Barium aluminate hydrates—VI. 2BaO.Al2O3.5H2O and 2BaO.Al2O3.H2O

The compound 2BaO.Al₂O₃.5H₂O has been synthesised and studied by infra-red, X-ray and thermal analytical techniques. The compound of approximate formula 2BaO.Al₂O₃.H₂O forms as a dehydration product. The results are interpreted in terms of the known structure.     

Barium aluminate hydrates III. BaO.Al2O3.2H2o and BaO.Al2O3.0.5H2O

Two compounds of formula BaO.Al₂O₃.2H₂O have been synthesised and studied by infra-red, X-ray and thermal analytical techniques. One form yielded another crystalline product, BaO.Al₂O₃.0.5H₂O, as an intermediate during dehydration. The results are interpreted in terms of the known crystal structure of one of the forms of the dihydrate.     

Barium aluminate hydrates II. BaO.Al2O3.H2O or 1.1 BaO.Al2O3.H2O

The compound of approximate formula BaO.Al₂O₃.H₂O has been synthesised. Infra-red and X-ray studies suggest a structure based on a framework of AlO₄ tetrahedra. Thermal dehydration and differential thermal analysis curves are presented, and are explained in terms of the suggested structure.     

Barium aluminate hydrates: Part V. 2BaO·Al2O3·2H2O and 2BaO·Al2O3

A new compound of formula 2BaO·Al₂O₃·2H₂O has been synthesised and studied by infra-red, X-ray and thermal analytical techniques. This hydrate yielded another crystalline product, 2BaO·Al₂O₃, during dehydration.     

Improving the Activity of Rh/Al2O3 Catalyst for NO Reduction by Na Addition in the Presences of H2O and O2

The effect of Na addition on the performance of Rh/Al₂O₃ catalyst for NO reduction with CO in the presence of H₂O and O₂ was investigated. The reacted catalysts were analyzed by the FTIR technique to identify the products for further investigation on the possible catalytic reaction mechanisms and the reasons behind the H₂O poisoning. Experimental results show that the removal efficiency of NO by Rh/Al₂O₃ catalyst was 63% at 250 °C but that decreased as the H₂O content increased. Adding Na to modify the Rh/Al₂O₃ catalyst significantly enhanced the conversion of NO to 99% at 250–300 °C even as the H₂O content was 1.6 vol%. The FTIR analyses results reveal that the abundant H₂O in the flue gas can compete with NO to adsorb on the surfaces of Rh/Al₂O₃ and Rh-Na/Al₂O₃ catalysts and further enhance the formation of NO₃ that reacts with H. The effects of H₂O on Rh/Al₂O₃ and Rh-Na/Al₂O₃ catalysts can be eliminated by increasing the reaction temperature to higher than 300 °C. Rh-Na/Al₂O₃ is a feasible catalyst for NO reduction at such condition with relative high H₂O and O₂ contents.     

PRELIMINARY STUDY ON PORTIONS OF SYSTEMS Na2O-CaO-AI2O3-Fe2O3 AND Na2O-CaO-Fe2O3-SiO2*

Portions of the quaternary system Na₂O-CaO-Al₂O₃-Fe₂O₃ have been studied by the exploration of (1) the plane CaO-4CaO.Al₂O₃°Fe₂O₃-(Na₂O + 3Al₂O₃) and (2) planes above the base system CaO.5CaO.3Al₂O3–2CaO.Fe₂O₃ which contain successively increasing amounts of Na₂O up to 6%. A portion of the quaternary system Na₂O-CaO-Fe₂O₃-SiO₂ has been studied by the exploration of a plane containing 5% of Na₂O above the base system CaO-2CaO.SiO₂-CaO.Fe₂O₃. In the pseudosystem CaO-4CaO.Al₂O₃.Fe₂O₃-(Na₂O + 3A1₂O₃) the compound Na₂O.-8CaO.3A1₂O₈ was found to exist as a primary phase, and the area in which the plane cuts the Na₂O.8CaO.3A1₂O₃ primary-phase volume was established. Three points on uni-variant curves were located. The iron phase (4CaO.A1₂O₃.Fe₂O₃ solid solution) was observed to exist in a solid-solution series. In the system Na₂O-CaO-5CaO.3Al₂O_3--2CaO.Fe₂O₃ it was found that the compound Na₂O.8CaO.3Al₂O3 appears at an Na₂O concentration of 4.2%. As soda, however, is taken into solid solution by other phases, it was not feasible at this time to determine the invariant point for Na₂O.8CaO.3A1₂O₃, 3CaO.Al₂O₃, 5CaO.3A1₂O₃, and 4CaO.Al₂O₃.-Fe₂O_a solid solution. In the system Na₂O-CaO-2CaO.SiO₂-CaO.Fe₂O₃ no ternary compounds were observed up to the 5% limit of Na₂O employed. A soda-containing phase occurred in solid solution with α-2CaO.SiO₂, which may precipitate on cooling, forming inclusions in the ß-2CaO.SiO₂, or enter into reaction with the glassy phase.     

