Membrane Separations

Microfiltration
Dan Libotean - Alessandro Patti PhD students Universitat Rovira i Virgili, Tarragona, Catalunya

Definition of a membrane
A membrane can be defined as a barrier (not necessarily solid) that separates two phases as a selective wall to the mass transfer, making the separation of the components in a mixture possible.

IDEAL MEMBRANE REAL MEMBRANE

Permeate

Feed
Driving Force

Phase 2

Phase 1
2

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The growing use of MF

1. More attention paid to environmental problems linked to drinking and non-drinking water 2. Increased demand for water (using currently available sources more effectively) 3. Market power

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Membranes market in W. Europe

45 40 35 30 25 20 15 10 5 0

MF

Dialysis

UF

RO

Other

% of total 1997 consumption in Western Europe

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Demand in U.S.A., 2001

MF has been used more and more MF has been used more and more to eliminate particles and micro to eliminate particles and micro organisms in untreated water, organisms in untreated water, leading to aalower consumption leading to lower consumption of disinfectant and to aalower of disinfectant and to lower concentration of SPD (subconcentration of SPD (subproducts of disinfections). products of disinfections).

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Cumulative capacity of MF
50 40 30 20 10 0 '86-'88 '89-'90 '91-'92 '93-'94 '95-'96

Number of plants

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Driving Forces
A driving force can make the mass transfer through the membrane possible; A driving force can make the mass transfer through the membrane possible; usually, the driving force can be aapressure difference (P), aaconcentration usually, the driving force can be pressure difference (P), concentration difference (c), an electrical potential difference (E). difference (c), an electrical potential difference (E). Membranes can be classified according their driving forces: Membranes can be classified according their driving forces:
P Microfiltration
Ultrafiltration Nanofiltration Reverse osmosis Piezodialysis

c
Pervaporation Gas separation Vapour permeation Dialysis Diffusion dialysis

T
Thermo-osmosis Membrane distillation

E
Electrodialysis Electro-osmosis Membrane electrolysis

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Pressure driven processes

P= MF 10-300 kPa UF 50-500 kPa NF 0.5-1.5 MPa RO 0.5-1.5 MPa

Mid-size organic substances, Bacteria, parasites, particles substances, single charged ions HighLow molecular molecular substances, viruses multiple charged ions
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Pore size of MF membranes

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Pores and pore geometries

Porous MF membranes consist of polymeric matrix in which pores Porous MF membranes consist of polymeric matrix in which pores are present. are present. The existence of different pore geometries implies that different The existence of different pore geometries implies that different mathematical models have been developed to describe transport mathematical models have been developed to describe transport phenomena. phenomena.
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Transport equations
The Hagen-Poiseuille and the Kozeny-Carman equations can be applied to demonstrate the flow of water through membranes. The use of these equations depends on the shapes and sizes of the pores. 1. Hagen-Poiseuille J the solvent flux P pressure difference x thickness of membrane tortuosity viscosity r the pore radius surface porosity

r P J= 8 x
2

cylindrical pores

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Transport equations
2. Kozeny-Carman

P J= 2 KS x
3

closely packed spheres

S surface area per unit volume K Kozeny-Carman constant (depends on the pore geometry)

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How to prepare MF membranes

Semycristalline polymers (PTFE, PE, PP) Semycristalline polymers (PTFE, PE, PP) if stretched perpendicular to the axis of if stretched perpendicular to the axis of crystallite orientation, may fracture in such aa crystallite orientation, may fracture in such way as to make reproducible microchannels. way as to make reproducible microchannels. The porosity of these membranes is very high, The porosity of these membranes is very high, and values up to 90% can be obtained. and values up to 90% can be obtained.

