Isomerization of light alkanes: preparation and characterization of platinum promoted sulfated zirconia catalysts

Summary Platinum-promoted sulfated zirconia catalysts active in n-hexane isomerization were prepared in a one-step synthesis and characterized. The crystallinity and sulfur contents depend mainly on the calcination temperature. The stability of the sulphate in the presence of hydrogen is reduced by the presence of Pt.     

Silica supported sulfated zirconia prepared by a sol-gel process: Effect of solvent evacuation procedure on the structural, textural and catalytic properties

Sol-gel process was used to prepare silica supported sulfated zirconia catalysts. The main parameter studied in this work was the gel drying method through four different ways of solvent evacuation. Textural, structural as well as the acidic properties of the four samples were studied using N₂ physisorption, X-ray diffraction, mass spectrometry, sulfur chemical analysis and adsorption-desorption of pyridine. The isomerization of n-hexane was used as a catalytic test. The surface areas and the pore distributions are highly affected by the drying mode. One of the four drying methods leads to a solid having improved textural properties and presenting both the crystalline ZrO₂ tetragonal phase and a particular type of sulfate mode bond. It seems that these three conditions are necessary for achieving high catalytic activity.     

Acid-base, electron donating and catalytic properties of sulfated zirconia

The electron donating properties of sulfated zirconia were studied from the adsorption of electron acceptors of various electron affinity. The surface acidity and basicity of the oxides have also been determined by titration method using a set of Hammett indicators. The data have been correlated with the catalytic activity of the oxide towards esterification of acetic acid usingn-butanol, reduction of cyclohexanol in 2-propanol and oxidation of cyclohexanol with benzophenone.     

Suppression of radical-cationic benzene oligomerization on sulfated zirconia

The effect of catalyst activation conditions on transformations of benzene cation radicals on sulfated zirconia has been studied by in situ ESR spectroscopy. After the catalyst activation at 300°C there was no oligomerization of the cation radicals to biphenyl and heavier products, which is observed after catalyst calcination at 500°C. It has been suggested that the oligomerization is suppressed by the presence of strong Br?nsted sites on the surface.     

Pd-based sulfated zirconia prepared by a single step sol–gel procedure for lean NOx reduction

Pd-based sulfated zirconia catalysts have been prepared through a single step (one-pot) sol–gel preparation technique, in which both sulfate and Pd precursors were dissolved in an organic solution before the gelation step. Observation of the calcination procedure through TGA/DSC and mass spectrometry revealed that the addition of increasing amounts of Pd resulted in the evolution of organic precursor species at lower temperatures. In situ XRD experiments showed that tetragonal zirconia is formed at lower temperatures and larger zirconia crystallites are formed when Pd is added to the gel. Although tetragonal zirconia was the only phase observed through XRD, Raman spectra of samples calcined at 700 °C showed the presence of both the tetragonal and the monoclinic phase, indicating a surface phase transition. DRIFTS experiments showed NO species adsorbed on Pd²⁺ cations. Pd/SZ catalysts prepared through this single step method were active for the reduction of NO₂ with CH₄ under lean conditions. Calcination temperature had a significant effect on this activity, with samples calcined at 700 °C being much more active than those calcined at 600 °C, despite the observed transition to the monoclinic phase. This activity may be linked to observed changes in the surface sulfate species at higher calcination temperatures.     

