Nametech. Nano4water workshop Aachen, 26 October Inge Genné -VITO

Transcription

1 Nametech Nano4water workshop Aachen, 26 October 2010 Inge Genné -VITO

2 Content of presentation Introduction The consortium S&T Approach Technology lines Technology and impact assessment Conclusions 15/11/2010 2

3 Nametech: introduction Development of intensified water treatment concepts by integrating NAno- and MEmbrane TECHnologies Europeanwater industry: Leadingrolein the world Largest companies world-wide are European Membrane industry Current UF market dominated by non-european players No European RO manufacturers 15/11/2010 3

4 Nametech: Introduction General objective To strengthen the European membrane market by making nanotechnology available to large scale European membrane manufacturers Start: June 1, 2009 Duration: 36 months Project budget: Total project: keuro EC contribution: keuro 46% of total budget allocated to industrial partners 15/11/2010 4

5 Nametech: the consortium Scientific experience membrane technology P. no. Partners Short name Country Scientific experience nano technology 1 Vlaamse Instelling voor Technologisch Onderzoek N.V. VITO Belgium 2 Rheinisch-Westfälische Technische Hochschule Aachen RWTH Germany 3 Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO The Netherlands 4 The University of Manchester UM UK 5 Norit Process Technology B.V. NOR The Netherlands 6 AGFA-GEVAERT N.V. AGFA Belgium 7 Consorzio Venezia Ricerche CVR Italy 8 Technical University of Liberec TUL Czech Republic 9 Aquatest AS AQT Czech Republic 10 Suez Environnement - CIRSEE SUEZ France 11 Fachhochschule Nordwestschweiz FHNW Switzerland Industrial involvement membrane manufacturers CVR AQT VITO: Industrial SME involvement Industrial involvement end-user point of view 15/11/2010 5

6 Norit Process Technology BV» Membrane producer (X-Flow) and OEM er» European market leader UF» Membrane configuration» Capillary» Tubular» Inside-out membrane modules 15/11/2010 6

7 Agfa Gevaert» Film manufacturing - coating specialist» Membrane fabrication by slot / extrusion coating» Membrane configuration» Flat sheet» New concept: IPC membrane» Outside-in (submerged) membranes 15/11/2010 7

8 S&T approach Aim: To leverage on the existing technologies in the field of nano-activated materials to improve the performance of the membrane filtration in water treatment Developed nano-activated materials Ultrafiltration or nanofiltration membrane Alter physical or chemical properties Nano-activated membrane = NAM Intensified water treatment: - separation - purification - detoxification 15/11/2010 8

9 S&T approach The development of the NAMs will be performed in three different technology paths, namely Technology Path 1 (TP1): High-flux UF nano-activated membrane (reduced fouling) Technology Path 2 (TP2): Nano-activated nanofiltrationmembrane Technology Path 3 (TP3): NAM concepts based on textile build-in ultrafiltration membrane (IPC concept) Envisaged applications for the NAMs UF for highly and lowly loaded streams (MBR, drinking water production, waste water treatment) NF membranes with improved disinfection or micropollutant removal 15/11/2010 9

10 S&T approach 15/11/

11 Nametechtechnology lines Nano-scale biomagnetite(um) TiO 2 (RWTH, TNO) Polyelectrolytes(RWTH) NanoZrO 2 /Si0 2 (VITO) Silver On the surface via the L-b-L technique (TNO) patent application Dispersed in the membrane structure (AGFA, VITO- Zilki/Zirfon) In nano-fibresvia electrospinning(tul) 3 1 2

12 1. Nanoscalebiomagnetite Concept NB Catalytic coatings can be applied (nanopd)

13 1. Nanoscalebiomagnetite Production

14 1. Nanoscale biomagnetite HF membranes Norit 1 Cr(VI) C/C0 0,8 Control (no magnetite) 0,6 Pd magnetite Magnetite + formate 0,4 Pd magnetite + formate Sustained removal of Cr(VI) 0, Time (Days) Mag Pd 50µM Cr(VI) test solution at a pump rate of 0.1ml/min +/sodium formate (20mM) to recharge reducing power of NPs, shows sustained 70% reductive removal over > 19 days with biomagnetite + nanopd

15 1. Nanoscalebiomagnetite Zirfon membranes VITO 1 0,8 C/C0 0,6 0,4 0,2 DYE ZIRFON DYE PES Cr(IV) ZIRFON Cr(VI) PES Time (seconds) Zirfonoutperforms PES membrane (removal of 10µM RBB azodye or 30µM Cr(VI) at 1ml/min in flow-through cell ) Zirfon has much higher loadings of magnetite (x7) than in PES & better dispersed Aim is to extend performance of Zirfon membrane with biomagnetite+pd

16 1. Nanoscalebiomagnetite Technology assessment Nanoparticle Nano-scale magnetites synthesised by bacterial systems Added functionality? Catalyticmembrane surface with focus on remediation applications Suitable for FS (AGFA) and HF (Norit)? Envisaged applications? Availabilityon large scale? Any need to adjust membrane concept? Both; Incorporated in the matrix (Zirfon) or on the surface Treatmentof toxic organics (nitrobenzene, chlorinated organics ) and high valence metals, radionuclides; Cr(VI), Tc(VII), U(VI) Prevention of the oxidation and release of aqueous silver Potentially yes, in kg quantities (scale-up studies in the UK Jan 2011) Doesnot seem to be needed, maybe requirements for contact times depending on selected application

