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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

MF - UF - NF

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

MF - UF - NF

3

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 MF .UF .NF 4 .

organisms in untreated water.A.S. 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).NF 5 .Demand in U..UF . 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. products of disinfections). MF .

UF .NF 6 .Cumulative capacity of MF 50 40 30 20 10 0 '86-'88 '89-'90 '91-'92 '93-'94 '95-'96 Number of plants MF .

NF 7 . the driving force can be aapressure difference (∆P).UF . A driving force can make the mass transfer through the membrane possible. an electrical potential difference (∆E). usually. the driving force can be pressure difference (∆P). 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 MF . difference (∆c). an electrical potential difference (∆E). concentration difference (∆c).Driving Forces A driving force can make the mass transfer through the membrane possible. aaconcentration usually.

NF 8 . parasites. particles substances. single charged ions HighLow molecular molecular substances.UF .5 MPa Mid-size organic substances.Pressure driven processes ∆P= MF 10-300 kPa UF 50-500 kPa NF 0.5-1. viruses multiple charged ions MF .5-1.5 MPa RO 0. Bacteria.

UF .Pore size of MF membranes MF .NF 9 .

phenomena. 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.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. MF . are present.NF 10 .UF .

NF 11 . Hagen-Poiseuille J – the solvent flux ∆P – pressure difference ∆x – thickness of membrane τ− tortuosity η − viscosity r – the pore radius ε – surface porosity ε ⋅ r ∆P J= 8ητ ∆x 2 cylindrical pores MF . 1. The use of these equations depends on the shapes and sizes of the pores.UF .Transport equations The Hagen-Poiseuille and the Kozeny-Carman equations can be applied to demonstrate the flow of water through membranes.

Kozeny-Carman ε ∆P J= 2 KηS ∆x 3 closely packed spheres S – surface area per unit volume K – Kozeny-Carman constant (depends on the pore geometry) MF .Transport equations 2.UF .NF 12 .

UF . PE. way as to make reproducible microchannels. and values up to 90% can be obtained. PP) if stretched perpendicular to the axis of if stretched perpendicular to the axis of crystallite orientation. The porosity of these membranes is very high. and values up to 90% can be obtained. PP) Semycristalline polymers (PTFE.NF 13 . may fracture in such aa crystallite orientation. PE.How to prepare MF membranes Semycristalline polymers (PTFE. . may fracture in such way as to make reproducible microchannels. Stretching Stretching Stretched PTFE membrane MF . The porosity of these membranes is very high.

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.UF .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. damaged polymer. radiation source membrane polymer film etching bath MF .4 μm PC membrane .NF 14 2. Track-etching Track-etching Track-etched 0.

solvent is prepared at high temperatures. After being transformed into its final shape. MF . After being transformed into its final shape. addition of nonsolvent.UF . Phase inversion (PI) Phase inversion (PI) Chemical phase inversion 0. then precipitated through the slow film. aasudden drop in solution temperature causes sudden drop in solution temperature causes the polymer to precipitate. usually water. 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. The solvent is the polymer to precipitate. then washed out. The solution is spread into aathin solvent. usually water.45 μm PVDF membrane 15 .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. sometimes from the vapour phase.NF . The solution is spread into thin film. then precipitated through the slow addition of aanonsolvent. The solvent is then washed out.

HEAT pore MF . given size and sintering at high temperatures. The required temperature depends on the material used.UF . The required temperature depends on the material used.How to prepare MF membranes 4. Sintering 4.NF 16 . 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.

ZrO2 Titania. SiC Silicium Carbide. TiO2 Titania. SiC MF . 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 17 . ZrO2 Zirconia. TiO2 Silicium Carbide.UF .NF PTFE.Materials used Synthetic polymeric membranes: a) Hydrophobic a) Hydrophilic Ceramic membranes Alumina. Al2O3 Alumina. Al2O3 Zirconia.

Polymeric MF membranes Stretching Phase inversion Track-etching MF .NF 18 .UF .Materials used 1.

