafilter 840 L of a solution containing 0.061 wt% of a


protein used as a vaccine for herpes. This protein has a diffusion coefficient of 1.1
10-6 cm2/s and a molecular weight of 16,900. We would like to get the
concentration up to about 2% by weight. The ultrafilter, which we hope to use,
has eight hollow fiber cartridges, each of which has a surface area of 1.20 m2. It is
cooled to 4C during the operation. The membrane in these cartridges gives an
initial flux of 5.7 10-5 cm/s under a pressure drop of 31 atm. Assuming negligible
concentration polarization, estimate the time to complete this filtration.

Solution (contd):
Initial
flux:

c10 RT

1
n1 RT V0 n1 RT / P

(
V

V
)

ln
0
AL p P

P
V

n
RT
/

jv LP ( P )
0.03 mol
L - atm

0
.
082
(
277
K ) = 8.11 104 atm

840 L
mol- K

5.7 10-5 = Lp (31 8.11 10-4)


Lp = 1.84 10-6

cm
s - atm

(To be continued)

[Example] Ultrafiltration of a vaccine for herpes.


The ultrafilter, which we hope to use, has eight hollow fiber cartridges, each of
which has a surface area of 1.20 m2.
Assuming negligible concentration polarization, estimate the time to complete
this filtration.

Solution (contd):
ALpP = (8 1.2 104)(1.84 106)(31) = 5.48 cm3/s = 5.48 103 L/s
1
n1RT V0 n1RT / P

t
ln
(V0 V )
ALp P
P V n1RT / P

5.48 10 3

840 0.02
(840 25.62) 0.02 ln 25.62 0.02

= 1.486 105 s = 41.3 h


840 0.02
0.07
25.62 0.02

Note : 0.02 ln

CONCENTRATION POLARIZATION IN
ULTRAFILTRATION
Material balance for solute in
the boundary layer:
(Flux of solute in due to
convection)
= (flux of solute out due to
diffusion)
dc
jv c D

dx

c1

jv
dc
c c D 0 dx
10

c10
jv jv
ln

c1
D kc

ln

c10
j j
v v
c1
D kc

Correlation for flow inside pipes (for turbulent flow):


N Sh 0.0096 N Re

0.913

N Sc

0.346

or

N Sh 0.082 N Re

0.69

N Sc

0.33

kc d
NSh (Sherwood number) = D (d: pipe diameter)

vd
NRe (Reynolds number) =

NSc (Schmidt number) = D

* Equivalent diameter of the flow channel

cross - sectional area

wetted perimeter

c10
* Concentration polarization becomes severe when c 10.
1

CONCENTRATION POLARIZATION IN ULTRAFILTRATION (3/3)

* Prediction of liquid diffusivitiesStokes-Einstein


equation (for particles or large spherical molecules, VA >
500 cm3/mol)
7.32 10 16 T
D
r0
T = absolute temperature, K
r0 = radius of the particles, cm

= viscosity of solution, cP
VA = molar volume of solute as liquid at its normal
boiling point, cm3/g mol

[Example] Equipment is available for ultrafiltration of a


protein solution at constant volume to remove low molecular
weight species (achieved by the addition of water or buffer to
the feed in an operation called diafiltration). The flow
channels for this system are tubes 0.1 cm in diameter and 100
cm long. The protein has a diffusion coefficient of 9 107
cm2/s. The solution has a viscosity of 1.2 cp and a density of
1.1 g/cm3. The system is capable of operating at bulk stream
velocity of 300 cm/s. At this velocity, determine the
polarization modulus (c10/c1) for a transmembrane flux of 45 L
m2 h1.
c
j
kc d
Solution: ln 10 v N Sh 0.082 N Re 0.69 N Sc 0.33
N

Sh D
c1 k c

N Re

g
cm
1.1 3 300
0.1 cm
vd
cm
s

2750
g

1.2 10 - 2
(To be continued)
cm - s

Example: Determination of the polarization modulus (c10/c1).

Solution (contd):
N Sh 0.082 N Re
N Sc

N Sc

0.33

; N Re 2750

g
4
cm - s

1
.
21

10
2

cm

9 10 7
s

1.2 10 2

1.1

N Sh

0.69

cm 3

kcd

0.082( 2750) 0.69 (1.21 10 4 ) 0.33 431


D

N Sh

kc d
D

cm 2
9 10
D
s 3.88 10 3 cm
k c N Sh 431
d
0.1 cm
s
7

(To be continued)

Example: Determination of the polarization modulus (c10/c1).

