Pozzolanic activity of oil-refining catalyst: evaluation by electron and atomic microscopy

The reuse of waste fluid catalytic cracking (FCC) catalyst as partial surrogate for cement can reduce the environmental impact of both the oil-refinery and cement production industries [1,2]. FCC catalysts can be considered as pozzolanic materials since in the presence of water they tend to chemically react with calcium hydroxide to produce compounds possessing cementitious properties [3,4]. In addition, partial replacement of cement with FCC catalysts can enhance the performance of pastes and mortars, namely by improving their compressive strength [5,6]. In the present work the reaction of waste FCC catalyst with Ca(OH)2 has been investigated after a curing time of 28 days by scanning electron microscopy (SEM) with electron backscattered signal (BSE) combined with X-ray energy dispersive spectroscopy (EDS) carried out with a JEOL JSM 7001F instrument operated at 15 kV coupled to an INCA pentaFetx3 Oxford spectrometer. The polished cross-sections of FCC particles embedded in resin have also been evaluated by atomic force microscopy (AFM) in contact mode (CM) using a NanoSurf EasyScan 2 instrument. The SEM/EDS results revealed that an inward migration of Ca occurred during the reaction. A weaker outward migration of Si and Al was also apparent (Fig. 1). The migration of Ca was not homogeneous and tended to follow high-diffusivity paths within the porous waste FCC catalyst particles. The present study suggests that the porosity of waste FCC catalysts is key for the migration/reaction of Ca from the surrounding matrix, playing an important role in the pozzolanic activity of the system. The topography images and surface roughness parameters obtained by atomic force microscopy can be used to infer the local porosity in waste FCC catalyst particles (Fig. 2).

Assessment of exposure to airborne ultrafine particles in the urban environment of Lisbon, Portugal

The aim of this study was the assessment of exposure to ultrafine in the urban environment of Lisbon, Portugal, due to automobile traffic, and consisted of the determination of deposited alveolar surface area in an avenue leading to the town center during late spring. This study revealed differentiated patterns for weekdays and weekends, which could be related with the fluxes of automobile traffic. During a typical week, ultrafine particles alveolar deposited surface area varied between 35.0 and 89.2 μm2/cm3, which is comparable with levels reported for other towns such in Germany and the United States. These measurements were also complemented by measuring the electrical mobility diameter (varying from 18.3 to 128.3 nm) and number of particles that showed higher values than those previously reported for Madrid and Brisbane. Also, electron microscopy showed that the collected particles were composed of carbonaceous agglomerates, typical of particles emitted by the exhaustion of diesel vehicles. Implications: The approach of this study considers the measurement of surface deposited alveolar area of particles in the outdoor urban environment of Lisbon, Portugal. This type of measurements has not been done so far. Only particulate matter with aerodynamic diameters <2.5 (PM2.5) and >10 (PM10) μm have been measured in outdoor environments and the levels found cannot be found responsible for all the observed health effects. Therefore, the exposure to nano- and ultrafine particles has not been assessed systematically, and several authors consider this as a real knowledge gap and claim for data such as these that will allow for deriving better and more comprehensive epidemiologic studies. Nanoparticle surface area monitor (NSAM) equipments are recent ones and their use has been limited to indoor atmospheres. However, as this study shows, NSAM is a very powerful tool for outdoor environments also. As most lung diseases are, in fact, related to deposition of the alveolar region of the lung, the metric used in this study is the ideal one.

Comparison of indoor and outdoor fungi and particles in poultry units

A descriptive study was developed in order to compare indoor and outdoor air contamination caused by fungi and particles in seven poultry units. Twenty eight air samples of 25 litters were collected through the impaction method on malt extract agar. Air sampling and particles concentration measurement were done in the interior and also outside premises of the poultries’ pavilions. Regarding the fungal load in the air, indoor concentration of mold was higher than outside air in six poultry units. Twenty eight species / genera of fungi were identified indoor, being Scopulariopsis brevicaulis (40.5%) the most commonly isolated species and Rhizopus sp. (30.0%) the most commonly isolated genus. Concerning outdoor, eighteen species/genera of fungi were isolated, being Scopulariopsis brevicaulis (62.6%) also the most isolated. All the poultry farms analyzed presented indoor fungi different from the ones identified outdoors. Regarding particles’ contamination, PM2.5, PM5.0 and PM10 had a statistically significant difference (Mann-Whitney U test) between the inside and outside of the pavilions, with the inside more contaminated (p=.006; p=.005; p=.005, respectively). The analyzed poultry units are potential reservoirs of substantial amounts of fungi and particles and could therefore free them in the atmospheric air. The developed study showed that indoor air was more contaminated than outdoors, and this can result in emission of potentially pathogenic fungi and particles via aerosols from poultry units to the environment, which may post a considerable risk to public health and contribute to environmental pollution.

