R. Murillo

Assessment of PAH emissions as a function of coal combustion variables

The influence of fluidized bed combustion (FBC) temperature and coal rank on polycyclic aromatic hydrocarbon (PAH) emissions was assessed. A low-rank coal and a high-rank coal were burnt in a fluidized bed reactor (FBR) on a laboratory scale. An outlet gas sample was passed through a capture system provided with three traps: nylon filter, Teflon filter and XAD-2 resin. The PAH captured were analysed by fluorescence spectroscopy (FS) after sonic extraction with dimethylformamide (DMF). The results show that the total PAH emission depends mainly on the pyrolytic process and to a lesser degree on the combustion efficiency. Although the total amount of PAH emitted follows a specific trend as a function of the combustion temperature, the amount of each PAH emitted seems to be consequence of a random distribution due to PAH interconversion and association. Under all conditions of combustion, the amount of PAH emitted in the gas phase is higher than that collected in two cyclones preceding the gas sampling location.

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.

New CO2 capture process for hydrogen production combining Ca and Cu chemical loops.

This paper presents a new solids looping process for capturing CO2 while generating hydrogen and/or electricity from natural gas. The process is based on the sorption enhanced reforming of CH4, employing CaO as a high temperature CO2 sorbent, combined with a second chemical loop of CuO/Cu. The exothermic reduction of CuO with CH4 is used to obtain the heat necessary for the decomposition of the CaCO3 formed in the reforming step. The main part of the process is completed by the oxidation of Cu to CuO, which is carried out with air diluted with a product gas recycle of this reactor at sufficiently low temperatures and high pressures to avoid the decomposition of a substantial fraction of CaCO3.

Valorisation of waste tyre by pyrolysis in a moving bed reactor

The aim of this work is to assess the behaviour of a moving bed reactor, based on a screw transporter design, in waste tyre pyrolysis under several experimental conditions. Waste tyre represents a significant problem in developed countries and it is necessary to develop new technology that could easily process big amounts of this potentially raw material. In this work, the influence of the main pyrolysis process variables (temperature, solid residence time, mass flow rate and inert gas flow) has been studied by a thorough analysis of product yields and properties. It has been found that regardless the process operational parameters, a total waste tyre devolatilisation is achieved, producing a pyrolytic carbon black with a volatile matter content under 5 wt.%. In addition, it has been proven that, in the range studied, the most influencing process variables are temperature and solid mass flow rate, mainly because both variables modify the gas residence time inside the reactor. In addition, it has been found that the modification of these variables affects to the chemical properties of the products. This fact is mainly associated to the different cracking reaction of the primary pyrolysis products.

Production of activated carbon by waste tire thermochemical degradation with CO2

The thermochemical degradation of waste tires in a CO(2) atmosphere without previous treatment of devolatilization (pyrolysis) in order to obtain activated carbons with good textural properties such as surface area and porosity was studied. The operating variables studied were CO(2) flow rate (50 and 150 mL/min), temperature (800 and 900 degrees C) and reaction time (1, 1.5, 2, 2.5 and 3h). Results show a considerable effect of the temperature and the reaction time in the porosity development. Kinetic measurements showed that the reactions involved in the thermochemical degradation of waste tire with CO(2), are similar to those developed in the pyrolysis process carried out under N(2) atmosphere and temperatures below 760 degrees C, for particles sizes of 500 microm and heating rate of 5 degrees C/min. For temperatures higher than 760 degrees C the CO(2) starts to oxidize the remaining carbon black. Activated carbon with a 414-m(2)/g surface area at 900 degrees C of temperature, 150 mL/min of CO(2) volumetric flow and 180 min of reaction time was obtained. In this work it is considering the no reactivity of CO(2) for devolatilization of the tires (up to 760 degrees C), and also the partial oxidation of residual char at high temperature for activation (>760 degrees C). It is confirmed that there are two consecutive stages (devolatilization and activation) developed from the same process.

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.

Some inferences on the mechanism of atmospheric gas/particle partitioning of polycyclic aromatic hydrocarbons (PAH) at Zaragoza (Spain)

Gas/particle partitioning of pollutants is an important mechanism determining atmospheric processing and its impact to environmental and human health. In this paper, the gas-particle partitioning of polycyclic aromatic hydrocarbons (PAH) has been studied with the aim of determining the main mechanism of PAH partitioning in Zaragoza (Spain) aerosols. To reach this goal, the ambient concentrations of PAH (gas and particle phase) collected in this city for one year period (2003-2004) have been analyzed. The partitioning between the particle and gas phases was studied according to three different models: the Junge adsorption model, the absorption into the organic matter model using the octanol-air (K(OA)) partition coefficient and the absorption into the organic matter plus the adsorption onto the soot carbon model using the soot-air (K(SA)) partition coefficients. Experimental gas/particle partition coefficients (K(P)) correlated well with the subcooled liquid vapour pressures (P(L)(0)) of PAH but with slopes higher than the expected value of -1. Experimental K(p) values were well fit to the modelled ones when, in addition to absorption into organic matter, adsorption onto the soot carbon was considered. It could be concluded that the main partition mechanism in Zaragoza aerosols was explained by adsorption onto the soot carbon. However, K(p) modelled values were affected by the different thermodynamic parameters related to soot types. The influence of the organic matter and elemental carbon fractions on the K(p) modelling was also studied. The different particle characteristics, local factors, the presence of non-exchangeable fraction and non-equilibrium were considered like main keys to explain deviations of the experimental K(p) values from predictions according to models.

CO2 Capture from Cement Plants Using Oxyfired Precalcination and/or Calcium Looping

This paper compares two alternatives to capture CO(2) from cement plants: the first is designed to exploit the material and energy synergies with calcium looping technologies, CaL, and the second implements an oxyfired circulating fluidized bed precalcination step. The necessary mass and heat integration balances for these two options are solved and compared with a common reference cement plant and a cost analysis exercise is carried out. The CaL process applied to the flue gases of a clinker kiln oven is substantially identical to those proposed for similar applications to power plants flue gases. It translates into avoided cost of of 23

Valorisation of forestry waste by pyrolysis in an auger reactor.

/tCO(2) capturing up to 99% of the total CO(2) emitted in the plant. The avoided cost of an equivalent system with an oxyfired CFBC precalcination only, goes down to 16

Critical review on atmospheric PAH. Assessment of reported data in the Mediterranean basin

/tCO(2) but only captures 89% of the CO(2) emitted in the plant. Both cases reveal that the application of CaL or oxyfired CFBC for precalcination of CaCO(3) in a cement plant, at scales in the order of 50 MWth (referred to the oxyfired CFB calciner) is an important early opportunity for the development of CaL processes in large scale industrial applications as well as for the development of zero emissions cement plants.