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Industrial Chemistry & Reaction Engineering Technical Chemistry – Department of Chemistry
Åbo Akademi University Umeå University
Sari Hyvärinen, M. Vaher, M.E. Lienque, D. Yu. Murzin,
M. Kaljurand, M. Koel, and J.-P. Mikkola
COST ACTION CM0903COST ACTION CM0903
Ionic liquid mediated
biomass deconstruction:
from analysis challenges to
fermentable sugars
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The focus/aim of the research
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Saccharides & their derivatives – why?
•Furfural
•5-HMF
•Cellobiose
•Gal
•Glc
•Man
•Fru
•Ara
•Xyl
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Valuable platform chemicals
monosaccharides
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Background & reasons for this research work
Climate change
EU legislation to promote the biofuels &
renewable energy sources
Increased demand for oil, especially in Asia
We should not be too dependent on oil
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…Background
How about possibilities to compensate or substitute petrochemical based industry?
Replacing of some oil based industrial products with the ethanol based ones:
E.g. Örnsköldsvik, Sweden in wartime
Paper mill cellulose Glc fermentation to EtOH used as fuel etc.
USA and Brazil are interested in ethanol as a chemical feedstock
(e.g. ethylene from ethanol instead of olefins from petrochemical
steam cracking)
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SAMPLES
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The studied LIGNOCELLULOSICS
Softwood
from Central Finland:
•Scots pine (Pinus sylvestris)
•Norway spruce (Picea abies)
•Silver Birch (Betula pendula)
Forest residues:
• Eucalyptus
• Lenga Nothofagus pumilio
Crops residues:
Corn
Wheat straw
…and in Chile
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EXPERIMENTAL PROCEDURES
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Experimental conditions & procedures:
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IONIC LIQUIDS (ILs)
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1-Ethyl-3-methylimidazolium chloride EmimCl or [emim]+ [Cl]-
Molar mass: 146,62 g/mol
Density 1,1120 g/cm3 (at 80 °C)
Melting point 77-80 °C impurities effect
Flash point: 186 °C
Viscosity 47.4 mPas (at 80 °C)
Flame point 515 °C
Solubility in water ∞
Very hygroscopic
Information concerning melting point varies in literature
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1-Ethyl-3-methylimidazolium acetate EmimOAc or [emim]+ [CH3COO]-
• Molar mass: 170,21 g/mol
• Density 1.027 g/cm3 at 25 °C
• Melting point > 30 °C
• Flash point: 164 °C
• Viscosity 10 mPas (at 80 °C)
• Solubility in water ∞
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THE ANALYSIS METHODS (CE, GC & HPLC)
AND COMPARISON OF THEM IN THIS PARTICULAR CASE
(FOR ANALYSIS OF CARBOHYDRATES & THEIR DEGRADATION PRODUCTS IN LIGNOCELLULOSIC SAMPLES IN THE PRESENCE OF IONIC LIQUIDS)
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GC, HPLC & CE
GC analysis HPLC analysis
• calibration samples in eluent solution • no derivatization/silylation needed
CE analysis
• calibration: STD sugars + ISTD (e.g. sucrose) • no derivatization/silylation needed • liquid phase can be analyzed after centrifuging and filtering
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Differences in analysis methods Sample results: GC analysis
Reliability problem with GC monosaccharide calibration
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HPLC analysis
Chromatography involves a mass transfer process involving adsorption
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CE (Capillary electrophoresis)
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• Separates ions based on their electrophoretic mobility
• Electrophoretic mobility depends on the charge of the molecule, the viscosity, and the atom's radius.
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CE (Capillary electrophoresis)
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• Detector: diode array UV/Vis
• Background electrolyte/buffer solution:
130 mM NaOH containing 36 mM Na2HPO4
must always be fresh
Sample derivatization is not needed
instead: dilution, centrifugation & filtration
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CE calibration standards
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A typical example of CE results
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HMF
in pine, spruce and birch samples
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7,56
6,57
5,76
1,41
1,18
1,30
0,00
1,00
2,00
3,00
4,00
5,00
6,00
7,00
8,00
0,00 20,00 40,00 60,00 80,00 100,00 120,00
mg/g
IL and heating treatment time in hours
5-HMF in pine, spruce & birch: amount per sample's total mass vs. wood in the sample (samples consist of wood & IL)
pine,HMF/wood
spruce,HMF/wood
birch,HMF/wood
birch,HMF/sample
spruce, HMF/sample
pine, HMF/sample
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Comparison summary (CE, HPLC, GC)
• CE analysis is the method of choice
• GC (+ STD sugar column) is unreliable when ILs are present: concentration of IL is critical
• HPLC suffers from peak overlapping
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Conclusions
IL pretreatment leads to significant formation of HMF and in some cases furfural
(like all depolymerization/ degradation processes) – good indicator to follow up (e.g. fermentation inhibitors, degree of depolymerization, colorization …)
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Thank you!
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Acknowledgements for funding:
• The Academy of Finland
• Raisio Oyj:n Tutkimussäätiö
• Cost action CM0903 (UbioChem)
• European Social Fund’s Doctoral Studies and Internationalisation
Programme DoRa (carried out by Foundation Archimedes) • Åbo Akademis “Doktorandstudiernas slutskede”- stipend
COST ACTION CM0903COST ACTION CM0903