Cooperation of Ag/Al2O3 and Sn/Al2O3 Catalysts for the Selective Reduction of NO by Propene

Compared to the Ag/Al₂O₃ catalyst, a two‐stage catalyst composed of an Ag/Al₂O₃ layer followed by a Sn/Al₂O₃ layer shows higher low‐temperature activity and a wider temperature window. Its activity below 350 °C is enhanced in the presence of SO₂. Even in the presence of H₂O and SO₂, the performance of the same catalytic system is still satisfactory.     

Changes in Ba Phases in BaO/Al2O3 upon Thermal Aging and H2O Treatment

The effects of thermal aging and H₂O treatment on the physicochemical properties of BaO/Al₂O₃ (the NO_x storage component in the lean NO_x trap systems) were investigated by means of X-ray diffraction (XRD), BET, TEM/EDX and NO₂ TPD. Thermal aging at 1000 °C for 10 h converted dispersed BaO/BaCO₃ on Al₂O₃ into low surface area crystalline BaAl₂O₄. TEM/EDX and XRD analysis showed that H₂O treatment at room temperature facilitated a dissolution/reprecipitation process, resulting in the formation of a highly crystalline BaCO₃ phase segregated from the Al₂O₃ support. Crystalline BaCO₃ was formed from conversion of both BaAl₂O₄ and a dispersed BaO/BaCO₃ phase, initially present on the Al₂O₃ support material after calcinations at 1000 and 500 °C, respectively. Such a phase change proceeded rapidly for dispersed BaO/BaCO₃/Al₂O₃ samples calcined at relatively low temperatures with large BaCO₃ crystallites observed in XRD within 10 min after contacting the sample with water. Significantly, we also find that the change in barium phase occurs even at room temperature in an ambient atmosphere by contact of the sample with moisture in the air, although the rate is relatively slow. These phenomena imply that special care to prevent the water contact must be taken during catalyst synthesis/storage, and during realistic operation of Pt/BaO/Al₂O₃ NO_x trap catalysts since both processes involve potential exposure of the material to CO₂ and liquid and/or vapor H₂O. Based on the results, a model that describes the behavior of Ba-containing species upon thermal aging and H₂O treatment is proposed.     

Trapping of CH3O formed from CO + H2

Methoxy formed on Al₂O₃ from¹³CO and H₂ coadsorption on Ni/Al₂O₃ was trapped by C₂H₅OH adsorption and temperature-programmed reaction (TPR). The presence of excess C₂H₅OH significantly increases the rate of¹³CH₃OH and (¹³CH₃)₂O formation. The¹³CH₃OH forms by the reaction of C₂H₅OH with¹³CH₃O on Al₂O₃. In the absence of C₂H₅OH,TPR following¹³CO and H₂ coadsorption did not produce significant amounts of¹³CH₃OHor(¹³CH₃)₂O.     