Kinetics of colloid formation during the preparation of sol-gel zirconia

The formation of zirconia colloids by hydrolysing zirconium n-propoxide in n-propanol has been investigated by simultaneous, multi-angle static and dynamic light scattering, and vibrational spectroscopy, as a function of reactant concentration, water-to-alkoxide mole ratio and temperature.The overall hydrolysis/condensation reaction followed pseudo 2nd-order kinetics at 303 K, with an induction period of <1 to 24 hours. The induction period could be substantially reduced by increasing the temperature to 348 K. For hydrolysis with 3.6 moles of water per mole of alkoxide, the apparent activation energy was 24 kJ mol^–1. Such a low activation energy implies that hydrolysis occurs readily over the temperature range investigated (303–348 K). During the induction period, processing with stoichiometric, or excess, water produced oxy-hydroxides, while hydrated oxides formed under water-deficient conditions.The hydrolysis reactions yielded zirconia colloids with equivalent spherical, z-averaged diameters of <200 nm. The colloids exhibited fractal dimensions of 3.0, with a low size-polydispersity, inferring the formation of dense, monodispersed spherical particles. SEM observations confirmed these results.     

Zeolite and sulfated zirconia as catalysts for the synthesis of 5-substituted 1H-tetrazoles via [2+3] cycloaddition of nitriles and sodium azide

The [2+3] cycloaddition between various nitriles and sodium azide proceeds smoothly in the presence of zeolite and sulfated zirconia as effective catalysts, in water and DMF/MeOH, to give the corresponding 5-substituted 1H-tetrazoles in good to high yields. The reaction most probably proceeds through the in situ formation of catalyst azide species, followed by a successive [2+3] cycloaddition with the nitriles. This method has the advantages of high yields, simple methodology and easy work-up. The catalyst can be recovered by simple filtration and reused with good yields.     

The effects of ammonium sulfate and sulfamic acid on the surface acidity of sulfated zirconia

In this work, sulfated zirconia (SZ) was prepared by a solvent-free method, ammonium sulfate ((NH₄)₂SO₄) and sulfamic acid (NH₂SO₃H) were as sulfur sources, respectively. The resulting catalysts were characterized by powder X-ray diffraction (XRD), thermogravimetric analysis and differential scanning calorimetry (TGA-DSC), N₂ adsorption–desorption isotherms, inductively coupled plasma (ICP) and pyridine-FTIR. The characterization of the catalysts revealed that SZ prepared with (NH₄)₂SO₄ as sulfur source contained more Lewis acid sites and less Brønsted acid sites. The effects of sulfur sources on the catalytic activity of catalysts were studied. Catalytic testing showed that SZ prepared with (NH₄)₂SO₄ as sulfur source had a better catalytic performance for removing trace olefins from aromatics.     

One-pot synthesis of superacid catalytic material SO4/ZrO2-SiO2 with thermostable well-ordered mesoporous structure

A superacid mesostructured catalyst was directly synthesized by adding sulfuric acid to mesoporous zirconia-silica synthesis mixtures, and was characterized by HRTEM, XRD, UV-Vis, nitrogen sorption, NH₃-TPD, and Pyridine-FTIR. The XRD patterns and electron diffraction micrographs of the calcined samples showed the ordered mesoporous structure and tetragonal crystalline in frameworks. The ammonia TPD, pyridine in situ FTIR, and paraffin isomerization illustrated a new acidic property of the samples. The synthesis of the mesoporous materials, which have stable crystalline frameworks, high surface area, and strong acidity, is very likely to have important technological implications for catalytic reactions of large molecules.     

Oxidative dehydrogenation of ethane over sufated zirconia supported oxides catalysts

The oxidative dehydrogenation of ethane into ethylene has been investigated on metal oxide-based sulfated zirconia catalysts at temperatures of 400–600°C. It is found that the activity and selectivity toward ethylene depend on the nature of metal oxide and temperature and that Ni and V oxides supported on sulfated zirconia exhibited higher ethylene yields.     

