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!