Support effect on the properties of iron–molybdenum hydrodesulfurization catalysts

Two series of Mo and Fe containing catalysts have been prepared over alumina and titania supports using H₃PMo₁₂O₄₀ heteropolyacid (HPMo) and Fe salt of HPMo. Catalysts have been characterized by BET, SEM, IR, TPR, XPS methods and by their HDS activity in the reaction of thiophene conversion. The TiO₂-supported catalysts with low Mo concentration (6 wt%) show higher HDS activity than the catalyst with 12 wt% Mo. Iron promoting effect (Fe/Mo ~ 0.1) is observed with both, the alumina- and titania-supported catalysts. Iron supported over alumina increases Mo reducibility and decreases it on TiO₂-supported catalysts. Compared to alumina-supported catalysts, the TiO₂-supported catalysts show higher surface concentration of Mo⁶⁺ and Mo⁵⁺ in octahedral coordination – Mo(Oh). Iron increases the Mo(Oh) concentration even more. After sulfidation the Fe-containing catalysts show formation of different Mo valence states (Mo⁴⁺, Mo⁵⁺, Mo⁶⁺), Fe–P, Mo–P and/or Fe–Mo–P bonds, which affect the HDS catalytic activity.     

Deposition of CoO onto MoO3/Al2O3 hydrodesulfurization catalysts by solvent assisted spreading

Solvent assisted spreading of CoO over monolayer MoO₃/Al₂O₃ catalysts has been studied. CoCO₃ · Co(OH)₂ and CoCO₃ reacted with MoO₃/Al₂O₃ in water slurries. CoO deposition over MoO₃/Al₂O₃ extrudates was followed by EPMA. In the set of eleven MoO₃/Al₂O₃ catalysts, the amount of CoO adsorbed was roughly proportional to the surface area of MoO₃ monolayer. The adsorbed Co species efficiently enhanced the HDS activity.     

The effect of Pd/Al2O3 pretreatment on catalytic activity in cyclopentane/deuterium exchange

Big variations in overall activity and product selectivity in the cyclopentane/deuterium exchange reaction were found in effect of various pretreatments of two chlorine‐free Pd/γ‐Al₂O₃ catalysts. The most important changes are observed when severely prereduced (at 600 °C) Pd/Al₂O₃ catalysts have been reoxidised and mildly rereduced: the multiple type of exchange, typical of mildly pretreated Pd catalysts, is replaced by a stepwise mode, and a big increase in catalytic activity occurs. At this state, the Pd/γ‐Al₂O₃ catalysts retain some water (as surface hydroxyls) generated by reoxidation and mild reduction. Deuterium spillover from Pd onto alumina and changes in acidity of alumina are invoked to rationalize the kinetic results. Changes in the state of Pd after various pretreatments, as probed by temperature‐programmed hydride decomposition, can hardly be correlated with changes in the catalytic behaviour in the exchange reaction. This revised version was published online in August 2006 with corrections to the Cover Date.     

Support Dependence of MeOH Decomposition Over Size-Selected Pt Nanoparticles

We present here the decomposition of methanol over Pt nanoparticles supported on a series of oxide powders. The samples tested may be roughly grouped in two categories consisting of large (∼15–18 nm) and small (∼8–9 nm) Pt particles deposited on reducible (CeO₂, TiO₂) and non-reducible (SiO₂, ZrO₂, Al₂O₃) supports. The smallest particles (∼8 nm), deposited on ZrO₂, were found to be cationic and the most active for the decomposition of methanol. Furthermore, the stability of metallic Pt and its oxides was observed to be dependent on the choice of support. In all Pt containing samples the reaction proceeds via he direct decomposition of methanol, as no significant amounts of by-products were detected in the experimental range of 100–300 °C.     

Correlation of the deactivation of CoMo/Al2O3 in hydrodesulfurization with surface carbon species

The deactivation of CoMo/Al₂O₃ in the hydrodesulfurization (HDS) of dibenzothiophene (DBT) was investigated under laboratory conditions that allowed the accelerated deposition of coke on the catalyst. The coke deposition was enhanced at low H₂ pressures and when naphthalene was added to the reaction solution. Characterization of deactivated catalysts by elemental analysis (EA) and temperature-programmed oxidation (TPO) identified two types of carbonaceous species deposited on the catalysts, the reactive and the refractory species. The refractory deposit, or hard coke, was a major contributor to the deactivation and, therefore, the amounts of hard coke present on the catalyst determined the overall activity. A correlation was established in this study between the activity and the amounts of deposited hard coke based on the results of accelerated deactivation treatment. A similar relation was also observed between the two parameters when the catalyst was used in an industrial process for long periods. The above findings suggest that the reaction periods of two different scales, i.e., in laboratory and industrial processes, can be correlated with each other based on the amounts of hard coke when coking is the major mechanism of catalyst deactivation.     