The surface structure of sulfated zirconia: Studies of XPS and thermal analysis

Sulfated zirconias were prepared using two kinds of amorphous zirconia gels, XZO 631 and 632 supplied by MEL Chemicals, and their thermal gravimetrical analyses were carried out. DTG of the former sample showed two peaks based on decomposition of the sulfate species on the surface, the first peak at 680 °C and the second broad one centered at 850 °C. The latter sample indicated only broad peak at 850 °C in the range from 700 to >1000 °C. The first peak for the former sample was ascribed to the decomposition of Zr(SO₄)₂ remained on the surface, and the broad one at 700 to >1000 °C for the both samples was attributed to the catalytically active species. The acidic character of sulfated zirconia calcined at 1000 °C was examined in acid-catalyzed reactions of cumene, ethylbenzene, and butane together with the adsorption heat of Ar, showing a solid acid with acidity higher than that of silica-alumina. It was indicated from the XPS analysis that the S species are composed of SO₄²⁻. The results led to a structural model of the active surface to be polysulfate species containing mainly three or four S atoms with two ionic bonds of SOZr in addition to coordination bonds of SO with Zr, the active site being Lewis sites on the S atoms.     

Multicomponent synthesis of 4-aryl-NH-1,2,3-triazoles in the presence of Al-MCM-41 and sulfated zirconia

The acid properties of Al-MCM-41 and sulfated zirconia were used to develop a strategy for the synthesis of 4-aryl-NH-1,2,3-triazoles via a multicomponent reaction involving various benzaldehydes, sodium azide and nitromethane. The efficiency of the process is analysed from the perspective of the difference in acids among the catalysts used.     

Regioselective ring-opening of aziridines with potassium thiocyanate and thiols using sulfated zirconia as a heterogeneous recyclable catalyst

Ring-opening of aziridines with potassium thiocyanate and thiols has efficiently been carried out at room temperature in the presence of sulfated zirconia to give the corresponding β-aminothiocyanates and β-aminosulfides, respectively, in high yields within 2 h and with high regioselectivity. The catalyst, a solid acid, functions under heterogeneous conditions.     

Control of the nanocrystalline zirconia structure through a colloidal sol-gel process

A simple method to synthesize tetragonal zirconia stabilized at ambient temperature is developed and allows the monitoring of the tetragonal-monoclinic transition via a colloidal sol-gel process. By increasing the pH of an aqueous solution consisted of a zirconium precursor and a complexing agent (acetylacetone), a colloidal sol and then a gel can be formed under slightly acidic condition. After a drying step, tetragonal zirconia is easily obtained with an adequate thermal treatment at low temperature. The tetragonal-monoclinic transition occurs when the calcination temperature is increased. The relationship between the crystallite size, the crystallographic structure and the thermal treatment has been investigated by X-Ray Diffraction and the behaviour of the system from the gel state to the final powder has been studied by using Small Angle X-Ray Scattering and thermal analysis techniques. We demonstrate that compared to a chemical precipitation route, this colloidal sol-gel process allows the nanostructure of the material to be controlled due to the formation of primary nanoparticles. The presence of these nanoparticles makes possible the specific determination of the zirconia crystallographic phase through an accurate control of the nanostructure during the thermal treatment.     

Effect of metals on the catalytic activity of sulfated zirconia for light naphtha isomerization

