Chemical Synthesis of Transportation Fuels in Ionic Liquid Solvent Medium

Arush Dhawan, Mandan Chidambaram and Alexis T. Bell University of California Berkeley, CA 94720
Conversion of Glucose to fuel products
Hydrogenation
Rh/Al 2O3 or Raney Ni H2

Two Step Glucose Conversion

(Hydrogenation followed by dehydration)

Glucose

Sorbitol

5-HMF

5-methylfurfural

Reaction Conditions: Temperature (120 C), Hydrogen (900 psi), Time (12 h hydrogenation and 3 h dehydration). Raney Ni used as co catalyst

Reaction conditions: Ionic Liquid (10 mmol); Glucose(1 mmol); Catalyst (0.02 mmol); Temperature(120 C); Time (3 h); Hydrogen(900 psi); Co-catalyst (Raney Nickel)

Effect of Alumina Support

In case of alumina support, dehydration products with similar yields are obtained without addition of sulfuric acid.

Challenges
Develop catalysts for the selective conversion of glucose to fuels such as functionalized transition metals and metal complexes. Reduction of viscosity of solution using some external agent. These 4 catalysts gave the best results. Rhodium highly active while alumina nickel highly selective. Addition of co catalyst greatly improved the product distribution.
5-HMF

Hydrogenation of 5-HMF
Pd/Carbon 3H2, -2H2O

2,5-dimethylfuran

(gasoline)

Ionic Liquid Overview

General Considerations A solution comprised completely of ions. Negligible vapor pressure. Thermal stability up to 200 C. Consideration for catalysis Ionic nature as solvent. High solubility of H2, CO, O2. Highly polar yet non coordinating solvents. Cellulose/Sugar chemistry properties Chloride ion containing ILs have cellulose solubility in the range 12- 25%. Viscosity of cellulose/sugar and IL solution can reach up to 300 times of water. Viscosity can be decreased up to 30 times by using a co solvent.
H2SO4 -3H2O

Dehydration

Effect of cosolvent
Butyronitrile used as co solvent. Large decrease in the viscosity of the system. Condensation product of 5-HMF formed due to interaction with cosolvent.

Glucose

5-HMF

5-(chloromethyl) furfural

Conclusions

Reaction Conditions: Temperature (80 C), Hydrogen(900 psi), Time (3 h), IL : Cosolvent(3:1)

Ionic Liquida Temperature (C) Cellulose Dissolved (wt.%)a

[Bmim][OAc] [Bmim][Cl] [Bmpy][Cl]
a Reaction

100 100 110

10.6% 15.5% 26.1%

Condition: ILs (3 g); BMIM Cl (1-butyl-3-methylimidazolium chloride); BMIM OAc (1-butyl-3-methylimidazolium acetate); and BMPy Cl (1-butyl-3-methylpyridinium chloride); Rotation (1000 rpm); Time (1 h).

Cellulose Depolymerisation
Reaction Condition : IL (2 gm), Glucose (220 mg), Catalyst(22 mg), Temperature (110 C), Time(3 h)

Mineral acid provides hydrogen ion to activate C-O-C bond. Acid converts cellulose to either cellobiose or glucose. Cellulose can then decompose to glucose. Increasing acid concentration decreases yield of glucose while increasing yield of HMF and other products.

Hydrogenation:Rh/C shows maximum activity while AlNi shows higher selectivity. Raney Ni forms almost 100% HMF. Dehydration: Sulfuric acid shows better activity despite being less acidic then HCl. Two Step Conversion: Higher yield of HMF is obtained. HMF Hydrogenation: Cosolvent decreases the viscosity of the solution. Although in presence of cosolvent better activity is achieved but in Ru on Carbon interaction between 5-HMF and cosolvent results in the formation of a condensation product.
References
Bao Q. X.; Qiao, K.; Tomida, D.; Yokoyuma, C., Preparation of 5 hydroxymethylfurfural by dehydration of fructose in the presence of acidic Ionic liquid. Catalysis communications 2008, 9(6), 1383-1388 Zhao, H.B,; Holladay J.E.; Brown H.; Zhang, Z.C., Metal Chlorides in ionic liquids convert sugars to 5hydroxymethylfurfural. Science 2007, 316(5831), 1597-1600

Dehydration was carried out using 20 different catalysts.

Acknowledgements
Prof. Saikat Chakraborty IIT-UCB Collaboration Program EBI for funding

HCl ionizes HMF to CMF hence lower yield is obtained as compared to sulfuric acid. Polyphosphoric acids are highly selective to HMF.