Comparative study on catalytic and non-catalytic pyrolysis of olive mill solid wastes

In this study, catalytic and non-catalytic fast pyrolysis of dried olive husk and olive kernels was carried out. A bubbling fluidised bed reactor was used for the non-catalytic processing of the solid olive wastes. In-situ catalytic upgrading of biomass fast pyrolysis vapours was performed in a fixed bed bench-scale reactor at 500 °C, for catalyst screening purposes. A maximum bio-oil yield of 47.35 wt.% (on dry biomass) was obtained from non-catalytic fast pyrolysis at a reaction temperature of 450 °C, while the bio-oil yield was decreased at 37.14 wt.% when the temperature was increased to 500 °C. In the case of the fixed bed unit tests, the highest liquid (52.66 wt.%) and organics (30.99 wt.%) yield was achieved with the use of the non-catalytic silica sand. Depending on the catalytic material, the liquid yield ranged from 47.03 to 43.96 wt.% the organic yield from 21.15 to 16.34 wt.% on dry biomass. Solid products were increased from 28.23 wt.% for the non-catalytic run to 32.81 wt.% on dry biomass, when MgO (5% Co) was used

Nitrous oxide decomposition over Al2O3 supported noble metals (Pt, Pd, Ir): Effect of metal loading and feed composition

Δημοσίευση σε επιστημονικό περιοδικόSummarization: The N2O decomposition (de-N2O) performance of Al2O3 supported, low content (0.25, 0.5 and 1.0 wt.%) noble metal (Pt, Pd, Ir) catalysts, is comparatively explored in the present study. The effect of metal content, operation temperature and feed composition on de-N2O performance is investigated. Characterization studies involving BET, XRD, TEM and H2-TPR were also carried out to reveal the impact of metal entity and content on the structural, morphological and redox characteristics of the catalysts. The catalytic results imply that the de-N2O performance is in general increased upon increasing metal loading, a fact being more intense over Ir-based catalysts. Under oxygen deficient conditions, N2O conversions as high as ∼100% and ∼80% are reached at 600 °C over Ir- and Pd-based catalysts, respectively, instead of only ∼30%, achieved over Pt-based catalysts. A moderate degradation in oxygen excess conditions is observed with Ir and Pd catalysts, while Pt-based catalysts are almost fully depressed. The superior de-N2O performance of Ir-, Pd-based catalysts can be mainly interpreted by taking into account the formation of metal oxide phases, not easily susceptible to oxygen poisoning. For Ir-based catalysts the active phase seems to be mainly the metal oxide phase (IrO2), as revealed by H2-TPR, XRD and TEM experiments. In the case of palladium catalysts two different metal phases, i.e. PdO and metallic Pd0 were detected. On the other hand, platinum catalysts presented only metallic Pt0 species, which are prone to poisoning by strongly adsorbed oxygen atoms.Παρουσιάστηκε στο: Journal of Environmental Chemical Engineerin

Effect of alkali promoters (K) on nitrous oxide abatement over Ir/Al2O3 catalysts

Summarization: The promoting impact of potassium (0–1 wt% K) on nitrous oxide (N2O) catalytic decomposition over Ir/Al2O3 is investigated under both oxygen deficient and oxygen excess conditions. All samples were characterized by means of X-ray powder diffraction (XRD), temperature-programmed reduction (H2-TPR), ammonia desorption (NH3-TPD) and Fourier Transform Infrared Spectroscopy of pyridine adsorption (FTIR-Pyridine). The results reveal that the K-free Ir/Al2O3 catalyst consists mainly of the IrO2 phase, exhibiting also significant Lewis acidity, which is gradually eliminated by the addition of K. Catalytic performance results showed that the deN2O performance in the absence of O2 in the feed mixture is negatively affected upon increasing potassium loading. However, under oxygen excess conditions, a pronounced effect of K is observed. Although the catalytic performance of the un-doped catalyst is drastically hindered by the presence of O2, the K-promotion notably prohibits the oxygen poisoning. The optimum deN2O performance under oxygen excess conditions is obtained with potassium loading of 0.5 wt% K, which offers complete conversion of N2O at 580 °C, instead of the corresponding 50 % N2O conversion achieved with the un-modified sample. On the basis of characterization results, it was concluded that alkali-doping in combination with oxygen excess conditions are required towards the formation of active Ir entities.Presented on: Topics in Catalysi

