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The metal ion effect on the bulk VPO was investigated using the aldol condensation of methyl acetate and formaldehyde to methyl acrylate. The VPO catalyst with 2 mol % Zr exhibited the highest methyl acrylate formation rate of 18.6 μmol·g–1·min–1. A combination of X-ray diffraction, BET, TPD, XPS, and EPR, together with activity testing data, was utilized to analyze and explain the origin of the metal ion effects. The promotion of methyl acrylate production by the intercalation of Zr was associated with its interaction with the VPO phase. When Zr concentration attained 2 mol %, the Zr4+ ion was distributed in the surface adjacent layers and partially incorporated into VPO species, giving rise to a higher fraction of the β-VOPO4 entity and a relatively higher amount of the badly distorted (VO)2P2O7 entity. These findings suggested that both β-VOPO4 and distorted (VO)2P2O7 phases were required for the formation of methyl acrylate.

One‐step catalytic synthesis of methyl acrylate from methyl acetate and trioxane, with 90.7% yield and 91.8% selectivity, was realized at 10–25°5. NMR analysis confirmed the ester enolization with generation of [i‐Pr2EtN‐H]+[TfO]− in the presence of i‐Pr2EtN and Bu2BOTf, which was affected by solvent and base. The depolymerization of trioxane into formaldehyde was catalyzed by Bu2BOTf. The in‐situ catalytic mechanism and efficiency of [i‐Pr2EtN‐H]+[TfO]− was determined and analyzed. Mechanism‐based kinetic and thermodynamic studies were conducted for better understanding of this route. Also the primary process design and product separation simulation were carried out. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1359–1372, 2018

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