. Stretching Stretching

Stretched PTFE membrane

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How to prepare MF membranes

These membranes are now made by exposing These membranes are now made by exposing aathin polymer film to aacollimated bearn of thin polymer film to collimated bearn of radiation strong enough to break chemical radiation strong enough to break chemical bonds in the polymer chains. The film is then bonds in the polymer chains. The film is then etched in aabath which selectively attacks the etched in bath which selectively attacks the damaged polymer. damaged polymer. radiation source membrane polymer film etching bath
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2. Track-etching Track-etching

Track-etched 0.4 m PC membrane

How to prepare MF membranes

Chemical PI involves preparing aa Chemical PI involves preparing concentrated solution of aapolymer in aa concentrated solution of polymer in solvent. The solution is spread into aathin solvent. The solution is spread into thin film, then precipitated through the slow film, then precipitated through the slow addition of aanonsolvent, usually water, addition of nonsolvent, usually water, sometimes from the vapour phase. sometimes from the vapour phase. In thermal PI aasolution of polymer in poor In thermal PI solution of polymer in poor solvent is prepared at high temperatures. solvent is prepared at high temperatures. After being transformed into its final shape, After being transformed into its final shape, aasudden drop in solution temperature causes sudden drop in solution temperature causes the polymer to precipitate. The solvent is the polymer to precipitate. The solvent is then washed out. then washed out.
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. Phase inversion (PI) Phase inversion (PI)

Chemical phase inversion 0.45 m PVDF membrane

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How to prepare MF membranes

4. Sintering 4. Sintering This method involves compressing aapowder consisting of particles This method involves compressing powder consisting of particles of of aagiven size and sintering at high temperatures. given size and sintering at high temperatures. The required temperature depends on the material used. The required temperature depends on the material used.

HEAT pore

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Materials used
Synthetic polymeric membranes: a) Hydrophobic a) Hydrophilic Ceramic membranes Alumina, Al2O3 Alumina, Al2O3 Zirconia, ZrO2 Zirconia, ZrO2 Titania, TiO2 Titania, TiO2 Silicium Carbide, SiC Silicium Carbide, SiC
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PTFE, teflon PTFE, teflon PVDF PVDF PP PP PE PE Cellulose esters Cellulose esters PC PC PSf/PES PSf/PES PI/PEI PI/PEI PA PA PEEK PEEK

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Materials used
1. Polymeric MF membranes

Stretching Phase inversion

Track-etching
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Materials used
2. Ceramic MF membranes

Anodec, anodic oxidation (surface)

US Filter, sintering (cross section, upper part)

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Modules
A module is the simplest membrane element that can be used in practice. Module design must deal with the following issues: 1. Economy of manufacture 1. Economy of manufacture 2. Membrane integrity against 2. Membrane integrity against damage and leaks damage and leaks 3. Sufficient mass transfer to keep 3. Sufficient mass transfer to keep polarization in control polarization in control
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4. Minimum waste of energy 4. Minimum waste of energy 5. Easy egress of 5. Easy egress of permeate permeate 6. Permit the membrane 6. Permit the membrane to be cleaned to be cleaned
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Modules: tubular
Membranes diameter: >0.5 mm Active layer: inside the tube Flux velocity: high (up to 5 m/s) Tube: reinforced with fiberglass or stainless steel Number of tubes: 4-18 Flux: one or more channels Cleaning: easy Surface area/volume: low
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Diameter tubular membrane assembly

Modules: hollow fiber

Fibers: 300 5000 per module Fibers diameter: <0.5 mm Flux velocity: low (up to 2.5 m/s) Feed: inside-out or outside-in Surface area/volume: high Pressure drop: low (up to 1 bar) Maintenance: hard Cleaning: poor
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Hollow fiber module (inside-out)

Symmetric membranes
The cross section The cross section shows aa uniform shows uniform and regular structure and regular structure

cross section Symmetric ceramic membrane (Al2O3)

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surface

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Asymmetric membranes
0.1/0.5 m

Same material!
Porous irregular layer Porous with toplayer

50/150 m

The active layer is supported The active layer is supported over the porous layer. over the porous layer.

Cross-section of an asymmetric PSf membrane.

