Nano- and micrometre additions of SiO2, ZrO2 and TiO2 in fine grained alumina refractory ceramics for improved thermal shock performance

The present contribution investigates the influence of micro-metre- as well as nano-metre-additions of zirconia (ZrO₂), titania (TiO₂), silica (SiO₂) and magnesia (MgO) into alumina-rich fine grained ceramic materials for refractory applications. Slip casted samples in the system alumina–zirconia–titania (AZT), alumina–zirconia–titania–silica (AZTS) and alumina–zirconia–titania–magnesia (AZTM) were sintered and the physical as well as mechanical properties were investigated as fired and after thermal shock treatments. The generation of a micro-crack network after sintering due to the formation of phases with different thermal expansion coefficients and the formation and decomposition of aluminium titanate (Al₂TiO₅) before and after thermal shock exposure leads to higher strengths after thermal shock attack.     

Characterization of some perovskite oxides based on YBa2Cu3O7 − x in relation to their use in methanol production

The oxidized and weakly reducible perovskite oxide YBa₂Cu₃O_{7 − x} (YBCO) has been prepared as a catalyst, supported on γ‐Al₂O₃. It was further modified by (i) impregnation with Ru and Pd and (ii) cobalt incorporation via co‐precipitation. All the catalysts were either 20% (w/w) YBCO/γ‐Al₂O₃ or 2% (w/w) Ru, Pd or Co/20% (w/w) YBCO/γ‐Al₂O₃. The catalysts were characterized using temperature programmed reduction (TPR), surface area measurements and X‐ray diffraction (XRD) studies before and after various treatments. They were studied as catalysts in the pressure range 20–50 atmospheres and in the temperature range 523–573 K in an autoclave equipped with a spinning basket catalyst container. The Pd‐, Ru‐ and Co‐modified catalysts gave predominantly methanation products, along with some C₂–C₄ hydrocarbons. However the YBCO/γ‐Al₂O₃ catalyst exhibited significant methanol selectivity at 50 atmospheres and at 523 K X‐ray diffraction studies revealed the presence of Cu(0), Cu(I) and Cu(II) after reduction and the species Cu(0) and Cu(I) are probably essential to CH₃OH production. © 2000 Society of Chemical Industry     

Heterogen katalysierte Hydrierung von Kohlendioxid zu Methan unter erhöhten Drücken

Ni‐ and Ru‐containing supported catalysts were prepared and used for the CO₂ hydrogenation to methane (Sabatier reaction) in the gas phase. Tests on the effect of the reaction temperature and pressure were in the focus. ZrO₂ and γ‐Al₂O₃ were used as suitable catalyst supports. CO₂ and H₂ conversions of 70 – 80 % and selectivity to methane of > 99 % were reached. TiO₂ and SiO₂ based catalysts exclusively lead to CO and seem to be not suited for this reaction. The investigations on the pressure effect impressively demonstrated the influence on the chemical equilibrium. CO₂ and H₂ can be nearly completely converted with > 99.9 % selectivity to methane over Ru/ZrO₂.     

Physical effects on Fischer–tropsch synthesis over composite Ru catalysts

Fischer–Tropsch synthesis was studied over composite catalysts formed by adding SiO₂ to Ru/Al₂O₃ and to Ru/TiO₂. The two Ru primary catalysts alone had reasonably similar catalytic properties for this synthesis. It was found that the presence of excess amounts of SiO₂ with the primary Ru catalysts can produce significant changes in conversion and product selectivity, depending upon the support used. It is suggested that the effects produced by the physical presence of this inert material are due to a combination of primary catalyst activity, product selectivities, possible secondary reactions, heat and mass transfer effects, and reaction conditions. These results emphasize the importance of considering both physical and chemical effects when developing any composite catalyst mechanism.     

