Levulinate
is one of the high added-value biomass-derived chemicals
that is primarily produced from hexoses in cellulose and hemicellulose.
Producing levulinate from pentoses in hemicellulose that is extensively
distributed in biomass is still highly challenging. In this study,
biomass materials and carbohydrates (including cellulose, xylan, glucose,
fructose, and xylose) were collaboratively converted into levulinates
efficiently over various zeolites with ethanol/dimethoxymethane as
cosolvents. The key process for converting pentoses into levulinates
is the synthesis of intermediates (furfural) into alkoxy methyl furfural
via electrophilic substitution or their conversion into furfuryl alcohol
via in situ hydrogenation. The substitution was achieved by the synergic
effect between bifunctional catalysts and cosolvents, which promotes
conversion of furfural into alkoxy methyl furfural via the electrophilic
addition of alkoxy methyl radicals. Hydrogenation of furfural into
furfuryl alcohol was impelled by the cooperative process between in
situ generated H-donor from alcohol solvents and zeolite catalysts.
Moreover, a favorable yield of 21.05 mol % of levulinates was achieved
by simultaneous and collaborative conversion of cellulose and hemicellulose
with the one-pot process using ethanol/dimethoxymethane as a cosolvent
and the zeolite with B and L acid sites as a catalyst.
In this work, acid-catalyzed conversion of cellulose into levulinic acid in a biphasic solvent system was developed. Compared to a series of catalysts investigated in this study, the Amberlyst-15 as a more efficient acid catalyst was used in the hydrolysis of cellulose and further dehydration of derived intermediates into levulinic acid. Besides, the mechanism of biphasic solvent system in the conversion of cellulose was studied in detail, and the results showed biphasic solvent system can promote the conversion of cellulose and suppress the polymerization of the by-products (such as lactic acid).The reaction conditions, such as temperature, time, and catalyst loading were changed to investigate the effect on the yield of levulinic acid. The results indicated that an appealing LA yield of 59.24% was achieved at 200°C and 180 min with a 2:1 ratio of Amberlyst-15 catalyst and cellulose in GVL/H2O under N2 pressure. The influence of different amounts of NaCl addition to this reaction was also investigated. This study provides an economical and environmental-friendly method for the acid-catalyzed conversion of cellulose and high yield of the value-added chemical.
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