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Fouling and resistance

Fouling depends on: concentration, temperature Fouling depends on: concentration, temperature pH, molecular interactions pH, molecular interactions

Resistances-in-series model to describe the flux decline: Resistances-in-series model to describe the flux decline:
J: flow P: pressure drop : viscosity Rm: membrane resistance time, t Rc: cake resistance
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P J= ( Rm + Rc )
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flux, J

Fouling and resistance

The build-up layer and the clogging of the pores are referred to as a fouling layer. gel layer porous membrane

R p : pore blocking Ra : adsorption Rm : membrane Rg : gel layer formation Rcp : concentration polarization
Rm= Rm(t=0)+Ra+Rp;; Rc=Rg+Rcp Rm= Rm(t=0)+Ra+Rp Rc=Rg+Rcp Rtot=Rm+Rc Rtot=Rm+Rc
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Rp Ra Rm
Rcp Rg

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Methods to reduce fouling

1. Pretreatment of the feed solution 1. Pretreatment of the feed solution 2. Membrane properties 2. Membrane properties 3. Module and process conditions 3. Module and process conditions 4. Cleaning 4. Cleaning

Back-flushing

a. Heat treatment Hydraulic cleaning Hydraulic cleaning a.a.a. Reducing pore size distribution a. Narrow pore size distribution a. Reducingconcentration polarisation a.a. Heat treatment Narrow concentration polarisation b. pH adjustament velocity b. a1.Mechanicalcleaning b. Mechanical cleaning b. Hydrophilic flux velocity pH adjustament b. a1.Increasingmembranes Increasing flux b. Addition of complexing agents Hydrophilic membranes c. Chemical of complexing agents c.c. a2.Chemicalcleaning c. a2.Using low flux membranes Additionlow flux membranes Using cleaning d. Chlorination d. Electric cleaning Electric promoters b.d. Turbulencecleaning d. Turbulencepromoters Chlorination b. e. Adsorption onto active carbon e. Adsorption onto active carbon f. Chemical clarification f. Chemical clarification

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Back-flushing
permeate suspension

permeate suspension

permeate

P J

Restorable pressure with back-flushing Irreversible fouling Restorable flux with back-flushing Irreversible fouling starting points starting points

permeate

t
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Dead end and cross-flow

To reduce fouling two process modes exist:

1. Dead-end
Feed

2. Cross-flow

Feed

Retentate

Permeate

Cake layer
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Permeate
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Available MF membranes
Pore size, m Module Material 2, 3, 5 1.4 1 0.45 0.45 0.2 0.2 0.2 0.1 0.1 T T T T FH T FH FH T FH C C C C PSf C PP PP/PF C PSf Membrane area per module, m2 0.02 7.1 0.005 7.4 0.09 10.0 0.13 11.5 0.01 3.7 0.02 7.1 2.0 10.8 15 0.02 7.1 0.01 3.7
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Producer US Filters US Filters CTI TechSep Ceramen AG Technology US Filters Akzo Memtec US Filters AG Technology
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MF process applications
1. To replace four unit operations in the waste water treatment process.
Waste water COAG/ FLOC MF

MIX

Pre Filter

SED

FILT Water Residual disinfectant

Disinfectants & Coagulants

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MF process applications
2. To eliminate organic matter using MF after a pre-treatment with coagulants
Waste water

Pre Filter

MF
Coagulants

Water

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MF process applications
3. MF as pre-treatment for RO or NF RO
Waste water Water

Pre Filter

MF

NF

Water

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Retentate: how will it be used?

1. 1. 2. 2. 3. 3. 4. 4. 5. 5.

