Tomás García

Spatial and temporal PAH concentrations in Zaragoza, Spain

The concentration of seven polycyclic aromatic hydrocarbons (PAH) associated with the atmospheric solid phase was measured in the Zaragoza (North-East of Spain) atmosphere using fluorescence spectroscopy in the synchronous mode (FS). The PAH results were reported for four different urban and suburban places, located within the city and during the period October 1999-September 2001. The PAH data obtained indicated the importance of local sources generated from urban/industrial areas. Although the PAH total concentration was quite similar in all the sampling sites, the main differences were due to Benzo[a]pyrene (BaP) and Coronene (Cor) concentrations, reaching the highest values in the sites associated with heavy traffic (trucks, lorries, etc.). The temporal evolution of atmospheric solid phase PAH concentrations indicated a seasonal trend. Higher PAH concentrations were found during colder seasons for the four sampling sites. The influence of environmental parameters such as temperature, rain, relative humidity, wind speed and direction on the PAH emissions was analyzed observing a positive correlation between the total PAH concentration and the relative humidity and a negative one with the temperature. With regard to the wind direction, higher PAH emissions were detected when wind was coming from an east and north-east direction. Wind from a north-westerly direction showed lower PAH emissions associated with the cierzo wind which provided cleaner air.

Toxic organic emissions from coal combustion

Atmospheric fluidized bed combustion (AFBC) is considered to be an environmentally favorable combustion technology where the control of emissions can be integrated into the combustion system. FBC operates at low temperatures, 800–900°C, to prevent thermal NO formation and to favor the sulfur removal by the sorbent, but it has not been taken into account that when coal is burnt, not only NOx, SOx and COx are emitted. In addition, volatile organic pollutants (VOCs) are emitted. From these VOCs, the polycyclic aromatic hydrocarbons (PAHs) constitute one of the most dangerous compounds because of the possibility of interacting with biological nucleophiles. It is expected that new legislation about the regulation on PAH emissions will be very restrictive. In this work, PAH emissions from coal AFBC as a function of the coal combustion variables (combustion temperature, gas flow and percentage of excess oxygen) are reported. In addition, the effect of bed nature on PAH emissions is also assessed. Polyaromatic hydrocarbon emissions at the standard conditions used at the AFBC power stations are assessed by the study carried out in an AFBC laboratory pilot plant. The PAHs listed by the US EPA as priority pollutants are analyzed by fluorescence spectroscopy (FS) at the synchronous mode.

Catalytic pyrolysis of wood biomass in an auger reactor using calcium-based catalysts

Wood catalytic pyrolysis using calcium-based materials was studied in an auger reactor at 450°C. Two different catalysts, CaO and CaO·MgO were evaluated and upgraded bio-oils were obtained in both cases. Whilst acidity and oxygen content remarkable decrease, both pH and calorific value increase with respect to the non-catalytic test. Upgrading process was linked to the fact that calcium-based materials could not only fix the CO2-like compounds but also promoted the dehydration reactions. In addition, process simulation demonstrated that the addition of these catalysts, especially CaO, could favour the energetic integration since a lowest circulation of heat carrier between combustor and auger reactor should be needed. An energy self-sustained system was obtained where thermal energy required for biomass drying and for pyrolysis reaction was supplied by non-condensable gas and char combustion, respectively.

Valorisation of forestry waste by pyrolysis in an auger reactor.

Pyrolysis of forestry waste has been carried out in an auger reactor to study the influence of operational variables on the reactor performance and the properties of the related products. Pine woodchips were used for the first time as raw material and fed continuously into the reactor. Ten experiments were carried out under inert atmosphere at: (i) different reaction temperature (1073, 973, 873, 823 and 773 K); (ii) different solid residence time (5, 3, 2 and 1.5 min); and (iii) different biomass flow rate (3.9, 4.8 and 6.9 kg/h). Results show that the greatest yields for liquid production (59%) and optimum product characterisation were obtained at the lowest temperature studied (773 K) and applying solid residence times longer than 2 min. Regarding bio-oil properties, GC/MS qualitative identification show that the most abundant compounds are volatile polar compounds, phenols and benzenediols; and very few differences can be observed among the samples regardless of the pyrolysis operating conditions. On the whole, experimental results demonstrate that complete reaction of forest woodchips can be achieved in an auger reactor in most of the experimental conditions tested. Moreover, this study presents the initial steps for the future scaling up of the auger reactor with the aim of converting it into a mobile plant which will be able to remotely process biomass such as energy crops, forestry and agricultural wastes to obtain bio-oil that, in turn, can be used as energy vector to avoid high transport costs.

