Advanced Membrane Technologies Stanford University, May 07, 2008

Membranes for Water Treatment: Properties and Characterization

Ingo Pinnau, Ph.D.

Membrane Separation Processes and Characteristics

Process
Particle Filtration Microfiltration (MF) Ultrafiltration (UF) Reverse Osmosis (RO)

Separation Mechanism
Size Exclusion Size Exclusion Size Exclusion Solution/ Diffusion

Pore Size ()
> 50,000 500 - 50,000 20 - 500 < 10

Transport Regime
Macropores Macropores Mesopores Molecular (Nonporous)

Membrane Separation Processes and Characteristics

(m) 0.0001 0.001
Aqueous salts Metal ions

0.01
Albumin protein

0.1

1.0

10
Yeast cells

100

1,000

Beach sand

Paint pigment Endotoxin/ Pyrogen Viruses Bacteria Oil emulsion Granular activated carbon

Pesticides/ Herbicides Sugars

Colloidal silica Asbestos

Human hair

Reverse Osmosis

Ultrafiltration

Particle Filtration Microfiltration

Nanofiltration

Membrane Characteristics: Porous Membranes

Microfiltration
Monovalent Multivalent Water ions ions Suspended Bacteria solids

Viruses

Ultrafiltration

Monovalent Multivalent Water ions ions

Viruses

Suspended Bacteria solids

Membrane Characteristics: Non-Porous Membranes

Nanofiltration
Monovalent Multivalent Water ions ions Viruses Suspended Bacteria solids

Reverse Osmosis

Monovalent Multivalent Water ions ions

Viruses

Suspended Bacteria solids

Ideal Membranes for UF, NF and RO Applications

High water flux (low capital cost) High solute rejection (high water purity) Long-term stability of water flux and rejection (Membrane fouling) Mechanical, chemical and thermal stability Minimum pre-treatment (backflushing and chemical treatment) Can be processed into large-scale membranes and modules Inexpensive!

Problems of Current Membranes Used in UF and RO Applications

Poor long-term stability of water flux (Membrane Fouling) Backflushing and chemical treatment High membrane replacement cost Poor resistance to chlorine Membrane system size

Major Foulant Types in Natural and Industrial Wastewater

Scaling

Colloidal Fouling Organic Fouling

Biofouling

Surface Structure of a Typical UF Membrane

Membrane Separation Processes and Characteristics

Unfouled Membrane
Porous Surface

Fouled Membrane
Surface Fouling

Internal Fouling

Schematic Structures of Porous and Non-Porous UF Membranes Non-Porous

Microporous Ultrafiltration Membrane
Selective skin layer Porous substrate

Non-Porous Ultrafiltration Membrane

Non-porous hydrophilic Surface coating (0.1-0.5 m) Porous substrate

Cross-Section of a Non-Porous UF Membrane

Nonporous Polymer Coating Layer (~ 0.3 m)

Microporous Support Membrane

Long-Term Water Flux of Porous and Non-Porous Ultrafiltration Membranes

1,000
pure water Feed: 1% motor oil in water Feed pressure: 150 psig Feed temperature: 23C

Microporous PVDF module

Water flux (L/m 2h)

water flush

100 Non-porous Pebax 1074/PVDF module

water flush

10

10

15

20

25

30

35

Permeation Time (Days)

Fouling Index of Porous and NonPorous Ultrafiltration Membranes for Separation of Oil/Water Emulsions
1

Pebax 1074 module

pure water

Fouling Index 0.1 H2 O(t)/JH2 O(0)

Microporous PVDF module
water flush water flush

0.01

10

15

20

25

30

35

Permeation Time (Days)

Long-Term Permeation Properties of Porous Ceramic and Ceramic/Polymer Composite Membranes

Feed: Bilge water ; permeate flux: 40 gfd
2.5 Backflush 2 Ceramic Module Ceramic/Pebax 1074 Module

1.5

Permeation Resistance (psi/gfd)

