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Interaction of hemicelluloses and cellulose and
their influence on the cellulose microfibrillation
process
EUROPEAN FIBRE ...
Outline
« InTechFibres’ property – do not divulgate » - EFPRO 2015 - LFV 2
Context and objective
1- Xylan extraction
1.1 P...
CONTEXT: MFC production
« InTechFibres’ property – do not divulgate » - EFPRO 2015 - LFV 3
 MFC production: process in 2 ...
CONTEXT: Objective and programm
« InTechFibres’ property – do not divulgate » - EFPRO 2015 - LFV 4
Objective: to acquire a...
Solid state NMR (400 MHz) presentation
« InTechFibres’ property – do not divulgate » - EFPRO 2015 - LFV 5
 NMR spectra ar...
1- Xylan extraction
« InTechFibres’ property – do not divulgate » - EFPRO 2015 - LFV 6
1- Exchange of solvent water/tert-b...
1- Xylan characterisation
« InTechFibres’ property – do not divulgate » - EFPRO 2015 - LFV 7
 Xy – wood: is branched with...
1- Comparison of NMR spectrum before and after
xylan extraction
« InTechFibres’ property – do not divulgate » - EFPRO 2015...
2- Xylan conformation change by re-adsorption
experiment
« InTechFibres’ property – do not divulgate » - EFPRO 2015 - LFV ...
2- Theoretical estimation of the xylan surface
covering area
« InTechFibres’ property – do not divulgate » - EFPRO 2015 - ...
3- Interaction cellulose/xylan
« InTechFibres’ property – do not divulgate » - EFPRO 2015 - LFV 11
 The sandwiches format...
Conclusion
« InTechFibres’ property – do not divulgate » - EFPRO 2015 - LFV 12
 65% of xylan could be extracted from MFC ...
Acknowledgements
« InTechFibres’ property – do not divulgate » - EFPRO 2015 - LFV 13
Laurent Heux
Karim Mazeau
Yoshiharu N...
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Interaction of hemicelluloses and cellulose and their influence on the cellulose microfibrillation process

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By Lea Falcoz Vigne, Centre Technique du Papier (CTP). This was presented during the New Ideas for the Paper Industry: Young Researchers' Presentations session, organised as part of European Paper Week 2015. More at http://www.cepi.org/epw

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Interaction of hemicelluloses and cellulose and their influence on the cellulose microfibrillation process

