1 research outputs found
Acid-Functionalized SBA-15-Type Periodic Mesoporous Organosilicas and Their Use in the Continuous Production of 5‑Hydroxymethylfurfural
The activity, selectivity, and stability of several supported
acid
catalysts were evaluated in tubular reactors designed to produce 5-hydroxymethylfurfural
(HMF) continuously from fructose dissolved in a single-phase solution
of THF and H<sub>2</sub>O (4:1 w/w). The reactors, packed with the
solid catalysts, were operated at 403 K for extended periods, up to
190 h. The behaviors of three propylsulfonic acid-functionalized,
ordered porous silicas (one inorganic SBA-15-type silica, and two
ethane-bridged SBA-15-type organosilicas) were compared with that
of a propylsulfonic acid-modified, nonordered, porous silica. The
HMF selectivity of the catalysts with ordered pore structures ranged
from 60 to 75%, whereas the selectivity of the nonordered catalyst
under the same reaction conditions peaked at 20%. The latter was also
the least stable, deactivating with a first-order rate constant of
0.152 h<sup>–1</sup>. The organosilicas are more hydrothermally
stable and maintained a steady catalytic activity longer than the
inorganic SBA-15-type silica. The organosilica with an
intermediate framework ethane content of 45 mol % was more stable,
with a first-order deactivation rate constant of only 0.012 h<sup>–1</sup>, than the organosilica containing 90 mol % ethane
linkers in the framework. The catalysts were recovered and characterized
after use by <sup>13</sup>C and <sup>29</sup>Si solid-state NMR, elemental
analysis, nitrogen adsorption/desorption, X-ray diffraction, and SEM/TEM.
Deactivation under flow conditions is caused primarily by hydrolytic
cleavage of acid sites, which can be (to some) extent recaptured by
the free surface hydroxyl groups of the silica surface