Effect of metal‐support interface on hydrogen permeation through palladium membranes

Thin palladium membranes of different thicknesses were prepared on sol‐gel derived mesoporous γ‐alumina/α‐alumina and yttria‐stabilized zirconia/α‐alumina supports by a method combining sputter deposition and electroless plating. The effect of metal‐support interface on hydrogen transport permeation properties was investigated by comparing hydrogen permeation data for these membranes measured under different conditions. Hydrogen permeation fluxes for the Pd/γ‐Al₂O₃/α‐Al₂O₃ membranes are significantly smaller than those for the Pd/YSZ/α‐Al₂O₃ membranes under similar conditions. As the palladium membrane thickness increases, the difference in permeation fluxes between these two groups of membranes decreases and the pressure exponent for permeation flux approaches 0.5 from 1. Analysis of the permeation data with a permeation model shows that both groups of membranes have similar hydrogen permeability for bulk diffusion, but the Pd/γ‐Al₂O₃/α‐Al₂O₃ membranes exhibit a much lower surface reaction rate constant with higher activation energy, due possibly to the formation of Pd‐Al alloy, than the Pd/YSZ/α‐Al₂O₃ membranes. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Properties and microstructural aspects of TiO2‐doped sintered Alumina‐Zirconia composite ceramics

The effect of titania content on the densification, the phase transformation, the microstructures, and mechanical properties of 50 wt% Al₂O₃‐50 wt% ZrO₂ (12 mol% CeO₂) was evaluated. Ceramic composites with different TiO₂ content (0.27, 5, 10 wt%) were prepared by pressureless sintering at low temperature (1400°C) for 2 hours in air. Dense ceramic was obtained by adding 5 wt% of TiO₂ loading to improved mechanical properties. The microstructure analysis provided lots of information about solid‐state reactivity in alumina‐zirconia‐titania ternary system. The content of TiO₂ strongly affected the phases evolution and the grain growth during sintering. Furthermore, a significant effect on mechanical properties and fracture behavior was also observed.     

Promoting effect of rhenium on catalytic performance of Ru catalysts in hydrogenolysis of glycerol to propanediol

Ru/Al₂O₃, Ru/C and Ru/ZrO₂ catalysts were applied to the hydrogenolysis of glycerol to propanediol, and the effect of Re as an additive on the catalytic performance of Ru catalysts was examined. The catalyst systems were characterized by N₂ adsorption/desorption, XRD, TEM-EDX and XPS. The hydrogenolysis of glycerol was carried out under the conditions of 120–180 °C, 4–10 MPa hydrogen pressure and 4–8 h, and the conversion of glycerol varied from 18.7% to 29.7% over Ru/Al₂O₃, Ru/C and Ru/ZrO₂ catalysts. The reaction results indicate that Re possesses high promoting effect on the catalytic performance of Ru catalysts in glycerol hydrogenolysis.     

Cyclohexene hydrogenation using Group VIII metal complexes as catalysts in heterogeneous and homogeneous conditions

The stability and catalytic behaviour of a ruthenium complex with chloride and tridecylamine as ligands were studied. The hydrogenation of cyclohexene carried out in mild conditions, both in homogeneous and heterogeneous conditions, was used as a test reaction. FTIR and XPS results show that the active species is the complex itself, which is stable under the reaction conditions. XPS determination shows that the ruthenium complex is tetra‐coordinated, suggesting that its formula is [RuCl₂(NH₂(CH₂)₁₂CH₃)₂]. This ruthenium complex supported on γ‐Al₂O₃ is more active and sulfur‐resistant than the same complex unsupported and even more than a nickel complex with the above mentioned ligands. The Ru complex, supported or not, is also more active and sulfur‐resistant than a conventional Ru/γ‐Al₂O₃ catalyst evaluated in the same operational conditions. © 2001 Society of Chemical Industry     

Catalytic activity of ethylene oxidation over Au,Ag and Au–Ag catalysts: Support effect

