novel ionic liquids and wood fractionation mechanisms
DESCRIPTION
FuBio Seminar 27.8.2013TRANSCRIPT
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FuBio 2 | JR2 | WP2 Novel Ionic Liquids and Fractionation Mechanisms
Alistair W. T. King University of Helsinki
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Overview – Work Package Status & Highlights
• Why ionic liquids?
• Wood & Wood Biopolymer Solubility
• Wood & Pulp Fractionation Mechanisms
• Brief Highlights: Autohydrolysis, Fibrillation, IONCELL
• Novel and Recyclable Ionic Liquids
• Conclusions
2
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WP2: Objectives
• FuBio (Future Biorefinery) – Research oriented (process development)
– Cellulose
– Joint Research 2
• Work Package 2 – Novel Biomass Fractionation (Ionic Liquids)
• The main objective is to develop efficient and sustainable methods for biomass fractionation using recyclable ionic liquids
3 Alistair W. T. King
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What is an Ionic Liquid?
4 Alistair W. T. King
‘Ionic Liquids’ are essentially ‘molten salts’ containing one or more organic ions! Unsolvated ‘Molten Salts’ (m.p.)
– NaCl 801 oC – [mmim]Cl 125 oC – [emim]Cl 87 oC – [emim][NTf2] -3 oC – [emim][OAc] -45 oC
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Ionic Liquid Anatomy & Cellulose Dissolution
5 Alistair W. T. King
N NMe
Cl-
π−ππ−π
VDVH
H-bond acidity
H-bond bacisity
COLUMBIC
VDVProperties are dictated by the interplay of Columbic, Polar, H-bonding
and dispersion interactions
Cellulose dissolution dependent on H-bond basicity & acidity. Hydrophobic interactions may also play a part
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What Makes Ionic Liquids Unique?
Cellulose
Lignin Hemicellulose
Hot Water
Organic Solvents
Basic Ionic Liquids Solubility for each component dependent on entropic component of Gibbs equation (MW, Temp) and chemical stability of components in the solvents
Alistair W. T. King
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Wood Processing – Idealised Schemes
7
Dissolution (Homogeneous)
Degradation
Selective Precipitation
Chemical Modification
Regeneration
Extraction (Heterogeneous)
Chips or Sawdust
Pure fractions, e.g. Cellulose, hemis, lignin
+ LCCs
Biofuels & Chemicals
Pure fractions, e.g. Cellulose, hemis, lignin & LCCs
Materials, e.g. Films, Fibres,
Composites, Moldable
Variable degrees of cellulose
swelling
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Parameterising Wood Solubility
8
Swell/Dissolve (90 oC, 18 hr)
Wood Meal + Ionic Liquid ([amim]Cl)
Phosphitylate Hydroxyls
Quantitative 31P NMR
Integrate in Solution-state
• Pre-dissolution/swelling occurs into [amim]Cl under mild conditions • Quantitative 31P NMR as a measure of wood ‘solubility’
• Kyllönen, et al., On the solubility of wood in ionic liquids., Green Chem., DOI:10.1039/C3GC41273C, 2013.
Wood ‘solubility’
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Wood Solubility vs Particle Size (micro)
9
0
2
4
6
8
10
12
-1 4 9 14 19 24
Tota
l Hyd
roxy
ls (m
mol
/g)
Planetary Milling Time (hr)
Spruce
Birch
• Sawdust (0 hr) planetary milled and subjected to 31P NMR • Both hard and softwoods are not soluble until finely pulverised
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Birch Wood Solubility vs Chip Size
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10.7
3.2
1.3 1.7 1.8
0.3 0.0 0.0
2.0
4.0
6.0
8.0
10.0
12.0
PM 24 hr <0.16mm 0.16-0.4mm 0.4-1mm 1-3mm 3-6mm >6mm
Tota
l Hyd
roxy
ls (m
mol
/g)
Planetary Milling Time or Particle Size Range
• As particle size increases towards chip size, solubility decreases drastically
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Highlight: Autohydrolysis (PHWE)
Alistair W. T. King University of Helsinki
• Hauru, Sixta et al. RSC Advances, 2013 (‘Enhancement of ionic liquid-aided fractionation of birchwood. Part 1: Autohydrolysis pretreatment’)
• Autohydrolysis (pressurised hot water extraction) is an existing industrial wood pre-treatment method (pre-hydrolysis kraft pulp)
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Effect of Autohydrolysis on Wood Solubility
12
• Birch chips were autohydrolysed and then Wiley-milled to pass a 1mm sieve • After autohydrolysis, even very low P-factors increase solubility drastically
10.7
1.4
5.3
11.9 11.5
13.4 11.9
12.6 12.8 12.8
0.0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
16.0
PM 24 hr
0 50 170 260 770 1060 1320 3600 8170
Tota
l Hyd
roxy
ls (m
mol
/g)
Planetary Milling Time or P-Factor
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Autohydrolysed Wood Solubility vs Chip Size
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10.7 11.9 11.9
12.6
10.8 10.8 12.0
0.0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
PM 24 hr <0.16mm 0.16-0.4mm 0.4-1mm 1-3mm 3-6mm >6mm
Tota
l Hyd
roxy
ls (m
mol
/g)
Planetary Milling Time or Particle Size Range
• For a P-Factor of 1060, solubility is now consistent over a wide particle size range, unlike the untreated birch which is essentially insoluble approaching 1 mm.
