TiO2–ZrO2 mixed oxide as a support for hydrotreating catalyst

Pure TiO₂, ZrO₂ and TiO₂–ZrO₂ mixed oxides are prepared by urea hydrolysis. Hydrotreating catalysts containing 12 wt% molybdenum are prepared using these oxides and characterized by BET surface area, pore volume, XRD and oxygen chemisorption. It is observed that oxides produced by the method of urea hydrolysis have higher surface area as compared to those available commercially. With increasing zirconia content in the mixed oxide, the surface area increases and a maximum value is obtained for a mixed oxide having Ti and Zr molar ratio of 65/35. XRD results indicate that mixed oxides are poorly crystalline in nature. Thiophene hydrodesulfurization, cyclohexene hydrogenation and tetrahydrofuran hydrodeoxygenation are taken as model reactions for evaluating catalytic activities. It is found that both O₂ uptake and catalytic activities increase with increasing zirconia content in mixed oxide and reach maximum values for the 12 wt% Mo/TiO₂–ZrO₂ (65/35) catalyst. With further increases in zirconia content, O₂ uptake and catalytic activities decrease and the lowest values are observed for the pure ZrO₂ supported catalyst.     

Catalytic Activities of Al2O3-promoted NiSO4/TiO2 for Acid Catalysis

A series of catalysts, NiSO₄/Al₂O₃–TiO₂, for acid catalysis was prepared by the impregnation method, where support, Al₂O₃–TiO₂ was prepared by the coprecipitation method using a mixed aqueous solution of titanium tetrachloride and aluminum nitrate solution followed by adding an aqueous ammonia solution. The addition of nickel sulfate (or Al₂O₃) to TiO₂ shifted the phase transition of TiO₂ from amorphous to anatase to higher temperature because of the interaction between nickel sulfate (or Al₂O₃) and TiO₂. 15-NiSO₄/5-Al₂O₃–TiO₂ containing 15 wt% NiSO₄ and 5 mol% Al₂O₃, and calcined at 400°C exhibited maximum catalytic activities for both reactions, 2-propanol dehydration and cumene dealkylation. The catalytic activities for both reactions were correlated with the acidity of catalysts measured by the ammonia chemisorption method. The charge transfer from Ti atoms to the neighboring Al atoms strengthens the Al–O bond between Al and the surface sulfate species. The addition of Al₂O₃ up to 5 mol% enhanced the acidity, thermal property, and catalytic activities of NiSO₄/Al₂O₃–TiO₂ gradually due to the interaction between Al₂O₃ and TiO₂ and consequent formation of Al–O–Ti bond.     

Hydrogen production by steam reforming of LNG over Ni/Al2O3-ZrO2 catalysts: Effect of ZrO2 and preparation method of Al2O3-ZrO2

An Al₂O₃-ZrO₂ support was prepared by grafting a zirconium precursor onto the surface of commercial γ-Al₂O₃. A physical mixture of Al₂O₃-ZrO₂ was also prepared for the purpose of comparison. Ni/Al₂O₃-ZrO₂ catalysts were then prepared by an impregnation method, and were applied to the hydrogen production by steam reforming of liquefied natural gas (LNG). The effect ZrO₂ and preparation method of Al₂O₃-ZrO₂ on the performance of supported nickel catalysts in the steam reforming of LNG was investigated. The Al₂O₃-ZrO₂ prepared by a grafting method was more efficient as a support for nickel catalyst than the physical mixture of Al₂O₃-ZrO₂ in the hydrogen production by steam reforming of LNG. The well-developed tetragonal phase of ZrO₂ and the high dispersion of ZrO₂ on the surface of γ-Al₂O₃ were responsible for the enhanced catalytic performance of Ni/Al₂O₃-ZrO₂ prepared by way of a grafting method.     

Dehydrogenation of ethylbenzene to styrene over Fe2O3/Al2O3 catalysts in the presence of carbon dioxide

An Fe₂O₃ (10 wt%)/Al₂O₃ (90 wt%) catalyst prepared by a coprecipitation method was found to be effective for dehydrogenation of ethylbenzene to produce styrene in the presence of CO₂ instead of steam used in commercial processes. The dehydrogenation of ethylbenzene over the catalyst in the presence of CO₂ was considered to proceed both via a one-step pathway and via a two-step pathway. CO₂ was found to suppress the deactivation of the catalyst during the dehydrogenation of ethylbenzene. This revised version was published online in July 2006 with corrections to the Cover Date.     

