Biomass Treatment and Transformation Using Ionic Liquids Sanan Eminov, Imperial College London,...
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Transcript of Biomass Treatment and Transformation Using Ionic Liquids Sanan Eminov, Imperial College London,...
Biomass Treatment and Transformation Using
Ionic Liquids
Sanan Eminov, Imperial College London, London, UK, 20132nd year PhD student
Energy demand It is estimated that the current consumption of petroleum is
at a rate 100.000 times faster than nature can replace it.
Alternatives:
• Wind• Solar• Nuclear• Hydro
• Biomass
Biomass is the only non-fossil option for organic chemical production .
http://cr.middlebury.edu/es/altenergylife/sbiomass.htm
http://www.nature.com/nature/journal/v454/n7206/fig_tab/nature07190_F2.html
A pathway from biomass to platform chemicals
Raines, R. T.; Binder, J. B. J. Am. Chem. Soc. 2009, 131, 1979-1985
Ionic Liquids + Metal Catalysts
Ionic liquids are low melting organic salts (<100 0C) that potentially comprise wide application due to their fascinating properties and have emerged as promising “green” replacement for volatile organic solvents.
Like the conventional salts, ionic liquids are mainly composed of ions which are positively and negatively charge.
The most attractive properties of ILs are their chemical and thermal stability, non-flammability, and negligible vapour pressure.
NN
R R
N R
N
N,N'-Dialkylimidazolium N-Alkylpyridinium
R R
N,N'-Dialkylpyrrolidinium
Cations
Anions
Cl-, Br-, I-, [BF4]-, [PF6]-, [AsF6]-, [AuCl4]-
Typical cations and anions used in ionic liquids
HMF yields in different ionic liquids
Hu, S.; Zhang, Z.; Song, J.; Zhou, Y.; Han, B.; Dalton Trans 2010, 39, 4080- 4089
OHH
HO H
H OH
O
OHHOO
OHO
H
Sulphate-based ionic liquids
80 oC, 3 h
CrCl2
[bmim]HSO4
- 3 H2O
O
OH
O
+H OH
O
80 oC, 3 h
CrCl2
+ 2 H2O
O
OHO
H
Fructose HMF
HMFLevulinic
Acid
Formic Acid
x
Ionic Liquid
Catalyst Temp.(oC)
HMF Yields (%)
3 hours
HMF yields (%)24 hours
[bmim]HSO4 CrCl3 ∙ 6H2O +
(15%) water
80 65 85
[bmim]HSO4 CrCl3 ∙ 6H2O 80 75 83
[bmim]HSO4 CrCl2 80 70 76
[bmim]HSO4 CrCl3 80 32 65
[bmim]HSO4 Sc(OTf)3 80 43 49
[bmim]HSO4 La(OTf)3 80 49 49
[bmim]HSO4 Y(OTf)3 80 49 60
[bmim]HSO4 WCl4 80 60 65
[bmim]HSO4 NiCl2 80 41 54
[bmim]HSO4 ZnCl2 80 32 38
Ionic Liquid
Catalyst Temp.(oC)
HMF Yields (%)
3 hours
HMF Yields (%)
24 hours
[bmim]HSO
4
No catalyst + (15%) water
80 11 44
[bmim]HSO
4
No catalyst 80 27 41
[bmim]HSO
4
CrCl3 ∙ 6H2O +
(15%) water80 65 85
OHH
HO H
H OH
O
OHHO
80 oC, t
[bmim]HSO4
- 3 H2O
O
OHO
H
Fructose HMF
Ionic Liquid
Catalyst Temp.(oC)
HMF Yields (%)
1 hours
HMF Yields (%)
3 hours
[bmim]HSO
4
CrCl3 ∙ 6H2O 100 87 96
[bmim]HSO
4
No catalyst 100 69 69
[bmim]HSO
4
CrCl3 ∙ 6H2O 120 87 89
[bmim]HSO
4
No catalyst 120 71 78
High Temperatures
Conclusion
Synthesis of RTILs (room temperature ionic liquids).
High HMF yields without any side products.
Around 45 % HMF yield without the use of catalyst.
One of the highest (96%) HMF yields in the literature.
High reaction rate.
Thank You!