Cellulose Membrane Technology for Water Purification...UF (Ultra-Filtration): 10 – 100 nm MF...

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‘ Cellulose Membrane Technology for Water Purification A Breakthrough Innovation 1 Benjamin S. Hsiao Distinguished Professor Chemistry Department

Transcript of Cellulose Membrane Technology for Water Purification...UF (Ultra-Filtration): 10 – 100 nm MF...

Page 1: Cellulose Membrane Technology for Water Purification...UF (Ultra-Filtration): 10 – 100 nm MF (Micro-Filtration): 0.1 – 50 µ m Aqueous salts: 0.3 – 1.2 nm Pesticides, herbicides:

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Cellulose Membrane Technology for Water Purification

A Breakthrough Innovation

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Benjamin S. HsiaoDistinguished Professor Chemistry Department

Page 2: Cellulose Membrane Technology for Water Purification...UF (Ultra-Filtration): 10 – 100 nm MF (Micro-Filtration): 0.1 – 50 µ m Aqueous salts: 0.3 – 1.2 nm Pesticides, herbicides:

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Classification of Membrane Filtration

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Nanofiltration

(NF)

Reverse Osmosis

(RO)

Ultrafiltration(UF)

Microfiltration(MF)

Conventional Filtration

H2O

Inorganic Ions

Sugars & Multivalen

t Ions

Natural Organic Matters

Colloidal Silica

Virus Bacteria Yeast Cell

Membrane Pore Size

0.1 nm 1 nm 0.1 µm 10 µm

100 – 10 bar 20 – 5.0 bar

5.0 – 1.0 bar

2.0 – 0.1 bar

Driven Force

Can be gravity-driven

* P. Robert, Journal of Membrane Science, 83, 81-150 (1993)

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Conventional Water Filtration Membranes (since 70’s)

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Size exclusion rangeRO (Reverse Osmosis): < 1 nm

NF (Nano-Filtration): 1 – 10 nmUF (Ultra-Filtration): 10 – 100 nmMF (Micro-Filtration): 0.1 – 50 µm

Aqueous salts: 0.3 – 1.2 nmPesticides, herbicides: 0.7 – 1.2 nm

Virus: 10 – 100 nmBacterial: 200 nm – 30 µm

RO/NF layerUF layerNon-woven MF support

120 µm

40 µm

~ 0.2 µm

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Fiber Diameter and Pore Size in Non-woven Membranes

4H. Y. Ma, C. Burger, B. S. Hsiao, B. Chu. J. Mater. Chem., 21(21), 7507 – 7510 (2011)

Fiber diameter ratio: 1 : 3 : 10; Porosity: 80 %

Smaller fiber diameter, smaller effective pore size

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Hierarchical Structure of Plant Cellulose

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1 µm∼100 nm diameter fiber

0.02-1 µm thick5 nm fiber diameter

20 μm∼10 µm diameter fiber

New Concept: Nanofibrous Membranes with Hierarchical Fiber Diameters

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Preparation of Cellulose Nanofibers

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100 µm 100 µm 0.50 µm

TEMPO/NaBr/NaClO Mechanical treatment

O O

OO

OOH

OHHOHO

OHHO

OHHO

OH

OH

n-2

OHO O

O

OHHOHO

OH

HO

OH

OH

OH

OO

OOHHO

NaOOC

OHC

OH

m

O

O

OHHO

HOOH

O

o p

Carboxylate groups (negatively charges and chelation): 0.70 mmol/(g cellulose)Aldehyde groups (chemical reactivity): 0.25 mmol/(g cellulose)Hydroxyl groups (chemical reactivity): 2.0 mmol/(g cellulose)

Cellulose wood pulpFiber diameter ~ 40 μm

Cellulose nanofibersFiber diameter ~ 5 nmOxidized cellulose fibers

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Waterborne Diseases Caused by Bacteria, Viruses and Heavy Metals

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Leptospirosis0.2 µm in diameter

10~20 µm long

http://www.hyfluxmembranes.com/http://en.wikipedia.org/wiki/

SARS100 nmpI = 4.5

Hepatitis A20-30 nmpI = 3～4

Filtered by Size Exclusion Adsorbed by Charge Interactions

2 µm

200 nm

200 nm

Most viruses have pI ＜7, with negative charges at pH = 7

E. Coli0.5 µm in diameter

2 µm long2 µm

Most bacteria have sizes over 0.2 µm

As (III), (V)in pesticide and

burning coal

Cr (VI)in dye and

paint

Most heavy metal ions have charges and can be interacted via chelating agents

Adsorbed by Charge Interactions & Chelating Agents

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Cellulose Nanofibers MF Membrane for Removal of E. Coli by Size Exclusion

9A. Sato, R. Wang, H. Y. Ma, B. S. Hsiao, B. Chu, J. Electron Microsc., 60, 201-209 (2011)

The surface of the membrane was covered by E. Coli particles, whereas the

retention ratio was 99.9999 %.

Cross-sectional view after filtration

Top view after filtration

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Cellulose Nanofibers MF Membrane for Removal of Virus and Toxic Metal by Adsorption

10H. Y. Ma, B. S. Hsiao, B. Chu, ACS Macro Lett., 1, 213-216 (2012)

The adsorption capacity of UCN for UO22+ was 167

mg/g;

The adsorption capacity of commercially available activated carbon for UO2

2+ was 57 mg/g.

UO22+

MS2

The adsorption capacity of CN based MF membrane for MS2 was 99%, i.e., ∼10X better than the adsorption capacity of commercially

available GS9035 for MS2 which was 90%.

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www.liquico.comCORPORATION

http://www.liquico.com
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Nanofibrous UF Membranes

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• Permeation flux of nanofibrous UF membrane can be 10 X higher than conventional UF membranes (at the same rejection ratio) - due to higher porosity (80%) of non-wovens

• Cellulose nanofibers barrier layer is anti-fouling and more chemical resistant

H. Ma, et al., Journal of Materials, 20(22), 4692-4704 (2010)

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Nanofibrous NF/RO Membranes

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The nanocomposite barrier layer (cellulose nanofibers + polyamide matrix)• is stronger than the conventional barrier layer• introduces “directed water channels” to increase the flux by 2-5 X for RO

desalination

H. Ma, C. Burger, B.S. Hsiao B. Chu, ACS Macro Letters, 1(6), 723-726 (2012)

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Sources of Cellulose in Nature

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• Higher plants (fibers, parenchyma etc.)

• Seaweeds (Valonia, etc.)

• Animals (Tunicates, Salpae etc.)

• Bacteria (Acetobacter, etc.)

• Fungi (Saprolegnia, etc.)

• Amoebae (Dictyostelium, etc.)

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Our GoalSustainable membrane fabrication (MF, UF, NF RO, and MBR ) using nanocelluloses from diverse biomass sources to treat a wide range of water problems.


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