Membrane processes

Paul Ashall, 2007

 Membrane processes
Microfiltration
Ultrafiltration
Reverse osmosis
Gas separation/permeation
Pervaporation
Dialysis
Electrodialysis
Liquid membranes

Paul Ashall, 2007

Etc
 Membrane applications in the
pharmaceutical industry
UP water (RO)
Nitrogen from air
Controlled drug delivery
Dehydration of solvents
Waste water treatment
Separation of isomers (e.g. naproxen) (Membrane
Technology and Applications pp517, 518)
Membrane extraction
Sterile filtration

Paul Ashall, 2007

 Specific industrial applications

Dialysis hemodialysis (removal of waste metabolites, excess body water

and restoration of electrolyte balance in blood)
Microfiltration sterilization of pharmaceuticals; purification of
antibiotics;separation of mammalian cells from a liquid
Ultrafiltration recovery of vaccines and antibiotics from fermentation
broth

etc

Ref. Seader p715

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 RETENTATE

FEED
PERMEATE

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 Membrane structure (dense, microporous,
asymmetric, composite, membrane support)

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 Membrane types - isotropic
Microporous pores 0.01 to 10 microns
diam.; separation of solutes is a function of
molecular size and pore size distribution
Dense non-porous driving force;
diffusion; solubility
Electrically charged microporous

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 Anisotropic (asymmetric)
Thin active surface layer supported on
thicker porous layer
Composite different polymers in layers
Others ceramic, metal, liquid

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Asymmetric membranes

Thin dense layer

Microporous support

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 Membrane materials
Polymers
Metal membranes
Ceramic membranes (metal oxide, carbon,
glass)
Liquid membranes

Paul Ashall, 2007

 Membrane fabrication
Isotropic
Solution casting
Melt extrusion
Track etch membranes (Baker fig. 3.4)
Expanded film membranes (Baker fig. 3.5)

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 continued
Anisotropic
Phase separation (Loeb Sourirajan
method) (see Baker fig. 3.12)
Interfacial polymerisation
Solution coated composite membranes
Plasma deposition

Paul Ashall, 2007

 Membrane modules
Plate and frame - flat sheets stacked into an
element
Tubular (tubes)
Spiral wound designs using flat sheets
Hollow fibre - down to 40 microns diam.
and possibly several metres long ; active
layer on outside and a bundle with
thousands of closely packed fibres is sealed
in a cylinder Paul Ashall, 2007
Paul Ashall, 2007
Spiral wound module

Paul Ashall, 2007

Membrane filtration Buss-SMS-Canzler

Paul Ashall, 2007

 Operating considerations

Membrane fouling
Concentration polarisation (the layer of solution
immediately adjacent to the membrane surface
becomes depleted in the permeating solute on the
feed side of the membrane and enriched in this
component on the permeate side, which reduces
the permeating components concentration
difference across the membrane, thereby lowering
the flux and the membrane selectivity)
Flow mode (cross flow, co-flow, counter flow)
Paul Ashall, 2007
 Aspects
Crossflow (as opposed to dead end)
cross flow velocity is an important
operating parameter
Sub-micron particles
Thermodynamic driving force (P, T, c etc)
for transport through membrane is activity
gradient in membrane
Flux (kg m-2 h-1)
Selectivity
Paul Ashall, 2007

Membrane area
Characteristics of filtration processes
Process Separation Size range MWCO
technology principle

MF Size 0.1-1m -

UF Size,charge 1nm-100nm >1000

NF Size, charge, 1nm 200-1000

affinity

RO Size, charge, < 1nm <200

affinity

Paul Ashall, 2007

Process Typical Feed recovery Rejected species
technology operating (%)
pressure (bar)
MF 0.5-2 90-99.99 Bacteria, cysts,
spores

