František Kovanda

Characterization of activated Cu/Mg/Al hydrotalcites and their catalytic activity in toluene combustion

Five hydrotalcite-type compounds containing different amounts of Cu2+ and Mg2+ cations were prepared by coprecipitation method (the molar ratio Cu2+:Mg2+:Al3+ in brucite-like layers varied as follows: 0:4:2, 1:3:2, 2:2:2, 3:1:2, and 4:0:2). The products were characterized by XRD, TG and DTA measurements. The increasing content of Cu2+ decreased both the dehydration and decomposition temperatures. Extrudates prepared from the solids were calcined at different temperatures and the properties of the resulting materials (surface area, pore volume, TPR, surface basicity and acidity) were examined. Maximum of the Mg/Al hydrotalcite surface area was observed at 400°C, basicity at 450°C and acidity at 550°C. Incorporation of Cu2+ into brucite-like layers caused a substantial decrease in both basicity and acidity. Acidity rose with increasing amounts of copper in the layers and basicity went through a local minimum. An increase in the amount of magnesium in the precursors manifested itself in a decreased reducibility of the Cu2+ component. The oxidation activity in the toluene combustion increased with increasing amounts of Cu2+ in the solids and corresponded with the amount of easily reducible copper component.

Thermal behaviour of synthetic pyroaurite-like anionic clay

Thermal behaviour of synthetic pyroaurite-like anionic clay with molar ratio Mg/Fe=2 was studied in the range of 60-1100°C during heating in air. TG/DTA coupled with evolved gas analysis, emanation thermal analysis (ETA), surface area measurements, XRD, IR and Mössbauer spectroscopy were used. Microstructure changes characterized by ETA were in a good agreement with the results of surface area measurements and other methods. After the thermal decomposition of the pyroaurite-like anionic clay, which took place mainly up to 400°C, a predominantly amorphous mixture of oxides is formed. A gradual crystallization of MgO (periclase) and Fe2O3 (maghemite) was observed at 400-700°C by XRD. The MgFe2O4 spinel and periclase were detected at 800-1100°C. The spinel formation was also confirmed by Mössbauer spectroscopy.

Mg-Al layered double hydroxide intercalated with porphyrin anions: molecular simulations and experiments.

Molecular modeling in combination with powder X-ray diffraction (XRD) provided new information on the organization of the interlayer space of Mg-Al layered double hydroxide (LDH) containing intercalated porphyrin anions [5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS)]. Anion-exchange and rehydration procedures were used for the preparation of TPPS-containing LDH with an Mg/Al molar ratio of 2. Molecular modeling was carried out in the Cerius2 and Materials Studio modeling environment. Three types of models were created in order to simulate the experimental XRD patterns of LDH intercalates with a TPPS loading of 70–80% with respect to the theoretical anion exchange capacity (AEC). The models represent single-phase systems with a 100% TPPS loading in the interlayer space (Type 1) and models represent the coexistence of two phases corresponding to the total exchange from 75 to 92% (Type 2). To cover other possible arrangements, models with the coexistence of both TPPS and NO3− anions in the same interlayer space were calculated (Type 3). The models are described and compared with experimental data. In all cases, guest TPPS anions are tilted with respect to the hydroxide layers, and are horizontally shifted to each other by up to one-half of the TPPS diameter. According to the energy characteristics and simulated XRD, the most probable arrangement is of Type 2, where some layers are saturated with TPPS anions and others are filled with original NO3− anions.

Calcined Ni—Al layered double hydroxide as a catalyst for total oxidation of volatile organic compounds: Effect of precursor crystallinity

The effect of hydrothermal treatment on properties (crystallinity, porous structure, reducibility, acidity, basicity, and catalytic activity and selectivity in toluene and ethanol total oxidation) of Ni—Al layered double hydroxide precursors and related mixed oxides was examined. The hydrothermal treatment increased considerably both the content of crystalline phase and LDH crystallite size. On the other hand, only a slight effect of the precursor hydrothermal treatment on crystallinity of the related Ni—Al mixed oxides obtained by calcination at 450°C was observed. The reducibility of NiO particles appeared to be hindered considerably compared to the reducibility of pure NiO. Catalytic activity of the Ni—Al mixed oxides prepared from the precursors hydrothermally treated for a short time (4 h) was the highest. The highest amount of acetaldehyde formed during the total oxidation of ethanol, i.e. the worst selectivity was found for the calcined Ni—Al LDH without hydrothermal treatment.

Simulation of N2O Abatement in Waste Gases by Its Decomposition over a K-Promoted Co-Mn-Al Mixed Oxide Catalyst

Abstract Intrinsic data of N 2 O catalytic decomposition over a K-promoted Co-Mn-Al mixed oxide prepared by the thermal treatment of a layered double hydroxide was used for the design of a pilot reactor for the abatement of N 2 O emissions from the off-gases in HNO 3 production. A pseudo-homogeneous one-dimensional model of an ideal plug flow reactor under an isothermal regime (450°C) was used for reactor design. A catalyst particle diameter of 3 mm is a compromise size because increasing the size of the catalyst particle leads to a decrease in the reaction rate because of an internal diffusion limitation, and particles with a smaller diameter cause a large pressure drop. A catalyst bed of 11.5 m 3 was estimated for the target N 2 O conversion of 90% upon the treatment of 30000 m 3 /h of exhaust gas (0.1 mol% N 2 O, 0.005 mol% NO, 0.9 mol% H 2 O, 5 mol% O 2 ) at 450°C and 130 kPa.