Au, Ag and Au–Ag catalysts on different supports of alumina, titania and ceria were studied for their catalytic activity of ethylene oxidation reactions. An addition of an appropriate amount of Au on Ag/Al₂O₃ catalyst was found to enhance the catalytic activity of the ethylene epoxidation reaction because Au acts as a diluting agent on the Ag surface creating new single silver sites which favor molecular oxygen adsorption. The Ag catalysts on both titania and ceria supports exhibited very poor catalytic activity toward the epoxidation reaction of ethylene, so pure Au catalysts on these two supports were investigated. The Au/TiO₂ catalysts provided the highest selectivity of ethylene oxide with relatively low ethylene conversion whereas, the Au/CeO₂ catalysts was shown to favor the total oxidation reaction over the epoxidation reaction at very low temperatures. In comparisons among the studied catalysts, the bimetallic Au–Ag/Al₂O₃ catalyst is the best candidate for the ethylene epoxidation. The catalytic activity of the gold catalysts was found to depend on the support material and catalyst preparation method which govern the Au particle size and the interaction between the Au particles and the support.     

o-xylene hydrogenation on supported ruthenium catalysts

The influence of the support on the surface properties and catalytic activity of finely divided ruthenium catalysts is reported. The catalysts were prepared using an organometallic precursor, Ru(acac)₂, and three different supports, Al₂O₃, TiO₂ and SiO₂. In order to study the influence of the particle size on the catalytic performance, the effect of the calcination temperature was also evaluated. XPS suggests that the state of ruthenium is essentially Ru⁰, and chemisorption measurements indicate a decrease in metal dispersion from catalysts supported on Al₂O₃ > TiO₂ > SiO₂. The turnover number in the o-xylene hydrogenation showed significant differences depending on the support and on the particle size. Additionally, an increase in the selectivity to cis-dimethylcyclohexane with particle size was observed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Effect of support on hydrogen production by auto-thermal reforming of ethanol over supported nickel catalysts

Nickel catalysts supported on various supports such as ZnO, MgO, ZrO₂, TiO₂, and Al₂O₃ were prepared by an impregnation method to investigate the effect of support on catalytic performance in hydrogen production by auto-thermal reforming of ethanol. Among the supported catalysts, the Ni/ZrO₂ and Ni/TiO₂ catalysts showed better catalytic performance than the other catalysts. The electronic structure of nickel species supported on ZrO₂ and TiO₂ was favorably modified for the reaction, and thus, the reducibility of nickel species supported on ZrO₂ and TiO₂ was increased due to the weak interaction between nickel and support. On the other hand, the Ni/MgO and Ni/ZnO catalysts exhibited poor catalytic performance in the auto-thermal reforming of ethanol due to the formation of a solid solution phase.     

Preparation of Zirconia Promoted Sulfated Titania System with High Catalytic Activity

SO₄^2–/TiO₂‐ZrO₂ (STZ) solid superacid catalysts were prepared using the coprecipitation‐impregnation method and characterized by FT‐IR, XRD, NH₃‐TPD, N₂ adsorption‐desorption isotherms, and SEM. It was observed that the sulfur content and the specific surface area of STZ changes with the ZrO₂ content, and passes through a maximum at Zr/Ti = 1/4. The results indicate that the molar ratio of Zr/Ti and nonionic surfactant, PEG, were helpful for increasing the surface areas and stabilizing the sulfate species on the surfaces of the catalysts. The catalytic activity results were supported by the hydrolysis reaction rate of 2‐methyl‐1,3‐dioxane (2MD) that was strongly dependent on the sulfur content in the zirconia promoted sulfated titania catalyst.     

SO42−/ZrO2 supported on γ‐Al2O3 as a catalyst for CO2 desorption from CO2‐loaded monoethanolamine solutions

In this work, the composite catalysts, SO₄²/ZrO₂/γ‐Al₂O₃ (SZA), with different ZrO₂ and γ‐Al₂O₃ mass ratios were prepared and used for the first time for the carbon dioxide (CO₂)‐loaded monoethanolamine (MEA) solvent regeneration process to reduce the heat duty. The regeneration characteristics with five catalysts (three SZA catalysts and two parent catalysts) of a 5 M MEA solution with an initial CO₂ loading of 0.5 mol CO₂/mol amine at 98°C were investigated in terms of CO₂ desorption performance and compared with those of a blank test. All the catalysts were characterized using X‐ray diffraction, Fourier transform infrared spectroscopy, N₂ adsorption–desorption experiment, ammonia temperature programmed desorption, and pyridine‐adsorption infrared spectroscopy. The results indicate that the SZA catalysts exhibited superior catalytic activity to the parent catalysts. A possible catalytic mechanism for the CO₂ desorption process over SZA catalyst was proposed. The results reveal that SZA1/1, which possesses the highest joint value of Brφnsted acid sites (BASs) and mesopore surface area (MSA), presented the highest catalytic performance, decreasing the heat duty by 36.9% as compared to the catalyst‐free run. The SZA1/1 catalyst shows the best catalytic performance as compared with the reported catalyst for this purpose. Moreover, the SZA catalyst has advantages of low cost, good cyclic stability, easy regeneration and has no effect on the CO₂ absorption performance of MEA. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3988–4001, 2018     

