Solvothermal Synthesis of Vanadium Phosphate Catalysts for n-Butane Oxidation


In this paper, we have developed a simple, low-cost, template-free and surfactant-free solvothermal process for synthesis of vanadyl hydrogen phosphate hemihydrate (VOHPO₄·0.5H₂O) with well defined crystal size. The synthesis was performed by reaction of VPO₄·2H₂O with an aliphatic alcohol (isobutyl alcohol, 1-pentanol, 1-hexanol, 1-heptanol or 1-decanol). This afforded well crystallized VOHPO₄·0.5H₂O by solvothermal methods at 120°C temperature. This new method significantly reduced the preparation time and lowered production temperature (50%) of catalyst precursor (VOHPO₄·0.5H₂O) when compared to conventional hydrothermal synthesis methods. By varying the reducing agent, the solvothermal evolution process from layered tetragonal phase VOHPO₄·0.5H₂O to orthorhombic phase VOHPO₄·0.5H₂O was observed. It was found that the length of carbon chain in an alcohol in the solvothermal condition had a great impact on chemical and physical properties of resulting catalysts. Interestingly, there was no trace of VO(H₂PO₄)₂ an impurity noted to be readily formed under solvothermal preparation condition. Therefore, this study introduces a more facile synthetic pathway to V(III) compounds. In addition, the microwave-synthesized catalysts exhibited some properties superior to those of conventionally synthesized catalyst such as better stability, crystallinity, and catalytic activity in the production of maleic anhydride. The characterization of both precursors and calcined catalysts was carried out using X-ray diffraction (XRD), inductively coupled plasma-atomic emission spectrometer (ICP-AES), N₂ physisorption, temperature programmed reduction (H₂-TPR) and scanning electron microscopy (SEM). The XRD pattern of the active catalyst prepared by this solvothermal method confirmed the presence of smaller crystal size (between 6 and 13 nm along 0 2 0 planes) of vanadium phosphate catalyst with higher specific surface area. Finally, the yield of maleic anhydride was significantly increased from 29% for conventional catalyst to 44% for the new solvothermal catalyst.


Chemical and Biochemical Engineering

Keywords and Phrases

High Pressure; High Pressure Autoclave; N-Butane Oxidation; Primary Alcohols; Solvothermal Synthesis; Vanadium Phosphates; Vanadyl Hydrogen Phosphate Hemihydrate; Atomic Emission Spectroscopy; Boilers; Butane; Calcination; Catalysis; Catalyst Activity; Crystal Impurities; Grain Size and Shape; Heating; Hydrogen; Inductively Coupled Plasma; Liquefied Petroleum Gas; Maleic Anhydride; Microwave Heating; Microwaves; Organic Polymers; Oxidation; Physisorption; Pressure Vessels; Scanning Electron Microscopy; Surface Active Agents; Vanadium Alloys; Vanadium Compounds; X Ray Diffraction; Hydrothermal Synthesis

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