Impact of the synthesis parameters on the solid state properties and the CO oxidation performance of ceria nanoparticles

Summarization: Ceria-based materials have received considerable attention in catalysis field due to their unique physicochemical characteristics. Compared to bulk ceria, nanosized ceria received particular interest, due to its high surface to volume ratio, improved reducibility and optimal morphological features. Hence, the fine-tuning of ceria properties by means of advanced synthesis routes is of particular importance. In this regard, the present work aims at investigating the impact of synthesis parameters on the solid state properties of CeO2 materials. Four different time- and cost-effective preparation methods were followed, i.e. thermal decomposition, co-precipitation and hydrothermal method of low and high NaOH concentration, employing in all cases Ce(NO3)3·6H2O as cerium precursor. A complementary characterization study, involving N2 adsorption at -196 °C (BET method), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), H2 temperature-programmed reduction (H2-TPR) and scanning/transmission electron microscopy (SEM/TEM), was carried out to gain insight into the impact of synthesis route on the textural, structural, morphological and redox properties. The results revealed the superiority of the hydrothermal method towards the development of ceria nanoparticles of high specific surface area (>90 m2 g-1), well-defined geometry (nanorods) and improved redox properties. CO oxidation was employed as a probe reaction to gain insight into the structure-activity correlation. Ceria nanorods prepared by hydrothermal method of high NaOH concentration demonstrated the optimum CO oxidation performance. A direct quantitative correlation between the catalytic activity and the abundance of easily reduced, loosely bound oxygen species, was revealed. Hence, this particular reactivity descriptor can potentially be used for the rational design of ceria-based materials.Presented on: RSC Advance

A comparative study of the H2-assisted selective catalytic reduction of nitric oxide by propene over noble metal (Pt, Pd, Ir)/γ-Al2O3 catalysts

Summarization: The impact of H2 as additional reducing agent on the SCR of NO with C3H6 in excess oxygen, was comparatively explored over low noble metal loading (0.5 wt%), Pt/γ-Al2O3, Pd/γ-Al2O3, Ir/γ-Al2O3 catalysts. To gain insight into the role of H2, the reactions NO + C3H6 + O2 (R#1), NO + C3H6 + O2 + H2 (R#2), NO + H2 + O2 (R#3) were employed. In respect to propene oxidation, the Pd > Pt > Ir sequence was obtained under R#1, since they exhibit complete conversion at 220, 250, 325 °C, respectively; all metals exhibit moderate deNOx performances (XNO, <40%). H2 co-presence (R#2) promotes both the NO and C3H6 conversions, which is valid in the whole temperature interval investigated (50-400 °C), being more substantial for Pt/γ-Al2O3 and Ir/γ-Al2O3, less beneficial for Pd/γ-Al2O3. A two-maxima feature is obtained on XNO pattern (at ∼100 and ∼230 °C) of Pt and Pd during R#2. The low temperature maximum-attributed to NO reduction by H2-is substantially more pronounced on Pt than Pd, offering XNO ∼90% and SN2 ∼85%; the high temperature maximum-attributed to NO reduction by C3H6-is higher by ∼15% on both Pt and Pd, in respect to the values obtained during R#1, while SN2 remained unaffected. Different XNO pattern with one maximum is obtained over Ir, implying a synergistic interaction between H2 and C3H6. This synergy is accompanied by a substantial widening of the NO reduction window toward lower temperatures and a considerable increase on both XNO,max and SN2 (from XNO ∼30% with SN2 ∼55% during R#1 to XNO ∼70% with SN2 ∼95% during R#2). The specific features of all reactions and metals employed are comparatively discussed.Presented on: Journal of Environmental Chemical Engineerin