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A Significant FuBio Result
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• Allow for true homogeneous processing of wood using an existing pulping pre-treatment (pre-hydrolysis)
• Degradation of the cellulosic fraction is minimised during this pre-treatment
• An extracted hemicellulose fraction can add value to the process
• Industrial-sized chips can now be used (sawdust or further milling not required)
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Highlight: Fibrillation
Alistair W. T. King University of Helsinki
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Fibrillation of Wood Chips in Ionic Liquid
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• When chips are treated with ionic liquid they fibrillate, not dissolve.
• Fibre yield is high (typically > 90%) • Thought to be a result of removal of pectin
from the middle lamella. Lignin is preserved • Materials are now being assessed by partners
for potential applications
[emim] [Me2PO4]
140 oC / 6 hr
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Highlight: IONCELL
Alistair W. T. King University of Helsinki
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IONCELL: Kraft Pulp Fractionation
Alistair W. T. King
pure Cellulose I
+
3 4 5 6 70,0
0,5
1,0
1,5
dm/d
(log
MM
)
log MMHemi-rich Kraft pulp
pure Hemi
Ionic Liquid + Co-Solvent 3 4 5 6 7
0,0
0,5
1,0
1,5dm
/dlo
g(M
M)
log MM
3 4 5 6 70,0
0,5
1,0
1,5
dm/d
(log
MM
)
log MM
Poster: IONCELL: Selective xylan extraction with ionic liquids, A. Roselli, M. Hummel, H. Sixta (Aalto University)
High selectivity of extraction and recovery of pure fractions
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Predominant Structures Studied in FuBio
19 Alistair W. T. King
Ionic Liquid: Imidazoliums ‘Distillable’ ‘Switchable’ Applicability Cellulose Dissolution & Wood
Chip Fibrillation/ Hemicellulose Extraction (IONCELL)
Cellulose Dissolution/Wood Fractionation
Wood Extraction
Thermal Stability Moderate Stability/Variable Unstable Unstable
Recyclability Low Distillable Distillable
Water Miscibility Most Fully Yes Yes
Toxicity Moderate-Low Moderate-Low High-Low
Cost (> ton) High (< 60 €/kg) Low (15-60 €/kg) Low (< 20 €/kg)
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Alternative Structures Studied in FuBio
20 Alistair W. T. King
8/28/13
Ionic Liquid: Hydrophobic & Non-basic imidazoliums
Phosphonium Carboxylates
Cholinium Carboxylates
Applicability Can selectively dissolve lignin over polysaccharide
DMSO electrolytes dissolve polysaccharide but neat ILs are selective for lignin (tuneable)
Known to dissolve lignin but not cellulose
Thermal Stability Relatively High Stability Highest Stability Lowest Stability
Recyclability Low Phase-separable Low
Water Miscibility Miscible Tunable miscibility Fully Miscible
Toxicity Moderate Toxicity Moderate-High Toxicity Lowest
Cost High High Low
* BASF patent does not cover these structures!
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Distillable Ionic Liquids (DILs)
Alistair W. T. King University of Helsinki
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[emim][OAc] Distillability
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22
Kugelrohr 0.3 mbar/170-180 oC alkylimidazoles recovered
Sublimation Apparatus (wt boiling stones) 0.03 mbar/130-145 oC ‘Pure’ [emim][OAc] recovered
Distillable only below 170 oC
using short-path distillation apparatus
BASF Patent (WO 09027250)
0.05 mbar / 170 oC
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Distillable acid-base conjugates
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King et al, Distillable acid-base conjugate ionic liquids for cellulose dissolution and processing. Angew. Chem. Int. Ed., 2011, 50, 6301.
