Membrane Separation

Chapter 8
 Contents
1. Introduction
2. Type of processes
3. Membrane configuration
4. Flux equation for reverse osmosis
 Objectives
Estimate the extent of concentration polarization in crossflow filtration
Select filtration unit operations to meet product requirements, consistent
with product properties
1. Introduction
Membranes are materials which have voids in them letting some molecules
pass more conveniently than some other molecules.

A semi-permeable membrane is a VERY THIN

film that allows some types of matter to pass
through while leaving others behind
What Is A Membrane?
How Separaton Occurs
Difference in permeabilities through a membrane:
Difference in size,
Affinity to the membrane,
Charge, etc.
Drvng Forces

Pressure difference,
Concentration difference,
Voltage difference, etc.
Advantages

Continuous separation
Low energy requirement
Meet various separation demands
Dsadvantages

Fouling
Short service periods
2. Types Of Processes
Classification aaccording to pore size
Microfiltration
Ultrafiltration
Nanofiltration
Reverse Osmosis
a. Reverse Osmoss
 Characteristic
Only remove some suspended materials larger than 1 micron
The process eliminates the dissolved solids, bacteria, viruses and
other germs contained in the water
Only water molecules allowed to pass via very big pressure
Asymmetric type membranes (decrease the driving pressure of the
flux)
Almost all membranes are made polymers, cellulosic acetate and
matic polyamide types rated at 96%-99+% NaCl rejection
Application
Extensive applications:
potable water from sea or brackish water
ultrapure water for food processing and electronic industries
harmaceutical grade water
water for chemical, pulp & paper industry
waste treatment
Future directions:
municipal and industrial waste treatment
process water for boilers
de-watering of feed streams
processing high temperature feed- streams
b. Mcrofltraton
 Characteristic

largest pores
a sterile filtration with pores 0.1-10.0 microns
micro-organisms cannot pass through them
operated at low pressure differences
used to filter particles.
may or may not be assymmetric
Applications
wide array of applications:
parenterals and sterile water for pharmaceutical industry
food & beverages
chemical industry
microelectronics industry
fermentation
laboratory/analytical uses
Mcrofltraton
Applications in the near future:
biotechnology (concentration of biomass)
diatomaceous earth displacement
non-sewage waste treatment (removing intractable particles in oily fluids)
paints (separating solvents from pigments)
c. Ultrafltraton
 Characteristic
to separate a solution; mixture of desirable and undesirable components
has smaller pores than microfiltration membranes
driving force pressure differential (2-10 bars to 25-30 bars)
used to separate species with pore sizes 10-1000 (103-0.1 microns)
Can be obtained down to a molecular weight cutoff (MWCO) level of
1000 Daltons (Da) and up to as high as 1 000 000 Da.
asymmetric; the pores are small

The unified atomic mass unit or Dalton (symbol: u, or Da) is a standard unit of mass that
quantifies mass on an atomic or molecular scale (atomic mass).
Applications
Wide range of applications :
oil emulsion waste treatment
treatment of whey in dairy industries
concentration of biological macromolecules
electrocoat paint recovery
concentration of textile sizing
concentration of heat sensitive proteins for food additives
many more
wide range of applications in the near future:
ultraflitration of milk
bioprocessing (separation and concentration of biologically active
components)
protein harvesting
refining of oils
D. Nanofltraton
Characteristics
less pore sizes than ultrafiltration membranes
the mass transfer mechanism is diffusion & separate small molecules from
the solution (assymmetric)
cellulosic acetate and aromatic polyamide type membranes (salt rejections;
95% for divalent salts to 40% for monovalent salts)
can typically operate at higher recoveries; conserving total water usage due
to a lower concentrate stream flow rate (advantage over reverse osmosis)
not effective on small molecular weight organics (e.g.methanol)
Nanofltraton
Typical applications:
desalination of food, dairy and beverage products or byproducts
partial desalination of whey, UF permeate or retentate as required
desalination of dyes and optical brighteners
purification of spent clean-in-place (CIP) chemicals
color reduction or manipulation of food products
concentration of food, dairy and beverage products or byproducts
fermentation byproduct concentration
 Dissolved salts Colloids Suspended solids

