Estudo de catalisadores modelo à base de CeO2-ZrO2 dopado com cobre para controle de emissões de NOx

Convencionalmente, metais nobres são empregados como metais ativos em catalisadores automotivos, mas o uso de cobre vem sendo estudado pelo fato de promover sítios ativos para adsorção química e redução de NOx. Diante deste contexto, esta dissertação visa testar novas formulações de catalisadores, com foco em seu desempenho na reação de redução do NO pelo CO e sua seletividade a N2. Foram avaliados o método de adição de cobre no preparo e os teores de cobre utilizados na preparação. Os métodos de adição utilizados foram impregnação a seco (IS), reação em estado sólido (RS) e coprecipitação (CO). Os teores de cobre estudados ficaram entre 0,36 e 6,9% (m/m). Além disso, foi estudado o impacto no desempenho do catalisador após envelhecimento térmico a 950C por 12h. Foram empregadas as seguintes técnicas de caracterização textural e físico-química como espectrometria de absorção atômica, fisissorção de N2, difração de raios X, espectroscopia Raman e redução a temperatura programada. Os catalisadores também foram avaliados na reação de redução do NO pelo CO. A análise textural indicou que o método de coprecipitação levou a características texturais diferentes dos outros catalisadores. Análises de DRX mostraram a formação de CuO cristalino para teores iguais ou superiores a 3,3% (m/m) de cobre. As análises de Redução a Temperatura Programada (RTP) indicaram que ocorreu uma forte interação na interface entre o suporte e as espécies de cobre dispersas, acompanhada da diminuição da temperatura de redução do CuO e da redução parcial da céria em temperaturas mais baixas. Os testes catalíticos mostraram um melhor desempenho dos catalisadores (IS) que apresentaram conversões mais elevadas em menores temperaturas. Com relação ao envelhecimento, observou-se uma diminuição significativa da eficiência dos catalisadores. Uma comparação com catalisadores à base de metal nobre mostrou um bom desempenho dos catalisadores à base de cobre, com a vantagem destes apresentarem emissão de N2O restrita a baixas temperaturas

Gasoline-range hydrocarbon synthesis over cobalt-based Fischer-Tropsch catalysts supported onSiO2/HZSM-5

Two types of SiO2 with different mesopore size and HZSM-5 zeolite were used to prepare hybrid supported cobalt-based catalysts. The textual and structural properties of the catalysts were studied using N-2 physisorption, X-ray diffraction (XRD), and H-2 temperature-programmed reduction (TPR) techniques. Fischer-Tropsch synthesis (FTS) performances of the catalysts were carried out in a fixed-bed reactor. The combination effects of the meso- and micropores of the supports as well as the interaction between supports and cobalt particles on FTS activity are discussed. The results indicate that the catalyst supported on the tailor-made SiO2 and HZSM-5 hybrid maintained both meso- and micropore pores during the preparation process without HZSM-5 particles agglomerating. The mesopores provided quick mass transfer channels, while the micropores contributed to high metal dispersion and accelerated hydrocracking/hydroisomerization reaction rate. High CO conversion of 83.9% and selectivity to gasoline-range hydrocarbons (C-5-C-12) of 55%, including more than 10% isoparaffins, were achieved simultaneously on this type of catalyst.

Influence of iron promoter on catalytic properties of Rh-Mn-Li/SiO2 for CO hydrogenation