UF 1-5 80-98 Proteins, viruses,

endotoxins,
pyrogens
NF 3-15 50-95 Sugars,
pesticides

RO 10-60 30-90 Salts, sugars

Paul Ashall, 2007

 Models
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.
Paul Ashall, 2007
 Simple model (liquid flow
through a pore using Poiseuilles
J = p d 2
law)
32 l
J = flux
l = pore length
d = pore diam.
p = pressure difference across pore
= liquid viscosity
= porosity ( d2 N/4, where N is number of pores per cm2)
J/p permeance

Typical pore diameter: MF 1micron; UF 0.01 micron

Paul Ashall, 2007

 Mechanisms for transport
through membranes
Bulk flow
Diffusion
Solution-diffusion (dense membranes RO,
PV, gas permeation)

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 continued
Dense membranes: transport by a solution-
diffusion mechanism
Microporous membranes: pores
interconnected

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 Separation of liquids
Porous membranes
Asymmetric membranes/dense polymer
membranes

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 continued
With porous membranes separation may depend
just on differences in diffusivity.
With dense membranes permeation of liquids
occurs by a solution-diffusion mechanism.
Selectivity depends on the solubility ratio as well
as the diffusivity ratio and these ratios are
dependent on the chemical structure of the
polymer and the liquids. The driving force for
transport is the activity gradient in the membrane,
but in contrast to gas separation, the driving force
cannot be changed over a wide range by
increasing the upstream pressure, since pressure
has little effect on activity in the liquid phase.
Paul Ashall, 2007
 Microporous membranes
Porosity ()
Tortuosity () (measure of path length compared
to pore diameter)
Pore diameter (d)

Ref. Baker p68 Fig 2.30

Paul Ashall, 2007
 Microporous membranes
Screen filters (see Baker fig. 2.31) separation of
particles at membrane surface.
Depth filters (see Baker fig. 2.34) separation of
particles in interior of the membrane by a capture
mechanism; mechanisms are sieving and
adsorption (inertial capture, Brownian diffusion,
electrostatic adsorption)

Ref. Baker pp69, 73

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 Filtration
Microfiltration (bacteria potable water, 0.5 5
microns). Pore size specified.
Ultrafiltration (macromolecules, molecular mass
1000 106, 0.5 10-3 microns). Cut-off mol. wt.
specified.
Nanofiltration (low molecular weight, non-volatile
organics from water e.g. sugars). Cut off mol. wt.
specified.
Reverse osmosis (salts)

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 continued
Crossflow operation (as opposed to dead end
filtration)

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 Membrane types
Dense
High porosity
Narrow pore size distribution

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 Ultrafiltration(UF)
Uses a finely porous membrane to separate water
and microsolutes from macromolecules and
colloids.
Membrane pore diameter 0.001 0.1 m.
Nominal cut off molecular weight rating assigned
to membrane.
Membrane performance affected by:
Concentration polarisation
Membrane fouling
Membrane cleaning
Operating pressure Paul Ashall, 2007
Spiral wound UF module

Paul Ashall, 2007

 UF
Membrane materials (Loeb- Sourirajan process)
Polyacrylonitrile (PAN)
PVC/PAN copolymers
Polysulphone
PVDF (polyvinylidene difluoride)
PES (polyethersulfone)
Cellulose acetate (CA)

Paul Ashall, 2007

 UF
Modules
Tubular
Plate and frame
Spiral wound
Capillary hollow fibre

Paul Ashall, 2007

 UF applications
Protein concentration

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 Microfiltration (MF)
Porous membrane; particle diameter 0.1 10 m
Microfiltration lies between UF and conventional
filtration.
In-line or crossflow operation.
Screen filters/depth filters (see Baker fig. 7.3, p 279)
Challenge tests developed for pore diameter and pore
size.