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[TMGH][OAc] Extract Distillation
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• [emim][OAc] distillation:
• 130 oC / 0.05 mbar
• [TMGH][OAc] distillation
• 130 oC / 5 mbar!
[TMGH][OAc] Pine extract distilled at JBEI
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Switchable Ionic Liquids (SILs)
Alistair W. T. King University of Helsinki
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Switchable Ionic Liquids (SILs): The Concept
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§ Solvent before and after switching mixed with Nile red dye to show the transformation from low polarity to high polarity
§ Solvent is ‘switched’ back again by bubbling N2 or heating.
+ CO2
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Switchable Ionic Liquids (SILs): The Concept
27
N
N+
NH+
N
CO2+
CO2-NH2OH
NH2O
O
O-
Gas flow in Gas flow out
MEA SIL
Poster: Different pre-treatment methods and their effects before SIL wood fractionation, I. Anugwom, P. Virtanen, P. Mäki-Arvela, J-P. Mikkola (Åbo Akademi University)
DBU
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Phase-Separable Ionic Liquids (PSILs)
Alistair W. T. King University of Helsinki
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Hydrophobic ‘Phase-Separable’ Ionic Liquids (PSILs)
29
Chlorides, provided by CYTEC, were converted to the acetates using ion exchange resin.
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HSQC of MCC Dissolved in [P8881][OAc]/d6-DMSO (7 % MCC, 50 oC)
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1H NMR of MCC Dissolved in [P8881][OAc]/d6-DMSO (7 % MCC, 50 oC)
31
C1 C6
C3 C4
C5
C2
Polymeric AGU C1-1H Anomeric Glu C1-1H (reducing end) Terminal Glu C1-1H
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Assignment of C1-1H NMR Resonances
32
Based on 2D NMR assignments of low to high DP samples: • Cellobiose (DP 2) • sc-H2O extracted MCC (DP 15) • MCC & Avicel (DP 100) • Bahia PHK pulp (DP 500) • Borregaard Super VS sulfite
pulp (DP 1000)
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8/28/13
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Matemaattis-luonnontieteellinen tiedekunta / Henkilön nimi / Esityksen nimi
% Recovery of [P8881][OAc] Per Cycle at Different Co-Solvent Compositions
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Gibbs Diagram: [P8881][OAc], DMSO & Water
34
Poster: An NMR study of wood and wood biopolymers dissolved in phase-separable ionic liquids (PSILs), A. Holding, V. Mäkelä, J. Helminen, L. Tolonen, H. Sixta, I. Kilpeläinen, A. King (Aalto & U. Helsinki)
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Conclusions
35
• Basic ionic liquids are highly effective media for homogeneous processing of wood
• True homogeneous processing requires pre-treatment methods such as pre-hydrolysis/autohydrolysis
• It is possible to fibrillate wood chips upon treatment with certain ionic liquids
• It is possible to convert kraft pulp to high purity cellulose and xylan with ionic liquid-co-solvent treatments (IONCELL)
• New recyclable ionic liquids for lignocellulose processing have been developed: Switchable (SIL), distillable (DIL), phase-separable (PSIL)
• PSIL-DMSO electrolytes are excellent media for cellulose dissolution and NMR analysis.
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Acknowledgements
8/28/13
36
• Ilkka Kilpeläinen (University of Helsinki) • Ionic Liquid Development • Arno Parviainen, Ashley Holding, Somdatta Deb, Pirkko
Karuhnen, Jorma Matikainen, Laura Lemetti, Tia Kakko, Valtteri Mäkelä
• Herbert Sixta (Aalto University) • Fractionation Scheme Development • Application of ILs for fibre spinning • Yibo Ma, Lasse Tolonen, Lauri Hauru, Michael Hummel, Anne
Michud, Annariika Roselli
• Jyri-Pekka Mikkola (Åbo Akademi University) • Switchable Ionic Liquids
• Ikenna Anugwom, Valerie Eta, Pasi Virtanen, Paivi Mäki-Arvela
• Martin Lawoko (Wallenberg Wood Science Center, KTH) • Seema Singh (Joint Bioenergy Institute, CA, USA)
PROC ESS C HEMISTRY C ENTRE ÅAÅBO AKADEMIUN IV E R S I TY