The effect of iron promoter on the catalytic properties of Rh-Mn-Li/SiO2 catalyst in the synthesis Of C-2 oxygenates from syngas was investigated by means of the following techniques: CO hydrogenation reaction, temperature-programmed reduction (TPR), temperature-programmed desorption and reaction of adsorbed CO (CO-TPD and TPSR) and pulse adsorption of CO. The results showed that the addition of iron promoter could improve the activity of the catalysts. Unexpectedly, the yield of C-2 oxygenates increased greatly from 331.6 up to 457.5 g/(kg h) when 0.05% Fe was added into Rh-Mn-Li/SiO2 catalyst, while no change in the selectivity to C-2 oxygenates was observed. However, the activity and selectivity Of C-2 oxygenates were greatly decreased if the Fe amount exceeded 1.0%. The existence of a little iron decreased the reducibility of Rh precursor, while the reduction of Fe component itself became easier. CO uptake decreased with increasing the quantity of Fe addition. This phenomenon was further confirmed by CO-TPD results. The CO-TPD and TPSR results showed that only the strongly adsorbed CO could be hydrogenated, while the weakly adsorbed CO was desorbed. We propose that Fe is highly dispersed and in close contact with Rh and Mn; such arrangements were responsible for the high yield Of C-2 oxygenates. (C) 2002 Elsevier Science B.V. All rights reserved.

Study of the alkylation of isobutane with n-butene over WO3/ZrO2 strong solid acid. 1. Effect of the preparation method, WO3 loading, and calcination temperature

A series of strong solid acids composed of WO3/ZrO2 were prepared. Their crystal structure, surface state, and acidity were determined by the methods of X-ray diffraction, thermal gravimetric and differential thermal analysis, temperature-programmed reduction, laser Raman, and acidity measurement. The results revealed that ZrO2 in WO3/ZrO2 existed mainly in the tetragonal phase, the addition of WO3 plays an important role in stabilizing the tetragonal phase of ZrO2, and all of the samples possessed large surface areas. WO3 in WO3/ZrO2 is mainly monolayer dispersed, and a small amount crystallized on the ZrO2 surface and partly reacted with ZrO2 to form the bond of Zr-O-W, acting as the strong solid acid center. The catalytic properties of WO3/ZrO2 strong solid;acids for alkylation of isobutane with butene at different conditions were investigated. They had a better reaction performance than other strong solid acids; a parallel relationship could be drawn between the catalytic activity and the acid amounts as well as the acidic strength of the catalysts.

Adsorption and interaction of H2S/SO2 on TiO2

Adsorption and interaction of H2S/SO2 on titania as well as on alumina for comparison has been studied by temperature programmed desorption (TPD), infrared (IR) spectroscopy and temperature programmed electronic conductivity (TPEC) techniques. It was found that the adsorption of both H2S acid SO2 on TiO2 is much greater than on Al2O3. The electronic conductivity of TiO2 measured by TPEC varies significantly as adsorption and desorption takes place on TiO2, showing a strong interaction between TiO2 and adsorbates. At temperature above 200 degrees C, H2S or SO2 adsorbed on TiO2 can be converted into S, H2O and SO2 or SO3. While on the hydrogen treated TiO2, H2S is decomposed into S and H-2, SO2 into S. The active sites on TiO2 surface cannot be so strongly adsorbed by SO2 that it is much more resistant to the sulfation reaction. Unlike TiO2, Al2O3 only provides surface adsorption sites, which can be readily sulfated. The data obtained support one's understanding why TiO2 exhibits a better catalytic performance than that of Al2O3 as a Claus reaction catalyst. (C) 1999 Elsevier Science B.V. All rights reserved.

Synthesis and characterization of gallium-based perovskite-type dense membrane with oxygen semipermeability

La0.15Sr0.85Ga0.3Fe0.7O3-delta (LSGFO) and La0.15Sr0.85Co0.3Fe0.7O3-delta (LSCFO) mixed oxygen-ion and electron conducting oxides were synthesized by using a combined EDTA and citrate complexing method, and the corresponding dense membranes were fabricated. The properties of the oxide powders and membranes were characterized with combined SEM, XRD, H-2-TPR, O-2-TPD techniques, mechanical strength and oxygen permeation measurement. The results showed that LSGFO had much higher thermochemical stability than LSCFO due to the higher valence stability of Ga3+. After the temperature-programmed reduction by 5% H-2 in Ar from 20 degreesC to 1020 degreesC, the basic perovskite structure of LSGFO was successfully preserved. LSGFO also favors the oxygen vacancy formation better than LSCFO. Oxygen permeation measurement demonstrated that LSGFO had higher oxygen permeation flux than LSCFO, but they had similar activation energy for oxygen transportation, with a value of 110 and 117 kJ . mol(-1), respectively The difference in oxygen permeation fluxes was correlated with the difference in oxygen vacancy concentrations for the two materials.

