SOLVENT/SUBSTRATE BEHAVIOR BETWEEN PULP FIBERS AND 1-BUTYL-3- METHYLIMIDAZOLIUM HYDROGEN SULFATE

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1 COST FP1205 Training school Pretreatment and dissolution of cellulose 7 th -9 th, April, 2015 SOLVENT/SUBSTRATE BEHAVIOR BETWEEN PULP FIBERS AND 1-BUTYL-3- METHYLIMIDAZOLIUM HYDROGEN SULFATE Jia Mao 1, 2, Hatem Abushammala 1,2, Laura Barcellos Pereira 3, Heiko Winter 1, 2, Marie-Pierre Laborie * 1, 2 1 Chair of Forest Biomaterials, Faculty of Environment and Natural Resources, University of Freiburg, Werthmannstr. 6, Freiburg, Germany 2 Freiburg Materials Research Center (FMF), University of Freiburg, Stefan-Meier Str. 21, Freiburg, Germany 3 PEMM/COPPE, Universidade Federal do Rio de Janeiro, Rio de Janeiro, RJ, Brazil

2 Cellulose Nanocrystals (CNCs) (Mao et al.; 2013) First: Rånby in 1949 Chemical hydrolyzed Rod-like Highly crystalline W: 3-10 nm L: nm Acids Con.(mol/L) T ( ) t (h) Yield (%) H 2 SO HCl HBr H 3 PO Maleic acid Acetic acid H 3 PW 12 O H + H + H + H + Low yield Corrosive acids Bondeson et al. 2006; Araki and Kuga. 2001; Sadeghifar et al. 2011; Li et al

3 Nanocellulose Industry 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 Company Country Productivity Launch Invenntia Sweden 100 kg/day 2010 Celluforce Canada 1 ton/day 2011 US Forest Products Laboratory US kg/day 2012 Bio Vision Technology Inc. US 11 kg/day 2012 Daicel Co. Japan - - BASF/Zelfo Germany AITF Canada 100 kg/day 2014 Sappi Netherlands - Expected

4 Problems and Alternatives 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 4

5 Designer Solvents: Ionic Liquids 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

6 Nanocellulose Production using IL One-pot two-stage swelling-hydrolysis for CNCs 1 st stage 2 nd stage Swelling with [Bmim]Cl Hydrolyzing with H 2 SO 4 (Lazko, et al.; 2014) 80 C 2% w/w 1-2 hours Stirring at 200 rpm 80 C 1-4% w/w 2-16 hours Stirring at 200 rpm CNCs Cellulose Nanofibers using Pure [Bmim]HSO 4 : 6 + Microcrystalline Cellulose (MCC) 70, 80, 90, 1 hour CNFs/CNCs (W=14-22 nm) [Bmim]HSO 4 (Man, et al. 2011) 7

7 Motivation: One-stage IL-based Extraction Cellulose Nanocrystals using Aqueous [Bmim]HSO H 2 O + MCC 48±2% 24 hour CNC suspension Acid hydrolysis [Bmim]HSO4 can act as both Swelling agent and Hydrolysis catalyst? Mao, J., Osorio-Madrazo, A., Laborie, M-P. Cellulose, 2013, 20:

8 Pretreatment Step MCC [Bmim]HSO 4 + H 2 O + Hydrolysis hours Swelling 1st 2nd CNC yield ~ 48 % ~? % Swelling MCC in the ionic liquid as a pretreatment before the hydrolysis to improve the CNC yield and lower the reaction severity? 8

9 Microscopic Study Slides Coverslip IL pulp fiber Hot stage - Pure IL (water content: %) - Hardwood kraft pulp (freeze-dried) - T ( ): RT, 50, t (h): 14 days 9

10 Incubation 1:5 (w/w) Incubation Filtration Oven-drying (50, vacuum) Hardwood BmimHSO 4 kraft pulp (freeze-dried) W H2O:IL (w/w) T ( ) pulp/il Mixture t (h) 7.5:2.5 RT 8,24 2.5: ,24 0: , 0.3, 0.5, 1,2,4,8,24 ph 7 Treated pulp Mass Loss Crystallinity index Degree of polymerization 10

11 Pretreatment for CNC Production Hydrolysis MCC + H 2 O + [Bmim]HSO 4 Swelling 1st + H 2 O RT 24 hours 2nd hours CNC yield ~ 48 % ~ 66 % More combinations of swelling and hydrolysis can be designed and optimized! Sources Hydrolysis condition Yield(%) T( ) t(h) W H2O:IL (w/w) Softwood pulp : ±2.9 Hardwood pulp : ±1.9 MCC : ±3.0 11

12 Conclusions [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 12

13 Acknowledgement Exchange Students: Laura Pereira, Raphael Campos Ms. Elke Stibal Ms.Barbara Heck Prof. Günter Reiter Prof. Wolfgang Glasser 13

14 Thank You for Your Attention! 14