Low temperature oxidation of coals—a calorimetric study

The rates of heat liberation and oxygen consumption due to coal oxidation were measured in the temperature range 20–170 °C using coals ranging from subbituminous to anthracite. It was found that the Elovitch equation fit the results for the heat generation rate excellently when it was modified slightly to include a corrective term representing the heat generation rate at the steady state. The oxygen consumption rate at a given temperature was found to be proportional to the product of the internal surface area and oxygen content of the coals, indicating that the oxygen containing surface groups are acting as reactive sites. Using these results, the heat evolved per mole of oxygen at steady state was calculated to be 75–90 kcal/mol.     

Filamentous carbon templated SiO2–NiO aerogel: structure and catalytic properties for direct oxidation of hydrogen sulfide into sulfur

Silica aerogels comprising nickel oxide nanoparticles were synthesized with no use of supercritical drying. A high specific surface area (more than 1000 m²/g), mesoporous structure and considerable stability to sintering up to 900 °C are characteristic of these aerogels. The aerogels were synthesized using the sol–gel method. Filamentous carbon was templated by silica, tetraethoxysilane being used for supplying silica. Carbon was burnt later. Analysis of the aerogel structure revealed the presence of silica nanotubes and nanofibers. Aerogel testing for direct oxidation of H₂S into S⁰ demonstrated as high as 60% conversion of hydrogen sulfide at almost 100% selectivity under stoichiometric conditions at the temperature range of 300–350 °C and 73% conversion at 100% selectivity at a considerable excess of oxygen at 160 °C. This revised version was published online in July 2006 with corrections to the Cover Date.     

Effect of supports in hydrogen sulfide oxidation on vanadium−based catalysts

Selective oxidation of hydrogen sulfide to sulfur was carried out over V₂O₅ and V−Sb−O mixed−oxide catalysts supported on TiO₂, ZrO₂ and −Al₂O₃. TiO₂−supported catalysts exhibited the highest sulfur yield and the highest areal rate. Catalyst reducibility was studied by temperature−programmed reduction. This revised version was published online in July 2006 with corrections to the Cover Date.     

Effect of Ni loading and calcination temperature on catalyst performance and catalyst deactivation of Ni/SiO2 in the hydrodechlorination of 1,2‐dichloropropane into propylene

The hydrodechlorination of 1,2‐dichloropropane (DCPA), a chlorinated organic waste which is produced in the epichlorohydrin process, to propylene was carried out over Ni/SiO₂ catalysts. The effects of Ni loading and calcination temperature on catalyst performance and catalyst deactivation of Ni/SiO₂ were systematically investigated. The Ni/SiO₂ catalysts efficiently converted DCPA into propylene in 95% selectivity or higher. The particle size of Ni on SiO₂ was strongly related to the catalyst stability. In terms of the effect of Ni loading, the largest Ni particles on SiO₂ showed the best durability against deactivation. A series of TPR and UV‐DRS measurements revealed that nickel hydrosilicate was formed as the result of the interaction between Ni and SiO₂. Nickel hydrosilicate was found to be responsible for the catalyst stability leading to low catalyst deactivation. HCl adsorption on Ni/SiO₂ was the main reason for catalyst deactivation. HCl modified the crystal structure of metallic Ni to NiCl₂ and led to irreversible deactivation and metal sintering. This revised version was published online in July 2006 with corrections to the Cover Date.     

Direct liquid‐phase side‐chain oxidation of alkylbenzenes over 2 catalyst

Only the side‐chain oxidation of alkylbenzenes (R–C₆H₃–R′–R″ R=H, Me, Et, Prⁱ R′=H, Me; and R″=H, Me) by oxygen (35–50 atm, 200)C° is promoted in the presence of [Pd(phen)(OAc)₂]. This revised version was published online in July 2006 with corrections to the Cover Date.     

Effect of silicon/graphite ratio and temperature on oxidation protective properties of SiC/ZrB2–SiC coatings prepared by pack cementation

To investigate the silicon/graphite ratio and temperature on preparation and properties of ZrB₂–SiC coatings, ZrB₂, silicon, and graphite powders were used as pack powders to prepare ZrB₂–SiC coatings on SiC coated graphite samples at different temperatures by pack cementation method. The composition, microstructure, thermal shock, and oxidation resistance of these coatings were characterized and assessed. High silicon/graphite ratio (in this case, 2) did not guarantee higher coating density, instead could be harmful to coating formation and led to the lump of pack powders, especially at temperatures of 2100 and 2200 °C. But residual silicon in the coating is beneficial for high density and oxidation protection ability. The SiC/ZrB₂–SiC (ZS50-2) coating prepared at 2000 °C showed excellent oxidation protective ability, owing to the residual silicon in the coating and dense coating structure. The weight loss of ZS50-2 after 15 thermal shocks between 1500 °C and room temperature, and oxidation for 19 h at 1500 °C are 6.5% and 2.9%, respectively.     