Influence of homogeneous decane oxidation on the catalytic performance of lean NO x catalysts

Extensive homogeneous gasphase reactions were observed when decane was used as the hydrocarbon reductant for the selective reduction of NO _x . The catalytic performance of a SnO₂/CoO _x /Al₂O₃ catalyst was found to be strongly dependent on the extent of the homogeneous reaction in the precatalytic volume. The effect of the homogeneous reaction on the catalytic performance also depended on whether SO₂ was present in the feed. By filling the precatalytic volume with 25–35 mesh irregularly shaped quartz chips, gasphase reaction was suppressed significantly. This methodology was used to evaluate the inherent catalytic performance of SnO₂/CoO _x /Al₂O₃ and SnO₂/Al₂O₃ catalysts with decane as a reductant. It was found that in the absence of SO₂, SnO₂/Al₂O₃ was a better catalyst than SnO₂/CoO _x /Al₂O₃, but in the presence of 30 ppm of SO₂ the latter was a far better catalyst.     

On the development of metallic particles and their initial catalytic properties in the CO + H2 reaction over Co/Al2O3 catalyst

Formation of Co^o phases with different surface structure over 10 wt% Co/Al₂O₃ and their catalytic properties were induced by pretreatments in H₂ at 570 K for 1 h or 20 h. Electronic behaviour of the Co^o phase, which consists of small (after 1 h reduction) or large bulk-like particles (after 20 h reduction), did not change during the CO hydrogenation after 5 h on stream as was determined by XPS. On the basis of the measured C₂₊ hydrocarbon selectivities the CO molecules are suggested to dissociate on small Co particles to a larger extent than on large cobalt particles. The slight decrease in the catalytic activity with increasing time on stream obtained for the long-term reduced sample is explained by the change in the surface Co^o content detected by XPS. The increase in the catalytic activity along with the change in olefin selectivity, measured for the sample reduced for 1 h, is interpreted by the change of a reaction path involving the Co^o-support interface during the initial period of the reaction.     

Characteristics of intermetallic NdNi5 as an unsupported catalyst in thiophene hydrodesulfurization

A systematic research is carried out on intermetallic NdNi₅ for the hydrodesulfurization (HDS) of thiophene. The effect of calcination and presulfidation of intermetallic NdNi₅ on thiophene HDS was examined and property changes of the catalyst during calcination, presulfidation, and reaction were observed by XRD, SEM, and surface area techniques. The intermetallic compound of NdNi₅ is disintegrated to fine powder and recrystallized to Nd/Ni oxide and sulfide by calcination, presulfidation, and reaction. A model for the surface area increase of the catalyst during calcination, presulfidation, and reaction was proposed and the role of neodymium was explained.     

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.     

Characterization of hydrodesulfurization catalyst prepared by impregnating cobalt nitrate solution onto the sulfided MoO3/Al2O3 catalyst

CoMo/Al₂O₃ catalysts were prepared by impregnating Cobalt nitrate solution into oxidic or sulfided Mo/Al₂O₃. The properties of CoMo/Al₂O₃ catalysts were characterized by XRD, TPS, oxygen chemisorption and ESR. Catalytic activity of CoMo/Al₂O₃ catalyst was evaluated by thiophene HDS as a probe reaction. When CoMo/Al₂O₃ catalyst was prepared by impregnating Cobalt nitrate solution into sulfided Mo/Al₂O₃, the interaction between Mo and alumina became weaker and the formation of synergic phase was facilitated. These structural changes may explain higher HDS activity of CoMo/Al₂O₃ catalyst prepared by impregnating Cobalt nitrate solution into sulfided Mo/Al₂O₃.     

