IR and DRS study of TiO2-supported 12-molybdophosphoric heteropoly compounds

The effects of molybdenum concentration, countercation (Co, Ni) and heat treatment on the state of heteropoly anion (HPA) in the oxide form of titania-supported 12-molybdophosphoric acid and its Co(Ni) salts have been studied using IR and DRS.     

Titania-supported mixed HPMoV polyoxometallates as precursors of hydrodesulfurization catalysts

HDS catalysts were prepared by loading H₃PMo₁₂O₄₀ or H₄PMo₁₁V₁O₄₀ polyoxometallates on TiO₂ (0.5 and 1.0 mmol (Mo+V)). Activity of the catalysts was tested in the HDS of thiophene. The activity of catalysts of low concentration was 2–3 times higher than the activity of those of high concentration. Temperature programmed reduction (TPR) and IR spectroscopy were used to determine the properties of the catalyst. TPR measurements proved that vanadium promotes and stabilizes HDS activity due to an increase in the Mo⁵⁺/Mo⁴⁺ ratio.     

NO adsorption sites in TiO2-supported 12-molybdophosphoric heteropoly compounds

The effect of metal loading and counterion (Co, Ni) on the surface structures in the oxide and reduced form of the titania-supported 12-molybdophosphoric acid and its Co(Ni) salts has been studied by Fourier transform IR of adsorbed nitric oxide.     

State of cobalt and molybdenum in cobalt-molybdenum-containing zeolites

NaY and CaHY zeolites containing 7 wt.% Mo and 0.7 wt.% Co have been studied by means of IR and diffuse reflectance spectroscopy (DRS). It is shown that ammonium heptamolybdate (AHM) interacts with the zeolite forming a silicon molybdenum heteropoly complex (SiMo HPC). In contrast to NaY, along with SiMo HPC, MoO₃ is formed on CaHY after calcining.

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NaY CaY , 7 .% Mo 0,7 .% Co, . , , (SiMo HPC). NaY, CaHY SiMo HPC MoO₃.

     

Synthesis and properties of hydrodesulfurization catalysts. IV. Thiophene hydrodesulfurization on molybdenum catalysts containing heteropoly compounds

Water soluble analogues of aluminium and cobalt heteropolymolybdates have been shown as possible precursors of active sites for thiophene hydrodesulfurization along with other molybdenum compounds. For the characterization of the catalysts Raman spectroscopy has been applied, and the catalytic activity of the samples is discussed.

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Study of iron state in titania-supported FeMo catalysts of hydrodesulfurization

Summary Thiophene conversion on, and Mössbauer spectra of sulfided FePMo/TiO₂ catalysts prepared using H₃PMo₁₂O₄₀ and its Fe salt have been studied. Iron and phosphorus promoting effect on catalytic activity of the HDS catalysts is discussed.     

Thiophene hydrodesulfurization activity of alumina supported heteropoly compounds: nickel effect

Summary Hydrotreating nickel tungsten catalysts have been prepared by impregnation of g-alumina with solutions of H₃PW₁₂O₄₀ acid and its Ni salt. It is shown that the initial heteropolyanion, its lacunar analog, nickel substituted heteropolyanion and other new formed phases are present on the surface. The thiophene conversion is related to the presence of mixed NiWS phase and to the close cooperation between WS₂ and NiS_x phases.     

Synthesis and properties of hydrodesulfurization catalysts, III. Support effect on the catalytic activity of Co?Mo?Al2O3 catalysts

By means of DTA, reflectanc spectra and measurement of catalytic activity in thiophene hydrogenolysis, the effect of support (aluminium hydroxide and oxide) as well as of the order of introduction of molybdenum and cobalt compounds on the structure and catalytic surface of Co–Mo–Al₂O₃ catalysts is shown.

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, ( ) , Co–Mo–Al₂O₃.

     

Characterization of silica-supported molybdenum catalysts by ESR, XPS and thiophene hydrodesulfurization

Two Mo/SiO₂ samples have been prepared by impregnation of silica gel with aqueous solution of molybdophosphoric heteropoly acid or ammonium heptamolybdate. The catalysts were studied by ESR and IR spectroscopy, X-ray diffraction, and XPS. Their activity was measured in the reaction of thiophene hydrodesulfurization. The silica-supported P–Mo heteropoly acid, with a preserved Keggin structure of the heteropoly anion and sulfided by H₂S, exhibited two times higher steady conversion in comparison with ammonium heptamolybdate supported on silica at pH=11 and calcined and sulfided at 500°C.     

Tungsten/Alumina Catalysts: Effect of H3PW12O40 Countercation on Surface Properties and Hydrodesulfurization Activity

H₃PW₁₂O₄₀ heteropoly acid (HPW₁₂) and its Co, Fe, Ni salts supported on alumina have been used to model hydrodesulfurization catalysts of different activity. All catalysts revealed a promoting effect of the countercation in thiophene hydrodesulfurization, that of the nickel cation being the highest. The catalysts were characterized by measurements of surface area, HDS activity, TPR, FTIR, and DR spectra. IR spectra confirmed an effect of the countercation on the phase composition of the supported heteropoly compounds. 12-Tungstoaluminate heteropoly anions and coordinately unsaturated anions of HPW₁₂ were detected in the IR spectra of the catalysts. The hydrotreating activity of the catalysts was proportional to the amount of hydrogen consumed in the range 20–500°C during TPR.