Les nanocelluloses, une nouvelle voie de valorisation de la ......Global potential market for...

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 »


• 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 »


• 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.








Le prix







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


Origin of nanocelluloses


Postek M., et al., Meas. Sci. Technol, 2011, 22, 024005

Origin of nanocelluloses


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


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


Lengths: 100 – 250 nm

for plant cellulose

BNC Bacterial nanocellulose

Bacterial / Microbial cellulose

Bio-cellulose


Different types of

networks

Nanocelluloses dimensions and characteristics


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


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









Le prix







Production of nanocelluloses - Technologies


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



• ~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


•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


• Motor: 5.5 kW – Capacity: 50 L/h

• Cooling system

• Production limited at 1kg at 3%

consistency (33 litres)

Nanocelluloses at InTechFibres – Pilot scale


•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


• Motor: 55 kW – Capacity: 1 m3/h

• Cooling system

• Production limited at ~ 30 kg at 3% (1 m3)








Le prix







The intellectual property


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


CTP/FCBA French patent based on specific mechano-enzymatic technology








Le prix







Nanocelluloses utilisations

Main utilisations: • Composites

• Films

• Electronics

• Sensors

• Filtration

• Energy

• Medical

• Papers

• Cosmetics

• Textiles

• Excipients

• 3D printing


Volume of industry demand


Nanocelluloses utilisations – TRLs



Mechano-enzymatic MFC

TEMPO MFC

Development of nanocellulose use at CTP


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


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