A fluidized bed process for the one-step synthesis of methyl acrylate (MA) using methyl acetate (Ma) and formaldehyde (FA) was developed for the first time. New spherical antiwear acid−base catalysts Cs−P/γ-Al 2 O 3 were prepared using ultrasonic impregnation method and characterized with XRD, BET, SEM, PSD, ICP, TG/DTA, NH 3 -TPD, and CO 2 -TPD methods. Catalytic performance was evaluated, and 10.0 wt % Cs−5.0 wt % P/γ-Al 2 O 3 with weak acid−base sites was determined to be the best catalyst for MA production. Response surface methodology (RSM) was employed to optimize aldol condensation of Ma with FA over 10.0 wt % Cs−5.0 wt % P/γ-Al 2 O 3 . The effects of various process parameters such as reaction temperature, molar ratio of Ma and FA, and liquid hourly space velocity (LHSV) on MA yield were addressed by Box−Behnken experimental design (BBD). The coefficient of determination (R 2 ) of this model was 0.997, and 39.5 mol % yield of MA was obtained after optimization. The developed catalyst exhibited high stability, with no significant decrease in catalytic activity after 1000 h of lifetime evaluation.
3-Hydroxypropanal
(3-HPA) is formed by the cross-aldol reaction
of formaldehyde (HCHO) with acetaldehyde (CH3CHO), which
further converts to 1,3-propanediol (1,3-PDO). Mg/SiO2 and
X-5Mg/SiO2 (X = Mn, Fe, Co, Ni) catalysts were prepared
using the sol–gel method and characterized with XRD, BET, TEM,
and NH3- and CO2-TPD methods. The 5Mg/SiO2 showed higher activity in terms of the yield and selectivity
due to its suitable basic and acidic density. The addition of Mn to
the 5Mg/SiO2 catalyst caused dispelling of weak basic sites
but maintained strong basic sites, and the high CH3CHO
conversion was maintained. The increase of weak acidic sites contributed
to the increase of 3-HPA selectivity for the 1Mn-5Mg/SiO2 catalyst. The cross-aldol reaction of HCHO with CH3CHO
to produce 3-HPA more easily proceeded than the self-aldol reaction
of CH3CHO according to the reaction kinetic analysis. Furthermore,
Raney nickel was successfully applied to the hydrogenation process
of 3-HPA to 1,3-PDO with over 90% HPA conversion and 1,3-PDO selectivity.
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