Reduction of lean NOx by ethanol over Ag/Al2O3 catalysts in the presence of H2O and SO2

The reduction of lean NOx using ethanol in simulated diesel engine exhaust was carried out over Ag/Al₂O₃ catalysts in the presence of H₂O and SO₂. The Ag/Al₂O₃ catalysts are highly active for the reduction of lean NOx by ethanol but the reaction is accompanied by side reactions to form CH₃CHO, CO along with small amounts of hydrocarbons (C₃H₆, C₂H₄, C₂H₂ and CH₄) and nitrogen compounds such as NH₃ and N₂O. The presence of H₂O enhances the NOx reduction while SO₂ suppresses the reduction. The presence of SO₂ along with H₂O suppresses the formation of acetaldehyde and NH₃. By infrared spectroscopy, it was revealed that the reactivity of NCO species formed in the course of the reaction was greatly enhanced in the presence of H₂O. The NCO species readily reacts with NO in the presence of O₂ and H₂O at room temperature, being converted to N₂ and CO₂ (CO). Addition of SO₂ suppresses the formation of NCO species and lowers the reactivity of the NCO species. However, the reduction of NOx is still kept at high conversion levels in the presence of H₂O and SO₂ over the present catalysts. About 80% of NOx in the simulated diesel engine exhaust was removed at 743 K. This revised version was published online in July 2006 with corrections to the Cover Date.     

Influence of Preparation Methods of In2O3/Al2O3 Catalyst on Selective Catalytic Reduction of NO by Propene in the Presence of Oxygen

Selective catalytic reduction of NO with propene was investigated over In₂O₃/Al₂O₃ catalysts prepared by three methods, namely, a single sol-gel (SG), impregnation (IM), and co-precipitation method (CP). The catalysts were characterized by means of BET, XRD, XPS, and TPD. The maximum NO conversion over In₂O₃/Al₂ O₃ prepared by sol-gel method was 95% at 400 °C in the absence of H₂O, and the activity decreased slightly in the presence of H₂O, and it was still 76% even in the presence of H₂O and SO₂. Although the retarding effect of SO₂ on the activity was observed for the three catalysts, In₂O₃/Al₂O₃ (SG) showed relatively high activity. It is found that the high surface area and low average pore diameter are important to the catalytic activity, and the strong interaction between indium and alumina for In₂O₃/Al₂O₃ catalyst prepared by sol-gel method may be the reason of high activity for NO reduction. The reaction and surface studies showed that NO₃⁻ and partially oxidized hydrocarbons (RCOO⁻ species) are mainly intermediates, and the oxidation C₃H₆ to RCOO⁻ species maybe the key reaction process in the SCR of NO with C₃H₆.     

EQUILIBRIUM RELATIONSHIPS ON THE LIQUIDUS SURFACE IN PART OF THE MnO-Al2O3-SiO2 SYSTEM*

The minerals found to have a stability range on the liquidus surface in the system MnO-Al₂O₃-SiO₂ are cristobalite and tridymite, SiO₂; mullite, 3Al₂O₃. 2SiO₂; corundum, Al₂O₃; rhodonite, MnO.SiO₂; tephroite, 2MnO.SiO₂; galaxite, MnO.Al₂O₃; spessartite, 3MnO.Al₂O₃.3SiO₂; and a new compound, 2MnO.2Al₂O₃.5SiO₂. The quintuple points and boundary lines found in that part of the MnO.Al₂O₃.SiO₂ system bounded by the systems 3MnO.Al₂O₃.3SiO₂-SiO₂, 3MnO.Al₂O₃.3SiO₂-Al₂O₃, and Al₂O₃-SiO₂have been determined. Quintuple points and boundary lines involving the area inclosed by the systems 2MnO . SiO₂-3MnO . Al₂O₃ . 3SiO₂, 3MnO . Al₂O₃ . 3SiO₂-SiO₂, and 2MnO.-SiO₂-SiO₂ are indicated. Isotherms and isofracts (lines of equal refractive index) are given for the portion of the system investigated. X-ray data show that crystals of the compound 3MnO.Al₂O₃.3SiO₂ have the same structure as the garnet mineral spessartite (manganese garnet). The compound 2MnO. 2Al₂O₃ . 5SiO₂, which is shown by X-ray data to have a basic structure similar to cordierite, 2MgO.2Al₂O₃.5SiO₂, seldom crystallizes from the glass, but a third substance which has a high extinction angle crystallizes readily from the reheated glass. These high extinction angle crystals are replaced by 2MnO .2Al₂O₃.5SiO₂ when a proper heating cycle is employed, and they are not found again until the product is melted and crystallization is repeated.     