Paul Ashall, 2007

 MF
Membrane materials
Cellulose acetate/cellulose nitrate
PAN PVC
PVDF
PS

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 MF
Modules
Plate and frame
Cartridge filters (see Baker figs. 7.11/7.13,
p288, 290)

Paul Ashall, 2007

 MF operation
Fouling
Backflushing
Constant flux operation

Paul Ashall, 2007

 MF uses
Sterile filtration of pharmaceuticals (0.22
m rated filter)
Drinking water treatment

Paul Ashall, 2007

 Reverse osmosis
Miscible solutions of different concentration
separated by a membrane that is permeable to
solvent but impermeable to solute. Diffusion of
solvent occurs from less concentrated to a more
concentrated solution where solvent activity is
lower (osmosis).
Osmotic pressure is pressure required to equalise
solvent activities.
If P > osmotic pressure is applied to more
concentrated solution, solvent will diffuse from
concentrated solution to dilute solution through
membrane (reverse osmosis).
Paul Ashall, 2007
 Reverse osmosis
The permeate is nearly pure water at ~ 1atm.
and very high pressure is applied to the feed
solution to make the activity of the water
slightly greater than that in the permeate.
This provides an activity gradient across the
membrane even though the concentration of
water in the product is higher than that in
the feed.
Paul Ashall, 2007
 Reverse osmosis
Permeate is pure water at 1 atm. and room
temperature and feed solution is at high P.
No phase change.
Polymeric membranes used e.g. cellulose
acetate
20 50 atm. operating pressure.
Concentration polarisation at membrane
surface.
Paul Ashall, 2007
 RO

P1 P P2

P1 P2

Paul Ashall, 2007

 Model
Flux equations
Salt rejection coefficient

Paul Ashall, 2007

 Water flux
Jw = cwDwvw (P )
RT z

Dw is diffusivity in membrane, cm2 s-1

cw is average water conc. in membrane, g cm-3 (~ 0.2)
vw is partial molar volume of water, cm3g-1
P pressure difference
R gas constant
T temperature
osmotic pressure
z membrane thickness Paul Ashall, 2007
 Salt flux
Js = Ds Ss (cs)
z
Ds diffusivity
Ss solubility coefficient
cs difference in solution concentration

Ref. Baker pp 34, 195

Paul Ashall, 2007
Jw increases with P and selectivity increases
also since Js does not depend on P.

Paul Ashall, 2007

 Membrane materials
Asymmetric cellulose acetate
Polyamides
Sulphonated polysulphones
Substituted PVA
Interfacial composite membranes
Composite membranes
Nanofiltration membranes (lower pressure, lower
rejection; used for lower feed solution
concentrations)
Paul Ashall, 2007
Ref. Baker p203
 RO modules
Hollow fibre modules (skin on outside, bundle in sealed
metal cylinder and water collected from fibre lumens;
individual fibres characterised by outside and inside
diameters)
Spiral wound modules (flat sheets with porous spacer
sheets, through which product drains, and sealed edges; a
plastic screen is placed on top as a feed distributor and
sandwich is rolled in a spiral around a small perforated
drain pipe) (see McCabe fig. 26.19)
Tubular membranes

Paul Ashall, 2007

 Operational issues
Membrane fouling
Pre-treatment of feed solutions
Membrane cleaning
Concentration polarisation (higher conc. of solute at
membrane surface than in bulk solution reduces water
flux because the increase in osmotic pressure reduces
driving force for water transport and solute rejection
decreases because of lower water flux and greater salt
conc. at membrane surface increases solute flux) (Baker
ch. 4)
> 99% salt rejection
Paul Ashall, 2007
 Example
See McCabe p893

Paul Ashall, 2007

 Applications
UP water (spec. Baker pp 226, 227)

Paul Ashall, 2007

 Dialysis
A 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. Solutes of high mol. wt. are mostly retained in
the feed solution, because their diffusivity is low and
because diffusion in small pores is greatly hindered when
the molecules are almost as large as the pores.
Uses thin porous membranes.

Paul Ashall, 2007

 Electrodialysis
Ions removed using ion selective membranes
across which an electric field is applied.
Used to produce potable water from brackish
water. Uses an array of alternate cation and
anion permeable membranes.

Paul Ashall, 2007

 Pervaporation (PV)
In 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.

