The production of 5-hydroxymethylfurfural (HMF) from
cellulose
is a crucial step in the production of high-value chemicals and fuels
from renewable cellulosic biomass. In this study, the influences of
the H2O/organic solvent ratio, the type of organic solvents,
the addition of NaCl, and the type and concentration of catalysts
on the catalytic conversion of cellulose into HMF in biphasic systems
were comprehensively studied, and the highest HMF yield of 45.7% was
obtained from cellulose in the H2O–tetrahydrofuran
(THF) biphasic system with Al2(SO4)3 as the catalyst. Further investigation reveals that the excellent
performance of the H2O–THF–Al2(SO4)3 reaction system was ascribed to the
high V
org/V
aque (60/1), high C[Al2(SO4)3]aque (0.38 g/mL), and low C[Al2(SO4)3]org (10–4 g/mL) of the reaction system.
Moreover, the byproduct formed during the conversion of cellulose
in the H2O–THF–Al2(SO4)3 reaction system was characterized by liquid chromatography–mass
spectrometry (LC–MS) and LC–MS2 to detect
considerable initial polymers. One plausible mechanism of glucose
conversion in the H2O–THF biphasic system was proposed
based on the detected compounds.
Catalytic conversion of cellulose into the novel platform
molecule
2,5-hexanedione (HXD) is regarded as one feasible approach for high-value
utilization of biomass resources. Here, we reported one efficient
way of one-pot conversion of cellulose into HXD with high yield of
80.3% in H2O and tetrahydrofuran (THF) mixture within Al2(SO4)3 combined with Pd/C as a catalyst.
In the catalytic reaction system, Al2(SO4)3 could catalyze the conversion of cellulose into 5-hydroxymethylfurfural
(HMF), and Pd/C combined with Al2(SO4)3 could catalyze the hydrogenolysis of HMF into furanic intermediates
such as 5-methylfurfuryl alcohol and 2,5-dimethylfuran (DMF) without
causing over-hydrogenation of these furanic intermediates. These furanic
intermediates were finally transformed into HXD catalyzed by Al2(SO4)3. Besides, the H2O/THF
ratio could significantly influence the reactivity of the hydrolytic
furanic ring-opening of the furanic intermediates. The catalytic system
also showed excellent performance on the conversion of other carbohydrates
(glucose and sucrose) into HXD.
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