Performance of V2O5/NPTiO2–Al2O3-nanoparticle- and V2O5/NTiO2–Al2O3-nanotube model catalysts in the SCR–NO with NH3

In this study, the NO reduction by NH₃ over V₂O₅/NPTiO₂–Al₂O₃ (nanoparticles) and V₂O₅/NTiO₂–Al₂O₃ (nanotubes) catalysts synthesized by the sol–gel method with 10 and 5 wt.% of Al₂O₃ and V₂O₅, respectively, is reported. The V₂O₅/NPTiO₂–Al₂O₃ and V₂O₅/NTiO₂–Al₂O₃ catalysts showed remarkable conversion, high acidity, structure stability, N₂ selectivity and a high resistance to deactivation in the presence of 10 vol.% of H₂O within the 200 to 500 °C temperature interval. The nanostructured catalysts developed in this work are an excellent alternative to improve the SCR–NH₃ process, both expanding its operation window and preventing deactivation by H₂O at high temperatures.     

Catalytic decomposition of propellant N2O Over Ir/Al2O3 catalyst

N₂O, as a green propellant alternative to N₂H₄, shows potential application in satellite propulsion system. The state of Ir species and the reaction behaviors on Ir/Al₂O₃ in the oxidative environment during N₂O decomposition were identified here. Two types of Ir sites existed in this catalyst and affected the process of N₂O decomposition. The strong Ir sites facilitated the dissociative adsorption of N₂O to form N₂ and adsorbed O atoms with adsorption heat of as high as 281 kJ/mol, which promoted the desorption of adsorbed O atoms and favored the self‐sustaining decomposition of N₂O by raising the catalyst bed temperature. The other Ir sites interacted weakly with O atoms but facilitated their combination to form O₂. The Ir/Al₂O₃ catalyst then exhibited an excellent performance in initiating the decomposition of N₂O at low temperature of 200°C and good stability in 0.1 N microthruster for orbit adjustment and attitude control of satellite. © 2016 American Institute of Chemical Engineers AIChE J, 62: 3973–3981, 2016     

Effect of La2O3 promoter on NiO/Al2O3 catalyst in CO methanation

A series of NiO/Al2O3 catalysts promoted by different La₂O₃ contents were prepared by impregnation method. The physicochemical properties of NiO-La₂O₃/Al₂O₃ were characterized by N₂ adsorption-desorption, X-ray diffraction (XRD), H₂ temperature programmed reduction (H₂-TPR) and H₂ chemisorption. The effect of La₂O₃ on the activity of NiO/Al₂O₃ for CO methanation was investigated in a fixed bed reactor. A lifetime test, as well as thermogravimetric (TG) analysis, was performed to investigate the stability performance and anti-carbon deposition of catalysts. The results showed that the addition of La₂O₃ can restrain the growth of NiO particles, increase the H₂ uptake and Ni dispersion, and therefore enhance the activity of catalysts. When the La₂O₃ content was 3 wt%, a CO conversion of 98% and a selectivity to CH₄ of 96% were obtained at 400 °C. Furthermore, the catalyst NiO-La₂O₃/Al₂O₃ with 3 wt% La₂O₃ content displayed highly stable performance in long-term tests, especially exhibiting good anti-carbon deposition property.     

Effect of SO2 on NOx reduction by ethanol over Ag/Al2O3 catalyst

A new Ag/Al₂O₃ catalyst for removing NO_x in diesel engine exhaust gas was developed. The influence of SO₂ on the reduction of lean NO_x by ethanol over the Ag/Al₂O₃ catalyst was evaluated in simulated diesel exhaust and characterized using TPD, XRD, XPS, SEM and BET measurements. The Ag/Al₂O₃ catalyst was highly active for the reduction of NO_x with ethanol in the presence of SO₂ although the reduction of NO_x is suppressed at lower temperatures. The activity for NO_x reduction is high even on the Ag/Al₂O₃ catalyst exposed to a SO₂ (200 ppm)/O₂ (10%)/H₂O (10%) flow for 20 h at 723 K and comparable to that on the fresh Ag/Al₂O₃ catalyst. No crystallized Ag metal and Ag compounds were formed by the SO₂/O₂/H₂O exposure. On the other hand, crystallized Ag₂SO₄ was easily formed when the Ag/Al₂O₃ catalyst was exposed to a SO₂ (200 ppm)/O₂ (10%)/NO (800 ppm)/H₂O (10%) flow for 10 h at 723 K. XRD, SEM and XPS studies showed that the formation of crystallized Ag₂SO₄ results in growing of Ag particles in larger size and lowering the surface content of Ag particles. In addition, the specific surface area of the Ag/Al₂O₃ catalyst decreases from 221 to 193 m²/g. Although the dispersion of Ag particles was decreased by the formation of Ag₂SO₄, the activity for the reduction of lean NO_x was, remarkably, not affected. This suggests that the Ag–alumina sites created by the Ag₂SO₄ formation are still active for the lean catalytic reduction of NO_x. This revised version was published online in July 2006 with corrections to the Cover Date.     

