TEM Studies of High Temperature Corrosion Behaviour of TiAl Intermetallics with Surface Modifications

The oxidation/sulphidation behaviour of a Ti‐46.7Al‐1.9W‐0.5Si alloy with a TiAl₃ diffusion coating was studied in an environment of H₂/H₂S/H₂O at 850^oC. The kinetic results demonstrate that the TiAl₃ coating significantly increased the high temperature corrosion resistance of Ti‐46.7Al‐1.9W‐0.5Si. The SEM, EDX, XRD and TEM analysis reveals that the formation of an Al₂O₃ scale on the surface of the TiAl₃‐coated sample was responsible for the enhancement of the corroison resistance. The Ti‐46.7Al‐1.9W‐0.5Si alloy was also modified by Nb ion implantation. The Nb ion implanted and as received sampels were subjected to cyclic oxidation in an open air at 800^oC. The Nb ion implantation not only increased the oxidation resistance but also substantially improved the adhesion of scale to the substrate.     

A novel way to treat refractory waste: Sonication followed by wet oxidation (SONIWO)

The effectiveness of the hybrid system sonication followed by wet oxidation (SONIWO) to treat otherwise refractory waste has been demonstrated. In such a hybrid system homogeneous CuSO₄ catalyst was found to be very efficient.     

Nitric oxide reduction and carbon monoxide oxidation over carbon-supported copper-chromium catalysts

Carbon supported copper-chromium catalysts are shown to be very active for both the reduction of nitric oxide with carbon monoxide and the oxidation of carbon monoxide with oxygen. Mixed copper-chromium oxide active phases have good activity in the simultaneous removal of nitric oxide and carbon monoxide from exhaust gases. The influence of several catalyst variables has been investigated. The activity per volume of catalyst increases with increasing loading, while the intrinsic activity shows a maximum around C/M=100−50. An optimum catalyst for nitric oxide reduction and carbon monoxide oxidation has a copper/chromium ratio of 2/1. The apparent activation energy for the carbon monoxide oxidation over carbon supported copper-chromium catalysts is 77 kJ/mol, suggesting that the Cu---O bond rupture is the rate-limiting process. The reduction of nitric oxide takes place at higher temperatures. Since all catalysts have a low selectivity for molecular nitrogen formation at lower temperatures, the dissociation of nitric oxide is probably rate determining, resulting in a slightly reduced catalyst system. In an excess of carbon monoxide the reaction is first-order in nitric oxide and zero-order in carbon monoxide. Moisture inhibits the reaction by reversible competitive adsorption, whereas carbon dioxide does not. Oxygen completely inhibits the reduction of nitric oxide due to the more rapid reoxidation of the catalytic sites compared to nitric oxide. Therefore, the reduction of nitric oxide takes place only when all oxygen has been converted and, hence, is shifted to higher temperatures. As a possible consequence, the production of nitrous oxide is reduced. Nitric oxide and molecular oxygen react preferentially with carbon monoxide, so, in an excess of oxidizing component, gasification of the carbon support occurs at higher temperatures after carbon monoxide has been completely consumed.     

Simultaneous sulfide and acetate oxidation under denitrifying conditions using an inverse fluidized bed reactor

BACKGROUND: Simultaneous removal of sulfur, nitrogen and carbon compounds from wastewaters is a commercially important biological process. The objective was to evaluate the influence of the CH₃COO^?/NO₃^? molar ratio on the sulfide oxidation process using an inverse fluidized bed reactor (IFBR). RESULTS: Three molar ratios of CH₃COO^?/NO₃^? (0.85, 0.72 and 0.62) with a constant S^2?/NO₃^? molar ratio of 0.13 were evaluated. At a CH₃COO^?/NO₃^? molar ratio of 0.85, the nitrate, acetate and sulfide removal efficiencies were approximately 100%. The N₂ yield (g N₂ g^?1 NO₃^?‐N consumed) was 0.81. Acetate was mineralized, resulting in a yield of 0.65 g inorganic‐C g^?1 CH₃COO^?‐C consumed. Sulfide was partially oxidized to S⁰, and 71% of the S^2? consumed was recovered as elemental sulfur by a settler installed in the IFBR. At a CH₃COO^?/NO₃^? molar ratio of 0.72, the efficiencies of nitrate, acetate and sulfide consumption were of 100%, with N₂ and inorganic‐C yields of 0.84 and 0.69, respectively. The sulfide was recovered as sulfate instead of S⁰, with a yield of 0.92 g SO₄^2?‐S g^?1 S^2? consumed. CONCLUSIONS: The CH₃COO^?/NO₃^? molar ratio was shown to be an important parameter that can be used to control the fate of sulfide oxidation to either S⁰ or sulfate. In this study, the potential of denitrification for the simultaneous removal of organic matter, sulfide and nitrate from wastewaters was demonstrated, obtaining CO₂, S⁰ and N₂ as the major end products. Copyright © 2008 Society of Chemical Industry     

Reactivity of steam in exhaust gas catalysis III. Steam and oxygen/steam conversions of propane on a Pd/Al2O3 catalyst

A 1% Pd catalyst (38% dispersion) was prepared by impregnating a γ-alumina with palladium acetylacetonate dissolved in acetone. The behaviour of this catalyst in oxidation and steam reforming (SR) of propane was investigated. Temperature-programmed reactions of C₃H₈ with O₂ or with O₂ + H₂O were carried out with different stoichiometric ratios S(S =[O₂]/5[C₃H₈]). The conversion profiles of C₃H₈ for the reaction carried out in substoichiometry of O₂ (S < 1) showed two discrete domains of conversion: oxidation at temperatures below 350°C and SR at temperatures above 350°C. The presence of steam in the inlet gases is not necessary for SR to occur: there is sufficient water produced in the oxidation to form H₂ and carbon oxides by this reaction. Contrary to what was observed with Pt, an apparent deactivation between 310 and 385°C could be observed with Pd in oxidation. This is due to a reduction of PdO_x into Pd⁰, which is much less active than the oxide in propane oxidation. Steam added to the reactants inhibits oxidation while it prevents the reduction of PdO_x into Pd⁰. Compared to Pt and to Rh, Pd has a higher thermal resistance: no deactivation occurred after treatment up to 700°C and limited deactivation after treatment up to 900°C, provided that the catalyst is maintained in an oxygen-rich atmosphere during the cooling.     

