Tetrahedron Letters 52 (2011) 58915893

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Tetrahedron Letters
journal homepage: www.elsevier.com/locate/tetlet

Effect of NaCl on the conversion of cellulose to glucose and levulinic acid via solid supported acid catalysis
Joshua Potvin, Erin Sorlien, Jessica Hegner, Brenton DeBoef , Brett L. Lucht
Department of Chemistry, University of Rhode Island, Kingston, RI 02881, USA

a r t i c l e

i n f o

a b s t r a c t
Cellulose is hydrolyzed to glucose, which is further converted to levulinic acid in the presence of Naon, as a surface supported acid catalyst. The addition of simple alkali metal halide salts, including NaCl, provides signicant enhancement to the yield. The catalyst can be recycled suggesting possible extension into a continuous ow reactor for the synthesis of the biofuel precursors. 2011 Elsevier Ltd. All rights reserved.

Article history: Received 14 July 2011 Revised 1 September 2011 Accepted 4 September 2011 Available online 8 September 2011 Keywords: Biofuels Cellulose Solid-supported catalyst Naon

The development of methods for hydrolyzing raw biomass from renewable, non-food bearing plants either to glucose or directly to biofuels is highly desirable. One of the primary constituents of plant matter is cellulose which is a biopolymer that consists of glucose units joined by b(1?4) linkages. The structure of cellulose is very robust due to strong interchain hydrogen bonding, which limits water solubility and makes degradation of cellulose very difcult. Large scale economical conversion of cellulose is not readily feasible using the current best technology, which employs cellulolytic enzymes, as they require aqueous solvents and mild conditions under which cellulose is not readily soluble.1 The chemical degradation of cellulose has also generated significant interest.2 Most of the recently reported chemical methods for converting biomass use either very strongly aqueous acidic conditions3 or acid catalysts in the presence of ionic liquids.46 While many of the current methods for decomposing cellulose produce furan derivatives, levulinic acid has recently been identied as a precursor of the valeric biofuels.79 Consequently, the development of a novel method to convert cellulose into levulinic acid in neutral aqueous conditions would be preferable. The use of solid supported acid catalysis for the depolymerization of cellulose in water has been investigated. Recent reports describe the hydrolysis of cellulose by solid catalysts such as Amberlyst resin acid modied amorphous carbon, layered transition metal oxides, or sulfonated silica/carbon nanocomposites1013 These surface acidic species were quite efcient for the conversion of cellulose into smal Corresponding authors. Tel.: +1 401 874 9480; fax: +1 401 874 5072.
E-mail addresses: (B.L. Lucht). bdeboef@chm.uri.edu (B. DeBoef), blucht@chm.uri.edu

ler, water soluble b(1?4)-linked glucans, but conversion to glucose or other small biofuel precursors was limited. As an expansion of our previously reported use of Naon as a solid supported acid catalyst for the conversion of cellulose to glucose and levulinic acid,14 we report on a method to enhance the reactions yield via incorporation of alkali metal salts.15 A bomb ask was charged with cellulose (2.00 g), Naon SAC-13 catalyst (1.00 g), and 30 mL of deionized water with and without added salt. This mixture was allowed to react between 190200 C for 5 days. Following the reaction, the reaction appeared homogeneous. The solution was ltered to separate any traces of waterinsoluble starting materials from the water-soluble products. The aqueous solution, which contained both levulinic acid and NaCl was evaporated to dryness. Five 50 mL aliquots of ethanol (95%) was successively added to the mixture to extract the levulinic acid from the solid residue. After each aliquot, the liquid was collected and vacuum ltered. The ltrate was again concentrated via rotary evaporation to isolate the major product, levulinic acid. Experiments conducted in the absence of salts provided low yields of levulinic acid [14% (mol/mol)]. However, upon incorporation of low concentrations of NaCl, the yield of levulinic acid was increased signicantly (Table 1). The addition of 10% NaCl solution as the solvent increased the yield of levulinic acid 3.5-fold. Increasing the concentration of sodium chloride slightly increased the yield of levulinic acid. The 20% NaCl solution and the 25% NaCl solution provided yields of 70% and 72%. We hypothesize that the greater concentration of NaCl allows for a greater concentration of ions in solution. These charged particles interact with the hydrogen bonding network of the cellulose structure. Simultaneously, the high temperatures of the reaction allow for more cellulose to dissolve

