extracting nanocelluloses from underutilized biomass for ... · natural organic matters colloidal...
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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
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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/
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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
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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)
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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
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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
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A startup based on nanofibers
A 2015 TechCrunch Winner
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BUT ...
no existing technologies are
affordable for this circumstance
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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)
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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
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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)
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The histograms of the width were based on a
count of 227 fibers in 11 TEM images.
Cellulose nanofibers characterized by TEM
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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)
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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
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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
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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)
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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%.
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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)
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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)
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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)
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Nanocellulose can be extracted from
underutilized raw (untreated) biomass
Agave Switchgrass Miscanthus Bamboo
Cellulose
Fiber
Cellulose
Nanofiber Cellulose
Microfibril Plant Cell Wall
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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
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WAXD Spinifex crystallinity ~ 60%
CNF crystallinity ~ 30%
CNF extracted from Spinifex using
nitro-oxidation method
TEM
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(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)
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• 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
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NO-CNF shows the highest maximum
adsorption capability
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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)
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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
Nanofibrous NF/RO membranes
H. Ma, C. Burger, B.S. Hsiao B. Chu, ACS Macro Letters, 1(6), 723-726 (2012)
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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!
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Our Vision
• Sustainable membrane fabrication (MF, UF, NF and
RO ) using nanocelluloses from diverse biomass
sources to treat a wide range of water problems.
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July 4, 2016
Stony Brook University
Financial Support:
NSF-SusChEM
Electric Power Research Institute
New York State - CIEES
2017 November US Thanksgiving Dinner