Materials used 2. upper part) MF . anodic oxidation (surface) US Filter.UF . sintering (cross section. Ceramic MF membranes Anodec.NF 19 .

Minimum waste of energy 4. Easy egress of 5. Membrane integrity against damage and leaks damage and leaks 3. Easy egress of permeate permeate 6. Permit the membrane to be cleaned to be cleaned 20 .Modules A module is the simplest membrane element that can be used in practice. Economy of manufacture 1. Sufficient mass transfer to keep 3.UF . Module design must deal with the following issues: 1. Economy of manufacture 2. Membrane integrity against 2.NF 4. Minimum waste of energy 5. Permit the membrane 6. Sufficient mass transfer to keep polarization in control polarization in control MF .

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 MF .UF .NF 21 Diameter tubular membrane assembly .Modules: tubular • Membranes 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 MF .NF 22 Hollow fiber module (inside-out) .UF .Modules: hollow fiber • Fibers: 300 – 5000 per module • Fibers diameter: <0.

UF .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) MF .NF surface 23 .

over the porous layer.Asymmetric membranes 0.5 μm Same material! Porous irregular layer Porous with toplayer 50/150 μm The active layer is supported The active layer is supported over the porous layer. MF .UF . Cross-section of an asymmetric PSf membrane.1/0.NF 24 .

Fouling and resistance Fouling depends on: concentration.NF flux. molecular interactions pH. temperature Fouling depends on: concentration. molecular interactions Resistances-in-series model to describe the flux decline: Resistances-in-series model to describe the flux decline: J: flow ΔP: pressure drop η: viscosity Rm: membrane resistance time. t Rc: cake resistance 25 ∆P J= η ( Rm + Rc ) MF .UF . temperature pH. J .

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.Fouling and resistance The build-up layer and the clogging of the pores are referred to as a fouling layer.NF Rp Ra Rm Rcp Rg 26 . Rc=Rg+Rcp Rm= Rm(t=0)+Ra+Rp Rc=Rg+Rcp Rtot=Rm+Rc Rtot=Rm+Rc MF .UF ..

a. pH adjustament velocity b. Reducing pore size distribution a.Chemicalcleaning c. Adsorption onto active carbon f.UF .c. Mechanical cleaning b. Heat treatment Hydraulic cleaning Hydraulic cleaning a. Chemical clarification MF . Module and process conditions 3. Membrane properties 3. e. Chemical clarification f. Membrane properties 2.NF 27 . a2. Chlorination d.Methods to reduce fouling 1.Using low flux membranes Additionlow flux membranes Using cleaning d.a. Turbulencepromoters Chlorination b.d.a. a1. Adsorption onto active carbon e. a2. Narrow pore size distribution a. Reducingconcentration polarisation a.Mechanicalcleaning b. Addition of complexing agents Hydrophilic membranes c. Electric cleaning Electric promoters b. Cleaning Back-flushing a. Pretreatment of the feed solution 1. Hydrophilic flux velocity pH adjustament b.Increasingmembranes Increasing flux b. a1. Chemical of complexing agents c. Cleaning 4. Module and process conditions 4. Heat treatment Narrow concentration polarisation b. Turbulencecleaning d. Pretreatment of the feed solution 2.

UF .NF 28 .Back-flushing permeate suspension permeate suspension permeate ΔP J Restorable pressure with back-flushing Irreversible fouling Restorable flux with back-flushing Irreversible fouling starting points starting points permeate t MF .

Cross-flow Feed Retentate Permeate Cake layer MF . Dead-end Feed 2.NF Permeate 29 .Dead end and cross-flow To reduce fouling two process modes exist: 1.UF .

02 – 7.8 – 15 0.02 – 7.45 0.4 1 0.2 0.02 – 7.1 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.0 10.1 0. m2 0.5 0.4 0. 5 1.0 0.005 – 7.7 0. 3.UF . μm Module Material 2.1 2.13 – 11.45 0.7 MF .1 0.09 – 10.NF Producer US Filters US Filters CTI TechSep Ceramen AG Technology US Filters Akzo Memtec US Filters AG Technology 30 .01 – 3.Available MF membranes Pore size.01 – 3.2 0.1 0.2 0.