17 2. Layer by layer technique Concept polycation rinsing rinsing Polyanion

18 2. Layer by layer technique Production Tuning the morphology via type of polyelectrolytes pair synthetic/biocompatible strong/strong, strong/weak, weak/weak Number of layers odd-even effect Last layer deposited Charge density loops and trains ionic strength Electrostatic screening nature of salts Ion-specificity ph, surface charge, deposition time 8-layer modified PES-150 membrane

19 2. Layer by layer technique Production Build-up of multilayers Contact angle, θ / P D A D M A C P S S P D AD M A C P S S P D AD M A C P D AD M A C PS S N um be r of laye rs, N Attenuated total reflection-ir -PDADMAC/PSS -focus on the sulfonate group at 1037cm-1 Absorbance, A / a.u. Contact angle-even-odd effect -different hydrophilicity of employed polyelectrolytes 0,5 0,4 0,3 0,2 0,1 N um be r o f laye rs N = 0 N = 2 N = 4 N = 6 N = 8 0, W avenum ber, λ / cm -1

20 2. Layer by layer technique Research objectives Tailoring the separation performance via optimisation of coating parameters (number of layers, ionic strength etc.) Antibacterial UF membranes 'Dense membranes' based on UF ( NF membranes) Preparation of photo-catalytic membranes based on deposition of TiO 2 by using thin polyelectrolyte films as precoat

21 2. Layer by layer technique Characterisation Antibacterial properties O T R (m m o l/(h.l)) PES HC/UV HC/HT LC/UV LC/HT Time (h) Oxygen Transfer Rates of E. coli exposed to bare and differently post-treated Ag 0 -polyelectrolyte-modified membranes

22 2. Layer by layer technique Characterisation Tailoring the separation SEC of discharged permeate through PEI/PSS modified membranes

23 2. Layer by layer technique Technology assessment Nanoparticle Polyelectrolytes Added functionality? Tailoring thefiltrationperformance, preparation of dense membranes, pre-coat for other nanoparticles (Ag, TiO 2 ) Suitable for FS (AGFA) and HF (Norit)? Envisaged applications? Availabilityon large scale? Any need to adjust membrane concept? Both; -Pre-treatment step for RO membranes. -PE+Ag as antibacterial membranes preventing bio-fouling -Preparation of NF membranes with antibacterial properties (Ag) which are resistible to chemical cleaning (NaOCl) -Pre-coat for TiO 2 deposition Yes; low prices None

24 3) Ag in nanofibers Concept Example of product PUR nanofibres with AgNO 3.

25 3) Ag in nanofibers Research items Experiments with PVA, PUR and PES nanofibres with silver addition (Ag nanoparticles and precursors) Amount of silver in Polyurethanefibres upto 800 mg/m 2 Thermal low pressurefixation of nanofibre PUR layer on flat sheet UF Nadir membranes Same technique with meltblown Polyethyleneprotection surface layer

26 3) Ag in nanofibers Technology assessment Nanoparticle Added functionality? Suitable for FS (AGFA) and HF (Norit)? Envisaged applications? Availabilityon large scale? Ag dispersed in PVA, PUR, PES nanofibre Surface deposition of nanofibreswith homogenous delivery of Ag particles (or precursors of nanoparticles). Deposition is possible on membrane surface or backbone. The most promising way is fixation into membrane structure due to the weak mechanical properties of nanofibers layer. This layer should be covered by another layer. This type of deposition is nowadays possible only on flat sheet membranes achievement of biocidal antifouling properties Nanofibres(PUR, PVA) are available on industrial scale by continual electrospinning. PUR nanofibreswith Ag nanoparticlesprecursors are avaiability on large scale Any need to adjust membrane concept?

27 Technology and Impact assessment In WP6 Technology and impact assessment, the potential impacts coming from the use of developed NAMs will be evaluated by using different approaches and methods in an integrated manner: hazard characterization of nanoparticles, Life Cycle Analysis, and estimation of nanoparticles release form membranes.

28 Technology and impact assessment Objective: Understanding of the risk posed by nanoparticles Tasks Toxicity impact of available nanoparticles Literature review: identification of the nanoparticlesthat can be safely applied on membranes Suitability for (drinking) water treatment applications? EU LEGISLATION!! Life Cycle Assessment (LCA) approach to evaluate the potential environmental impacts of specific nano-based application. Estimation of possible nanoparticle release from membranes. 15/11/

29 Technology and impact assessment Life Cycle Assessment (LCA) the environmental impacts of NAMs production process (ISO14040:2006). end of life (disposal, recycling, etc.) identified according to Life Cycle Thinking (LCT) Potential nanoparticles release assessment during applications of NAMs and under real working conditions Nanoactivated membrane Potential entry route of NP to environment Exposure route: water

30 Conclusions Promising technologies for the synthesis of nano-activated membranes are being evaluated Availability and economic feasibility for commercial application of nanoparticles in membranes is limited Dispersion of particles technology + cost issue Required concentration (wt%) to reach desired functionality Concern about introduction of new materials in (drinking) water treatment, will they leave the lab? Combination of hazard characterization, LCTand analysis of nanomaterialsreleaseoffers a suitable approach to evaluate potential impacts provide sound basis for decision making by industry and regulators.