Paul Ashall, 2007

 PV
The phase change occurs in the membrane and the
heat of vapourisation 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 and this usually limits the application
of PV to removal of small amounts of feed,
typically 2 to 5 % for 1-stage separation. If a
greater removal is needed, several stages are used
in series with intermediate heaters.
Paul Ashall, 2007
 Pervaporation (PV)
Hydrophilic membranes (PVA) e.g.
ethanol/water
Hydrophobic membranes (organophilic) e.g.
PDMS

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 PV
Composite membrane (dense layer + porous
supporting layer)

Ref. Baker p366

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 Modules
Plate & frame (Sulzer/GFT)

Paul Ashall, 2007

 PV
Solution diffusion mechanism
Selectivity dependent on chemical structure
of polymer and liquids

Paul Ashall, 2007

 PV
Activity driving force is provided by
difference in pressure between feed and
permeate side of membrane.
Component flux is proportional to
concentration and diffusivity in dense
membrane layer.
Flux is inversely proportional to membrane
thickness.

Paul Ashall, 2007

 Models
Solution diffusion model
Experimental evidence (ref. Baker pp 43
48)

Paul Ashall, 2007

 continued
Ji = PiG (pio pil)
l
Ji flux, g/cm2s
PiG gas separation permeability coefficient, gcm.
cm-2 s-1. cmHg-1
l membrane thickness
pio partial v.p. i on feed side of membrane
pil partial vp i on permeate side
Paul Ashall, 2007
 PV selectivity
= (cil/cjl)
(cio/cjo)

cio conc. i on feed side of membrane

cil conc. i on permeate side of membrane
cjo conc. j on feed side
cjl conc. j on permeate side

Paul Ashall, 2007

 continued
Structure permeability relationships
Sorption coefficient, K (relates
concentration in fluid phase and membrane
polymer phase)
Diffusion coefficient, D

Ref. Baker p48

Paul Ashall, 2007
 continued
Diffusion in polymers
Glass transition temperature,Tg
Molecular weight, Mr
Polymer type and chemical structure,
Membrane swelling,
Free volume correlations

Paul Ashall, 2007

 continued
Sorption coefficients in polymers vary much less
than diffusion coefficients, D.

nim = pi/pisat , where nim is mole fraction i absorbed,

pi is partial pressure of gas and pisat is saturation
vapour pressure at pressure and temperature of
liquid.

Vi = pi/pisat , where Vi is volume fraction of gas

2.72 absorbed by an ideal polymer
Paul Ashall, 2007
 Dual sorption model
Gas sorption in a polymer occurs in two types
of site (equilibrium free volume and excess
free volume (glassy polymers only)).

Baker pp56-58
Paul Ashall, 2007
 continued
Flux through a dense polymer is inversely
proportional to membrane thickness.
Flux generally increases with temperature (J =
Jo exp (-E/RT).
An increase in temperature generally
decreases membrane selectivity.

Paul Ashall, 2007

 PV process design
Vacuum driven process
Condenser
Liquid feed has low conc. of more permeable
species

Ref. Baker p 370

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 Applications
Dehydration of solvents e.g. ethanol (see
McCabe pp886-889, fig. 26.16/example
26.3)
Water purification/dissolved organics e.g.
low conc. VOC in water with limited
solubility
Organic/organic separations

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PV hybrid processes using
distillation

Paul Ashall, 2007

 continued
Measures of selectivity
Rate (flux, membrane area)
Solution diffusion model in polymeric
membranes (RO, PV etc)
Concentration polarisation at membrane
surface
Membrane fouling
Batch or continuous operation
Paul Ashall, 2007
 Gas separation
When a gas mixture diffuses through a porous
membrane to a region of lower pressure, the
gas permeating the membrane is enriched in
the lower mol. wt. component(s), since they
diffuse more rapidly.

