Band 68, Heft 9

Conversion of methanol to light olefins is a promising alternative for the conversion of new feed-stocks such as gas, coal or biomass to ethylene and propylene via the methanol-to-olefins (MTO) process. During the last decade, the use of structured catalysts in this reaction has received increasing attention. The effect of such structured catalysts on the stability and selectivity is discussed in this review. The reaction and coking mechanism show the importance of good mass transfer properties of the catalyst in the MTO reaction. Important aspects such as thickness of the coating, crystal size of the zeolite and architecture of the support on the mass transfer properties of the final catalyst are highlighted. An overview of the results of structured catalysts used in the MTO reaction is presented.

The most relevant information about the different active phases that have been studied for the catalytic combustion of soot is reviewed and discussed in this article. Many catalysts have been reported to accelerate soot combustion, including formulations with noble metals, alkaline metals and alkaline earth metals, transition metals that can accomplish redox cycles (V, Mn, Co, Cu, Fe, etc.), and internal transition metals. Platinum catalysts are among those of most interest for practical applications, and an important feature of these catalysts is that sulphur-resistant platinum formulations have been prepared. Some metal oxide-based catalysts also appear to be promising candidates for soot combustion in practical applications, including ceria-based formulations and mixed oxides with perovskite and spinel structures. Some of these metal oxide catalysts produce highly reactive active oxygen species that promote efficient soot combustion. Thermal stability is an important requirement for a soot combustion catalyst, which precludes the practical utilisation of several potential catalysts such as most alkaline metal catalysts, molten salts, and metal chlorides. Some noble metal catalysts are also unstable due to the formation of volatile oxides (ruthenium, iridium, and osmium).

Chlorine-containing organic compounds (Cl-VOC) require special attention due to their distinct toxicity, high stability and persistence in the environment. Removal of Cl-VOC by catalytic oxidation over a wide variety of catalysts has been presented in literature. This paper reviews the state of the art in this subject, including different model compounds, nature of catalysts, and oxidation activity. Catalyst selectivity (CO2 vs. CO and HCl vs. Cl2), by-products formation and the causes of deactivation are also analyzed as the most important factors in the catalyst selection for practical applications.

The effect of Zn on the catalytic performance of ZSM-5 in the methanol-to-olefin conversion was investigated. The samples were characterised by X-ray diffraction, N2 adsorption, FTIR, temperature-programmed desorption of ammonia and water, and Py-IR. The experimental results revealed Znmodified ZSM-5 to show a lower selectivity to light olefin at the higher reaction temperature of 520°C but a higher selectivity to light olefin at lower temperatures. As a comparison, the catalytic performance of Ca-modified ZSM-5 for the methanol conversion is also given. From the above results, it is concluded that Zn may play another role in the methanol conversion in addition to tuning the surface acidic property after modification.

Sulphate- and phosphate-loaded silicas were synthesised using the sol-gel method with different sulphate and phosphate loadings. These catalysts were characterised using Fourier transform infrared spectroscopy (FT-IR), the Brunauer-Emmett-Teller (BET) method and X-ray photoelectron spectroscopy (XPS). Acidity was measured using the temperature-programmed desorption of ammonia (TPD-NH3) method. The results showed that glycerol esterification with acetic acid conversion decreased as follows: α(H2SO4) (100 %) > α(H3PO4) (99 %) > α(silica loaded with 20 % sulphuric acid) (SS-20; 98 %) > α(silica loaded with 20 % phosphoric acid) (PS-20; 83 %). These studies suggest that the solid acid catalytic activity in the esterification of glycerol is highly dependent on catalyst acidity strength, pore size and surface area.

Bio-oil resulting from the pyrolysis of lignocellulose is a complex mixture of polar low molecular mass oxygenated compounds of various functionalities and non-polar high molecular mass lignin derivatives. Several approaches to the upgrading of bio-oil are currently in progress. This study investigates the valorisation of crude bio-oil using physical and chemical methods. The effects of methanol addition on some properties of the bio-oil are investigated. Stable bio-oil/diesel oil emulsions are produced by the addition of surfactants with a hydrophilic-lipophilic balance value of 5–6. An alternative approach towards the upgrading of bio-oil is the hydrotreatment of the water-soluble fraction of bio-oil. Two-stage hydroprocessing with noble-metal catalysts Ru/C and Pt/C increases the intrinsic hydrogen content of the water-soluble fraction. The results show that the thermally unstable components including sugars, ketones and aldehydes are readily converted to diols and alcohols at pressures of 5 MPa. These observations can be explained by a set of reaction pathways for the compounds identified.

Wurtzite-type Zn1−x MnxO (x = 0, 0.03, 0.05, 0.07) nanostructures were successfully synthesised using a simple microwave-assisted hydrothermal route and their catalytic properties were investigated in the cellulose conversion. The morphology of the nanocatalysts is dopant-dependent. Pure ZnO presented multi-plate morphology with a flower-like shape of nanometric sizes, while the Zn0.97Mn0.03O sample is formed by nanoplates with the presence of spherical nanoparticles; the Zn0.95Mn0.05O and Zn0.93Mn0.07O samples are mainly formed by nanorods with the presence of a small quantity of spherical nanoparticles. The catalyst without Mn did not show any catalytic activity in the cellulose conversion. The Mn doping promoted an increase in the density of weak acid sites which, according to the catalytic results, favoured promotion of the reaction.