Physico-Chemical Properties of Cobalt–Ruthenium (10% Co–0.5% Ru) Catalysts Supported on Binary Oxides 8.5%ZrO<Subscript>2</Subscript>/Support (SiO<Subscript>2</Subscript>, Al<Subscript>2</Subscript>O<Subscript>3</Subscript>, TiO<Subscript>2</Subscript>) for Fischer-Tropsch Synthesis

The promotion of Fischer-Tropsch catalysts 10%Co/Al₂O₃, 10%Co/SiO₂, 10%Co/TiO₂ by 0.5% Ru and the modification of supports by 8.5 wt% ZrO₂ have been studied. The following properties: catalyst specific surface area as well as reducibility and dispersion of metallic phase were studied by different techniques: BET, TPR, and H₂ chemisorption. The modification of supports by non-reducible ZrO₂, results in a decrease of cobalt oxide reduction on Al₂O₃ and TiO₂ but not on SiO₂ supports. Additionally the enhancement of cobalt dispersion was found for all catalysts with ZrO₂ modified supports. The impact of Ru promotion is likely due to the stabilization of applied supports, prevention or blockage of interaction between surface Co species and support and an increase in cobalt oxide reducibility to the catalytically active metallic cobalt phase.     

Morphology and deactivation behaviour of Co–Ru/γ‐Al2O3 Fischer–Tropsch synthesis catalyst

Deactivation of Co–Ru/γ‐Al₂O₃ Fischer–Tropsch (FT) synthesis catalyst along the catalytic bed over 850 h of time‐on‐stream (TOS) was investigated. Catalytic bed was divided into four parts and structural changes of the spent catalysts collected from each catalytic bed after FT synthesis were studied using BET, ICP, XRD, TPR, carbon determination, H₂ chemisorption and oxygen titration techniques. Rapid deactivation was observed during first 200 h of FT synthesis. In this case, the deactivation rate was not dependent on the number of the catalyst active sites. It was zero order to CO conversion and independent of the size of active sites. Beyond the TOS of 200 h, the deactivation could be simulated with a power law expression: . The physical properties of the catalyst charged in 1st half of the reactor did not change significantly. Interaction of cobalt with alumina and formation of mixed oxides of the form xCoO·yAl₂O₃ and CoAl₂O₄ was increased along the catalytic bed. Percentage reducibility and dispersion decreased by 2.4–25.5% and 0.5–8.8% for the catalyst in the beds 1 and 4, respectively. Particle diameter increased by 0.8–6.1% for the catalyst in the beds 1 and 4 respectively suggesting higher rate of sintering at last catalytic bed. The amount of coke formation in the 4th catalytic bed was 6 times more than that of in bed 1.     

Effects of promoters on catalytic activity and carbon deposition of Ni/γ‐Al2O3 catalysts in CO2 reforming of CH4

Catalytic reforming of methane with carbon dioxide was studied in a fixed‐bed reactor using unpromoted and promoted Ni/γ‐Al₂O₃ catalysts. The effects of promoters, such as alkali metal oxide (Na₂O), alkaline‐earth metal oxides (MgO, CaO) and rare‐earth metal oxides (La₂O₃, CeO₂), on the catalytic activity and stability in terms of coking resistance and coke reactivity were systematically examined. CaO‐, La₂O₃‐ and CeO₂‐promoted Ni/γ‐Al₂O₃ catalysts exhibited higher stability whereas MgO‐ and Na₂O‐promoted catalysts demonstrated lower activity and significant deactivation. Metal‐oxide promoters (Na₂O, MgO, La₂O₃, and CeO₂) suppressed the carbon deposition, primarily due to the enhanced basicities of the supports and highly reactive carbon species formed during the reaction. In contrast, CaO increased the carbon deposition; however, it promoted the carbon reactivity. © 2000 Society of Chemical Industry     