Simultaneous hydrodesulfurization of thiophene and hydrogenation of cyclohexene over dimolybdenum nitride catalysts

A series of unsupported dimolybdenum nitride (gamma-Mo(2)N) catalysts differing in surface area were prepared by temperature programmed reduction of MoO(3) with a mixture of NH(3):N(2) (90:10). Characterization of catalysts by BET, XRD, TPR and XPS techniques was carried out. The samples were used as catalysts in hydrotreating reactions (simultaneous hydrodesulfurization of thiophene and hydrogenation of cyclohexene). Low surface area gamma-Mo(2)N materials show much higher specific conversions than those with higher surface area. These results indicate that HDS and HYD reactions over gamma-Mo(2)N seem to be structure-sensitive. The relative exposure extent of crystalline planes (111) and (200) over the different catalysts can be associated with their hydrogen adsorption capacities and with their catalytic performances. The catalytic activities are significantly affected by the catalyst pretreatment conditions. (C) 1999 Elsevier Science B.V. All rights reserved.

Structure and base properties of calcined hydrotalcites

Five hydrotalcites with Mg/Al molar ratio range of 3-15 were prepared. The structure and basicity of Mg-Al mixed oxides (Mg(Al)O) transformed from hydrotalcites were investigated by TPD, XPS, XRD, FT-IR and NMR techniques. The results of elemental analysis and XPS indicate that Al is enriched in the surface regions of Mg(Al)O, and its amount increases with the Mg/Al molar ratio and, the calcination temperature. Al-27-MAS-NMR results show that Al exists in two chemical environments: tetrahedral aluminium (Al(t)) and octahedral aluminium (Al(o)) in Mg(AI)O. The amount of Al(t) increases with the Mg/Al molar ratio and the calcination temperature. It is assumed that Al(t) may be mainly from the surface Al. Temperature-programmed desorption (TPD) of CO2 shows that the number of basic sites of Mg(Al)O samples increases with the Mg/Al molar ratio, and the maximum number of basic sites is obtained for hydrotalcite calcined at 773 K. Infrared spectra of adsorbed CO2 and B(OCH3)(3) reveal that there are two kinds of basic sites: weak basic OH- sites and strong basic O2- sites on the Mg(AI)O samples, the base strength depends on the Mg/Al molar ratio and calcination temperature.

Different mechanisms for the formation of acetaldehyde and ethanol on the Rh-based catalysts

Different mechanisms for the formation of acetaldehyde and ethanol on the Rh-based catalysts were investigated by the TPR (temperature programmed reaction) method, and the active sites were studied by CO-TPD, TPSR (temperature programmed surface reaction of preadsorbed CO by H-2) and XPS techniques. The TPR results indicated that ethanol and acetaldehyde might be formed through different intermediates, whereas ethanol and methanol might result from the same intermediate. Results of CO-TPD, TPSR, and XPS showed that on the Rh-based catalyst, the structure of the active sites for the formation of C-2-oxygenates is ((RhxRhy+)-Rh-0)-O-Mn+ (M=Mn or Zr, x>>y, 2 less than or equal ton less than or equal to4). The tilt-adsorbed CO species is the main precursor for CO dissociation and the precursor for the formation of ethanol and methanol. Most of the linear and geminal adsorbed CO species desorbed below 500 K. Based on the suggested model of the active sites, detailed mechanisms for the formation of acetaldehyde and ethanol are proposed. Ethanol is formed by direct hydrogenation of the tilt-adsorbed CO molecules, followed by CH2 insertion into the surface CH2-O species and the succeeding hydrogenation step. Acetaldehyde is formed through CO insertion into the surface CH3-Rh species followed by hydrogenation, and the role of the promoters was to stabilize the intermediate of the surface acetyl species. (C) 2000 Academic Press.