0.5

0 0 20 40 60 80 100 120

Time (hours)

Membrane Types Used in Ultrafiltration, Nanofiltration and Reverse Osmosis

Integral asymmetric membrane (Cellulose acetate) Selective layer (Material A) Microporous substrate (Material A) Thin-film composite membrane (Polyamide) Selective layer (Material A) Microporous substrate (Material B)

2003 RO/NF Membrane Sales

Company Dow/Filmtech Nitto Denko/ Hydranautics Toray GE Osmonics Koch/ Fluid Systems Toyobo TriSep Others

Sales ($ MM) 115 99 36 27 18 15 12 15

Share (%) 34 30 11 8 5 4 4 4

R. Truby, Water Executive, September/October 2004, p.11 (Supplement of Ultrapure Water 21, 2004)

2003 RO/NF Module Sales Distribution

Module Type Polyamide spiral-wound (8x40) Cellulose acetate hollow fiber module

Market Share (%) 91 5 4

Plate-and-frame

Expected RO/NF membrane lifetime ~ 3-5 years. Actual RO/NF membrane lifetime ~ 7-12 years. Membrane replacement makes up for ~ 60% of annual sales.
R. Truby, Water Executive, September/October 2004, p.9 (Supplement of Ultrapure Water 21, 2004)

Incremental Changes in SpiralWound RO Module Performance

Figure of Merit = (Productivity) x (1/Salt Passage) Cost
Year Cost (Normalized to 1980 U.S.$) 1.00 0.65 0.34 0.19 0.14 Productivity (Normalized to 1980) 1.00 1.10 1.32 1.66 1.94 Reciprocal Salt Passage (Normalized to 1980) 1.00 1.56 2.01 3.52 7.04 Figure of Merit 1.0 2.6 7.9 30.8 99.3
Dave Furukawa (1999)

1980 1985 1990 1995 1999

Interfacial Polymerization for Preparation of Thin-Film Composite RO Membranes

Hydrocarbon/ acid chloride solution

Aqueous amine solution Porous support Heat cure Polyamide layer ~ 0.1-0.2 m

Formation of FT 30 Thin-Film Composite Membrane

NH2

ClOC

COCl

NH2

COCl

NH

NHCO

CO

HN

NHCO

CO

CO

COOH

1- n

Formation of PEC 1000 Thin-Film Composite Membrane

CH2CH2OH O N O H2SO4 N HOH2CH2C O CH2CH2 O N O N CH2CH2OH O CH2OH

CH2

CH2CH2

N CH2CH2OCH2CH2

O HO3S

CH2

N O C H2 O

N CH2CH2O

Rejection and Water Flux of RO Seawater Desalination Membranes

Organic Solute Rejection of Commercial RO Membranes

Surface Structures of Interfacial Aromatic Polyamide Composite Membranes

28 gfd

28 gfd

37 gfd

45 gfd

S.-Y. Kwak, D.W. Ihm, J. Membrane Sci. 158 (1999) 143-153

Cross-Section of Interfacial Polyamide Composite Membranes (BW 30)

Ridge and valley structure ~ 0.2 - 0.5 m Selective layer ~ 500 - 1,000

Surface Structure of Uncoated and Coated RO Membranes

Uncoated

Coated

Surface Structure of Uncoated and Coated RO Membranes (AFM)

ESPA-3 ESPA-3 - coated

AFM pictures courtesy of Jennifer Louie, Stanford University

Performance of Commercial and Modified RO Membranes for Wastewater Treatment

50
Feed: 900 ppm mineral oil; 100 surfactant DC 193 Pressure: 500 psig Temperature: 25C

40

30

Water Flux (L/m h)

2 20

SWC-2 SWC-2/Pebax 4011

10

0 0 5 10 15 20 25 30

Permeation Time (Days)

Acknowledgements Ackno

Financial support was provided by Office of Naval Research and SERDP Special thanks to my colleagues Isabelle Ciobanu, Sylvie Thomas and Alvin Ng.