Viruses Bacteria

Org. macro. molecules Parasites

0.0001 0.001 0.01 0.1 1 10 100mm

polio smallest Crypto- hair

virus micro- sporidium
organis
m
Reverse Osmosis Ultrafiltration Sand filtration

Nanofiltration Microfiltration

ZW1000: 0.02 um ZW500: 0.04 um

Summary
3.Membrane Configurations
i. Flat membranes
Mainly used to fabricate
In some cases modules are stacked together like a multilayer sandwich
or plate-and-frame filter press
Three basic structures are commonly uses for membranes:
homogeneous (no significant variation in pore diameter from the
filtering surface to the other side),
asymmetric (has a thin layer next to the filtering surface that has very
pores), and
composite (containing very small pores next to the filtering surface;
however, the thin and thick layers of this membrane are made of two
different types of material)
ii. Spiral wound membranes
Constructed from flat sheet membranes separated by spacer screens
Consists of a sandwich of four sheets wrapped around a central core of a
perforated collecting tube
The four sheets consist of a top sheet of an open separator grid for feed channel, a
membrane, a porous felt backing for the permeate channel, and another membrane
The feed solution is fed into one end of the module and flows through the
separator screens along the surface of the membranes
 The retentate is the collected in the other end of the module
The permeate spirals radially inward, eventually to be collected through a
central tube
The flow in these systems tend to be turbulent
The main advantage of spiral-wound modules is that they are susceptible to
fouling by particulates because of the narrow and irregular flow through
spacers
Spiral-wound elements and assembly

Local solution flow paths for spiral-wound separator.

iii. Hollow-fiber membranes
The membranes are in the shape of very-small-diameter hollow fibers
Typically, the high-pressure feed enters the shell side at one end and leaves
at the other end
The hollow fibers are closed at one end of the tube bundles
 The permeate solution inside the fibers flows countercurrent to the shell-side
flow and is collected in a chamber where the open ends of the fibers
terminate
Then the permeate exits the device
Hollow-fiber separator assembly.
4. Flux Equation for Reverse Osmosis
i.Osmotic pressure of solutions
Experimental data shows that the osmotic pressure of a solution is proportional to
the concentration of the solute and temperature T
Vant Hoff originally showed that the relationship is similar to that for pressure of an
ideal gas
 For example, for dilute water solutions,
n: number of kg mol of solute,
Vm: volume of pure solvent water in m3
(1) associated with n kg mol of solute,
R: gas law constant 82.057 x 10-3 m3atm/kg molK,
T: temperature in K.

If a solute exists as two or more ions in solution, n represents the total

number of ions
For more concentrated solutions, Eq. (1) is modified using the osmotic
coefficient , which is the ratio of the actual osmotic pressure to the
ideal calculated from the equation
 Example 1
Calculate the osmotic pressure of a solution containing 0.10 g mol NaCl/1000 g
H20 at 25C.
Solution:
The density of water = 997.0 kg/m3 and then, n = 2 x 0.10 x 10-3 =
2.00 x 10-4 kg mol (NaCl gives two ions). Also, the volume of the
pure solvent water Vm = 1.00 kg/(997.0 kg/m3). Substituting into
Eq. (1),

This compares with the experimental value in Table 1 of 4.56 atm.

