Post on 04-Oct-2020
Les nanocelluloses, une nouvelle voie de
valorisation de la cellulose
Michel PETIT-CONIL
Divonne-les-Bains – 15 juin 2017
Sommaire de la présentation
• Définition des nanocelluloses
Définition, origine et caractéristiques
Avantages et inconvénients
• Production de nanocelluloses
Les technologies utilisées
Les principaux producteurs
Le prix
Les capacités de production d’InTechFibres
• La propriété intellectuelle
• Les utilisations potentielles
Les secteurs envisagées
Les applications développées par le CTP
« InTechFibres’ property – do not divulgate » - JournéeAFPV / MPC / 15.05.2017 2
« Thinking small is leading to big changes »
« InTechFibres’ property – do not divulgate » - JournéeAFPV / MPC / 15.05.2017 3
• Nanotechnology is helping to improve products and to
create new products for the future.
•The U.S. National Nanotechnology initiative defines this
revolutionary science as "the science, engineering, and technology
conducted at the nanoscale, ~1-100nm "
• It could be a potential important opportunity for the pulp and paper
industry
• In 2011, 9 main groups of nano-objects in more than 2000
products were identified in the world
•Ceramic nanoparticles, Metal nanoparticles
•Nanoporous materials, Carbon nanotubes, Nano-structured
materials,
•Dendrimeters, Quantum dots, Fullerens, Nanofibres
« Thinking small is leading to big changes »
« InTechFibres’ property – do not divulgate » - JournéeAFPV / MPC / 15.05.2017 4
• Global potential market for products using nanotechnology
is estimated at ~US $ 1 to 3 trillion by 2020.
•Wood products would capture 20% of this market
• Nanocellulose is the most relevant nanomaterial for wood-
based industry
•Cellulose is the most abundant natural polymer on Earth
•Renewable, recyclable, biodegradable with exceptional properties
• Commercial success of nanocellulose requires investments
for the production but also methods for its characterisation
and for the potential risks of exposure.
Sommaire de la présentation
• Définition des nanocelluloses
Définition, origine et caractéristiques
Avantages et inconvénients
• Production de nanocelluloses
Les technologies utilisées
Les principaux producteurs
Le prix
Les capacités de production d’InTechFibres
• La propriété intellectuelle
• Les utilisations potentielles
Les secteurs envisagées
Les applications développées par le CTP
« InTechFibres’ property – do not divulgate » - JournéeAFPV / MPC / 15.05.2017 5
Definition of the term “nanocellulose”
• From European recommendation (2011/696),
Nanomaterial means a natural, incidental or manufactured
material containing particles, in an unbound state or as an
aggregate or as an agglomerate and where, for 50% or more of
the particles in the number size distribution, one or more external
dimensions is in the size range of 1 – 100 nm.
•Particle: minute piece of matter with with well defined phyiscal
boundaries
•Aggregate: particle comprising of strongly bound or fused particles
•Agglomerate: collection of weakly bound particles or aggregates
where the external surface area is similar to the sum of the surface
areas of the individual components.
• Nanocellulose is a nanomaterial composed of cellulose
« InTechFibres’ property – do not divulgate » - JournéeAFPV / MPC / 15.05.2017 6
Origin of nanocelluloses
« InTechFibres’ property – do not divulgate » - JournéeAFPV / MPC / 15.05.2017 7
Postek M., et al., Meas. Sci. Technol, 2011, 22, 024005
Origin of nanocelluloses
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Natural Cellulose Fibres
Micro/Nano fibrillated cellulose
Adapted from Pääkkö, et al. 2007
Mechanical
shearing
Micro/Nano crystalline cellulose Whiskers
Strong acid
hydrolysis
+/- pre-treatments
Nanocelluloses dimensions
« InTechFibres’ property – do not divulgate » - JournéeAFPV / MPC / 15.05.2017 9
Denomination Dimensions
MFC
NFC
Micro/Nano fibrillated Cellulose,
Microfibrils or microfibrillated cellulose
Nanofibrils or nanofibrillated cellulose
Diameter: 10 – 100 nm
Lengths: several µm
NCC Nanocrystalline cellulose
Whiskers
Rod-like cellulose
Microcrystals
Diameter: 5 – 70 nm
Lengths: 100 – 250 nm
for plant cellulose
BNC Bacterial nanocellulose
Bacterial / Microbial cellulose
Bio-cellulose
Diameter: 20 – 100 nm
Different types of
networks
Nanocelluloses dimensions and characteristics
« InTechFibres’ property – do not divulgate » - JournéeAFPV / MPC / 15.05.2017 10
Future Markets. 2017
Cellulose crystals are potentially stronger than steel
and similar to Kevlar®
Experimental Young’s modulus : 137 GPa
Theoretical Young’s modulus : 167.5 GPa
Nanocelluloses - SWOT
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Strengths Weaknesses
Renewable
Sustainable
Mechanical performance
Filming behaviour
Thermal stability
Large surface area
Optical transparency
Non-petroleum based/natural
Energy consumption
Cost/Price
Characterisation tools
Drying
Dry matter content
Opportunities Threats
Bio-based materials demand
Green chemicals market increase
New barrier packagings materials
New products from forest industry
Public acceptance
Nanoparticle size
Safety – Toxicity – Risks
Regulation