Solution (contd):
kc 3.88 103

cm
s

c10 jv
ln

c1 k c

jv
c10

exp
c1
kc

L 1000 cm 3
m2
h

4

45 2
2
m -h
L
10 cm 3600 s

exp
1.38
cm

-3
3.88

10

[Example] A tubular membrane with a diameter of 2 cm and


a water permeability of 250 L/m2-h-atm is used for
ultrafiltration of cheese whey. The solution velocity is 1.5 m/s
and the protein concentration is 10 g/L. The whey proteins
have an average diffusivity of 4 107 cm2/s, and the osmotic
pressure in atm is given by Jonssons equation:
= 4.4 103c 1.7 106c2 + 7.9 108c3
where c is the protein concentration in g/L. Calculate the
applied pressure if the permeate flux is 103 cm/s. Assume the
protein rejection is 100 percent and the bulk solution has the
same density and viscosity as water.
Solution:
jv LP ( P ) Need c to estimate .
10
c10
jv
ln

Need kc.
c1 k c
(To be continued)

[Example] d = 2 cm; Lp = 250 L/m2-h-atm; v = 1.5 m/s; c1 = 10 g/L; D =


4 10-7 cm2/s; = 4.4 10-3c10 1.7 10-6c102 + 7.9 10-8c103 ;
= 1 g/cm3; = 1 cp; jv = 10-3 cm/s; P = ?

Solution (contd):
N Re

vd (1 g/cm 3 )(150 cm/s)(2 cm)

30,000

0.01 g/cm - s

0.01 g/cm - s
N Sc

25,000
3
7
2
D (1 g/cm )( 4 10 cm / s)
N Sh

kc d

= 0.0096NRe0.913NSc0.346 = 3.9 103


D

N Sh D (3.9 103 )( 4 10 7 )
kc

7.8 10 4 cm/s
d
2
(To be continued)

[Example] d = 2 cm; Lp = 250 L/m2-h-atm; v = 1.5 m/s; c1 = 10 g/L; D =


4 10-7 cm2/s; = 4.4 10-3c10 1.7 10-6c102 + 7.9 10-8c103 ;
= 1 g/cm3; = 1 cp; jv = 10-3 cm/s; P = ?

Solution (contd):
c10
jv
ln

c1 k c

kc 7.8 104 cm/s

c10
10 3
ln

c10 = 36.04 g/L


10 7.8 10 4

= 4.4 10-3c 1.7 106c2 + 7.9 108c3 = 0.16 atm


1000 cm 3
L
Permeability, Lp 250 2

m - h - atm
L

m2
10000 cm 2

h
3600 s

= 6.94 10-3 cm/s-atm


Permeate flux, jv LP ( P )
0.001 = 6.94 103 (P 0.16) P = 0.304 atm

CONCENTRATION POLARIZATION IN
ULTRAFILTRATION WITH PARTIAL
REJECTION OF SOLUTES

dc
jv c D
jv c2
dx

B.C.1: c = c10 at x = 0
B.C.2: c = c1 at x =
The solution is:
c10 c 2
jv jv
ln

c1 c 2
D kc
Recall:

D c10
dc
cjv D
0 j v ln

c1
dx

CONCENTRATION POLARIZATION WITH PARTIAL REJECTION OF SOLUTES (2/4)

c10 c 2
jv jv
ln

c1 c 2
D kc

c10 c2 = (c1 c2)exp

jv
kc

c10 = c2 + (c1 c2)exp

jv
kc

c2

c2
jv
j
c10 c1
1 exp c1 1 R Rexp v
c1
kc
kc

c1

c2
where R 1 , the fraction rejected
c1

CONCENTRATION POLARIZATION WITH PARTIAL REJECTION OF SOLUTES (3/4)

jv
c10 c1 1 R Rexp
kc

c2
R 1
c1

Assume the permeate concentration, c2, is in equilibrium


with c10, i.e., c2 = Kc10.
c10
j
c
j
1
2 1 R Rexp v
(1 R ) 1 R Rexp v
c1 Kc1
kc
K
kc

j
1
R
1
exp v
K
1 R
kc

j
1
1 K
R
1

exp v
K
K
1 R
kc

1 R K exp jv
R

1 K

kc

CONCENTRATION POLARIZATION WITH PARTIAL REJECTION OF SOLUTES (4/4)

1 R
K
j

exp v
R
1 K
kc

c2 = Kc10
K is a constant, and
R varies with jv.

