PAH formation in one-dimensional premixed fuel-rich atmospheric pressure ethylbenzene and ethyl alcohol flames

This study addresses health-hazardous emissions from combustion of aromatic and oxygenated components of engine fuel blends. An investigation was conducted on the evolution of polycyclic aromatic hydrocarbons (PAH) and other pollutants (soot, CO, unburned light hydrocarbons) emitted from one-dimensional ethylbenzene and ethyl alcohol flames. The study of ethylbenzene combustion is also pertinent to that of waste polystyrene, as past work has indicated that ethylbenzene may be a surrogate for initial products of polystyrene pyrolysis. Both liquid fuels were prevaporized in nitrogen, mixed with oxygen and additional nitrogen, and upon ignition, premixed flat flames were stabilized over a burner. Temperature measurements and product sampling were conducted at various heights above the burner. Results showed that ethyl alcohol combustion generated small yields of PAH, even under the adverse fuel-rich conditions of this study (?=2.5). PAH mole fractions in the ethyl alcohol flame were 2-5 orders of magnitude lower than those in the ethylbenzene flame at the same location. PAH mole fractions often peaked in the postflame region and remained at relatively high levels thereafter. PAH mole fractions in premixed fuel-rich benzene, ethane, ethylene, and methane flames, published in the literature, were typically in between those found in the two flames of this study. Computations were conducted using a currently developed detailed kinetic model, allowing for the prediction of formation and depletion of major PAH and soot particles of different sizes. The computed chemical flame structures were compared to experimental data obtained in the present work. Predicted mole fractions were often close to the experimentally obtained values or, at worse, within the same order of magnitude for both fuels. Reaction pathways are discussed.     

Kinetics of pore formation and resulting properties of lightweight inorganic polymers

Inorganic polymer (IP) foams could be used as an alternative to commonly available cellular concretes. To do so, however, it is crucial to understand how the foaming kinetics and the final foam properties can be controlled and tailored to delivered the desired performance. The research reported in this article investigates the influence of the SiO₂/Na₂O ratio of the activating solution, addition time of foaming agent, and temperature, on the reaction kinetics and final properties of a porous IP. The IPs were formed by activating fayalite slag, a by-product of secondary copper production, with a sodium-silicate solution. Foaming was achieved by introducing metallic Al into the formulation, oxidizing it in the alkaline environment, liberating H₂ gas, and entrapping it. Reaction kinetics were assessed using isothermal calorimetry, rheology, and a dedicated setup to record the foaming. The mechanical and physical properties of the foam were assessed via compressive strength and water absorption measurements. Microstructural analysis was undertaken using electron microscopy and computed tomography. The results showed that by decreasing the SiO₂/Na₂O ratio and/or increasing the temperature, the reaction kinetics were accelerated. Regarding the properties, postponing the initiation of the foaming led to more uniform and smaller pores, resulting in an increased compressive strength-to-density ratio.     

The fate of iron during the alkali‐activation of synthetic (CaO‐)FeOx‐SiO2 slags: An Fe K‐edge XANES study

Slags from the nonferrous metals industry have great potential to be used as feedstocks for the production of alkali‐activated materials. Until now, however, only very limited information has been available about the structural characteristics of these materials. In the work presented herein, synthetic slags in the CaO–FeO_x–SiO₂ system, representing typical compositions of Fe‐rich slags, and inorganic polymers (IPs) produced from the synthetic slags by activation with alkali silicate solutions have been studied by means of X‐ray absorption near‐edge structure (XANES) spectroscopy at the Fe K‐edge. The iron in the slags was largely Fe²⁺, with an average coordination number of approximately 5 for the iron in the amorphous fraction. The increase in average oxidation number after alkali‐activation was conceptualized as the consequence of slag dissolution and IP precipitation, and employed to calculate the degrees of reaction of the slags. The degree of reaction of the slags increased with increasing amorphous fraction. The iron in the IPs had an average coordination number of approximately 5; thus, IPs produced from the Fe‐rich slags studied here are not Fe‐analogs of aluminosilicate geopolymers, but differ significantly in terms of structure from the latter.     

