Membrane Technology & Separation

Processes

(Electrodialysis & Concentration

Polarization)
Module- 23

Lec- 23

Dr. Shishir Sinha

Dept. of Chemical Engineering
IIT Roorkee
Mixing vs Separation

Two substances a and b will mix or separate depending on free enthalpy of mixing(G )
m

G = H TS
m m m

where H is the enhalpy of mixing and S is the entropy of mixing.

m m

G < 0:Spontaneous mixing ;

m

G > 0:Spontaneous separation

m

In most cases and always when A and B are gases the mixing occurs spontaneously and
minimum amount of energy, W = G
min m

The actual energy requirement for the separation will bemany times greater than W
min

The actual energy requirement depends on the type of separation processes

Membrane Separations

What is a membrane?

A membrane is a physical barrier (no necessarily solid) that gives, or at least helps, the separation
of the components in a mixture.
- Membrane processes are not based in thermodynamic equilibrium but based in the different
transport rate of each species through the membrane.

- The membrane market is still growing. In the 1986-96 decade, the sales related to membrane
products and systems doubled.

- In 1998, these sales were over 5000 million .

Advantages

Energy savings. The energy consumption is very low as there is no phase change.

Low temperature operation. Almost all processes proceed at room temperature, thus they can
deal with compounds that are not resistant at high temperatures.

Recovery. Both the concentrate and the permeate could be recovered to use.

Water reuse. When applied to recover water, they avoid the transport of large water volumes
and permit the reduction of the Chemical Oxygen Demand (COD) loading in sewage plants.

Compact operation. Which permits to save space .

Easy scale-up. Because usually they are designed in modules, which can be easily connected.

Automatic operation. The most of the membrane plants are managed by expert systems.

Tailored systems. In many cases, the membranes and systems can be specifically designed
according the problem.
Disadvantages

High cost. Membranes (and associated systems) are costly, but for low selective separations.

Lack of selectivity. In many cases, the separation factors are still insufficient.

Low fluxes. The permeat flowrate available are still too low for some applications.

Sensitive to chemical attack. Many materials can be damaged by acids, oxidants or organic
solvents.

Lack of mechanical resistance. Many materials do not withstand abrasion, vibrations, high
temperatures or pressures.

Membrane Separations

- The membrane operations more widely used are those based in applying a pressure difference
between both sides of the membrane.

Micro Filtration (MF)

(10-0.1m)
Bacteria, suspended particles

Ultrafiltration (UF)
(0.05-0.005m)
Colloids, macromolecules
Nanofiltration (NF)
5e-3-5.e-4 m
Sugars, dyes, divalent salts
Reverse Osmosis (RO)
(1.e-4-1e-5 m)
Monovalent salts, ionic metals

Water

Microfiltration (MF).
 Ultrafiltration (UF)).

Nanofilltration (NF)).

Reversee osmosis (R
RO).

- Althoug
gh similar in
n appearance, the involv
ved mechannisms in the separation can be veryy very
different..

Name off the membrrane process as function of the parrticle size.

- There are
a other sep
paration opeerations where a membraane is the reesponsible oof the la seleective
separatio
on of the com
mpounds:

Dialysis. meation (GP)).

Gas perm Eleectrodialysiss (ED).

Liquid membranes.. Pervaporration.

- In otherrs, the memb ponsible for the separation but it acttively particiipates
brane is not directly resp
in:

Membrrane extractio
on.

Membrrane distillatiion.

Osmotic distillation
n.

Membra
ane Separations

Type of filtration
n.
Membra
ane Separations

Simp
ple scheme of
o a membrrane modulee.

Membra
ane Separations

- Synthettic membran
nes are solid barriers thatt allow prefeerentially to pass specificc compoundds due
to some driving
d forcee.
(Very) Siimple schem
me for somee mechanism
ms of selectivve separatioon on a porous membrrane.

Membra
ane Separations

- The sep
paration abiliity of a synth
hetic materiaal depends oon its physicaal, chemicall properties.

Pore sizze and structture

Design

Chemiccal characterristics

Electriccal charge

ane Separations
Membra

- The meembranes can

n be roughly
y divided in two
t main grooups: porouss and non poorous.
- Porous membranes give separation due to...

size

shape

charge

...of the species.

