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MEMBRANE SEPARATION

1.1 What is a membrane/membrane separation?

MEMBRANE is an interface that separates the two


phases and restricts the transport of various
chemical species through it.
Membrane can be homogeneous, heterogeneous,
symmetric, asymmetric, charged, neutral.

In a membrane separation process, a feed


consisting of a mixture of two or more components is
partially separated by means of a semipermeable
barrier (the membrane) through which one or more
species move faster than another or other species.
Driving force(s)

Separation in membrane is the result of differences in the


transport rates of chemical species through it.

Transport rate is determined by the driving force acting


on individual components, their mobility, concentration
of solute in membrane phase, etc..

Mobility: Depending on solute size and structure of


membrane.

Concentration: Chemical compatibility of solute &


interface material.
Source: Seader & Henley
1.2 Definitions / Terminology

TMP transmembrane pressure

The term filtrate is used for normal flow filtration (NFF), i.e.,
no retentate.

The term permeate us used for tangential flow filtration (TFF).


Source: Seader & Henley
Flux (J)
J = volumetric permeate flow rate / membrane area

Permeability (L)
a measure of sensitivity of flux to TMP

L = flux / TMP

Recovery or conversion ratio (CR)


measure of efficiency of a membrane module

CR = permeate flow rate / feed flow rate


PERMEANCE VS PERMEABILITY

PERMEANCE volume flowing through the


membrane per unit area per unit time. The
measure of the effectiveness of a membrane in
separating a mixture. (analogous to a mass transfer
coefficient)
PERMEABILITY transport flux of material
through a membrane per unit driving force per unit
membrane thickness. This characterizes the
transport capability of the barrier itself.
Concentration polarization
occurs when solutes entrained by the permeate flow are
retained by the membrane, resulting in solute accumulation on
the membrane surface and forming a region of high
concentration called the polarization boundary layer.
Sieving coefficient (S)
S = cP / cF

cP permeate concentration; cF feed concentration

Rejection (R)
a measure of retention of the solute

R=1S
1.3 Types of Membrane Barrier

Homogeneous barrier
Pore size is 2-10
Diffusion is the controlling mechanism.

Microporous barrier
Pore size is 10-1000
Both convection and diffusion are dominant mechanism.
Asymmetric barrier
In this case, a thin polymeric skin is cast on another polymeric
support. The skin acts like a membrane. Since the thickness of
the skin is really small, the resistance offered is less and one
can expect a higher flux compared to homogeneous
membranes.
Schematic of an asymmetric membrane
Transmembrane permeate flux is inversely proportional to the
membrane thickness. If homogeneous barrier is the skin, microporous
barrier may be the support.
COMMON MEMBRANE MODULES:
(a) plate-and-frame; (b) spiral wound
COMMON MEMBRANE MODULES:
(c) 4-leaf spiral wound; (d) hollow fiber
COMMON MEMBRANE MODULES:
(e) Tubular ; (f) monolithic
1.4 Motion of Molecules Through Barrier

A. PERMEATION
Dissolution of permeating molecules in the membrane

Diffusion of dissolved molecules

Desorption of penetrant molecules to the downstream side

KNUDSEN DIFFUSION (d/ < 0.2)


Single molecules diffuse under rarefied conditions so that the
mean free path is larger than the pore diameter.
CONVECTION (d/ > 20)
Viscous flow through the pores (e.g., ultrafiltration,
microfiltration).
Source: Seader & Henley
1.5 Process Categories
REVERSE OSMOSIS (RO)
Small solute particles to be separated.

Molecular weight < 100


Pore size: 2 10
Pressure: > 25 atm (0.30 to 10.5 Mpa)

Permeation is main transport mechanism

Example: Filtration of salt solution


Component transport in RO

Jw
Pw
P P
P3
l l 20-73 PCHE HB 8ed

J i cw c p Pc w
P2 P3
l l
Note: Pw water permeabiliy , P2 solute permeability, P3 -
(PCHE HB nomenclature).

