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SOLVENT/SUBSTRATE BEHAVIOR
BETWEEN PULP FIBERS AND 1-BUTYL-3-
METHYLIMIDAZOLIUM HYDROGEN SULFATE
COST FP1205 Training school
Pretreatment and dissolution of cellulose7th -9th , April, 2015
Jia Mao 1, 2, Hatem Abushammala 1,2, Laura Barcellos Pereira 3, Heiko Winter1, 2, Marie-Pierre Laborie* 1, 2
1 Chair of Forest Biomaterials, Faculty of Environment and Natural Resources, University of
Freiburg, Werthmannstr. 6, 79085 Freiburg, Germany
2 Freiburg Materials Research Center (FMF), University of Freiburg, Stefan-Meier Str. 21, 79104
Freiburg, Germany
3 PEMM/COPPE, Universidade Federal do Rio de Janeiro, Rio de Janeiro, RJ, Brazil
Cellulose Nanocrystals (CNCs)
2
(Mao et al.; 2013)
• First: Rånby in 1949
• Chemical hydrolyzed
• Rod-like
• Highly crystalline
• W: 3-10 nm L: 100-400 nm
Acids Con.(mol/L) T (℃) t (h) Yield (%)
H2SO4 9-10 45-55 1-2 20-40
HCl 4-6 80 3-4 10-20
HBr 2.5 100 3 70
H3PO4 15 100 1.5-2 76-80
Maleic acid 1.6 75 7 61
Acetic acid 17.5 80-105 2-7 15-35
H3PW12O40 1 90 30 60
H+ H+
H+
H+
Bondeson et al. 2006; Araki and Kuga. 2001; Sadeghifar et al. 2011; Li et al. 2013
Low yield
Corrosive acids
Nanocellulose Industry
3
Company Country Productivity Launch
Invenntia Sweden 100 kg/day 2010
Celluforce Canada 1 ton/day 2011
US Forest Products Laboratory US 35-50 kg/day 2012
Bio Vision Technology Inc. US 11 kg/day 2012
Daicel Co. Japan - -
BASF/Zelfo Germany - 2013
AITF Canada 100 kg/day 2014
Sappi Netherlands - Expected 2016
NORTH
AMERICA
CelluForce
BGB
FPI/Domtar
AITF
FPL(both)
Bio Vision
APA
Verso Paper
UMaine
GL&V
EUROPE
Rettenmaier
Borregaard
UPM
Stora Enso
Innventia
Billerud Korsnas
BASF/Zelfo
Norske Skog
Sappi
ASIA
Melodea
Hiroshima
Daicel
Nippon Paper
Asahi Kasei
Oji Paper
Problems and Alternatives
4
The disadvantages of the strong acid method triggered the
development of alternative methods:
• Economic consideration - low yield
• Safety issues and environmental concerns – Corrosive
Alternatives:
• Pretreatments
• Milder and efficient catalysts
• Recyclable solvent systems
Ionic liquids: a promising class of solvents
Designer Solvents: Ionic Liquids
5
Cation
Anion
Advantages:
• Little vapor pressure: non-volatile
• Thermal and chemical stability
• Recyclability and Reusability.
• Tunable properties: solvation, swelling, density, viscosity, …….
Olivier-Bourbigou et al. 2010.
Nanocellulose Production using IL
6 Cellulose Nanofibers using Pure [Bmim]HSO4:
70, 80, 90 ℃,
1 hour
Microcrystalline
Cellulose (MCC) CNFs/CNCs
(Man, et al. 2011)
[Bmim]HSO4
+
(W=14-22 nm)
Swelling with [Bmim]Cl Hydrolyzing with H2SO4
80 °C2% w/w
1-2 hours
Stirring at 200 rpm
80 °C1-4% w/w
2-16 hours
Stirring at 200 rpm
1st stage 2nd stage
One-pot two-stage swelling-hydrolysis for CNCs
CNCs
(Lazko, et al.; 2014)
7
Motivation: One-stage IL-based Extraction
Cellulose Nanocrystals using Aqueous [Bmim]HSO4
7
120 ℃
24 hour
MCC
CNC suspension
Mao, J., Osorio-Madrazo, A., Laborie, M-P. Cellulose, 2013, 20: 1829-1840.
+ 48±2%
Acid hydrolysis
H2O +
[Bmim]HSO4 can act as both
Swelling agent and Hydrolysis
catalyst?
Pretreatment Step
Swelling MCC in the ionic liquid as a pretreatment before the
hydrolysis to improve the CNC yield and lower the reaction
severity?
8
MCC [Bmim]HSO4
Hydrolysis
H2O
Swelling
~ 48 %
~ ? %
+ +
CNC yield
1st2nd
120 ℃24 hours
Microscopic Study
9
Hot stage
Slides
Coverslip
pulp fiber
IL
- Pure IL (water content: 0.1-0.5%)
- Hardwood kraft pulp (freeze-dried)
- T (℃): RT, 50, 120
- t (h): 14 days
Incubation
10
1:5
(w/w)
Hardwood
kraft pulp
(freeze-dried)
BmimHSO4 pulp/IL Mixture
Filtration
pH≈7
Oven-drying
(50 ℃, vacuum)
Incubation
WH2O:IL (w/w) T
(℃)
t
(h)
7.5:2.5 RT 8,24
2.5:7.5 50 8,24
0:10 120 0.2, 0.3, 0.5,
1,2,4,8,24
Treated pulp
• Mass Loss
• Crystallinity index
• Degree of polymerization
Pretreatment for CNC Production
11
Sources Hydrolysis condition Yield(%)
T(℃) t(h) W H2O:IL(w/w)
Softwood pulp 130 12 2.5:7.5 57.8±2.9
Hardwood pulp 130 12 2.5:7.5 57.1±1.9
MCC 100 12 2.5:7.5 76.0±3.0
MCC [Bmim]HSO4
Hydrolysis
120 ℃24 hours
H2O
Swelling RT
24 hours
+ H2O
~ 48 %
~ 66 %
+ +
CNC yield
1st
2nd
More combinations of swelling
and hydrolysis can be designed
and optimized!
[Bmim]HSO4 acts as both swelling agent and
hydrolysis catalyst, controlled mainly by temperature.
Maximal swelling was obtained at RT for 24h, which
was selected as pretreatment condition for CNC
production in higher yield
More combinations of swelling and hydrolysis can be
designed and optimized
Pure IL and IL/Water mixtures behave differently, and
water content has no obvious effect
Conclusions
12
Acknowledgement
13
• Exchange Students: Laura
Pereira, Raphael Campos
• Ms. Elke Stibal
• Ms.Barbara Heck
• Prof. Günter Reiter
• Prof. Wolfgang Glasser
Thank You for Your Attention !
14
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