N2O catalytic decomposition — effect of pelleting pressure on activity of Co-Mn-Al mixed oxide catalysts

The effect of pelleting pressure (0–10 MPa) during the preparation of Co-Mn-Al mixed oxide catalyst on its texture and activity for N2O catalytic decomposition was examined for small grain sizes used in laboratory experiments, and for model industry catalyst particles. Adsorption/desorption measurements of nitrogen, mercury porosimetry and helium pycnometry were used for detail characterization of porous structure. A volume of micropores of about 20 mm3 g−1 was evaluated using modified BET equation. This value did practically not change with the increasing pelletization pressure except that of the sample formed at the pressure of 10 MPa. Although an increase of pelleting pressure caused an increase in bulk density and a decrease in pore size and pore volume of the prepared catalyst (resulting in lower values of N2O effective diffusion coefficient), no direct correlation between pelleting pressure used and catalyst activity has been found. In contrary, estimation of the internal diffusion limitation according to the Weisz-Prater criterion indicated that even laboratory experimental data obtained for catalyst grains with particle size lower than 0.315 mm pelletized at higher pressures could be influenced by internal diffusion. Estimation of the internal mass transfer limitation in industrial catalyst particles described by the effectiveness factor showed that effectiveness factor of about 0.07 and 0.2 can be obtained for spheres with the radius of 1.5 mm and 0.5 mm, respectively, if pelleting pressure of about 6 MPa was used for the catalyst preparation.

Mixed oxides of transition metals as catalysts for total ethanol oxidation

Oxides of transition metals could be suitable alternatives to catalysts based on noble metals in the oxidation processes used for the abatement of volatile organic compounds. Mixed oxides of transition metals can exhibit good efficiency and thermal stability, as well as being inexpensive. In this work, oxide catalysts containing various combinations of Cu, Co, Ni, Mn, and Al, grained or supported on oxidised aluminium foil Al2O3/Al, were studied in terms of their chemical and physical properties, including their chemical composition, porous structure, phase composition, reducibility, and activity in total ethanol oxidation. Ternary co-precipitated catalysts in the form of grains obtained from layered double hydroxide-like precursors were highly active, especially those containing manganese. Deposition of the selected precursors on an anodised aluminium foil-support afforded less active catalysts, mainly because the required metal molar ratios were not achieved, and insufficient amounts of metals were deposited. However, by controlling the preparation conditions (pH), higher loading of active components and higher catalytic activity were obtained.

THE FORMATION OF LAYERED DOUBLE HYDROXIDES ON ALUMINA SURFACE IN AQUEOUS SOLUTIONS CONTAINING DIVALENT METAL CATIONS

Layered double hydroxides (LDHs) are often used as precursors for mixed-oxide catalysts and the deposition of a LDH layer on supporting materials would be advantageous because of better utilization of active components. The purpose of the present study was to investigate the formation of LDHs on Al2O3/Al supports prepared by the anodic oxidation of aluminum foil in dilute aqueous solutions of Co, Mn, and/or Ni nitrates. The LDH deposition was carried out under hydrothermal conditions at 80–180°C for periods ranging from 8 h to 7 days. In the initial stages of the reaction, a surface alumina hydration was observed. The LDH phase was detected after long-term deposition (3–7 days) at 120–160°C and only a small amount of Mn was incorporated in the LDHs deposited. In solutions containing only Co and Mn cations, scanning electron microscopy (SEM) images show a gradual growth of platy crystals resulting in the formation of discrete bulky aggregates with sizes up to several tens of micrometers. The adhesion of aggregates to the support probably decreased with increasing size and oversized aggregates fell away; none was found in SEM images of the samples obtained after prolonged reaction times. When Ni cations were present in the solution, they were incorporated preferentially into the LDH phase; an homogeneous layer was formed, with single platy crystals oriented perpendicular to the support. After calcination at 500°C, the products formed on Al2O3/Al support exhibited a shift of reduction maxima to higher temperatures in comparison with mixed oxides obtained by thermal decomposition of coprecipitated LDHs.

Cobalt oxides supported over ceria-zirconia coated cordierite monoliths as catalysts for deep oxidation of ethanol and N2O decomposition

Cordierite monoliths coated with ceria–zirconia supporting cobalt oxide were prepared, examined in the deep oxidation of ethanol and N2O decomposition, and compared with pelletized commercial cobalt oxide catalyst. Interaction of Co3O4 with ceria–zirconia washcoat led to formation of Co3O4 particles with slightly worse structure ordering resulting in better reducibility than that observed for the commercial Co3O4 catalyst. In oxidation of ethanol, activity of the Co3O4-containing monoliths was comparable with that of pelletized cobalt oxide catalyst with nearly seven times higher content of active components. However, conversions of N2O over the monolith catalysts were lower. Nevertheless, incorporation of Co3O4 onto ZrO2–CeO2 washcoat increased rate of both catalytic reactions, i.e., N2O decomposition and deep ethanol oxidation.Graphical Abstract