- Non porous membranes give separation due to...

selective adsorption

diffusion

...of the species.

Membrane Separations

Main parameters.

- Rejection, R, if there is just one component (RO)

CA ,f CA, p C
R (%) 100 100 1 A,p
CA ,f CA,f

- Separation factor - Enrichment factor

CA,p /CB,p A CA,p

A,B A
CA,f /CB,f B CA,f
for two or more component

Membrane Separations

Main parameters.

- In RO, often we use the Recovery (Y)

Qp
Y (%) 100
Qf

3
Q : Permeate flowrate (m /s)
p

3
Q : Feed flowrate (m /s)
f

Membrane Separations

Main parameters.

- Passive transport in membranes. The permeate flux is proportional to a given driving force
(some difference in a property).

Flux (J) Constant (A)

Driving Force (X)

Driving forces:

Pressure (total o partial)

Concentration
 Electric Potential

Membrane Separations

Main parameters.

Membrane processes and driving force.

Feed phase Permeate phase Driving Force

Process

Microfiltration L L P

Ultrafiltration L L P

Nanofiltration L L P

Reverse Osmosis L L P

Dialysis L L c

Electrodialysis L L

Pervaporation L G P

Gas Permeation G G P

Membrane Separations

Main parameters.
- Permeate flux.
In MF and UF, porous membrane model is assumed, where the a stream freely flows through the
pore. Then, the transport law follows the Hagen-Poiseuille equation.
2
J w Q w r P
A m 8 d
3 2 3 2
J : Solvent flux (m /sm ) Q : Solvent flowrate (m /s) A : Membrane area (m )
w w m

d: Membrane thickness (m) : Viscosity (Pa s) P: Hydraulic pressure difference (Pa)

r: Pore radius (m) : Porosity : Tortuosity

Membrane Separations

Main parameters.

- The above model is good for cylindrical pores. However, if the membrane is rather formed by a
aggregated particles, then the Kozeny-Carman relation works much better.

Jw Qw 3 P
A m K S2 1 2 d

3 2 3
J : Solvent flux (m /sm ) Q : Solvent flowrate (m /s)
W W

2 3
S: Particle surface area (m /m ) K: Kozeny-Carman constant

2
A : Membrane area (m ) d: Membrane thickness (m) : Viscosity (Pa s)
m

Membrane Separations
- In the operations governed
g by
y the pressurre, a phenom
menon calleed concentraation polarissation
appears, which must be carefully
y controlled. This is due to the solutee accumulattion neighboouring
the memb
brane surfacce.

Forrmation of the
t polarisaation layer.

Membra
ane Separations

- Concen
ntration polarrisation.

(It is not fouling!!!)

Membra
ane Separations
- Fouling
g: Irreversiblle reduction of the flux th
hroughout thhe time.
Pore sizze reduction by irreversible adsorptio
on of compoounds.

Pore plu
ugging.

Formatiion of a gel layer

l over th
he membranee surface (caake).

Membra
ane Separations
- Membrane can be classified in several ways, but always there are arbitrary classifications.

Structure: symmetric, asymmetric

Configuration: flat, tubular, hollow fiber

Material: organic, inorganic

Surface charge: positive, negative, neutral

...and even other divisions and subdivisions

Membrane Separations

- Structure:

Symmetric. Also called homogeneous. A cross section shows a uniform porous structure.

Asymmetric. In a cross section, one can see two different structures, a thin dense layer and
below a porous support layer.

- Integral: the layers are continuous.

- Composites: the active layer (thickness 0.1-0.5 m) is supported over a highly porous layer (50-
150 m), sometimes both layers are of different materials.

Membrane Separations
Symmetrric UF memb 5 m made of
brane of 0.45 o cellulose acetate (Milllipore).

Membra
ane Separations

Surface Cross sectioon

TM
Symmetrric ceramic membrane
m off 0.2 m maade of aluminna (Al O ) (A
Anopore )).
2 3

Membra
ane Separations
Asymmeetric ceramicc membrane made of -A
Al O (Membbralox).
2 3

Membra
ane Separations

UF
U integral assymmetric membrane
m m
made of polyppropylene.