Complete oxidation of methane at low temperature over Pt and Pd catalysts for the abatement of lean-burn natural gas fuelled vehicles emissions: influence of water and sulphur containing compounds

The catalytic activity of fresh Pd and Pt catalysts supported on γ-alumina in the complete oxidation of CH₄ traces under lean-burn conditions was studied in the presence or the absence of water or H₂S. Steam-aged catalysts were also studied in order to simulate long-term ageing in real lean-burn natural gas fuelled vehicles (NGVs) exhaust conditions. Without water or H₂S added to the feed, Pd catalysts exhibit a superior catalytic activity in methane oxidation compared to Pt ones, whatever the catalysts were fresh or aged. The addition of 10 vol.% water vapour to the feed strongly affects the activity of the fresh Pd catalyst, thus being only slightly more efficient than the fresh Pt one. H₂S has a strong poisoning effect on the catalytic activity of Pd catalysts, while Pt catalysts are more resistant. The fresh H₂S-poisoned Pd/Al₂O₃ catalyst was studied by TPD in O₂/He. Poisoning species decompose above 873 K as SO₂ and O₂ in relative concentrations consistent with the decomposition of surface sulphate species. However, a treatment in O₂/He at temperatures as high as 923 K does not allow the complete regeneration of the catalytic activity of H₂S-poisoned Pd/Al₂O₃. A mechanism involving the poisoning of PdO by sulphate species is proposed. Different diffusion processes by which these sulphate species can migrate back and forth between PdO and the support, depending on the experimental conditions, are suggested.     

Modified Imidazoles: Degradation Inhibitors and Adhesion Promoters for Polyimide Films on Copper Substrates

Polyimide films on copper substrates that are exposed to elevated temperatures and an oxidizing environment will be subject to degradation. In order to halt this degradation without changing the properties of the system, a polymeric agent could be placed between the polyimide and the copper. This paper will investigate three such materials that will not only slow down the degradation of the polyimide and the oxidation of the copper, but will also improve adhesion within the system. Fourier transform infrared reflection-absorption spectroscopy (FTIR-RAS) will be used to investigate the polyimide/polymeric agent/copper system.     

Some kinetic aspects of unsteady-state partial oxidation reactions. Dynamic processes on metal oxide surfaces

It is shown that steady-state kinetic data do not allow the discrimination between the redox and associated mechanisms of the partial oxidation reactions. A discrimination between these mechanisms was performed using transient experiments. The obtained rate expressions are in agreement with experimental kinetic data for catalytic partial oxidation of o-xylene.

An influence of the conjugate oxidation of a catalyst surface on dynamics and kinetics of the heterogeneous catalytic oxidative reactions is considered. Computing simulation of methane oxidative coupling of methane reaction at lowered temperature and elevated pressure has been performed. It showed that the reaction order with respect to oxygen exceeding unity is consistent with the chain branching mechanism of the reaction in the presence of TiSi₂ and TiB₂ and showed the important role of the branching chain cycles in the low-temperature OCM reaction at elevated pressure.     

Technique for Producing Mullite and Other Mixed-Oxide Systems

Mixed-oxide systems are of interest in a variety of technical ceramic applications. The key in many systems is to achieve a high degree of homogeneity, approaching the molecular level. A technique for producing mixed oxides via direct oxidation of mixtures of organometallic compounds is discussed as a potential route. Preliminary work performed on producing mullite is discussed.     

Photoelectrocatalytic humic acid degradation kinetics and effect of pH,applied potential and inorganic ions

This study addresses the removal of humic acid (HA) dissolved in an aqueous medium by a photoelectrocatalytic process. UV₂₅₄ removal and the degradation of color (Vis₄₀₀) followed pseudo‐first order kinetics. Rate constants were 1.1 × 10^?1 min^?1, 8.3 × 10^?2 min^?1 and 2.49 × 10^?2 min^?1 (R² > 0.97) for UV₂₅₄ degradation and 1.7 × 10^?1 min^?1, 6.5 × 10^?2 min^?1 and 2.0 × 10^?2 min^?1 for color removal from 5 mg dm^?3, 10 mg dm^?3 and 25 mg dm^?3 HA respectively. Following a 2 h irradiation time, 96% of the color, 98% of the humic acid and 85% of the total organic carbon (TOC) was removed from an initial 25 mg dm^?3 HA solution in the photoanode cell. Photocatalytic removal on the same photoanode was also studied in order to compare the two methods of degradation. Results showed that the photoelectrocatalytic method was much more effective than the photocatalytic method especially at high pH values and with respect to UV₂₅₄ removal. The effect of other important reaction variables, eg pH, external potential and electrolyte concentration, on the photoelectrocatalytic HA degradation was also studied. Copyright © 2003 Society of Chemical Industry