The intercalation of natural montmorillonite with SiO2, SiO2-Al2O3 or SiO2-TiO2 pillars by the surfactant-directed method resulted in the formation of high surface area porous materials; these were tested as catalytic supports for the process of selective catalytic reduction of NO (DeNOx). The incorporation of titanium or aluminium into the structure of the silica pillars significantly increased the surface acidity of the clay samples. Iron and copper were deposited onto the surface of the pillared clays mainly in the form of monomeric isolated cations and oligomeric metal oxide species. The contribution of the latter species was higher in the clay intercalated with SiO2-TiO2 pillars than in the samples modified with SiO2 and SiO2-Al2O3 pillars. The pillared clay-based catalysts were active in the DeNOx process but, in this group, the best results were obtained for the clay intercalated with SiO2-TiO2 pillars and doped with iron and copper. The catalytic performance of the samples is discussed in respect of their surface acidity and active forms of transition metal species deposited.

Fe- and Cu-oxides supported on γ-alumina (γ-Al2O3; metal loading of 3 mass %) were investigated as alternative catalysts to the conventional Ag-based system in the selective catalytic reduction of NO with ethanol (EtOH-SCR). The catalysts were characterized by elemental analysis, N2 sorption, X-ray diffraction, temperature-prgrammed desorption of NH3, temperature-programmed reduction with H2, diffuse reflectance UV-VIS (DR-UV-VIS) spectroscopy, and compared with 3 mass % Ag/γ-Al2O3 as a reference catalyst. Catalytic experiments were carried out between 423 K and 773 K in the steady state and by temperature-programmed surface reaction (TPSR) experiments. For all catalysts, the highest NO conversion (900 ppm (ppm = parts of the mixture component per million parts of all mixture components) NO, 900 ppm EtOH, 0.5 vol. % H2O, 4 vol. % O2 in He) was found at 573 K. While 84 % of NO were converted over the Ag-based catalysts, only 20–60 % NO conversion was observed for the Fe- and Cu-containing catalysts. Total oxidation of ethanol as an unwanted side reaction occurs over 3 mass % Cu on γ-Al2O3 already at 573 K, whereas the highest activity of 3 mass % Fe on γ-Al2O3 for this conversion was reached at 743 K. For lower temperatures, partial oxidation of ethanol leads to organic by-products which can act as active intermediates in EtOH-SCR. TPSR experiments show that ethanol reacts over both the Fe- and the Cu-based catalysts to organic by-products, such as ethene or acetaldehyde, which affect the EtOH-SCR reaction.

This work reports on the characterization of LaRhO3 perovskite as a catalyst for dry reforming of methane. The catalyst was studied using CH4-temperature programmed reduction (TPR), H2-TPR, and temperature programmed surface reaction (TPSR), and the changes in the crystal structure of the catalyst due to these treatments were studied by X-ray diffraction (XRD). XRD pattern of the freshly calcined perovskites showed the formation of highly crystalline LaRhO3 and La2O3 phases. H2-TPR of the fresh calcined catalyst showed a shoulder at 342°C and a broad peak at 448°C, suggesting that the reduction of Rh in perovskite occurs in multiple steps. XRD pattern of the reduced catalyst suggests complete reduction of the LaRhO3 phase and the formation of metallic Rh and minor amounts of La(OH)3. The CH4-TPR data show qualitatively similar results as H2-TPR, with a shoulder and a broad peak in the same temperature range. Following the H2-TPR up to 950°C, the same batch of catalyst was oxidized by flowing 5 vol. % O2/He up to 500°C and a second H2-TPR (also up to 950°C) was conducted. This second H2-TPR differed significantly from that of the fresh calcined catalyst. The single sharp peak at 163°C in the second H2-TPR suggests a significant change in the catalyst, probably causedby the transformation of about 90 % of the perovskite into Rh/La2O3. This was confirmed by the XRD studies of the catalyst reduced after the oxidation at 500°C. TPSR of the dry reforming reaction on the fresh calcined catalyst showed CO and H2 formation starting at 400°C, with complete consumption of the reactants at 650°C. The uneven consumption of reactants between 400°C and 650°C suggests that reactions other than DRM occur, including reverse water gas shift (RWGS) and the Boudouard reaction (BR), probably as a result of in-situ changes in the catalyst, consistent with the H2-TPR results. TPSR, after a H2-TPR up to 950°C, showed that the dry reforming reaction did not light off until 570°C, which is much higher temperature than the one observed using fresh calcined catalyst. This shows that the uniform sites produced during the 950°C H2-TPR are catalytically less active than those of the fresh calcined catalyst, and that no significant side reactions such as RWGS or the Boudouard reaction occur. This suggests that reduction leads to the formation of a single type of sites which do not catalyze simultaneous side reactions.