Membra
ane Separations
 RO comp
posite membrranes.

Membra
ane Separations

- Configu
uration and modules
m

Configu
uration: geom
metric form given to thee synthetic m
membranes.

Modulee: name of th
he devices su
upporting on
ne or several membraness (housing).

The mod
dule seals an
nd isolates th
he different streams. Thee geometry and specificc fluid moveement
through the
t confined
d space charaacterises each module. T
The type of fflux, the trannsport mechaanism
and the membrane
m su
urface pheno
omena depen
nd on the moodule designn.

Membra
ane Separations

- Configu
uration:

Flat.
- The acttive layer is a flat.

- Synthessised as a continuous lay

yer.

- Later, one
o can selecct a desired geometry
g (reectangle, circcle,...) to be placed in the module.

- Used in
n two kind off modules: plate-and-fra
p ame and spiraal wound.

- High su
urface area/v
volume ratio..

Membra
ane Separations

Plaate-and-Fram
me Membranne System.
Consists of layers of
o membranees separated
d by corrugaated structurral sheets, aalternating llayers
d material fllowing in an
with feed nd retentate flowing outt in one direection, whilee permeate fflows
out in thee other direction.

Membra
ane Separations
 Spiral-w
wound moduule.

Membra
ane Separations

Spiral-w
wound moduule.

Membra
ane Separations
- Configu
uration:

Tubularr.

- It is likee a tube.

- Usually
y the active layer
l is insid
de.

- The perrmeate crossses the memb

brane layer to
t the outsidee (this is, thee feed flows inside).

- Low su
urface are/volume ratio.

- Severall lengths and

d diameter (>
>10 mm).

- Modulees grouping one

o or variou
us membran
nes.

Membra
ane Separations

Different
D typees of tubularr modules.

Membra
ane Separations
 Hollow
w fiber moduule.

Membra
ane Separations

Cross secction of hollo

ow fiber (Monsanto). Co
omparison w
with a clip.

Membra
ane Separations
Hollow fiber
f cross seection of pollyamide for RO (DuPonnt).

Membra
ane Separations

Hollow fiber
f ne ( 1 mm
made of polysulfon m) for UF (ddetail).

Membra
ane Separations
Hollow fiber
f cross seection of 1 mm (Mo
onsanto).

Membra
ane Separations

Hollow fiber
f surface of polyproppylene (Celggard).

Membra
ane Separations
 - Comparison between modular configurations.

Module

Parameter Tubular Spiral-wound Hollow fiber

Specific surface area (m2/m3) 300 1000 15000

Inside diameter or spread (mm) 20-50 4-20 0.5-2

Flux (L/m2 day) 300-1000 300-1000 30-100

Production (m3/m3 per module & day) 100-1000 300-1000 450-1500

Space velocity (cm/s) 100-500 25-50 0.5

Pressure loss (bar) 2-3 1-2 0.3

Pretreatment Simple Medium High

Plugging Small Medium Elevated

Replacement Easy Difficult Impossible

Cleaning:

Mechanical Possible Not possible Not possible

Chemical Possible Possible Possible

Membrane Separations
- Comparison between modular configurations.
Modular configurations and processes.

Module

Operation Tubular Spiral-wound Hollow fiber

Reverse Osmosis A VA VA

Ultrafiltration VA A NA

Microfiltration VA NA NA

Pervaporation A VA VA

Gas Permeation NA VA VA

VA = Very appropriate; A = Appropriate; NA = Not appropriate

Membrane Separations

- Material:

Organic.

- Made of polymers or polymer blends.

- Low cost.

- Problems with their mechanical, chemical resistance.

Temperature

pH, Solvents

Pressure
Membra
ane Separations

Polyprropylene witth 0.2 m poores (Accureel).

Membra
ane Separations

Polyttetrafluoroettylene with 00.2 m poress.

Membra
ane Technology
 Dialysis

- Applied
d since the 70s.

- Low ind
dustrial interrest.

- Ions & species of lo

ow MW (<100 Da).

- Ionic Membranes
M (jjust like ED)).

