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)

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(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

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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

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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

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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)

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Motivation: One-stage IL-based Extraction

Cellulose Nanocrystals using Aqueous [Bmim]HSO4

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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?

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MCC [Bmim]HSO4

Hydrolysis

H2O

Swelling

~ 48 %

~ ? %

+ +

CNC yield

1st2nd

120 ℃24 hours

Microscopic Study

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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

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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

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Acknowledgement

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• Exchange Students: Laura

Pereira, Raphael Campos

• Ms. Elke Stibal

• Ms.Barbara Heck

• Prof. Günter Reiter

• Prof. Wolfgang Glasser

Thank You for Your Attention !

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