0040-4039/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.tetlet.2011.09.013

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J. Potvin et al. / Tetrahedron Letters 52 (2011) 58915893 Table 1 Conversion of cellulose to levulinic acid by solid supported acid catalysts with different concentrations of salt

OH O HO O OH
n

Nafion-SAC 13 Salt, H2O 190-200 C 5 days

OH HO HO O OH OH

Cellulose

Glucose (not observed)

Salt None (DI H2O) 5% NaCl 10% NaCl 15% NaCl 20% NaCl 25% NaCl 5% KCl 10% KCl
a

% Yield 14
O

39 49 48 70 72 48 34

HO O Levulinic acid

Yields were calculated as the ratios of moles of product to theoretical moles of glucose contained in a given amount of cellulose.

Figure 1. Representative 1H NMR of crude reaction.

in the solvent. This enables the Naon SAC-13 catalyst to hydrolyze the cellulose more effectively to generate glucose. Over a period of

5 days, the glucose will be converted to levulinic acid, the sole product that was observed in these reactions.

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Figure 1 shows a 1H NMR spectrum of a typical reaction. The crude material coming directly from the reaction is essentially pure. The resonances are characteristic of levulinic acid and are identical to a commercial standard. The 1H NMR spectrum is consistent with high product purity and contains no 1H NMR resonances characteristic of glucose, which are observed in the 34 ppm region. Furthermore, the lower solubility of sodium chloride in ethanol compared to glucose in ethanol would suggest low concentrations of NaCl in the isolated levulinic acid. This assumption was further supported by preparing NMR samples of isolated levulinic acid and commercial levulinic acid containing internal standards. The 1H NMR integrations of the isolated and commercial levulinic acid, compared to the internal standard, are identical, further supporting very low concentration of NaCl in the isolated levulinic acid. A 20% NaCl solution was used under identical reaction conditions to examine the recyclability of the catalyst. After isolating the pure levulinic acid, the residual solids were collected and returned to the bomb ask to which additional starting materials, cellulose (2.00 g), and 30 mL of the 20% NaCl solution, were also added. The reaction mixture was heated again to 190200 C for an additional 5 days. This process was repeated a third time to test the recyclability of the catalyst over 3 separate cycles. The yields for the three runs were 69%, 52%, and 41%, respectively. While there is some reduction in the product yield, the results suggest that the catalyst has the potential to be recycled. The use of a different salt, such as potassium chloride, was also investigated to determine if the salt effect was general. Reactions using 10% KCl induced higher yields than deionized water; however, the yields were lower than reactions with comparable concentrations of NaCl. On the contrary, the 5% KCl solution induced higher yields than the 5% NaCl solution. The yields were not signicantly different between the sodium and potassium chloride trials indicating that cation size may not have a large affect on the product yield. The effect of added salts on Naon as a solid acid catalyst for the hydrolysis of cellulose was investigated. The yield of levulinic acid can be increased 5-fold from 14% to 72% upon incorporation of a 25% NaCl solution. The dramatic increase in yield indicates that sodium chloride is effective in interrupting the hydrogen bonding network at high temperatures and pressures. Additionally, other

salts such as potassium chloride are also efcient at increasing the yields of levulinic acid, and the catalyst can be recycled with a moderate reduction in yield. Thus, aqueous salt suspensions of cellulose can be readily decomposed to generate biofuel precursors in the presence of solid supported acid catalysts. Though the overall reaction is energy intensive, in terms of time and temperature, the use of a simple brine solvent, as opposed to expensive ionic liquids, to dissolve cellulose could have important applications for the production of biofuels on an industrial scale. Acknowledgments The authors thank the College of the Environment and Life Sciences at the University of Rhode Island and the USDA Hatch Program for nancial support of this research. Undergraduate students performed the entirety of this work. References and notes
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