Characterizations and activities of the nano-sized Ni/Al2O3 and Ni/La-Al2O3 catalysts for NH3 decomposition

A series of nano-sized Ni/Al2O3 and Ni/La-Al2O3 catalysts that possess high activities for NH3 decomposition have been successfully synthesized by a coprecipitation method. The catalytic performance was investigated under the atmospheric conditions and a significant enhancement in the activity after the introduction of La was observed. Aiming to study the influence of La promoter on the physicochemical properties, we characterized the catalysts by N-2 adsorption/desorption, XRD, H-2-TPR, chemisorption and TEM techniques. Physisorption results suggested a high specific surface area and XRD spectra showed that nickel particles are in a highly dispersed state. A combination of XRD, TEM and chemisorption showed that Ni-0 particles with the average size lower, than 5.0 nm are always obtained even though the Ni loading ranged widely from 4 to 63 %. Compared with the Ni/Al2O3 catalysts, the Ni/La-Al2O3 ones with an appropriate amount of promoter enjoy a more open mesoporous structure and higher dispersion of Ni. Reduction kinetic studies of prepared catalysts were investigated by temperature-programmed reduction (TPR) method and the fact that La additive partially destroyed the metastable Ni-Al mixed oxide phase was detailed. (c) 2005 Elsevier B.V. All rights reserved.

Resolution prediction and optimization of temperature programme in comprehensive two-dimensional gas chromatography

A model is developed for predicting the resolution of interested component pair and calculating the optimum temperature programming condition in the comprehensive two-dimensional gas chromatography (GC x GC). Based on at least three isothermal runs, retention times and the peak widths at half-height on both dimensions are predicted for any kind of linear temperature-programmed run on the first dimension and isothermal runs on the second dimension. The calculation of the optimum temperature programming condition is based on the prediction of the resolution of "difficult-to-separate components" in a given mixture. The resolution of all the neighboring peaks on the first dimension is obtained by the predicted retention time and peak width on the first dimension, the resolution on the second dimension is calculated only for the adjacent components with un-enough resolution on the first dimension and eluted within a same modulation period on the second dimension. The optimum temperature programming condition is acquired when the resolutions of all components of interest by GC x GC separation meet the analytical requirement and the analysis time is the shortest. The validity of the model has been proven by using it to predict and optimize GC x GC temperature programming condition of an alkylpyridine mixture. (c) 2005 Elsevier B.V. All rights reserved.

CO hydrogenation to light alkenes over Mn/Fe catalysts prepared by coprecipitation and sol-gel methods

CO hydrogenation to light alkenes was carried out on manganese promoted iron catalysts prepared by coprecipitation and sol-gel techniques. Addition of manganese in the range of 1-4 mol.% by means of coprecipitation could improve notably the percentage of C-2 (=) similar to C-4 (=) in the products, but it was not so efficient when the sol-gel method was employed. XRD and H-2-TPR measurements showed that the catalyst samples giving high C-2 (=) similar to C-4 (=) yields possessed ultra. ne particles in the form of pure alpha-(Fe1-xMnx)(2)O-3, and high quality in lowering the reduction temperature of the iron oxide. Furthermore, these samples displayed deep extent of carburization and different surface procedures to the others in the tests of Temperature Programmed Surface Carburization (TPSC). The different surface procedures of these samples were considered to have close relationship with the evolving of surface oxygen. It was also suggested that for the catalysts with high C-2 (=) similar to C-4 (=) yields, the turnover rate of the active site could be kept at a relatively high level due to the improved reducing and carburizing capabilities. Consequently, there would be a large number of sites for CO adsorption/dissociation and an enhanced carburization environment on the catalyst surface, so that the process of hydrogenation could be suppressed relatively to a low level. As a result, the percentage of the light alkenes in the products could be raised.