Direct synthesis of mesoporous silicalite-1 supported TiO2–ZrO2 for the dehydrogenation of EB to styrene with CO2

Direct synthesis route was developed to support TiO₂–ZrO₂ binary metal oxide onto the carbon templated mesoporous silicalite-1 (CS-1). Metal hydroxide modified carbon particles could play a role as hard template and simultaneously support metal components on the mesopores during the crystallization of zeolites. Such supported TiO₂–ZrO₂ binary metal oxides (TZ/CS-1) showed better resistance to deactivation in the oxidative dehydrogenation of ethylbenzene (ODHEB) in the presence of CO₂. These catalysts were found to be active, selective and catalytically stable (10 h of time-on-stream) at 600 °C for the dehydrogenation of ethylbenzene (EB) to styrene (Sty).     

Effect of ceria on the structure and catalytic activity of V2O5/TiO2–ZrO2 for oxidehydrogenation of ethylbenzene to styrene utilizing CO2 as soft oxidant

The present study was undertaken to investigate the influence of ceria on the physicochemical and catalytic properties of V₂O₅/TiO₂–ZrO₂ for oxidative dehydrogenation of ethylbenzene to styrene utilizing CO₂ as a soft oxidant. Monolayer equivalents of ceria, vanadia and ceria–vanadia combination over TiO₂–ZrO₂ (TZ) support were impregnated by a coprecipitation and wet impregnation methods. Synthesized catalysts were characterized by using X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, temperature programmed reduction, transmission electron microscopy and BET surface area methods. The XRD profiles of 550 °C calcined samples revealed amorphous nature of the materials. Upon increasing calcination temperature to 750 °C, in addition to ZrTiO₄ peaks, few other lines due to ZrV₂O₇ and CeVO₄ were observed. The XPS V 2p results revealed the existence of V⁴⁺ and V⁵⁺ species at 550 and 750 °C calcinations temperatures, respectively. TEM analysis suggested the presence of nanosized (<7 nm) particles with narrow range distribution. Raman measurements confirmed the formation ZrTiO₄ under high temperature treatments. TPR measurements suggested a facile reduction of CeO₂–V₂O₅/TZ sample. Among various samples evaluated, the CeO₂–V₂O₅/TZ sample exhibited highest conversion and nearly 100% product selectivity. In particular, the addition of ceria to V₂O₅/TZ suppressed the coke deposition and allowed a stable and high catalytic activity.     

How oxide carriers affect the reactivity of V2O5 catalysts in the oxidative dehydrogenation of propane

The catalytic pattern of several oxide carriers (MgO, Al₂O₃, ZrO₂, TiO₂, SiO₂, HY zeolite) and supported V₂O₅ (4.7–5.3 wt%) catalysts in the oxidative dehydrogenation of propane to propylene (PODH) has been comparatively investigated. The fundamental role of the oxide support on both reducibility and reactivity of vanadia catalysts has been assessed. A direct relationship between the specific surface activity of oxide carriers and that of vanadia catalysts is discussed. The inverse relationship between the specific activity and the onset temperature of reduction marks the prevailing redox behaviour of V₂O₅ catalysts in the PODH reaction. This revised version was published online in July 2006 with corrections to the Cover Date.     

Oxidative dehydrogenation of 4-vinylcyclohexene into styrene over ZrO2 catalyst promoted with Fe2O3 and CaO

The oxidative dehydrogenation of 4-vinylcyclohexene (VCH) into styrene was carried out in the presence of oxygen over a ZrO₂ catalyst promoted with Fe₂O₃ and CaO. Intrinsically, ZrO₂ showed high dehydrogenation activity, which resulted in 80% styrene selectivity with 45% conversion at 425 °C and LHSV 3 h⁻¹. When the ZrO₂ was further promoted with calcium and iron, CaO/Fe₂O₃/ZrO₂, the highest styrene selectivity of 88.9% was obtained as well as the lowest deactivation. The deactivation of catalyst was prohibited properly through the introduction of oxygen in the reactant together with the modification of Fe₂O₃/ZrO₂ with CaO. The CaO/Fe₂O₃/ZrO₂ showed constant catalytic activity and selectivity for more than 50 h without deactivation. The selectivity of styrene was strongly influenced by the mole ratio of O₂/VCH and 95% selectivity with 80% conversion was obtained at O₂/VCH mole ratio of 6 over Fe₂O₃/ZrO₂. It is thought that the oxidative dehydrogenation proceeds through the dehydrogenation (DH) of ring-hydrocarbon of VCH followed by selective combustion of hydrogen (SHC) and the high selectivity of styrene was achieved by the bi-functional role of ZrO₂ for DH and SHC reactions. This revised version was published online in July 2006 with corrections to the Cover Date.     

