Biomass Treatment and Transformation
Using Ionic Liquids
Sanan Eminov, Imperial College London, London, UK, 2013
2nd 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.
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
Sulphate-based ionic liquids
H
O
H
HO
OH
H
OH
[bm im ]H SO 4
80 o C , 3 h
- 3 H 2O
OH
H
HO
O
C rC l 2
HO
O
Fructose
HMF
H
O
HO
x
C rC l 2
O
80 o C , 3 h
+ 2 H 2O
HMF
O
O
OH
+
H
OH
O
Levulinic
Acid
Formic
Acid
Ionic
Liquid
[bmim]HSO4
Catalyst
HMF
Temp.
(oC) Yields (%)
3 hours
HMF
yields (%)
24 hours
80
65
85
[bmim]HSO4
CrCl3 ∙ 6H2O +
(15%) water
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
H
O
H
HO
OH
OH
80 o C , t
H
OH
HO
H
O
[bm im ]H SO 4
HO
O
- 3 H 2O
Fructose
HMF
Ionic
Liquid
Catalyst
Temp.
(oC)
[bmim]HSO4
No catalyst +
(15%) water
No catalyst
CrCl3 ∙ 6H2O +
(15%) water
[bmim]HSO4
[bmim]HSO4
80
HMF
Yields
(%)
3 hours
11
HMF
Yields
(%)
24 hours
44
80
27
41
80
65
85
High Temperatures
Ionic
Liquid
Catalyst
HMF
Temp.
Yields (%)
(oC)
1 hours
HMF
Yields (%)
3 hours
[bmim]HSO4
CrCl3 ∙ 6H2O
100
87
96
[bmim]HSO4
No catalyst
100
69
69
[bmim]HSO4
CrCl3 ∙ 6H2O
120
87
89
[bmim]HSO4
No catalyst
120
71
78
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!