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Thrust 2 - Desalination"Advanced Membrane Materials
for Water Treatment"
Harry Ridgway, Res. DirectorOrange County Water District
Fountain Valley, California&
Robert L. Riley, PresidentSeparation Systems Technology
San Diego, California
Advanced Materials for Water Purification
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Background...
Opportunities exist for innovation in the design of improved membrane materials for water purification.
Modern water treatment is rapidly becoming dependent on membranes.
Bio-organic fouling is the major problem with the current generation of membrane separations (Example = biofouling).
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Popular Membrane Materials...
•random, helical, non-X-linked
•low flux/high salt rejection
•can be biodegraded
•poor organics rejection
•dense, smooth, neutral surface
•low fouling tendency
General Properties...
•chlorine tolerant
Asymmetric Cellulose Acetate
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Polyamide Thin-FilmComposites (TFCs)
Popular Membrane Materials...
•random, X-linked
•high flux/salt rejection
•not biodegradable
•good organics rejection
•rough, charged surface
•high fouling tendency
General Properties...
•chlorine sensitive
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Cross-FlowFeed Water
SemipermeableMembrane
(~0.2 micrometers)
Asymmetric CAMembrane
Porous Interior(~0.5 mm thick)
Flux
Permeate
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Thin-Film Composite (TFC) Membranes...(Polyamide Layer)(Polyamide Layer)
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How are modern TFC membrane materials made?
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Aqueous Phase
Organic Phase (Heptane, etc.)
N
NH2
COCl
C
COCl
H
O
+ HClReaction
+ Acid Chloride
COCl
COCl
COCl
Random Structure
Cross-Link or Extension Cross-Link or Extension
Cross-Link or Extension
Diffusion
NH2
NH2
Di-Functional Amine+
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Ultrastructure of TFC Membranes...
PS Support
PA Layer
PS Support
PA Layer
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AFM Image of PA Surface
AFM Image of PA Surface
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The Issues...1. Bio-organic
Fouling
Molecular Adsorption
2. Physico-Chemical Integrity
De-lamination
PA
PS
1
-Flux loss-Solute passage
Chlorine Attack
2
Flux & Organics Rejection
3
Swelling
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...is to design a new generation of advanced membrane materials having...
The Challenge...
1. Low-fouling surfaces
2. Greater physico-chemical integrity
3. Improved flux and solute rejections
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Bacteria and organics respond to a host of membrane surface properties.
A multi-variate approach is needed to identify which properties of membranes contribute to bio-organics adsorption.
The Approach...
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Correlation of Membrane Surface Propertieswith Bacterial Attachment
MembraneProperties
(independent variables)
BacterialAdhesion
(dependent variable)
Multivariate ModelsMLR AnalysisPC Analysis
Cluster AnalysisANN Analysis
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Hydrophobicity & Pore Aspect Ratio
FluxThickness
Charge
Flux & Pore Diameter
A
D
G
B
E
H
C
F
I
HydrophobicRoughness
Material Matrices...
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SPEES-PES...
Membranes
S
=
=
O
OCH3
CH3
C O O
n
polysulfone (PS)
S
=
=O
O
O
1
S
=
=
O
O
O
5
O
SO3H
sulfonated polyether-ethersulfone/polyethersulfone (SPEES/PES)(sulfonation number = SPEES/PES = 1/5)
+
Polymer A Polymer B
Neutral Charged
Knoell et al., 1999, Journal of Membrane Science
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Bacteria Respond to Multiple Signals...
MembraneTopologyMembrane
Hydrophobicity Membrane Charge
Bacterium A(Mycobacterium)
Bacterium B(Flavobacterium)
Knoell et al., 1999
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•Enhanced flux & solute rejection-increased cross-linking; catalytic membranes
•Anti-fouling surfaces-neutral, hydrophilic, smooth
•Oxidation-resistant surfaces-new materials (e.g., CPTC)
Research Directions...
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-More X-linking-Tri-amines, etc.-Stereochemistry-Other polymers?
Incorporation of catalyts in membranes
ChemicalResistance
Anti-foulingSurfaces
CatalyticSurfacesStructural
Integrity
-Charged PS layer-Fully aromatic-Glut. X-link MPD
Surface Modifications...-smooth, hydrophilic, neutral,mobile, renewable
Directions...
Directions...Directions...
Directions...
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CH2
CH2
CH2
NH H..
-OH
3-amino-1-propanol
To Increase the Hydrophilicity of TFC Surfaces...
HCl
H
..CH2
CH2
CH2
N
-OH
OC
=
Covalent Amide-OH
O ClC
=
PA Membrane
Un-ReactedAcid Chloride
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To Improve Chlorine Resistance...
X X XX X
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Catalytic Membrane Materials...
PA Layer
Polyester Support
Porous PS
Pure water
N-N CH 3
CH 3
=O
Catalyst(s)(Pd, PEIs, etc.)
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Mobile Membrane Surfaces...
PA Layer
Polyester Support
Porous PS
Magnetic Particles
Kishore Rajagopalan [[email protected]]
+
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Self-Assembling Renewable Surfaces...
Isolation &Purification Re-Assembly
•Transport?•Stability?Pore-Like Structure
Flexibacter polymorphus
a marine gliding bacterium(Ridgway et al. 1977. J. Bacteriol.)
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Self-assembled crystalline protein-lipid arrays
Hierarchical self-assembly: 2 states of organization• Self-organization of long actin protein rods into 2D crystalline sheets
• Spontaneous folding of sheets into nested tubules
Potential applications• Molecular ‘fly-paper’ for bacteria
• Spontaneous entrapment of bacteria in tubules
Gerard C. L. Wong et al., Science 288, 2035-2039 (2000)
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Novel Materials & Processesfor Water Purification
Surfaces, Biofilms,Mol. Modeling & Evals.
Surface-Active Materialsfor Disinfection
Clark-AtlantaACFs, Macrocycle Gates,Hyperbranched PEIs, etc.
UIUC
Applications R&D & Evaluations
Waste Management
Biofilms & Oxidation Studies
Industry Affiliates
Pilot-Scale Studies &Demonstrations
Stanford
SST
TFCs
Catalysis
OCWD
Surface-ModifiedTFC Membranes
Biofilms
Catalytic Membranes
Synergies & Collaborations...
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$Lower Costs of Desalination
Expected Benefits of Research...New knowledge of
materials/interactions
More robust LFmembranes
Less pretreatment,cleaning, downtime
Improved flux, rejection, efficiency, lifetime
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End of Thrust #2..."Desalination"
Next Presentation...Thrust #3..."Membrane Fouling
and Mitigation"