(1)
The rejection, R, approaches (1 K) as the
permeate flux, jv, approaches zero.
(2)
The rejection decreases with increasing the
permeate flux.

[Example] Ultrafiltration tests with a 1.5-cm tubular


membrane at NRe = 25,000 gave a permeate flux of 40 L m2 h1
and 75 percent rejection for a 5 percent polymer solution. The
polymer has an estimated diffusivity of 5 107 cm2/s. The bulk
solution has the same density and viscosity as water. Predict
the fraction rejected for a flux of 20 L m2 h1. What is the
maximum rejection?
Solution:

j
1 R
K

exp v
R
1 K
kc

Need K and kc.

0.01 g/cm - s
N Sc

20,000
3
7
2
D (1 g/cm )(5 10 cm /s)

kc d
N Sh
= 0.0096NRe0.913NSc0.346 = 3060
D
N Sh D (3060)(5 10 7 )
3
k

1
.
02

10
cm/s

c
d
1.5
(To be continued)

[Example] d = 1.5 cm; NRe = 25,000; jv = 40 L m-2 h-1; R = 0.75; D = 5 10-7


cm2/s. Predict the fraction rejected for a flux of 20 L m 2 h1. What is the
maximum rejection?

Solution (contd):
j
1 R
K

exp v ;
R
1 K
kc

kc 1.02 10 3 cm/s

Permeate flux, jv = 40 L m2 h1 = 1.11 103 cm/s


j
1 R
K

exp v
R
1 K
kc

1 0.75
K
1.11 10 3

exp
0.75
1 K
1.02 10 3

K = 0.101
(To be continued)

[Example] d = 1.5 cm; NRe = 25,000; jv = 40 L m-2 h-1; R = 0.75; D = 5 10-7


cm2/s. Predict the fraction rejected for a flux of 20 L m 2 h1. What is the
maximum rejection?

Solution (contd):
j
1 R
K

exp v
R
1 K
kc

3
; kc 1.02 10 cm/s ; K = 0.101

If the permeate flux is 20 L m2 h1 or 0.556 103 cm/s,


1 R
0.101
0.556 10 3

exp
R
1 0.101
1.02 10 3

R = 0.84

The maximum rejection occurs as the flux approaches zero.


Rmax = 1 K = 0.899

Abatement of Concentration Polarization in


Ultrafiltration
Concentration polarization increases the osmotic
pressure, hampers the permeate flux, and adds to the
severity of membrane fouling.
Air sparging (injecting air into the feed stream) has been
the most popular technique proposed for the reduction of
concentration polarization.
The injected air induces hydrodynamic disturbances
in the filtration module, which destabilizes the
concentration layer over the membrane surface.

Abatement of Concentration Polarization in Ultrafiltration (2/4)

Gas-liquid two phase flow patterns:

Abatement of Concentration Polarization in Ultrafiltration (3/4)

An alternative idea: using n-hexadecane in place of air to


generate two-phase flow.

n-Hexadecane has a viscosity two order of


magnitude higher than air (3.032 103 Pa s at
25C compared to 1.86 105 Pa s at 27C).
When the oil droplets rub the surface of the
membrane, the shear force and hence the
disturbances generated by n-hexadecane
droplets could be much more effective than that
by air bubbles.

Abatement of Concentration Polarization in Ultrafiltration (4/4)

Permeate Flux (m3m-2h-1)

0.04

0.02

0.00
0

30

60

90

Time (min)

Comparison of permeate fluxes for the conventional, air/water, and


n-hexadecane/water ultrafiltrations of a lipase solution. Symbols:
() conventional, () air/water, and () n-hexadecane/water.

DIAFILTRATION
Batch concentration versus diafiltration
Batch concentration:

DIAFILTRATION (2/4)

Batch concentration versus diafiltration (2/2)

Diafiltration:

In diafiltration, the dialyzate (or wash solvent) is added at


a rate equal to removal of ultrafiltrate.