Low-Carbon Cement with Waste Oil-Cracking Catalyst Incorporation

The present paper shows preliminary results of an ongoing project which one of the goals is to investigate the viability of using waste FCC catalyst (wFCC), originated from Portuguese oil refinery, to produce low carbon blended cements. For this purpose, four blended cements were produced by substituting cement CEM I 42.5R up to 20% (w/w) by waste FCC catalyst. Initial and final setting times, consistency of standard paste, soundness and compressive strengths after 2, 7 and 28 days were measured. It was observed that the wFCC blended cements developed similar strength, at 28 days, compared to the reference cement, CEM I 42.5R. Moreover, cements with waste FCC catalyst incorporation up to 15% w/w meet European Standard EN 197-1 specifications for CEM II/A type cement, in the 42.5R strength class.

Phase diagrams of particles with dissimilar patches: X-junctions and Y-junctions

We use Wertheim's first-order perturbation theory to investigate the phase behaviour and the structure of coexisting fluid phases for a model of patchy particles with dissimilar patches (two patches of type A and f(B) patches of type B). A patch of type alpha = {A, B} can bond to a patch of type beta = {A, B} in a volume nu(alpha beta), thereby decreasing the internal energy by epsilon(alpha beta). We analyse the range of model parameters where AB bonds, or Y-junctions, are energetically disfavoured (epsilon(AB) < epsilon(AA)/2) but entropically favoured (nu(AB) >> nu(alpha alpha)), and BB bonds, or X-junctions, are energetically favoured (epsilon(BB) > 0). We show that, for low values of epsilon(BB)/epsilon(AA), the phase diagram has three different regions: (i) close to the critical temperature a low-density liquid composed of long chains and rich in Y-junctions coexists with a vapour of chains; (ii) at intermediate temperatures there is coexistence between a vapour of short chains and a liquid of very long chains with X-and Y-junctions; (iii) at low temperatures an ideal gas coexists with a high-density liquid with all possible AA and BB bonds formed. It is also shown that in region (i) the liquid binodal is reentrant (its density decreases with decreasing temperature) for the lower values of epsilon(BB)/epsilon(AA). The existence of these three regions is a consequence of the competition between the formation of X- and Y-junctions: X-junctions are energetically favoured and thus dominate at low temperatures, whereas Y-junctions are entropically favoured and dominate at higher temperatures.

On the assessment of exposure to airborne ultrafine particles in urban environments

The aim of this study was to contribute to the assessment of exposure levels of ultrafine particles in the urban environment of Lisbon, Portugal, due to automobile traffic, by monitoring lung deposited alveolar surface area (resulting from exposure to ultrafine particles) in a major avenue leading to the town center during late spring, as well as in indoor buildings facing it. Data revealed differentiated patterns for week days and weekends, consistent with PM2.5 and PM10 patterns currently monitored by air quality stations in Lisbon. The observed ultrafine particulate levels may be directly correlated with fluxes in automobile traffic. During a typical week, amounts of ultrafine particles per alveolar deposited surface area varied between 35 and 89.2 μm2/cm3, which are comparable with levels reported for other towns in Germany and the United States. The measured values allowed for determination of the number of ultrafine particles per cubic centimeter, which are comparable to levels reported for Madrid and Brisbane. In what concerns outdoor/indoor levels, we observed higher levels (32 to 63%) outdoors, which is somewhat lower than levels observed in houses in Ontario.

Comparison of deposited surface area of airborne ultrafine particles generated from two welding processes

This article describes work performed on the assessment of the levels of airborne ultrafine particles emitted in two welding processes metal-active gas (MAG) of carbon steel and friction-stir welding (FSW) of aluminium in terms of deposited area in alveolar tract of the lung using a nanoparticle surface area monitor analyser. The obtained results showed the dependence from process parameters on emitted ultrafine particles and clearly demonstrated the presence of ultrafine particles, when compared with background levels. The obtained results showed that the process that results on the lower levels of alveolar-deposited surface area is FSW, unlike MAG. Nevertheless, all the tested processes resulted in important doses of ultrafine particles that are to be deposited in the human lung of exposed workers.