MF process applications 1.UF .NF 31 . 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 MF .

NF 32 .MF process applications 2.UF . To eliminate organic matter using MF after a pre-treatment with coagulants Waste water Pre Filter MF Coagulants Water MF .

NF 33 . MF as pre-treatment for RO or NF RO Waste water Water Pre Filter MF NF Water MF .MF process applications 3.UF .

2. 5. 1.Retentate: how will it be used? 1. 5.NF 34 .UF . 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 MF . 2. 3. 4. 3. 4.

6.NF 35 . 9. wine and beer Clarification of fruit juice. 4. 7. 5. 7. 3. 1. 2. 8. Waste-water treatment Waste-water treatment Clarification of fruit juice. 4. 9.Some industrial applications 1. 2. 3. 6. 8. 5.UF . 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 MF . 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.

Membrane Separations Ultrafiltration & Nanofiltration .

2-0.6-1.8 0.Membrane separation SPECIES RANGE OF DIMENSIONS (NM) Yeasts and fungi Bacteria Oil emulsions Colloidal solids Viruses Proteins.2 37 .2 0. polysaccharides Enzymes Common antibiotics Organic molecules Inorganic ions Water MF .NF 1000-10000 300-10000 100-10000 100-1000 30-300 2-10 2-5 0.UF .4 0.3-0.

NF 38 .UF .Membrane separation MF .

NF 39 .Membrane separation MF .UF .

NF 40 .UF .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 MF .

1 bar) pressure difference (0.1 .NF .UF .Membrane characterization Membranes  porous nonporous  macropore φ >50nm mesopore 2nm<φ <50nm micropore φ <2nm φ = pore diameter Membrane Pore macropore mesopore micropore Separation principle filtration filtration filtration/ electrostatic interaction/ solution-diffusion 41 Process Microfiltration Ultrafiltration Nanofiltration Driving force pressure difference (0.5 – 10 bar) pressure difference (5 – 20 bar) MF .

NF 42 . shape of the pore (pore geometry) MF .The characterization of porous membranes 1.UF .

NF 43 . Pore geometries Hagen-Poiseuille equation ε ⋅ r ΔP J= ⋅ 8 ⋅ η ⋅ τ Δx 2 J – the solvent flux ∆P – pressure difference ∆x – thickness of membrane τ − tortuosity η − viscosity r – the pore radius ε – the surface porosity MF .UF .1.

UF . Pore geometries S – the internal surface area K – Kozeny-Carman constant Kozeny-Carman relationship ε ΔP J= ⋅ 2 2 K ⋅ η ⋅ S ⋅ (1 − ε ) Δx MF .NF 44 3 .1.

MF .UF .1.NF commercial interest 45 . Pore geometries top layer thickness 0.1-1µm sub layer thickness 50-150µm The flux is inversely proportional to the thickness.

NF 46 .UF . pore size distribution MF .The characterization of porous membranes 2.

NF 47 .1-1% MF .The characterization of porous membranes 3. surface porosity π⋅r ε = np ⋅ Am 2 r – the pore radius np – number of pores Am – membrane area Microfiltration membranes: ε ≅ 5-70% Ultrafiltration membranes: ε ≅ 0.UF .

top layer thickness. pore size distribution.NF 48 .UF .‘cut-off’ measurements*) * ‘cut-off’ is defined as the molecular weight which is 90% rejected by the membrane MF . surface porosity) s permeation-related parameters (actual separation parameters using solutes that are more or less retained by the membranes .The characterization of porous membranes Characterization methods: s structure-related parameters (pore size.

NF 49 .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 MF .UF .

h).5bar) MF . at an operating pressure of 50 psig (~ 3..05 µm to 1nm.66.UF .Ultrafiltration .10-24g) average flux around 50-200 GFD (~ 80-340 l/m2. with membrane pore sizes ranging from 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. separation of one component of a solution from another component by means of pressure and flow exerted on a semipermeable membrane.NF 50 . is used begining with years ‘30 the operating pressure 0..