DIAFILTRATION (3/4)

For microspecies (i.e., solutes) that are freely permeable to


the membrane,

d (CV0 ) CdV

Cf

dC
1
C C V0
0

Vw

dV
0

ln

C 0 Vw

C f V0

where
V0 = volume of initial preparation added to the cell (being
constant)
C0 = initial microsolute concentration in the reservoir
Cf = microsolute concentration after volume Vw of wash
solution has passed through the cell

DIAFILTRATION (4/4)

C
V
d (CV0 ) CdV ln 0 w
C f V0

For microspecies (i.e., solutes) that are partially permeable


to the membrane,
ln

C0
V
(1 R ) w
Cf
V0

where R = product retention (dimensionless).


Note:
*R=0

Complete product passage through the


membrane.
* R = 1 Rejected solute.

[Example] It is desired to use a crossflow filtration system


to desalt 1000 L of a protein solution containing NaCl. The
system has a membrane area of 100 m2 and is capable of
operating at a transmembrane flux of 30 L m2 h1. To
remove 99.99% of the salt, determine the time and the
volume of water required.
Solution:
ln

C 0 Vw

C f V0

Vw
1
ln

0.0001 1000

Vw = Jv A t
t = 3.07 h

Vw = 9210 L

L
9210 L 30 2 100 m 2 t
m h

REVERSE OSMOSIS
Adding a soluble salt to water.
Reducing the chemical potential of the water.
Osmotic flow.

REVERSE OSMOSIS (2/19)

The osmotic pressure of a solution:

= 1.12(T + 273)mi
= osmotic pressure, psi
T = temperature, C
mi = summation of molalities (mol/1000 g of
water) of all ionic and nonionic constituents in the
solution
* = 15 psi, for a typical brackish water; = 350 psi,
for seawater.

REVERSE OSMOSIS (3/19)

External pressure applied for reverse osmosis to occur:


400600 psig for brackish water
8001,000 psig for seawater
Reverse osmosis is used most extensively in the
purification of water and the concentration of biological
and food processing streams.

REVERSE OSMOSIS (4/19)

Performance variables of reverse osmosis:


A simple schematic of an RO system:

REVERSE OSMOSIS (5/19)

Performance variables of reverse osmosis (2/5):

The rate of water passage through a semipermeable


membrane is defined by:
Qw = kwA(P )/
Qw = water flow rate through the membrane
kw = membrane permeability coefficient for water
A = membrane area
P = hydraulic pressure differential across the membrane

= osmotic pressure differential across the membrane


= membrane thickness

REVERSE OSMOSIS (6/19)

Performance variables of reverse osmosis (3/5):

The rate of salt flow through the membrane is given by:


Qs = ksAc/
Qs = flow rate of salt through the membrane
c = salt concentration differential across the membrane
ks = membrane permeability coefficient for salt

REVERSE OSMOSIS (7/19)

Performance variables of reverse osmosis (4/5):

Qw = kwA(P )/ ; Qs = ksAc/

The rate of water flow through the


membrane is proportional to the pressure
differential across the membrane.

The rate of salt flow is proportional to the


concentration differential, and is independent of the
applied pressure.

An increase in operating pressure will


increase the water flow without changing the salt
flow.

REVERSE OSMOSIS (8/19)

Performance variables of reverse osmosis (5/5):

Recovery (or conversion) is defined by:


Y = 100Qp/Qf
Y = % recovery
Qp = product water flow rate
Qf = feed water flow rate
Salt passage is defined by:
SP = 100cp/cf
SP = % salt passage
cp = salt concentration in the product stream
cf = salt concentration in the feed stream

REVERSE OSMOSIS (9/19)

The membranes used in reverse osmosis are asymmetric.

The thin skin is supported by a porous substructure.

REVERSE OSMOSIS (10/19)

The membranes used in reverse osmosis are asymmetric. (2/2)

The rate-determining step for water transport is across


the skin.
The flow rate through a membrane is inversely
proportional to the membrane thickness.
These membranes provide high water transport
while still maintaining the important ability to
reject salts.

REVERSE OSMOSIS (11/19)

Cellulose acetate membranes (discovered by Loeb and


Sourirajan at UCLA in the early 1960s) have two major
limitations.
(1) They are susceptible to degradation from biological
attack.
Using chlorinated feed water to prevent such
attack.
(2) They hydrolyze back to cellulose under acidic and
particularly basic conditions.
Control the pH of the system at 4.5 to 7.5.

REVERSE OSMOSIS (12/19)

Reverse Osmosis DevicesTubular

* The membrane is either inserted into, or coated onto, the surface of a


porous tube designed to withstand the operating pressure.

