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Removal of particles Removal of macromolecules Removal of multivalent ions and relatively (small) organic molecules Removal of ions and (small) organic molecules
Nanofiltration
5-15 bar
1.4-12
Reverse osmosis
10-100 bar
0.05-1.4
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Research on nanofiltration
10000 Number of publications 1000 UF 100 NF RO 10
1 1985
1988
1991
1994
1997
2000
2003
2006
Year
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Some principles
NF membranes membranes Tight vs. loose NF
near RO near UF
PA, PI
P(E)S, ceramics
Process performance
Flux equation: Hagen-Poiseuille
J .r P 8 x
surface porosity ( ) pore radius (r) tortuosity ( ) membrane thickness ( x)
Rejection:
Ri (%)
(1
c p ,i c f ,i
).100
.(1 F ) 1 .F
exp(
1 Ps
.J )
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Not only MW
Desal-HL-51, MWCO = 150-300 100 80 60 40 20 0 0 50 100 150 Molecular weight 200
Retentie (%) D e sal- H L- 5 1 100 80 60 40 20 0 -4 -2 0 lo g P 2 4
Retention (%)
Rejection (%)
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NF: Challenges?
1. Advanced Membrane Technology and Applications (Eds. Norman N. Li, Anthony G. Fane, W.S. Winston Ho, Takeshi Matsuura), Wiley, 2008. Van der Bruggen, B.; Mnttri, M.; Nystrm, M. Drawbacks of applying nanofiltration and how to avoid them: a review. Separ. Purif. Technol. 2008, 63, 251-263.
BMG-NMG Posterdag Antwerpen (BE), 26 Nov. 2008
2.
NF: Challenges
I. II. III. IV. V. VI. avoiding membrane fouling, and possibilities to remediate improving the separation between solutes that can be achieved further treatment of concentrates chemical resistance and limited lifetime of membranes insufficient rejection of pollutants in water treatment the need for modelling and simulation tools
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NF: Challenges
Not exhaustive in particular towards engineering aspects module development for special applications (solvents, extreme pH) membrane configurations with improved performance (surface area per volume, hydrodynamics) NF applications will not wait for answers and are already successful improvements will broaden up the range and make life easier
BMG-NMG Posterdag Antwerpen (BE), 26 Nov. 2008
Membrane fouling
Interactions to be understood at nanoscale Pretreatment, membrane cleaning, limited recoveries and feed water loss, and short lifetimes of membranes
120 100
120 100
time (min)
time (min)
NF270 (HP11) NFPES10 (HP11) water cleaning NF270 (HP11) water cleaning NFPES10 (HP11) BMG-NMG Posterdag NF270 (rim cleaner) NFPES10 (rim cleaner) Antwerpen (BE), 26 Nov. 2008 water cleaning NF270 (rim cleaner) water cleaning NFPES10 (rim cleaner)
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Molecule or membrane charge CP Surface morphology Permeate flux (High recovery) Pressure
Electrostatic repulsion
Membrane fouling
Fouling vs. compaction
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Membrane fouling
Organic fouling
Adsorption on the membrane surface Parameters of influence: log P, dipole moment, solubility membrane hydrophobicity (contact angle) Electrostatic attraction repulsion for charged solutes Related to surface roughness of membranes Hydrophobicity and charge interaction play a role Concentration and size of the colloids
Colloidal fouling
-
Membrane fouling
Scaling
Calcium carbonate, gypsum, barium/strontium sulphate and silica Thermodynamical problem module design? Mainly bacteria and (in some cases) fungi Biofilms 20-30 m Indirect problems: cake layer, exopolymeric substances
Biofouling
-
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Solutions to fouling
Pretreatment
When? Provide UF quality feed water Ultrafiltration and microfiltration, ozonation or UV/H2O2 oxidation, adsorption (PAC) and flocculation
Solutions to fouling
Cleaning
When? In all cases Physical cleaning by flushing (backflush, forward flush, reverse flush), scrubbing, air sparging, vibrations and sonication Chemical cleaning: hydrolysis, saponification, solubilisation, dispersion, chelation, and peptisation Various cleaning solutions and protocols
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Solutions to fouling
Membrane modifications
Hydrophilic groups into a polymeric structure: grafting, ion beam irradiation, plasma treatment, adsorption, self-assembling nanoparticles Ceramic membranes (titania, alumina, zirconia) Development, upscaling needed
Solutions to fouling
Membrane manufacturing
Surface charge Surface roughness Biofouling: e.g., silver nanoparticles
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100 80 60 40 20 0 0 2 4 6 8 10 12 14 16
a)
Pressure, bar
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Rejection (%)
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and possibly:
100 90 80 70 60 50 40 30 20 10 0 0 50 100 150 200 250 300 350 400 450 500 Molecular size
BMG-NMG Posterdag Antwerpen (BE), 26 Nov. 2008
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Stripping section
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Membrane cascades 2 3
BMG-NMG Posterdag Antwerpen (BE), 26 Nov. 2008
Rejection curves
N30F
100 90
NF270
100
Desal-HL-51
Desal-5-DL
(1) (2)
100
100 90 80 Retjection (%) 70 60 50 40 30 20 10 0 0
90 80
80 70 60
(1) (2)
(1) (2) 200 300 MW 400 500 (3) 600
50 30 40 20 30 10 20 0 10 0 0
100
(3)
100
200
300 MW
400
500
600
100
200
200
300 MW
300 MW400
400
500
500
600
600
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Nitrate removal
Health effects?
