Study of Perovskite Type Oxide Catalysts for Partial Oxidation of Methane

Studium bylo provedeno na perovskitových systémech obecného vzorce A1-xA‘xB1-yB‘yO3± (A=La, Sm, A´=Ca, B´=Al, B=Co,Fe,Mn a Cr) . Zkoumané perovskitové oxidy byly syntetizovány polymeračními metodami a charakterizovány rentgenovou strukturní analýzou, BET, SEM a EDX. TPD spektra a katalytické testy byly provedeny ve vysokoteplotním reaktoru s pístovým tokem a analyza produktů provedena hmotnostním spektrometrem. Bylo zjištěno, že oxidace metanu při poměrech O2/CH40,5 silně závisí na teplotě. Při teplotách mezi 300-700oC dochází k úplné oxidaci metanu na oxid uhličitý a vodu, zatímco při teplotách nad 700oC probíhá parciální oxidace metanu (POM) na vodík a oxid uhelnatý (syngas). To je vysvětlováno rovnováhou O2 mezi plynnou fází a pevným perovskitem. Bylo použito osm perovskitových systémů, na kterých probíhají tyto reakce stejným způsobem. Reformace probíhá nad teplotu 700oC. Mezi nejlepší katalytické systémy patřily perovskity typu kobaltitu a feritu. Na základě získaných výsledků byl navržen pro oxidace a reformace perovskitovými systémy Mars van Krevelenův mechanismus. Bylo dokázáno, že POM probíhá dvoustupňovým mechanismem. V první kroku vznikají produkty úplné, totální oxidace (TO), které v druhém kroku přecházejí na syntézní plyn (H2+CO).Research was curried out on the perovskite systems with general formula A1-xA‘xB1-yB‘yO3± (where A=La, Sm, A´=Ca, B´=Al, B=Co,Fe,Mn and Cr). Perovskite oxides were sythesized by polymerisation methods and characterised by RTG analysis, BET method, SEM and EDX. TPD spectra and catalyst testing were measured in high temperature plug flow reactor and products were analysed by mass spectrometry. It was found, that metane oxidation at ratio O2/CH40,5 depended on the temperature. Total oxidation proceeded at the temperature betwen 300-700oC to the carbon dioxide and water, while the partial oxidation of metane (POM) occured at above 700oC to the hydrogen and carbon oxid (syngas). This was ascribed by equilibrium of O2 betwen gas phase and solid perovskite. There was used 12 perovskite systems, which catalysed methane oxidation by the same way. Dry reforming of methane run above temperature 700oC. Cobaltite and ferite type perovskites were found as the most active catalytic systems. On the base of obtained results the Mars van Krevelen mechanism was established for explanation of oxidation and reformation of methane by perovskite systems. It was showed, that POM was running by two steps mechanism. Products of total oxidation was occured in the first step, which were passed over to the syngas (H2+CO) in the second step.

Zirconia / Alumina Composite Foams with Calcium Phosphate Coating

In this study, mechanical properties of calcium phosphate foams were enhanced by zirconia/alumina porous cores prepared by polymer replica technique. This technique was chosen to ensure interconnected pores of optimal size for cell migration and attachment. The porosity of ZA cores (50 – 99%) was controlled by multistep impregnation process, the size of pore windows was 300 – 500 μm. Sintered ZA cores were impregnated by hydroxyapatite or β-tricalcium phosphate slurry to improve bioactivity. The bone like apatite layer was formed on coatings when immersed in a simulated body fluid. Neither of tested materials was cytotoxic. Thus, the composite foam can be potentially used as a permanent substitute of cancellous bone

Zirconia / Alumina Composite Foams with Calcium Phosphate Coating

In this study, mechanical properties of calcium phosphate foams were enhanced by zirconia/alumina porous cores prepared by polymer replica technique. This technique was chosen to ensure interconnected pores of optimal size for cell migration and attachment. The porosity of ZA cores (50 – 99%) was controlled by multistep impregnation process, the size of pore windows was 300 – 500 μm. Sintered ZA cores were impregnated by hydroxyapatite or β-tricalcium phosphate slurry to improve bioactivity. The bone like apatite layer was formed on coatings when immersed in a simulated body fluid. Neither of tested materials was cytotoxic. Thus, the composite foam can be potentially used as a permanent substitute of cancellous bone

Zirconia / Alumina Composite Foams with Calcium Phosphate Coating

In this study, mechanical properties of calcium phosphate foams were enhanced by zirconia/alumina porous cores prepared by polymer replica technique. This technique was chosen to ensure interconnected pores of optimal size for cell migration and attachment. The porosity of ZA cores (50 – 99%) was controlled by multistep impregnation process, the size of pore windows was 300 – 500 μm. Sintered ZA cores were impregnated by hydroxyapatite or β-tricalcium phosphate slurry to improve bioactivity. The bone like apatite layer was formed on coatings when immersed in a simulated body fluid. Neither of tested materials was cytotoxic. Thus, the composite foam can be potentially used as a permanent substitute of cancellous bone

Heat treatment induced phase transformations in zirconia and yttriastabilized zirconia monolithic aerogels

Monolithic, structurally stable zirconia (ZrO2) aerogels can be used in high temperature applications and as medical implants. The macroscopic properties of these solids can be fine-tuned by the appropriate thermal treatment of the amorphous aerogels. Herein, we investigate the thermally induced phase transitions of ZrO2 and yttria-stabilized zirconia (YSZ) monolithic aerogels. All aerogels were produced by an acid-catalyzed sol-gel technique and subsequent supercritical drying (SCD). A complete reaction mechanism is proposed for the formation of the wet gel network. Also, the phase transformations taking place during calcination were followed as function of temperature by in-situ X-ray diffraction measurements. Composition and size of the forming crystallites were calculated from the XRD data. Phase transition is controlled by the temperature-dependent growth of crystallite size during calcination up to 1200 °C. Both tetragonal and monoclinic zirconia form in pure ZrO2 aerogels, and a single tetragonal phase forms in YSZ aerogels

Heat treatment induced phase transformations in zirconia and yttria-stabilized zirconia monolithic aerogels

Monolithic, structurally stable zirconia (ZrO2) aerogels can be used in high temperature applications and as medical implants. The macroscopic properties of these solids can be fine-tuned by the appropriate thermal treatment of the amorphous aerogels. Herein, we investigate the thermally induced phase transitions of ZrO2 and yttria-stabilized zirconia (YSZ) monolithic aerogels. All aerogels were produced by an acid-catalyzed sol-gel technique and subsequent supercritical drying (SCD). A complete reaction mechanism is proposed for the formation of the wet gel network. Also, the phase transformations taking place during calcination were followed as function of temperature by in-situ X-ray diffraction measurements. Composition and size of the forming crystallites were calculated from the XRD data. Phase transition is controlled by the temperature-dependent growth of crystallite size during calcination up to 1200 °C. Both tetragonal and monoclinic zirconia form in pure ZrO2 aerogels, and a single tetragonal phase forms in YSZ aerogels