Combustion behavior in air of single particles from three different coal ranks and from sugarcane bagasse

Comparative combustion studies were performed on particles of pulverized coal samples from three different ranks: a high-volatile bituminous coal, a sub-bituminous coal, and two lignite coals. The study was augmented to include observations on burning pulverized woody biomass residues, in the form of sugarcane bagasse. Fuel particles, in the range of 75–90 μm, were injected in a bench-scale, transparent drop-tube furnace, electrically-heated to 1400 K, where they experienced high-heating rates, ignited and burned. The combustion of individual particles in air was observed with three-color pyrometry and high-speed high-resolution cinematography to obtain temperature–time–size histories. Based on combined observations from these techniques, in conjunction to morphological examinations of particles, a comprehensive understanding of the combustion behaviors of these fuels was developed. Observed differences among the coals have been striking. Upon pyrolysis, the bituminous coal chars experienced the phenomena of softening, melting, swelling and formation of large blowholes through which volatile matter escaped. Combustion of the volatile matter was sooty and very luminous with large co-tails forming in the wake of the particle trajectories. Only after the volatile matter flames extinguished, the char combustion commenced and was also very luminous. In contrast, upon pyrolysis, lignite coals became fragile and experienced extensive fragmentation, immediately followed by ignition of the char fragments (numbering in the order of 10–100, depending on the origin of the lignite coal) spread apart into a relatively large volume. As no separate volatile matter combustion period was evident, it is likely that volatiles burned on the surface of the chars. The combustion of the sub-bituminous coal was also different. Most particles experienced limited fragmentation, upon pyrolysis, to several char fragments, with or without the presence of brief and low-luminosity volatile flames; other particles did not fragment and directly proceeded to char combustion. Finally combustion of bagasse was once again very distinctive. Upon pyrolysis, long-lasting, low-luminosity, nearly-transparent spherical flames formed around slowly-settling devolatilizing particles. They were followed by bright, short-lived combustion of the chars. Both volatiles and chars experienced shrinking core mode of burning. For all fuels, flame and char temperature profiles were deduced from pyrometric data and burnout times were measured. Combustion rates were calculated from luminous carbon disappearance measurements, and were compared with predictions based on published kinetic expressions.     

Free and immobilized Lactobacillus casei ATCC 393 on whey protein as starter cultures for probiotic Feta-type cheese production

The use of free and immobilized Lactobacillus casei ATCC 393 on whey protein as starter culture in probiotic Feta-type cheese production was evaluated. The probiotic cultures resulted in significantly higher acidity; lower pH; reduced counts of coliforms, enterobacteria, and staphylococci; and improved quality characteristics compared with cheese with no culture. Microbiological and strain-specific multiplex PCR analysis showed that both free and immobilized L. casei ATCC 393 were detected in the novel products at levels required for conferring a probiotic effect at the end of the ripening. The effect of starter culture on production of volatile compounds was investigated by the solid-phase microextraction gas chromatography-mass spectrometry analysis technique. The immobilized cells resulted in an improved profile of aroma-related compounds and the overall high quality of the novel products was ascertained by the preliminary sensory test. Finally, the high added value produced by exploitation of whey, which is an extremely polluting industrial waste, was highlighted and assessed.     

Classical and alternative fuel mix optimization in cement production using mathematical programming

In this paper a systematic methodology is presented for the simultaneous optimal selection of raw materials, fossil fuels and alternative fuels in cement production. The aim is to offer a generic mathematical formulation that can be used as the basis for developing case specific mathematical formulations that can assist the strategic decision-making process. The mathematical model presented takes into consideration the essential elements of a cement plant operation. The final formulation is a mixed integer linear programming problem that aims at minimizing the overall operating cost. A realistic case study is presented which demonstrates the usefulness of the proposed mathematical programming methodology.     

Heat transport limitations and reaction scheme of partial oxidation of methane to synthesis gas over supported rhodium catalysts

The partial oxidation of methane to synthesis gas over supported Rh catalysts is investigated, paying particular attention to removing heat transport limitations and identifying the reaction conditions within the kinetic-controlling regime. The results obtained suggest that the reaction follows the sequence of total oxidation to CO₂ and H₂O, followed by reforming reactions to synthesis gas.