Professional Documents
Culture Documents
Membrane Processes: Paul Ashall, 2007
Membrane Processes: Paul Ashall, 2007
Membrane processes
Microfiltration Ultrafiltration Reverse osmosis Gas separation/permeation Pervaporation Dialysis Electrodialysis Liquid membranes Paul Ashall, 2007 Etc
RETENTATE
FEED PERMEATE
Anisotropic (asymmetric)
Thin active surface layer supported on thicker porous layer Composite different polymers in layers Others ceramic, metal, liquid
Asymmetric membranes
Microporous support
Membrane materials
Polymers Metal membranes Ceramic membranes (metal oxide, carbon, glass) Liquid membranes
Membrane fabrication
Isotropic Solution casting Melt extrusion Track etch membranes (Baker fig. 3.4) Expanded film membranes (Baker fig. 3.5)
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 Paul Ashall, 2007 in a cylinder
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
Size range
0.1-1m 1nm-100nm
MWCO
>1000 200-1000 <200
MF UF NF RO
Process technology
MF UF
Rejected species
Bacteria, cysts, spores Proteins, viruses, endotoxins, pyrogens Sugars, pesticides Salts, sugars
NF RO
3-15 10-60
50-95 30-90
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
continued
Dense membranes: transport by a solutiondiffusion mechanism Microporous membranes: pores interconnected
Separation of liquids
Porous membranes Asymmetric membranes/dense polymer membranes
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 2007 the liquid phase. in Paul Ashall,
Microporous membranes
Porosity () Tortuosity () (measure of path length compared to pore diameter) Pore diameter (d)
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)
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)
Paul Ashall, 2007
continued
Crossflow operation (as opposed to dead end filtration)
Membrane types
Dense High porosity Narrow pore size distribution
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
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
UF applications
Protein concentration
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.
MF
Membrane materials Cellulose acetate/cellulose nitrate PAN PVC PVDF PS
MF
Modules Plate and frame Cartridge filters (see Baker figs. 7.11/7.13, p288, 290)
MF operation
Fouling Backflushing Constant flux operation
MF uses
Sterile filtration of pharmaceuticals (0.22 m rated filter) Drinking water treatment
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
F
P1
P2
P1 P2
Paul Ashall, 2007
Model
Flux equations Salt rejection coefficient
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
Jw increases with P and selectivity increases also since Js does not depend on P.
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
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
Applications
UP water (spec. Baker pp 226, 227)
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.
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
PV
Composite membrane (dense layer + porous supporting layer)
Modules
Plate & frame (Sulzer/GFT)
PV
Solution diffusion mechanism Selectivity dependent on chemical structure of polymer and liquids
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)
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
continued
Structure permeability relationships Sorption coefficient, K (relates concentration in fluid phase and membrane polymer phase) Diffusion coefficient, D
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
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.
PV process design
Vacuum driven process Condenser Liquid feed has low conc. of more permeable species
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
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.
Gas separation
The transport of gases through dense (non-porous) polymer membranes occurs by a solutiondiffusion 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)
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
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
O2 3.6
N2 1.4
CO2 0.54
CH4 0.17
PET
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
Modules
Spiral wound Hollow fibre
Flow patterns
Counter-current Co-/counter Radial flow crossflow
System design
Feed/permeate pressure (p = 1 20 atm.) Degree of separation Multistep operation
Applications
Oxygen/nitrogen separation from air (95 99% nitrogen) Dehydration of air/air drying
PV demonstration
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, McGrawHill, 6th edition, 2001 Transport Processes and Unit Operations, C. J. Geankoplis, Prentice-Hall, 3rd edition, 1993 Membrane Processes: A Technology Guide, P. T. Paul RSC, Cardew and M. S. Le, 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