Support Effect in a WGSR Catalyzed by Na2CO3 Activated [Ru(bpy)(CO)2Cl2] Catalyst

The support effects on the water gas shift reaction activity of [Ru(bpy)(CO)₂Cl₂] based catalyst were investigated. A series of oxide supports, Al₂O₃, TiO₂, SiO₂, Zeolites, ZrO₂ and ZrSiO₄, was studied. The catalytic activity was significantly improved when the catalyst was supported on weakly acidic alumina.     

Effect of support on the apparent activity of palladium oxide in catalytic methane combustion

The support effect on the low temperature catalytic oxidation of methane over palladium catalysts was studied by comparing a series of metal oxides as the support. Samples of 0.010 g/g Pd catalysts supported on different grades and/or phases of TiO₂, Al₂O₃, and ZrO₂ were prepared via incipient impregnation and their catalytic activity was evaluated using a laboratory plug-flow reactor. The specific surface area of the supports determined by nitrogen adsorption varied from about 13-220 m²/g. Initial experiments conducted with titania (anatase) as a support showed a low apparent activity and a poor thermal stability. Focusing on anatase, we have successfully improved its thermal stability by additions of Al₂O₃ or by doping with CeO₂, or La₂O₃. However, contrary to expectations based on some information in the literature, we have found that the activity decreased in the sequence of Al₂O₃ > ZrO₂ > TiO₂, and was not a direct function of specific surface area. This was especially evident in the case of titania. The surface structure of the support and the nature of its interaction with the active component PdO seem to play a far more important role in activity than the apparent specific surface area. Moreover, anatase-supported catalysts present a very rapid deactivation, whereas rutile-supported catalysts are relatively stable. The observed phenomena could potentially be related to the interaction between support and the active phase of palladium. Several models have been proposed to describe the strong metal-support interaction, but either charge transfer or encapsulation seems to be the most probable.     

Catalytic decomposition of CH2Cl2 over supported Ru catalysts

Ru/TiO₂ and Ru/Al₂O₃ were prepared by wet impregnation of TiO₂ and Al₂O₃, and tested in the catalytic decomposition of dichloromethane (DCM). Ru/TiO₂ catalyst presents the higher activity than Ru/Al₂O₃ catalyst, with 50% and 90% conversion occurring at 235 and 267 °C, respectively. Moreover, the higher stability on Ru/TiO₂ catalyst is observed, which can be related to ready removal of Cl species produced during DCM decomposition. The chlorine uptake on Ru/TiO₂ catalyst is estimated at 240 °C to be 0.36 mmol Cl/g_cat, while on Ru/Al₂O₃, the value is 1.46 mmol Cl/g_cat.     

Catalytic activities and selectivities of MoO3NiSO4 supported on various oxides for hydrocracking of solvent refined lignite: Novel low surface area active catalysts

The hydrocracking of solvent refined lignite (SRL) was studied over MoO₃NiSO₄ catalysts supported on TiO₂ ZrO₂, TiO₂SiO₂ and three kinds of aluminas at 450°C under an initial pressure of 2500 p.s.i. hydrogen. MoO₃NiSO₄ supported on a fibrous alumina, Al₂O₃ (FF), was found to show the highest activity, the total conversion of SRL being 92%. The activities per unit surface area of the catalysts supported on TiO₂ and ZrO₂ were much higher than those of other catalysts. A presulfided MoO₃NiSO₄Al₂O₃(FF) gave the largest amount of total liquid fractions. The best catalysts for the formation of gasoline fractions were presulfided MoO₃NiSO₄Al₂O₃(FF) and a commercially available catalyst, MoO₃NiOAl₂O₃(HT-100), which was also presulfided. It was shown that there is no correlation between acidic properties of the catalysts and their activities or selectivities.