Enhanced Catalytic Activity with Oxygen for Methyl Acrylate Production via Cross‐Aldol Condensation Reaction

Abstract

An innovative technology for the production of methyl acrylate via vapor-phase cross-aldol condensation is described. Catalytic process intensification was realized through the enhanced catalytic activity with oxygen by catalyst design and adjustment of active sites. Crystal phases with different V valences in vanadium phosphate catalysts were controllably synthesized in the presence of oxygen. Donating electron and withdrawing electron sites arose when oxygen moved from one crystalline phase to another, just for the a-H removal of methyl acetate and formaldehyde protonation. The reaction pathway and transition states were confirmed via molecular simulation with quantum chemistry theory. The catalytic activity was evaluated in a fixed-bed reactor by adjusting the percentage of oxygen in the carrier gas. Finally, the mechanism of a-H removal of methyl acetate through the activated oxygen was clarified.

Influence of Al Oxides on Cs-SiO2 Catalysts for Vapor Phase Aldol Condensation of Methyl Acetate and Formaldehyde

“…Methyl acrylate (MA), as a fundamental chemical raw material, is widely applied in numerous commercial processes, especially in the production of plastics, adhesives, paints, PAN fibers, biomimetic materials, etc. − A multitude of ways have emerged for the synthesis of MA in the past few decades. Among them, the two-stage oxidation of propylene is the primary route to fabricate the acrylic acid (AA) and MA in the commercial production. , However, an ever-increasing crude oil price induces an increase of costs for this petroleum-based process as the propylene feedstock is closely dependent on the limited petroleum resources .…”

Kinetics and optimization studies of modified VPO/γ-Al2O3 catalyst prepared in situ for cross-aldol condensation

“…There are two types of decomposition: one resulting in products C and H 2 O, and the other resulting in products CO and H 2 . 40 Both types of decomposition lead to the accumulation of carbon in the catalyst, which reduces catalytic activity. Medium-to-strong acidic sites can effectively reduce the onset of carbon build-up and improve catalytic activity.…”

“…This is because under the condition of high-temperature calcination, the increase in particle size blocked the pore channels of catalyst. 38 According to the analysis results of different VPO loadings, it can be seen that the 60% VPO/γ-Al 2 O 3 exhibited the largest specific surface area and pore 40 Both types of decomposition lead to the accumulation of carbon in the catalyst, which reduces catalytic activity. Medium-to-strong acidic sites can effectively reduce the onset of carbon build-up and improve catalytic activity.…”