Ozone Decomposition on α-Fe2O3 Catalyst

The catalytic decomposition of ozone on an α-Fe₂O₃ catalyst has been investigated within the temperature range 23-65°C. A high initial decomposition degree followed by a decrease is observed. It is found that the water vapor in the air-ozone mixture exercises almost no effect on the process. IR-spectroscopy has shown that the nitrogen oxides formed in the ozone generator are the main reason for the deactivation of the catalyst. A scheme of the deactivation process is proposed.     

Structure and photocatalytic performance of magnetically separable titania photocatalysts for the degradation of propachlor

A magnetic photocatalyst was prepared by modification of TiO₂ nanoparticles (Degussa P25) with nanocrystalline γ-Fe₂O₃ nanoparticles through a protective lining made up of two oppositely charged polyelectrolytes. As-prepared magnetically separable photocatalysts differing in γ-Fe₂O₃ loading (3, 8, 13, 20 and 30 wt.%) were characterized by XRD, TEM, thermal analysis, Mössbauer and magnetic measurements. The photocatalytic efficiency of the nanocomposite catalysts was evaluated using a chloroacetanilide herbicide (propachlor) in water as model compound. The primary degradation of propachlor followed pseudo-first-order kinetics according to the Langmuir–Hinshelwood model. Generally, all magnetic photocatalysts exhibit good catalytic activity towards organic pollutants, do not suffer from photodissolution and can be reused several times without any decrease in their photocatalytic activity.     

Investigation of the sulfidation of Mo/TiO2-Al2O3 catalysts by TPS and LRS

A series of Mo/Al₂O₃ and Mo/TiO₂-Al₂O₃ catalysts were investigated by temperature programmed sulfiding (TPS) and laser Raman spectroscopy (LRS). The effect of TiO₂ on the sulfidability of molybdena was studied in detail. It is found that Mo/Al₂O₃ catalysts can be partially sulfided by O-S exchange at low temperature, forming molybdenum oxysulfide. The Mo-S bond subsequently ruptures in the presence of H₂ to produce H₂S. At 530–550 K deep sulfiding of molybdenum oxysulfide occurs forming crystalline MoS₂. When the surface of Al₂O₃ was covered by a monolayer of TiO₂, the sulfiding rate of molybdena at low temperature was not only greatly increased, but H₂S produced in the reduction of Mo-S species caused deep sulfiding of the catalyst which resulted in a decrease of the TPS peak temperature by 80–100 K. The results indicate that this promotion of the sulfiding of molybdena is enhanced with TiO₂ loading. The function of TiO₂ is explained by the weakened interaction between MoO₃ and Al₂O₃ due to the coverage of the Al₂O₃ surface by TiO₂.     

Improvement of coke resistance of Ni/Al2O3 catalyst in CH4/CO2 reforming by ZrO2 addition

This work investigates the improvement of Ni/Al₂O₃ catalyst stability by ZrO₂ addition for H₂ gas production from CH₄/CO₂ reforming reactions. The initial effect of Ni addition was followed by the effect of increasing operating temperature to 500–700 °C as well as the effect of ZrO₂ loading and the promoted catalyst preparation methods by using a feed gas mixture at a CH₄:CO₂ ratio of 1:1.25. The experimental results showed that a high reaction temperature of 700 °C was favored by an endothermic dry reforming reaction. In this reaction the deactivation of Ni/Al₂O₃ was mainly due to coke deposition. This deactivation was evidently inhibited by ZrO₂, as it enhances dissociation of CO₂ forming oxygen intermediates near the contact between ZrO₂ and nickel where the deposited coke is gasified afterwards. The texture of the catalyst or BET surface area was affected by the catalyst preparation method. The change of the catalyst texture resulted from the formation of ZrO₂–Al₂O₃ composite and the plugging of Al₂O₃ pore by ZrO₂. The 15% Ni/10% ZrO₂/Al₂O₃ co-impregnated catalyst showed a higher BET surface area and catalytic activity than the sequentially impregnated catalyst whereas coke inhibition capability of the promoted catalysts prepared by either method was comparable. Further study on long-term catalyst stability should be made.     