- Driving
g Force: conccentration grradient.
- Slow and low
w selective.

Membra
ane Technology

Dialysis

- Artificiaal kidney.

- NaOH recovery
r in textile
t efflueents, alcoholl removal froom beer, saltts removal (ppharmaceutiical
industry)).
Membra
ane Technology

Dialysis

Looks no
ot very impo
ortant...?.

PV
V
GS ED

HD MF

UF
F
RO

Membran
ne and modu
ule markets

ane Technology
Membra

Electrodialysis (ED
D)

- First ap
pplications baack at 30s.

- Ion Sep
parations.

- Ionic Membranes
M (n
non porous).
- Driving
g Force: grad
dient in electtrical potentiial.

- Potentiaal: 1-2 V.

- Flat con
nfiguration.

- Hundreeds of anionic and cation

nic membran
nes placed altternatively.

- Orthogo
onal electrical field.

Membra
ane Technology

Electrodialysis (ED
D)

ane Technology
Membra

Electrodialysis (ED
D)
Membra
ane Technology

Electrodialysis (ED
D)

- Ionic Membranes
M (n
non porous).

- Based on
o polystyren
ne or polyprropylene with
h sulfonic annd quaternarry amine grooups.

- Thickneess: 0.15-0.6
6 mm.

- ED with
h reverse polarization (E
EDR).

- ED at high
h temperaature (60C).

- ED with
h electrolysiis.

Membra
ane Technology
 Electrodialysis (ED)

- Required membrane area

Mass balance (in equivalents)

Vc
C out
j
j dAm VC z dc 0

Vc
c in
2
Charge flow i: electric current density (A/m )
2
Am: membrane surface (m )

j F dI
i combining
dAm

N VC cin cout

z F V cin cout

z F
AT N Am
i i

2
: global electrical efficiency (~0.5 commercial equipment) j: cation flow (eq/m s)

F: Faraday constant (96500 C/eq)

N: number cells in the equipment

z: cation charge (eq/mol)

Membrane Technology
 Electrodialysis (ED)

- Then the required energy, E (J), is

E N UC I t N I2 R C t UC: potential gradient in a cell (V)

RC: total resistance in a cell ()

as

VC cin cout

z F
I i Am

then

2 2
V c z F V c z F
E N C RC t P N C RC

P: required Power (J/s)

Membrane Technology

Electrodialysis (ED)

3
Where, the required specific energy, (J/m ), is

2
E c z F
E VC RC
N VC t

La cell resistance can be estimated from a model based on series of resistances where the
resistances to transport are considered through two membranes and the compartments
concentrate and diluted.
Membra
ane Technology

Electrodialysis (ED
D)

- How to determine operational

o i?
i

Cation Transport

i z cD cDM

i t
tM D
F F

D F z cD cDM

M
i
tM t

+
If c =0
DM

D F z cD
ilim
tM t
Usually: i = 0.8i
lim

ort number
t: transpo

D: diffusion coefficieent

Membra
ane Technology

Electrodialysis (ED
D)

- Intensitty Evolution versus applied potentiall

Membra
ane Technology

Electrodialysis (ED
D)
- Fields of
o application:
Water
W desalin
nation.
- Competting to RO.
- Econom
mically moree interesting at very high
h or very saltt concentratiions.
- Other fields
fi of appllication:
Food Industry
y.
Treatment
T of heavy metall polluted waater.
Membrane Technology

Electrodialysis (ED)
- Examples:

Production of drinking water from salty water.

Water softening.

Nitrate removal.

Lactose demineralization.

Acid removal in fruit juice.

Tartrate removal from wines.

Heavy metal recovery.

Production of chlorine and sodium hydroxide.

Membrane Technology

Electrodialysis (ED)
 electtrolytic Celll for the pro
oduction of chlorine an
nd sodium hydroxide with cationicc
membrane.
m

Membra
ane Technology

Electrodialysis (ED
D)
 Electrrolytic cell for
f the prod
duction of su
ulfuric acid and sodium
m hydroxidee with bipollar
membrane.
m

Membra
ane Technology

Electrodialysis (ED
D)

Hydrogeen fuel cell with a catioonic membrrane.