‫מארזי ממברנות בתעשייה‬

‫מכללת סמי שמעון ‪2011‬‬

 ‫ממברנות שטוחות‬
• Microfiltration
• Ultrafiltration
• Reverse osmosis
• Gas separation/permeation
• Pervaporation
• Dialysis
• Electrodialysis
• Liquid membranes
• Etc
Paul Ashall, 2007
 ‫ממברנות סיבים חלולים‬
• 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

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 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

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 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

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 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
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Spiral wound module

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Membrane filtration – Buss-SMS-Canzler

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

MF Size 0.1-1μm -

UF Size,charge 1nm-100nm >1000

NF Size, charge, 1nm 200-1000

affinity

RO Size, charge, < 1nm <200

affinity

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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

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 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.
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 Simple model (liquid flow
through a pore using Poiseuilles
J = Δp ε d
law)
2

32 μ l
J = flux
l = pore length
d = pore diam.
Δp = pressure difference across pore
μ = liquid viscosity
ε = porosity (π d2 N/4, where N is number of pores per cm2)
J/Δp – permeance

Typical pore diameter: MF – 1micron; UF – 0.01 micron

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 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.

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 Microporous membranes
• Porosity (ε)
• Tortuosity (τ) (measure of path length compared
to pore diameter)
• Pore diameter (d)

Ref. Baker p68 – Fig 2.30

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 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 μm.
Nominal ‘cut off’ molecular weight rating assigned to
membrane.
Membrane performance affected by:
• Concentration polarisation
• Membrane fouling
• Membrane cleaning
• Operating pressure
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Spiral wound UF module

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

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 UF
Modules
• Tubular
• Plate and frame
• Spiral wound
• Capillary hollow fibre

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 UF applications
• Protein concentration

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 Microfiltration (MF)
Porous membrane; particle diameter 0.1 – 10 μm
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.

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 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)

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 MF operation
• Fouling
• Backflushing
• Constant flux operation

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

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 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).

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 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.
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 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.
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 RO

P1 P P2

P1 » P2

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 Model
• Flux equations
• Salt rejection coefficient

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 Water flux
Jw = cwDwvw (ΔP – Δπ)
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
ΔP pressure difference
R gas constant
T temperature
Δπ osmotic pressure
z membrane thickness
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 Salt flux
Js = Ds Ss (Δcs)
z
Ds diffusivity
Ss solubility coefficient
Δcs difference in solution concentration

Ref. Baker pp 34, 195

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Jw increases with ΔP and selectivity increases
also since Js does not depend on ΔP.

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 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)

Ref. Baker p203

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 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

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 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
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 Example
See McCabe p893

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

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 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.

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 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.

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 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.

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 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.
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 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)

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

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 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.

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

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 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
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 PV selectivity
β = (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

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

Ref. Baker p48

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

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 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

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 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
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 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.

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 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

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 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
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 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.

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 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.
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 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.

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 Mechanisms
• Convective flow (large pore size 0.1 – 10 μm; no
separation)
• Knudsen diffusion (pore size < 0.1μm; flux α
1/(Mr)1/2)
• Molecular sieving (0.0005 – 0.002 μm)
• Solution-diffusion (dense membranes)

(See Baker fig. 8.2, p303)

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 Knudsen diffusion
Knudsen diffusion occurs when the ratio of
the pore radius to the gas mean free path (λ
~ 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.

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 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/λ > 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

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 Membrane selectivity
α = 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)

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Diffusion coefficients in PET (x
10 at 25 C, cm s )
9 o 2 -1

Polymer O2 N2 CO2 CH4

PET 3.6 1.4 0.54 0.17

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 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

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 Modules
• Spiral wound
• Hollow fibre

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

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

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 Applications

• Oxygen/nitrogen separation from air (95 – 99%

nitrogen)
• Dehydration of air/air drying

Ref. Baker p350

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

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PV demonstration

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 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, 1998
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 continued
• Perry’s 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

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