- None for adults - Methemoglobinemia (children < 6 m) related to nitrite - Synergetic toxic effects?
Membrane NF90 HG19 SX10 SV10 SX01 BQ01 MX07 NF70 NF45 UTC-20 UTC-60 MPS44 NF70 Desal ESNA-1 LF NF NF90 OPMN-K OPMN-P
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Boron removal
Micronutrient with narrow range between deficiency and excess Not a primary target compound but the times they are a-changin ( low concentration by preference) Neutral pH: undissociated boric acid, removal with complexes (e.g., mannitol) Acid conditions (or alkaline conditions): removal in ionic form NF has a disadvantage
BMG-NMG Posterdag Antwerpen (BE), 26 Nov. 2008
Organic micropollutants
Including: natural and synthetic hormones; industrial pollutants such as phthalates, alkylphenols, bisphenol-A, PCBs (polychlorinated biphenyls), PAHs (polyaromatic hydrocarbons), NDMA (N-nitrosodimethylamine) and MTBE (methyl tertiarybutyl ether); pesticides; pharmaceuticals; personal care products and disinfection by-products (DBPs) priority compounds in view of drinking water production: Verliefde, Environ. Pollut. 2007, 146 (1), 281-289
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Organic micropollutants
Component Type Surrogate 2-naft ol EDC 4-phenylphenol 1,5-naftal ene Surrogate disulfonic acid Surrogate 2-naftalene sulfonic acid Surrogate 9-ACA Atrazine Bentazone Pesticide Pesticide MW 144 170 288 208 222 216 240 Log Kow Size [nm] 2,7 3,28 -3,15 0,63 3,85 2,82 1,67 0,8 0,8 0,71 0,55 pKa 9,5 9,55 / / 3,65 Component Estrone Fenacetine Fluoranthene Ibuprofen Isopropylantipyrine Type EDC PhAC EDC PhAC PhAC Pesticide Pesticide Pesticide Pesticide Pesticide Pesticide PhAC Surrogate Pesticide PhAC DBP Pesticide MW 270 179 202 206 231 206 215 202 278 214 238 218 138 202 253 163 230 Log Kow Size [nm] 3,43 0,8 1,58 4,93 3,79 1,94 2,84 2,94 1,44 2,38 1,49 1,4 0,73 2,24 2,4 0,48 1,33 3,27 0,75 0,81 0,49 0,5 0,44 0,79 0,5 pKa 10,4 / / 4,91 / / 3,78 / / 1 (weak base) 4,53 (weak base) / 2,97 1,67 (weak base) / 0,51 2 (weak base)
1,7 (weak Isoproturon base) 3,3 Mecoprop Metamitron Metazachlorine Metribuzin 10 / Pirimicarb Primidone
0,33
0,83
0,63 (weak Salicylic acid base) 1,26 Simazine 4,15 / 10,7 Sulphamethoxazole TCAA Terbutylazine
0,49
Organic micropollutants
Modelling and prediction of rejections is still difficult qualitative appraisal of rejections
- classification of compound/membrane combinations - based on molecular weight, molecular weight cut-off of the membrane, pKa (solute charge) and log Kow (hydrophobicity) - See J. Chem. Technol. Biotechnol. 2006, 81 (7), 1166-1176
Relatively low rejections for uncharged hydrophobic compounds, e.g., 2-naphtol, 4-phenylphenol, estradiol, ibuprofen, fluoranthene and bisphenol-A, estradiol, estrone, atrazine, simazine, diuron, and isoproturon Small hydrophilic compounds (e.g., NDMA) are problematic BMG-NMG Posterdag
Antwerpen (BE), 26 Nov. 2008
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Acknowledgements
-My colleagues from Lappeenranta University of Technology (LUT): Mika Mnttri & Marianne Nystrm
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