Monitoring exposure to airborne ultrafine particles in Lisbon, Portugal

The aim of this study is to contribute to the assessment of exposure levels of ultrafine particles (UFP) in the urban environment of Lisbon, Portugal, due to automobile traffic, by monitoring lung-deposited alveolar surface area (resulting from exposure to UFP) in a major avenue leading to the town centre during late Spring, as well as in indoor buildings facing it. This study revealed differentiated patterns for week days and weekends, consistent with PM(2.5) and PM(10) patterns currently monitored by air quality stations in Lisbon. The observed ultrafine particulate levels could be directly related with the fluxes of automobile traffic. During a typical week, UFP alveolar deposited surface area varied between 35.0 and 89.2 µm(2)/cm(3), which is comparable with levels reported for other towns such in Germany and United States. The measured values allowed the determination of the number of UFP per cm(3), which are comparable to levels reported for Madrid and Brisbane. In what concerns outdoor/indoor levels, we observed higher levels (32-63%) outdoor, which is somewhat lower than levels observed in houses in Ontario.

Exposure to airborne ultrafine particles from cooking in Portuguese homes

Cooking was found to be a main source of submicrometer and ultrafine aerosols from gas combustion in stoves. Therefore, this study consisted of the determination of the alveolar deposited surface area due to aerosols resulting from common domestic cooking activities (boiling fish, vegetables, or pasta, and frying hamburgers and eggs). The concentration of ultrafine particles during the cooking events significantly increased from a baseline of 42.7 μm2/cm3 (increased to 72.9 μm2/cm3 due to gas burning) to a maximum of 890.3 μm2/cm3 measured during fish boiling in water, and a maximum of 4500 μm2/cm3 during meat frying. This clearly shows that a domestic activity such as cooking can lead to exposures as high as those of occupational exposure activities.

A strategy to extend reactive distillation column performance under catalyst deactivation

This work addresses the effects of catalyst deactivation and investigates methods to reduce their impact on the reactive distillation columns performance. The use of variable feed quality and reboil ratio are investigated using a rigorous dynamic model developed in gPROMS and applied to an illustrative example, i.e., the olefin metathesis system, wherein 2-pentene reacts to form 2-butene and 3-hexene. Three designs and different strategies on column energy supply to tackle catalyst deactivation are investigated and the results compared.

Catalytic combustion of toluene on Pt zeolite coated cordierite foams

The catalytic properties of Pt based cordierite foam catalysts have been evaluated in catalytic combustion of toluene (800 ppm in air). The catalysts contain identical Pt content (0.1%) which was introduced by three different ways: Pt ion exchange on MFI zeolite and then coating on the foam; Pt ion exchange after zeolite coating and finally Pt directly wet impregnated on the cordierite foam. The catalytic behaviour of Pt foam based catalysts was compared with that of PtMFI zeolite under powder form. Pt exchanged MFI supported on the cordierite foams present an improvement of activity for toluene combustion of about 50 degrees C on the light off temperature (T-50%). The enhanced performance of the structured catalysts is due not only to the open structure of foams and homogeneous thin layers catalyst deposited on their cell walls, but also to the fact that the size and location of Pt particles present in MFI zeolite are changed during the dipping step. Indeed, as prepared Pt samples and those used in the preparation of the slurry were observed by transmission electron microscopy revealing that the chemical interaction of PtMFI zeolite with the binder and detergent, both present in the slurry, leads to an increase of Pt particles size which were found to migrate from internal pores to the external surface of zeolite crystallites thereby increasing catalytic activity. (C) 2011 Elsevier B.V. All rights reserved.

Patching up dipoles: can dipolar particles be viewed as patchy colloids?