Standards in progress
Future Markets. 2017
Sommaire de la présentation
• Définition des nanocelluloses
Définition, origine et caractéristiques
Avantages et inconvénients
• Production de nanocelluloses
Les technologies utilisées
Les principaux producteurs
Le prix
Les capacités de production d’InTechFibres
• La propriété intellectuelle
• Les utilisations potentielles
Les secteurs envisagées
Les applications développées par le CTP
« InTechFibres’ property – do not divulgate » - JournéeAFPV / MPC / 15.05.2017 12
Production of nanocelluloses - Technologies
« InTechFibres’ property – do not divulgate » - JournéeAFPV / MPC / 15.05.2017 13
2 ways of production for nanocelluloses from
paper pulps:
• "bottom-up" method: ascending approach, particles
are formed atom by atom or molecule by molecule
Bacterial nanocellulose (BNC): production from
specific fungi with bacteria
• "top down" method: descending method, reduction
of an object by division/ fractionation
Micro/Nanofibrillated cellulose (MFC/ NFC):
Chemical and/or mechano-enzymatic pre-
treatments followed by a strong mechanical
treatment (grinding, cryocrushing, refining,
homogenisation and microfluidisation
Nanocrystalline cellulose: strong acid hydrolysis
to extract crystalline particles
The main producers
« InTechFibres’ property – do not divulgate » - JournéeAFPV / MPC / 15.05.2017 14
Future Markets. 2017
• ~30 MFC « producers » from 2 kg/d up to 500 kg/d
At commercial scale: American Process Inc, Imerys, Cellucomp, Asahi Kasei, Chuetsu,
Pulp & Paper, Daicel, Daiichi Kogyo, Daio Paper, Nippon Paper, Oji Holdings, Sugino
Machine, UPM, JRS, Stora Enso
At pilot scale : CTP/FCBA, Innventia, US Forest Products Laboratory, University of
Maine, VTT, FP Innovation, Celluforce/Domtar, BioVision, BillerudKornäs, Borregaard,
Akzo Nobel, Suzano.
• Production of nanocellulose
Cost: 50 to 1000 US$/kg
Optimistic projection demand
Up to 2,5 M tons
(due to use as excipients)
Europe 10%
North America
30% Asia-Pacific
55%
Rest of the world 5%
Nanocelluloses at InTechFibres – Lab scale
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•Laboratory equipment • MicroFluidizer from Microfluidics
• Pressure up to 2000 bar
• Production limited at ~100 g maxi
•Laboratory/pilot equipment • Homogeniser from GEA Niro Soavi
NS3006
• Pressure up to 1500 bar
• Motor: 5.5 kW – Capacity: 50 L/h
• Cooling system
• Production limited at 1kg at 3%
consistency (33 litres)
Nanocelluloses at InTechFibres – Pilot scale
« InTechFibres’ property – do not divulgate » - JournéeAFPV / MPC / 15.05.2017 16
•Pilot equipment
• Low consistency refining pilot plant to treat
up to 10 kg of pulp at 4-5% consistency
• Homogeniser from GEA Niro Soavi
NS3075
• Pressure up to 1500 bar
• Motor: 55 kW – Capacity: 1 m3/h
• Cooling system
• Production limited at ~ 30 kg at 3% (1 m3)
Sommaire de la présentation
• Définition des nanocelluloses
Définition, origine et caractéristiques
Avantages et inconvénients
• Production de nanocelluloses
Les technologies utilisées
Les principaux producteurs
Le prix
Les capacités de production d’InTechFibres
• La propriété intellectuelle
• Les utilisations potentielles
Les secteurs envisagées
Les applications développées par le CTP
« InTechFibres’ property – do not divulgate » - JournéeAFPV / MPC / 15.05.2017 17
The intellectual property
« InTechFibres’ property – do not divulgate » - JournéeAFPV / MPC / 15.05.2017 18
0
100
200
300
400
500
600
700
800
Patents
Publications Patent fields:
22% Composites
10% Paper coatings
9% Medical
9% Film
8% Paper furnish
5% Nanopaper
4% Coatings
Future Markets. 2017
CTP/FCBA French patent based on specific mechano-enzymatic technology
Sommaire de la présentation
• Définition des nanocelluloses
Définition, origine et caractéristiques
Avantages et inconvénients
• Production de nanocelluloses
Les technologies utilisées
Les principaux producteurs
Le prix
Les capacités de production d’InTechFibres
• La propriété intellectuelle
• Les utilisations potentielles
Les secteurs envisagées
Les applications développées par le CTP
« InTechFibres’ property – do not divulgate » - JournéeAFPV / MPC / 15.05.2017 19
Nanocelluloses utilisations
Main utilisations: • Composites
• Films
• Electronics
• Sensors
• Filtration
• Energy
• Medical
• Papers
• Cosmetics
• Textiles
• Excipients
• 3D printing
« InTechFibres’ property – do not divulgate » - JournéeAFPV / MPC / 15.05.2017 20
Volume of industry demand
Future Markets. 2017
Nanocelluloses utilisations – TRLs
« InTechFibres’ property – do not divulgate » - JournéeAFPV / MPC / 15.05.2017 21
Future Markets. 2017
Mechano-enzymatic MFC
TEMPO MFC
Development of nanocellulose use at CTP
« InTechFibres’ property – do not divulgate » - JournéeAFPV / MPC / 15.05.2017 22
Self standing films
Packaging market
Electronics
100% MFC
MFC in mass
MFC coatings
Papers and boards
Packaging market
Electronics
CTP patent
100% cellulose
Composite Coatings
Papers and boards
Few % of MFC
Use of MFC for papers and films
VTT
« InTechFibres’ property – do not divulgate » - JournéeAFPV / MPC / 15.05.2017 23
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