Synthesis of porous Al2O3/ZrO2 nanocomposites by chemical vapour deposition

Al₂O₃/ZrO₂ one-dimensional nanocomposite structures were synthesised by chemical vapour deposition using Al₂O₃ nanowires and a ZrCl₄ powder source at a temperature of 800?°C and a pressure of 130?Pa. The samples were characterised using X-ray diffraction, the scanning electron microscopy, the transmission electron microscopy, and N₂ adsorption–desorption. The results revealed that Al₂O₃/ZrO₂ composite nanowires coated with surface-embedded ZrO₂ nanocrystals were formed and that the ZrO₂ macroporous and mesoporous structures changed as the ZrO₂ deposition time increased. The pore structure and surface area were also elucidated from the N₂ adsorption–desorption measurements.     

Chromium Oxide Supported on Mesoporous SBA-15 as Propane Dehydrogenation and Oxidative Dehydrogenation Catalysts

The catalytic activity and selectivity of Cr₂O₃ supported on mesoporous SBA-15 for non-oxidative and oxidative dehydrogenation of propane by O₂ and CO₂ have been studied and compared with those of Cr₂O₃/ZrO₂ and Cr₂O₃/-Al₂O₃ catalysts. Cr₂O₃/SBA-15 and Cr₂O₃/ZrO₂/SBA-15 are more selective to propene and more resistant to coking in comparison with Cr₂O₃/ZrO₂ and Cr₂O₃/-Al₂O₃ for non-oxidative dehydrogenation of propane. In oxidative dehydrogenation of propane by O₂ and CO₂, Cr₂O₃/SBA-15 also displays better activity, selectivity and stability than the other two supported catalysts. The propane conversion and propene yield on Cr₂O₃/SBA-15 catalyst for oxidative dehydrogenation of propane by CO₂ at 823 K reach 24.2 and 20.3%, respectively. XPS and TG/DTA have been used to characterize the catalysts before and after reaction. The differences in catalytic behavior of various supported Cr₂O₃ catalysts in the reactions have been discussed on the basis of the characterization results.     

Correlation between acidic properties of nickel sulfate supported on TiO2-ZrO2 and catalytic activity for ethylene dimerization

A series of catalysts, NiSO₄/TiO₂-ZrO₂, for ethylene dimerization was prepared by the impregnation method using an aqueous solution of nickel sulfate. For NiSO₄/TiO₂ -ZrO₂ sample, no diffraction line of nickel sulfate was observed up to 30 wt%, indicating good dispersion of nickel sulfate on the surface of TiO₂-ZrO₂. The addition of nickel sulfate to TiO₂-ZrO₂ shifted the phase transition of TiZrO₄ from amorphous to orthorhombic to a higher temperature because of the interaction between nickel sulfate and TiO₂-ZrO₂. The number of acid sites of NiSO₄/TiO₂-ZrO₂ increased in proportion to the nickel sulfate content up to 20 wt% of NiSO₄. Nickel sulfate supported on TiO₂-ZrO₂ was found to be very active even at room temperature, giving a maximum in both activity and acidity when the catalyst containing 20% NiSO₄ was calcined and evacuated at 500°C The asymmetric stretching frequency of the S=O bonds for NiSO₄/TiO₂-ZrO₂ samples was related to the acidic properties and catalytic activity. That is, the higher the frequency, the higher both the number of acid sites and the catalytic activity for ethylene dimerization.     

Simultaneous dehydrogenation and isomerization of n-butane to isobutene over Cr/WO3–ZrO2 catalysts

A series of WO₃-promoted Cr₂O₃-based catalysts were prepared and tested for the simultaneous dehydrogenation and isomerization of n-butane to isobutene. It is found that a Cr₂O₃/WO₃–ZrO₂ system is an effective catalyst for this reaction; however, the catalytic behavior is dependent on Cr₂O₃ and WO₃ contents, space velocity and temperature. 10 wt% Cr₂O₃/20 wt% WO₃–ZrO₂ can give high initial conversion and isobutene selectivity, but it deactivates rapidly due to the variation of surface properties and pore structure caused by carbon deposition. This revised version was published online in July 2006 with corrections to the Cover Date.     