REVERSE OSMOSIS (13/19)

Reverse Osmosis DevicesSpiral-Wound


* This device is
like a huge
envelope made
of membrane
and containing
a feed spacer.

* Feed flowing around the envelope at high pressure goes


across the membrane and is collected inside the envelope.
The envelope is wound spirally about a plastic tube that
receives the permeate.

REVERSE OSMOSIS (14/19)

Reverse Osmosis DevicesHollow Fiber

________

Aramid
membranes:
commercialized by
Du Pont in 1970,
made from an
aromatic polyamide
polymer, operated
at pH range of 411,
not susceptible to
biological attack
and resist
hydrolysis. (But,
they are degraded
by chlorine.)

REVERSE OSMOSIS (15/19)

Reverse Osmosis DevicesHollow Fiber

____________
* Pressurized water passes through the fiber wall into the
fiber bore. The salts and other impurities remain in the
brine, which flows to the outer perimeter of the fiber bundle.

REVERSE OSMOSIS (16/19)

RO system design:

REVERSE OSMOSIS (17/19)

___

Remarks:
* Cartridge filter: remove large-particle matter that could
damage the high-pressure pump or cause device plugging.

REVERSE OSMOSIS (18/19)

______

______

* Low-pressure shutdown switch: prevent pump operation at


inadequate flow rate.
* Valve on the pump discharge: control the pressure of the feed
water.
* Temperature switch: protect the permeator.

REVERSE OSMOSIS (19/19)

______

____

* High-pressure shutdown switch or pressure-relief device:


prevent the permeator from over-pressurization.
* Flow-control valve on the brine: set conversion.

CONCENTRATION POLARIZATION IN
REVERSE OSMOSIS

Concentration polarization has two deleterious


effects:
(1) The increase in c10 increases .
Qw = kwA(P )/

It necessitates a greater applied total


pressure to produce a given water flux across the
membrane.
(2) The increase in c10 serves to increase the driving
force for salt transport through the membrane.
Qs = ksAc/

CONCENTRATION POLARIZATION IN REVERSE OSMOSIS (2/3)

When the concentration of retained solutes at the


membrane surface, c10, exceeds the solubility limit, it
forms a thixotropic gel.
It is referred to the phenomenon as fouling of the
membrane.

[Example] A reverse osmosis process is used for


desalination of seawater. The volumetric flux of water
through the membrane is 3 105 m/s (or m3 s1 m2), and
the applied feed pressure is 8.0 MPa greater than the
product-water pressure. For seawater, the osmotic pressure
is 2.5 MPa. What is the water velocity through the
membrane if the polarization modulus (c10/c1) rises to 1.2fold of the original?
Solution:
Osmotic pressure of seawater, = 1.12(T + 273)mi

2 (mi ) 2

1.2 2= 1.2 1 = 1.2 2.5 = 3.0 MPa


1 (mi )1

(To be continued)

[Example] Reverse osmosis process for desalination of seawater.


Flux of water = 3 10-5 m/s (or m3 s-1 m-2); P = 8.0 MPa; = 2.5 MPa.
What is the water velocity through the membrane if the polarization
modulus (c10/c1) rises to 1.2-fold of the original?

Solution (contd):
2 = 3.0 MPa

Rate of water passage through the membrane:


Qw = kwA(P )/ or Qw/A = jv = Lp(P )
jv 2 ( P ) 2 8.0 3.0

0.91
jv1 ( P )1 8.0 2.5

jv2 = 0.91jv1 = 0.91 (3 105) = 2.73 105 m/s


#

CONCENTRATION POLARIZATION IN REVERSE OSMOSIS (3/3)

Correlation of Dittus and Boelter (1930) for concentration


polarization in turbulent flow:

c10
jv d h0.2 ( / ) 0.47
exp
c1
0.023v 0.8 D 0.67
where jv = the volume of solvent per area per time
dh = equivalent hydraulic diameter

= viscosity of fluid
= density of fluid
v = average velocity of fluid
D = local solute diffusivity in solution

[Example] A reverse osmosis desalting process is carried


out using turbulent flow through a tubular 1.0-cm-diameter
membrane with a system temperature of 18.5C. Which of
the following factors would be effective in reducing the
degree of concentration polarization if the water flux is held
constant? (a) Reduced temperature; (b) reduced tube
diameter with the same mass flow rate of seawater; and (c)
recirculation of the seawater with the same size and length.
Solution:

c10
jv d h0.2 ( / ) 0.47
exp
c1
0.023v 0.8 D 0.67

(a) Lower temperature increases the viscosity and lowers the


diffusivity.
Lower temperature makes concentration
polarization more severe.
(To be continued)

[Example (contd)] Which of the following factors would be effective in


reducing the degree of concentration polarization if the water flux is
held constant? (b) Reduced tube diameter with the same mass flow
rate of seawater; and (c) recirculation of the seawater with the same
size and length.