Sent to aatreatment plant Sent to treatment plant Discharged into aabody of water Discharged into body of water Sent to aastorage facility Sent to storage facility For ground applications For ground applications Recycled back to water source Recycled back to water source

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Some industrial applications

1. 1. 2. 2. 3. 3. 4. 4. 5. 5. 6. 6. 7. 7. 8. 8. 9. 9. Waste-water treatment Waste-water treatment Clarification of fruit juice, wine and beer Clarification of fruit juice, wine and beer Ultrapure water in the semiconductor industry Ultrapure water in the semiconductor industry Metal recovery as colloidal oxides or hydroxides Metal recovery as colloidal oxides or hydroxides Cold sterilization of beverages and pharmaceuticals Cold sterilization of beverages and pharmaceuticals Medical applications: transfusion filter set, purification of Medical applications: transfusion filter set, purification of surgical water surgical water Continuous fermentation Continuous fermentation Purification of condensed water at nuclear plants Purification of condensed water at nuclear plants Separation of oil-water emulsions Separation of oil-water emulsions
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Membrane Separations
Ultrafiltration & Nanofiltration

Membrane separation
SPECIES RANGE OF DIMENSIONS (NM)

Yeasts and fungi Bacteria Oil emulsions Colloidal solids Viruses Proteins, polysaccharides Enzymes Common antibiotics Organic molecules Inorganic ions Water
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1000-10000 300-10000 100-10000 100-1000 30-300 2-10 2-5 0.6-1.2 0.3-0.8 0.2-0.4 0.2
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Membrane separation

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Membrane separation

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Membrane characterization
Membrane properties Membrane separation properties
rejection rejection separation factor separation factor enrichment factor enrichment factor

pore size pore size pore size distribution pore size distribution free volume free volume crystalinity crystalinity

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Membrane characterization
Membranes

porous nonporous

macropore >50nm mesopore 2nm< <50nm micropore <2nm = pore diameter

Membrane Pore macropore mesopore micropore Separation principle filtration filtration filtration/ electrostatic interaction/ solution-diffusion
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Process Microfiltration Ultrafiltration Nanofiltration

Driving force pressure difference (0.1 - 1 bar) pressure difference (0.5 10 bar) pressure difference (5 20 bar)

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The characterization of porous membranes

1. shape of the pore (pore geometry)

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1. Pore geometries

Hagen-Poiseuille equation

r P J= 8 x
2

J the solvent flux P pressure difference x thickness of membrane tortuosity viscosity r the pore radius the surface porosity

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1. Pore geometries

S the internal surface area K Kozeny-Carman constant Kozeny-Carman relationship

P J= 2 2 K S (1 ) x
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1. Pore geometries
top layer thickness 0.1-1m sub layer thickness 50-150m

The flux is inversely proportional to the thickness.

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The characterization of porous membranes

2. pore size distribution

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The characterization of porous membranes

3. surface porosity

r = np Am

r the pore radius np number of pores Am membrane area

Microfiltration membranes: 5-70% Ultrafiltration membranes: 0.1-1%

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The characterization of porous membranes

Characterization methods:
s structure-related parameters

(pore size, pore size distribution, top layer thickness, surface porosity) s permeation-related parameters (actual separation parameters using solutes that are more or less retained by the membranes - cut-off measurements*)

* cut-off is defined as the molecular weight which is 90% rejected by the membrane

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The characterization of porous membranes

Microfiltration Characterization methods Ultrafiltration

scanning electron microscopy bubble-point method mercury intrusion porometry permeation measurements

gas adsorption-desorption thermoporometry permporometry liquid displacement rejection measurement transmission electron microscopy

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Ultrafiltration
... separation of one component of a solution from another component by means of pressure and flow exerted on a semipermeable membrane, with membrane pore sizes ranging from 0.05 m to 1nm. is used begining with years 30 the operating pressure 0.1-5 bar typically used to retain macromolecules and colloids the lower limit are solutes with molecular weights of a few thousands Daltons (1Dalton 1.66.10-24g) average flux around 50-200 GFD (~ 80-340 l/m2.h), at an operating pressure of 50 psig (~ 3,5bar)

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Ultrafiltration
Membranes used:
polymeric - polysulfone/poly(ether sulfone)/sulfonated polysulfone - poly(vinylidene fluoride) - polyacrilonitrile - cellulosics - polyimide/poly(ether imide) - aliphatic polyamides - polyetheretherketone ceramic - alumina (Al2O3) - zirconia (ZrO2)
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Ultrafiltration
Process performance do not depend only to the intrinsic membrane properties, but also to the occurence of different phenomena: concentration polarization fouling adsorption

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Concentration polarization
The concentration of removed species is higher near the membrane surface than it is in the bulk of the stream. Result: a boundary layer of substantially high concentration permeate of inferior quality Resolution: high fluid velocities are maintaned along the membrane surface
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Fouling
Build-up of impurities in the membrane that can keep it from functioning properly.