The positive effect of hydrogen on the reaction of nitric oxide with carbon monoxide over platinum and rhodium catalysts

The effect of adding 330–4930 ppm hydrogen to a reaction mixture of NO and CO (2000 ppm each) over platinum and rhodium catalysts has been investigated at temperatures around 200–250°C. Hydrogen causes large increases in the conversion of NO and, surprisingly, also of CO. Oxygen atoms from the additional NO converted are eventually combined with CO to give CO₂ rather than react with hydrogen to form water. This reaction is described by CO + NO +3/2H₂ CO₂ + NH₃ and accounts for 50–100% of the CO₂ formed with Pt/Al₂O₃ and 20–50% with Rh/Al₂O₃. With the latter catalyst a substantial amount of NO converted produces nitrous oxide. Comparison with a known study of unsupported noble metals suggests that isocyanic acid (HNCO) might be an important intermediate in a reaction system with NO, CO and H₂ present.     

Wire-mesh honeycomb catalysts for selective catalytic reduction of NO with NH3

Both flat and corrugated wire mesh sheets were coated with aluminum powder by using electrophoretic deposition (EPD) method. Controlled thermal sintering of coated samples yielded uniform porous aluminum layer with a thickness of 100 μm that was attached firmly on the wire meshes. Subsequent controlled calcination formed a finite thickness of Al₂O₃ layer on the outer surface of each deposited aluminum particles, which resulted in the formation of Al₂O₃/Al double-layered composite particles that were attached firmly on the wire surface to form a certain thickness of porous layer. A rectangular-shaped wire-mesh honeycomb (WMH) module with triangular-shaped channels was manufactured by packing alternately the flat sheet and corrugated sheet of the Al₂O₃/Al-coated wire meshes. This WMH was further coated with V₂O₅-MoO₃-WO₃ catalyst by wash-coating method to be applied for the selective catalytic reduction (SCR) of NO with NH₃. With an optimized catalyst loading of 16 wt%, WMH catalyst module shows more than 90% NO conversion at 240 °C and almost complete NO conversion at temperatures higher than 300 °C at GHSV 5,000 h⁻¹. When compared with conventional ceramic honeycomb catalyst, WMH catalyst gives NO conversion higher by 20% due to reduced mass transfer resistance by the existence of three dimensional opening holes in WMH.     

Effect of MgF2 and Al2O3 supports on the structure and catalytic activity of copper–manganese oxide catalysts

Structure and catalytic activity of double copper–manganese oxide catalysts supported on MgF₂ and Al₂O₃ have been studied. All samples were calcined at 400 °C and those supported on Al₂O₃ also at 550 and 950 °C. The properties of surface species have been characterized by low temperature adsorption of nitrogen, XRD and TPR-H₂. The catalytic activities have been tested in low-temperature CO oxidation and in NO reduction by propene. The supported oxides react with each other during calcination to form CuMn₂O₄ spinel. The spinel seems to be responsible for the catalytic activity of the double copper–manganese catalysts. The temperature of calcination changes the strength of interaction between the active phase and the supports influencing the catalytic activity.     

The effect of sodium on the catalytic activity of ZnO–Al2O3/ZSM-5 and SnO–Al2O3/ZSM-5 for the transesterification of vegetable oil with methanol

In order to elucidate the effect of sodium on the activity of ZSM-5 supported metal oxides catalysts (ZnO–Al₂O₃/ZSM-5 and SnO–Al₂O₃/ZSM-5) for the transesterification of soybean oil with methanol, ZSM-5 supported metal oxides were prepared with and without sodium hydroxide by impregnation. The metal compositions of the ZSM-5 supported metal oxide catalysts and the metal concentrations dissolved from the catalysts to the methylester phase were measured by SEM-EDS and inductive coupled plasma spectroscopy, respectively. The catalytic activity of ZnO–Al₂O₃/ZSM-5 and SnO–Al₂O₃/ZSM-5 containing sodium did not originate from surface metal oxides sites, but from surface sodium sites or dissolved sodium leached from the catalyst surface.     

SSITKA studies of the catalytic flameless combustion of methane

This paper presents results which were obtained for the flameless combustion of methane over the Pd(PdO)/Al₂O₃ catalyst by using the steady state isotopic transient kinetic analysis method. During the reaction switches between ¹⁶O₂/Ar/CH₄/He and ¹⁸O₂/CH₄/He were carried out. The obtained results indicate the presence of large amounts of oxygen as well as of intermediates leading to the formation of carbon dioxide on the surface of the palladium catalyst. Additionally, information was obtained proving that the complete oxidation of methane over Pd/Al₂O₃ catalyst proceeds according to the Mars and van Krevelen redox mechanism. With the increase of the reaction temperature there is an increase in the number of active centres on the Pd(PdO)/Al₂O₃ catalyst surface—a larger amount of oxygen from the lattice of the catalyst is accessible for the reaction of methane oxidation.     