N2O decomposition over ceria-promoted Ir/Al2O3 catalysts: the role of ceria

Περίληψη: The impact of CeO2 in the Al2O3-20wt% CeO2 support prepared by the co-precipitation method on the Ir particle size, morphology and oxidation state, and in turn on the deN2O catalytic activity (1000ppmN2O) of supported Ir catalysts were investigated in the absence and presence of excess O2 (2vol%) conditions. It was demonstrated that the deN2O activity of Ir/Al2O3 is notably suppressed by the presence of oxygen in the feed stream, namely, the N2O conversion at 600°C is declined to 65% in the presence of oxygen as compared to 100% in the absence of oxygen. A similar detrimental catalytic effect was also observed for the Ir/CeO2 solid. On the contrary, the deN2O performance of CeO2-modified Ir/Al2O3 catalyst is only slightly affected by the presence of oxygen. An extensive characterization study involving surface texture analysis (N2 adsorption-desorption at -196°C), temperature-programmed reduction in H2 (H2-TPR), X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy (STEM), electron energy loss spectroscopy (EELS) and diffuse reflectance infrared Fourier transform spectroscopy of CO adsorption and desorption (CO-DRIFTS) was carried out to gain insight into the origin of the CeO2-induced promotional effect. The characterization results revealed the existence of IrO2 phase (H2-TPR, XRD, HRTEM, EELS and CO-DRIFTS) as well as of very small isolated particles of Ir on the Al2O3, CeO2 and CeO2-Al2O3 supports (STEM) but to a notably different extent. The coexistence of large IrO2 particles of perfect crystallite structure and very small Ir particles located at the Ir-ceria interface was revealed only in Ir/AlCe. The establishment of a certain Irδ+/Ιr0 ratio and oxygen vacant sites (VO) concentration in ceria around very small Ir particles under oxidative reaction conditions seem to largely promote N2O adsorption and subsequent decomposition into N2 and O2 over the CeO2-promoted Ir/Al catalyst. In the case of Ir/Al, a different deN2O decomposition mechanism occurs, where the site reactivity of Irδ+/Ιr0 established under oxidizing conditions is reduced significantly.Presented on: Applied Catalysis B: Environmenta

Ceria nanoparticles shape effects on the structural defects and surface chemistry: implications in CO oxidation by Cu/CeO2 catalysts

Summarization: Copper-ceria binary oxides have been extensively used in a wide variety of catalytic processes due to their unique catalytic features in conjunction to their lower cost as compared to noble metal-based systems. However, various parameters related to different counterparts characteristics, such as particle size and morphology, can exert a profound influence on the structural/redox properties of binary oxides and, consequently, on their catalytic performance. Here, we report on ceria nanoparticles shape effects: nanorods (NR), nanopolyhedra (NP) and nanocubes (NC) on the solid state properties of copper-ceria binary oxides. A thorough characterization study by both ex situ (surface area determination, X-ray diffraction, X-ray fluorescence, H2-temperature programmed reduction, transmission electron microscopy, X-ray photoelectron spectroscopy) and in situ (Raman spectroscopy) techniques was undertaken to gain insight into the impact of the support morphology on the surface, structural and redox properties. A novel approach based on sequential in situ Raman spectra obtained under alternating oxidizing and reducing atmospheres was employed to reveal the impact of ceria exposed facets on the structural defects. CO oxidation was employed as a probe reaction to disclose structure-property relationships. The results clearly revealed the key role of ceria morphology rather than structural/textural characteristics on the reducibility and oxygen mobility, following the sequence: NR > NP > NC. The latter seems to have a profound influence on copper-ceria interactions towards the stabilization of Cu+ species, via Ce4+/Ce3+ and Cu2+/Cu+ redox equilibrium. Interestingly, CuO incorporation in different ceria carriers boosts the catalytic activity without, however, affecting the order observed for bare ceria, i.e., CeO2-NR > CeO2-NP > CeO2-NC, implying the key role of support. The Cu/CeO2 sample with the rod-like morphology exhibited the highest catalytic performance, offering almost complete CO elimination at temperatures as low as 100 °C. A perfect relationship between the catalytic performance and the following parameters was disclosed, on the basis of a Mars-van Krevelen mechanism: i) abundance of weakly bound oxygen species, ii) relative population of Cu+/Ce3+ redox pairs, iii) relative abundance of defects and oxygen vacancies.Presented on: Applied Catalysis B: Environmenta