Solute Retention (Eq. 20-75):


cp Ji P2 P3P
Ri 1 1
cw cw J w Pw P
NANOFILTRATION

Particles to be separated with Molecular weight: 200


1000
Pore size: 5 20
Pressure: 15 25 atm.
Particle retention of salts.

Example: Filtration of dyes, small molecular weight


organics, etc.
ULTRAFILTRATION

Molecular weight of particles : 103 - 105

Pore size: 20 1000 A0

Pressure: 6 8 atm (0.2 1 Mpa)

Transport Mechanism: Convection (main) + diffusion

Example: Filtration of protein, Red blood cells, polymers, etc.


MICROFILTRATION

Molecular weight > 1 lakh

Pore size: more than 1000

Pressure: 2 4 atm.

Example: Filtration of clay solution, latex, paint, etc.


GAS PERMEATION (GP)

In GP, the feed gas, at high pressure, contains some low-MW


species (MW < 50) to be separated from small amounts of
high-MW species. Usually a sweep gas is not used, but the
other side of the membrane is maintained at a much lower
pressure, often near ambient.
PERVAPORATION
In pervaporation, the feed is a liquid mixture (e.g., alcohol-
water azeotrope) at a usually ambient pressure or elevated
high enough to maintain a liquid phase as the feed is depleted
of species A and B to produce the product retentate.
Gas Permeation vs Pervaporation
Pervaporation one side of the dense membrane
is exposed to the feed liquid at atmospheric
pressure and vacuum is used to form a vapour
phase on the permeate side. This lowers the partial
pressure of the permeating species and provides an
activity driving force for permeation.
Gas Permeation no phase change occurs during
permeation from the feed to the permeate side
DIALYSIS
In dialysis, the feed is liquid, at pressure P1, containing
solvent, solutes of type A, and solutes of type and/or insoluble,
but dispersed, colloidal matter. A sweep liquid or wash of the
same solvent is fed at pressure P2 to the other side of the
membrane.
At a differential location in a dialyzer, the rate of mass transfer of solute
across the dialysis membrane is given by:

dni Ki ciF ciP dAM


n K A c
For nearly
countercurrent
i i M i LM
flow
Where Ki is the overall mass-transfer coefficient, which is given in terms of
the individual coefficients :

1 1 lM 1

K i kiF PMi kiP
ELECTRODIALYSIS (ED)
A separation process in which the ionic species are separated
from water, macrosolutes, and all uncharged solutes. Ions are
induced to move by an electrical potential, and separation is
facilitated by ion-exchange membranes.
DIALYSIS VS ELECTRODIALYSIS
DIALYSIS process for selectively removing low
mol. wt. solutes from solution by allowing them to
diffuse into a region of lower concentration
through thin porous membranes. There is little or
no pressure difference across the membrane and
the flux of each solute is proportional to the
concentration difference
ELECTRODIALYSIS Ions removed using ion
selective membranes across which an electric field
is applied. Uses an array of alternate cation and
anion permeable membranes.
OTHER MODELS OF TRANSPORT
MECHANISM

Ficks law (solution-diffusion model)


Free volume elements (pores) are spaces
between polymer chains caused by thermal
motion of polymer molecules.

Darcys law (pore flow model)


Pores are large and fixed and connected.
Describes bulk flow applications like
filtration through the cake.
PORE RESISTANCE TO FLOW

Consider bulk flow of liquid due to pressure difference


through an idealized, straight cylindrical pore (Hagen-
Poiseuille Law)
N = P D2
32 lM
N = flux
lM = pore length
D = pore diam.
p = pressure difference across pore
= liquid viscosity
= porosity ( D2 n/4, where n is number of pores per cm2)
N/p permeance

Typical pore diameter: MF 1micron; UF 0.01 micron


PORE RESISTANCE TO FLOW

In terms of a bulk flow permeability


N = PMP
lM
Where PM = 3
2(1 )2 av2
Pressure Drop through a membrane

It is desired to pass water at 70F through a


supported polypropylene membrane with a skin of
0.003-cm thickness and 35% porosity at the rate of
200 m3/m2 membrane surface area/day. The pores
can be considered straight cylinders of uniform
diameter equal to 0.2 m. If the pressure on the
downstream side of the membrane is 150kPa,
estimate the required pressure on the upstream side
of the membrane. The pressure drop through the
support is negligible