A study on the dispersion and catalytic activity of gamma alumina-supported palladium catalysts

Electron spectroscopy for chemical analysis (ESCA) and carbon monoxide adsorption techniques have been applied to study the percent exposed (i.e., dispersion) and Pd deposition in the pores of highly porous gamma alumina-supported Pd catalysts. A correlation has been found between Pd dispersion and its extent of penetration into the pores: more edge-coated catalysts are less dispersed. The dispersion of Pd is controlled by a carrier-catalyst interaction that originates in part from electron transfer from the support to the supported Pd. This electronic interaction is demonstrated by the broadening of the ESCA peaks. The activity of the catalysts, measured by the hydrogenation of nitrobenzene to aniline, is dependent on the dispersion of palladium.     

The effect of alumina contamination from the ball-milling of fused silica on the high temperature properties of injection moulded silica ceramic components

The amount of alumina contamination present in ball-milled silica powders has been shown to increase with increased mill time for materials manufactured during the same time period. This alumina contamination level has also been observed to vary depending on the date, and possibly the state of repair, of the ball mill itself. The associated alumina level has been shown to significantly influence the high temperature properties (at 1475 °C) of the materials, with high contamination levels not only resulting in increased flexural strength and creep resistance, but also increasing the thermal contraction of the materials when dilatometer measurements were performed to 1600 °C.     

Effects of electron-beam irradiation,a thin-Ti layer,and a BeO additive on the diffusion of titanium in synthetic sapphire

Titanium was allowed to diffuse into synthetic sapphire (α-Al₂O₃) at 1773–1923 K for 200 h in air. Specimens were prepared by four different methods. Samples were irradiated with a 10 MeV electron beam to fluencies of 2×10¹⁷ cm⁻² for 1 h to induce vacancy formation. A 1-μm layer of titanium was sputtered onto sapphire samples to provide intimate contact with the diffusing elements. Ti diffusion was performed using TiO₂ powder or a mixture of TiO₂ and BeO powders in a ratio of 95:5 to take advantage of the beryllium activity. Ti diffusion was profiled using scanning electron microscope-energy dispersive X-ray spectrometry (SEM–EDX). The diffusion coefficients of Ti were as follows:     

Investigation of CH4 Reforming with CO2 on Meso-Porous Al2O3-Supported Ni Catalyst

Meso-porous Al₂O₃-supported Ni catalysts exhibited the highest activity, stability and excellent coke-resistance ability for CH₄ reforming with CO₂ among several oxide-supported Ni catalysts (meso-porous Al₂O₃ (Yas1-2, Yas3-8), -Al₂O₃, -Al₂O₃, SiO₂, MgO, La₂O₃, CeO₂ and ZrO₂). The properties of deposited carbons depended on the properties of the supports, and on the meso-porous Al₂O₃-supported Ni catalyst, only the intermediate carbon of the reforming reaction formed. XRD and H₂-TPR analysis found that mainly spinel NiAl₂O₄ formed in meso-porous Al₂O₃ and -Al₂O₃-supported catalysts, while only NiO was detected in -Al₂O₃, SiO₂, CeO₂, La₂O₃ and ZrO₂ supports. The strong interaction between Ni and meso-porous Al₂O₃ improved the dispersion of Ni, retarded its sintering and improved the activated adsorption of CO₂. The coking reaction via CH₄ temperature-programed decomposition indicated that meso-porous Al₂O₃-supported Ni catalysts were less active for carbon formation by CH₄ decomposition than Ni/-Al₂O₃ and Ni/-Al₂O₃.     

Reduced strength degradation of alumina–aluminium titanate composite subjected to low-velocity impact loading

The impact behaviour of monophase alumina and alumina–aluminium titanate monolithic composite ceramics that present flaw tolerant behaviour was studied. Low-velocity impact loading tests were performed on bending bars and the residual strength after the impact was evaluated by four-point bending tests. The impact tests were monitored using an instrumented drop-weight machine. During impact, the composites absorbed higher energy than the monophase material. The strength retention, in percentage, after the impact was significantly higher for the composite that presented damage tolerance for impact energy levels higher than monophase alumina. These results are discussed and fractographic analysis was used to identify the mechanisms responsible for the lower strength degradation of the composite.