extracting nanocelluloses from underutilized biomass for ... · natural organic matters colloidal...

Extracting nanocelluloses from

underutilized biomass for water

purification

Benjamin S. Hsiao

Stony Brook University BiMaC Innovation, KTH

Stockholm, Sweden, January 29, 2018

Distinguished Professor of Chemistry

Co-Director, Innovative Global Energy Solutions Center

Director, Center Integrated Electric Energy Systems

Stony Brook University

New York, USA

Water crisis

• One in six people worldwide do not

have access to safe fresh water1.

• 3.5 billion people will NOT have

safe-drinking water by 2025.2

• Every year, more than 2.2 million

people die of water related diseases

in the world.1

1 http://en.wikipedia.org/wiki/Water_scarcity_in_Africa#cite_note-bpn-1. 2 Service, R. F. Science, 2006, 313, 1088-1090.

http://www.afronline.org/?p=1439

http://accessafricanpeople.org/clean-water/

Classification of membrane filtration

Nanofiltration

(NF)

Reverse

Osmosis

(RO)

Ultrafiltration

(UF)

Microfiltration

(MF)

Conventional

Filtration

H2O

Inorganic

Ions

Sugars &

Multivalent

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

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

Can be gravity-driven

Conventional water filtration membranes (since 70’s)

120 µm

40 µm

~ 0.2 µmRO/NF layer

UF layer

Non-woven MF support

http://www.dow.com

Size exclusion range

RO (Reverse Osmosis): < 1 nm

NF (Nano-Filtration): 1 – 10 nm

UF (Ultra-Filtration): 10 – 100 nm

MF (Micro-Filtration): 0.1 – 50 mm Aqueous salts: 0.3 – 1.2 nm

Pesticides, herbicides: 0.7 – 1.2 nm

Virus: 10 – 100 nm

Bacterial: 200 nm – 30 mm

0.03 – 0.40(Brackish water : 1000 – 5000 ppm salts;

Seawater : 35,000 ppm of salts)

70 – 400 (Brackish Water)

600 – 1200 (Seawater)RO

0.22 – 0.66 (e.g. 2000 ppm MgSO4)70 - 400NF

3 – 100 (pure water)15 – 150UF

Flux (l/m2h)Pressure (psi)

0.03 – 0.40(Brackish water : 1000 – 5000 ppm salts;

Seawater : 35,000 ppm of salts)

70 – 400 (Brackish Water)

600 – 1200 (Seawater)RO

0.22 – 0.66 (e.g. 2000 ppm MgSO4)70 - 400NF

3 – 100 (pure water)15 – 150UF

Flux (l/m2h)Pressure (psi)

1 µm 100 nm

diameter fiber

0.02-1 µm thick

5 nm fiber diameter

20 μm 10 mm

diameter fiber New Concept: Nanofibrous Membranes with

Hierarchical Fiber Diameters

Multi-jet electrospinning process

to fabricate nanofibrous mid-layer scaffold

• Stony Brook instrumentation scalable to large production

• Controlled environmental conditions (e.g. humidity,

temperature) to fabricate high quality nanofibrous scaffolds

Electrospinning

Schematic

http://nano.mtu.edu/Electro

spinning_start.html

A startup based on nanofibers

A 2015 TechCrunch Winner

BUT ...

no existing technologies are

affordable for this circumstance

Hierarchical structure of plant cellulose Plant

Plant

Plant cell Plant cell wall

Cellulose fiber

Cellulose nanofiber/

microfibril aggregate

Cellulose microfibril/

nascent crystal

Cellulose molecular

chains (cross-section

view)

Width 20-30 µm Length 1-3 mm

Width 10-20 nm

Width 3-4 nm Length > 2 µm

Delamination

Cellulose nanostrip

Cellulose molecular chain (side view)

100 µm 100 µm 0.50 µm

TEMPO/NaBr/NaClO Mechanical treatment

OO

OO

OOH

OHHO

HO

OHHO

OH

HO

OH

OH

n-2

OHO

O

O

OHHO

HO

OH

HO

OH

OH

OH

OO

OOHHO

NaOOC

OHC

OH

m

O

O

OHHO

HO

OH

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 pulp

Fiber diameter ~ 40 μm

Cellulose nanofibers

Fiber diameter ~ 5 nm

Oxidized cellulose

fibers

Preparation of cellulose nanofibers

Using chemistry to break cellulose down

into nanosize - nanocellulose

Carboxylate at C6 position on cellulose surface

Y. Okita, T. Saito and A. Isogai, Biomacromolecules, 11, 1696–1700 (2010)

The histograms of the width were based on a

count of 227 fibers in 11 TEM images.

