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Membrane Separations: Microfiltration
Membrane Separations: Microfiltration
Microfiltration
Used extensively in bioprocesses as sterile filter for both liquid and gas streams.
They are used to filter-sterilize heat-sensitive media.
Ultrafiltration
Being able to retain dissolved proteins with molecular weights as low as a few
thousand.
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.
Electrodialysis
Employ semi-permeable ion-exchange membranes that are impervious to water.
* Concentration polarization:
accumulation of solute near the
membrane surface
In ultrafiltration, the species transported is the solvent and the chief force is the
transmembrane pressure (P).
Solvent velocity force on solvent
k P
Darcy's law: v P jv L p P
( Rm R p )
jv LP ( P )
The van’t Hoff equation should only be used at low molar concentrations.
* Osmotic pressure of aqueous sucrose solutions at 30C:
The van’t 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 van’t 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.
n1 n
When x2 >> x1 ln x 2 ln(1 x1 ) x1 1
n1 n 2 n2
RT n1
c1 RT
V2 n2
[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
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
D c10
B. C. 2: x = , c = c1 jv ln
c1
Solution:
D c10
jv ln
c1
I. C.: t = 0, V = V0
1 n1 RT V0 n1 RT / P
t (V0 V ) ln
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.
1 n1 RT V0 n1 RT / P
Solution: t (V0 V ) ln
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
1 840 0.02
(840 25.62) 0.02 ln 25.62 0.02 = 1.486 10 s = 41.3 h
5
5.48 10 3
#
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)
c1
dc dc jv
jv c D
dx
c c D 0 dx
10
c10 j j
ln v v
c1 D kc
N Sh 0.0096N Re N Sh 0.082 N Re
0.913 0.346 0.69 0.33
N Sc or N Sc
kc d
NSh (Sherwood number) = (d: pipe diameter)
D
vd
NRe (Reynolds number) =
NSc (Schmidt number) =
D
c10
* Concentration polarization becomes severe when 10.
c1
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.
Solution:
N Sh 0.082 N Re
0.69 0.33
N Sc
g cm
1.1 3 300 0.1 cm
vd cm s
N Re 2750
1.2 10 -2 g
cm - s
g
1.2 10 2
cm - s
N Sc 1.21 10 4
D g 7 cm
2
1.1 3 9 10
cm s
kcd
N Sh 0.082( 2750) 0.69 (1.21 10 4 ) 0.33 431
D
cm 2
9 10 7
D s 3.88 10 3 cm
k c N Sh 431
d 0.1 cm s
L 1000 cm 3 m2 h
45 2 4
c10 jv c10 jv m -h L 10 cm 2 3600 s
ln exp exp 1.38
c1 k c c1 kc - 3 cm
3.88 10
s
#
[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
Jonsson’s 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:
vd (1 g/cm 3 )(150 cm/s)(2 cm)
N Re 30,000
0.01 g/cm - s
0.01 g/cm - s
N Sc 25,000
D (1 g/cm 3 )( 4 10 7 cm 2 / s)
kc d
N Sh = 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
c10 j c10 10 3
ln v ln c10 = 36.04 g/L
c1 k c 10 7.8 10 4
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 j j
ln v v
c1 c 2 D kc
jv jv
c10 c2 = (c1 c2)exp c10 = c2 + (c1 c2)exp
kc kc
c c j j
c10 c1 2 1 2 exp v c1 1 R Rexp v
c1 c1 kc kc
c2
where R 1 , the fraction rejected
c1
Assume the permeate concentration, c2, is in equilibrium with c10, i.e., c2 = Kc10.
c10 c j 1 j
2 1 R Rexp v (1 R ) 1 R Rexp v
c1 Kc1 kc K kc
1 R j 1 1 K R j
1 exp v 1 exp v
K 1 R kc K K 1 R kc
1 R K j
exp v
R 1 K kc
Solution:
0.01 g/cm - s
N Sc 20,000
D (1 g/cm 3 )(5 10 7 cm 2 /s)
kc d
N Sh = 0.0096NRe0.913NSc0.346 = 3060
D
N Sh D (3060)(5 10 7 )
kc 1.02 10 3 cm/s
d 1.5
Permeate flux, jv = 40 L m2 h1 = 1.11 103 cm/s
1 R K j
exp v
R 1 K kc
1 0.75 K 1.11 10 3
exp K = 0.101
0.75 1 K 1.02 10 3
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 = 0.84
R 1 0.101 1.02 10 3
The maximum rejection occurs as the flux approaches zero.
Rmax = 1 K = 0.899
#
Abatement of Concentration Polarization in Ultrafiltration
air/water, and
n-hexadecane/water
3
ultrafiltrations of a lipase
solution. Symbols: (○)
0.02 conventional, (▲) air/water,
and (■) n-hexadecane/water.
0.00
0 30 60 90
Time (min)
DIAFILTRATION
dV C
V0
dV
For microspecies (i.e., solutes) that are freely permeable to the membrane,
Cf Vw
dC 1 C 0 Vw
d (CV0 ) CdV C C V0 dV
0
ln
C f V0
0
For microspecies (i.e., solutes) that are partially permeable to the membrane,
C0 V
ln (1 R ) w
Cf V0
Solution:
C 0 Vw 1 V
ln ln w Vw = 9210 L
C f V0 0.0001 1000
9210 L 30 2 100 m 2 t
L
Vw = Jv A t t = 3.07 h
m h
#
REVERSE OSMOSIS
Osmotic flow.
* The membrane is either inserted into, or coated onto, the surface of a porous
tube designed to withstand the operating pressure.
(2) Spiral-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.
(3) Hollow 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.
RO system design:
Remarks:
* Cartridge filter: remove large-particle matter that could damage the
high-pressure pump or cause device plugging.
* 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.
* 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
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.
Solution:
Osmotic pressure of seawater, = 1.12(T + 273)mi
2 (mi ) 2
1.2 2= 1.21 = 1.2 2.5 = 3.0 MPa
1 (mi )1
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
[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.
(a) Lower temperature increases the viscosity and lowers the diffusivity.
Lower temperature makes concentration polarization more severe.
(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
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
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.
Semipermeable glass fibers: hollow-bore fibers whose glass walls contain pores of
controlled size
( C F 1 C D 2 ) ( C F 2 C D1 )
Clm
ln[(C F 1 C D 2 ) /(C F 2 C D1 )]
Solution:
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) C D 2 36 g/L
(C F 1 C D 2 ) (C F 2 C D1 ) (100 36) (10 0)
Clm 29.1 g/L
ln[(C F 1 C D 2 ) /(C F 2 C D1 )] ln[(100 36) /(10 0)]
QF (C F 1 C F 2 ) 200(100 10)
A 14,905 cm 2
KClm (0.0415)( 29.1)
#
PERVAPORATION
Composite membranes are used with the dense layer in contact with the liquid and
the porous supporting layer exposed to the vapor.
Phase change occurs in the membrane, and the heat of vaporization is supplied by
the sensible heat of the liquid conducted through the thin dense layer.
The decrease in temperature of the liquid as it passes through the separator
lowers the rate of permeation.