Solution:

c10
jv d h0.2 ( / ) 0.47
exp
c1
0.023v 0.8 D 0.67

(b) Reducing tube diameter with the same mass flow rate of
water will raise v.
Concentration polarization will be reduced.
(c) Recirculation of the seawater will increase v.
It alleviates concentration polarization but does so at
the expense of much more pumping power (more flow
and more pressure drop).

* Production of Low Alcohol Beer Using Reverse Osmosis

_____________

* Production of Low Alcohol Beer Using Reverse Osmosis


(2/2)

Remarks
* Some flavor components
that have a molecular
weight or size similar to
ethanol also pass through
the membrane.
Some flavor losses occur.
* The membrane cost is high.
The annual replacement
cost is up to 7% of the
original capital cost.

DIALYSIS

At equilibrium, the concentration of small molecules is


the same inside and outside the membrane.

DIALYSIS (2/3)

The external fluid must be repeatedly changed to reach


the required final composition.

_____________________________
___________

DIALYSIS (3/3)

Place a stirrer of some kind in the external fluid (or inside


the bag).
To increase the rate of movement.

REVERSE DIALYSIS
The filled bag is packed in a dry, water-soluble
polymer which cannot enter the membrane.

REVERSE DIALYSIS (2/2)

Remarks of reverse dialysis:

It is used to concentrate the material in the bag.

Equilibrium is never reached.


Water and salts are continuously removed until
the sample is totally dry.
Most macromolecules become irreversibly
bound to the dialysis tubing. (They are lost.)

GLASS FIBER DIALYSIS


Semipermeable glass fibers: hollow-bore fibers whose
glass walls contain pores of controlled size

GLASS FIBER DIALYSIS (2/2)

Two ways of using hollow fibers: dialysis and concentration.

ANALYSIS OF DIALYZER
A shell-and-tube type of hollow-fiber dialyzer:

Q = flow rate, A = area of membrane, K = dialysis coefficient

ANALYSIS OF DIALYZER (2/2)

For a counterflow dialyzer,


The rate of salt removed

Q F (C F 1 C F 2 ) Q D (C D 2 C D1 ) KAClm
( C F 1 C D 2 ) ( C F 2 C D1 )
Clm
ln[(C F 1 C D 2 ) /(C F 2 C D1 )]

[Example] A solution of raffinose containing 100 g/L of NaCl


is to be dialysed in a shell-and-tube type of hollow-fiber
dialyzer operating countercurrently. With a dialyzer having
1000 cm2 area of membranes the dialysis coefficient for NaCl
was determined to be 0.0415 cm/min, when the feed rate was
200 cm3/min, and the flow rate of pure water was 500
cm3/min. If 90% of the salt is to be removed, what area of the
hollow-fiber membranes will be needed, if the same flow rates
for feed and water are used?
Solution:

QF (CF 1 CF 2 ) KAClm

The rate of salt removed Q F (C F 1 C F 2 ) Q D (C D 2 C D1 )


200(100 0.1 100) 500(C D 2 0)

CD 2 36 g/L

(To be continued)

[Example] Shell-and-tube type of hollow-fiber dialyzer


CF1 = 100 g/L; K = 0.0415 cm/min; QF = 200 cm3/min; QD = 500
cm3/min. If 90% of the salt is to be removed, what area of the hollowfiber membranes will be needed?

Solution (contd):
CD 2 36 g/L

( C F 1 C D 2 ) ( C F 2 C D1 )
Clm
ln[(C F 1 C D 2 ) /(C F 2 C D1 )]
(100 36) (10 0)

29.1 g/L
ln[(100 36) /(10 0)]

QF (CF 1 CF 2 ) KAClm

Q F (C F 1 C F 2 ) 200(100 10)

14,905 cm 2
KClm
(0.0415)( 29.1)