Selective oxidation of propane on MgO/γ‐Al2O3‐supported molybdenum catalyst: influence of promoters

The influence of promoters, potassium and samarium, on molybdenum supported over MgO–γ‐Al₂O₃ catalyst has been investigated in the oxidative dehydrogenation of propane. The acidities of catalysts were determined by temperature‐programmed desorption of NH₃ and by decomposition of 2‐propanol. The K‐promoted catalyst showed the lower acidity followed by the Sm, whereas the unpromoted sample showed the highest acidity. The higher the acid character of the catalyst, the lower the selectivity to propene. Redox properties determined from EPR spectra change with the addition of the promoter. A parallelism between Mo⁶⁺ reducibility and catalytic activity was found. This revised version was published online in July 2006 with corrections to the Cover Date.     

High-stable CuPd–Cu2O/Ti-powder catalyst for low-temperature gas-phase selective oxidation of alcohols

The oxidation of alcohols to carbonyl compounds in gas-phase is of great importance in organic chemistry and industrial process. Herein, the catalyst CuPd–Cu₂O/Ti-powder is prepared by depositing Cu(NO₃)₂ and Pd(NO₃)₂ on Ti powder support followed by in-situ activation in reaction stream, which delivers high-performance for the gas-phase oxidation of alcohols. Compared with Cu/Ti-powder and Pd/Ti-powder, CuPd–Cu₂O/Ti-powder exhibits higher stability and activity in alcohol oxidation reaction. The catalyst is characterized by XRD, XPS, TEM and ICP. The results indicate that CuPd(alloy)–Cu₂O formed during the reaction contributes to the high activity and stability.     

Effect of La2O3 addition on long-term oxidation kinetics of ZrB2–SiC and HfB2–SiC ultra-high temperature ceramics

Long-term oxidation kinetics of SiC-reinforced UHTCs and La₂O₃-doped UHTCs over an intermediate temperature range (1400–1600 °C) reveal partially protective behavior for the former characterized by an oxidation kinetic exponent 1 < n < 2. In addition, unstable oxidation behavior was observed in HfB₂-based UHTCs due to the presence of SiC agglomerates. On the other hand, La₂O₃-doped UHTCs were found to be protective over the whole temperature range studied (n = 2), in particular at 1600 °C, where oxidation kinetic exponents as high as 8 were observed as a consequence of formation of new oxidation protective particles, MeO_xC_y, where Me is Zr, Hf or Si. Adsorption of oxygen-containing species formed protective MeO_xC_y phases, which enhanced the thermal stability of the oxide scale as well as providing protection against oxidation for long exposure times at 1600 °C.     

Low temperature catalytic oxidation of nitric oxide over the Mn–CoOx catalyst modified by nonthermal plasma

Nonthermal plasma (NTP) treatment was investigated to modify the Mn–CoO_x catalyst for the low-temperature oxidation of nitric oxide. The catalysts were characterized by XRD, BET, TGA and XPS techniques. The results showed that the activity of NTP-treated catalysts improved significantly, and that NTP treatment has the advantage of changing the structural and morphological properties (higher surface areas and pore volume) and varying the relative surface concentration and oxidation states of surface species over catalysts. High surface areas and pore volume, high concentration of chemisorbed oxygen, Mn^4 + and Co^2 +, and the efficient synergetic catalytic effect between Co and Mn ions were thought to be the main reasons for the high activity of NTP-treated catalysts.     

Low‐temperature oxidation of methane to form formaldehyde: role of Fe and Mo on Fe–Mo/SiO2 catalysts, and their synergistic effects

The partial oxidation of methane with molecular oxygen was performed on Fe–Mo/SiO₂ catalysts. Iron was loaded on the Mo/SiO₂ catalyst by chemical vapor deposition of Fe₃(CO)₁₂. The catalyst showed good low‐temperature activities at 723–823 K. Formaldehyde was a major condensable liquid product on the prepared catalyst. There were synergistic effects between iron and molybdenum in Fe–Mo/SiO₂ catalysts for the production of formaldehyde from the methane partial oxidation. The activation energy of Mo/SiO₂ decreased with the addition of iron and approached that of the Fe/SiO₂. The concentration of isolated molybdenum species (the peak at 1148 K in TPR experiments) decreased as the ion concentration increased and had a linear relationship with the selectivity of methane to formaldehyde. The role of Fe and Mo in the Fe–Mo/SiO₂ catalyst was proposed: Fe is the center for the C–H activation to generate reaction intermediates, and Mo is the one for the transformation of intermediates into formaldehyde. Those phenomena were predominant below 775 K. This revised version was published online in July 2006 with corrections to the Cover Date.     

