ChemSusChem · 2012 · 271 citations · 35 references
The fraction of chemicals and energy derived from renewable resources such as lignin is expected to rise as fossil feedstock reserves dwindle. The authors demonstrate a catalytic process that valorizes kraft, organosolv, and sugarcane bagasse lignin using inexpensive, bio‑renewable ethanol/water as solvent. Ethanol/water mixtures solubilize lignin, reduce its molecular weight (confirmed by GPC and HSQC NMR), and then undergo liquid‑phase reforming over Pt/Al₂O₃ at 498 K/58 bar or a supported transition‑metal catalyst at 473 K/30 bar H₂ to generate aromatic oxygenates and cyclic hydrocarbons. The reforming produces up to 17 % combined monomeric aromatic oxygenates (e.g., guaiacol) and hydrogen, while the hydrogen‑assisted reduction yields up to 6 % cyclic hydrocarbons and aromatics.
Abstract With dwindling reserves of fossil feedstock as a resource for chemicals production, the fraction of chemicals and energy supplied by alternative, renewable resources, such as lignin, can be expected to increase in the foreseeable future. Here, we demonstrate a catalytic process to valorize lignin (exemplified with kraft, organosolv, and sugarcane bagasse lignin) using a mixture of cheap, bio‐renewable ethanol and water as solvent. Ethanol/water mixtures readily solubilize lignin under moderate temperatures and pressures with little residual solids. The molecular weight of the dissolved lignins was shown to be reduced by gel permeation chromatography and quantitative HSQC NMR methods. The use of liquid‐phase reforming of the solubilized lignin over a Pt/Al 2 O 3 catalyst at 498 K and 58 bar is introduced to yield up to 17 % combined yield of monomeric aromatic oxygenates such as guaiacol and substituted guaiacols generating hydrogen as a useful by‐product. Reduction of the lignin dissolved in ethanol/water using a supported transition metal catalyst at 473 K and 30 bar hydrogen yields up to 6 % of cyclic hydrocarbons and aromatics.
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Lignin chemistry?past, present and future
Erich Adler · Wood Science and Technology · 1977 · 1.7K citations