Titanium dioxide is a promising catalyst for application in the photodegradation of organic pollutants in water due to its powerful oxidising property and long-term photostability. This study presents the production of titanium dioxide using the sol-gel process, dye sensitisation of the TiO2 electrode, and the performance of that cell. Sensitisation of titanium dioxide was performed using a dye, i.e., Fe(II)-polypyridyl complexes. The photoelectrocatalytic degradation of rhodamine B (RB) using ITO/TiO2/dye as electrode was investigated via a series of potentials, from +1.0 V to −1.0 V, and at various pH and NaCl concentration values (ITO is indium tin oxide conductive glass). The photoelectrocatalytic degradation of RB was performed with a visible light lamp. The change in the absorbance of RB with various potentials indicated that the absorbance of RB in solution systems with the sensitised TiO2 electrodes decreased with increasing anodic potential bias. The degradation cell exhibited better performance when the positive anodic bias was applied. The pH values of RB in solution systems also influence the photoelectrodegradation process because of the different RB species present. NaCl concentration also affects the activity of RB photoelectrocatalytic degradation due to changes in the ionic strength character of the electrolyte.

Cadmium sulfide/titanium dioxide (CdS/TiO2) composite films were grown on glass by the chemical bath deposition (DBQ) and sol-gel/dip coating methods, respectively, in order to increase the photocatalytic activity of TiO2 in photodegradation processes. The influence of the CdS deposition time on the morphology, optical absorption, and phononic modes of the composites were examined. Scanning electron microscopy (SEM) images showed clearly the CdS deposit on the TiO2 surface. The absorbance spectra indicated that the absorption of composites depends on the CdS deposition time and the absorption edges are shifted to the visible range. Micro Raman spectra exhibited the phonons associated with the TiO2 anatase and the longitudinal optic (LO) phonon of CdS whose intensity increases with the CdS deposition time. Photodegradation of methylene blue (MB) under visible light irradiation was observed in all films and the results were compared with those obtained with TiO2 films. The decomposition is higher for the composite with the CdS deposition time of 15 min. This optimal deposition time allows maximal enhancement of the charge carriers transfer to TiO2 involved in the photocatalysis. No signal associated with cadmium was detected by the atomic absorption spectroscopy (AAS), which means that the CdS photocorrosion does not occur since trap centers such as OH-Cd-S and Cl−, which trap holes and inhibit the photocorrosion, are produced during the growth process.

For air-cleaning, TiO2 photocatalysis represents one of the very efficient advanced oxidation processes (AOPs) that can decompose chemically and microbiologically stable volatile organic compounds (VOCs). However, the photocatalytic activity of nanocrystalline TiO2 powders can be significantly suppressed due to TiO2’s poor adsorption characteristics for organic compounds and its relatively low surface area. The present study sought to solve this problem by immobilising nanocrystalline TiO2 in the porous silicate substrate. Two titania sources were used in an aqueous solution form: a suspension from a TiO2 producer in Slovenia, Cinkarna Celje (CC-40) and a TiO2 sol, prepared by a low-temperature synthesis developed at the University of Nova Gorica (TiO2-UNG). Two different types of mesoporous silica were used: SBA-15 with an ordered hexagonal pore arrangement and KIL-2 with disordered inter-particle mesoporosity. The structural characteristics, adsorption properties and photocatalytic activity of catalysts deposited on aluminium plates as thin films were investigated. CC-40 exhibited higher adsorption and photocatalytic activity than TiO2-UNG due to the greater quantity of Ti-OH groups on its surface. The addition of mesoporous silica led to higher adsorption and catalytic activity for both TiO2 sources. SBA-15 was more efficient than KIL-2.

In the commercialisation of photocatalytic air purifiers, the performance as well as the cost of the catalytic material plays an important role. Where most comparative studies only regard the photocatalytic activity as a decisive parameter, in this study both activity and cost are taken into account. Using a cost-effectiveness analysis, six different commercially available TiO2-based catalysts are evaluated in terms of their activities in photocatalytic degradation of acetaldehyde as a model reaction for indoor air purification.

Combined thermal desorption and catalytic oxidation for soil decontamination was studied at the pilot plant scale. Gasoline, xylene, and 2-methylnaphthalene were used as model contaminants in the concentrations from 2 g to 10 g per kg of soil. To guarantee the flow of the exhaust gas from the thermal desorption unit into the catalytic oxidation unit, a Venturi pump was used. Based on the laboratory scale catalytic tests, the commercial catalyst EnviCat® VOC-1544 was employed in the catalytic oxidation. Residual concentrations of hydrocarbons in soil after the thermal desorption were below the detection limits of the applied analytical method (GC-MS). Although the contaminant concentrations at the inlet of the catalytic reactor significantly varied during the experiments, the efficiency of catalytic oxidation was higher than 90 % in all cases.