Example 1
Table 1. Osmotic Pressure of Various Aqueous Solutions at 25C
ii. Diffusion-type models
For diffusion type membranes, the steady-state equations
governing the transport of solvent and solute are to a first
approximation.
For the diffusion of the solvent through the membrane,

(2)

(3)

where Nw is the solvent (water) flux in kg/sm2; Pw the

solvent membrane permeability, kg solvent/smatm; Lm the
membrane thickness, m; Aw the solvent permeability
constant, kg solvent/sm2atm; P = P1 - P2 (hydrostatic
pressure difference with P1 pressure exerted on feed and P2
on product solution), atm; and = 1 - 2 (osmotic pressure
of feed solution - osmotic pressure of product solution), atm.
 For the diffusion of the solute through a membrane, an
approximation for the flux of the solute is
(4)

(5)

where Ns is the solute (salt) flux in kg solute/sm2; Ds the

diffusivity of solute in membrane, m2/s; Ks = cm/c (distribution
coefficient), concentration of solute in membrane/concentration
of solute in solution; As is the solute permeability constant, m/s;
c1 the solute concentration in upstream or feed (concentrate)
solution, kg solute/m3; and c2 the solute concentration in
downstream or product (permeate) solution, kg solute/m3. The
distribution coefficient Ks is approximately constant over the
membrane.
 Making a material balance at steady state for the solute, the solute
diffusing through the membrane must equal the amount of solute is
leaving in the downstream or product ( permeate) solution:

(6)

where cw2 is the concentration of solvent in stream 2 (permeate), kg

solvent/m3. If the stream 2 is dilute in solute, cw2 is approximately the
density of the solvent.
In reverse osmosis, the solute rejection R is defined as the ration
concentration difference across the membrane divided by the bulk
concentration on the feed or concentrate side (fraction of solute
remaining in the feed stream):
(7)
 This can be related to the flux equation as follows, by first substituting
Eq. (2) and (4) into (6) to eliminate Nw and Ns in Eq. (6)
Then, solving for c2/c1 and substituting this result to Eq. (7)

(8) where B is in atm-1

(9)
Example 2
Experiments at 25C were performed to determine the permeabilities of a
cellulose acetate membrane. The laboratory test section shown in Fig. 3 has
membrane area A = 2.00 x 10-3 m2. The inlet feed solution concentration of
NaCl is c1 = 10.0kg NaCl/m3 solution (10.0 g NaCI/L, 1 = 1004 kg
solution/m3). The water recovery is assumed low so that the concentration c1
in the entering feed solution flowing past the membrane and the
concentration of the exit feed solution are essentially equal. The product
solution contains c2 = 0.39 kg NaCl/m3 solution (2 = 997 kg solution/m3) and
its measured flow rate is 1.92 x 10-8 m3 solution/s. A pressure differential of
5514 kPa (54.42 atm) is used. Calculate the permeability constants of the
membrane and the solute rejection R.

FIGURE. Process flow diagram

of experimental reverse-osmosis
laboratory unit.
Solution:
Since c2 is very low (dilute solution), the value of c2 can be assumed as the
density of water (Table 1), or cw2 = 997 kg solvent/m3. To convert the product
flow rate to water flux, Nw, using an area of 2.00 x 10-3 m2,

Substituting into Eq. (6),

To determine the osmotic pressures from Table 1, the concentrations are
converted as follows. For c1, 10 kg NaCl is in 1004 kg solution/m3 (1 = 1004).
Then, 1004 10 = 994 kg H2O in 1 m3 solution. Hence, in the feed solution,
where the molecular weight of NaCl = 58.45, (10.00 X 1000)/ (994 x 58.45) =
0.1721 g mol NaC1/kg H2O. From Table 1, 1 = 7.80 atm by linear interpolation.
Substituting into Eq. (1), the predicted = 8.39 atm, which is higher than the
experimental value. For the product solution, 997 - 0.39 = 996.6 kg H2O. Hence,
(0.39 x 1000)/(996.6 x 58.45) = 0.00670 g mol NaCl/kg H2O. From Table 1, 2 =
0.32 atm. Then, = 1 - 2 =7.80 - 0.32 = 7.48 atm and P = 54.42
atm.Substituting into Eq. (2),
Solving, (Pw/Lm) = A = 2.039 x 10-4 kg solvent/s m2 atm. Substituting into Eq.
(4),

Solving, (DsKs/Lm) = As = 3.896 x 10-7 m/s.To calculate the solute rejection R by

substituting into Eq. (7),

Also, substituting into Eq. (9) and then Eq. (8),

Thank you