We investigate whether the liquid-vapour phase transition of strongly dipolar fluids can be understood using a model of patchy colloids. These consist of hard spherical particles with three short-ranged attractive sites (patches) on their surfaces. Two of the patches are of type A and one is of type B. Patches A on a particle may bond either to a patch A or to a patch B on another particle. Formation of an AA (AB) bond lowers the energy by epsilon AA (epsilon AB). In the limit [image omitted], this patchy model exhibits condensation driven by AB-bonds (Y-junctions). Y-junctions are also present in low-density, strongly dipolar fluids, and have been conjectured to play a key role in determining their critical behaviour. We map the dipolar Yukawa hard-sphere (DYHS) fluid onto this 2A + 1B patchy model by requiring that the latter reproduce the correct DYHS critical point as a function of the isotropic interaction strength epsilon Y. This is achieved for sensible values of epsilon AB and the bond volumes. Results for the internal energy and the particle coordination number are in qualitative agreement with simulations of DYHSs. Finally, by taking the limit [image omitted], we arrive at a new estimate for the critical point of the dipolar hard-sphere fluid, which agrees with extrapolations from simulation.

Study of Pt/MCM-22 based catalysts in the transformation of n-hexane: effect of rare earth elements and mode of platinum introduction

The bifunctional transformation of n-hexane was carried out over Pt/MCM-22 based catalysts. MCM-22 was synthesized and submitted to ion exchange with rare earth nitrate solutions of La, Nd and Yb, followed by Pt introduction. Three different methods were used to introduce about 1 wt% of Pt in the zeolite: ion exchange, incipient wetness impregnation and mechanical mixture with Pt/Al(2)O(3). The bifunctional catalysts were characterized by transmission electron microscopy and by the model reaction of toluene hydrogenation. These experiments showed that, in the ion exchanged sample, Pt is located both within the inner micropores and on the outer surface, whereas in the impregnated one, the metal is essentially located on the outer surface under the form of large particles. The presence of RE elements increases the hydrogenating activity of Pt/MCM-22 since the location of these species at the vicinity of metal particles causes modification on its electronic properties. Whatever the mode of Pt introduction, a fast initial decrease in conversion is observed for n-hexane transformation, followed by a plateau related to the occurrence of the catalytic transformations at the hemicages located at the outer surface of the crystals. The effect of rare earth elements on the hydrogenating function leads to a lower selectivity in dibranched isomers and increased amounts of light products.

Wrinkling Labyrinth Patterns on Elastomeric Janus Particles

We describe a novel, low-cost and low-tech method for the fabrication of elastomeric Janus particles with diameters ranging from micrometers to millimeters. This consists of UV-irradiating soft urethane/urea elastomer spheres, which are then extracted in toluene and dried. The spheres are thus composed of a single material: no coating or film deposition steps are required. Furthermore, the whole procedure is carried out at ambient temperature and pressure. Long, labyrinthine corrugations ("wrinkles") appear on the irradiated portions of the particles' surfaces, the spatial periodicity of which can be controlled by varying the sizes of particles. The asymmetric morphology of the resulting Janus particles has been confirmed by scanning electron microscopy, atomic force microscopy, and optical microscopy. We have also established that the spheres behave elastically by performing bouncing tests with dried and swollen spheres. Results can be interpreted by assuming that each sphere consists of a thin, stiff surface layer ("skin") lying atop a thicker, softer substrate ("bulk"). The skin's higher stiffness is hypothesized to result from the more extensive cross-linking of the polymer chains located near the surface by the UV radiation. Textures then arise from competition between the effects of bending the skin and compressing the bulk, as the solvent evaporates and the sphere shrinks.

Impact of Sahara dust transport on Cape Verde atmospheric element particles

The objectives of this study were to (1) conduct an elemental characterization of airborne particles sampled in Cape Verde and (2) assess the influence of Sahara desert on local suspended particles. Particulate matter (PM10) was collected in Praia city (14°94'N; 23°49'W) with a low-volume sampler in order to characterize its chemical composition by k0-INAA. The filter samples were first weighed and subsequently irradiated at the Portuguese Research Reactor. Results showed that PM10 concentrations in Cape Verde markedly exceeded the health-based air quality standards defined by the European Union (EU), World Health Organization (WHO), and U.S. Environmental Protection Agency (EPA), in part due to the influence of Sahara dust transport. The PM10 composition was characterized essentially by high concentrations of elements originating from the soil (K, Sm, Co, Fe, Sc, Rb, Cr, Ce, and Ba) and sea (Na), and low concentrations of anthropogenic elements (As, Zn, and Sb). In addition, the high concentrations of PM measured in Cape Verde suggest that health of the population may be less affected compared with other sites where PM10 concentrations are lower but more enriched with toxic elements.