Preparation, characterization and catalytic behavior for propanepartial oxidation of Ga-promoted MoVTeO catalysts

[EN] Two sets of Ga-promoted MoVTeO catalysts were synthesized hydrothermally and heat-treated at 600 degrees C in N-2: (i) materials prepared from gels with Mo/V/Te/Ga atomic ratios of 1/0.60/0.17/x (x=0-0.12) (A-series) and (ii) materials prepared from gels with Mo/V/Te/Ga atomic ratios of 1/0.60-x/0.17/x (x=0.15 or 0.25) (B-series). In addition, a Ga-containing MoVTeO catalyst was also prepared from M1-containing MoVTeO material by impregnation with aqueous solution of gallium and heat-treated at 450 degrees C in N-2. Catalysts were characterized by means of powder XRD, TEM, Raman spectroscopy, NH3-TPD and XPS and tested in the partial oxidation of propane. The results showed that the addition of small amount of gallium significantly increase the selectivity to acrylic acid (AA) at low propane conversion. However, at high propane conversion, the selectivity to AA strongly depends on both the catalyst composition and the gallium incorporation method. The higher selectivity to acrylic acid over Ga-containing MoVTeO catalysts has been related to: (i) structural changes in the M1 phase by the incorporation of Ga3+ into the octahedral structural framework and/or (ii) incorporation of Ga3+ species on the catalyst surface thus modifying catalysts acid properties. (C) 2014 Elsevier B.V. All rights reserved.Financial support from DGICYT in Spain (Project CTQ2012-37925-C03-1 and Program Severo Ochoa SEV-2012-0267) is gratefully acknowledged. EGG acknowledges finantial support through spanish project MAT2010-19837-C06-05 and the ICTS-Microscopia Electronica in Madrid for facilities.Hernández Morejudo, S.; Massó Ramírez, A.; García-González, E.; Concepción Heydorn, P.; López Nieto, JM. (2015). Preparation, characterization and catalytic behavior for propanepartial oxidation of Ga-promoted MoVTeO catalysts. Applied Catalysis A: General. 504:51-61. https://doi.org/10.1016/j.apcata.2014.12.039S516150

A MAS NMR and DRIFT study of the Ga species in Ga/H-ZSM5 catalysts and their effect on propane ammoxidation

71Ga, 27Al and 29Si MAS-NMR and DRIFT spectroscopies were used to characterize the state of gallium in Ga/H-ZSM5 catalysts tested for their ability to catalyse the ammoxidation of propane. Ga-species were observed in two different possible environments: octahedrally-coordinated gallium in small Ga2O3 particles at the external surface of the zeolite crystals, octahedrally-coordinated gallium in GaO(OH) or related species, and tetrahedrally-coordinated gallium in cationic-exchange positions inside the zeolite. Redox (H2-O2) cycles promote the migration of gallium from the GaO(OH) or Ga2O3 species at the external surface of the zeolite crystals to cationic-exchange sites within the zeolite channels. The redox treatment definitely had a beneficial effect on its catalytic performance for the ammoxidation of propane, which is known to occur via a bifunctional mechanism. The main product was acetonitrile at high Ga and Al contents while acrylonitrile was also observed as a side product at high Ga and low Al contents

A MAS NMR and DRIFT study of the Ga species in Ga/H-ZSM5 catalysts and their effect on propane ammoxidation

71Ga, 27Al and 29Si MAS-NMR and DRIFT spectroscopies were used to characterize the state of gallium in Ga/H-ZSM5 catalysts tested for their ability to catalyse the ammoxidation of propane. Ga-species were observed in two different possible environments: octahedrally-coordinated gallium in small Ga2O3 particles at the external surface of the zeolite crystals, octahedrally-coordinated gallium in GaO(OH) or related species, and tetrahedrally-coordinated gallium in cationic-exchange positions inside the zeolite. Redox (H2-O2) cycles promote the migration of gallium from the GaO(OH) or Ga2O3 species at the external surface of the zeolite crystals to cationic-exchange sites within the zeolite channels. The redox treatment definitely had a beneficial effect on its catalytic performance for the ammoxidation of propane, which is known to occur via a bifunctional mechanism. The main product was acetonitrile at high Ga and Al contents while acrylonitrile was also observed as a side product at high Ga and low Al contents