Redox cycling of Ni-YSZ anode investigated by TPR technique

Effect of redox cycling on a Ni-YSZ anode prepared from 50 wt.% NiO and 50 wt.% YSZ was investigated by using temperature-programmed reduction (TPR), XRD and SEM techniques. XRD results showed that NiO was formed during re-oxidation. Both the XRD and TPR results depicted that the conversion of nickel to NiO depended on the re-oxidation temperature. The oxidation of Ni to NiO occurred quickly in the initial several minutes and then reached a quasi equilibrium. The TPR profiles tracing the redox cycling showed that it brought continuous changes in the NiO micro-structure at 800 degrees C, whereas at 600 degrees C it had only little effects on the reduction of NiO. Re-oxidation resulted in the formation of spongy aggregates of NiO crystallites. Redox cycling at 800 degrees C led to a continuous decrease in the primary crystallite size of NiO and a high dispersion of the Ni particles. A continuous expansion of the slice sample was observed in both of the oxidized and reduced states during the redox cycling at 800 degrees C, whereas this process did not occur during the redox cycling at 600 degrees C. (c) 2005 Elsevier B.V All rights reserved.

New Cu-Based Catalysts Supported on TiO2 Films for Ullmann SNAr-Type C-O Coupling Reactions

New routes for the preparation of highly active TiO2-supported Cu and CuZn catalysts have been developed for C-O coupling reactions. Slurries of a titania precursor were dip-coated onto glass beads to obtain either structured mesoporous or non-porous titania thin films. The Cu and CuZn nanoparticles, synthesized using a reduction by solvent method, were deposited onto calcined films to obtain a Cu loading of 2 wt%. The catalysts were characterized by inductively coupled plasma (ICP) spectroscopy, temperature-programmed oxidation/reduction (TPO/TPR) techniques, Cu-63 nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction (XRD), scanning and transmission electron microscopy (S/TEM-EDX) and X-ray photo-electron spectroscopy (XPS). The activity and stability of the catalysts obtained have been studied in the C-O Ullmann coupling of 4-chloropyridine and potassium phenolate. The titania-supported nanoparticles retained catalyst activity for up to 12 h. However, catalyst deactivation was observed for longer operation times due to oxidation of the Cu nanoparticles. The oxidation rate could be significantly reduced over the CuZn/TiO2 catalytic films due to the presence of Zn. The 4-phenoxypyridine yield was 64% on the Cu/nonporous TiO2 at 120 degrees C. The highest product yield of 84% was obtained on the Cu/mesoporous TiO2 at 140 degrees C, corresponding to an initial reaction rate of 104 mmol g(cat)(-1) s(-1). The activation energy on the Cu/mesoporous TiO2 catalyst was found to be (144 +/- 5) kJ mol(-1), which is close to the value obtained for the reaction over unsupported CuZn nanoparticles (123 +/- 3 kJ mol(-1)) and almost twice the value observed over the catalysts deposited onto the non-porous TiO2 support (75 +/- 2 kJ mol(-1)).

Effect of vanadia on physico-chemical and catalytic characteristics of dysprosia

Physico-chemical characterization of DY203/V2O5 systems prepared through wet impregnation method has been carried out using various techniques like EDX, XRD, FTIR. thermal studies, BET surface area, pore volume and pore size distribution analysis. The amount of vanadia incorporated has been found to influence the surface properties of dysprosia. The spectroscopic results combining with X-ray analysis reveal that vanadia species exist predominantly as isolated amorphous vanadyl units along with crystalline dysprosium orthovanadate. Basicity studies have been conducted by adsorption of electron acceptors and acidity and acid strength distribution by temperature programmed desorption of ammonia. Cyclohexanol decomposition has been employed as a chemical probe reaction to examine the effect of vanadia on the acid base property of Dy2O3. Incorporation of vanadia titrates thc Lewis acid and base sites of Dy2O3, while an enhancement of Bronsted acid sites has been noticed. Data have been correlated with the catalytic activity of these oxides towards the vapour phase methylation of phenol