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Nanofiltration: drawbacks for application - research challenges

Bart Van der Bruggen Department of Chemical Engineering K.U.Leuven, Belgium
bart.vanderbruggen@cit.kuleuven.be

Nanofiltration compared to other pressure driven membrane processes

Applied pressure Microfiltration Ultrafiltration 0.1-2 bar 1-5 bar Flux range (l/m/h/bar) > 50 10-50 Transport mechanism Sieving Sieving Application range

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

Sieving Diffusion Charge effects Diffusion

Reverse osmosis

10-100 bar

0.05-1.4

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Nanofiltration: some history

1970s: low pressure reverse osmosis becomes nanofiltration (NF) 1980s: NF applications: softening, NOM removal in drinking water treatment 1987: first journal publication on NF

BMG-NMG Posterdag Antwerpen (BE), 26 Nov. 2008

Nanofiltration: some history

1970s: low pressure reverse osmosis becomes nanofiltration (NF) 1980s: NF applications: softening, NOM removal in drinking water treatment 1987: first journal publication on NF
Conlon, W.J., McClellan, S.A., 1989. Membrane softening: treatment process comes of age, J. AWWA 81(11), 47-51. Eriksson, P., 1988. Nanofiltration extends the range of membrane filtration. Environm. Prog. 7 (1), 58-62. D. Watson, C.D. Hornburg, Low energy membrane nanofiltration for removal of color organics and hardness from water supplies, Desalination 72 (1989) 11

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Nanofiltration: some history

1970s: low pressure reverse osmosis becomes nanofiltration (NF) 1980s: NF applications: softening, NOM removal in drinking water treatment 1987: first journal publication on NF 1990s: process coming to age
Scientific research booming Applications from small scale to large scale (Mry-sur-Oise)

>2000: fouling resistant membranes, ceramic NF membranes, solvent resistant NF

BMG-NMG Posterdag Antwerpen (BE), 26 Nov. 2008

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

Ca, SO4 > 99% Na, Cl 60-90% MW 200 organics

Ca, SO4 90-99% Na, Cl 10-60% MW 500-1000 organics

PA, PI

P(E)S, ceramics

BMG-NMG Posterdag Antwerpen (BE), 26 Nov. 2008

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

(MWCO?) Spiegler & Kedem:

.(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 (%)

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Cut-off curve: sharp or diffuse

Molecular weight cut-off

100 %

Rejection (%)

0% 100 500 750 1 000

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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
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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

relative flux (%)

relative flux (%)

80 60 40 20 0 0 100 200 300 400

80 60 40 20 0 0 100 200 300 400

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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Parameters influencing NOM fouling

Value Ionic strength concentration pH Divalent cations NOM fraction Increased High pH Low pH Presence Hydrophobic Hydrophilic High charge High Higher Higher Higher NOM fouling Rate Increased Increased Increased Increased Increased Decreased Increase Increased Increased Increased Increased Valley blocking Hydrophobicity Compaction Cause Electrostatic repulsion Hydrofobic forces Electrostatic repulsion Electrostatic repulsion and bridging between NOM and surface Hydrophobicity

Molecule or membrane charge CP Surface morphology Permeate flux (High recovery) Pressure

Electrostatic repulsion

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Membrane fouling
Fouling vs. compaction

Membrane thickness 170 m

Membrane thickness 150 m

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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
-

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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

BMG-NMG Posterdag Antwerpen (BE), 26 Nov. 2008

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

BMG-NMG Posterdag Antwerpen (BE), 26 Nov. 2008

Solutions to fouling
Membrane manufacturing
Surface charge Surface roughness Biofouling: e.g., silver nanoparticles

25 years of experience but many aspects yet to learn

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Synthesis of polymeric membranes

Parameters determining the membrane structure: wt% polymer Type of solvent Temperature Air humidity Additives

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The concept of critical flux

The membrane has a limited capacity
represents the shift from repulsive interaction (dispersed matterpolarised layer) to attractive interaction (condensed matterdeposit) Sustainable flux: protection against fouling depends on hydrodynamics, feed conditions and process time
120 . Flux, l/(mh)
2

100 80 60 40 20 0 0 2 4 6 8 10 12 14 16

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a)

Pressure, bar

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II. Can we achieve complete separation?

Membranes are not an absolute barrier Filtration in series: removal of a given compound increases with each step added
10 1 0.1 0.01

Rejection is not only determined by solute size vs. pore size

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Typical rejection curve

100 90 80 70 60 50 40 30 20 10 0 0 50 100 150 200 250 300 350 400 450 500 Molecular size
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Rejection (%)

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Ideal rejection curve

100 90 80 70 60 50 40 30 20 10 0 0 50 100 150 200 250 300 350 400 450 500 Molecular size
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Rejection (%) Rejection (%)

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
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How to achieve this?

Membrane stack: N membranes in a single module N modules in series

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Combined cascades: distillation

Distillation Overhead vapour Enrichment section Feed Total condensor Reflux drum 1 2 f N Partial reboiler Bottom products Feed tray Boilup Reflux Distillate

Stripping section

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Membrane cascades 2 3
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Rejection curves
N30F
100 90

NF270

100

80 Rejection (%) 70 60 50 40 30 20 10 0 0 100

Desal-HL-51
Desal-5-DL
(1) (2)

100
100 90 80 Retjection (%) 70 60 50 40 30 20 10 0 0

90 80

90 Rejection (%) Rejection (%)

70 60 50 40

80 70 60

(1) (3) (2) (3)

(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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Separation of solutes from one another?

Applications in pharmaceutical industry Diafiltration may be possible for product recovery, not for separation Food industry: xylose/glucose, stevioside, tailormade milk products

BMG-NMG Posterdag Antwerpen (BE), 26 Nov. 2008

Ion separation, organicinorganic separation?

NF270, rejection (single passage) NaCl 59% CaCl2 63% - Na2SO4 96% Rejections too high to apply in cascade (no separation) Rejections organic inorganic not feasible Membrane optimisation: lower salt rejections required
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Ion separation, organicinorganic separation?

N30F: rejection (single passage) NaCl ca. 10% rejection maltose 63% In cascade: NaCl overall rejection ca. 20% rejection maltose 97% Not (yet) perfect Membrane tailoring in terms of separation potential
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V. Insufficient rejection of individual compounds

Originally: partial softening, bulk organics removal New trend = complete absence of all possible pollutants, even at ultra-low concentrations
- Subjective customer criterion not necessarily based on risks or toxicity - But a reality

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Nitrate removal
Health effects?
- None for adults - Methemoglobinemia (children < 6 m) related to nitrite - Synergetic toxic effects?

Standards are under debate NF: partial removal

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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

Nitrate rejection (%) 94-98 9 32 28 25 12 8 76 16 32 11 90 90 60 75-80 65-80 85-95 25-50 40-70 50 85 33

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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
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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

Bisphenol A Carbamazepin e Cyanazine DCAA Diclofenac Diuron Estradiol

EDC PhAC Pesticide DBP PhAC Pesticide EDC

228 236 240 129 296 233 272

3,64 2,25 2,51 0,92 4,02 2,67 3,94

0,33

0,83

0,63 (weak Salicylic acid base) 1,26 Simazine 4,15 / 10,7 Sulphamethoxazole TCAA Terbutylazine

0,49

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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
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Acknowledgements
-My colleagues from Lappeenranta University of Technology (LUT): Mika Mnttri & Marianne Nystrm

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