Ammoxidation of 3-Picoline to Nicotinonitrile over Highly Dispersed V2O5/ZrO2 Catalysts†

Chary, Komandur V. R.; Kishan, Gurram; Narayana, K.V.; Bhaskar, Thallada

doi:10.1039/a705267g

Cited by 12 publications

(8 citation statements)

References 15 publications

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“…To this end, a method such as oxygen chemisorption was studied extensively in recent years to find active phase dispersion in supported vanadium systems. [34][35][36][37][38][39][40] We have reported in our earlier studies the characterization and reactivity of vanadium oxide supported on alumina 35 and titania. 39 The ammoxidation of 3-picoline to nicotinonitrile is a reaction of interest since the nicotinonitrile can be further transformed either to nicotinamide, a component of the vitamin B group, or to the provitamin nicotinic acid.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization, and Catalytic Properties of Vanadium Oxide Catalysts Supported on AlPO₄

et al. 2003

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A series of V2O5/AlPO4 catalysts with vanadia loadings ranging from 2.5 to 20 wt % was prepared and characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy, electron spin resonance spectroscopy, temperature-programmed reduction (TPR), temperature-programmed desorption (TPD) of NH3, BET surface area, and oxygen chemisorption methods. The catalytic properties were evaluated for the vapor phase ammoxidation of 3-picoline to nicotinonitrile. TPR results indicated that the appearance of a single reduction peak corresponds to V5+ to V3+. The XRD results suggest that, at low vanadia loadings AlPO4 is found to be amorphous. However, at V2O5 loading of 7.38 wt % and above, AlPO4 exist as α-cristobalite form in addition to V2O5. TPD results show that the acidity increases with vanadia loading and decreases at 7.38% and above loadings. The ESR spectra obtained under ambient conditions for the samples reduced at 640 K show the presence of V4+ in axial symmetry. Dispersion of vanadia was determined by oxygen chemisorption at 640 K and by the static method on the samples prereduced at the same temperature. The oxygen uptake measured at 640 K increases with increase in vanadia loading, whereas dispersion of vanadia was decreased. The decrease in dispersion of vanadia was discussed in terms of formation of crystalline forms of V2O5 and AlPO4. The ammoxidation activity and selectivity of nicotinonitrile formation increase with vanadia loading up to 9.5 wt % and did not change appreciably at higher loadings. The catalytic properties during ammoxidation are related to the oxygen chemisorption sites.

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Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization, and Catalytic Properties of Vanadium Oxide Catalysts Supported on AlPO₄

et al. 2003

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“…EPR spectra of V 2 O 5 , ZrO 2 and V 2 O 5 /ZrO 2 , recorded on a JEOL ER-300 model ESR spectrometer. The spectra support presence of V 4+ on zirconia (Chary et al, 1998). The IR spectra of these catalysts were recorded on Shimadzu IR 460 spectrometer.…”

Section: Catalyst Characterization Surface Area and Acidity Measuremmentioning

confidence: 85%

“…Some of the latest developed catalysts are: V/Ti (Bond et al, 1982), V/Mo (Chary et al, 2001), V/Sb (Sanati et al, 1998), VPO (Martin et al, 1996), VSAPO (Kulkarni et al, 1996), oxide catalyst has been found to be more active than Al 2 O 3 supported vanadium oxide catalysts and less active than TiO 2 supported vanadium oxide in ammoxidation of 3-picoline. Important physico-chemical data such as oxygen uptake, dispersion, oxygen atom site density and surface area of various V 2 O 5 -ZrO 2 catalysts are available in literature (Chary et al, 1998).…”

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confidence: 99%

Kinetic studies and Mechanism Evolution of the Ammoxidation of 3-picoline Over V2O5/ZrO2 Catalyst

et al. 2008

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A kinetic investigation of the ammoxidation of 3‐picoline to 3‐cyanopyrdine has been studied over V2O5/ZRO2 Catalyst in a differential flow reactor in the temperature range 573‐683 K. The partial pressures of 3‐picoline, oxygen and ammonia were varied and rates were measured for the formation of 3‐cyanopyridine. Kinetics studies reveal that the mechanism of the reaction is of the “Redox” type. The rate equation deduced, assuming a study state involving a three stage oxidation‐reduction process, represented the data most satisfactorily for conversion of 3‐picoline to nicotinonitrile. Catalysts have been characterized using IR, XRD, ESR, Surface area and ammonia desorption methods with a view to understanding the structure and nature of bonding over the surface of the catalyst. A tentative mechanism of the process has been suggested.