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Ultrafiltration
Crossflow Mode

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Ultrafiltration
Dead End Mode

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Cleaning
Cleaning in Backwash mode

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Cleaning
Cleaning in Forward Flush mode

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Adsorption
The main factor enhancing this phenomenon is hydrophobic interaction between the surface of the membrane and substance molecules. Hydrophobic groups are more prone to adsorbtion than hydrophilic groups

Hydrophobic
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Hydrophilic
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Adsorption
The number of molecules adsorbed on the surface, can be reduced by modifying hydrophobic membrane surface to hydrophylic membrane surface.

It is also easy to clean a hydrophilic membrane.

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Ultrafiltration
Applications:
food and dairy industry (the concentration of milk and cheese making, the recovery of whey proteins, the recovery of potato starch and proteins, the concentration of egg products, the clarification of fruit juices and alcoholic beverages) pharmaceutical industry (enzymes, antibiotics, pyrogens) textile industry chemical industry metallurgy (oil-water emulsions, electropaint recovery) paper industry leather industry sub layers in composite mebranes for nanofiltration, reverse osmosis, gas separation or prevaporation
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Ultrafiltration
Factors affecting the performance: flow across the membrane surface high flow velocity high permeate rate operating pressure due to increased fouling and compaction, pressures rarely exceed 100 psig (1 psig=0.068948 bar) operating temperature high temperature high permeate rate

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Nanofiltration
...used when low molecular weight solutes as inorganic salts or small organic molecules (glucose, sucrose) have to be separated. pore size < 2 nm the operating pressure 10-20 bar material directly influences the separation nanofiltration membranes are considered intermediate between porous and nonporous membranes most of the nanofiltration membranes are charged two models for the separation mechanism 1. permeation through a micropore 2. the solution-diffusion into the membrane matrix
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1. The permeation mechanism

...is explained in terms of charge and/or size effects. uncharged solutes charged components The Donnan potential
m

sieving Donnan exclusion mechanism

Don

RT a A RT a B = = ln m = ln m z A F a A z BF a B

- the electrical potential z - the valence R - the gas constant F - the Faraday constant T - the temperature a - the activity of the solutes m refers to the membrane phase, while A and B are the components in the solution
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2. The solution-diffusion mechanism

membrane behaves as a nonporous diffusion barrier each component dissolves in the membrane in accordance with an equilibrium distribution law each component diffuses through the membrane by a diffusion mechanism in response to the concentration and pressure differences

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Nanofiltration
Membranes for which the Donnan exclusion seems to play an important role

negatively charged membrane

pozitively charged membrane

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Nanofiltration
Membranes for which the diffusion seems to play an important role

nonporous membrane
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Nanofiltration
Membranes used:
asymmetric structure: top layer <1m, sub layer ~50-150m asymmetric membranes (prepared by phase inversion techniques) - cellulose esters pH range 5-7, temperature < 30oC (for avoiding the hydrolysis of the polymer) - polyamides - polybenzimidazoles, polybenzimidazolones, polyamidehydrazide, polyimides composite membranes - first stage is preparing the porous sub layer - placing a thin dense layer on the top of the sub layer: dip coating, in-situ polymerization, interfacial polymerization, plasma polymerization
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Nanofiltration
Applications:
desalination of brackish and seawater to produce potable water producing ultrapure water for the semiconductor industry retention of bivalent ions such as Ca2+, CO32retention of micropollutants and microsolutes such as: herbicides, insecticides, pesticides, dyes, sugar

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