Single-step conversion of cellulose to 5-hydroxymethylfurfural (HMF), a versatile platform chemical

Journal Article · Sat Jun 20 04:00:00 EDT 2009 · Applied Catalysis. A, General, 361(1-2):117-122

DOI:https://doi.org/10.1016/j.apcata.2009.04.002· OSTI ID:973991

Su, Yu; Brown, Heather M; Huang, Xiwen; Zhou, Xiao Dong; Amonette, James E; Zhang, Z Conrad

The ability to use cellulosic biomass as feedstock for the production of fuels and chemicals currently derived from petroleum depends critically on the development of effective low-temperature processes. While HMF, as a versatile platform chemical suitable for use in polymer synthesis or production of liquid biofuels, can currently be made from fructose and glucose, synthesis of HMF directly from raw natural cellulose represents the last major barrier toward the development of a sustainable HMF platform. Here we report an unprecedented single-step pathway that depolymerizes cellulose rapidly under mild conditions and converts the resulting glucose to hydroxymethylfurfural (HMF). A pair of metal chlorides (CuCl2 and CrCl2) dissolved in 1-ethyl-3-methylimidazolium chloride at temperatures of 80-120°C catalyzes cellulose depolymerization and the subsequent glucose conversion to HMF with 95% selectivity among recoverable products (at 56% HMF yield). Cellulose depolymerization, which can also be catalyzed by other metalchloride pairs such as CuCl2 paired with PdCl2, CrCl3, or FeCl3, occurs at a rate that is more than one order of magnitude faster than conventional acid-catalyzed hydrolysis. In contrast, single-metal chlorides at the same total loading showed low activity under similar conditions. Mechanistic studies suggest that the C2 hydrogen of the imidazolium ring is activated by the paired metal-chloride catalysts.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 973991
• Report Number(s): PNNL-SA-59545; 25401
• Journal Information: Applied Catalysis. A, General, 361(1-2):117-122, Journal Name: Applied Catalysis. A, General, 361(1-2):117-122 Journal Issue: 1-2 Vol. 361; ISSN ACAGE4; ISSN 0926-860X
• Country of Publication: United States
• Language: English

Related Subjects

02 PETROLEUM
08 HYDROGEN
09 BIOMASS FUELS
1-Alkyl-3-methylimidazolium chloride
1-Ethyl-3-methyl-imidazolium chloride
5-Hydroxymethylfurfural
BIOFUELS
BIOMASS
CATALYSTS
CELLULOSE
CHLORIDES
Cellobiose
Cellulose conversion
CrCl2
CuCl2
DEPOLYMERIZATION
Environmental Molecular Sciences Laboratory
FRUCTOSE
GLUCOSE
Glucose
HMF
HYDROGEN
HYDROLYSIS
Ionic liquid
Maltose
PETROLEUM
POLYMERS
PRODUCTION
Paired metal chlorides
SYNTHESIS