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“…Vanadium-zirconium oxide catalysts showed high selectivity in the process of oxidative ammonolysis of 3-picoline [12,13]. We have previously shown that the oxide vanadium-titanium-zirconium catalyst exhibits high activity and selectivity in the oxidative ammonolysis of 4-methylpyridine, making it possible to obtain 4-cyanopyridine with a yield of 90-95% at a temperature of 260-270 °C and minimum consumption of ammonia [13].…”

mentioning

confidence: 99%

Oxidative Ammonolysis of 4-Methylpyridine on Oxide Vanadium-Titanium-Zirconium Catalyst Modified by Tin and Tungsten Oxides

Mikhailovskaya

Kurmakyzy

Tolemisova³

et al. 2021

Chem. J. of Kaz.

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Catalysts based on vanadium pentoxide modified by Ti, Sn, Zr and W oxides were tested in the oxidative ammonolysis of 4-methylpyridine. The role of the main process parameters such as temperature, the ratio of the initial components in the conversion of the methyl group to the nitrile one, and the optimal conditions for the oxidative ammonolysis of 4-methylpyridine were determined. It is determined that the V-Ti-Zr-O-catalyst and the sample containing 9% of tungsten oxide are superior in catalytic activity to the V-Ti-Zr-Sn-O contact. Conditions that ensure a high selectivity for the formation of 4-cyanopyridine were found. The highest yield of the target product (85-86%) was obtained on V-Ti-Zr-W-O at 270 °C, and the yield of 4-cyanopyridine was 87.5% at 310° C on the V-Ti-Zr-Sn-O catalyst. The phase composition and structural changes occurring in modified vanadium oxide catalysts have been studied. It is determined that mixed V-Ti-Zr-Sn-O and V-Ti-Zr-W-O catalysts contain ZrV2O7, the monoclinic modification of ZrO2 (baddeleyite), TiO2 (anatase), SnO2, WO3, and V2O5. In catalysts, it can exist in small amounts as a separate VO2 phase. The V-Ti-Zr-W-O catalyst showed the best catalytic properties. It has highactivity and selectivity towards 4-cyanopyridine.

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Ammoxidation of 3-Picoline to Nicotinonitrile over Highly Dispersed V2O5/ZrO2 Catalysts†

Cited by 12 publications

References 15 publications

Synthesis, Characterization, and Catalytic Properties of Vanadium Oxide Catalysts Supported on AlPO₄

Synthesis, Characterization, and Catalytic Properties of Vanadium Oxide Catalysts Supported on AlPO₄

Kinetic studies and Mechanism Evolution of the Ammoxidation of 3-picoline Over V2O5/ZrO2 Catalyst

Oxidative Ammonolysis of 4-Methylpyridine on Oxide Vanadium-Titanium-Zirconium Catalyst Modified by Tin and Tungsten Oxides

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Ammoxidation of 3-Picoline to Nicotinonitrile over Highly Dispersed V2O5/ZrO2 Catalysts†

Cited by 12 publications

References 15 publications

Synthesis, Characterization, and Catalytic Properties of Vanadium Oxide Catalysts Supported on AlPO4

Synthesis, Characterization, and Catalytic Properties of Vanadium Oxide Catalysts Supported on AlPO4

Kinetic studies and Mechanism Evolution of the Ammoxidation of 3-picoline Over V2O5/ZrO2 Catalyst

Oxidative Ammonolysis of 4-Methylpyridine on Oxide Vanadium-Titanium-Zirconium Catalyst Modified by Tin and Tungsten Oxides

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Synthesis, Characterization, and Catalytic Properties of Vanadium Oxide Catalysts Supported on AlPO₄

Synthesis, Characterization, and Catalytic Properties of Vanadium Oxide Catalysts Supported on AlPO₄