Hydrodesulphurization performance of NiW/TiO2-Al2O3 catalyst for ultra clean diesel

TiO₂-Al₂O₃ binary oxide supports were obtained by sol–gel methods from Tetra-n-butyl-titanate and pseudoboehmite/aluminium chloride resources. The typical physico-chemical properties of NiW/TiO₂-Al₂O₃ catalysts with different TiO₂ loadings and their supports were characterized by means of BET, XRD and UV–vis DRS, etc. The BET results indicated that the specific surface areas of NiW/TiO₂-Al₂O₃ catalysts were as higher as that over pure γ-Al₂O₃ support, and the pore diameters were also large. The XRD and UV–vis DRS analyzing results showed that the Ti-containing supported catalysts existed as anatase TiO₂ species and the incorporation of TiO₂ could adjust the interaction between support and active metal, and impelled the higher reducibility of tungsten. The hydrodesulphurization (HDS) performance of the series catalysts were evaluated with diesel feedstock in a micro-reactor unit, and the HDS results showed that NiW/TiO₂-Al₂O₃ catalysts exhibited higher activities of ultra deep hydrodesulphurization of diesel oil than that of NiW/Al₂O₃ catalyst. The optimal TiO₂ content of NiW/TiO₂-Al₂O₃ catalysts was about 15 m%, and the corresponding HDS efficiency could reach to 100%. The sulphur contents of diesel products over NiW/TiO₂-Al₂O₃ (from pseudoboehmite/AlCl₃) catalysts with suitable TiO₂ content could be less than 15 ppmw, which met the sulphur regulation of Euro IV specification of ultra clean diesel fuel.     

Characterization of Supported NiSO4 and Effect of TiO2–ZrO2 Composition on Catalytic Activity for Acid Catalysis

A series of catalysts, NiSO₄/TiO₂–ZrO₂ having different TiO₂–ZrO₂ composition, for acid catalysis was prepared by the impregnation method using an aqueous solution of nickel sulfate. The addition of TiO₂ to ZrO₂ improved the surface area of the catalyst and enhanced its acidity remarkably because of the formation of new acid sites through the charge imbalance of Ti–O–Zr bonding. The binary oxide, TiO₂–ZrO₂ calcined above 600 °C resulted in the formation of crystalline orthorhombic phase of ZrTiO₄. Therefore, NiSO₄/TiO₂–ZrO₂ calcined at 500 °C exhibited a maximum catalytic activity for acid catalysis, and then the catalytic activity decreased with the calcination temperature. The correlation between catalytic activity and acidity held for both reaction, 2-propanol dehydration and cumene dealkylation. NiSO₄ supported on 50TiO₂–50ZrO₂ (TiO₂/ZrO₂ ratio = 1) among TiO₂–ZrO₂ binary oxides exhibited the highest catalytic activity for acid catalysis.     

Influence of the V2O5 Loading on the Structure and Activity of V2O5/TiO2 SCR Catalysts for Vehicle Application

In this paper the effect of the vanadium oxide loading on the surface vanadia structure and the activity as well as selectivity in the catalytic reduction of NO with NH₃ was studied for a V₂O₅/TiO₂ model system. A series of TiO₂ (WO _x stabilized anatase) supported vanadia catalysts with varying loadings were characterized by laser Raman spectroscopy, ⁵¹V MAS-NMR, V K XANES. To determine the acidic properties, DRIFTS measurements were done with pyridine adsorbed on the samples. The measurements indicate that with increasing active phase loading square pyramidal coordinated surface vanadia species are replaced by an amorphous highly dispersed vanadium oxide phase with a coordination like V₂O₅. In addition, the ratio of Brønsted to Lewis acid sites is shifted from a comparatively low to an equal level at high loadings. This structural change is accompanied by a clearly improved catalytic activity and selectivity.     

The reduction behavior of Mo/TiO2-Al2O3 catalyst

The effect of TiO₂ modified Al₂O₃ surface on the reducibility of MoO₃ has been studied by TPR and XPS. The results show that Mo⁶⁺ in Mo/TiO₂-Al₂O₃ can be reduced to much lower valency, especially at low Mo loading. The influence of the calcination temperature on the reduction of Mo⁶⁺ on Al₂O₃ and TiO₂-Al₂O₃ carriers is different. The data reveals that the reducibility of Mo⁶⁺ on Al₂O₃ slightly decreased, while that on TiO₂-Al₂O₃ increased when the calcination temperature was raised. It is suggested that the stronger tetrahedral site of the Al₂O₃ surface was first occupied by TiO₂ and main octahedral Mo⁶⁺ in polymeric species-; and a small crystalline MoO₃ formed on TiO₂-Al₂O₃, whereas the formation of tetrahedral Mo⁶⁺ species and Al₂(MoO₄)₃ phase was inhibited.