Cellulose nanofibers characterized by TEM

B A

C

0 50 100 150 200 250 300 350

-0.5

0.0

0.5

1.0

1.5

2.0

2.5

A

B

C

He

igh

t (n

m)

nmWidth (nm)

AFM Measurement of cellulose nanostrips

AFM measurements demonstrated that the thickness of a single nanostrip could be

around 0.5 nm. The thickness larger than 2 nm might be caused by the stacking of

nanostrips.

Y. Su, C. Burger, H. Ma, B. Chu, B. S. Hsiao, Biomacromolecules, 16(4), 1201 (2015)

Leptospirosis

0.2 µm in diameter

10~20 µm long

http://www.hyfluxmembranes.com/

http://en.wikipedia.org/wiki/

Waterborne diseases caused

by bacteria, viruses and heavy metals

SARS

100 nm

pI = 4.5

Hepatitis A

20-30 nm

pI = 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. Coli

0.5 µm in diameter

2 µm long 2 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

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

Cellulose nanofibers MF membrane for removal of

E. Coli by size exclusion

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

SEM Images of cellulose nanofibrous MF membrane

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

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

Cellulose nanofibrous MF membrane for removal of

virus and toxic metal ions by adsorption

The adsorption capacity of UCN for

UO22+ was 167 mg/g;

The adsorption capacity of commercially

available activated carbon for UO22+ 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%.

Cellulose nanofibrous MF membrane for removal

of Crystal Violet dye

N N

N

Cl

Sample Carboxylate

(mmol/g)

Amine

(mmol/g)

Zeta

potential

(mV)

Oxidized CN ～1.2 0 - 52.5

CN - diamine ～1.0 ～0.1 - 25.6

CN - PEI ～1.0 ～0.5 16.4

H. Ma, C. Burger, B. S. Hsiao, B. Chu, Biomacromolecules, 13(1), 180-186 (2012)

But …

the TEMPO chemistry was expensive

and not environmentally friendly

O

O

OH

OHHO

O

O

OH

OHHO

N O

N O

N OH

O

NaBr

NaBrO

NaClO

NaCl

O

O

H

OHHO

O

O

ONa

OHHO

O

NaOH

n

n

n n

O

T. Saito, S. Kimura, Y. Nishiyama, A. Isogai, Biomacromolecules, 8(8), 2485–2491 (2007)

The simple nitro-oxidation method

NaNO3 (sodium nitrate) is a fertilizer

P. Sharma, R. Joshi, S. Sharma, B. S. Hsiao, Biomacromolecules, 18(8), 2333–2342 (2017)

Nanocellulose can be extracted from

underutilized raw (untreated) biomass

Agave Switchgrass Miscanthus Bamboo

Cellulose

Fiber

Cellulose

Nanofiber Cellulose

Microfibril Plant Cell Wall

Spinifex – an underutlized resource in Australia

“The Outback” – 70% of Australia, yet < 5% of the population

http://www.pewtrusts.org/en/research-and-analysis/reports/2014/10/the-modern-outback

WAXD Spinifex crystallinity ~ 60%

CNF crystallinity ~ 30%

CNF extracted from Spinifex using

nitro-oxidation method

TEM

(left) Solution of 5000 ppm of

cadmium nitrate, (right) 5 mL of

a CNF suspension (0.20 wt%)

mixed the cadmium nitrate

solution (5,000 ppm) at pH 7

FTIR spectra of (A) CNF and (B) floc

obtained from the mixture of cadmium nitrate

solution (500 ppm of Cd2+) and CNF

suspension (0.20 wt%).

Spinifex-based NO-CNF: a very effective adsorbent

PR Sharma, et al., ACS Sustainable Chem. Eng., just published (2018)

• TEM image of the floc containing NO-CNF and Cd(OH)2 nanocrystals

• WAXD profile indexed by the unit cells of cellulose I and Cd(OH)2)

Adsorption mechanisms:

electrostatic interactions + mineralization

Cd+2: an effective crosslinking agent for NO-CNF

NO-CNF shows the highest maximum

adsorption capability

Nanofibrous UF membranes

• 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

0 10 20 30 40 500

100

200

300

400

500 Cellulose nanofibrous membrane

PAN10

PAN400

PAN400-rej.

PAN10-rej.

Cellulose nanofibrous membrane-rej.

2x

Time (h)

Perm

eati

on

Flu

x (

L/m

2h)

11x

90

92

94

96

98

100

Re

jectio

n (%

)

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

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

Nanofibrous NF/RO membranes

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

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

Nanocomposite membranes containing directed

water channels have higher flux!

Our Vision

• Sustainable membrane fabrication (MF, UF, NF and

RO ) using nanocelluloses from diverse biomass

sources to treat a wide range of water problems.

July 4, 2016

Stony Brook University

Financial Support:

NSF-SusChEM

Electric Power Research Institute

New York State - CIEES

2017 November US Thanksgiving Dinner