Paul Ashall, 2007

 Gas separation
The transport of gases through dense (non-porous)
polymer membranes occurs by a solution-
diffusion mechanism.The gas is absorbed in the
polymer at the high pressure side of the
membrane, diffuses through the polymer phase
and desorbs at the low pressure side. The
diffusivities in the membrane depend more
strongly on the size and shape of the molecules
than do gas phase diffusivities.
Paul Ashall, 2007
 continued
Gas separation processes operate with pressure
differences of 1 20 atm., so the thin membrane
must be supported by a porous structure capable of
withstanding such pressures but offering little
resistance to the flow of gas. Special methods of
casting are used to prepare asymmetric membranes,
which have a thin, dense layer or skin on one side
and a highly porous substructure over the rest of the
membrane. Typical asymmetric membranes are 50
to 200 microns thick with a 0.1 to 1 micron dense
layer.
Paul Ashall, 2007
 Mechanisms
Convective flow (large pore size 0.1 10 m; no
separation)
Knudsen diffusion (pore size < 0.1m; flux
1/(Mr)1/2)
Molecular sieving (0.0005 0.002 m)
Solution-diffusion (dense membranes)

(See Baker fig. 8.2, p303)

Paul Ashall, 2007
 Knudsen diffusion
Knudsen diffusion occurs when the ratio of
the pore radius to the gas mean free path (
~ 0.1 micron) is less than 1. Diffusing gas
molecules then have more collisions with
the pore walls than with other gas
molecules. Gases with high D permeate
preferentially.

Paul Ashall, 2007

 Poiseuille flow
If the pores of a microporous membrane are
0.1 micron or larger, gas flow takes place
by normal convective flow.i.e. r/ > 1

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Transport of gases through dense
membranes
JA = QA (pA1 pA2)

QA is permeability (L (stp) m-2 h-1 atm-1)

pA1 partial pressure A feed
pA2 partial pressure A permeate

Paul Ashall, 2007

 Membrane selectivity
= QA/QB = DASA/DBSB

D is diffusion coefficient
S is solubility coefficient (mol cm-3 atm-1) i.e. cA =
pASA, cB = pBSB

(Ref. McCabe ch. 26 pp859 860)

Paul Ashall, 2007
Diffusion coefficients in PET (x
109 at 25oC, cm2 s-1)

Polymer O2 N2 CO2 CH4

PET 3.6 1.4 0.54 0.17

Paul Ashall, 2007

 Membrane materials
Metal (Pd Ag alloys/Johnson Matthey for
UP hydrogen)
Polymers (typical asymmetric membranes
are 50 to 200 microns thick with a 0.1 to 1
micron skin)
Ceramic/zeolite

Paul Ashall, 2007

 Modules
Spiral wound
Hollow fibre

Paul Ashall, 2007

 Flow patterns
Counter-current
Co-/counter
Radial flow
crossflow

Paul Ashall, 2007

 System design
Feed/permeate pressure (p = 1 20 atm.)
Degree of separation
Multistep operation

Paul Ashall, 2007

 Applications

Oxygen/nitrogen separation from air (95 99%

nitrogen)
Dehydration of air/air drying

Ref. Baker p350

Paul Ashall, 2007
 Other membrane processes
Ion exchange
Electrodialysis e.g. UP water
Liquid membranes/carrier facilitated
transport e.g. metal recovery from aqueous
solutions

Paul Ashall, 2007

PV demonstration

Paul Ashall, 2007

 Reference texts
Membrane Technology and Applications, R. W.
Baker, 2nd edition, John Wiley, 2004
Handbook of Industrial Membranes, Elsevier,
1995
Unit Operations in Chemical Engineering ch. 26,
W. McCabe, J. Smith and P. Harriot, McGraw-
Hill, 6th edition, 2001
Transport Processes and Unit Operations, C. J.
Geankoplis, Prentice-Hall, 3rd edition, 1993
Membrane Processes: A Technology Guide, P. T.
Cardew and M. S. Le, RSC,
Paul Ashall, 20071998
 continued
Perrys Chemical Engineers Handbook, 7th
edition, R. H. Perry and D. W. Green,
McGraw-Hill, 1998
Separation Process Principles, J. D. Seader
and E. J. Henley, John Wiley, 1998
Membrane Technology in the Chemical
Industry, S. P. Nunes and K. V. Peinemann
(Eds.), Wiley-VCH, 2001

Paul Ashall, 2007