3-Medicine_Biology_and_Chemistry
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Transcript 3-Medicine_Biology_and_Chemistry
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!