We studied on the function of the metal in the sulfated zirconia(SO₄^2–/ZrO₂) catalyst for the isomerization reaction of light paraffins. The addition of Pt to the SO₄^2–/ZrO₂ carrier could keep the high catalytic activity. The improvement in this isomerization activity is because Pt promotes removal of the coke precursor deposited on the catalyst surface. Though this catalytic function was observed in other transition metals, such as Pd, Ru, Ni, Rh and W, Pt exhibited the highest effect among them. It was further found that the Pd/SO₄^2–/ZrO₂–Al₂O₃ catalyst possessed a catalytic function for desulfurization of sulfur-containing light naphtha in addition to the skeletal isomerization. The sulfur tolerance of catalyst depended on the method of adding Pd, and the catalyst prepared by impregnation of the SO₄^2–/ZrO₂–Al₂O₃ with an aqueous solution of Pd exhibited the highest sulfur tolerance.Further, we investigated the improvement in sulfur tolerance of the Pt/SO₄^2–/ZrO₂–Al₂O₃ catalyst by impregnation of Pd. The results of EPMA analysis indicated that this catalyst was a hybrid-type one (Pt/SO₄^2–/ZrO₂–Pd/Al₂O₃) in which Pt/SO₄^2–/ZrO₂ particles and Pd/Al₂O₃ particles adjoined closely. This hybrid catalyst possessed a very high sulfur tolerance to the raw light naphtha that was obtained from the atmospheric distillation apparatus, although this light naphtha contained much sulfur. We assume that such a high sulfur tolerance in the hybrid catalyst is brought about by the isomerization function of Pt/SO₄^2–/ZrO₂ particles and the hydrodesulfurization function of Pd/Al₂O₃ particles. Besides, since the hybrid catalyst also provides high catalytic activity in the isomerization of HDS light naphtha, we suggest that the Pd/Al₂O₃ particles supply atomic hydrogen to the Pt/SO₄^2–/ZrO₂ particles by homolytic dissociation of gaseous hydrogen and also enhance the sulfur tolerance of Pt/SO₄^2–/ZrO₂ particles. Finally, we also propose the most suitable location of Pd and Pt in the metal-supported SO₄^2–/ZrO₂–Al₂O₃ catalyst.     

Oxidative dehydrogenation of ethane with carbon dioxide over sulfated zirconia supported metal oxides catalysts

Several metal oxides supported on sulfated zirconia catalysts were tested for the oxidative dehydrogenation of ethane into ethylene by carbon dioxide. It is found that the catalytic behavior of supported oxide catalysts differ depending on the nature of metal oxides. Chromium oxide-sulfated zirconia exhibits the highest ethane conversion and medium level of ethylene selectivity, producing 38% ethylene yield at 50% ethane conversion at 650°C.     

Stereocontrolled glycosidations using a heterogeneous solid acid, sulfated zirconia, for the direct syntheses of α- and β-manno- and 2-deoxyglucopyranosides

Novel α- and β-stereocontrolled glycosidations using a heterogeneous solid acid, sulfated zirconia (SO₄/ZrO₂), as an activator have been developed. The glycosidations of manno- and 2-deoxyglucopyranosyl α-fluorides with several alcohols using SO₄/ZrO₂ in MeCN proceeded α-stereoselectively, while those with the same activator in the presence of MS 5A in Et₂O occurred with β-stereoselectivity. Thus, both the α- and β-manno- and 2-deoxyglucopyranosides were effectively obtained by the present glycosidations.     

Preparation of superacid of ruthenium-sulfated zirconia for reaction of butane to isobutane

A highly active superacid of 2–4 wt.% Ru-sulfated ZrO₂ for the isomerization of butane to isobutane was obtained by exposing RuO_x/ZrO₂ to 1 N H₂SO₄ followed by calcining in air at 550°C. The RuO_x/ZrO₂ was prepared by impregnating zirconium hydroxide with a solution of RuCl₃ followed by drying at 300°C. The catalyst was much more active than the superacid of sulfated zirconia, the temperature difference to show the same conversion between both catalysts being more than 145°C.     

A simple and efficient one-pot synthesis of β-acetamido carbonyl compounds using sulfated zirconia as a heterogeneous recyclable catalyst

Sulfated zirconia has been employed as an efficient recyclable catalyst for the preparation of various β-acetamidoketones or esters at room temperature. The process involves the one-pot multicomponent reactions of aromatic aldehydes, enolizable ketones or β-ketoesters and acetonitrile in the presence of acetyl chloride.     

The preparation of silica entrapped homogeneous hydrogenation catalysts by conventional and ionic liquid mediated sol-gel routes

[RhCl(PPh₃)₃] has been entrapped inside silica matrices by two methods: a conventional sol-gel synthesis in ethanol/water and a new route performed in an ionic liquid. The activity of these heterogenised catalysts has been tested for the hydrogenation of styrene. The catalyst prepared in an ionic liquid was found to be more active and have low Rh leaching.