Formation of stratlingite, 2CaO.SiO2.Al2O3.8H2O,in relation to the hydration of high alumina cement

2CaO.Al₂O₃.8H₂O may be formed by hydrating mixtures of β-C₂S, alumina gel and 10% Ca(OH)₂, by reacting prehydrated alite with alumina gel and by reacting CAH₁₀ with CSH. It is shown that C₂ASH₈ has strength giving properties. Attempts to produce sufficient C₂ASH₈ to give a significant increase in strength using Commercial HAC and prehydrated ordinary Portland cement have been unsuccessful.     

The Effects of Na2O and SiO2 on Liquid Phase Sintering of Bayer Al2O3

To determine how grain‐boundary composition affects the liquid phase sintering of MgO‐free Bayer process aluminas, samples were singly or co‐doped with up to 1029 ppm Na₂O and 603 ppm SiO₂ and heated at 1525°C up to 8 h. Na₂O retards densification of samples from the onset of sintering and up to hold times of 30 min at 1525°C compared to the undoped samples, but similar to the as‐received, MgO‐free Al₂O₃, Na₂O‐doped samples sinter to 98% density with average grain sizes of ~3 μm after 8 h. Increasing SiO₂ concentration significantly retards densification at all hold times up to 8 h. The estimated viscosities (20?400 Pa·s) of the 0.3 to 1.8 nm thick siliceous grain‐boundary films in this study indicate that diffusion greatly depends on the composition of the liquid grain‐boundary phase. For low Na₂O/SiO₂ ratios, densification of Bayer Al₂O₃ at 1525°C is controlled by diffusion of Al³⁺ through the grain‐boundary liquid, whereas for high Na₂O/SiO₂ ratios, densification can be governed by either the interface reaction (i.e., dissolution) of Al₂O₃ or diffusion of Al³⁺. Increasing Na₂O in SiO₂‐doped samples increases diffusion of Al³⁺ and Al₂O₃ solubility in the liquid, and thus densification increases by 1%. Based on these findings, we conclude that Bayer Al₂O₃ densification can be manipulated by adjusting the Na₂O to SiO₂ ratio.     

Preferential CO oxidation over Pt–SnO2/Al2O3 in hydrogen rich streams containing CO2 and H2O (CO removal from H2 with PROX)

The effects of reaction gases including CO₂ and H₂O and temperature on the selective low-temperature oxidation of CO were studied in hydrogen rich streams using a flow micro-reactor packed with a Pt–SnO₂/Al₂O₃ sol–gel catalyst that was initially designed and optimized for operation in the absence of CO₂ and H₂O. 100% CO conversion was achieved over the 1 wt% Pt–3 wt% SnO₂/Al₂O₃ catalyst at 110 °C using a feed composition of 1.0% CO, 1.5% O₂, 25% CO₂, 10% H₂O, 58% H₂ and He as balance at a space velocity of 24,000 cm³/(g h). CO₂ in the feed was found to decrease CO conversion significantly while the presence of H₂O in the feed increased CO conversion, balancing the effect of CO₂.     

Marked Effect of Mo and Fe Addition Upon Liquid Phase Methanol Reforming with Water Over Al2O3 Supported Pt Catalysts

Successively impregnated Pt–Mo/Al₂O₃ and Pt–Fe/Al₂O₃ catalysts exhibited large enhancement effect in H₂ formation rate of liquid phase methanol reforming. Added Mo oxide forms monolayer on Al₂O₃ and facilitates the higher dispersion of Pt particles. In the case of Fe, formation of some surface bimetallic clusters between Pt and Fe was confirmed by XAS analysis, which causes the enhancement effect of H₂ formation in MeOH–H₂O reaction.