Deep oxidation of pollutants using gold deposited on a high surface area cobalt oxide prepared by a nanocasting route

Gold deposited on a cobalt oxide with high surface area (138 m(2)g(-1)), obtained through a nanocasting route using a siliceous KIT-6 mesoporous material as a hard template, has demonstrated high activity for the total oxidation of propane and toluene, and ambient temperature CO oxidation. The addition of gold promotes the activity when compared to a gold-free Co(3)O(4) catalyst prepared using the same nanocasting technique. The enhanced catalytic activity when gold is present has been explained for the deep oxidation of propane and toluene in terms of the improved reducibility of cobalt oxide when gold is added, rather than to the intrinsic activity of metallic gold particles. The improved behaviour for CO oxidation has been linked to the simultaneous presence of Au(δ+) and Au°.

Optimisation of scrap automotive tyres recycling into valuable liquid fuels

The recycling of rubber from old tyres by batch hydrogenation has been performed using tubing bomb reactors. Important process variables like temperature, reaction time, initial hydrogen pressure and nature of gas used have been studied. In all the runs the maximum total conversion was achieved. Conversion products are comprised of oils and gases, being the asphaltene yield lower than 1% in all conditions tested. The most valuable conversion products, oils, have been systematically analysed by TLC-FID1 and the influence of the process variables in oils composition has been assessed. From the obtained results, it can be deduced that the conversion of rubber in oils is a fast thermal process, which is neither affected by initial pressure nor the nature of gas used. But on the other hand, the nature of obtained oils and gases is a function of process variables.

High activity mesoporous copper doped cerium oxide catalysts for the total oxidation of polyaromatic hydrocarbon pollutants

The doping of mesoporous ceria with copper significantly enhances activity for naphthalene total oxidation, the enhanced performance is controlled by the increased concentration of surface oxygen defects.

Assessment of PAH emissions as a function of coal combustion variables in fluidised bed. 2. Air excess percentage

Abstract A low rank coal combustion was carried out in a fluidised bed combustion pilot plant at laboratory scale, with the aim of studying the influence of the air excess percentage on the PAH formation and emission. The experiments were performed at 850°C with a constant air total flow of 860 L h −1 , varying the coal feeding rate and therefore the air excess percentages. In each experiment, five samples have been collected from two cyclones, bubbling system, nylon filter, and adsorption system. The PAH contained in these five samples have been analysed by FS (fluorescence spectroscopy in mode synchronous) after extraction by sonication with dimethyl-formamide (DMF) The analyses show that the total PAH amount keeps a close relationship with the air excess percentage: the higher the air excess, the lower the total PAH amount emitted.

Demonstration of the waste tire pyrolysis process on pilot scale in a continuous auger reactor.

This work shows the technical feasibility for valorizing waste tires by pyrolysis using a pilot scale facility with a nominal capacity of 150 kWth. A continuous auger reactor was operated to perform thirteen independent experiments that conducted to the processing of more than 500 kg of shredded waste tires in 100 h of operation. The reaction temperature was 550°C and the pressure was 1 bar in all the runs. Under these conditions, yields to solid, liquid and gas were 40.5 ± 0.3, 42.6 ± 0.1 and 16.9 ± 0.3 wt.% respectively. Ultimate and proximate analyses as well as heating value analysis were conducted for both the solid and liquid fraction. pH, water content, total acid number (TAN), viscosity and density were also assessed for the liquid and compared to the specifications of marine fuels (standard ISO 8217). Gas chromatography was used to calculate the composition of the gaseous fraction. It was observed that all these properties remained practically invariable along the experiments without any significant technical problem. In addition, the reaction enthalpy necessary to perform the waste tire pyrolysis process (907.1 ± 40.0 kJ/kg) was determined from the combustion and formation enthalpies of waste tire and conversion products. Finally, a mass balance closure was performed showing an excellent reliability of the data obtained from the experimental campaign.

Porosity–Acidity Interplay in Hierarchical ZSM‐5 Zeolites for Pyrolysis Oil Valorization to Aromatics

The properties of crude bio-oils attained by the pyrolysis of lignocellulosic biomass can be greatly enhanced by means of catalytic upgrading. Here, we demonstrate an efficient process concept coupling the production of pyrolysis oil from pine wood with a consecutive catalytic upgrading step over hierarchically structured ZSM-5 zeolites to attain aromatic-rich bio-oils. The selective upgrading of these complex mixtures is shown to be tightly connected to the extent of mesopore development and the density of Brønsted acid sites at the mesopore surface. A full product analysis enables elucidation of the impact of mesopore introduction and the acidic properties on the complex reaction network. The preferential occurrence of decarbonylation reactions in hierarchical zeolites versus dehydration transformations in the bulk counterparts is believed to be decisive in promoting increased aromatics formation.