Influence of calcination temperature on the hydrolysis of carbonyl sulfide over hydrotalcite-derived Zn–Ni–Al catalyst

A novel catalyst for low temperature hydrolysis of carbonyl sulfide (COS) was prepared by thermal decomposition of Zn–Ni–Al hydrotalcite-like compounds (HTLCs). As the key factors of catalyst activity, effects of calcination temperature have been studied. The samples were carefully characterized by XRD, FTIR, SEM, CO₂-TPD and N₂ adsorption/desorption. Results showed that HTLCs calcined at 350 °C exhibited excellent activity due to the production of more M–O pairs which are active sites of the hydrolysis of COS. However, calcination at 500 °C led to the destruction of pore structure and reduction of active sites, ultimately led to a lower COS conversion.     

Influence of the source of sulfur on the hydroconversion of 1-methylnaphthalene over a Pt–Pd/USY catalyst

Hydroconversion of 1-methylnaphthalene was performed over a Pt–Pd/USY catalyst in a batch reactor at 310 °C and 5 MPa of hydrogen pressure in cyclohexane as the solvent and in the presence of 800 ppm of sulfur resulting from different sources, hydrogen sulfide, thiophene and dibenzothiophene. In a general manner, hydrogenation of 1-methylnaphthalene into the corresponding mixture of methyltetralines is not significantly affected by the nature of the sulfur species present in the starting feed. On the contrary, going from hydrogen sulfide to thiophene and finally to dibenzothiophene, hydrogenation of methyltetralines into methyldecalines is lowered and ring-opening of methyltetralines to alkylbenzenes is enhanced. This would agree with the expected sequence of appearance of hydrogen sulfide in the feed.These results are in agreement with dissociation of hydrogen into protonic and hydride species, as already proposed in the presence of sulfided catalysts, i.e., protonic species would be involved for the hydrogenation steps and hydride species for the ring-opening steps. Hydrogen sulfide present as such or resulting from the transformation of thiophene or dibenzothiophene would then reduce the hydrogenation route, and, as a consequence, increase the hydrogenolysis route.     

Influence of CO2 on storage and release of NOx on barium‐containing catalyst

A barium‐containing three‐way automotive emission catalyst was submitted to a NO_x storage step in flowing lean gas mixture containing 340 ppm NO and 8 vol% O₂ in helium. NO_x release was carried out in the 250–550°C temperature range, either in pure helium or in the presence of a 10 vol% CO₂ in helium mixture. It was shown that at 450–550°C all of the stored NO_x on the barium trap can be released fastly in the CO₂‐containing gas mixture or, after a longer time, in pure helium: these data show that NO_x release can occur in the absence of a reducing agent. The NO_x release was not complete at 350°C and did not occur at 250°C. The assisting effect of CO₂ as regards to NO_x release was interpreted in terms of the existence of the CO_2,gas + *NO_2,stored ⇌ *CO_2,stored + NO_2,gas equilibrium, suggesting the competitive storage of CO₂ and NO₂ for a unique type of barium storage sites (*). This revised version was published online in July 2006 with corrections to the Cover Date.     

High temperature oxidation of SiC under helium with low-pressure oxygen. Part 3: β-SiC-SiC/PyC/SiC

In the frame of generation IV gas-cooled fast reactor (GFR), the cladding materials currently considered is a SiC/SiC-based composite with a pyrocarbon interphase and a β-SiC coating on the surface to close the porosity (noted β-SiC-SiC/PyC/SiC). These elements are subjected to temperatures going from 1300 to 1500 K in nominal operating conditions to 1900-2300 K in accidental conditions. The coolant gas considered is helium pressurized at 7 MPa.After a thermodynamic study carried out on the oxidation of β-SiC under helium and low oxygen partial pressures, an experimental approach was made on β-SiC-SiC/PyC/SiC composites under active oxidation conditions (1400 ≤ T ≤ 2300 K; 0.2 ≤ pO₂ ≤ 2 Pa). This study follows two preceding studies carried out on two polytypes of SiC: α (Part 1) and β (Part 2) under the same conditions. In these studies, the influence of the crystalline structure on the transition temperature between passive and active oxidation and on the mass loss rate was discussed.The experimental study allows to determine the oxidation rates in incidental and accidental conditions under pO₂ = 0.2 and 2 Pa. The variation of the mass loss rates according to the temperature for β-SiC-SiC/PyC/SiC oxidized under pO₂ = 0.2 and 2 Pa shows the existence of three domains in the zone of active oxidation. These tests also show the weak impact of the oxygen partial pressure on the mass loss rate of the material in this range of pressure for temperatures lower than 2070 K. On the other hand, beyond 2070 K, an increase of the mass loss rate leading to important damage of the material has been observed, at lower temperature under pO₂ = 0.2 Pa than under pO₂ = 2 Pa. This variation was associated to the effect of the oxygen partial pressure on the sublimation temperature of SiC. Similar experiments were performed on pre-oxidized samples and on the face without CVD β-SiC coating and both the results are close to the ones obtained for the face with the CVD β-SiC layer.     