NF 51 .Ultrafiltration Membranes used: polymeric .UF .zirconia (ZrO2) MF .polyimide/poly(ether imide) .aliphatic polyamides .polysulfone/poly(ether sulfone)/sulfonated polysulfone .alumina (Al2O3) .poly(vinylidene fluoride) .polyacrilonitrile .cellulosics .polyetheretherketone ceramic .

UF . but also to the occurence of different phenomena: concentration polarization fouling adsorption MF .NF 52 .Ultrafiltration Process performance do not depend only to the intrinsic membrane properties.

UF . Result:  a boundary layer of substantially high concentration  permeate of inferior quality Resolution:  high fluid velocities are maintaned along the membrane surface MF .Concentration polarization The concentration of removed species is higher near the membrane surface than it is in the bulk of the stream.NF 53 .

MF .UF .Fouling Build-up of impurities in the membrane that can keep it from functioning properly.NF 54 .

Ultrafiltration Crossflow Mode MF .NF 55 .UF .

Ultrafiltration Dead End Mode MF .NF 56 .UF .

Cleaning Cleaning in Backwash mode MF .UF .NF 57 .

Cleaning
Cleaning in Forward Flush mode

MF - UF - NF

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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
MF - UF - NF

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.
MF - UF - NF 60

the concentration of egg products. the clarification of fruit juices and alcoholic beverages) pharmaceutical industry (enzymes.NF 61 . electropaint recovery) paper industry leather industry sub layers in composite mebranes for nanofiltration. the recovery of potato starch and proteins. the recovery of whey proteins. pyrogens) textile industry chemical industry metallurgy (oil-water emulsions. gas separation or prevaporation MF . antibiotics.UF .Ultrafiltration Applications: food and dairy industry (the concentration of milk and cheese making. reverse osmosis.

pressures rarely exceed 100 psig (1 psig=0.Ultrafiltration Factors affecting the performance: flow across the membrane surface high flow velocity high permeate rate operating pressure due to increased fouling and compaction.UF .068948 bar) operating temperature high temperature high permeate rate MF .NF 62 .

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.Nanofiltration . permeation through a micropore 2.UF .used when low molecular weight solutes as inorganic salts or small organic molecules (glucose.NF 63 ... the solution-diffusion into the membrane matrix MF . sucrose) have to be separated.

the electrical potential z . while “A” and “B” are the components in the solution MF .the valence R .1..UF ..the Faraday constant T . uncharged solutes charged components The Donnan potential m sieving Donnan exclusion mechanism Ψ Don RT a A RT a B = Ψ −Ψ = ln m = ln m z A F a A z BF a B Ψ .NF 64 .the gas constant F . The permeation mechanism .is explained in terms of charge and/or size effects.the temperature a .the activity of the solutes “m” refers to the membrane phase.

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 MF .2.UF .NF 65 .

UF .NF .Nanofiltration Membranes for which the Donnan exclusion seems to play an important role negatively charged membrane pozitively charged membrane 66 MF .

UF .Nanofiltration Membranes for which the diffusion seems to play an important role nonporous membrane MF .NF 67 .

plasma polymerization MF .polybenzimidazoles. sub layer ~50-150µm asymmetric membranes (prepared by phase inversion techniques) .first stage is preparing the porous sub layer .UF . interfacial polymerization.Nanofiltration Membranes used: asymmetric structure: top layer <1µm. polyimides composite membranes . polyamidehydrazide.cellulose esters pH range 5-7. temperature < 30oC (for avoiding the hydrolysis of the polymer) .placing a thin dense layer on the top of the sub layer: dip coating. in-situ polymerization.NF 68 .polyamides . polybenzimidazolones.

dyes. pesticides.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+. insecticides.NF 69 . sugar MF .UF . CO32retention of micropollutants and microsolutes such as: herbicides.