  1. 1. Interaction of hemicelluloses and cellulose and their influence on the cellulose microfibrillation process EUROPEAN FIBRE AND PAPER RESEARCH ORGANISATIONS 17th - 19th November 2015 in Brussels L. Falcoz-Vigne L. Heux, K. Mazeau, Y. Nishiyama V. Meyer, M. Petit-Conil
  2. 2. Outline « InTechFibres’ property – do not divulgate » - EFPRO 2015 - LFV 2 Context and objective 1- Xylan extraction 1.1 Protocol of xylan extraction from MFC 1.2 Characterization of extracted xylan 1.3 Characterization of MFC after xylan extraction 2- Xylan re-adsorption experiment 3- Cellulose-xylan interaction Conclusion
  3. 3. CONTEXT: MFC production « InTechFibres’ property – do not divulgate » - EFPRO 2015 - LFV 3  MFC production: process in 2 steps 1- Pre-treatment Enzyme + Refining 2- Homogenisation at high pressure 1 pass at 1000 bar + 4 passes at 1500 bar MFCPre-treated fibresKraft/sulfite pulps 200µm  Homogenizer Pre-treated fibers MFC Microfibrillation Valve Impact ring  High energy consumption (10 MWh/t)  Enzymatic treatments are effective but quite empirical
  4. 4. CONTEXT: Objective and programm « InTechFibres’ property – do not divulgate » - EFPRO 2015 - LFV 4 Objective: to acquire a fundamental knowledge of the interactions between the polysaccharides of the fibre wall  To optimise the fibres pre-treatment  To decrease the energy consumption of the MFC production by at least 20% (1 pass into the homogenizer)
  5. 5. Solid state NMR (400 MHz) presentation « InTechFibres’ property – do not divulgate » - EFPRO 2015 - LFV 5  NMR spectra are sensitive to local environment and conformation (conformation around glycosidic linkage, hydroxymethyl conformation) 1 23 4 5 6 cellulose  The spectra are dependent on hemicelluloses concentration in MFC  The hemicelluloses contribution to MFC signal will be validated after xylan extraction from MFC from birch Kraft and NMR analysis A.Teleman, P.T.Larsson and T.Iversen, Cellulose, 2001, 8, 209-215 Wet MFC from birch Kraft: rich in hemicelluloses (23.5%) Wet MFC from M. pine sulfite: poor in hemicelluloses (2.5%) 5060708090100110120 Chemical shift (ppm) C6C4 crystalline C1 C2, C3 and C5 C4 disordered Crystalline core Disordered surface
  6. 6. 1- Xylan extraction « InTechFibres’ property – do not divulgate » - EFPRO 2015 - LFV 6 1- Exchange of solvent water/tert-buthyl alcohol (TBA) and MFC freeze-drying in TBA Fumagalli,M., Ouhab, D., Boisseau M., S., Heux, L., Biomacromolecules, 2013, 14, 3246-3255 Increase the MFC accessible surfaces MFC freeze-dried in water (Sspe = 13 m²/g) MFC freeze-dried in TBA (Sspe = 158 m²/g) 3- Separation and purification: Centrifugation, dialysis, freeze drying 2- Xylan extraction: MFC is redispersed in DMSO - 5% LiCl (24 h, 25°C) Hägglund E., Lindberg B., McPherson J., Acta chemica Scandinavica, 1956, 10, 1160-1164 Yield of xylan extraction: 65% +/- 4.5%
  7. 7. 1- Xylan characterisation « InTechFibres’ property – do not divulgate » - EFPRO 2015 - LFV 7  Xy – wood: is branched with glucuronic acid  Xy – MFC: homopolymer of xylose Habibi Y. and Vignon M.R., Carbohydrate Polymers, 2005, 340, 1431-1436 The extracted xylan Xy – MFC is compared with a xylan extracted from wood chips with 10% NaOH Xy – wood:
  8. 8. 1- Comparison of NMR spectrum before and after xylan extraction « InTechFibres’ property – do not divulgate » - EFPRO 2015 - LFV 8  The solid state NMR MFC signal is influenced by xylan extraction (especially on C4 and C6 area)  A ≠ B + C  The xylan conformation is modified when it is adsorbed onto the cellulose surface A = MFC before extraction B = MFC after extraction C = Xylan at 97% of relative humidity B + C A = MFC before extraction B = MFC after extraction C4 C6
  9. 9. 2- Xylan conformation change by re-adsorption experiment « InTechFibres’ property – do not divulgate » - EFPRO 2015 - LFV 9  Two model were reconstructed with:  Xylan conformation change when it is adsorbed onto the cellulose surface is validated in re-constructed model.  Adsorbed xylan: 13.5% on MFC from birch Kraft, 9% on MFC from pine sulfite “MFC after extraction” + extracted xylan in DMSO then dialysis 20% 13.5% Residual non adsorbed xylan MFC after extraction MFC before extraction MFC + 13.5% of xylan MFC + 20% of xylan Wet samples
  10. 10. 2- Theoretical estimation of the xylan surface covering area « InTechFibres’ property – do not divulgate » - EFPRO 2015 - LFV 10  Specific surface of MFC measured with BET (Sspe): • 158.0 m²/g for MFC from birch Kraft • 119.4 m²/g for MFC from pine sulfite  Molecular modelling predicts a monolayer adsorption with: 1 xylose per 0.25 nm² Mazeau K. and Charlier L., Cellulose, 2012, 19, 337-349  A monolayer of xylan is adsorbed onto the MFC surface  Re-adsorbed xylan content is controlled by the MFC accessible surface MFC from birch Kraft 0.14 g of xylan / g of cellulose Sspe x 0.25 10-18 x (Na / Mxylose) 0.10 g of xylan / g of cellulose MFC from pine sulfite NMR results 0.135 g of adsorbed xylan/ g of cellulose 0.09 g of adsorbed xylan/ g of cellulose Covering surface area 115% 95%
  11. 11. 3- Interaction cellulose/xylan « InTechFibres’ property – do not divulgate » - EFPRO 2015 - LFV 11  The sandwiches formation protocol was established Xylan Cellulose Cellulose  First traction tests were performed with dried sandwiches: the cellulose films broke before peeling Peeling tests will be performed at different conditions of humidity to soften the structure and be closer to the condition onto the homogenizer  Sandwiches were made with extracted xylan or labelled with fluorescein isothiocyante FITC (DS = 0,04%)  Cross sections were observed in microscopy Films of MFC Film of xylan 20 µm
  12. 12. Conclusion « InTechFibres’ property – do not divulgate » - EFPRO 2015 - LFV 12  65% of xylan could be extracted from MFC birch Kraft  The extracted xylan is a homopolymer of xylose XylanCellulose Xylan extraction  The adsorbed xylan content observed in NMR is correlated to the specific surface of cellulose measured in BET.  NMR analysis on re-adsorption confirmed xylan conformation change when it is adsorbed onto cellulose Xylan conformation  The xylan is adsorbed at the cellulose surface on a mono-layer  On dried sandwiches the interaction cellulose /xylan are stronger than MFC cohesion Interaction cellulose/xylan
  13. 13. Acknowledgements « InTechFibres’ property – do not divulgate » - EFPRO 2015 - LFV 13 Laurent Heux Karim Mazeau Yoshiharu Nishiyama Sonia Molina Boisseau Marie-France Métral Valérie Meyer Michel Petit-Conil Matthieu Schelcher François Cottin Arthur Janodet The Ph.D program is supported by: the Agence Nationale pour la recherche et la Technologie. the Institut Carnot PolyNat the Centre Technique du Papier. www.webCTP.com www.polynat.eu www.anrt.asso.fr

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