Oxidation of ZrB2–SiC ultra-high temperature composites over a wide range of SiC content

The oxidation performance of ZrB₂–SiC ultra-high temperature ceramics with SiC content ranging from 20 to 80 vol% has been evaluated at 1773 K for 50 h and at 2073 K for 20 min. Oxidation reaction pathways were interpreted using volatility diagrams of the ZrB₂–SiC system. At 1773 K for 50 h, all ZrB₂–SiC composites from 20 to 80 vol% SiC formed a protective SiO₂ surface coating. Samples with ≤50 vol% SiC developed a distinguishable SiC-depleted layer at 1773 K and 2073 K. High temperature torch testing for 20 min at approximately 2073 K revealed that samples with ≥65 vol% SiC exhibit a depression under the torch flame. Samples rich in ZrB₂ were dominated by a ZrO₂ layer after a similar exposure. The overall weight density of ultra-high temperature ceramics can be reduced with improved oxidation performance at 1773 K by adding at least 65 vol% SiC.     

An effective heterogeneous WO3/TiO2–SiO2 catalyst for selective oxidation of cyclopentene to glutaraldehyde by H2O2

TiO₂–SiO₂ mixed oxide with large pore size was synthesized by the xerogel method and it was then used to prepare the WO₃/TiO₂–SiO₂ catalyst by an incipient wetness method. The as‐prepared WO₃/TiO₂–SiO₂ sample was employed as the first heterogeneous catalyst in the liquid‐phase cyclopentene oxidation by aqueous H₂O₂, which exhibited higher selectivity (about 75%) to glutaraldehyde (GA) and, in turn, higher GA yield than the WO₃/SiO₂ heterogeneous catalyst and even the tungstic acid homogeneous catalyst under the same reaction conditions. The amorphous WO₃ phase was identified as the active sites and the loss of the active sites was proved to be not important. The lifetime of the catalyst was determined and its regeneration method was proposed. The effects of various factors on the catalytic behaviors, such as the WO₃ loading, the calcination temperature, the surface acidity and the reaction media, were investigated and discussed based on various characterizations including BET, XRD, XPS, FTIR, EXAFS and Raman spectra etc. This revised version was published online in July 2006 with corrections to the Cover Date.     

Complete oxidation of formaldehyde at ambient temperature over γ-Al2O3 supported Au catalyst

Au supported on γ-Al₂O₃ prepared by deposition–precipitation (DP) using urea is found to be a highly active catalyst for the total oxidation of HCHO at room temperature under humid air, without the need for a reducible oxide as support. In-situ DRIFTS studies suggested that the surface hydroxyl groups played a key role in the partial oxidation of HCHO into the formate intermediates, which can be further oxidized into CO₂ and H₂O with participation of nano-Au. This study challenges the traditional idea of supporting noble metals on reducible oxides for HCHO oxidation at room temperature.     

On the mechanism of CO adsorption on a silica‐supported ruthenium catalyst

The adsorption of CO at room temperature on a Ru/SiO₂ catalyst has been studied by means of FTIR spectroscopy. Spectral evidence for formation of water molecules and a quantity of very dispersed ruthenium on the catalyst surface during CO adsorption was found. On the basis of these experimental results a new reaction scheme for the interaction of CO with a silica‐supported ruthenium catalyst is proposed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Kinetic model of an oxygen‐free methane conversion on a platinum catalyst

In many metal‐catalyzed conversion processes of hydrocarbons at atmospheric pressure a carbonaceous overlayer quickly builds up at the catalyst covering nearly the whole surface. However, the metal still remains catalytically active. Several models have been proposed over the years to explain the crucial role of the carbonaceous overlayer during the conversion of hydrocarbons. The model presented here contemplates adsorbate effects, which means that surface carbon modifies the dehydrogenation activity of Pt. A hydrocarbon reaction mechanism on platinum, including C₁ and C₂ species, is established. The mechanism is based on elementary reactions offering the opportunity of using the same mechanism for a wide range of applications. It is also applied to extended simulations of higher pressures and smaller flow velocities revealing increased C₂H₆ yields under these conditions. This revised version was published online in July 2006 with corrections to the Cover Date.